Warren 2016

Lower Temperature Metals
in an Evaporitic Framework 15
Introduction chapter we will focus on stratabound Cu, Pb-Zn and U asso-

ciations in the low temperature realm (diagenetic and lower
Most subsurface evaporites ultimately dissolve and, through end of greenschist grade ores). The next chapter will focus
their ongoing dissolution and alteration, can create condi- on metalliferous ores (both gold and base metals) formed in
tions suitable for metal enrichment and entrapment in sub- those higher temperature igneous and metamorphic realms
surface settings ranging from the burial diagenetic through to that have interacted with evaporites.
the metamorphic and igneous realms. Within this framework, Let me clearly state at the outset of this discussion that I
this chapter explores relationships between evaporites and am not saying all large metal accumulations require evapo-
lower temperature ore deposits, where ore is defined as a rites or the highly-saline subsurface fluids that they can gen-
mineral, or an aggregate of minerals, from which a valuable erate, although some recent papers do argue for a widespread
constituent, especially a metal, can be profitably mined or role of evaporites in the Pb-Zn association (Fusswinkel et al.
extracted. The next chapter explores the significance of dis- 2013; Wilkinson et al. 2009). This and the next chapter are
solving and altering evaporites in ore deposits formed in the only about those deposits where evaporites have contributed
higher temperature igneous and metamorphic realms. to the metal accumulation in some way. However, as the vari-
An overview of a selection of the large-scale ore deposits ous tonnage-grade plots in this chapter and the next show,
associated with hypersaline brines and dissolving/altering many accumulations with an evaporite association tend to
salt masses, plotted on a topographic and salt basin base, plot at the larger end of their respective groupings.
shows that the many evaporite-associated ore deposits lie High levels of metals in all ore deposits, like thick salts in
outside areas occupied by actual evaporite salts (Fig. 15.1). evaporite basins across the sedimentary realm, are responses
Rather, they tend to be at or near the edges of a salt basin or to unusual conditions, related to fortuitous associations of
in areas where most or all of the actual salts have been long local and plate-scale tectonics and fluid systems. To become
gone (typically via subsurface dissolution or metamorphic an ore deposit, metals need to build, at specific precipitation
transformation). This is why the metal-evaporite association sites, to levels well above that of their background presence
is not widely recognised by the economic geology commu- in the carrier brines. This typically requires a chemical inter-
nity. Without the conceptual tools to recognise the former face that can be related to salinity/oxidation levels, or cool-
presence of evaporites (Chap. 7) and meta-evaporites (Chap. ing/heating interfaces. As such, it is no surprise that the same
14) the significance of disappearing salt masses, in focusing process sets created by conductivity and salinity/oxidation
and enhancing metal precipitation via the creation of levels tied to dissolution and reprecipitation of minerals are
chloride-rich brines, is not obvious. likely to be associated with conduits created by the passage
We have already discussed ore deposits where the evapo- of pore waters from altered buried evaporites and hydrother-
rite minerals constitute the ore, or have transformed into mal salts (e.g., Fusswinkel et al. 2013). As for the salts that
gemstones (Chaps. 11, 12, and 14). Earlier papers by accumulate in ancient evaporite basins, we can place ore
Kirkham 2001 and have noted parts of this association in the deposit frequencies in a time and plate tectonic framework
metals realm (Fig. 15.1), but have focused on the ore depos- and so perhaps better understand and predict occurrences
its themselves. This chapter and the next will approach this (Fig. 15.2; Groves et al. 2005).
problem a little differently. We shall place the various base Not all sediment-associated ore deposits are associated
and precious metal deposits in the framework of our deeper with evaporites. Only in those ore deposits that are classi-
understanding of evaporites and their residues and then use fied as anorogenic and/or continental margin can subsur-
this understanding to pigeonhole the deposits. So, in this face evaporite masses be involved in the same unusual
© Springer International Publishing Switzerland 2016 1469

J.K. Warren, Evaporites: A Geological Compendium, DOI 10.1007/978-3-319-13512-0_15
1470 15 Lower Temperature Metals in an Evaporitic Framework
Wernecke Coppermine
Ruby Ck. Kiruna
Redstone
Lubin Udokhan
Sustut Sullivan Volyn
White Pine Scharzwald Dzhezkazgan
Rock Ck. Malines
Balmat
Lisbon Valley Iron Mt. Muguria
Bou Grine Bafq Aynak
Meishan
Salton Sea Hockley Dome
Atlantis Deep Dongchuan
Salabo
Sediment-hosted stratiform Cu
Fungurume Kipushi
Salt-related Pb-Zn Corocoro McArthur
Tsumeb Nchanga Cadjebut
Mantos Blancos Mt. Isa
Kipushi-style Cu-Zn-Pb Lake N’Gami Nifty Ernest Henry
El Laco
Mount Isa-style Cu Candelaria Klein Aub Olympic Dam
El Romeral Broken Hill
Volcanic-related Cu El Soldado Blinman Kapunda
Fe-oxide Cu-Au
Kiruna-type apatite-Cu
Fig. 15.1 A selection of metalliferous ore deposit provinces where for- the next for further explanation of the various deposits). Also, positions
mation is tied to the presence of hypersaline brines and/or evaporites (In of the world’s larger halite-dominated basins are plotted as orange-
part after Kirkham 2001; see also Table 15.1 and text in this chapter and coloured areas, anhydrite-dominated as green
a Orogenic-convergent margin settings b Anorogenic or continental-basin settings

3 Ga 2 Ga 1 Ga 0 Ga 3 Ga 2 Ga 1 Ga 0 Ga
Cyprus-type (HA) Uranium in weathered

profile (E?)
VHMS (HA)
IOCG (E?)
Abitibi-type (HA) Kiruna-type

(HA & E?)
Olympic Dam type
(HA & E?)
Kuroko (HA)
Ilmenite-anorth. (HA?)
Orogenic gold (HA) Lead-zinc in clastic

sediments (E)
Paleoplacer
SEDEX-Style
and placer gold Lead-zinc in carb-

onates -MVT (E)
Porphyry (HA)
Porphyry Cu (HA) Copper in clastic

sediments (E)
Porphyry Mo (HA)
Archean Paleoprot. Mesopr. Neopr. Phan. Archean Paleoprot. Mesopr. Neopr. Phan.
3.6 2.5 1.6 1.0 0.542 3.6 2.5 1.6 1.0 0.542
Fig. 15.2 Ore deposit occurrences across geological time (Modified deposit style. E? indicates the presence of hypersaline brine associated
from Groves et al. 2005; see Meyer 1988 for more detail and other igneous with the formative ore process. Such brines may be magmatic or sedimen-
subsets). (a) Orogenic convergent margins, (b) Anorogenic or basin colli- tary/hydrothermal. HA indicates the presence or former presence of
sion settings. E indicates direct evidence of evaporites or derived brine in hydrothermal or igneous anhydrite precipitated by non evaporitic
the formative processes associated with some of the examples of this processes
c oncentration and alteration conditions that lead to the salinity conditions inherent to the ore forming environ-
creation of metalliferous ore deposits (indicated by E in ment, as in the formation of carbonatites (e.g. Afrikanda
Fig. 15.2). At other times mineral salts, such as anhydrite, and Bayan Obo; Wu 2008) and pegmatites (hydrothermal
can be an integral part of the ore accumulation, but their anhydrite is indicated by HA in Fig. 15.2). In such hot
occurrence may be unrelated to aridity. Rather, they are subsurface settings the role of any buried “true” evaporite
burial or magmatic hydrothermal salts formed by high may be, via its dissolution or alteration, to aid in the
Introduction 1471
c reation of highly-saline high-temperature basinal brines. chloride ions to the brine system. Salt beds that are thick
These brines can then act as either enhanced metal carri- enough tend to flow and so focus the upward and centripetal
ers or fixers. passage of basinal and hydrothermal fluid flows. Dissolving
The role of evaporites creating metalliferous ores is two- gypsum or anhydrite beds, typically deposited higher on the
fold; (1) In solution (halite-dominant precursor) they can act basin platform or diagenetically accumulated along salt
as chloride-rich metal carriers and (2) Locally, as beds or dissolution edges and touchdowns can supply sulphur, via
masses (especially of CaSO4), their dissolution products, bacterial or thermochemical sulphate reduction, while
especially if trapped, can supply sulphur (mostly as bacterio- simultaneously focusing metalliferous brine flows into the
genic or thermogenic H2S) and also set up chemical inter- precipitation interface.
faces that act as foci in the setup of brine mixing conditions When the chemistries of the dissolving salt beds and the
suitable for precipitation of metal sulphides or native ele- metal carriers interact so that redox fronts, salinity contrasts,
ments. Hence, many evaporite-associated ore systems tend and other precipitative interfaces are set up, an ore deposit
to be epigenetic, rather than syngenetic (Table 15.1). can form. Thus, in base and precious metal exploration in
Subsurface salt beds and masses are merely the solid part of evaporitic terranes, we are ultimately searching for those
a large ionic recycling system, dissolved metals are another parts of a subsurface ionic cycling system where the salt dis-
part and zones of mixing between the two are typically sites solution, salt beds and metal systems have interacted to cre-
where ores tend to accumulate. ate economic levels of metalliferous precipitates.
At the world-scale, both systems are driven by plate tec- Conceptually, this evaporite-related notion of regional
tonics. Halite-dominated sequences, deposited in the draw- fluid flow in a sedimentary/metasedimentary host is some-
down basin centres, tend to dissolve in burial, and so supply what different to the internal process and local mineralised
Table 15.1 Classic classification of ore deposits into epigenetic and syngenetic (e.g. as used by Evans 1993). The effects of evaporites within this
type of classification ranges across many subdivision -see text
Epigenetic Porphyry Cu-Mo
Mineral deposit formed much later Large, low grade, usually associated with porphyritic Cu (−Au)
than the rocks which enclose it intrusive body Mo (−W)
Skarn W-Cu (−Zn, −Mo)
Deposits formed by replacement of limestone by ore and Zn-Pb-Ag (−Cu, −W)
calc-silicate minerals, usually adjacent to a felsic or Cu (−Fe, −Au, −Ag, − Mo)
granitic intrusive body Fe (−Cu, − Au)
Sn (−Cu, −W, −Zn)
Au (−As, −Cu)
Vein Hypothermal –Cu (−Au)
Fracture filling deposits which often have great lateral and/ Mesothermal –Cu-Pb-Zn-Ag-Au
or depth extent but which are usually very narrow Epithermal –Au-Ag (−Hg)
Mississippi Valley Type Pb-Zn deposits with low Ag values
Named for the region where they were first described, these
deposits formed within porous carbonate rocks (limestone
reefs or caves)
Stratiform sediment-hosted redbed Cu Cu
Syngenetic Volcanic Massive Sulphide (VMS) Felsic
Mineral deposit which formed at the These deposits formed as massive (over 60 % sulphide) volcanic hosted –Cu-Pb-Zn-Ag-Au
same time as the rocks that enclose it lens-like accumulations on or near the sea floor in Mafic
association with volcanic activity volcanic hosted –Cu (−Zn, −Au)
Mixed volcanic/sedimentary – Cu-Zn
(−Au)
Sedimentary Massive Sulphide (SedEx) Pb-Zn-Ag
Deposits formed by hydrothermal emanations on or near Ba
the sea floor in association with the deposition of
sedimentary rocks
Magmatic-layered mafic intrusion PGM (Platinum group metals)
During the crystallization of a magma, usually mafic or Chromite
ultramafic, heavy, metal-rich liquids settle and accumulate Ni-Cu (−PGM)
at specific sites, often at the base, within the intrusion
Placer Au, diamond, cassiterite
Formed within sediments by the concentration of heavy
resistant minerals by stream or wave action
halo models that dominate our understanding of those world- etal-evaporite association is the understanding of; (1) evap-
m
class ore deposits related to the interior workings of igneous orite dissolution and halokinesis, (2) Migration of subsurface
systems. The latter are known as orthomagmatic systems and fluids, (3) creation of nearsurface redox fronts along with,
encompass the majority of the deposits listed in Fig. 15.2a. (4) the opening and closing of fault/shear focused fluid con-
There, interior igneous processes of fractional crystallisation duits, typically tied to, the coming and going of bedded and
and liquid immiscibility largely control ore formation in a halokinetic salts. These factors, rather than primary sediment
framework of the evolution of world-scale tectonics across wedge geometries, are the dominant controls as the mineral-
time, from Archaean greenstones to those of present-day ising system passes from the diagenetic into the metamor-
plate tectonism. Examples where buried evaporites have phic realm.
been assimilated into a magma chamber are discussed in the It is interesting that in a benchmark paper, discussing and
next chapter. Then there are the various ore deposits that are classifying the world’s ore deposits in a plate-tectonic-time
external to (paramagmatic) or unrelated to the emplacement framework, Groves et al. (2007) list almost all the major ore
of igneous bodies (nonmagmatic). In both cases, the miner- categories shown in Fig. 15.2b as belonging to the group of
alisation is typically part of an ongoing longterm sedimen- “…sediment-hosted deposits of non-diagnostic or variable
tary burial history, tied to dissolving and flowing masses and geodynamic setting.” Into this category they place all strati-
associated hydrothermal circulation. form to stratabound sediment-hosted deposits with variable
So, this chapter focuses on nonmagmatic ore deposits. proportions of Pb, Zn, Cu (including Zambian Copper belt,
The conceptualization of metal sources in a framework of Kupferschiefer and SedEx deposits). They go on to note
orthomagmatic versus paramagmatic versus nonmagmatic is (p. 26) that, although there is general agreement that the
important as it either ties the deposit style to times and loca- majority of these various deposits formed during active
tions of magmatism and associated metal/heat brine sources crustal extension, either in intracratonic rift basins or in pas-
or, in nonmagmatic settings, it does not. sive margin sediment hosts, there is considerable controversy
Evidence for hydrothermally-induced low-moderate tem- concerning their broader scale tectonic setting at the time of
perature mineralisation is often best preserved in textures in mineralisation and the driving force for hydrothermal fluid
the hydrothermally altered rock matrix, typically located flow at the time of their mineralisation.
outside the actual ore deposit (in its hydrothermal alteration Perhaps this lack of model specificity in the varied inter-
halo). From the hydrothermal perspective, one should see the pretations of sediment-hosted deposits reflects the fact that
role of evaporites and metal sulphides as each contributing one piece of significant information is missing from many
its part to a larger scale “mineral systems” paradigm, much ore genesis models. Namely, that the greater majority of
in the same way as, in a petroleum system, the integration of these poorly classified sediment-hosted deposits sat atop, or
concepts of source, carrier, seal and trap are fundamental adjacent to, or beneath, what were once thick evaporite
requirements to understand and predict economic oil and gas sequences. It was the dissolution of these salt masses, either
accumulations. bedded or halokinetic-allochthonous, that focused much of
This ore systems approach is not fully encompassed in a the ore-fluid flow in the sedimentary-diagenetic realm. The
number of economic geology studies that use sequence loss of salt as the basin sediments passed from the low tem-
stratigraphic sedimentological approaches for ore deposit perature diagenetic into the metamorphic realm, and as met-
prediction in greenschist terrains (Ruffell et al. 1998; alliferous fluid flow was focused into permeable conduits
McConachie and Dunster 1996). In my opinion, this about or above the dissolving and retreating, or flowing salt
approach can shift the interpretation paradigm too far into edges, is how salt-related ore deposits form.
the depositional realm. The problem with classic sequence This is why the majority of these deposits tend to occur
stratigraphic approaches, when trying to understand ore gen- outside salt basins that retain substantial salt masses still in
esis, is that sequence stratigraphy does not handle well the the diagenetic realm (Fig. 15.1). They are a response to the
concept of a mobile ephemeral subsurface salt body that dissolution of evaporites, or the residual seawater bitterns
climbs the stratigraphy via autochthonous and allochthonous created in underlying and subjacent settings as the salt beds
process sets (halokinesis). As the salt flows, it dissolves and were deposited, not the presence of evaporites. As we saw in
so brings with it the associated epigenetic influences of the previous chapter in our discussion of Proterozoic and
brine-driven diagenesis and metasomatism. Current sequence Archaean meta-evaporites, in most Precambrian evaporite
stratigraphic paradigms in the economic geology realm are associations the original salt mass is long gone from the
dominated by the assumption that the geometry of the units hosting succession, via varying combinations of halokinesis,
in the depositional system, and associated fault characteris- dissolution and metasomatism. Ore deposits of this age tend
tics, are relatively static within the buried sediment prism. to be linked to evaporite alteration products and residues and
Yet, in terms of most sediment-hosted hypersaline ore rarely preserve actual sedimentary salts (other than local
deposits, what is most important in understanding the
remains of hydrothermal anhydrite). In younger Phanerozoic
A Little Classification/Exploration Philosophy 1473
deposits, such as Kupferschiefer, the Atlantis II deep and I am not saying the varied interpreted process sets, that
Dzhezkazgan, portions of actual salt (brine source) remain in explain the SSC, MVT and SedEx deposits, are wrong,
the more deeply buried parts of the basin. only that the current classification sets are so broad that,
Metal sulphide precipitates are not rare or unique in the when exploring, they lack the ability to make specific on-
subsurface diagenetic fluid milieu, what is important in pre- ground target predictions. Other than a general notion that
diction of ore-grade levels of metal sulphide buildups is most of these deposits are typically tied to faults acting as
understanding where and why the metal precipitation system fluid conduits, there is little commonality in rock textures
was focused into particular structurally-controlled positions. and lithologies across the host rock spectrum. That is to
That is, evaporite associated ore deposits are no more than say, most of the host rock textures are extensive, but the
ancient subsurface hydrology-specific associations where faults are local, so we tend to target the fault or a set of fault
the precipitation system was stable enough, for long enough, trends, hoping to find mineralisation. Geochemistry of vari-
to allow ore-grade levels of metals sulphides to accumulate ous sorts is the tool used to highlight areas of “on ground”
from carrier brines. As such, they are part of the ore-forming interest and specify more targeted drilling; typically host
process set, spread across the epigenetic and syngenetic rock textures do not play much of a role as part of the
realms (Table 15.1). They were part of the regional evolution exploration paradigm.
of the fluid plumbing from time of deposition, into burial, But, if we can establish that evaporites (bedded or halo-
and on into the realm of metamorphic transformations. This kinetic) or their residues acted as foci to mineralisation in
means to holistically understand the ore system in an some types of SSC, SedEx and MVT deposits then, through
evaporite-entraining system one must integrate local ore recognition of positions of former evaporites either in out-
paragenesis with various aspects of the basin-scale geology, crop or core we can establish additional targeting parame-
sedimentology, sequence stratigraphy, diagenetic ters to define where these masses have intersected or
metamorphic-igneous facies, fluid flow conduits and struc- interacted with fluid-carrying faults. This gives us an
tural evolution of the evaporitic basin. improved ability to predict that ores are more likely to be
found at or near the intersections between faults and evapo-
rites or their residues. So for a subset of SSC, MVT and
Little Classification/Exploration
A SedEx deposits (the evaporite-related subset) we then have
Philosophy the ability to more reliably locate and orient drilling sites
and drilling grids.
Personally, I do not find much benefit in trying to create an Unfortunately, modelling paradigms in classic economic
exploration paradigm using the currently accepted somewhat geology typically concentrate on particularized ore paragen-
generalised SSC, MVT or SedEx groupings that capture eses and the detailed measurement of trace/rare-earth ele-
most low temperature base metal deposits. All the current ment constituent levels, which are tied to metal sulphide
compilations of Stratabound Sedimentary Copper (SSC), emplacement, within and about an ore deposit (aka the “indi-
Mississippi Valley Type (MVT) and Sedimentary Exhalative cator halo”). When exploring for new deposits, this halo
(SedEx) deposits tie a very broad range of range of stratiform understanding and associated data trends are used in design-
deposit styles into general association of metal precipitation ing geochemical and remote sensing approaches. Inherently,
occurring in sediment hosts, which may be redbeds, shelfal this approach is most fruitful in brownfields expansion stud-
carbonates or deeper/quieter water laminites (as an example ies, it gives the more localised understanding needed to pre-
see the excellent compilation of Cox and Singer 2007). All dict ore extensions and hence where to extend the current
these deposits are thought to form in low temperature set- mining operation. But in greenfield areas, where predictive
tings, still largely in the thermal range of diagenetic (not regional models are needed, it leads to less predictive ore
metamorphic) geosystems, and are fed and bathed in cross- exploration paradigms, other than a general concept of…
flowing basinal basement brines. Once formed, subsequent “let’s grid-drill (typically air-drill) around that fault with the
structuration and metamorphism can enhance ore quality. gossan, or in the region of the associated soil anomalies, and
Some SSC, MVT and SedEx models have the fluids see what we get back in the plots of the geochemical analy-
escaping from the basin during basin subsidence, others call ses of the rock flour”.
upon deep meteoric circulation driven by basin collision and With this in mind, I propose a somewhat different clas-
uplift of the basin margin, still others draw upon the convec- sification for those sediment-hosted (this chapter) and
tion of basinal brines beneath evaporite seaway sediments igneous-related (next chapter) ore deposits that can be
and or the mixing of basinal and basement brines. None are linked to evaporitic associations, which are indicated by
rock texture specific, so making the use of applied targeting remnant salt bed and masses, their residues or their altera-
approaches problematic, if based on textures seen in outcrop, tion products. It focuses on the nature of the evaporite, or
or recovered in core. former evaporite, (bedded or halokinetic residues) and the
ore deposits position relative to the former salt bed or salt Evaporite-Related Metalliferous Brines?
mass. When classifying these ore deposits at the intrabasin
scale, I ask; where in earth-space were these evaporite- Before we classify and discuss evaporite-linked ore deposits,
associated metalliferous ore deposits located (within the we need to discuss in general terms how metals are sourced,
diagenetic and early metamorphic evolution of the evapo- transported and fixed in the various subsurface fluids found
rite mass)? And I answer in terms of the following in sedimentary basins containing thick successions of dis-
criteria: solving evaporite salts. Chloride complexes, not organo-
metallic or bi-sulphide complexes are what transports the
(i) Is the ore deposit related to stratiform or halokinetic greater volume of base metals through the pore spaces in the
(allochthon) salt beds/masses and/or their residues? diagenetic realm of today’s sedimentary basins (Kharaka and
(ii) Is the ore deposit in a; subsalt (below a thick >50–100 m Hanor 2003). Through the inherently high pore brine densi-
salt bed/mass), intersalt (interbedded with ≈ 2–10 m ties created by subsurface halite dissolution, such high-
thick salt beds) or suprasalt position (above a thick chloride basinal brine densities can drive metal leaching
>50–100 m salt bed/mass)? waters deep into the understrata, including crystalline base-
(iii) What was the likely dominant mineralogy in the former ment (Chap. 8; Koziy et al. 2009; Fusswinkel et al. 2013).
now dissolved salt mass (halite, anhydrite, trona, nah- Also aiding the creation of metalliferous brines in the dia-
colite, etc.)? genetic realm is the sequential release of a metal series as
organic-rich shales are subject to burial compaction under
For the plate tectonic framework, I ask: increasing temperature and pressure (Table 15.3; Wallace
et al. 2002). The evolution parallels the maturation/genera-
(i) What was the plate tectonic setting at the time these ore tion of first liquid and then gaseous hydrocarbons (Chap. 9).
deposits formed; convergent, divergent, intracratonic Released metals are dissolved in the basin’s aqueous
sag or strike slip? (chloride-rich) fluids via a sequence of thermochemically
(ii) Does it relate to the plate tectonic association of the controlled metal-maturity windows. That is, metals are
interacting evaporites? If yes, then: What was the depo- released from maturing shale/mudstone source rocks in a
sitional style of the host sediments (shallow or deep progressive sequence, determined by ion concentrations and
water; marine or nonmarine)? This also relates to the degree of association of ion complexes (Helgeson 1969), so
style, scale and geometry of the salt-related plumbing at that metals of similar ionic strengths and ionic diameters are
the time of interaction/ dissolution: Was it a saltern or a released together. The temperatures at which these metal
basinwide salt unit, was it interbedded, massive strati- suites are released overlap, but the release from the shaly
form or halokinetic? If halokinetic, was it autochtho- diagenetic sources follows a consistent pattern with increas-
nous or allochthonous? ing depth of burial.
(iii) Was there a single metalliferous fluid or multiple fluids As well as this grey-bed leaching, metals can also be
linked to the mineralisation/diagenetic history? Was the leached diagenetically via redbed alteration in evolving
fluid source a burial water, or a magmatic or a metamor- saline oxidised nonmagmatic brine systems. In paramag-
phic fluid, or was it some type of hybrid? matic systems, igneous bodies can act as an additional source
(iv) Was the deformation history of the deposit simple or of brine products, as can leached volcaniclastics. Once
complex and does it relate to the metamorphic grade or released, as in a petroleum system, there must be carrier beds
early structural controls, including halokinetic struc- for the metalliferous brines, along with focusing mecha-
turation of the salt overburden? nisms and then traps and seals to focus accumulations. As we
shall see throughout this chapter and the next, this is how
The resulting illustrative listing of some nonmagmatic subsurface salt masses make substantial contributions to the
deposits given in Table 15.2 is by no means comprehen- formation of an economic metal accumulation. Before, or as,
sive. It showcases only some of the more well-known subsurface evaporite salts disappear, they generate various
Phanerozoic and Proterozoic examples where actual salts, brine chemistries that can transport, seal, trap, focus and pre-
or obvious residues, are still present. In the next chapter I cipitate ore. Thus, a buried evaporite unit can act as:
shall expand on it as we develop paramagmatic and ortho-
magmatic models. For the deposits listed in Table 15.2 the (i) An ionic source – As the salt dissolves or alters it acts as
depositional and diagenetic conditions are reasonably well a brine or volatile source feeding into the basin hydrol-
understood in terms of atmospheric, marine and subsur- ogy. It can supply economically important ions that,
face pore fluids conditions, most of these examples formed depending on the dissolving mineralogy, may be
within subsurface basin chemistries somewhat similar to chloride-rich or a source of sulphur and so act as both a
those seen today. leacher and transporter of metals.
Table 15.2 Classic ore deposit breakdown (stratiform redbed-related Cu versus MVT Pb-Zn deposits) of some of the many Phanerzoic-Neoproterozoic base-metal deposits formed in the diage-
netic realm in association with bedded, dissolving and flowing evaporites, mostly in situations where actual salts or remnant salts are still present. More comprehensive lists and discussions of less
obviously evaporite-linked ore deposits are discussed later in this chapter and the next
Deposit, location (age of Reserve
host) (106 tonnes) Cu (%) Pb (%) Zn (%) Evaporite role (relative position and mechanism) Evaporite association
Deposits associated with bedded evaporites or their residues
Redstone River, Canada Stratiform Small 2.7 – – Intersalt stratabound with subsalt focus to Redbeds with bedded algal limestone host and
(Neoproterozoic) -sediment hosted upwelling brine abundant nodular CaSO4
Creta, Oklahoma, USA copper (redbed) 1.9 2 – – Intersalt bedded (breccia), adjacent redox Redbed – evaporitic mudflat host with abundant
(Permian) deposit precipitates nodular CaSO4
Corocoro, Bolivia ≥7 ≈5 – – Intersalt bedded (breccia), brine reductant Redbed – greenbed host with gypsum and baryte in
(Eocene) veinlets and disseminated nodules
Evaporite-Related Metalliferous Brines?
Nanisivik, Baffin Island Mississippi 6.5 – 1.5 12 Intersalt?, bedded Host is a stratiform karst cavern: evaporites and
(Mesoproterozoic) Valley Type pseudomorphs in lateral equivalent beds
San Vincente, Peru deposit 12 – 1 12 Intersalt, bedded. Local supplier of sulphur via Ore hosted in cryptalgal laminites with
(Triassic – Jurassic) TSR pseudomorphs after CaSO4 in barrier-lagoon host
Cadjebut, NW Australia 3.8 – 17 % Intersalt, bedded (breccia). Local supplier of Bedded anhydrite as lateral equivalent to each ore
(Devonian) (Pb + Zn) sulphur via TSR lense and linked by evaporite dissolution breccias
Largentiére, France 9.6 – 0.7 3.7 Intersalt Disseminated CaSO4 cements and nodules within
(Triassic) evaporitic lagoonal beds
Peridiapiric deposits associated with halokinetic evaporite masses or their residues
Atlantis II Deep, Red Stratiform 150–200 0.8 Yes 5–6 Suprasalt allochthon acts as focus to resurging Dissolving salt allochthon underbelly supplies Cl-rich
Sea (Holocene) redbed -related Cu-Zn-Cl brine (salt partially covers ridge metalliferous brine to deep seafloor brine lake.
copper deposit basalts) Hydrothermal anhydrite is interbedded with laminites
Kupferschiefer-style, ≈2,000 >2 – – Subsalt, stratiform with brine focus creating the Anhydrite and halite in Zechstein hangingwall and
Lubin, Poland (Permian) Rote Faule contact and adjacent redox precipitates anhydrite in Rotliegende footwall – redbed ore source
Kupferschiefer-style, ≈7.5 ≈2.9 – ±1.8 Subsalt, stratiform with brine focus Anhydrite and halite in Zechstein hangingwall and
Mansfeld, Germany anhydrite in Rotliegende footwall – redbed ore
(Permian) source
Dzhezkazgan, ≈400 1.5 0.1–1.0 – Suprasalt diapiric, anticlinal focus to brine flow Interbedded redbed and greybed host with CaSO4
Kazakhstan and halite in underlying salt anticline and lateral
(Carboniferous) equivalents
Dongchuan deposits, 10–100 1.0–1.5 – – Suprasalt allochthon or intrasalt breccia. Stratabound ore in cryptalgal laminites adjacent to
China Allochthon acts as focus to resurging diapiric breccia
(Mesoproterozoic) metalliferous brine
Lisbon Valley, Utah, Small 1.4 – – Suprasalt allochthon, salt movement creates Ore in vein and pore fills adjacent to faults created
USA (Cretaceous) >0.15 orehosting faults in overburden by halokinesis
Jubilee, Nova Scotia Mississippi Not n/a n/a n/a Subsalt allochthon (tectonic breccia) stratiform, Interstratified fractured carbonate and anhydrite ore
(Carboniferous) Valley Type economic subsalt focus to brine flow host created by regional salt-induced gravity slide
Gays River, Nova Scotia deposit 2.4 – 8.6 6.3 Subsalt with subsalt focus to upwelling brine. Anhydrite both within main ore zone and as cement
(Carboniferous) Local supplier of sulphur via TSR in disseminated ore
Bou Grine, Tunisia 7.3 – 2.4 9.7 Suprasalt, peridiapiric, brine focus via Ore in peridiapiric organic-rich pyritic laminates
(Cretaceous) halokinesis adjacent to halite allochthons
Gulf Coast USA Not n/a n/a n/a Suprasalt allochthon capstone, brine focus via Anhydritic caprock undergoing bacteriogenic
1475
(Tertiary) economic halokinesis alteration in association with reservoired hydrocarbons

Table 15.3 Temperature ranges associated with various metal releases rying hydrocarbons, tend to be anoxic or, at best occasionally
in an organic-rich shale undergoing burial diagenesis dysaerobic. That is, levels of dissolved oxygen in subsurface
Metal maturity window Temperature (°C) petroleum-related waters are always low and typically unde-
U-V-(Th) 35–100 tectable (Collins 1975, p. 159). Shallower, primary reflux
Au-PGE 60–110 brines can retain somewhat higher oxygen levels, but, signifi-
Cu-Ag 60–120 cant dissolved oxygen levels in a brine occur only where sub-
Pb-Zn 70–180 surface waters are in hydrodynamic connection with the
Au-Co-Au 175–275 surface and are actively receiving a surface-recharge (Collins
After Wallace et al. (2002), Helgeson (1970) 1975, p.301). Kuznetsov (1957) measured the dissolved oxy-
gen content in brines from wells in the Groznyv oil district
and found up to 10.6 mg/l at a depth of 249 m. He also found
(ii) A seal and trap – Thick evaporite units act as a seal, limit- that in general, dissolved oxygen was found only in the zone
ing or preventing the free vertical escape of basinal, hydro- of active water circulation (surface recharge) and was lacking
thermal, hybrid or upwelling meteoric waters. Given the in zones of stagnant phreatic waters and below. This general
right geometry, an evaporite unit can also act as a fluid observation has important implications in understanding
barrier that, until it is breached, can pond or hold back depth-related controls on distribution of Rote Faule related
buoyant metalliferous basinal waters and hydrocarbons. ore zones, such as in the Kupferschiefer copper deposits of
(iii) A precipitative focus – Breach points or brine mixing NW Europe (discussed later).
zones tied to the edges of a dissolving evaporite mass In the deeper portions of most saline basins, the dominant
(i.e. the edge of bed or the edge of a salt body created by anion is Cl and the dominant cations Na and/or Ca (Houston
flowage, décollement, or faulting). The edge to an et al. 2011). Elevated levels of chloride in modern basinal
impervious salt mass tends to focus the escape/mixing brines are typically created by some combination of subsur-
of pressured subsurface waters into the zones above, face dissolution of halite (aka secondary brines; Land 1995a,
within or sometimes even below the breach (Chap. 8). b) and infiltration of subaerially evaporated seawater (aka
Additionally, hot metalliferous basinal water, escaping primary brines or reflux brines; Carpenter 1978). Both are
via a breach or conduit into a nearsurface and surface subject to further alteration in ionic proportions in response
setting, can create brine ponds and replacement haloes to other ongoing water-rock interactions, such as albitisation
about, near or atop the escape conduit. at lower salinities and dolomitisation at moderate salinities
(Houston et al. 2011).
Even after the actual salts have long gone, a zone of dis- In general, the salinity of modern basinal brines increases
solution residues can act as an aquifer or focus for ongoing with depth, especially in basins entraining thick deeply-
metalliferous brine flow. Recognising the process and timing buried salt masses (Fig. 15.3; Kharaka and Thordsen 1992).
under which an evaporite disappears or its residues become Basinal pore water salinities are typically higher than seawa-
an aquifer is often the most important step in understanding ter (35 g/l) and range to over 350 g/l in basins with thick
the evaporite ore deposit link. This is especially true of ore partially-dissolved basal salt units. In some basins there is a
deposits hosted in Proterozoic and Archaean rocks and progressive increase in salinity with depth, in others, espe-
metasediments where no actual salts remain, only indicators cially in Tertiary basins with thick dewatering shale units,
of the former evaporite protolith. Such saline metalliferous there may be a reversal of this trend with depth (California
flow paths may at times be indicated by the presence of and South Louisiana basins in Fig. 15.3). The salinity of a
hydrothermal zebra dolomites (Diehl et al. 2010). Na–Cl or Na–Ca–Cl brine can be estimated from its chlorin-
To better define the role of the various metal-carrying ity by the relationship; salinity ≈ 1.7 chlorinity. This is the
chloride brines in evaporitic basins, we will first discuss the basis for most of the salinities estimated from oilfield waters
nature and chemistry of modern subsurface basinal brines, and plotted in Fig. 15.3 (Hanor 1996).
then chemistries suitable for metal precipitation and then
look to likely examples of resultant ore deposits in the sedi- I norganic (Halogen) Components in Basinal
mentary and greenschist realms. Brines
Most basinal brines of moderate salinity are dominated by
dissolved Na and Cl and, as salinity increases, there is a pro-
Modern Basin Brines: Composition gression from Na-Cl to Na-Ca-Cl to Ca-Cl brines (Kharaka
and Hanor 2003; Houston et al. 2011). Chloride is the domi-
Sampled deep formation waters, in particular oilfield brines, nant anion in formation waters with salinities greater than
vary widely in salinity, composition and their metal-carrying 20,000 mg/l, while a transition zone between 20,000 and
capacity (Chap. 8). Most deeper saline brines, even if not car- 10,000 mg/l defines a total dissolved solid (TDS) boundary
Evaporite-Related Metalliferous Brines? 1477
0 basin. Thick beds of dissolving halite (the most common

Michigan
Phanerozoic evaporite salt) generate regional chloride-rich
Illinois brines. Leached anhydrite/gypsum successions are likely to
(E)
(E*) develop sulphate- or sulphide-enriched waters, depending on
the oxidation state of pore waters at the site of dissolution.
1 Associated brine reflux during subsurface dissolution can
drive convective circulation cells, as well as leach and trans-
port metals, within and through the adjacent sediments.
Alberta Ongoing reaction of this reflux brine with the nonevaporite
Depth of reservoir (km)
(E) matrix in nearby beds modifies overall brine chemistry (see

Chap. 8).
2
Ongoing interaction with a dissolving salt mass is seen in
the halogen water chemistry (Cl, Br, F, I) of Phanerozoic
California sedimentary basins. According to Worden (1996), the key
(TS)
geological parameters influencing chlorine and bromine (and
possibly fluorine) concentrations in the basinal waters are, in
3 order of importance: (1) Presence of salt in the basin, (2) Age
North
of the aquifer unit, and (3) Kerogen type within any signifi-
Louisiana (E)
South cant organic-rich rocks in the basin. Worden concluded the
Louisiana Central
presence of salt in a basin means that any connate water con-
(TS)
tributing to the basin water chemistry is hypersaline. More
Mississippi
4 importantly, he showed that most high chlorinity subsurface
(E) waters are not connate (i.e. not preserved seawater), but are
generated though pore-water salt bed interaction during
0 100 200 300 400 500 burial (e.g., Ferguson et al. 1992, 1993; Land 1995a, b).
sw
Water salinity (g/l) Worden 1996 found that brines in Tertiary-age basins
typically have much lower chlorine and bromine concentra-
Fig. 15.3 Salinity to depth profiles in selected basins (After Kharaka tions than pore waters in Mesozoic or Palaeozoic rocks. This
and Thordsen 1992) E evaporitic, E* former, now dissolved evaporite, age separation may simply reflect the different amount of
TS Tertiary shale-rich basin. Sw indicates seawater salinity
time the basinal waters had to interact with any buried salt
beds or that the effects of shale dewatering tends to dominate
below which the dominant anion is either bicarbonate, sul- in rapidly subsiding mud-rich portions of Tertiary sedimen-
phate, or acetate (Fig. 8.40). Sodium is the dominant cation tary basins (Fig. 15.3; California and South Louisiana
in basinal brines with salinities less than 300,000 mg/l. In basins).
general, the relative proportion of Na to K, Ca, or Mg Dominance of type II marine kerogen in a basin leads also
decreases with increasing salinity and Ca becomes the domi- to a higher bromine concentration in the basinal waters.
nant cation in basinal brines having salinities in excess of According to Worden this may reflect the dominance of
330,000 mg/l TDS. Between 300,000 and 330,000 mg/l marine influences in a type II entraining basin, which in turn
TDS, the dominant cation is either Na or Ca. Houston et al. is more likely to lead to greater volumes of salt deposition
(2011) show that most highly saline oilfield formation waters compared with a basin dominated by terrestrial/meteoric
have cation chemistries controlled by chemical equilibration inflows. Iodine concentrations in subsurface waters are inde-
with the host rocks. Thus basinal fluids are almost invariably pendent of all these parameters. He found that other geologi-
enriched in Ca relative to Na, when compared to evaporated cal parameters, such as depth of burial, temperature,
modern seawater of similar chlorinity. This is the result of basin-forming mechanism and reservoir lithology, exerted
ongoing diagenetic mineral-fluid interactions in the subsur- no recognisable influence upon halogen concentrations.
face and CaCl2 brines are the result. In general, the pH of subsurface waters decreases with
Evaporites are important contributors to the major ion increasing salinity from values of approximately 8 for salini-
chemistry of basinal brines through a combination of early ties near 20,000 mg/l to values between 3 and 4 for halite-
brine reflux, ongoing nearsurface and, more importantly, saturated brines with salinities near 330,000 mg/l, thus most
subsurface dissolution/alteration (Houston et al. 2011; Hanor Na–Cl and Na–Ca– Cl brines have a pH in the 4–8 range
and McIntosh 2007). The chemical make-up of a subsurface (Fig. 8.40). Acidity, and hence the ability to leach and carry
brine depends on the mineralogy of the dissolving salt metals, can be augmented by the presence of dissolved
sequence and labile components in other sediments in the organic acids, and CO2, but the proportion of both, relative to
chlorinity, tends to drop off with increasing salinity In addition to Cl−, a variety of different ligands (electron
(Fig. 15.5a). Outside of oilfield waters, true in situ pH values
donors or electronegative ions with lone pairs of valence
in deep subsurface brines are not well known, nor are the electrons) will affect the solubility of metals in solution
relative contributions of the various diagenetic processes that(Robb 2005). Ligands (particularly those that are chloride-
create and maintain acidity. Whatever the other possible car- associated in the high salinity sedimentary realm) combine
riers in a basinal or hydrothermal water it has been known with metallic ions by the formation of a coordinate bond,
for 40 years that elevated salinity (chlorinity) is the key to which is a type of covalent bond where the shared electron
metal transport in the sedimentary diagenetic realm. pair is provided by one of the participating molecules (the
ligand in this case) rather than the normal situation where the
Metals, Ligands and Salinity shared electrons are supplied from each of the two participat-
Oil field brine chemistry, including Holland’s (1972) now- ing components. A ligand that promotes the formation of
classic experiments, show that the solubility of metals such complexes by coordination bonding will typically increase
as Pb, Zn, Mn, and Fe varies as an exponential function of the solubility of metals in aqueous ore-forming solutions
the chloride ion (Cl−) concentration or salinity of the fluid (Fig. 15.4).
and temperature (Figs. 15.4 and 15.6a). Both natural pore How metals go into solution in basinal and hydrothermal
fluid chemistry and laboratory experiments show aqueous fluids can be understood using the concept of Lewis acids
solutions tend to contain other dissolved ingredients that and bases (Robb 2005). Conventional acids and bases are
metals can bond to, thereby promoting metal dissolution. For defined as substances capable, respectively, of contributing
example, the solubility of a mineral such as galena (PbS) in H+ ions to, or taking up H+ ions from, a solution. In contrast,
pure water, even at high temperatures, is extremely small. Lewis acid/base concepts are applicable to subsurface fluid
Wood and Samson (1998) calculated that the amount of Pb situations where H+ ions are not present, and this has particu-
that could be dissolved in an aqueous solution (with 10−3 lar relevance to geological situations (Gill 1994). A Lewis
molal H2S and in equilibrium with galena at 200 °C) would acid is defined as an atom or molecule that can accept a lone
be a trivial 47.4 ppb. If 5.5 wt% NaCl is added to this solu- pair of valence electrons, whereas a Lewis base can donate
tion, the solubility of Pb at the same temperature increases an electron pair to a bond.
significantly to 1,038 ppm and will continue to rise with “Hard” Lewis acids are strongly electropositive metals
increasing temperature (Fig. 15.4). (with high charges and/or small atomic radii) such as the
alkali and alkaline earth metals (e.g. Na+, K+, Mg2+, Ca2+)
that form ionic bonds with strongly electronegative elements,
8 like oxygen (O2−). “Soft” Lewis acids have an abundance of
+l easily accessible electrons in their outer shells and prefer to
C
7 Zn form covalent bonds with soft bases (Table 15.4, Robb 2005).
Soft acids are typified by the chalcophile metals (i.e. those
6
that have an affinity with sulphur, such as Cu, Pb, Zn, Ag, Bi,
5 Cd), which tend to form covalent bonds with ligands of low
+l 3
C + electronegativity, such as S2−. The principle stating that, in a
Cl
U 0
4 b g Cl competitive situation, hard metals (acids or electron accep-
P A
Log β1
3
+ Table 15.4 Classification of selected metals and ligands in terms of
2 Cl l+ Lewis acid/base principles
Mn FeC
1 Hard metals Borderline Soft metals
Li+, Na+, K+, Rb+, Cs+, Divalent transition Au+, Ag+, Cu+,
0 Be2+, Sr2+, Ba2+, Fe3+, metals Hg2+, Cd2+, Sn2+,
Ce4+, Sn4+, Mo4+, W4+, Zn2+, Pb2+, Fe2+, etc. Pt2+, Pd2+,
-1 V4+, Mb4+, Au3+, Tl3+
As5+, Sb5+, U6+
0 100 200 300 400
Hard ligands Borderline Soft ligands
Temperature (°C)
NH3, Cl−, Br− HS−, I−, CN−, H2,
OH−, F−, NO3−, CH3, S, S2, O32−
Fig. 15.4 Plot of the effective stability of a metal complex (expressed COO−, CO32−, SO42−,
in terms of β1, which is the equilibrium formation constant) versus tem- PO43−
perature (After Seward and Barnes 1997). The stabilities of metal–chlo-
ride complexes shown increase by several orders of magnitude as After Robb (2005) and references therein
temperature increases, as will their solubilities in aqueous solution Major ligands in basinal and hydrothermal waters shown in bold italic
(Redrawn from Robb 2005) text
tors) will tend to complex with hard ligands (bases or elec- Cl−, HS−, OH−, HCO3−, and CO32− (Robb 2005). At relatively
tron donors), and soft metals with soft ligands, is commonly low temperatures and high pH, and in fluids with high bisul-
referred to as Pearson’s Principle, and underpins the solubil- phide concentrations but low salinities, a variety of Zn2+-
ity behaviour of metals in hydrothermal and basinal waters bisulphide complexes are stable, including Zn(HS)2,
and the notion that different leach lithologies provide differ- Zn(HS)3−, and Zn(HS)42−. In contrast, at higher temperatures
ent metal proportions in the leachate fluids, which is the and salinities and under more acidic conditions, a host of
basis for Fig. 15.4. chloride complexes predominate, including Zn(Cl)+, Zn(Cl)2,
A “borderline” category is added to accommodate the fact Zn(Cl)3−, and Zn(Cl)42−.
that some metals (such as Fe and Pb) can complex readily Lead is the softest of the borderline Lewis acids and forms
with both hard and soft ligands, forming a range of minerals stronger bonds with Cl− and HS− ligands than with OH− or
such as sulphides (pyrite FeS2, galena PbS) and carbonates HCO3−. The valence state and complexing behaviour of lead
(siderite FeCO3, cerrusite PbCO3). Likewise, Cl− can be an is very similar to that of zinc. Pb2+-bisulphide complexes are
effective complexing agent for both hard and soft metals, and more stable than chloride complexes in low temperature,
therefore promotes the solubility of a wide range of metals in neutral to alkaline, low salinity solutions. Different Pb2+-
hydrothermal aqueous solutions. bisulphide complexes form as a function of pH, and these
The classification of aqueous ionic species into hard and include Pb(HS)2 under acidic conditions and Pb(HS)3− at
soft Lewis acids/bases assists considerably in understanding higher pH (i.e. >6). At higher temperatures and lower pH,
the nature of metal–ligand complexation, and, therefore, the however, a variety of Pb2+chloride complexes form and these
controls on solubility, in basinal/hydrothermal solutions include Pb(Cl)+, Pb(Cl)2, Pb(Cl)3−, and Pb(Cl)42−. Pb2+-
(Robb 2005; Seward and Barnes 1997; Wood and Samson carbonate or Pb2+-bicarbonate complexes can form in CO2-
1998). In addition, it is well known that temperature plays a bearing fluids but their solubilities are typically low and they
very important role in determining the degree to which met- are unlikely, therefore, to have relevance in ore-forming
als enter solution. In most cases stabilities of metal–ligand processes.
complexes such as PbCl+ and ZnCl+ will increase by several There is also compelling evidence that lead, and to a
orders of magnitude as temperature increases from ambient lesser extent zinc, can be transported by organo-metallic
values to 300 °C (Seward and Barnes 1997). This is illus- complexes (Table 15.5), especially in relatively low tempera-
trated, together with data for other metal–chloride com- ture environments such as those related to the formation of
plexes, in Fig. 15.4. By contrast, an increase in pressure will some Mississippi Valley type Pb–Zn deposits, where the
have the opposite effect to temperature and the stabilities of hydrothermal/basinal fluids are known to contain hydrocar-
metal–ligand complexes will tend to decrease because of bons. The acetate ligand (CH3COO−) is one of a number of
bond dissociation and the formation of free metal ions. In organic molecules that have been implicated in base metal
general, however, the effect on solubilities of pressure transport, others include thiols and sulphur-bearing organic
increases are minimal and more than offset by the significant compounds.
changes associated with temperature increases (Seward and
Barnes 1997). rganic Components in Metalliferous Brines
O
So let us now consider the significance of Lewis princi- Concentrations of carboxylic acid anions in modern petro-
ples in the transport of the base metals (Cu, Zn and Pb) in the leum field brines are highly variable with respect to their
lower temperature sedimentary brine settings discussed in major known controls, including age and temperature of res-
this chapter. In subsurface brines, copper occurs in both Cu+ ervoir rocks, type and amount of kerogen in source rocks,
and Cu2+ valence states, although the monovalent state is pre- and the nature of metastable equilibria and water rock inter-
dominant in most hydrothermal and basinal fluids (Robb actions that characterize organic-matter interactions in the
2005). It is a relatively soft Lewis acid and forms stable Cu+ reservoir (Seewald 2003). Although concentrations vary with
chloride and Cu+-bisulphide complexes, as well as Cu+- temperature and reservoir depth for any given petroleum
hydroxide complexes if other ligands are not available. field, maximum values are generally present in Cenozoic-
Movement of copper in basinal solutions occurs under a age reservoir rocks of moderate salinities in the temperature
wide range of conditions and is most likely to carried as Cu+– range 80–120 °C (Fig. 15.5a, b; Kharaka and Hanor 2003;
chloride complexes in the form CuCl2−. Although copper– Seewald 2003). Within such brines, monocarboxylate anions
bisulphide complexes will form in high-sulphur (mainly acetate, propionate, butyrate, n-valerate) and dicar-
environments, they are not likely to play a significant role in boxylate anions (mainly malonate, succinate, glutarate,
most hydrothermal/basinal brine ore-forming environments maleate) are the dominant organic acid species. These
where chloride dominates. organic acids are typically detected in moderate salinity for-
The dominant divalent zinc cation, Zn2+, is a borderline mation waters, associated with petroleum, and mostly reside
Lewis acid that complexes with a variety of ligands, including in reservoirs with temperatures ranging from 20° to 200 °C
Table 15.5 Modern oil field brines constituents and their Pb-Zn contents
Low ΣH2S, high trace metal content Low ΣH2S, low trace metal content High ΣH2S, low trace
Parameter (brine 1) (brine 2) metal content (brine 3)
Temp (°C) 50 to 250 50 to 250 50 to 250
TDS (mg/l) 100,000 to 330,000 20,000 to 330,000 20,000 to 330,000
ΣCl−1 (mg/l) 60,000 to 210,000 12,000 to 210,000 12,000 to 210,000
pH 4 to 6.5 4 to 8 4 to 8
a
ΣH2S (mg/l) <0.1 <1.0 1.0 to 1,000
a
ΣmH2S <10−5.5 <10−4.5 <10−4.5 to 10−1.4
b
ΣSO4 (mg/l) 0.1 to 1,000 0.1 to 10,000 0.1 to 1,000
b
ΣmSO4 10−6 to 10−2 10−6 to 10−2 10−6 to 10−2
c
Σmonocbx (mg/l) <1.0 to 300 <1.0 to 10,000 <1.0 to 10,000
c
Σmmonocbx <10−4.8 to 0.005 <10−4.8 to ≈ 0.15 <10−4.8 to ≈ 0.15
d
Σdicbx (mg/l) <1.0 <1.0 to 2,600 <1.0 to 2,600
e
Σmdicbx <10−5 <10−5 to 0.025 <10 −5 to 0.025
e
ΣmCI/SmCbx >340 8 to >1,000 8 to >1,000
Σmmonocbx/Smdicbx ≈30 to 300 >20 >20
Pb (mg/l) 5 to 70 (cluster) <1.0 (cluster) <0.1 (cluster)
Pb (mg/l) range 1 to 111 BDL to 0.9 BDL to 0.9
Zn (mg/l) 15 to 250 (cluster) <1.0 (cluster) <0.1 (cluster)
Zn (mg/l) range 1 to 575 BDL to 0.9 BDL to 0.9
After Giordano (2003)
Cluster indicates most common values observed for modern petroleum field brines not the total range
BDL below detection limit, usually less than about 0.01 mg/l
Explanation of selected parameters
a
Total dissolved inorganic sulphide defined as ΣH2 S = H2 S + HS− (mg/l) and ΣmH2S = mH2S + mHS (mol kg21)
b
Total dissolved sulphate is defined as the sum of all dissolved sulphate species in mg/l (ΣSO4) and as the molal sum of all dissolved sulphate spe-
cies (ΣmSO4) in mol kg−1
c
Total monocbx = sum of monocarboxylate anions, as listed by Giordano (2002) in mg/l (Σmonocbx), while Σmmonocbx = total molality of dissolved
monocbx in mol kg−1
d
dicbx = sum of dicarbonxylate anions, as listed by Giordano (2002) in mg/l (Σdicbx), while eΣmdicbx = total dissolved dicbx in mol kg−1
(Kharaka et al. 2000). At higher temperatures they are brines are malonate, succinate, and glutarate. Each of these
destroyed by various decarboxylation reactions with CO2 as species is not likely to have concentrations greater than about
the ultimate byproduct (Seewald 2003) 100 mg/l, but controversially high values for oxalate
Plots of organic acid (carboxylate anions) concentration (494 mg/l) and malonate (2,540 mg/l) have been reported
versus salinity in this temperature range show a pronounced (MacGowan and Surdam 1988). Reported total dicarboxyl-
decrease in organic acid concentration with increasing salin- ate anion concentrations (Σdicbx) range from 0 to 2,640 mg/l
ity (Fig. 15.5a; Hanor 1994a, b). Highest concentrations are but values higher than 300 mg/l are very rare.
found in pore waters with salinities less than 30,000 mg/l, Typically, brines high in dicarboxylate anions are also high
while these species do not appear to be major constituents of in monocarboxylate anions; however, brines high in monocar-
petroleum field brines having salinities that exceed boxylate species are not always enriched in dicarboxylate
100,000 mg/l. The total concentration of monocarboxylate anions. The total dicarboxylate anion concentration is typically
anions (Σmonocbx) in modern petroleum-field brines is gener- less than 5 % of the total carboxylate concentration for modern
ally less than 100 mg/l, however, many brines have concen- petroleumfield brines. Thus, the ratio of total monocarboxylate
trations in the 100–5,000 mg/l range (Table 15.5). The anions to total dicarboxylate anions (Σmmonocbx/Σmdicbx) for mod-
dominant monocarboxylate anion in most petroleum-field ern basinal brines is nearly always greater than 20 and even
brines is acetate, followed in order of decreasing concentra- higher in some brines with high trace metal contents (Table 15.5).
tion by propionate, butrate, and valerate. The highest con-
centration of acetate reported in a subsurface water is
10,000 mg/l but values above 5,000 mg/l are very rare Basinal Brines: Metal Carrying Capacity
(Lundegard and Kharaka 1994; Kharaka et al. 2000).
Typically acetate comprises 80–90 % of the total mono- The presence of halite (or indicators of its former presence)
carboxylate species (Giordano and Kharaka 1994). The in a basin fill announce that, if metals were present in suffi-
dominant dicarboxylate species in modern petroleum-field cient volumes in adjacent strata to become leachates, then
a 2,000 evaporites, are chloride-rich, somewhat acidic and in some

Organic acids settings, slightly oxidising. They can carry elevated levels of
metals as they become more saline, and so act as potential
1,500 metal “leachers and carriers” in the subsurface hydrology. In
order to qualify as a potential ore carrying fluid, a basinal
Organic acids (mg/l)
fluid must contain on the order of 1 mg/l or more of the

dissolved metal in question (Eugster 1989; Hanor 1994a, b).
1,000
Most basinal brines that achieve Pb, Zn or Cu values at or
above this level have pore salinities that are typically in
excess of 200,000 mg/l, with their entrained base metals
500
carried as chloride complexes (Fig. 15.6a). These saline

waters also tend to be acidic and have lower levels of
organic acids when compared to their less saline counter-
parts (Fig. 15.5a).
0 100,000 200,000 300,000 400,000
TDS (mg/l) ediments as Metal Sources
S
Much of the base metal content, including copper, in low
b Zone 1 Zone 2 Zone 3
10,000 temperature ore deposits in sedimentary basins has an intra-
basinal nonmagmatic source. Some researchers propose that
5,000 the metals in basinal brines are derived either from the altera-
tion and leaching of feldspars and clays that supply most of
the iron, lead, barium and strontium, or from the alteration of
carbonates to supply most of the zinc (Land and
Concentration of aliphatic acid anions (mg/l)
Prezbindowski 1981; Sverjensky 1986; Kharaka et al. 1987).

Others workers conclude that leaching of iron-oxide-
1,000
hydroxides from a redbed parent can source many metals
(Carpenter et al. 1974). When incorporated as detritus in
500 first-cycle redbeds, copper-rich mafic rocks such as basalt, or
copper-rich mafic minerals (such as hornblende, pyroxene,
biotite, oxides and sulphides) in felsic rocks, are ideal copper
sources (Fig. 15.7; Kirkham 1989; Brown 2005, 2006).
Flushing of metals sequestered into organic-rich evaporitic
100 mudstones are yet another possible source for base-metals
(Table 15.3).
Dissolving evaporite beds themselves have also been
50
evoked as possible metal sources. Thiede and Cameron
Texas (Pleist.)
(1978) argued that Cu remains in solution during the initial
Texas (Olig.)
evaporation process; whereas Pb and Zn enter solid precipi-
California (Mio-Cret) tates, such as gypsum and anhydrite. Later dissolution of
Alaska (Perm-Cret) such evaporites generates a metal source enriched in Pb and
10
Zn and depleted in Cu. More recent models have proposed it
40 60 80 100 120 140 220 240
is not the evaporites, but the residual bitterns, that have sank
Subsurface temperature (°C) (refluxed) into underlying and adjacent sediments, which act
Fig. 15.5 Organics in basinal brines. (a) Organic acids in saline brines
as the source of metals in diagenetic-realm base-metal accu-
(After Hanor 1994a, b). (b) Concentrations of aliphatic acid anions (C2 mulations for lead and zinc in MVT style deposits; for exam-
–C5) in formation waters from three sedimentary basins typified by ple, in Ireland and Arkansas, (Wilkinson et al. 2009; Kendrick
moderate salinities. The highest concentrations are at 80–120 °C and et al. 2011).
then decrease with increasing temperatures, as indicated by arrow, note
the scale break at 160 °C (After Kharaka and Hanor 2003)
Sverjensky (1989) further refined earlier brine transport
models by demonstrating that significant water-rock interac-
tion takes place as warm, subsurface chloride-rich brines tra-
metal transport as chloride complexes in high salinity brines verse and interact with various deep aquifers. He concluded
was highly likely at some stage in the diagenetic history of that, depending on the dominant lithology of the aquifer tra-
the basin. Modern basinal pore brines, located near dissolving versed by the chloride-rich brines, a single highly saline
a 1,000 b 10,000
Pb
Sulfate
Zn
100 Cu 1,000
Metal (mg/l)
10
SO4 (mg/l)
100
1 1 mg/l
10
0.1
1
0.01
0.1
0 100,000 200,000 300,000 100 1,000 10,000 100,000 1,000,000
TDS (mg/l) TDS (mg/l)
Fig. 15.6 Components of high-salinity basinal brines (After Hanor 1994a, b). (a) Metal content of subsurface waters showing elevated metal
contents (>1 mg/l) in more saline (chloride-rich) pore waters. (b) Sulphate as a function of salinity
Fig. 15.7 Influence of flushed McArthur River, Australia

Zn-rich ores
matrix mineralogy on the base Gays River, Canada
metal precipitated (After quifer Zn>Pb>>Cu Nanisivik, Canada
nate a
Sverjensky 1989) Carbo San Vicente, Peru
Basinal
Corocoro, central Andes
Brine Quartz sandstone aquifer Pb-rich ores Dzhezkazgan region, Kazakhstan
source Pb>Zn>>Cu Laisvall, Sweden
Southeast Missouri, USA
Anhyd
rite+re
d bed
aquife
r Cu-rich ores Mansfeld, Germany
Lubin, Poland
Cu>Pb+Zn Creta, USA
Redstone Belt, Canada
White Pine, USA
basinal brine may evolve chemically to become the ore- hematite-magnetite buffer prevents copper mobilisation (sol-
forming fluid for a wide range of sediment-hosted base-metal ubility of Cu in a typical basinal brine is ≈ 0.07 mg/l).
sulphide deposits. Migration through carbonate, quartz sand- Geochemical sampling by Wilde et al. (2005b) in the
stone, or anhydrite + redbed aquifers could result in the for- Canning Basin of West Australia confirms the theory out-
mation of Zn-, Pb-, or Cu-rich deposits, respectively lined by Sverjensky (1989). Lead isotope and permeability/
(Fig. 15.7). porosity data indicate that Carboniferous and Devonian
As a starting point he considered a typical chloride- feldspar-rich sandstones and siltstones are the most likely
enriched basinal brine that was initially saturated with reservoirs for ore-forming brines and metals in the various
galena, chalcopyrite, muscovite, kaolinite and quartz, but Pb-Zn deposits of the eastern Canning Basin. The Anderson
undersaturated with respect to sphalerite, with up to 1 mg/l Formation and Tandalgoo Sandstone are characterized by
Pb, 0.1 mg/l Cu and 5 mg/l Zn. Passage of this fluid through extreme depletion in Pb and Zn relative to Cu (Fig. 15.8).
a carbonate-cemented aquifer produces a metalliferous brine Conversely, limestones and dolomites in the Devonian and
characterised by high Zn/Pb and (Zn + Pb)/Cu ratios. Carboniferous rift-fill are enriched in Pb and Zn relative to
Transport of the same fluids through a quartz-cemented Cu. This enrichment, is interpreted as due to hydrothermal
sandstone exhausts the buffering capacity of the aquifer rela- circulation of chloride-rich waters derived from deep disso-
tively quickly, so that any mineral accumulations precipi- lution of the Mallowa salt mass. If so, it explains the numer-
tated from the resulting waters are galena-rich. Maintenance ous MVT deposits hosted in carbonate rocks of the eastern
of the oxidation state in a typical basinal brine near the margin of this Carboniferous-Devonian rift-fill.
Fig. 15.8 Average base metal

concentrations in various
stratigraphic units of the Fitzroy
Sandstone &
Trough and Lennard Shelf in the
Fairfield dolomitic siltstone
Canning Basin, Australia (Wilde 1,200 limestone
et al. 2005b)
Mudstone
Limestone &
dolomite
Basement rocks
(gneiss & diorite)
800
Average Pb + Zn (ppm)
d
tren
ment
Base
Anderson dolomite
400 Basement gneiss
Pillara limestone
Carribuddy mudstone GoGo mudstone
Pillara dolomite
Clanmeyer mudstone
Anderson formation
(redbed)
Tandalgoo sandstone (redbed)
0
0 40 80 120 160
Average Cu (ppm)
In a variation on the same theme of metalliferous saline Mildly reducing redox conditions, imposed by equilibra-
brines tied to leached sediments, and the corollary that mag- tion with a muddy metal source was most critical factor in
matic heat may enhance convective circulation of basinal the formation of such an effective ore-forming fluid system
brines, but not supply the metals in some paramagmatic (Fig. 15.9). Relatively metal-rich, but organic-poor, pyrite-
sediment-hosted ore deposits, Tornos and Heinrich (2008) bearing shales, undergoing dewatering and interaction with
have shown that shales interacting with highly saline hypersaline saline pore fluids created an effective source for
chloride-rich basinal brines are the main suppliers of metals the generation of sulphur-deficient, but relatively iron and
to the massive sulphide deposits of the Iberian Pyrite Belt base metal-rich, chloride brines (Fig. 15.9a). When tempera-
(Fig. 15.9). Historically, these deposits were interpreted as tures are in excess of 330–340 °C, even copper becomes
volcanogenic-hosted massive sulphide (VHMS) deposits, highly mobile in high salinity subsurface waters passing
and related to hydrothermal oceanic-rift analogs, such as the through compacting shales (Fig. 15.9a and Chap. 16). Thus,
Tag Mound or the massive sulphides of Cyprus, where the Tornos and Heinrich (2008) proposed that the giant deposits
metals have a magmatic source. But veinstyle deposits and of the Iberian Pyrite Belt owe their existence not to excep-
other indicators of magmatically-sourced fluids, typically tionally metal-enriched magmatic fluids, but to the existence
associated with this style of VHMS deposit, are largely lack- of a fairly ordinary, but volumetrically large (with depletion
ing in the massive sulphides of the Iberian pyrite belt. Tornos ratio of 1:200), metal source in these reactive fine-grained
and Heinrich (2008) argue that the deposit hydrology and (high grain-surface areas) siliciclastic sediments, flushed by
textural/geochemical signature is more akin to that of the chloride-rich evaporite-dissolution-derived basinal brines.
Sullivan and McArthur River styles of ore deposit. There, The convective fluid flow system may be tied to an underly-
brine pools tied to focused upwelling and venting of hyper- ing igneous heat source driving the regional fluid flow, but
saline basinal waters into closed depressions on deep sea- ore focusing and metal transport is more dependent on a par-
floor were the driving mechanisms creating the SedEx ticularly efficient mechanism of sulphide precipitation,
deposits. driven by mixing and reduction of the metalliferous brine
a b
mH2S = mSO4
mt-po-py (PPM)
100,000
mt-hm (HM)
100,000
10,000
10,000
1,000 Zn
S
100 Zn
1,000
Fe
ppm
ppm
10
Fe
1 100 Pb
S
0.1 Pb T = 300 °C
Cu
10 py-po
0.01 pH = kfs-plag-ms-Q pH = 4.5
fO2-fS2 = py-po-mt Cu
0.001 1
100 150 200 250 300 350 –40 –38 –36 –34 –32 –30
T°C log fO2
Increasing oxidation
Fig. 15.9 Metal solubility and fixation in shale as related to sulphur Mineral abbreviations are; hm hematite, mt magnetite, py pyrite, po pyr-
presence (After Tornos and Heinrich 2008). (a) Base metal and sulphur rhotite, kfs K feldspar, plag plagioclase, Ms muscovite, Q quartz. (b)
solubility as a function of temperature between 350 and 100 °C at a pH Reduced sulphur (S) and metal solubility in a shale-buffered reservoir at
buffered by the mineral assemblage observed in shales, for a total salin- 300 °C showing the strong dependence on the redox conditions.
ity of 9 wt.% NaCl equivalent and the fO2 –fS2 conditions defined by the Calculations performed at a constant pH of 4.5 and the fS2 controlled by
pyrite–pyrrhotite– magnetite equilibria. Base metal solubilities are cal- the pyrite–pyrrhotite equilibrium. The H2S:SO4 boundary is that defined
culated in equilibrium with excess sphalerite, galena and chalcopyrite. by equal molalities of reduced and oxidized sulphur species
with H2S-rich fluids at or near the seafloor (Fig. 15.9b; see gliding and halokinesis, and sometimes by more updip via
later SedEx discussion). We shall come back to this notion of interaction with bedded platform anhydrites.
chloride-rich basinal brines transporting and fixing metals a At the contact of an evaporitic sedimentary basin with its
number of times in this chapter, as we develop arguments in underlying basement, dense chloride brines derived from
support of dissolving salt masses aiding in the focusing and dissolution and reflux beneath thick salts can leach metals
trapping of brines and their outflows. from the underlying basement and then convectively trans-
Similar redox-controlled mineral equilibria are imposed port them into a metal-fixing redox front. Such brines leach
when saline chloride-enriched basinal fluids are buffered by a variety of metals from underlying igneous and metamor-
typical continental basement rocks (Fig. 15.7). This is how phic rocks and worldwide are responsible for a number of
copper can be mobilised and leached from the sediment, large unconformity-associated uranium deposits and SedEx
along with Pb and Zn. At redox conditions near and above the deposits (Fusswinkel et al. 2013; Wilkinson et al. 2009;
hematite–magnetite buffer, sulphate becomes the main sul- Boiron et al. 2010; Koziy et al. 2009).
phur species. This defines another diagenetic fluid environ-
ment proposed by Cooke et al. (2000) for base metal transport arrier Brines (Eh, pH and Chlorinity/Salinity)
C
in sediment-hosted deposits overlying oxidized sequences, as Numerous experimental studies have shown that chloride
at McArthur River (Australia). Leaching of retrograde miner- complexes are effective ligands for Zn and Pb in low tempera-
als and possibly residual salts from a magmatic or metamor- ture basinal brines. Bisulphide and organic complexes are less
phic protolith are expected to generate similar, variably effective, particularly in moderate to highly saline pore fluids
metal-rich, but relatively sulphide-deficient, fluids. Thus, in sediments in the presence of abundant Na and Ca (Giordano
according to Tornos and Heinrich (2008) the existence of 1985; Barrett and Anderson 1988; Sicree and Barnes 1996).
mildly-reducing saline sedimentary brines in sedimentary The presence of reduced sulphur in MVT and other basinal
hosts, not magmatic waters, can be the dominant chemical brines (typically a H2S association) greatly reduces the solu-
control in sourcing metalliferous fluids linked to many volca- bility of chloride-complexed Pb and Zn (Fig. 15.10b and
nogenic, Irish-type or SedEx deposits. Many of these brine- Table 15.5; compare Pb and Zn contents with respect to ΣH2S
related deposits are known to precipitate their metal load in in brines 1 and 3). Hence, the widely accepted model for for-
response to biogenic or thermochemical sulphide addition at mation of MVT deposits via saline basinal brines transporting
the ore deposition site. Typically this took place within metals to local areas containing reduced sulphur where the
depressions on seafloor with their downslope precipitative metals are fixed as solid metal sulphide phases (Anderson
positions maintained by a combination of extension, gravity 1983; Anderson and Macqueen 1988).
a 1.0 b 1.0
En
viro Lim 25°C
nm it o Contours
ent f st
s in
0.8 con abi
lity 0.8 of copper
tac of w solubility
Cu4(OH)6Cl2
Rainfall tw
ith a 10-4 (6 ppm)
atm ter O
osp
0.6 10 (64 ppm)
-3
0.6 her H 2
e 2 O
Cu2+
Deeply-circulated oxic
Shallow meteoric waters
0.4 Copper is
groundwater 0.4
in solution
Eh (v)
Conditions (via mixing)
Eh (v)
CuCl32+ CuO favorable to

0.2 0.2
Hydrothermal + CuCl2– significant copper
Seawater
waters solubilities in
0.0 CuS Cu redbed aquifer
Deeper 0.0 Cu2O
En S
viro groundwater an
2
Anoxic subsurface
nm
ent hypersaline waters
s is H dj
−0.2 ola −0.2 O
Lim ted Hypersaline
2
Cu
it o from
f st atm water
abi os Cu2S
lity
−0.4 of w pher −0.4
ate e
r
2 4 6 8 10 12
−0.6 pH
Eh - pH control
0 2 4 6 8 10 12 14
of copper solubility
pH
Fig. 15.10 Redox and copper solubility. (a) Eh-pH diagram with tral pH) in a redbed succession is in part created by mixing of deeply
occurrence fields of various surface and subsurface waters plotted. (b) circulating oxygenated meteoric and anoxic saline subsurface waters
Solubility of copper as cuprous chloride complexes in a low-temperature (In part after Rose 1976; Brown 2006). CuS covellite, Cu2S chalcocite,
brine, showing how a Cu-transporting brine(slightly oxidising and neu- Cu copper, Cu2O cuprite, CuO tenorite, Cu4(OH) 6Cl2 malachite
In terms of potential Pb and Zn carriers, there are three c orrelation between ΣH2S and ΣSO4, indicating a likely
main types of basin brine in today’s sedimentary basin, only relation to subsurface sulphate reduction (Fig. 15.6b; Hanor
one carrier has elevated levels of Pb and Zn (Table 15.5; 1994a, b).
Giordano 2003). The table shows the specific inorganic and The ability of chloride-rich basinal brines to become ore
organic fluid parameters that influence the concentration of forming fluids, capable of carrying and precipitating Pb-Zn
Pb and Zn in these subsurface waters. Modern oilfield brines minerals, is well illustrated by the Na-Ca-Cl oil field brines
are bimodal in terms of total reduced sulphur content (ΣH2S). in the Cheleken region of Turkmenistan (Lebedev 1972).
Low H2S brines have ΣH2S values less than 1.0 mg/l, with These brines contain up to 10 mg/l Zn + Pb and deposit native
the majority showing values less than 0.02 mg/l and often lead, sphalerite, galena and pyrite in the well pipes and hold-
showing values below the detection limit (Giodarno 2003 ing tanks at rates considered analogous to ore formation.
and references therein). Not all low H2S chloride-rich brines Some Na-Ca-Cl oil field brines in Jurassic and Cretaceous
carry elevated levels of Pb and Zn, only those that have formations in the Salt Dome Basin of central Mississippi,
passed through strata containing leachable levels of these USA, have total dissolved solid contents up to 350,000 mg/l,
base metals. densities that exceed 1.2 g/ml, and contain up to several hun-
High H2S brines have ΣH2S concentrations greater than dred mg/l of Pb + Zn (Fig. 15.6a; Carpenter et al. 1974;
1.0 mg/l, with the highest concentrations approaching Kharaka et al. 1987). Both these highly metalliferous brines
1,000 mg/l, especially in the vicinity of active fault conduits systems occur in regions underlain by thick dissolving evap-
carrying these H2S-rich waters (see Wade et al. 1989; orites with dissolution plumes moving through adjacent
Moldovanyi and Walter 1992). In high H2S formation waters, metal-carrying sediments (Chap. 8).
the most commonly observed ΣH2S values are in the Similarly, sphalerite and galena scale is forming today in the
10–600 mg/l range (see also Chap. 9). Total sulphate concen- pipes of producing geothermal wells in the Asal Rift in the
trations in modern petroleum-field brines rarely exceed Republic of Djibouti, Africa (D’Amore et al. 1998). Sulphide
1,000 mg/l and are more typically in the 0.1–250 mg/l range precipitation starts at the flash level (where hot pressurised
(Fig. 15.6b; Kharaka and Hanor 2003). There is no statistical water converts to steam), located at 850 m depth where tem-
correlation between the concentration of SO4 and chlorinity peratures are close to 260 °C, and extends deeper into the main
or salinity, although there appears to be a broad inverse reservoir. The main geothermal reservoir is located at depths
between 1,000 and 1,300 m with temperatures between 260 1989) argued that not all metalliferous brines are acidic. He
and 360 °C. Seawater seepage, with additional ionic input from notes that in a Green River style of ore deposit (a category in
dissolving salt beds, is the main source for the chloride-rich which Eugster includes the Mt Isa and Dugald River deposits
metalliferous brines in the field. As a result of sulphide precipi- of Australia) the brines were alkaline, with pH values of up
tation, about 90 % of H2S is removed from the original fluid to 11. If so, then metals were carried not as chloride com-
before it is discharged at the surface. Brines produced in the plexes, but as hydroxy or carbonate-complexes. Such non-
Asal thermal field all have salinities in excess of 100,000 ppm, chloride waters are generated today in saline continental rift
with a low gas content of the order of 0.6 mmol/mol. lakes where sodium bicarbonate evaporites dominate, there
If the subsurface brine migrates though a red bed succes- is no primary gypsum, and the lake evolves by the evapora-
sion that contains hematite and/or anhydrite, the oxidation tion of source waters that drain adjacent basic igneous or
state and the SO42−/H2S ratio of the fluid is increased by mix- metamorphic terranes (see Chaps. 2 and 3 for a discussion of
ing of oxygenated groundwaters and anoxic brines and by nonmarine brine evolution).
reactions such as: So far this discussion is largely theoretical or based on
analogy with modern basinal and oil field brines. But with
CaSO 4 = Ca + + + SO 4 2 -
improvements in microsampling and laser-ablation
+ + 2- inductively-coupled plasma mass spectrometry techniques
4 Fe 2 O3 + H 2 S + 14 H = 8 Fe 2 + SO 4 + 8H 2 O it has become possible to study the hydrogeochemistry of
The migration of this moderately oxidising saline fluid metal precipitating brines by analysing the chemical
through a red bed can then scavenge the necessary Cu, Zn makeup of individual brine inclusions in zoned quartz and
and Pb to form a mineralising fluid with elevated Cu content sphalerite crystals and so map the evolution of the metal
where Cu > Pb + Zn (Fig. 15.10; see also Rose 1976; Brown reprecipitating brines (Wilkinson et al. 2009; Fusswinkel
2006). Redox conditions of logfO2 > −46 at 125 °C are neces- et al. 2013). A study of fluid inclusions in sphalerite and a
sary in the brine to mobilise copper as cuprous chloride com- comparison with co-associate inclusions in quartz crystals
plexes (see Rose 1976 for relevant discussion). This explains from two geographically separate Pb-Zn MVT deposits in
the common association of copper sulphides with redox Ireland and Arkansas showed that the metal contents of the
haloes adjacent to leached redbeds in evaporitic basins (see sphalerite are up to two orders of magnitude higher than
later). associated quartz (Fig. 15.11). The difference between
So far, we have discussed slightly-acidic metal-rich saline sphalerite and associated quartz is much higher than previ-
chloride brines. However, high salinity in a subsurface water, ously thought and strongly suggests ore formation is linked
by itself, does not guarantee a high dissolved metal content, to an influx of anomalously metal-rich fluids into subsur-
nor are metals always carried in the subsurface as chloride face systems, dominated by basinal fluids that are other-
complexes in saline acidic brines. A large number of saline wise barren of metals. It could be argued that the fluid
basinal brines and formation waters are low in metals and inclusions in quartz represent spent ore fluids, trapped after
high in dissolved sulphides (Table 15.5). Figure 15.6a clearly sulphide precipitation had already taken place. This is
shows that many highly saline subsurface waters in sedimen- thought to be unlikely in the Irish deposits because the
tary basins worldwide contain <1 ppm metal. Such waters quartz was sampled from largely barren vein systems that
become metal-rich and sulphide-poor only when they flush formed beneath the ore deposits, in hydrothermal upflow
germane metalliferous sediment, such as redbeds, metal-rich zones, and the fluids show no signs of having substantially
shales or hydrothermally altered basalts (Ellis 1968; Coveney cooled or mixed (Wilkinson et al. 2009). A metal-pulse
1989). Metal leaching and chloride transport from such model for ore fluids has now been shown to be true of MVT
metal sources involves desorption of loosely bound metals, deposits based on inclusion chemistry at the microscale,
release of metals on mineral recrystallisation or replacement, rather than just inferred, as was done in many previous
or release of metals to the brine from metal-organic com- mineralisation transport models.
plexes through thermal alteration or thermal destruction of In the Tri-State MVT district, Wilkinson et al. (2009)
such complexes (Carpenter et al. 1974; Gize et al. 1991). found sphalerite- and quartz-hosted brine inclusions show
Acidification is an essential step in the acquisition of met- distinct halogen signatures, indicating that the fluids had
als in brines during dissolution or alteration of aquifer miner- separate origins. Fertile ore fluids appear to have originated
als. Chloride-rich, high salinity basinal fluids may become during strong evaporation of seawater at Earth’s surface,
acidified by pyrite oxidation, by decomposition of organic before later burial and expulsion. This contrasts with the bar-
matter, or by the precipitation of Mg silicates, such as smec- ren fluids that evolved from less strongly evaporated seawa-
tite or chlorite. Organic acids may also play an important ter. The metalliferous fluids were linked to the arid
role in leaching the metals from metalliferous source beds paleoclimate and the specific characteristics of the sedimen-
(Raiswell and Al-Biatty 1992). In contrast, Eugster (1985, tary aquifer within which they were trapped.
104 0
(P) (S) Predicted range of sphalerite- b=1
hosted fluids (Ireland) Zn:P
Predicted Zn concentrations
Qz (Ireland)
103 1
Qz (N.Arkansas) b=
Modern oilfield brines Zn:P
Salton Sea
102 0.1
Zn (ppm) b=
Zn:P
IRELAND
101
N.ARK
Predicted range of
100 sphalerite-hosted fluids
(N.Arkansas)
10-1
Qz (S) 78-85-104(S) G-1 (S) IRELAND Mean (P)
4
Qz (P) 78-85-104(P) UG-1 (P)
2 Sp Sp
Frequency
MC Qz (P)
10 MC Sp (P)
8 LD Sp (P) N.ARKANSAS Mean (P)
6 PA Sp (P)
4
2
10–1 100 101 102 103

Pb (ppm)
Fig. 15.11 Metals concentrations in natural subsurface waters (After fields, suggesting that they are anomalously metalliferous and indica-
Wilkinson et al. 2009). Concentrations of Zn versus Pb in quartz-hosted tive of viable ore-forming fluids. Typical Zn:Pb ratios (by mass) for
fluid inclusions and histograms showing measured Pb concentrations in natural fluids are in the range of 1–10 (dashed grey lines) are shown and
quartz- and sphalerite-hosted inclusions from Irish and North Arkansas all tend toward higher values at elevated concentrations. Also plotted
MVT deposits, compared with natural brine data from broadly analo- are data points from the Northern Arkansas MVT dataset with low
gous environments (subsurface Salton Sea and oilfield waters). detected Pb are inferred secondary inclusions (S vs P for primary inclu-
Predicted Pb-Zn covariation for sphalerite-hosted inclusions indicated sions). Qz quartz, Sp sphalerite, Deposits plotted are MC Monte Cristo,
by shaded fields, based on the extrapolation of empirical Pb-Zn concen- PA Philadelphia, LD Lucky Dog
trations. All data sets have values that fall in the “high-metal” fluid
In a refinement of this halogen approach to the interpre- (Fig. 15.12b, c). This is clear evidence of mixing of a
tation of the nature of ore fluids in quartz-fluorite-baryte- basement-derived metal-rich hypersaline brine and a metal-
Pb-Zn vein system, Fusswinkel et al. (2013) concluded poor formation brine that acquired its salinity from halite
mineralisation can be related to the mixing of two evaporite- dissolution in Triassic evaporites of the sedimentary cover
related brines (Fig. 15.12). Post-Variscan Mesozoic vein- (high Cl/Br and Na/Ca ratios are indicative of brines derived
type Pb-Zn mineralization is widespread in large parts of from subsurface halite dissolution, see Chap. 8). This mix-
western and central Europe, including Variscan basement ing of two distinct brines with comparable salinity is
complexes of Germany, France, England, and Spain. In recorded during the growth of individual quartz crystals
Germany, the vein-hosting crystalline basement is uncon- containing small galena inclusions, demonstrating the tran-
formably overlain by Permian and Lower Triassic redbed sient and episodic nature of fluid mixing during mineral
sedimentary rocks and Middle Triassic to Jurassic carbon- deposition. Once again, this reinforces the observation of
ates with intercalated claystones and evaporites. Utilising Wilkinson that at the microscale there is a pulsing of metal
laser ablation analysis of inclusion trails in zoned vein supply in an ore precipitating system in the diagenetic
quartz crystals they found evidence of two end-member realm. It points to the importance of syndepositional metal-
hypersaline brines, one was metal rich, the other metal poor liferous bitterns sinking into the underbelly sediments as
(Fig. 15.12a). salt successions precipitate in saline giant settings (the brine
They determined simultaneously the ore metal concen- curtain – Chap. 5).
trations and the Cl/Br ratio in texturally well constrained
inclusion assemblages from this basement-hosted quartz- Metal Fixers
fluorite-baryte-Pb-Zn vein system. There is an inverse cor- Metal transport-precipitation models breakdown into
relation between the Pb + Zn concentrations and the Na/Ca three end-members; (1) Mixing model, (2) Sulphate
and Cl/Br mass ratios in the fluid inclusions, respectively reduction model and, (3) Reduced sulphur model
a Table 15.6 Widely accepted models for transportation and precipita-

H2O
tion of base metals in low temperature (<250–300 °C) basin burial
40 40 (wt%) P1 PS2 settings
P3 PS4a (FIA 06)
P4 PS4b (FIA 09) Transportation of ore-
Eut = −52.0 °C P5 PS5
Eut′ = −21.2 °C forming constituents Precipitation mechanisms
Eut′′ = −49.8 °C
Per = −22.4 °C Mixing model (i) Mixing with fluids containing H2S
Per′ = +0.1 °C Ice Base metals transported (ii) Replacement of diagenetic iron
(Eut = eutectic by saline Cl-rich fluids sulphides
Per = peritectic) Metal-poor Halite without significant (iii) Thermal degradation of organic
Dissolution Brine
Metal-rich sulphur content compounds releasing sulphur
Eut′
Basement Brine (iv) Mixing of two hypersaline Cl-rich
Hydrohalite Per′
brines, one is metal-depleted the
e
Eut
cit
Eut′′ other is metal-rich

cti
tar
Halite Sulphate reduction models Reduction of sulphate by reactions

Per
An
Base metals transported with organic matter or hydrocarbons,

CaCl2 NaCl together with sulphate in especially methane (bacterial of
(wt%) (wt%) the same fluid thermogenic sulphate reduction)
b Reduced sulphur model (i) Cooling
7
Base metals transported (ii) Dilution
together with reduced (iii) Change in pH
6 P1 PS2 sulphur in the same
P3 PS4a (FIA 06) solutions
Na/Ca (mass ratio)
5 P4 PS4b (FIA 09)

P5 P
(Sverjensky 1986; Table 15.6). According to the most
4
commonly accepted mixing models, base metals are trans-
ported in one fluid and sulphide is transported separately
3
in another fluid, while precipitation occurs where the two
2
fluids mix (e.g. Anderson 1975; Beales and Jackson 1966).
Related theories, encompassed by the mixing model,
Mixing line
hypothesize that the source of reduced sulphur encoun-
0 200 400 600 800 1,000 1,200 tered at the precipitation site was in the form of H2S, dia-
Pb + Zn (µg/g)
genetic iron disulphides, or sulphur associated with
c petroliferous materials. In the sulphate reduction model,
1,000 base metals are transported in fluids along with sulphate,
P1 PS2
rather than sulphide, and precipitation is driven by a sul-
P3 PS4a (FIA 06)
800 phate reduction reaction, whereby sulphate is reduced to
P4 PS4b (FIA 09) sulphide, typically via oxidation of organic matter or
Cl/Br (massratio)
P5 PS5 methane (e.g. Anderson 1983; Powell and MacQueen

600
1984). According to the third model, the reduced-sulphur
400 model, base metals and reduced sulphur are transported
together in the same fluid, with precipitation driven by
200
varying combinations of pH change, cooling, dilution
Mixing line (e.g. Helgeson 1970; Anderson 1973; Sverjensky 1989).
0
All three precipitation interfaces in these models are typi-
0 200 400 600 800 1,000 1,200 cally tied to redox fronts and often relate also to pore
Pb + Zn (µg/g) water salinity/density mixing interfaces.
Copper minerals precipitated at a diagenetic redox front are
Fig. 15.12 Evaporite brine mixing creates metalliferous brines (After predominantly Cu-sulphides (covellite (CuS), chalcocite
Fusswinkel et al. 2013). (a) Fluid composition in ternary H2O-NaCl-
CaCl2 system as determined by microthermometry, showing close over- (Cu2S), chalcopyrite (CuFeS2), and bornite (Cu5FeS4), depend-
lap of two brine end members (metal-rich and metal-poor) in terms of ing on the concentration of ions in solution and Eh–pH condi-
their major element composition. P primary, PS pseudosecondary, FIA tions (Fig. 15.10a: Rose 1976; Wodzicki and Piestrzynski
fluid inclusion assemblage. (b) Microanalysis of single fluid inclusions 1994; Brown 1997; Robb 2005; Asael et al. 2009). Subsequent
shows close correlation between total base metal content (Pb + Zn) and
Ca/Na ratio. P primary, PS pseudosecondary, FIA fluid inclusion reoxidation of the sulphides may lead to the formation of
assemblage. (c) Close correlation between Pb + Zn and Cl/Br ratio, Cu(II) minerals, such as; malachite (Cu2(CO3)(OH)2), parata-
resulting from mixing of two brines with similar total salinity (a). (c) camite, (Cu,Zn)2(OH)3Cl), brochantite (Cu4(SO4)(OH)6) and
Major variation of total metal content at constant Pb/Zn ratio reflects chrysocolla (Cu,Al) H Si O (OH) ·n(H O). Typically, the for-
2 2 2 5 4 2
mixing of metal-bearing brine with metal-depleted fluid. Upper and
lower paired symbol shapes denote laser ablation analyses performed mation of redox fronts is attributed to the interface between a
with full and reduced element suites, respectively fresh meteoric and a saline water mass (Fig. 15.10b). But as
Fig. 15.13 Metal sulphide a

‘fixing’ at redox interfaces (a)
Eh–pH diagram showing the T = 40 °C
changes in the copper-chlorine 1.0
P = 1 atm
speciation in solution and the
position of the equi-concentra- A
tion boundaries between the
different copper complexes 5.0
(ligands) at varying values of the 0.5 1.5 1.0
0.5 B
chlorine activity aCl− (After 0.1
Asael et al. 2009). (b) Brine
mixing between two saline water 0.01
5.0
1.0 1.5
masses that are typical in the C
0.5
Eh [v]
vicinity of buried and dissolving 0.0
evaporites. One brine is less aCl– A B C 0.1
+ –
dense, metalliferous, somewhat 0.01 Cu2+ CuOH CuCl2
0.01
acidic and slightly oxidising, the 0.1 Cu2+ CuOH
+
CuCl2
–
other somewhat more saline, + + –
denser, anoxic and likely 0.5 CuCl CuOH CuCl2
−0.5
+ + 2–
carrying hydrocarbons and H2S. 1.0 CuCl CuOH CuCl3
(also does not destroy any 1.5 CuCl
+
CuOH
+
CuCl3
2–
organic matter in carrier beds as + 2–
it is a “pickling” brine -Chap. 8) 5.0 CuCl2 CuOH CuCl3
−1.0
0 2 4 6 8 10 12 14
pH
b
Red-orange-buff mottled carrier beds that can be coarser grained
etals and somewhat more permeable than greenbeds, carrying pore waters
of m
r e le ached slightly- that are less saline and hence less dense, but still chloride-rich, slightly
ta a line, oxidising and metalliferous (via leaching of shales(redbeds),
e stra ss sa ters
Sourc ewhat le al pore wa volcaniclastics and basement)
m
by so ised basin
oxid Mesolution
Mesolution REDOX INTERFACE
Orientation of this brine-mixing interface with respect to
bedding is controlled by whether the nearby denser greenbed
ed Eh
ntroll brine source is subsalt (bedded or halokinetic) or suprasalt
ity co tion
Salin (a stratiform or fault/fracture -controlled aquifer)
gra a zoned
d
sa e
create rous zon
ll if e
meta Green-grey carrier beds, typically tied to brine source beds with
lower permeability (may be finer grained muds or evaporite-
d, dissolution edge beds) carrying pore waters that are reducing
in e ralise
m
of un -fluid that and rich in H2S and hydrocarbons, or all three and perhaps
ource e
a r e the s w Eh por position locally with sulphate undergoing BSR or TSR)
Beds sa line, lo e the
bilis ce
highly nd and sta dox interfa
u s a e - r e
foc e b rin
of th
the variations in the a, and c plot fields in Fig. 15.13a show, the related brine plumes (Chap. 8). These interfaces play
they can also be set up at interfaces between,; (1) dense highly a significant role in localising and focusing metal precipita-
saline reduced brine masses (in the immediate vicinity of a tion in many evaporite-associated metal accumulations
dissolving salt mass) and (2) an adjacent, still saline, but some- (Fig. 15.13b). For example, the inherent highly saline and
what less so, chloride-dominant basinal brine that is also reducing conditions adjacent to and beneath a salt bed, salt
slightly oxidising and slightly acidic and capable of leaching structure or an at-surface brine pool are created by the high
copper. For example, compare the saline plot fields in salinity of the pore fluids in the vicinity of an evaporite unit
Fig. 15.10b and their positions in 15.13a when aCl− is in the and the likely co-occurrence of elevated levels of organics
range >4–5. This notion of dissolving evaporites contributing (Chap. 9). Further away from the dissolving salt mass the
to the leaching, transport and fixing of copper sulphides is not pore waters are typically still saline, although in some cases
new, aspects of it were detailed by Rose (1976). can be lower salinity waters, that are somewhat more acid
Redox fronts and density-driven mixing interfaces in the and slightly oxidising (e.g. Fig. 15.13b). Thus, the conditions
shallow to deep subsurface are consistently located about the suitable for the fixing of metal sulphides in zones of mixing
edge of dissolving salt beds and halokinetic salt masses, or between the two water masses, where redox interfaces form,
can be present from the time of deposition of the sedimen- to small scale examples of redox-related Cu-segregations
tary host through to the metamorphic realm. This dissolu- and small-scale Pb-Zn associations, almost all giant strati-
tion/density style of redox front precipitation is relevant to form redbed copper and Pb-Zn deposits can be tied to struc-
most sediment-hosted ore deposits found in evaporitic basins tures with current, or former, evaporite-induced redox
and encompasses formative mechanisms in stratiform interfaces, typically located near or adjacent to present or
Mississippi Valley-type Pb-Zn, redbed-related base metal, past halokinetic salt masses. Brines from dissolving evapo-
and salt allochthon related base metal accumulations. rites are not the source and, sometimes, not even the carriers
Redox fronts are typically indicated by a greenbed-redbed of metals. Rather, dissolving evaporite masses are the stabi-
halo (reduced-oxidised iron) adjacent to a dissolving salt bed lisers, both geographically and chemically, for the chemical/
or its dissolution breccia. When such a redox interface is set density subsurface interfaces that precipitate the various
up, between a reduced brine halo and slightly more oxygen- metals and/or act as hydrological termination sites to carriers
ated and acidic set of somewhat less saline basinal waters, it of sulphur to the precipitation site.
creates redox conditions suitable for base metal precipitation
(Fig. 15.13b). For example, the reflux underbelly and edges
of dissolving sequences of bedded or halokinetic salt masses ow Temperature Sediment-Hosted Ore
L
tend to focus and deflect the escape of basinal or meteoric Deposits (Evaporite-Related)
water along the underside or the feather-edge of a dissolving
evaporite (see Rote Faule discussion in next section). At the Work over the past four decades has shown many sediment-
same time, ongoing dissolution maintains a stable and con- hosted stratiform copper deposits are closely associated with
tinually renewed source of reduced anoxic brine, a near salt evaporites, or indicators of former evaporites, as are a number
edge situation which survives as a relatively stable interface of SedEx and MVT deposits (Fig. 15.1). Some ore deposits
until the evaporite bed is leached or breached. Ongoing halo- discussed in this chapter still retain the actual salts responsi-
kinesis, which tends to maintain salt supply over longer time ble for the association, especially gypsum or anhydrite relics,
frames than a dissolving salt bed edge, can further stabilise in close proximity to the ore. Such deposits include the
the long term position of the dissolution front in earth-space. Zambian and Redstone copperbelts, Creta, Boleo, Corocoro,
Dissolving BSR- or TSR- sulphate evaporite sites, pyrite, or Dzhezkazgan, Kupferschiefer (Lubin and Mansfeld regions),
hydrocarbons on the reducing side of such redox fronts are Largentière and the Mt Isa copper association. All these accu-
possible sources of sulphur. mulations of metals are associated with the formation of a
In this context it is important to note that redox fronts are burial diagenetic redox/ mixing front, where either copper or
not unique to evaporite dissolution zones. But what is unusual Pb-Zn sulphides tended to accumulate (Fig. 15.14).
about subsurface evaporite-dissolution zones in terms of any However, examples discussed in detail in the remainder of
associated mineralised redox zones is the long term chemical the chapter and the resulting classification of low-temperature
stability it maintains. Even as evaporites are precipitating, base metal associations is not inclusive of all styles of base
they are associated with a bittern or reflux underbelly that can metal associations in stratiform sediment-hosted Cu, SedEx
persists for long periods, long after salt deposition has ceased and MVT settings. It only considers examples where a tie to
(Chap. 8). And, once buried, the dissolving salt edge of a evaporites and associated brine fluid sourcing or focusing is
thick halokinetic salt bed or mass can maintain a redox inter- obvious (Table 15.2).
face in subsurface earth space over long time intervals, via One of the metalliferous deposits with an obvious tie to
replenishment from inflowing salt. Likewise, the same salt evaporites is the modern metalliferous deep of the Red Sea,
flow can maintain seismically-pumped suprasalt extension focused on the Atlantis II Deep. It is a modern example of a
faults. At the same time, away from the salt edge or touch- metalliferous laminite forming in a brine lake sump on the
down weld, dissolution of the underbelly of the salt mass deep seafloor where the brine lake and the stabilisation of the
aides circulation and high chloride content in density-driven precipitation interface is a result of dissolution of adjacent
convective brine flows (Fig. 8.18). Salt-floored extensional halokinetic salt masses. Most workers classify the metallifer-
faults passing out into the upper side of a salt mass can also ous Red Sea deeps as SedEx deposits, but the low levels of
act as conduits for significant volumes of dense anoxic brine lead and high levels of copper, along with its stratigraphic
that also supply seafloor brine lakes or sumps (DHAL). The position atop seafloor basalts, place it outside the usual
sump positions are stabilised by their location atop salt with- Pb-Zn dominant system that typifies SedEx deposits. Some
drawal sinks and so create stable seafloor positions for the economic geologists use the Atlantis Deeps as analogs for
formation of the laminites that constitute the prepared ground volcanic massive sulphides and some argue it even illustrates
for many SedEx deposits. aspects of some stratiform Cu accumulations. Many such
In my opinion, this stabilization of the redox/mixing front economic geology studies have a propensity to ignore the
may explain why, worldwide, in a plethora of subeconomic elephant in the room, that is the Red Sea deeps are the result
Low Temperature Sediment-Hosted Ore Deposits (Evaporite-Related) 1491
The variably metalliferous seafloor deeps or deepsea

THE RED SEA
hypersaline anoxic lakes (DHAL) are part of a world
association of DHALs that form in association with

shallowly-buried dissolving salt masses. But, what makes
Conrad the Red sea deeps unique is that they can host substantial
Shaban (massive sulphide vents) amounts of metal sulphides. And, as Pierret et al. (2010)
Al Wajh hydrothermal field show, a Red Sea deep without the seafloor brine lake, is not
significantly mineralised. It is the intersection of the DHAL
Oceanographer Kebrit (massive sulphide vents) setting with an active midocean ridge (ultimate metal source)
Shay Bara 25° that explains the size and extent of the Atlantis deposit. Its
Vema
Um Lay Hyd. F.
salt-dissolution related hydrology changes the typical mid-
Nereus
Gypsum ocean massive-sulphide ridge deposit (with volumes usually
Thetis
Hadarba around 300,000 and up to three million tonnes; Hannington
Hatiba et al. 2011) into a more stable brine-stratified bottom hydrol-
ogy, which can fix metals over longer time and stability
Valdivia Atlantis basin frames, so that the known sulphide accumulation in the
Wando Basin Atlantis II
Discovery Chain Albatross Atlantis II Deep has a reserve that exceeds 90 million tonnes.
Shagara Aswad The Atlantis II deep offers an evaporite-specific explora-
Erba 20°
Volcano tion paradigm for large-scale ancient counterparts.
Port Sudan Accordingly, we shall discuss modern metalliferous lami-
Suakin nites in the Red Sea DHALs separately to other evaporite-
Commission Plain associated Cu, Pb-Zn and U deposits described in this and
100
the next chapter. I offer it as our first example of the impor-

0
tance of nearby dissolving evaporites in stabilising the min-

300 km
eralisation interface in this case in a region adjacent to a
Deep with variable levels of volcanogenic/rift/hydrothermal heat source.
metalliferous sediments
15°
Deep with metalliferous
sediments and/or brine pool ed Sea – Modern Metalliferous Brine Lake
R
Laminite Beds
35° 40°
The Red Sea is a young intracratonic basin atop a region of

Fig. 15.14 Locality map of deeps along the Red Sea showing different
the crust that is currently transitional from continental to
characteristics, metalliferous versus brine (In part after Blum and
Puchelt 1991)
oceanic rift. It contains a thick sequence of middle Miocene
evaporites formed in the early stages of ongoing rifting that
is separating the African and Arabian plates. This same rift-
of a large Tertiary-age halokinetically plumbed seafloor ing facilitates formation of new basaltic ocean floor below
brine association. the axis of the growing rift basin (Ehrhardt et al. 2005).
In my mind what is most important about the brine lakes Beneath waters more than a kilometre deep, along the deep
on the deep seafloor of the Red Sea is the fact that they exist rift axis there are numerous brine pools and deeps, some of
with such large lateral extents only because of dissolution of which are underlain by metalliferous sediments (Fig. 15.14;
the hosting halokinetic slope salt mass. Seismic surveys con- Blanc and Anschutz 1995; Blum and Puchelt 1991).
ducted in the past decade in the Red Sea show extensive salt Economically, the most important brine pool is the
flows (submarine salt glaciers) along the whole of the Red Atlantis II Deep; other smaller deeps, with variable develop-
Sea Rift (at least from 19 to 23°N; Augustin et al. 2014). In ment of metalliferous muds and brine sumps, include;
places, these salt sheets flow into and completely blanket the Commission Plain, Hatiba, Thetis, Nereus, Vema, Gypsum,
axial region of the rift. Where not covered by namakiers, the Kebrit and Shaban Deeps (Fig. 15.14). Laminites of the
seafloor comprises volcanic terrain characteristic of a mid- Atlantis II Deep are highly metalliferous, while the Kebrit
ocean spreading axis. In the salt-covered areas, evidence and Shaban deeps are of metalliferous interest in that frag-
from bathymetry, volume-balance of the saltflows, and geo- ments of massive sulphide from hydrothermal chimney sul-
physical data all seems to support the conclusion that the phides were recovered in bottom grab samples (Blum and
sub-salt basement is also basaltic in nature and represents Puchelt 1991). All brine-filled deeps are located in depres-
oceanic crust (Augustin et al. 2014). sions or brine sumps along the spreading axis, in the region
of the median valley. Most of these axial troughs and deeps Three conditions favour the formation of the brine-filled
are also located where transverse faults, inferred from bathy- deeps: (1) The Red Sea is a narrow depression only 200 km
metric data, seismic, or from continuation of continental wide, with water circulation to the south limited by a shallow
fracture lines, cross the median rift valley in regions that are subsea sill near the connection with the Indian Ocean. (2)
also characterised by halokinetic Miocene salt. Not all deeps The surrounding hot arid desert hinterland facilitates a low
contain brine sumps and not all brine sumps overlie metal- levels of clastic and nutrient input so clastic and pelagic
liferous laminites. accretion rate are very low along the axial part of the rift; this
The Conrad Deep, one of the northernmost deeps, illus- prevents clastic dilution of DAHL sediments and allows
trates the plate tectonic transition from continental rift to open hydrothermal solutions and their precipitates to be important
ocean seafloor and the transition to a passive margin. Seismic aspects of sedimentation in the deeps. Hydrothermal outflows
across the deep shows how new seafloor ridge basalts have are perhaps focused by transverse-fault damage zones inter-
interacted with and penetrated the halokinetic Miocene salt acting with mobile gravity glide salt masses to influence the
mass (Fig. 15.15; Ehrhardt et al. 2005). Likewise, the Thetis topography of the seafloor and create hydrographically open
and Atlantis II deeps are intimately tied to halokinesis or closed seafloor depressions. (3) Nearby dissolving haloki-
(Mitchell et al. 2010; Feldens et al. 2012). Of the three well- netic salt contributes huge volumes of chloride-dominant
studied deeps or DHALs along the Red Sea axis, only Atlantis hydrothermal and basinal brine into the irregular bottom
contains significant volumes of metalliferous laminites. topography it creates (Ehrhardt et al. 2005; Mitchell et al.
Interestingly, where seismic is available it clearly shows dia- 2010; Feldens et al. 2012). Many deeps are filled by perma-
piric salt, not basalt underlies the deeps (Fig. 15.15a). This is nently-stagnant brine pools, derived either directly from the
in marked contrast to the typical basalt-dominant understory dissolution of nearby evaporites or overspill from adjacent
interpetations that dominate older pre-seismic schematics in brine pools. Others deeps, filled by episodic hydrothermal
the economic geology literature (e.g., Fig. 5.16b). brine seeps, may have been intermittently influenced by
a b
SP: 1800 1700 1600
Line 99-073 Miocene evaporites
1.5
Bright spot Sediments – Prekinematic
b 4 Sediments – Synkinematic
3
Brine Salt diapir/wall
s
TWT (s)
c
Volcanic intrusion-extrusion
2
2.0 s Low ridge
1
Extension
s Rise
Salt pillow
Diapir/ Volcanic
salt wall intrusion
NWB SEB? Heatflow

2.5 distribution
SP:5800 6000 6200 6400
Volcanic extrusion Line 99-081 Salt

wall
Volcanic
1.5 s intrusion
TWT (s)
Heatflow
b distribution
c
s
2.0 Eroded
diapir
Brine
? lake
? 2.5 km Volcanic
VE = 8.8 intrusion
2.5
Fig. 15.15 Conrad Deep at the northern end of the axial rift in the Red some are collapsing. Collapsed structures probably contribute to forma-
Sea. (a) Representative seismic showing the association of extension, tion of brines and brine pools. (b) Evolution of the features in the Conrad
diapirism and volcanism as the deep forms. Some structures are active Deep as it experiences ongoing extension (After Ehrhardt et al. 2005)
hydrothermal convection within the bottom brine mass. Still brine body has an area of 1.8 km2 and is about 150 m thick
others, such as Thetis deep, show little evidence of ever act- atop a sea bottom as deep as 2,040 m (Figs. 15.16b).
ing as a seafloor sump for ponded brine. Distribution of bottom sediment facies is directly tied to the
properties of the overlying brine column (Fig. 15.16b). In
tlantis II Deep, Red Sea
A 1977 the bottom brine had a temperature of 61.5 °C, a chlo-
The Deep is roughly elliptical in shape, 14 km long, 5 km rinity of 156 ‰, and contained no free oxygen. The overly-
wide and is located in the most geothermally active part of ing 50-m-thick brine layer, called the Transition Zone, was at
the central Red Sea (Fig. 15.14). The bottom of the brine 50 °C with 82 ‰ chlorinity. This partially oxygenated upper
pool is 2,200 m below sea level and is surrounded by thick brine was a transitional zone of mixing between the lower
sequences of halokinetic Miocene evaporites and thin brine and overlying normal seawater. (Anschutz and Blanc
veneers of Pliocene Recent clastics (Fig. 15.16a). Through 1996; Hartmann et al. 1998).
subsurface dissolution and convective flushing, these Since the 1960s the temperature of the lower brine mass
Miocene evaporites supply ions to the seafloor and to high has been steadily rising. By 2008 the temperature in the bot-
salinity brines caught up in hydrothermal flow cells beneath tom brine of the SW basin was 67.5 °C (Fig. 15.17). The
the flowing and dissolving underbelly of the salt units. Hot structure of the lower transition zone, between about 1,990 m
hybrid brines ultimately discharge onto the floor of the Deep, water depth and highly saline bottom brine has changed sig-
and settle into the lower part of the main depression to form nificantly, by the mid 1990s, when it contained two convec-
a two layered brine pool that is some 200 m thick and is tive layers with nearly constant internal temperatures (61°
underlain by hypersaline metalliferous muds (Fig. 15.16b). and 55 °C, respectively). Since then temperature in the thick
For example, the southwest portion of the Atlantis II Deep lower convective layer in the Atlantis II Deep has continued
contains 150–200 million tonnes of unconsolidated mud to increase but at a somewhat lower rate of 0.1 °C/year.
averaging 5–6 wt% Zn and 0.8 wt% Cu on a dry salt free Clearly, the temperature of all four convective layers in the
basis. These tonnages rival some of the larger SedEx depos- deep have increased since the 1960s at the same rate across
its in the world and represent the only known deposit of Fe, all four layers (Fig. 5.17). Based on the observed changes,
Mn, Zn, Cu, Ag and Au of economic proportions currently Swift et al. (2012) concluded that diffusive vertical heat flux
forming on the sea bottom (Shanks III 1983; Backer and between the various convective layers is rapid on time scales
Lange 1987). of 3–5 years and that heat is being continually lost from the
The Deep was first discovered in 1966, it contains about brine pools to overlying Red Sea Deep seawater. Heat bud-
5 km3 of brine, stratified into distinct dense and convective gets suggest that the heat flux from hydrothermal venting has
layers of differing temperature and chlorinity. The lower today decreased from 0.54 GW to 0.18 GW since 1966.
a b
38°03E 38°05E
Atlantis
Deeps
N
21
19
00
00
210
0
NE
00
E
20
W 21 Atlantis II 1,600
00 Deep
684
SW 1,700
Metres (below sea level)
22
683 1,800
00
SW Brine lake in deep

21°20N
seafloor sump 1,900
2000 Chain
Pliocene + 2,000
of Deeps 50 °C
recent Lower 61.5°
2,100
0 3 brine Evaporite ± shale
Discovery 190 km Basalt (halokinetic) 2,200
0 21°15N Evaporite ± shale and salt
Deep
19
(halokinetic) 2,300
00
Albatross
1900
2 1
20
Deep 0
20
Metalliferous sediments
00
00
Kilometres
Fig. 15.16 Atlantis II Deep region, Red Sea. (a) Bathymetry of the of Atlantis brine lake (DHAL) to adjacent dissolving masses of haloki-
Atlantis II deep and adjacent seafloor depressions, contours in metres netic Miocene salt (After Anschutz and Blanc 1995)
(After Anschutz and Blanc 1995). (b) Schematic showing relationship
Fig. 15.17 Temperature and In situ temperature (°C) Salinity (psu)

salinity profiles in 2008 in the
20 30 40 50 60 70 50 100 150 20 250
Atlantis II Deep (After Swift
et al. 2012). Dashed lines
indicate the depths of bottom 1,900
ridges controlling the brine lakes
1,950
Depth (m)
2,000
2,050
Clearly, the venting of highly saline hydrothermal brines into anhydrites, have accumulated beneath the Atlantis brine
the brine lake over the past 40 years has been continuous, but lake, atop a basement composed of a mixture of basaltic
at a variable rate. ridges and halokinetic salt (Shanks III and Bischoff 1980;
What is most significant geologically and mineralogically Pottorf and Barnes 1983; Anschutz and Blanc 1995; Mitchell
is the long term stability of this dense halokinetically-derived et al. 2010; Feldens et al. 2012). Metalliferous sediments
lower brine mass, with temperatures favouring anhydrite beneath the floor of the deep are composed of stacked deli-
over gypsum precipitates, and its ongoing hydrochemical cately banded mudstones with bright colours of red, yellow,
isolation from the overlying normal seawater column. For green, purple, black or white, indicating varying levels of
the last four decades, almost all additional heat and salt sup- oxidised or reduced iron and manganese related to varying
plied to the Deep has been confined to the depression sump oxidation levels and salinities in the overlying brine column.
and it drives an increase in temperature in bottom waters. Sediments are typically anhydritic and very fine grained,
That is, very little heat is dispersed into the overlying seawa- with 50–80 % of the sediment less than 2 μm in size.
ter (Anschutz and Blanc 1996; Swift et al. 2012). The rate of Intercrystalline pore brines constitute up to 95 wt% of the
heat input to the Deep was near constant during the period muds, with measured pore salinities as much as 26 wt% and
till 1996 and amounted to 0.54 × 109 W, which drove the doc- directly comparable to the salinity/density of the overlying
umented rise in bottom-brine temperature. Salt input from brine (Fig. 5.18; Pottorf and Barnes 1983).
the hydrothermal influx was also constant, and equalled The sulphide-rich layers are a metre to several metres
250–350 kg/s. thick and form laterally continuous beds that are several kilo-
The effect of longterm brine pool stability is the pre- metres across. Sulphides are dominated by very fine-grained
cipitation of sulphide minerals at the Deep’s redox inter- pyrrhotite, cubic cubanite, chalcopyrite, sphalerite, and
face, which is defined by the halocline contact with the pyrite, and are interlayered with iron-rich phyllosilicates
overlying seawater column, and the subsequent accumula- (Zierenberg and Shanks III 1983). Sulphur isotope composi-
tion of some rather unusual sulphide-rich saline bottom tions and carbon-sulphur relations indicate that some of
sediments. Interestingly, base metal laminites are not pres- these sulphide layers have a hydrothermal seawater compo-
ent on the floors of other deeps, such as Thetis, which lack nent, whereas others were formed by bacterial sulphate
a longterm brine sump (Pierret et al. 2010). The laminated reduction centred in the interface. Ongoing brine activity
nature of metalliferous sediment on the deep sea floor in began in the western part of the Deep some 23,000 years ago
the Atlantis II Deep is directly related to the oscillating with deposition of a lower and upper sulphide zone, and an
nature of the overlying brine and its halocline interface amorphous silicate zone (Fig. 15.19). The metalliferous and
(Fig. 15.18). nonmetalliferous sediments in the W basin accumulated at
In the last 28,000 years some 10–30 m of the oxidic- similar rates, averaging 150 kg/k.y./m2, while metalliferous
silicatic-
sulphidic laminites, along with hydrothermal sediments in the SW basin accumulated at a higher rate of
Red Sea deep water 24°C

Cl 22.6 ‰ Carbonate
pH 8.4 ooze
1,990 m
Transition zone
Mn(OH4) ies
e fac
2,005 m xid
M n-o
Upper convective layer 52.0°C
Cl 67 ‰ ies
fac
pH 5.7 Fe(OH)3 ide
-ox
2,039 m Fe
Lower convective layer 67.5°C Cl 158 ‰
pH 5.2
H 2S
Fe2+ FeS, ZnS, CuFeS2, Fe silicates
s Halokinetic evaporites
acie
Zn2+ sulfide f and basalts
ate-
Silic
Hot brine
vents
Fig. 15.18 Summary of the oceanographic and physical conditions in the Atlantis II Deep, Red Sea; not to scale (After Hovland et al. 2006b)
W Basin (core 684) SW Basin (core 683)

700 kg/k.y./m2 (Fig. 15.19; Anschutz and Blanc 1995). The Normative mineralogy (%) Normative mineralogy (%)
lowermost unit in the pile in the W basin consists mainly of
detrital biogenic carbonates, with occasional thin beds of red 0 20 40 60 80 100 0 20 40 60 80 100
iron oxides (mostly fine-grained hematite) or dark interbeds 0
AM
entraining sulphide minerals.

Hydrothermal anhydrite in the Atlantis II sediments 4
200
SU2
occurs both as at-surface nodular hydrothermal beds

around areas where hot fluid discharges onto the sea floor
3f
and as vein fills beneath the sea floor (Degens and Ross 400
1969; Pottorf and Barnes 1983; Ramboz and Danis 1990; 3e
U
Monnin and Ramboz 1996). White nodular to massive 600
anhydrite beds in the W basin are up to 20 cm thick and 3d
Depth (cm)
CO
composed of 20–50 μm plates and laths of anhydrite, typi-

3c 800
cally interlayered with sulphide and Fe-montmorillonite
3b
beds. The central portion of individual anhydrite crystals
3a
in these beds can be composed of marcasite. The lower- 1,000
most bedded unit in the SW basin contains much more
SU1
2 12,000
15,000 years
nodular anhydrite, along with fragments of basalt toward
1,200
its base. Its 4-m + anhydritic stratigraphy is not unlike that
1
DOP
of nodular sekko-oko ore in a Kuroko deposit, except that 23,000 years

L
any underlying volcanics are basaltic rather than felsic 1,400
(see Chap. 16).
The anhydrite-filled veins that crosscut the laminites act
1,600
as conduits by which hot, saline hydrothermal brines vent
Sulphide minerals Carbonates
onto the floor of the Deep. Authigenic talc and smectite dom-
inate in deeper, hotter vein fills, while shallower veins are Iron oxide/hydroxide Detrital silicates
rich in anhydrite cement (Zierenberg and Shanks III 1983). Clays and amorphous Fe
Manganese oxide/hydroxide
The vertical zoning of vein-mineral fill is related to heating
Hydrothermal anhydrite Magnesian phyllosilicates
haloes tied the same ascending hydrothermal fluids, with
stable isotope ratios in the various vein minerals indicating Fig. 15.19 Atlantis II Deep, Red Sea showing mineralogical propor-
precipitation temperatures ranging up to 300 °C. tions in cores from W and SW basins (After Anschutz and Blanc 1995)
Because of anhydrite’s retrograde solubility, it can form the brine column, and in brine-saturated sediments beneath
by a process as simple as heating hydrothermally-circulating areas covered by stable anoxic H2S-enriched brines. Brine
seawater to temperatures in excess of 150 °C. Pottorf and pool stability and an associated lack of mixing with overly-
Barnes (1983) concluded that the bedded anhydrite of the ing seawater (due to density/salinity stratification) allowed
Atlantis II Deep, like the vein fill, is a hydrothermal precipi- metal sulphides to accumulate as laminites across large areas
tate. Based on marcasite inclusions in the anhydrite units, it of the brine pool floor and not just near vent localities. Hence,
precipitated at temperatures down to 160 °C or less. At some the larger volume of the metal resource and the greater dis-
temperature between 60 and 160 °C, probably close to 100– persal of metal sulphides in the Atlantis II Deep compared to
120 °C, hydrothermal anhydrite precipitation ceased. Thus, the much smaller near-vent precipitation sites typical of
anhydrite distribution in the Atlantis II deep is related to the VHMS deposits, such as TAG Mound, the smokers of the
solution mixing and thermal anomalies associated with east Pacific rise, and Kuroko- and Cyprus-style deposits (see
hydrothermal seawater circulation. Chap. 16). It is the hydrological and hydrogeochemical
The fact that Holocene sediments in the Atlantis II Deep effects of the dissolving halokinetic evaporites that distin-
contain sulphate minerals and that particulate anhydrite is guish this style of hydrothermal “SedEx” precipitate from
still suspended in the lower brine body strongly suggests that less stable seafloor brine pools, tied to much smaller open
anhydrite is stable in the temperatures found at the bottom of marine VHMS deposits.
the water column or is at least only dissolving slowly. These
conclusions were clarified by Monnin and Ramboz (1996), ebrit and Shaban Deeps, Red Sea
K
who found that the Upper Convective Layer (UCL; or Massive sulphides dredged from the Kebrit Deep (Arabic for
Transition Zone) of the Atlantis II hydrothermal system was sulphur) represent black smoker fragments, novel to most
undersaturated with respect to hydrothermal anhydrite Red Sea brine pool deposits (Fig. 15.14; Blum and Puchelt
throughout their study period, 1965–1985. The system 1991). TV camera observations at 1,366 m depth in the
reached anhydrite saturation in the lower brine only for short Kebrit Deep, and just above the seawater/brine interface at
periods in 1966 and 1976. 1,370 m, imaged some 40+ inactive smokers. Brines below
What distinguishes the hydrothermal salts and sediments the interface in Kebrit Deep at a depth of 1,373 m have a
in the Atlantis II Deep from the much smaller hydrothermal temperature of 24.3 °C and a salinity of 256 ‰, making this
accumulations in volcanogenic hosted massive sulphide pool as saline but somewhat cooler (in the gypsum, not anhy-
(VHMS) deposits (Chap. 16) is that the hot metalliferous drite, temperature field) than the Atlantis II deep. Above the
brines now found on the seafloor achieved their elevated interface the Kebrit brine has a temperature of 21.5 °C and a
salinities, temperatures and acidic saline chemistries via salinity of 41.9 ‰. According to Hartmann et al. (1998) there
hybrid hydrothermal circulation through both seafloor were no significant changes in temperature, brine level or
basalts and dissolution of the edges and underbellies of halite chlorinity over the preceding 23 years. The transition in the
in nearby halokinetic Miocene salt masses. Heat to drive this column from high saline bottom brine to normal seawater
circulation probably came from the hot basaltic rocks salinity probably extends over a depth of only a few decime-
emplaced in the slowly spreading axial zone, while most of tres or less. As in the Atlantis II Deep, the dissolution of
the chloride and fluid focusing was due to circulation of nearby Miocene evaporites accounts for the very high salini-
marine-fed hydrothermal brines with significant, if not domi- ties in the bottom brine layer.
nant contributions from nearby dissolution of halokinetic Piston core sampling in the Kebrit Deep revealed strati-
salt tongues. Thus, a seawater/brine flushing of newly formed fied somewhat metal-enriched sediments in the upper por-
basalts, as well as of Miocene evaporitic sediments atop and tions of the sedimentary column, while box and dredge
below the halokinetic salt, both contribute metal to the brine sampling recovered specimens of elemental sulphur, sul-
pool. This is clearly seen in studies of lead isotopes in the phide and sulphates. These recovered sulphides consist pri-
brine pool laminites, which indicate that a substantial portion marily of Fe- Zn- and Pb-bearing phases that can be tar and
of the lead came from the Miocene evaporites and their asso- asphalt impregnated. They were probably derived by hydro-
ciated clastics and not from the basalts (Dupre et al. 1988). thermal cracking of organics held in adjacent sediments,
As in anoxic halokinetic brine pools (DHALs) that typify where TOC values are more than 4 % in Kebrit and can be
halokinetic brine sumps on suprasalt seafloors elsewhere in higher than 8 % in Shaban cores (Fig. 15.20 – see also Chap.
the world (such as in the Mediterranean and the Gulf of 9). The sphalerite typically forms banded colloform nodules.
Mexico), the reduced sulphur in the shallow pore brines and Concentration of Ni in discrete bravoite [(Fe,Ni,Co)S2]
the bottom brine layer in the deep were mostly derived from aggregates points to brine leaching of nearby basalts as a
bacteriogenic reactions, using seawater sulphate and source for at least some of the metals in the brine pool.
entrained organic matter. This created conditions suitable for Unlike the Atlantis II Deep, Cu-sulphides are virtually absent
widespread metal sulphide precipitation at the halocline, in from the paragenesis. This, and the presence of gypsum
a b
0
10
KC 17002-2 Shaban Deep
KC 17002-2 Shaban Deep (11.8–13.6 ka)
KC 17006-5 Kebrit deep
TOC
100
CaCO3
8
200
TOC (Wt%)
Depth (cm)
Sapropel (12 ka)

300
4
400
2
500
Shaban Deep
Kasten core
17002-2
600 0
0 5 10
TOC (wt %) 0 200 400 600 800 1,000
CaCO3 (wt %)/10 Baexcess (ppm wt)
Fig. 15.20 Organic matter in the Shaban and Kebrit deeps. (a) TOC and CaCO3 contents in the upper 6 m of the KC 17002–2 core from Shaban deep
showing elevated content in the laminites (deposited 11.8–136.6 ka). (b) Crossplot of TOC versus Baexcess in select core intervals (After Botz et al. 2007)
rather than anhydrite interlayers in chimney fragments points Deep that lies beneath the metalliferous sediments and simi-
to formation of metal sulphides at lower temperatures com- lar to the biogenic sediments found on the deep seafloor
pared to the Atlantis II Deep. Sulphide layering in the chim- above the zone defined by the more saline portions of the
neys shows classic zonation, with Zn-bearing phases brine lake (Fig. 15.18). This biogenic layer in the Shaban
preferentially lining the interiors of the chimneys while Deep overlies a tholeiitic ferro-basalt with transitional affini-
pyrite is dominant in the outer portions. ties, it too is different from the typical tholeiite basalt found
The bottom brine layers in the Shaban Deep in the north- further south. Thus, the Shaban Deep, the northernmost deep
ern part of the Red Sea are 200 m thick, but the brines are in the Red Sea rift, represents a very recent stage of oceanic
only 2–3 °C warmer than the normal bottom waters (Cocherie opening. The lack of pervasive hydrothermal signature in the
et al. 1994). An insignificant decrease in temperature (to Shaban Deep compared with the Atlantis II Deep is also seen
about 24.1 °C) occurred in the upper brine since detection of in both the Sr-Nd isotopes and the rare earth element signa-
the Shaban Deep in 1981 and no changes were found for the tures (Cocherie et al. 1994). Metal sulphides in Shaban Deep
brine-seawater level (Hartmann et al. 1998). The bottom are less frequent than those in Kebrit, with framboidal pyrite
sediment in the Shaban Deep is somewhat unusual compared being the dominant ore mineral.
with other brine pool sediments in the Red Sea in that the Gypsum occurs in the bottom sediments of both the
sediment consists almost entirely of biodetrital silicate mud Shaban and Kebrit deeps, as both euhedral prisms and len-
(diatomaceous), with occasional volcanic glass fragments ticular forms, up to several centimetres across. Crystals often
and only a thin (4 cm thick) hydrothermal sediment layer, interpenetrate the sediment layering to construct classic
along with intervals with more than 50 % biodetrital carbon- “desert rosette” morphologies, especially in the Kebrit Deep,
ate (Fig. 15.20a; note the plotted CaCO3 values are reduced where gypsum is commonplace. Deeper coring has yet to be
by an order of magnitude to allow plotting on the same scale undertaken in either of these deeps, but it is likely that this
as the TOC values). This biodetrital lithofacies is similar to gypsum forms atop areas of subcropping and dissolving
the more oxidised layer in the western part of the Atlantis II autochthonous salt in the same way morphologically
i dentical gypsum forms in sediments atop areas of dissolving hydrothermal brines as they convect through and flush
halokinetic salt in DHAL settings worldwide. adjacent sub-salt and suprasalt sediment and volcanics,

Sulphur isotopes from gypsum in the rosettes in Kebrit before ultimately venting and residing in the brine lake. That
Deep have values in the range +25.1‰ to +30.0 ‰. These is, the high chloride levels in the circulating brine increases
values exceed those of normal seawater-sulphate-derived the reaction rate of any saline fluids flushing metals from the
gypsum and imply a significant input of bacteriogenically basaltic basement and suitable first-cycle sediments. The
fractionated residual seawater sulphate. Some samples show presence of a dissolving salt aquiclude atop seafloor basalt
intimate intergrowths of idiomorphic gypsum and spongy also focuses reflux driven hydrothermal vent fluids into the
sulphide, pointing to coprecipitation of both minerals from outflow zones about the edges of the stable brine pools. The
the same hydrothermal fluid in the presence of possible bac- now increasingly documented role of salt allochthons as the
terial mediators. Inclusion studies show rather low sulphide dominant control on the location of the deeps on the Red Sea
and sulphate precipitation temperatures of 110–130 ° C in floor, means it is likely that synkinematic salt gliding drives
the Kebrit brine pool and 100 ° C in the Shaban Deep. In restriction and brine focusing on the sea floor depressions.
either deep, the gypsum, like the anhydrite in the Atlantis II However, the presence of salt allochthons is a focus for the
deep, is not a true solar-derived deepwater evaporite, but a mineralisation site (trap or seal), but salt focusing is not
hydrothermal or burial salt. directly sourcing the metals found in some of the Deeps. If it
There is a very interesting organic-rich laminite in the was then sediment fills in all brine-filled deeps along the Red
Shaban Deep with TOC values in excess of 5 wt%, qualify- Sea axis would be metalliferous. Rather there is still a need
ing it as a sapropel (Fig. 15.20a). The same interval also for a focused deeper mantle-source convection to source the
shows cemented carbonate layers between the organic-rich metals ultimately held in this type of deposit.
layers and elevated levels of Ba tied to elevated TOC
(Fig. 15.20b). The organic signature in this 11,800–
13,600 year old sapropel is largely unoxidised as it is bathed Stratiform Copper Deposits (Salt-Related)
in hypersaline pore waters (Botz et al. 2007). The excellent
correlation between TOC content and barium content sug- Sediment-hosted stratiform copper deposits comprise dis-
gests the sapropel formed via a productivity pulse in the seminated to veinlet Cu and Cu-Fe sulphides hosted in silici-
basin arguing organic productivity not hydrothermalism con- clastic or dolomitic sediments. In this chapter I am using the
trols the organic and Ba content of the Shaban sediments. term “sediment-hosted stratiform copper” (SSC) as defined
by Kirkham (1989). It encompasses a group of Cu deposits
ed Sea Summary
R that are not truly stratiform in that they may cut the stratigra-
Stable stagnant brine pools have developed in sea floor phy either locally or regionally. Yet, locally, most of these
depressions along the medial ridge of the Red Sea, in close deposits are not only stratabound (confined to a particular
association with dissolution of adjacent thick halokinetic stratum), but are more or less concordant or peneconcordant,
evaporites. Hot metalliferous brines focused by salt alloch- either with bedding or with the edge of a salt mass or its resi-
thons and escaping into the lower convective layers of these dues (stratiform).
pools become widely dispersed across the extent of the deep- SSC deposits worldwide rank second only to porphyry
water brine pool with the richest metalliferous laminites copper deposits in terms of copper production and they rep-
(Atlantis II Deep), corresponding to a brine lake (DHAL) resent the most important global source of cobalt (Figs. 15.21
positioned in the most geothermally active position in the and 15.2). Together, SSC deposits account for some 23 % of
axial trough. The Atlantis II brine lake also contains the hot- the world’s Cu production and known reserves, as well as
test brines. During active venting of metalliferous brines, the being significant sources of Co and Ag. Small SSC deposits
presence of a longterm brine pond facilitated stable anoxia at of various ages are commonplace, but large sediment-hosted
the sea bottom, as well as intra-brine-pool convection and stratiform copper deposits are rare (Hitzman et al. 2005;
the dispersal of metalliferous brine away from the immediate Brown 1997). Within the supergiant grouping, three evapo-
vent area. Diffusive mixing at the halocline atop the brine ritic basins, that contain enormous Cu deposits, dominate
pool precipitated metal sulphides, mostly as pyrite framboids (>24 million metric tons -Mt), they are; (1) the Permian
that then sank to the bottom carrying with them dispersed Basin Kupferschiefer of central Europe, (2) the
organic water. Thus, the longterm presence of a stable bot- Neoproterozoic Katangan Basin in central Africa, and (3) the
tom brine lake increases the area of prepared ground for any Paleoproterozoic Kodaro-Udokan in Siberia (Fig. 15.21 and
subsequent Fe, Pb, Zn and Cu emplacement. Table 15.7). Ore hosts in this group of supergiant deposits
Ongoing dissolution of adjacent thick halokinetic masses span lithologies that range from carbonates to siliciclastics
not only enhances the permanency of the brine pool, it and all the larger accumulations are associated with haloki-
also raises the metal-carrying capacity of chloride-rich netic evaporites or their residues.
Redstone district
(Mesoprot.)
Rock Ck district Lubin district Udokhan
(Mesoprot.) White Pine (Mesoprot.) Dzhezkazgan (Paleoprot.)
(Permian) (Carboniferous)
Kona (Paleoprot.)
Spar lake Lisbon Valley (Jurassic)
(Mesoprot.) Dongchuan
Creta (Permian)
district (Mesoprot.)
? Red Sea
(modern)
Katangan fold
belt (Mesoprot.)
Corocoro
(Eocene)
Adelaide fold belt
(Neoprot.)
Reduced Cu Revett Cu
Redbed Cu
Fig. 15.21 Sediment-hosted stratiform (SSC) Cu deposits with Cu reserves of more than 1 million tonnes and discussed in this chapter (see also
Fig. 15.22) (Data points extracted from Cox et al. 2007 and Salt Work database version 1.6)
Table 15.7 Selected evaporite-related sediment-hosted stratiform Cu likely focusing and trapping geometries created by interac-
(SSC) deposits related to salt style and position relative to the salt mass. tions between redox interfaces and dissolving evaporite
In many cases the salt bed or mass is partially or completely dissolved masses. The latter, now largely dissolved, evaporite masses
and only residues remain. Only deposits still in the diagenetic realm
were selected in this listing
were likely halokinetic in the case of the larger deposits and
some masses were possibly allochthonous, as they are in a
Halokinetic (peridiapiric)
number of the larger SedEx deposits. The positions of former
Ore deposit position Bedded salt salt
salt masses are now likely indicated by residues and altera-
Suprasalt and or its Lisbon Valley Utah
residues Flinders Ranges, South tion products, rather than actual salts.
Australia Current classifications of SSC deposits do not place them
Dongchuan, China in an understood evaporite framework, and the proximity of
Dzhezkazgan, Kazakhstan
most larger deposits to halokinesis at some time in their burial
Inter or lateral to salt Corocoro Katangan Copperbelt
edge and/or its Redstone, (Kipushi)
evolution, is rarely noted. Many current classifications do,
residues NWT Atlantis II Deep? however, note the typical association of redbed Cu with pres-
Subsalt or its Creta, USA Kupferschiefer (Lubin ent or former evaporites, but then tend to mismatch brine set-
residues district) tings and associations, making the noted evaporite association
useless as a pointer to mineralised positions. So, to simplify
and better understand the diagenetic processes associated
The problem with exploration-based targeting of this with copper ores tied to evaporite evolution, I have decided to
group of copper deposits, especially when they are associ- steer away from the classic subdivisions of sediment-hosted
ated with now dissolved evaporites, is that we are looking at Cu deposits; other than noting at the start of this section that
metal precipitation mechanisms that are diagenetic and this group of SSC deposits is currently subdivided in the lit-
dynamic. Ore positions are typically a reflection of a once erature into Reduced copper, Redbed copper and Revett cop-
rapidly evolving basin/ brine hydrology, which now is much per (as illustrated in Figs. 15.21 and 15.22). According to Cox
less active. Accordingly, the various copper ore precipitates et al. (2007) these are three subtypes of sediment-hosted cop-
are concordant with paleopermeability trends and chemical per deposits show significant differences in tonnage and cop-
interfaces, but they are not always concordant with regional per grade which can be used to help separate the three groups.
depositional bedding. Thus, to predict positions of likely In their world GIS compilation of SSC deposits they list 56
evaporite-associated stratiform copper occurrences within a reduced-facies Cu deposits, 32 redbed Cu deposits, and 15
basin, one must understand not just local depositional geom- Revett Cu deposits. They conclude that the three types differ
etries, but also the subsequent diagenetic history, as well as in the strength and efficiency of the reductant at the site of
Fig. 15.22 Resource plot for 10

sediment hosted stratiform copper
deposits. Halokinetic association Giant and supergiant deposits
indicated by H, bedded evaporite
association by B and Luanshya(H) Kolwezi(H)
metamorphic evaporite Dzhezkazgan(H)
association by M (Plotted data Mindola(H) Konkola(H)
values were extracted from Cox Mufulira(H) Fungurume(H)
et al. 2007, integrated with the Chambishi(H) Nchanga(H)
Lubin(H)
SSC evaporite association GIS Udokhan(M)
base and classification extracted
from the SaltWork database Rock Ck.(M)
version 1.6). Also shown is Cu grade (%) White Pine (B)
1
Olympic Dam (IOCG) and the Olympic Dam
La Escondida
four largest Porphyry-Cu deposits El Teniente
Rio Blanco
Chuquicamata
Reduced Cu Revett Cu
Redbed Cu Porphyry Cu
10
10
10
10
10
10
6
5
ton
ton
ton
ton
ton
ton
ne
ne
ne
ne
ne
ne
0.1
1
10
1,000
10,000
100,000
100
Ore Tonnage (million tonnes)
deposition. In classic SSC classifications, the reductant the Typing a deposit to its evaporite style makes it easier to
reduced-facies deposits is a marine or lacustrine fine-grained illustrate and understand the formative brine fluid hydrolo-
sediment, containing abundant organic matter. In redbed gies. Interestingly, almost all the world’s giant and supergi-
deposits, the reductant is more weakly distributed, usually ant SSC’s have a halokinetic evaporite basinwide association,
represented by patches of organic debris in sandstone. In rather than a bedded platform evaporite association
Revett Cu deposits, the reductant is broad and diffuse and in (Fig. 15.22). After discussing the various halokinetic asso-
some Phanerozoic deposits can be shown to be gaseous or ciations, I will consider sediment-hosted Cu deposits tied to
liquid hydrocarbon, or sulphide-rich sour gas. the bedded salt associations. This latter group tend encom-
I shall not use this three part terminology in this chapter pass much more numerous, but smaller, examples of copper
as it does little to improve our understanding of the role of accumulations. Worldwide, they are patchily distributed, so
dissolving salt in focusing and trapping processes associated deposit details are not as well documented (Fig. 15.21).
with ore creation within the group of salt-related copper By itself, this two-part breakdown into halokinetic versus
deposits that we will discuss. In terms of understanding how bedded and the understanding of extension, compression, and
these deposits relate to evaporite-derived brines and dissolu- structuration that is associated with an evaporite/brine genesis,
tion foci, the classic classifications confuse a significant fac- become exploration pointers or paradigms. So, as a rule of
tor of prime exploration importance, namely where did the thumb in a greenfield area, when looking for the larger SSC’s,
deposit form in relation to the associated evaporite mass and one should first focus on localities where the “prepared ground”
the redox front created by subsurface salt dissolution. units (organic shales or former hydrocarbon traps) lie adjacent
So, instead, I shall subdivide and discuss representative to stable halokinetic salt or rauhwacke masses, not to stratiform
stratiform Cu deposits using an understanding of halokinetic bedded salt associations. The latter tend to be smaller. We shall
and bedded salt associations. It is based on the geometry of revisit this observation, but with understanding, after we have
the adjacent salt mass, or its residues, and the relative position studied some representative examples (Table 15.7).
of the ore deposits with respect to the salt mass (Tables 15.2
and 15.7; subsalt, intrasalt or suprasalt). I shall consider the
halokinetic examples first, as they tend to be worldclass and Stratiform Cu Halokinetic-Salt Associations
currently exploited. Accordingly, the three dimensional
aspects of many of the facies and structural indicators for Within the sediment-hosted Cu association there are two
associated salts in the halokinetic group are well mapped, if styles of halokinetic salt: (1) Deposits where substantial
not well understood in terms of process significance. volumes of the halokinetic salt are nearby, such as the
Fig. 15.23 Distribution of the 16°E 18°E 20°E

Kupferschiefer copper deposits
in Poland (After Oszczepalski
and Blundell 2005) Polish basin
Rote faule
Poland
Germany
Copper
>5 kg/m2
Central basin 53°N
W
ol
sz
ynt
Ri
dg
e
Lower Poznan
Silesian
basin
52°N
Lubin
Fore-Sudetic 51°N
block Wroclaw
100 km
Lubin-Sieroszowice area (Cu >20 kg/m2)

Area under by dune beds of uppermost Rotliegend
Kupferschiefer, Lisbon Valley and the Dzhezkazgan depos- (c) Intersalt or halokinetic salt residue associated – various
its and, (2) Deposits where flowing salt was once present examples in the Donchuan District and Katangan Copper
but now is indicated by dissolution remnants, typically now belt and their more metamorphosed equivalents
in thrust terranes, but often showing evidence of an early (Udokhan)
gravity gliding stage of mineralisation later overprinted
compressional thrusting, given a rauhwacke association to upferschiefer/Rote Faule, Lubin Region, Poland
K
the current outcrop/subcrop expression. Widespread exam- The world’s largest sediment-hosted stratiform copper accu-
ples of type 2 deposits, where salt is no longer present, mulation is a subsalt copper association, centred on the
typify the Katangan copperbelt, copper in the Mt Isa mine Kupferschiefer shales in the Lubin-Sieroszowice copper dis-
region and the numerous small suprasalt Cu occurrences in trict, Poland (Fig. 15.23). Near the ore zone, is a partially
the Flinders Ranges, South Australia (see Chaps. 6 and 7 dissolved thick mass of halokinetic Zechstein salt. Facies
respectively for the geological background to these rauh- distribution preserves prima facie evidence of the influence
wacke associations). of a salt mass, both deeper in the basin where it acts as a
In this section I have chosen worldclass examples to source of dissolution-related basinal brines and nearer the
illustrate Cu accumulations where dissolving halokinetic basin margin where it focused the set-up of a halokinetically-
salt masses played a role, both in generating metalliferous stabilised brine-mixing redox front.
saline brines, and in focusing the ore precipitation process at Mineralisation typically occurs in reduced, Zechstein-
a salt-dissolution induced stable redox front. They are capped beds at the top of a thick continental volcanic and
(Table 15.7); redbed Rotliegende sequence, which was deposited within
a continental Permian rift basin known as the Polish Trough.
(a) Subsalt – Kupferschiefer in Poland and Germany. This is a generally north-west trending basin and is the
(b) Suprasalt -Dzhezkazgan and Lisbon Valley. southeastern extension of the main evaporite-filled
a b
Werra
Muschelkalk anhydrite
Buntsandstein Pb
Cu -Zn Dolomite
Limestone min
era min
Zechstein lisa era Zechstein
Fo R tion lisa limestone
o tion
re
- U. Rotliegendes t
bl Su e
oc de
k tic f Cu Pb-Zn ore
L. Rotliegendes a Kupferschiefer
ore
u
l
Fo onoc
Volcanics & e
re-
m
redbeds 2m
Su line
Sandstone
de
tic
2 km
b Sieroszowice Rudna mine region
ENE
WSW
13.6 %
13.5 %
2m
0 2 0 2 4
0 2 4
T
Dolomite with occasional anhydrite (Werra)

ran
sit
ion
Silty dolomite (residues?)

zo
ne
Ro
Bituminous dolomite (Kupferschiefer)

0 2 4
te
y
od
fa
0 2 eb
ule
%Cu
Sandstone (Weissliegende ) Or
Anhydrite 0 2 4
Fig. 15.24 Rote Faule and its influence on Kupferschiefer zone, shows higher Cu enrichment in Kupferschiefer with Cu values
mineralisation in the Lubin copper district, Poland. (a) Regional in excess of 13 %, but the greater thickness and volume of ore in the
schematic showing focus of upwelling of convective basinal waters Lubin district resides in the Upper Rotliegende sandstone, beneath a
toward basin edge and the Rote Faule Zone. (b) Enlargement of Rote Werra Anhydrite seal (Modified from Jowett 1992; Vaughan et al.
Faule area outlined in a, showing how the resultant mineralisation 1989; ore assays and associated stratigraphy after Wodzicki and
cross cuts the stratigraphy. (c) Distribution of Cu in the Lubin ore Piestrzynski 1994)
(Zechstein Series) halokinetic Southern Permian Basin (e.g., Wedepohl 1964). However, detailed work in Poland in
(Fig. 15.23; Krzywiec 2004). The mineralised district lies the last few decades has shown that the Cu mineralisation
along the southern edge of the halokinetic Zechstein cuts depositional boundaries (Fig. 15.24). Levels of miner-
sequence and is also proximal to the basin margin of the alisation in the Kupferschiefer Rote Faule interval in the
Lower Silesian Basin to the south. The ongoing ability of Lubin- Sieroszowice district are typically far higher than
flowing salt to maintain its seal capacity and its diagenetic background levels in the Kupferschiefer shale (Fig. 15.24c)
interfaces in earth-space adjacent to a basement high, even It should be pointed out that the using term shale in this con-
as the salt was dissolved and deformed, is in my opinion text to imply a terrigenous sediment is a misnomer, the
the reason why the Lubin-Sieroszowice District is world- Kupferschiefer is actually a finegrained (micritic) organic-
class. It has 2,369 Mt of ore, made up of 47.07 Mt Cu @ enriched, finely laminated dolomite mudstone, often with no
1.3–2.6 %, 135,000 t Ag @ 30–80 g/t (Oszczepalski and more than minor amounts of terrigenous material.
Blundell 2005). Locally, mineralisation transgresses depositional bound-
Stratabound Cu–Ag Kupferschiefer deposits were long aries as it is tied to the Rote Faule/saline brine interface and
considered classic examples of syngenetic mineralisation, not to the depositional pattern or solely to the distribution of
driven by syndepositional bacterial sulphate reduction the Kupferschiefer shale. Thus copper ore in the Lubin
d istrict is not just hosted in the organic laminites of the sediments were deposited in shallower shorezone areas about
Kupferschiefer and the Zechsteinkalk, it also occurs in parts the basin edge or atop basement highs. The anoxic organic-
of the Weissliegend aeolian sandstone, a unit that at the time rich laminates of the deeper water areas quickly became the
of deposition in a desert sand sea was exceptionally free of hosts to syndepositional bacterially mediated pyrite fram-
organics, organic laminites and pre-ore sulphides (Figs. 15.23 boids (Sawlowicz 1992). Regionally, much early metal sul-
and 15.24b, c). phide precipitation was dominated by this pyrite. Only
To the dismay of many syngeneticists, this depositionally locally was there any early Cu or Zn enrichment as this pyrite
organic-clean aeolian sandstone hosts half the economic and the associated organics were replaced by base metal sul-
Cu-sulphides in the Lubin-Sieroszowice copper district. That phides, which were further concentrated in regions adjacent
is, the richest intervals of mineralisation define low-angle to Rote Faule intervals (Sawlowicz 1992). This type of
transgressive metal zones tied to the redox edges adjacent to enrichment is sometimes call a two-fluid or multiple-fluid
diagenetic Rote Faule units (Jowett et al. 1987; Jowett 1987, ore forming process.
1989, 1992; Oszczepalski 1989, 1994; Vaughan et al. 1989; The high mineral content of the Kupferschiefer was
Hammer et al. 1990; Kucha 1990; Bechtel and Hoernes attained via a three-step process (Sun and Püttmann 1997):
1993; Wodzicki and Piestrzynski 1994; Bechtel et al. 1995; (1) framboidal pyrite and pyrite precursors were precipitated
Heppenheimer et al. 1995; Speczik 1995; Sun et al. 1995; by bacterial sulphate reduction during deposition of the
Large et al. 1995; Large and Gize 1996). The overlying evap- sediment; (2) pyrite and pyrite precursors were largely

oritic Zechstein sediments enhanced and focused the precipi- replaced by mixed Cu/Fe minerals and by chalcocite during
tation of base metals, both by forming prepared ground at the early diagenesis; and, (3) in those intervals with very high
time of deposition (pyritic and organic-rich evaporitic Cu contents (>8 %), the amount of reduced sulphur from
laminite host), and by creating a stable dissolution hydrology Fe-sulphide precursors was not sufficient for precipitation of
during diagenesis, which focused the greater volumes of Cu and other trace metals. In this part of the profile, thermo-
economic mineralisation into a redox zone immediately chemical sulphate reduction (TSR) occurred after pyrite
below the main evaporite mass and adjacent to the Rote replacement, as is indicated by the presence of pyrobitumen
Faule boundary. and sparry calcite.
The mesohaline setting of the Kupferschiefer laminites The maturation profiles of the kerogens in the ore zone and
created much of the “prepared ground”- organic-rich lami- the adjacent Rote Faule show the Rote Faule kerogen to be
nites below thick salt that would later control much of the highly oxidised and degraded compare to kerogens in the ore
mineralising fluid flows and interfaces. Away from the zone zone (Fig. 15.25a; Bechtel et al. 2002). Likewise, the stable
of organic degradation associated with the Rote Faule, the isotope profiles across the mineralised zone imply increasing
degree of methylation of 2-methyl-2-trimethyl-tridecylchro- oxidation in the Rote Faule (Fig. 15.25b). Biomarker profiles
mans (MTTC) in the shales indicate original euryhaline to within the mineralised zones also imply hydrothermal altera-
mesohaline (30–60 ‰) salinity during subaqueous laminite tion has occurred within locally elevated temperature regimes.
sedimentation. An abundance of biomarkers, derived from Some aspects of the profiles are similar to those of hydrother-
green/purple sulphur bacteria, suggests H2S saturation of the mal-cracked hydrocarbons in the modern Guayamas Basin
anoxic bottom waters and maximum water depths below (Rospondek et al. 2007). All this is consistent with the model
100 m. These organisms lived near the boundary between the of Brown (2006) arguing for a mixing of reduced metallifer-
photic zone and the anoxic (euxinic) bottom water at depths ous basinal fluids and surface-derived, somewhat more oxi-
of 10–30 m. Primary production in the upper water column dised, saline waters and indicated by Rote Faule (Fig. 15.24).
was dominated by photosynthetic cyanobacteria or green According to Brown, the descending oxidising waters become
algae. In the sediment, sulphate reduction was driven by the more saline by coming into contact with buried evaporites (in
availability of abundant sulphate and organic detritus settling this case it would have been the underside of the adjacent
from the overlying water column. Methanogenesis was Zechstein salt seal), or in some cases he argues the surface-
active mostly during early Kupferschiefer deposition; it is derived fluids are reflux brines.
indicated by the light carbon isotopic composition of the Rote Faule (“red rot”) describes a non-mineralised diage-
organic matter that originated from recycling of CO2, which netic zone and loosely encompasses barren red-coloured
was generated by methane-oxidizing bacteria in the water rocks typically found in the vicinity of high-grade ore. That
column (see Chap. 9 for detail). is, it describes an oxidised haematitic interval that is adjacent
Kupferschiefer matrix was deposited mostly from suspen- to reduced highly mineralised intervals throughout the
sion load in density-stratified subaqueous lacustrine/ Lubin-Sieroszowice copper district. Levels of mineralisation
restricted marine-fed brine lakes and seaways with reducing in the Kupferschiefer adjacent to a Rote Faule interval are
anoxic bottom waters (Glennie 1989a, b). Higher energy typically far higher than background levels in the
Fig. 15.25 Organic character in a OI (mg CO2/gCorg) b

the vicinity of Rote Faule. (a)
20 40 60 80 Calcite cements δ18OPDB
Upper figure is a modified van
I II Cu ore zone
Krevelen diagram plotting
HI (mg HC/gCorg)
400 3
Rock-Eval pyrolysis of samples Pb-Zn ore zone
from Kupferschiefer strata Lower Rote Faule zone
figure shows relationship 2
between hydrogen index (HI) 200
and temperature as measured by III
maximum pyrolysis yield (Tmax) 1
0 Reduced
of the same Kupferschiefer δ18OPDP
strata. Maturation pathways 600 0
typical for the different kerogen Type
HI (mg HC/gCorg) −10 −8 −4 −2
types are shown in both figures Type I
(b) δ13C versus δ18O plots of 400 II −1
calcite cements in the
Kupferschiefer in the vicinity of
200 Oxidised −2
the Rote Faule of SW Poland
(After Bechtel et al. 2002)
Type III
0 −3
420 460 500
0
Tmax (°C)
Kupferschiefer shales (Fig. 15.24c). Rote Faule is a diage- upwelling saline brine interface and not to the depositional
netic unit that is not formation specific and occurs in the pattern. That is, Kupferschiefer shales may constitute the rich-
Weissliegend, Kupferschiefer and Zechsteinkalk strata, est prepared ground in terms of their inherently high organic
wherever various types of red colour (“red rot”) have been content, but volumetrically are not necessarily the best ore
created by the diagenetic formation of disseminated authi- hosts. The likely seal to gases (mostly methane), trapped in the
genic hematite and goethite. Pyrite, and the original organics Weissliegend sandstones, was the overlying Zechstein evapo-
of the Zechstein carbonate and the Kupferschiefer mud- rites. Throughout Europe, and in the offshore southern
stones, are oxidised and largely removed in Rote Faule inter- Zechstein Basin in North Sea, the Weissliegend is a significant
vals, while the economic sulphides of Cu and Pb-Zn have gas reservoir. In Poland, the entrained gases are mainly meth-
been largely leached and deposited in adjacent areas ane and nitrogen and are often found in the same localities as
(Oszczepalski 1989). The organic degradation associated the significant sulphide concentrations (Peryt 1989). These depos-
development of more oxidised and leached Rote Faule is its cannot be mined unless vented by Alpine-age faults, as they
clearly seen in the degradation of the kerogen within this have been in the worldclass Lubin district. Venting of this
zone (Fig. 15.25a). gases is tied to the dissolution-driven destruction of the
The development of Rote Faule interval indicates the oxi- Zechstein salt seal. As in the rest of Europe, the methane was
dised portion of a redox front. In Poland, it is located near the largely sourced in the underlying Carboniferous coal beds and
basin margin at the top of the thick redbed sequence, which variably trapped beneath the Zechstein evaporite seal.
during burial dewatering was flushed by upwelling basinal Geometries of mineralisation show that the underside of
waters (Fig. 15.24a). Ore sulphides occur on the far side of the Zechstein evaporites acted as a longterm seal, which
this subhorizontal oxidation-reduction front (Fig. 15.24b; or, focused and locally ponded or trapped the upwelling basinal
in the words of the poet Byron, “a gilded halo hovering waters within the immediately underlying Kupferschiefer or
around decay”). Thus Rote Faule zones outline redox inter- its lateral equivalents in the Weissliegend (Fig. 15.24c). It
faces, centred immediately updip of the outflow positions of also acted as a pressure seal that aided hydrofracturing within
salt-seal focused hydrological conduits which carry ascend- the maturing organic laminates of the Kupferschiefer, as evi-
ing, highly saline, basinal chloride-rich brines. They define denced by numerous sulphide-calcite veinlets in the
the mixing zones between ascending basinal waters and telo- Kupferschiefer. An inherent lack of permeability in wide-
genetic waters of the basin margin, so that the sulphides are spread thick evaporites also meant the upper side of the
arranged in three distinct haloes around “Rote Faule”, in the Zechstein salt beds prevented vertical/downward percolation
order Cu, Pb and Zn (Fig. 15.24c). Thus, around and above of fresh oxygenated waters, which would otherwise have
the Rote Faule, base metals are zoned laterally and vertically destroyed the stability of the redox interface (mixing zone)
in successive mineralisation belts of chalcocite, bornite, along the edge/underside of the dissolving salt bed (the
chalcopyrite, galena and sphalerite. “block of ice” model for salt dissolution).
Mineralisation in Kupferschiefer-style deposits trans- Dissolving Zechstein evaporites (including basinwide
gresses depositional facies as it is tied to the Rote Faule/ sulphates) atop the Kupferschiefer laminates acted both as a
Fig. 15.26 Highly schematic

cross section of the Dzhezkazgan Sealing gypsum/shale
region showing Cu zonation at
py
the redbed/greybed interface
(After Kirkham 1989)
hem H2 S Reduced greybeds
Cu
sp
gn+ H2 S
py
hem cc py
cp
Cu bn+
py
Oxidised redbeds
(carboniferous) py
py
py
py
py Salt anticline
(devonian)
burial seal to escaping basinal brines (and gases) and as an for the Dzhezkazgan deposit, but based on questionable
ongoing focus to descending oxidised brines. The mixing Soviet era data, are around 400 million tonnes, with a cop-
zones (often structurally controlled by reactivated faults), per grade of 1.5 % (Kirkham 1989). The depositional setting
were not where the most significant regional mineralisation of the host was an intermontane closed-basin, which was
took place. It was the presence of an adjacent slowly dissolv- made up of deltaic-lagoonal, alluvial and saline lake
ing salt mass that enabled longterm maintenance of the redox sediments.
interface between the anoxic hydrology of the Kupferschiefer Hosts to the ore are siliciclastic redbeds that are laterally
laminates and the more oxidising metalliferous water of the equivalent to bedded evaporites and underlain by Early
Rote Faule and so created the worldclass ore deposits of the Carboniferous organic-rich sediments (presumed source
Kupferschiefer. Similar evaporite-enabled focusing of redox rock) and sealed by shaly carbonates. The main copper sul-
interfaces have created the somewhat smaller ore zones of phide and pyrite orebodies are tied to fault feeds that occur
the Harz Mountains and the Spessart ore district, Germany on or near the greenbed crest of an anticlinal trap, located
(Wedepohl and Rentzsch 2006; Wagner et al. 2010). along the flanks of a basement high, and sitting atop a salt
ridge (Fig. 15.26). The host redbed sandstones become
zhezkazgan Region, Kazakhstan
D more evaporitic basinward and coarser-grained toward a
The Dzhezkazgan copper deposit is a halokinetically pinchout along the basement highs. The mineralised sand-
focused suprasalt sandstone-hosted deposit (Fig. 15.26 and stone is pyritic, with reduced pore fluids created by
Table 15.7). It is located in a graben near the southern clo- entrained hydrocarbons and high salinities. In contrast, the
sure of a PermoCarboniferous basin, at the northern edge of interbedded shales are red due to more oxidising pore flu-
the first-order Chu-Sarysu Basin of central Kazakhstan. The ids. These redbeds were in part derived from continental
Basin contains several stratabound Cu and also Pb-Zn and U volcanics.
zones (Cu mineralisation is present in stacked sandstone The mineralised system is carried by 10 cupriferous
beds throughout a 70 km long belt with an area of 600 km2) stratabound bands, within the 380 m thick Dzhezkazgan
of which the Dzhezkazgan ore field is the largest. Ores are Formation. Only a limited number of these mineralised
hosted in Middle to Late Carboniferous continental bands are of ore grade at a given point in the regional Cu
successions of conglomerate, sandstone, shale and evapo- trend. The mineralised system covers an area of approxi-
rites (Gablina 1981; Susura et al. 1986). Reserves estimates mately 120 km2, extending down dip to a depth of 1,000 m
Table 15.8 Stratigraphic column of the Dzhezkazgan copper district

Unit Comments
Permian H5 30–2,500 m thick – marl, and interbedded marl and interbedded 20–30 m thick salt
beds. A major 1,000 m thick salt bed found in the middle of the unit. This unit is
widely developed above and to the south of Dzhezkazgan.
Black pyritic unit Average 0.2 m thick – a Kupferschiefer type pyritic and carbonaceous (2–5 %
TOC) shale layer. This unit is absent at Dzhezkazgan, but is found in the Tengiz
Basin, 350 km to the north, where it contains Cu mineralisation. In the
Dzhezkazgan area the units above and below the position of the absent shale are
red and lacustrine
H4 600–800 m thick – red beds, which have the same ratios of conglomerate:
sandstone: siltstone as the Dzhezkazgan Formation, but with no reduced grey or
green intervals and patches. There are also no carbonates. Halite and sylvite layers
are found low in the unit in the main basin to the south of Dzhezkazgan, while
some methane, helium and nitrogen accumulations have also been encountered
within it, less than 30 km to the south of the mine;
Sulphate unit 0–100 m thick – a discontinuous gypsum rich band up to a maximum of 100 m in
thickness, containing 3–5 % SrSO4
H3 Dzhezkazgan Fm. to 380 m thick – which hosts the Cu mineralisation of the major
Dzhezkazgan orebodies. This unit comprises a red, continental sequence of
conglomerates, sandstones and siltstones, which has been locally reduced to a grey
or greenish-grey colour in the vicinity of the orebody. The reduced beds consist of
compact, uniform, fine-, medium- and coarse-grained rocks with a grey and
greenish-grey colour. They contain angular 0.25–0.6 mm, and rarely up to 1 mm,
clasts of feldspar and quartz in a fine siliceous-carbonate matrix. The grey
sandstones are characterised by a clear stratification, emphasised by intercalations
of the red varieties. Grey siltstones are rare. The red siltstones and sandstones are
distinguished only by the somewhat smaller clasts and by the clay-carbonate
content of the matrix. The ratio of green: red lithologies is approximately 1:1. The
ratio of sandstone: siltstone is 1:1, and conglomerate:sandstone 1:30. Variable
amounts of ‘gypsum’ impregnate the sandstones. Conglomerates are present as
both intra- and inter-formational varieties. The former are generally 0.8–2 m thick,
locally grading laterally into sandstone and sometimes into siltstone. The clasts are
usually 0.5–1 cm in diameter and rarely up to 5 cm, comprising locally sourced
rock, in a matrix of the enclosing sandstones. The interformational conglomerates
have angular exotic clasts
Carboniferous H2 Lower Member, 3,000 m thick – marine limestone to clayey-limestone or marl,
with minor intercalated dolomite. Amorphous pyrite occurs within the marls.
– Upper Member, 200–500 m thick – shallow water, terriginous-derived, fine grained
calc-siltstone and mudstone, grading to calcarenite. In the top sections lenses of Cu
mineralisation up to 20 cm thick may be found at the contact with the overlying Unit
H3. This interval is characterised by thin banding and black sandstones;
H1 Marine limestone – up to 3,000 m thick
Transition bed A thin, discontinuous dolomite found at the transition from the Devonian to the
Carboniferous, marking the beginning of marine conditions. There is minor Pb/Zn
mineralisation and concentrations of Ba and Sr on its lower contact
Devonian F4 2,000–2,500 m thick – red terrigenous sandstone and siltstone with salt beds and
domes
F3 800–1,200 m thick – andesite, basalt and rhyolite belonging to the middle
Devonian volcanic arc
F2 Continental red beds
F1 Rhyolite, andesite and basalt, resting on lower Devonian granites
Unconformity
Ordovician Grey marine sediments of indeterminate thickness
After Porter (2004)
on its southern margin. Within the cupriferous bands, there ore-bearing Middle-Upper Carboniferous Dzhezkazgan
are a series of large, elongated, partially overlapping Suite comprises rhythmically alternating gray and red lithic
orebodies, developed at a number of different levels, cover- sandstone units that change facies laterally into saline
ing much of an approximately 9 × 6 km area. In that area the siltstone.
The paleo-environment is interpreted by Gablina (1981) as sulphides and the presence of pre-existing authigenic sul-
a closed saline intermontane basin with alluvial, deltaic- phate, which is possibly also concentrated in structural posi-
lagoonal and saline lake facies. There are 50+ red-gray inter- tions. Little hydrocarbon remains in the sulphide zone,
bedded cycles in the Dzhezkazgan Formation, each 2–42 m probably also having been consumed in the production of
thick, with variable colouration and mineralisation attributed carbonates and sulphide through the thermochemical reac-
to post-lithification basin brines moving updip along with tion/combination with the sulphates. Hydrocarbons are
hydrocarbon and H2S. The source of Cu is unclear, typically exploited within the main Dzhezkazgan Saryzu Trough to
it is attributed to the saline leaching of the regionally distrib- the south, trapped within Unit H4.
uted Devonian-Lower Carboniferous andesitic volcanics of Gablina (1981) suggested that an early salt weld juxta-
the Central Kazakhstan Andean-type margin (the Balkhash posed fluids of the marine/evaporitic rocks and lower-
porphyry-Cu province), which is broadly contemporaneous most redbeds that overlie the salt anticline. Bed
with the Cu sandstones and located several hundred kilome- geometries illustrated in Fig. 15.26 suggest this weld is
tres further east (Table 15.8). The mineralisation/depositional halotectonic. The breach allowed hydrocarbon-bearing
association shows some affinities with the Eocene Corocoro basinal waters to migrate vertically into the overlying
copper-hosting system in the Andes. The hosting sedimentary redbeds, where H2S was produced by thermochemical or
strata are gently open-folded and block faulted with much of bacterial sulphate-reduction. Extensive precipitation of
the structuration in the area controlled by halokinesis. copper and other metals occurred at the regional redox
Interestingly, there is a strong laterally and vertically front separating reducing evaporite-fed brines and adja-
zoned impregnation of gypsum and halite within mineralised cent red beds.
sections of the Permo-Carboniferous cover sequence. Within If so, the role of the catagenically dissolved evaporites
the Dzhezkazgan area, the red units contain appreciable was to supply reduced brines and to create precipitation foci,
‘gypsum’ within Unit H3, the Dzhezkazgan Formation atop a halokinetically controlled salt anticline. The precipita-
(Table 15.8; Porter Geoconsultancy 2004). Away from ore, tion mechanism and the metal zonation is the same as in the
on the shared limb of the Dzhezkazgan Syncline and the Kupferschiefer model, but in this case the relative position of
adjacent Zhaniu Anticline, where the sequence is almost the evaporite and the redbeds are adjacent and domal, rather
completely oxidised, all ten units that are mineralised within than salt dissolution edge. The main evaporite bed lies below
the ore zone contain abundant ‘gypsum.’ However, within the redbeds, which are the ultimate source of the metals.
the sulphide-bearing reduced rocks in the immediate vicinity Although the mineralised beds are stratiform, this deposit is
of Dzhezkazgan, there is little to no gypsum, although it is really a result of halokinesis; a similar, but less economically
present within interbanded red lithologies, particularly in the significant, analogue is to be found in the Lisbon Valley,
section above the orebodies. Within the sulphide-bearing USA.
reduced rocks the cement is mainly carbonate, rather than
gypsum. This is taken to imply that the sulphur of the ‘gyp- opper in the Lisbon Valley, Utah
C
sum’ has been consumed in the formation of sulphides. The ore deposits of the Lisbon valley are another example
There is also a lateral ‘primary’ variation in authigenic of halokinetic suprasalt deformation controlling structure
gypsum content. To the south into the Dzhezkazgan Saryzu and hence the position of redox mineralisation. Compared
Trough, the proportion of the red sequence containing gyp- to Dzhezkazgan, the deposits are much smaller (34 Mmt @
sum decreases, as does the gypsum content. Similarly, to the 0.53 %). Cu(±Ag). Ores in Lisbon Valley occur along
north into the Dzhezkazgan Syncline the number of units and suprasalt extensional faults, in redbed sediments of the
thickness of gypsum impregnation decreases, although on Paradox Basin and in coal-bearing horizons of the overly-
the margins of the syncline appreciable amounts are still ing Cretaceous Dakota Sandstone in SE Utah and SW
present. Mineralisation is also present in these same zones. Colorado (Fig. 15.27a). Deposits of this type occur at Salt
However, despite the drop in levels, regionally ‘gypsum’ is a Valley and Paradox Valley, with the largest deposits in the
relatively constant component of Unit H3. Lisbon Valley (Fig. 6.83; Morrison and Parry 1986). Cu is
Within Unit H3, the ‘gypsum’ is pseudomorphed by found as vein fillings, sandstone pore fillings, and as
SrSO4, with the sequence containing 6–8 % of celestite over replacement of coalified plant fossils. The deposits are
thicknesses of 50–80 m. Higher in the sequence, at the base clearly related to halokinetically-induced faults
of the exclusively red bed Unit H4, a thick band of gypsifer- (Fig. 15.27b, c). The largest deposits, Big Indian and
ous marl contains 3–5 % SrSO4. Higher still, in Unit H5, Blackbird, occur along the Lisbon Valley fault in coaly
halite and sylvite are abundant, with little or no associated horizons of the Cretaceous Dakota Formation. Almost all
gypsum. the mineable copper ore occurs within several hundred
According the Porter Geoconsultancy (2004) it is likely metres of either the Lisbon Valley fault or other major
that there is a relationship between the development of suprasalt fracture zones.
a b 10
Grand
Bo junction
un
da
Sa l
ry
HO -Fi of
Pa U
t
her rad m Lisbon Valley fault zone

s
ox co
B up mp (Breit and Meunier 1990)
-S
nb as
a d Va lif ah
i
lleys A in t g
n re
Cas 0
ticl
M tle ne
oa -Pa
i
b Moab rad
Va
δ18O
lle CR
y
An ox
La Sal Va
lle
tic ys A
lin Mts nti
e cli
SR
ne
CD –10 Dolores fault zone
CR = Copper River Gy CI
SR = Sunrise Lis ps (Breit and Meunier 1990)
bo um
CD = Cliff Dweller nV Va
CI = Cashin all lle
ey yA
HO = Hoosier -D nt
olo icl Hematite (Chan et al., 2000)
re ine
sA Water from calcite values
nt –20
0 10 20 icl
Utah Colo. ine
–1 0 1 2 3
Miles
δ87Sr
c Lisbon fault
Cretaceous
6,000′ Jurassic
Triassic
4,000′
2,000′ Halokinetic Cutler formation
Sea level Paradox salt (redbeds - Cu source)
2,000′ Honaker trail
4,000′ Paradox
6,000′ 0 6,000 Miss. - Cambrian
Precambrian
ft
le
sha
n c os u s)
Ma taceo
(cre Mancos shale
on (cretaceous)
C any )
rr o ds
& Bu reybe
a g
kot us
Da taceo
(cre
c)
ssi Cu-mineralisation
ura
e (J
ds ton Zone of reduction, due to
jo san
N ava hydrocarbons or organics
Warm saline metaliferous

chloride brines, rising along
faults (Paradox salt dissolution)
Fig. 15.27 Copper in Lisbon Valley salt anticline, Utah. (a) Regional (d) Detail of crestal position of Lisbon Fault showing distribution of Cu
distribution of salt anticlines (see also Fig. 6.83), (b) Isotope character ore (After Morrison and Parry 1986; Kirkham 1989)
of hematite and calcite. (c) Cross section of Lisbon Valley salt anticline.
All the deposits in the area are related by geologic setting ongchuan Copper, China
D
as well as ore and gangue mineralogy (Morrison and Parry Stratabound sediment-hosted copper deposits, associated
1986). Fluid inclusions, mineral chemistry, and C-O stable with a widespread halokinetic breccia unit, occur in a 450 km
isotopes in calcite gangue associated with Cu ores at Lisbon long rift in the Yunnan Province of China (Huichi et al.
Valley suggest they formed via subsurface mixing of two 1991). The Dongchuan area is the largest of five copper min-
diagenetic waters. Fluid temperatures ranged from 72 to ing districts in this north-trending rift, which contains sand-
103 °C, while salinities were 5–20 equiv. wt % NaCl during stone, shale, and carbonate rocks of the Dongchuan Group,
calcite deposition. Saline, salt dissolution-influenced basinal deposited in this late Paleoproterozoic rift as it was transi-
fluids migrated upward along fault zones, and upon mixing tioning into a passive margin (Fig. 15.28; Zhao et al. 2010;
with shallower reduced Ba-rich groundwater deposited ore Wang and Zhou 2014).
and gangue minerals. Mineral precipitation was induced by Deposits in the area range from 10 to 100 million tonnes
the combination of reduction and dilution of upwelling of ore with ore grades of 1–1.5 %. Three formations, total-
basinal brines. ling some 1,200 m, contain the copper deposits mostly in the
The metal-carrying fluid probably originated in the red- lower part (Fig. 15.29). They are from top to bottom: the
bed aquifers of the Permian Cutler Formation. The brines Etouchang (Heishan) Formation, mainly a carbonaceous
may have equilibrated for long periods in these Cutler slate; the Laoxue Formation, mainly a stromatolitic dolos-
Formation aquifers and only been released during faulting tone; and the Yinmin Formation, chiefly purple slate and
driven by halokinetic activity during the Late Cretaceous – sandstone. These formations are crosscut by breccia and
Early Tertiary Laramide orogeny. Then faults, such as the mafic igneous rocks.
Lisbon Valley Fault, breached the redbed aquifer and so Numerous transtratal breccia bodies occur in the
allowed pressurised, heated metalliferous fluids to escape Dongchuan Group, particularly within the Yinmin Formation,
upward along the faults until they encountered permeable and are collectively known as the Yinmin Breccia (Fig. 15.29).
units replete with reductants, such as in the Dakota and They are made up largely of clasts derived from the Yinmin
Wingate Sandstones (Kirkham 1989). Formation that are cemented in a matrix of rock flour and
In my opinion, the role of salt has not been given the possibly hydrothermal minerals (e.g. quartz, feldspar, carbon-
importance it deserves in the explanation of mineralisation in ate and biotite). The mechanism of brecciation is still unclear,
a Lisbon-Valley style deposit. The style of faulting that but is likely due to halokinesis sourced in what were once
focuses the mineralisation is a response to movement on the thick mother salt beds in the lower part of the Yinmin
underlying active salt structure (Fig. 15.27b, c). The ongoing Formation. Post emplacement, there were one or more leach-
dissolution of this underlying salt also supplied the chloride- ing/dissolution episodes (coupled with a hydrothermal over-
rich brines that maintained the interface with leached the print), creating textures similar to, but more metamorphically
metals from adjacent redbeds. It also created the thermal and evolved than seen in the Neoproterozoic diapiric breccias
brine density contrasts that drove the convection and metal exposed in the Flinders Ranges, Australia. Another example
enrichment of this brine. Without halokinesis and salt disso- of halokinetic focusing in China, but in a much more highly
lution there would be no focusing into this structurally con- metamorphosed milieu is seen in the Palaeoproterozoic
trolled deposit. Nor would there be any long-term Fe-Cu sulphide and borate deposits in eastern Liaoning,
maintenance of the redox haloes about the faults that allowed Northeastern China (Chap. 14; Wang et al. 1998a).
this deposit to accumulate. Without the underlying halo- Clasts of igneous rocks are locally present in the Yinmin
kinetic salt, economic levels of copper sulphides simply breccia, suggesting that at least some breccia bodies postdate
would not be there. As is to be expected, this cupriferous the igneous intrusions and were carried higher into the stra-
flow regime is very similar to, although less prolific than, tigraphy via salt flow. This is consistent with field relation-
those of the Dzhezkazgan region. The patchy ore distribution ships in which a number of gabbro bodies appear brecciated
means the various Lisbon Valley deposits are classified as (Zhao et al. 2010). It is also consistent with the common
Revett- style Cu deposits. association with gabbros and dolerite blocks in halokinetic
The same brine-related redox hydrology is also responsi- breccias that define outcrops of Miocene salt in the Middle
ble for a number of uranium deposits in the area (Lisbon East (Chap. 7). The position of the former mother salt mass
Valley, White Canyon, Monument Valley) totalling some 42.5 in the Yinmin Fm redbeds is also consistent with it once
Kt of produced uranium (Dahlkamp 1993). Tabular uranifer- being a basinwide halite bed that formed during the rift to
ous orebodies are peneconcordant with bedding and located drift transition indicated by the passage from rift redbeds of
in channel sandstones rich in coalified plant trash, mostly in the Yinmin formation to passive margin marine carbonates
the in fluvial channels of the Shinarump Sandstone member of the overlying Luoxue Formation.
of the Triassic Chinle Formation, with some reworking into Numerous sedimentary-hosted stratiform copper depos-
exposed or subcropping positions atop the salt anticline into its, known as the “Dongchuan-type” Cu deposits in Chinese
the Permian Cutler sandstones (Reynolds et al. 1985). literature, are hosted within dolomites, typically near the
Fig. 15.28 Geological map Panzhihua

showing the distribution of 102°E Huili
Proterozoic strata, granites and
gabbros in the SW Yangtze Block, Sichuan province
of southeastern China, while inset
shows position of the Yangtze
block in a simplified tectonic map
of China (After Zhao et al. 2010)
Lala
Yin min
r
ve
746 ± 10 Ma
Ri
(Zhao et al. 2007)
a
sh
–26°N Dongchuan
Jin
Yunnan province
Yinachang
Yuanmou
Proterozoic strata/intrusion
Granite
Wuding
Diorite
Yuanmou Pluton
746 ± 13 Ma Etouchang Gabbro
(Zhou et al. 2002a)
Yunnan province
Kunyang group
one
Dongchuan group
g fault z
Dahongshan group
Luzhijian
Sichuan province
Huili group
Hekou group
Others
Phanerozoic strata
Breccia body
Fe-Cu deposit
Fault
Inferred fault
Eshan Pluton
819 ± 8Ma North China
(Li et al. 2003a) Eshan Qin Craton
ling
lu
Su
Dahongshan
Tibetean Dab
ie
Plateau
–24°N
Yangtze Block
Re
dR
Cathaysia Block
ive
rF
Guangzhou
au
N
lt
0 20 km N
0 500 km
Yuanjiang Sin Quyen deposit
contact between the Yinmin and Luoxue Formations and h ighgrade vein-type ores crosscut the dolostone. Both ore
often associated with Yinmin breccia. Vein type ore bodies types contain bornite, chalcopyrite, chalcocite, and other
account for only 3 % of the total ore reserves in the area. minerals. Fluid inclusions in quartz veinlets contemporane-
Stratabound ores characteristically occur as disseminations ous with the copper mineralisation contain liquid, vapour
of sulphides along stromatolitic algal layers. Locally, and daughter minerals: NaCl, CaCl2, KCl and BaCl2. The
inclusions homogenise between 200 and 280 °C.
Hot reducing chloride-rich brines, circulating and cycling
upward along the flanks of the diapir, leached copper from
Kunyang
the oxidised Yinmin Formation and carried it to the base of
group the overlying Laoxue Formation (Huichi et al. 1991; Wu
Moude and Li Xiji 1981). There sulphide-rich fluids were
Luzhijiang Breccia/ formed by reaction of evaporitic sulphates with decayed
formation halokinetic? organic matter in the dolostones. Copper sulphide deposition
in the dolostones resulted from the mixing of these fluids.
Diabase Continued circulation leached all of the remaining salt from
Etouchang the diapir, and the overlying and surrounding rocks collapsed
formation Volcanic
interlayers to form the current breccia masses.
Cu-sulphides were precipitated at two sites: (1) as brec-
Dongchuan group
Slate cias, lenses, and veins around fluid-venting centres tied to

Luoxue
formation the breccias; and (2) as stratiform pyrite-chalcopyrites,
Dolostone which are associated with anhydrite located distal to the salt
domes (Fig. 15.30). Within each mining district the proximal
Yinmin Sandstone/ ores are associated with brecciated, albite-and tourmaline-
formation siltstone rich metasediments. The sulphides in the proximal ores have
δ34S values of 14.6 ‰–12.7 ‰, whereas the distal ores have
δ34S values of 2.6 ‰–14.5 ‰ for the sulphides and
7.9 ‰–19.0 ‰ for the anhydrite; suggesting a sulphate-
Fig. 15.29 Stratigraphy of the Dongchuan Group showing crosscut- dominated sulphur source, with the pyrite δ34S variations
ting (halokinetic?) distribution of breccia bodies arising mainly from decreasing temperatures away from the
70°
a b North
c
Luozue Fm.
Copper ore
Yinmin Fm. Etouchang
Yinmin mine
mine
Dolerite
1 km 200 m
Etouchang Fm.
Laoxue Fm.
Yinmin Fm.
Gabbro
Yinachang mine
75°
Breccia
1 km
Fault
Yinmin mine
20 m D. Phanerozoic
detail
Fig. 15.30 Geological map of (a) Yinmin mine in Dongchuan area, (b) Detail from an audit in the Yinmin mine, (c) Etouchang mine area,
(d) Yinachang mine area (After Zhao et al. 2010, 2013)
centres of the deposits. According to Wang et al. (1998a) the (Zhao and Zhou 2011). Isotopic dating and field relation-
origin of the deposits is best described by a model in which ships suggest that these deposits formed in the late
sulphate-carbonate rocks were deposited in peridiapir sinks Paleoproterozoic. Ore textures, mineralogy and alteration
during salt diapirism. The salt domes then acted as foci for characteristics are typical of IOCG-type deposits and thus
subsequent hydrothermal venting of chloride-rich metallifer- define a major IOCG metallogenic province with an evapo-
ous fluids and the adjacent peridiapir sediments became the ritic association. We shall come back to evaporitic associa-
centres of sulphide mineralization. The sulphides precipi- tions in some IOCG deposits in the next chapter
tated during interaction of the reduced, metal-bearing hydro- The Paleoproterozoic rift-related sedimentary sequences
thermal fluids with the in situ sulphates, which acted as the of the Dongchuan Group, South China, today constitute one
major in situ source of evaporitic sulphur. of the largest SSC districts in the world (Zhao et al. 2013).
At the broader scale the Dongchuan deposits can be One of the largest deposits in the Donchuan district, is the
related to the Dahongshan deposits, via a common parage- Yinmin deposit, which shows stratiform Cu orebodies
netic history, constituting a wider group of Paleoproterozoic intruded by dolerite dykes, which have a U-Pb age of
Fe-Cu deposits, in the Kangdian region of SW China 1,701 ± 28 Ma (Fig. 15.30a, b). This is slightly younger than
(Fig. 15.28; Zhao and Zhou 2011). The Dongchuan Group is the ore hosting strata which include a tuff with a zircon U-Pb
composed of siltstone, slate, and dolostone with minor vol- age of 1,742 ± 13 Ma. Sulphides in the ore yield ages around
canic rocks, whereas the Dahongshan Group has undergone 1,600 Ma, thus the Yinmin mineralisation and by inference
lower amphibolite facies metamorphism and consists of other Cu deposits in the Dongchuan district correspond to a
quartz mica-schist, albitite, quartzite, marble and amphibo- late Paleoproterozoic rifting event, likely tied to the breakup
lite with local migmatite. Deposits in the Dongchuan Group of the Columbia supercontinent (Wang and Zhou 2014).
are commonly localized in the cores of anticlines, in fault Zhao et al. 2013, argue this timing further supports the notion
bends and intersections, and at lithological contacts. of genetic and temporal links between episodes of more
Orebodies are closely associated with breccias, which are intense formation of SSC’s and the breakup of superconti-
locally derived from the host rocks. Fe-oxides (magnetite nents. In my mind, this also supports the redox interface
and/or haematite) and Cu-sulphides (chalcopyrite, bornite) association with proximity to flow and dissolving haloki-
form disseminated, vein-like and massive ores, and typically netic salt acting as deposit foci to adjacent leached redbeds.
fill open spaces in the host rocks. The deposits have exten- Thick and widespread halite supergiants are tied to super-
sive albite alteration and local K-feldspar alteration over- continent rifting events, last seen in the Phanerozoic in the
printed by quartz, carbonate, sericite and chlorite. Pangean break-up (Chap. 5) and by default to depositional
Deposits in the Dahongshan Group have orebodies sub- systems that have redbeds and thick halokinetic-salt masses
parallel to stratification and show crude stratal partitioning of at the base of the rift succession
metals. Fe-oxide ores occur as massive and/or banded
replacements within the breccia pipes, whereas Cu-sulphide n-Cu-Pb Kipushi Deposit, Africa
Z
ores occur predominantly as disseminations and veinlets The Neoproterozoic metallogenic province of Central Africa
within mica schists and massive magnetite ores. Ore textures contains rich stratiform concentrations of Cu and Co in both
suggest that Cu-sulphides formed somewhat later than the Shaba Province (Shaba cupriferous arc – Zaire) and
Fe-oxides, but are possibly within the same mineralization Congo-Zambian copper belts (Cailteux 1994; Kampunzu
event. Both ore minerals predated regional Neoproterozoic et al. 2009). Both provinces retain substantial evidence of
metamorphism. Both orebodies and host rocks have under- meta-evaporites. For example, scapolite is widespread in
gone extensive alteration of albite, scapolite, amphibole, bio- amphibolite-grade calcsilicate rocks and marbles in Katangan
tite, sericite and chlorite. Silica and carbonate alterations are rocks of the copper belt and in the central provinces in
also widespread. Ore-hosting strata have a LA-ICP-MS zir- Zambia. Ramsay and Ridgway (1977) point out that “scapo-
con U–Pb age of 1,681 ± 13 Ma, and a dolerite dyke cutting lite is rarely found in such abundance and Zambia must be
the Fe-oxide orebodies has an age of 1,659 ± 16 Ma. Thus, one of the major scapolite provinces in the world.”
the mineralization age of the Dahongshan deposit is con- Munyanyiwa (1990) argues for an evaporite precursor to this
strained at between the two. scapolite, he also notes that metasedimentary anhydrite is
All ores from the Donchuan and Dahongshan groups have still present in parts of the Katangan succession in the copper
high Fe and low Ti, with variable Cu contents. Locally they belt. We shall look in detail at the Kipushi deposit, but it is
are rich in Mo, Co, V, and REE, but all are poor in Pb and Zn. indicative of facies association in many other similar perhaps
Sulphides from the Fe–Cu deposits have δ34S values mostly more metamorphosed copper deposits in the region. Much of
in the range of +2 to +6 per mil, suggesting a mix of several the following description is taken from Kampunzu et al.
sources due to large-scale leaching of the strata, with the (2009), Van Wilderode et al. (2013), (Heijlen et al. 2008) and
involvement of evaporite-derived brines across all ore types references therein.
The Kipushi Zn-Pb-Cu deposit, hosted in Nguba Group Regionally these former salt intervals are defined by evapo-
strata is located in the northern extension of the central rite dissolution breccias. Such solution breccias occur in the
African Copper Belt in southeastern Zaire. Kipushi is per- lower part of the Katangan System and are interlayered with
haps the most significant Zn–(Cu)–Pb carbonate-hosted alternating sparry dolostones, black shales, and chlorito-
deposit in the Copperbelt of Central Africa with total metal talcose dolomitic siltstones (Fig. 15.31). Prior to dissolution,
production of 6,622,116 t Zn and 4,082,275 t Cu from 1922 the evaporites are thought to have acted as the mother salt
to 1993 when operations were suspended. The in-situ ore bed for the Kipushi allochthon and other halokinetic features
grade averaged 11.03 wt.% Zn and 6.80 wt.% Cu. Ore has in the region. The upper part of the Katangan System is made
been proven to a depth ≈ 1,800 m, but mine development up of the Lower and Upper Kundelungu Supergroup and is
stopped at 1,250 m depth. The remaining ore resources down composed mostly of siliciclastics with some limestones,
to the 1,500 m level are estimated at >5 Mt Zn, >500,000 t which are locally dolomitised.
Cu, and >100,000 t Pb from ores averaging 21.4 wt.% Zn, Portions of the Katangan System are now intensely folded
2.1 wt.% Cu and 0.88 wt.% Pb with additional trace metals in the copper belt, with a disharmonic style reminiscent of
of Cd (763 ppm), Co (100 ppm), Ge (68 ppm), Ag (28 ppm) the salt-cored European Jura. Cores of many anticlines in the
and Re (3 ppm) (Cailteux 1986, 1994). Other rare metals copper belt are formed by megabreccias, containing blocks
include As, Ga, Mo, Bi, Hg, Ni, Sb, Se, Sn, Te and V. of Roan metasediment. Regionally, some of the larger clasts
The Kipushi deposit is hosted on the northern flank of a contain sufficient stratabound Cu-Co sulphides to be actively
regional NW–SE trending anticline characterized by a mined. The matrix between the blocks is a dolomitic meta-
faulted axial core filled with a transtratal megabreccia known siltstone, which also contains gypsum and anhydrite pseudo-
as the “Axial Breccia” (Fig. 15.31a). The dip is 60–70° SW morphs (De Magnee and Francois 1988). Regionally, the
on the southern flank and 75–85° NE on the northern flank. megabreccias cut into the flanks of many megabreccia cored
The Axial Breccia is barren and consists of a heterogeneous anticlines and reach into Upper Kundelungu strata. This is
layer-parallel breccia made up of highly strained and brecci- the case at Kipushi (Fig. 15.31a).
ated or rounded fragments of Roan and Nguba Group rocks The megabreccia and its crosscutting relationships are
as well as dolomites and meta-evaporites, and also includes very similar to outcropping halokinetic breccias in the
arkosic sandstones and metabasic rocks along with white Neoproterozoic Callanna Group megabreccias of the Flinders
talcose dolomites (Table 15.9). Near identical Roan breccias Ranges, South Australia (Chap. 7). There, many of the brec-
underlie most Katangan thrusts and are interpreted as a rauh- cia geometries reflect the falling or deflation stage of diapir
wacke, where much of the salt is long gone, leaving only evolution and are located along regional extensional faults.
pseudomorphs and patchy anhydrite (e.g., Jackson et al. Breccias in the Katangan System also follow major faults,
2003; Warren 1999, 2000b). which De Magnee and Francois (1988) called extrusion
The ore is a discordant body, parallel to the former salt faults. If analogies to the Flinders Ranges are valid, some of
flow margin (transtratal) at the contact between a halokinetic these “extrusion faults” may be examples of outcropping
breccia body and adjoining host rocks of the Upper fault welds. Once a basin undergoes inversion, such faults
Proterozoic Lower Kundelungu Group of the Katangan are often reactivated and can be easily misinterpreted as
System (Fig. 15.31b; De Magnee and Francois 1988; Heijlen solely due to late-stage thrusting.
et al. 2008). It is currently exposed at the surface at the north- The Kipushi structure is interpreted as a salt diapir/
east margin of a large plunging anticline. The halokinetic allochthon that, after emplacement, was subject to ongoing
breccia in the core of the anticline contains large blocks (up dissolution of the more soluble salts, along with associated
to 100 s of metres across) of Roan Supergroup rocks of sev- collapse brecciation. According to De Magnee and Francois
eral lithologies, as well as large blocks of gabbro. Much of (1988) and Chabu (1995), this dissolution process played an
the breccia at Kipushi is made up of fragments of white essential role in the base metal mineralisation, as it supplied
sparry dolomite, which are thought to have originally been an ongoing focus for the saline chloride-rich brines that
derived from the halokinetic and solution induced break-up leached and transported the heavy chalcophile metals. The
of the Dipeta Dolomite. The gabbro (now completely matrix dolomites adjacent to the mineralising show little
amphibitolised) is thought to have originally been emplaced evidence of thermal effects and only the gangue dolomite
as a sill in the Dipeta Dolomite within the Roan Supergroup indicate the elevation saline fluid temperatures associated
(Fig. 15.31c). with mineralisation (Fig. 15.32, Van Wilderode et al. 2013).
Most workers accept there is an association with former De Magnee and Francois (1988) went on to argue that sul-
evaporites and the Kipushi deposit breccias which host, or phur and organic matter must also be present to form a min-
are adjacent to, mineralisation. Roan Supergroup sediment eral deposit, as well as a high lateral thermal gradient to set
once contained several evaporite intervals (De Magnee and up the circulation cells and an appropriate permeability
Francois 1988; Jackson et al. 2003; Heijlen et al. 2008). structure to channel the ascending hydrothermal solutions.
114 000 27° 14′ 118 000

Fault
Mong
Kansuki Fm e Fm
Kipushi town Salt weld (?)

Kiubo
Fm
Zn-Cu-Pb ore Meng
e Fm
1 km Kania
nga F
m
194 000 Katet
Fm e Fm Kya
Fm nda
tete i da mu (
Ka t we apon Ka Kipu Petit
h n
us ko K Kapo kontwe F shi F Mon C
Kip Ka nda m m wezi gl) Fm
Mwale Fm Fm
Fm
Mw
Mwa
11° 47′ Gr ale le (G
an rand
Ki Ka dC Cgl)
pu ko o Fm
sh ntw Kapo ng
lom
Mwa
shya
Ka iF eF nda era Fm
tet m m Fm Mw
e te as Axial Breccia
Fm Fm hy
aF
a m (halokinetic)
Monw 0 250 m 750 m Plan view Surface

ezi Fm (underground)
lt
fau
Kipushi
D1
ec e
cia
br cos
fault
ial
Axia
Extruded axial
Ax
itic al
Roan breccia
m -t
D1
Mate
lo rito
l fau
(Serie te Fm
do hlo
Recur
)
lt
Fm
rente) C
ia
500 m
cc
o
iub
re
Kipus
hi Fm
eb
(K
ps
au
lla
be
Co
K akon
am
twe F
m
dL
itic
br
an
ab
Axial breccia
s lom
Gr
G
ia
ale o
cc
?
sh ilty d
Kapon
re
da Fm 1,000 m
eb
ite e
S
lom ntw
Mwale
ps
(Gran
do ako
lla
d Con
n
Co
Mwas glome
to
hya rat) Fm
os
b Fm
ol
D
Fault Breccia Dip ?

Stratigraphic limit Zn-Pb-Cu ore body
Reducing organic-hydrocarbon 1,500 m Lambeau

Saline basinal Ca-Cl brines
entraining pore waters (metal Ore
(slightly oxidising, metal
carriers)
Fault
?
1,800 m
Kipushi Zn-Cu-Pb deposit, Congo ? Other contact
100 m
c ?
Fig. 15.31 Kipushi Zn-Cu-Pb deposit, Congo. (a) Geological map of section through the Kipushi ore zone (generalised in a and b). After
the Kipushi area. (b) Generalised map (plan view) of underground Kampunzu et al. 2009, and de Magnee and Francois (1988)
structural features at the 750 m level in the Kipushi Mine. (c). Vertical
Table 15.9 Stratigraphy of the Neoproterozoic Nguba Group at Kipushi and indication of the kinematic and sedimentological setting
Kinematic and sedimentological
Formation Lithology at Kipushi setting
Nguba Group Bunkeya Subgroup Monwezi Dolomitic sandstones, siltstones and Transgressive clastic sequence
pelites prograding over the cap carbonates.
Katete “Serie Recurrente” Top (30–40 m): Persistence of northern proximal
alternation green chloritic shales with facies and southern open basin
nodules (e.g. gypsum) and white
dolomites Middle (120–130 m):
irregularly bedded greyish shales and
white dolomites Bottom (60 m): grey
dolomites and shales containing
dolomite nodules
Muombe Subgroup Kipushi Black carbonaceous dolomite with
oolites, cherts and shungite (100 m)
Kakontwe Upper (20–50 m): irregular bedded and Cap carbonates. Proximal facies in
carbonaceous dolomite with black the north, open basin towards the
cherts. Middle (60–70 m): bedded south
dolomite with oolites and algal
structures Lower (180–250 m): massive
fine-grained grey dolomite
Kaponda Top (90 m): dolomites with cherts at
the base, some shales Middle (30 m):
lenticular or massive, limonitic
dolomite Bottom (0–80 m):
carbonaceous dolomitic shale –
“Dolomie Tigree”
Mwale Grand Conglomerat (300–500 m): Sturtian glaciation and transition
green-grey, unsorted matrix supported from intracontinental rift into
conglomerate proto-oceanic basin with further
basin widening
After van Wilderode et al. (2013)
Katete Fm. (Serie Recurrente)

Kakontwe Fm. Fm. (upper)
Kakontwe (middle)
2
Kakontwe Fm. (lower)
Gangue dolomite
δ13CPDB
Fig. 15.32 Covariant –2
carbon-oxygen stable isotope
crossplot broken down by host
formation dolomites using values
extracted from Table 2 in Van
Wilderode et al. (2013). Clearly –4
illustrates the hotter fluid origin
(indicated by more negative –13 –12 –11 –10 –9 –8 –7 –6 –5 –4 –3 –2
carbon and oxygen values of the
δ18O PDB
gangue dolomites)
At Kipushi these conditions were created by a huge slab of induced focus to fluid flow and its associated redox front
silty dolomitic shale (Kundelungu Group), which lies along- is what is important. This relationship in a mineralised
side the wall of the halokinetic breccia and forms the current halokinetic province, even when metamorphosed, is pre-
roof of the ore body. De Magnée and Francois go on to draw dictable and mappable.
parallels with peridiapiric mineralised laminites in north Interestingly’ across the various documented SSC depos-
Africa. its, it seems that halokinetic associations constitute the larger
The genetic model of Heijlen et al. (2008) further refined deposits, rather than the bedded association we shall discuss
their model and concluded that halite dissolution was an next. This is because the dissolving edge of a flowing salt
important process for generating the saline mineralizing flu- mass can maintain its position in earth space as more salt will
ids that formed Kipushi, as indicated by Cl–Br–Na systemat- flow in and replace the salt that is lost by dissolution, until the
ics of fluid inclusions. The mineralising fluid of the main contact with the mother salt layer is lost via salt welding or
ore-forming phase had a salinity of ≈ 30–43 eq. wt.% NaCl the mother salt bed is depleted. In contrast, the redox front at
and likely originated from formation waters or metamorphic the edge of a bedded salt mass is more likely to be a retreating
fluids that were expelled late in the orogenic evolution. After front, and only the underside of a thick bedded mass is stable
dissolving evaporites and perhaps evolving scapolites, the over long enough time frames to form an economic sulphide
resulting saline fluids were capable of leaching metals from accumulation. We shall return to this discussion later in the
upper crustal country rocks during their rise to the surface, as chapter, after we have considered non-halokinetic examples.
indicated by lead isotopes. The relatively high metal content
(Ba, Zn, Fe, Pb) of the NaCl–KCl–CaCl2 fluid suggests that
the source rocks included felsic basement. The absence of ediment-Hosted Cu in Bedded Evaporite
S
baryte, despite the high Ba concentration in the fluid, indi- Context
cates that the mineralisation occurred in reducing conditions
and sulphur was locally available as sulphide. In this type of deposit the associated evaporite is typically
δ34S signatures of the main orebody demonstrate that the bedded and the size of the resource in individual is typically
sulphide was derived from seawater sulphate through ther- less than in the halokinetic association. We shall start this
mochemical sulphate reduction (TSR), simultaneously discussion with the Corocoro ore district of Bolivia as it
oxidising organic material and generating H2S. Part of the offers an interesting quandary as to the relative importance
sulphide in the concordant orebody along the contact of the halokinesis played in its genesis. The other deposits dis-
Kipushi Formation and the Série Récurrente, however, was cussed in this section have bedded evaporite not halokinetic
most likely derived from bacterial sulphate reduction (BSR) redox associations
during diagenesis. They may have been preserved in the
form of pyrites up to the time of ore formation. Heijlen et al. orocoro and Other Sandstone-Hosted Deposits
C
(2008) suggest that mineralisation took place when highly of the Central Andes
saline and metal-bearing fluids encountered an H2S-rich Stratabound deposits of copper (+Ag) hosted by variably-
hydrocarbon reservoir during fault-controlled expulsion. The dipping continental clastic sedimentary rocks occur in Central
Sr and Nd isotopic composition of the gangue dolomite and Andean intermontane basins and are known to postdate com-
the metal content of fluid inclusions, indicate that the miner- pressive deformation/uplift events in the region (Flint 1986,
alising fluid interacted with rocks of both mafic and felsic 1989). The deposits are relatively small and include; Negra
affinities in the basement and possibly in the Roan. These Huanusha, central Peru (Permo-Triassic); Caleta Coloso,
rocks provided the metals for the Kipushi mineralisation northern Chile (Lower Cretaceous); Corocoro, northwestern
(Van Wilderode et al. 2013). Bolivia (Oligo-Miocene); San Bartolo, northern Chile (Oligo-
For the purposes of “on ground” targeting of an analo- Miocene); and Yasyamayo, northwestern Argentina (Miocene-
gous deposit an exact distinction in terms of fluid timing Pliocene). The Corocoro area has produced the largest amount
may be largely academic when defining greenfield sites of copper in the Andean examples, something like 7.8 million
for a preliminary sampling program. What is obvious tonnes of copper at a grade of 7.1 % (Cox et al. 2007). The
from the relationship of mineralisation to the halokinetic location of mineralisation is controlled by structurally-
breccia at Kipushi is that the breccia margin in contact focused redox fronts in bedded sediment hosts, which abut a
with organic-rich sediments was the precipitational focus steeply-dipping translatent fault (Fig. 15.33). Deposits are
for the mineralising solutions. This occurred either as the irregular, usually elongate lenses of native metal, sulphides,
residual salt was still dissolving, or once it had dissolved and their oxidation products. Typically, deposits are hosted in
and scapolite transformations were supplying the metal- alluvial fan and playa sandstones or conglomerate facies that
entraining volatiles (Fig. 15.31). An exact determination also contain abundant gypsum and lesser halite. The under-
of the time of the mineralisation is not the fundamental sides of some copper sheets at Corocoro even preserve mud-
control on the location of the deposit. The salt structure crack polygons and bed-parallel burrow traces (Savrda et al.
Fig. 15.33 Cross section of the Toledo mine in the Toledo

Corocoro ore district (Adapted from Entwistle and W. mine E
Gouin 1955) 4,000 m
Stratabound with
Stratabound Cu with native Cu (”ramos”)
chalcocite (”vetas”)
Metres (asl)
3,800 m
Corocoro fault
(redox mineralisation
focused along a
salt thrust duplex-
3,600 m décollement
and/or salt weld?)
100 m Bedding traces
2006). Ore mimicry of mudcracks is not a feature controlled sedimentary structures, such as cross stratification (2) Ores
by on-for-one-replacement of organic material deposited in a in stacked channelized bodies, that show steep dips in struc-
sandstone, rather it is following preexisting permeability/ turally complex and folded zones with local brecciation.
redox contrasts. Native copper commonly fills thin laterally extensive sheets
The Corocoro deposits in Bolivia have been mined spo- in tectonic fractures in the limbs of such tight folds.
radically since they were first exploited by the local Indians, Ljunggren and Meyer (1964) interpreted these folded diage-
prior to the Spanish invasion in the sixteenth century and netic sheets of copper as a remobilization products precipi-
were largely exhausted in half a century of more intense tated during deformation of earlier matrix-pore filling
mining operations beginning in 1873 (Fig. 15.33). copper.
Sandstone and conglomerate matrices show evidence of Critical factors in Corocoro ore genesis include (Flint
bleaching and leaching of the original redbed host with 1989): (1) Stratigraphic association of evaporites, organic-
numerous red-greybed redox interfaces visible in the mined rich lacustrine mudstones, clastic reservoir rocks, and oro-
sequences. Ore minerals (dominantly native copper) are genic, igneous provenance areas for both basin-fill sediments
secondary fills within secondary intergranular pores cre- and metals; and (2) Intrabasinal evolution of metal-mobilising
ated by the dissolution of earlier carbonate and sulphate saline brines derived from the buried and dissolving lacus-
masses and intergranular cements. Twelve grey sandstone trine evaporites that flush volcaniclastics, volcanics and feld-
beds, which were host to the long worked-out native copper spathic sediments. The same saline diagenetic fluids also
ores, occur within a stratigraphic thickness of 60 m in a unit caused the dissolution of early, framework supporting
known as the Ramos Member which still hosts abundant cement and large aragonite prisms, all now pseudomorphed
CaSO4 as gypsum. by native copper.
Ores are stratabound, but not necessarily stratiform and The ore-hosting clastic horizons are consistently located in
the larger masses of native copper are typically present as the highly gypsiferous Vetas Member of the Ramos Formation,
vein fills. Sometimes the copper pseudomorphs large which was deposited as redbeds in braidplains or fluviodeltaic
orthagonal-ended aragonite prisms that can be several centi- playa margins centripetal to the edges of saline evaporitic
metres across. There are two main styles of mineralization; lakes that were accumulating gypsum and halite (Fig. 15.34;
(1) Ore minerals as a matrix to stratiform detrital silicates, Flint 1989). Abundant gypsum is still present in the Ramos
typically low dipping and commonly highlighting primary Member as nodules and satinspar vein fills, both are secondary
Degraded Salt Diapir (now a gypsum rind)

When the halite diapir was active and undergoing
burial dissolution it was a source of chloride-rich brines Alluvial fan delta system
Alluvial fan system that could form the reducing side of a redox front with (longitudinal section)
(medial) adjacent red beds and also supply saline waters to
adjacent lake
Debris flow
Bottomsets
Delta foresets (clay and silt)
(sand)
Saline lake /playa
Cu Ore Precipitates
Braided Stream Mostly found as passive void fill
Redbed/arkosic sediment on reduced side of redox front Grey Beds - Highstand tract
with iron oxides, ferromag- on the lower side of coarser- Mud-dominated, lower portions
nesian minerals and volca- grained clastic braid plain sands Evaporite Beds - Lowstand tract typically organic-rich due to density
or brine-carrying fractures and Subaqueous and saline mudfat salts. When
niclastics (potential Cu stratification of water body. Pore fluids
faults (diapir-related?) undergoing burial dissolution it was a source
sources). anoxic. Generates a zone of reduction
of chloride-rich brines that could form the
reducing side of an updip redox front when adjacent to redbed sands.
Fig. 15.34 Sedimentological model for precipitation of Corocoro ores (or both) and the resultant setup of the Cu-precipitating redox front
showing source of metalliferous chloride brines by early burial dissolu- (In part after Flint 1989; Warren 2000b)
tion of bedded evaporites or diapir or salt-décollement dissolution
evaporite textures likely implying dissolution of previously granular masses of the native metal. Associated with the
more voluminous CaSO4 and NaCl beds and masses. Gypsum enriched copper zones were more oxidised minerals such as
along with celestite are the most common gangue minerals malachite, chrysocolla, azurite, domeykite, and chalcocite.
associated with native copper veins in all the Corocoro deposits Singewald and Berry (1922) noted gypsum and salt were the
(Singewald and Berry 1922). In the geological analysis of the principal gangue minerals, while silver minerals were rare.
first two decades of last century the copper-bearing beds of the The vetas sediment hosts tended to be coarser grained, often
westerly-dipping series were called “vetas” and those of conglomeratic; whereas the ramos sediment hosts were finer-
the easterly-dipping beds “ramos” and, as a matter of conve- grained with copper present as smaller particles and masses.
nience, the names became attached to the rocks themselves. The currently accepted interpretation of the Corocoro
The term “veta” is Spanish for vein and “ramo” the Spanish copper is that it formed during early diagenesis within a
for branch (native copper). The 1922 paper by Singewald and saline playa depositional environment, and in combination
Berry noted that the veta horizons were traceable continuously with dissolution of the adjacent bedded lacustrine evaporites
for over 5 km in outcrop, but there were no obvious primary (Fig. 15.34). This bedded combination is thought to have
trends related to ramos outcrops (Fig. 15.33). controlled the formation, transport and precipitation of the
Six mineralized layers of each kind were exploited in copper ore (Flint 1989). Playa sandstones, sealed between
mining during the first two decades of last century, the thick- impervious evaporitic mudstones, created the plumbing for
nesses of which varied from a few centimetres to 7 m focused metalliferous fluid migration toward the basin mar-
(Fig. 15.33). Sheets and masses of native copper, called gin. It is argued that the carbonaceous material at Corocoro
charque, were up to 600 lb in weight, but larger volumes of was likely concentrated in the sandstones and conglomerates
copper were extracted from vetas sandstones where copper and not in the shalier members of the sedimentary sequence
was found generally as diffuse minute grains, pellets, or (Eugster 1989).
The organics were considered strata-entrained as primary

plant matter (e.g. spores) preferentially in the sandstones,
along with later possible catagenic/hydrothermally cracked Gypsum carapace to
products migrating as hydrocarbons out of the basin. This a salt diapir (inactive)
created locally reducing pore environments in the aquifers
wherever these reduced fluids met with somewhat more
oxidising updip pore waters. This updip migration of saline
reducing waters, in combination with sulphur supplied as
H2S from the adjacent dissolving calcium sulphate beds and
nodules, as well as from dissolving intergranular sulphate
cements, precipitated copper in the newly created secondary
porosity. The pore water chemistry and flow hydrology of
this sandstone-hosted Cu system is thought to show many
affinities with diagenetic uranium-redox precipitating sys-
tems, as defined by Shockey and Renfro (1974).
However there is, in my mind, a possible anomaly in this
model, which assumes organics were deposited in fluvial
sandstones at the time of deposition. It is highly unusual to
have higher plant material accumulating in large volumes in
a sandstone in a setting that is sufficiently arid and oxidising
to precipitate ongoing interbeds of halite and gypsum. Such
settings are typically too arid to allow abundant higher plant
growth. Also, as we saw in Chaps. 2 and 9, groundwaters that
are flowing basinward through bajada sandstones in Neogene
sediments of the Andes are ephemeral or too oxidising to
facilitate the longterm reducing conditions needed to pre-
serve significant volumes of higher-plant remains in the
sandstone aquifers. Corocoro Cu
What is also interesting in this sedimentological/diage-
1 km
netic model of Tertiary age cupriferous redbeds deposits in
the Andes, centred on Corocoro, but not considered in the
published literature base, is the question…What controlled
the folding, and the associated brecciation and perhaps even Fig. 15.35 Corocoro district, Bolivia. Satellite image showing a
subsurface brine interfaces responsible for the Cu precipita- gypsum-capped salt diapir that outcrops in a salt thrust décollement
around a kilometer north of the main Corocoro deposits. Location is
tion? All the stratabound Bolivian Cu deposits accumulated
plotted using SaltWork version 1.6 mounted on the public version of the
in sediment hosts that were deposited in fault-bound inter- Bing® image base
montane groundwater sumps. All are located in hydrologic
lows in the crustal shortening tectonic scenario that typifies
the Tertiary history of the Andes. most of the ore textures are passive precipitates, largely in
The variable ages of the host sediments and the predomi- pre-existing porosity. If so, perhaps these deposits are not a
nance of evaporite indicators including gypsum in outcrop variation on a roll-front uranium theme, which is predicated
(often as diagenetic masses in fluvial hosts) and all intimately on dispersed primary organic material in the host sandstones
tied to the Corocoro ore forces the question...., “was the fluid (Shockey and Renfro 1974).
focusing driving the Cu precipitation a response to When one plots the position of Corocoro using a GIS
compression-driven halokinesis in an evolving salt-lubricated overlay of the region, the 1,000-lb gorilla that has been
thrust belt?” Did this on-ground scenario occur in a haloki- standing in the corner of the room for the past century
netic hydrology, that was possibly related to a combination becomes obvious. The Corocoro redbed copper is located on
of thrust-driven telogenesis, redox setup, evaporite dissolu- a fault system that is linked across less than a kilometre to an
tion and aquifer focusing of brines with dissolution aiding outcropping gypsum-capped remnant of a salt diapir that has
local slumping? This, along with associated strike-slip intruded the anticlinal axis of a saline redbed/greybed
prisms, could possibly better explain the stability of redox Corocoro sequence (Fig. 15.35). The same diapir proximity
interfaces in sandstone aquifers across timeframes needed to is true of other nearby redbed copper deposits to the south-
accumulate significant native copper volumes. After all, southeast, such as Veta Verde and Callapa. It is highly likely
that the saline fluid interfaces forming the redbed Cu depos- Cambrian bimodal igneous rocks. Similar cupriferous, but
its of Corocoro, Veta Verde and Callapa were halokinetically noneconomic, sediments occur in several other locations
focused. A similar salt lubricated set of thrusts and strike-slip within Upper Permian strata in Oklahoma, Kansas, Texas
faults typifies halokinetic outcrops in Central Iran (Fig. and New Mexico. Regionally some 900–3,400 m of mixed
6.90). It is highly likely that much of the structuration that is clastic and chemical sediments of Ordovician to Permian age
controlling Corocoro ore positioning is a response to salt make up the Hollis-Hardeman basin fill, which, in turn, over-
flow related uplift and fracture creation, probably in redox lies a Precambrian to Cambrian basement made up of
interfaces induced and controlled by regional salt-lubricated metasediments and metavolcanics. Locally, in the vicinity of
compressional tectonism and the associated salt-structure the Creta deposit, sediment thickening is associated with
driven hydrology. movement on the Birch Fault, so that the sedimentary
Work by Rutland (1966) did make an observation that the sequence is locally 3,200 m thick and dominated by fine-
Corocoro ore deposits are related to an unconformity grained clastics that show a gradual upward increase in the
between the Ramos and Vetas Formations. Previously, the proportion of evaporites in to the Upper Permian section.
unconformity was interpreted as directly due to the outcrop Ore-grade material was mined, mostly as chalcocite, from
of the Corocoro Fault. He noted that the fault and the uncon- the Creta copper-bearing shale in southwestern Oklahoma
formity were one and the same. In the 1960s there was no from October 1965 to February 1975, when a drop in the
notion of a salt weld but it was nonetheless a highly astute price of copper forced the mine to close. Production from
observation by Roy Rutland. He went on to note a similar Creta between 1965 and 1975 totalled around 1.8 Mt @
unconformity is tied to the growth of the Chuquichambi salt 2.3 % Cu, 5.5 g/t Ag. The nearby Magnum deposit is believed
diapir, some 100 km southeast of Corocoro. Unfortunately, to have a sub-economic reserve of approximately 3.6 Mt @
the halokinetic implications of Rutland’s work were not con- 1 % Cu. This extracted volume makes Creta the second larg-
sidered 20 years later in Flint’s key 1989 paper inferring a est shale-hosted Cu deposit in the United States. Lead and
largely sedimentological origin for the Corocoro and other zinc levels are negligible at Creta. At nearby Magnum, mala-
similar SSC deposits. chite [CuCO3Cu(OH)2] is the most abundant copper mineral,
A possible halokinetic/weld association also leads to the although chalcocite may be the dominant ore mineral in the
question… Were the salt lakes, that are considered an inte- subsurface.
gral part of the depositional and saline ore-precipitation sys- According to Huyck and Chorey (1991), the mineralisa-
tems at Corocoro by Flint, also a response to dissolution of tion event at Creta was early diagenetic, as indicated by: (1)
the same nearby diapiric structures, when they were active in Copper sulphide replacing large spores and framboidal
the mid to late Tertiary? This tie, between diapir/weld brines pyrite, (2) Lack of compaction of replaced spores relative to
sourced in the drainage hinterland and bedded evaporite – unreplaced spores, (3) Enclosure of uncompacted mud and
lacustrine mud interbeds accumulating in the groundwater copper sulphides by early “matrix gypsum”, (4) Location of
outflow sumps, is the case with groundwater inflow for the the ore bed within a thick sequence of fine-grained low per-
Salar de Atacama infill, as it is in other Quaternary salt lakes meability sediments.
in the region. Figure 3.44 plots some of the many diapir rem- Seven lithologic units occur in the upper 19 m of the
nants that typify the Andes region. It seems that the Corocoro Flowerpot Shale and include the Prewitt Shale member,
style of Cu mineralisation is perhaps another example of which hosts the Creta deposit (Fig. 15.36). This interval is
suprasalt redox focusing in a halokinetic setting. characterised by two common features: (a) Satinspar gypsum
Whether the halokinetic scenario, or the currently veins and (b) Variegated red-green layers. The veins both
accepted non-halokinetic bedded arid-lacustrine evaporite crosscut and parallel shale bedding and partings. They typi-
scenario, explains the Cu mineralisation Corocoro is yet to cally terminate within either nodular or massive gypsum
be tested. But in terms of future copper exploration for simi- beds or in gypsiferous green shale beds. In mineralised zones
lar deposits, it probably requires an answer. A halokinetic they usually encapsulate shale intraclasts and copper miner-
association offers an exploration targeting mechanism, utilis- als. The variegated layers and lenses are composed of dis-
ing satellite imagery and aerial/gravimetric data, prior to the continuous silty (60–80 % silt) calcareous and gypsiferous
acquisition of on-ground land positions and geochemical red-brown layers. When the variegated layers are traced lat-
surveys. erally they pass into adjacent gypsum, the layers obviously
reflect dissolved gypsum or satinspar intervals.
Creta, Oklahoma The Prewitt Shale averages 2 % Cu in the mine area, with
The Creta deposit occurs in the upper part of the Flowerpot a matrix composed of illite and chlorite and as much as 20 %
Shale (Nippewala Group) within the Hollis-Hardeman Basin, satinspar gypsum. It is made up of three layers: a lower
Oklahoma. It is associated with the WNW-ESE trending blocky layer, a laminated layer and a discontinuous upper
Wichita basement high where the ore host strata overlie bed of impure gypsum (the “cap gypsum”). The lowest
a b
Creta mine, SW Oklahoma West Mine area
East
gypsum
Marty
dolomite
Cap
(mostly disseminated)
Copper bearing
interval
Prewitt shale
Meadows
shale
Unit A
0.2 m
Prewitt
shale
Nodular gypsum
Massive/laminated gypsum Redbed mudstone
Satinspar gypsum Gypsum bed
1m
Green mudstone
Clayshale
Green mudshale
Claystone Cu-veinlets
Green calcareous mudshale 100m
Mudstone
Satinspar veins Cu mineralisation
Fig. 15.36 Creta copper shale deposit, Oklahoma. (a) Mineralised stratigraphy in the Creta Mine. (b) Mine region stratigraphy showing intimate
association between mineralisation and evaporite occurrence (After Huyck and Chorey 1991)
blocky layer is a claystone to mudstone; copper, when pres- Most published work on this deposit documents satinspar
ent, occurs only in the upper 10–13 cm and is concentrated in gypsum as well as the cap gypsum, but none (including the
the mudstone (Fig. 15.36a). The overlying laminated shale, most comprehensive work by Huyck and Chorey 1991) dis-
which contains as much as 4.5 % Cu, includes both gypsifer- cuss its significance, nor do they mention the implications in
ous and nongypsiferous clayshale. Copper is concentrated in terms of fluid focussing of a thick now variably-dissolved
the silty laminae both in outcrop (as malachite) and in thin gypsum/anhydrite/halite units that dominate Blaine
section (as anilite). The cap gypsum bed directly overlies the Formation and situated immediately above the mineralised
laminated portion of the Prewitt Shale in the west, but portions of the Flowerpot Shale (Muir 1934; Askew 2013).
pinches out in the east (Fig. 15.36b). Where fully developed The presence of satinspar gypsum in the mineralised zone
the cap gypsum bed (10–25 cm thick) is made up of a lower indicates a likely combination of halite solution-collapse and
gypsum, a thin green clayshale, and an upper gypsum. gypsum rehydration. As such, the current forms of CaSO4 in
Copper mineralisation only occurs in association with the mine area are tertiary or telogenetic evaporites, a result of
concentrations of pyrite and spores. The main ore mineral is uplift and rehydration tied to salt dissolution (Chaps. 1 and 7).
anilite (Cu1.75S) and is concentrated along silty or sulphide The current evaporites were not responsible for the precipita-
rich layers in the laminated unit. In gypsiferous shale the tion of the sulphides as they postdate that event. They do,
opaques are concentrated along the edge of the satinspar however, indicate the former presence of a more substantial,
veins and within clay blebs in the matrix gypsum. Anilite is but now dissolved, evaporite unit composed either of anhy-
also weakly developed throughout the nongypsiferous por- drite, or perhaps a combination of halite and anhydrite that
tions of the Prewitt Shale. The association of Cu mineralisa- focused mineralisation below it into the prepared ground in
tion with evaporite occurrence in the Prewitt Shale is obvious, the Flowerpot shale. It was this former evaporite seal that was
and reflects a burial diagenetic mineralisation at a redox responsible for brine focusing and, through its dissolution
interface. In my opinion, it is associated with an anoxic (indicated by the cap and satinspar gypsum units), maintained
reduction front (red-green transition) that was generated and a redox front that precipitated the copper sulphides. Creta is
maintained by the dissolving evaporites indicated by the perhaps a smaller-scale subsalt example of a redox precipita-
satin-spar. tion hydrology similar to the Kupferschiefer/Rudna Rote
a b
East Hole 77Y-3
West
Coppercap mountan
Coates lake sp gn 5100 ppm
0 B6
77Y-3 py
km B5
Evaporitic
py
Limestone & dolomite
2 B4 Tan-green mudstone
0 12 py
and siltstone
Zone
km Red mudstone
Rapitan formation Transition zone cp py 4,750 and siltstone
B3
Coppercap formation Redstone River formation
Transition
cp bn
Depth (ft)
10 m
c
Dissolution edge
0
py py B2
py py cc bn
gn+ 4,850
s
hem cc n+cpp
b
bn: bornite
Cu cc: chalcocite B1
cp: chalcopyrite cc bn
s gn: galena
ine
nal br hem: hematite
B asi py: pyrite
Basement
sp: sphalerite
0 10 100 1000 10,000 100,000
Cu
Evaporites Redbed sandstone Mineral zone 0 100 200
Zn
Limestone Red mudstone Fault
Grey mudstone Redbed conglomerate 0 40 80
Basalt Ag
Fig. 15.37 Redstone Copper Belt, Canada. (a) E-W geological cross- Diagrammatic section across a redbed-evaporite rift margin showing
section of Coates Lake region showing well 77Y-3. (b) Stratigraphy and mineral zonation of precipitated sulphides. Modelled from Redstone
metal content of well 77Y-3 (After Chartrand et al. 1989). (c) Copper Belt, Northwest Territories, Canada (After Kirkham 1989)
Faule of Poland. Smaller perhaps, because the salt dissolution Sediments in the Transition Zone are made up of six
front was not maintained in a stable long-term position shoaling peritidal cycles, deposited along arid shorelines
because of the lack of halokinetically driven salt resupply. with sabkha affinities (Chartrand et al. 1989). Higher levels
of mineralisation are typically found within the evaporitic/
Redstone Copper Belt, Canada stromatolitic carbonate portion of each depositional cycle. At
Coates Lake is the largest stratiform redbed copper prospect the base of a typical cycle, red siltstone and mudstone grade
in the Redstone Copper Belt, Northwest Territories, Canada. up over a few decimetres into tan and green-coloured silt-
Associated with it are a number of smaller deposits (Hayhook, stone, exhibiting the same sedimentary textures and struc-
Keeles River), which all occur in a 250 km, northwest- tures as their underlying red counterparts (Fig. 15.37b).
trending, arcuate thrust belt made up of Neoproterozoic These terrigenous strata grade over a few centimetres into
(Helikian) carbonates and redbeds. These sediments are part grey-green dolosiltite and dololutite overlain by microbial
of the Mackenzie Mountain Supergroup (Fig. 15.37a and laminated carbonate, the principal host for the cupriferous
Table 15.10; Chartrand et al. 1989; Ruelle 1982; Brown sulphides. The dolosiltites and dololutites are capped by
1997). gypsum/ anhydrite-rich units that are decimetres thick.
Coates Lake and the smaller various copper deposits Evaporitic units are overlain by tan-green siltstone and mud-
occur at the contact (in the Transition Zone) between the stone and, finally, by red siltstone. Beds B4-B7 are domi-
continental alluvial redbeds of the Neoproterozoic (750 Ma) nated by tan-green colours with most of the entrained
Redstone River Formation (0–1,220 m thick) and the shal- mudstone and siltstone intervals containing more calcite
low marine/ evaporitic rocks of the overlying Lower and/or dolomite than their counterparts in beds B1-B3
Coppercap Formation (≈250 m thick). The Transition Zone (Fig. 15.37b). The succession is crosscut by late-stage calcite
host strata are composed of several blanket-like variably- and gypsum veins.
cupriferous units of dolomitic silty, evaporitic cryptalgal- Beneath the Transition Zone sediments, in the Lower
laminated carbonates that were deposited atop the fault-bound Redstone River Formation, Ruelle (1982) mentioned the
Coates Lake, Hayhook Lake and Keele River embayments. presence of an unusual high Na-Mg Precambrian evaporite
Table 15.10 Stratigraphy of Redstone Copper belt

Unit Description
Rapitan Formation (unconformable base) Turbiditic, siliceous red siltstones, maroon and green debris
flows and tillites, which lie with regional unconformity on the
Coates Lake and Little Dal Groups.
Mackenzie Mountain Supergroup Coppercap Formation (0–300 m) Upper Unit (0–165 m) of well bedded, stromatolitic limestone
and dolostone,
Middle Unit (0–72 m) of argillaceous carbonate and calcareous
shale,
Lower Unit (0–63 m) of evaporitic limestone and dolostone, and
laminated dolostone
(Lower Middle and Upper Coppercap Formation carbonate
sediments are all fetid and black).
Transition Zone (40 to over 110 m) Series of red, green, and tan coloured nearshore arid coastal
deposits. Copper occurrences are hosted by up to eight
fining-upwards, carbonate-evaporite beds, each composed of
dolosiltite, dololutite, dolostone, gypsum, anhydrite and capped
by a cryptalgal laminated carbonate bed.
Redstone Formation (0–1,220 m) A Lower “Evaporite” unit is composed of bedded and brecciated
gypsum-anhydrite, which thins at basin margins and reaches
thicknesses of over 215 m at basin centres. An Upper “Redbed”
subunit is dominated by maroon mudstones with thin marginal
fanglomerates.
Thundercloud Formation (0–300 m) Lower portion made up of basal volcaniclastics, alluvial
fanglomerates, tidal arenites and paralic mudstones. These are
overlain by rhythmically interbedded carbonate and dolostone
locally containing evaporites, followed by cyclically interbedded
sandstone and shale. Upper part of the formation is marked by
evaporitic algal dolostones.
Little Dal Formation contact Contact with the underlying Little Dal Formation is marked by
pillowed basaltic lava, or sandstone, dolomite, siltstone, and
mudstone with local gypsum and conglomerate. Where basaltic
lava is present the contact is conformable but the sedimentary
units mark a distinct unconformity.
Based on Aitken (1981), Ruelle (1982), and Jefferson and Ruelle (1986)
assemblage now largely marked by collapse residues and of 37 million tonnes, averaging 3.92 % Cu and 0.33 oz. per
breccias. Today, it is made up of 55 % glauberite tonne Ag (11.3 g/t). Mineralisation is best developed in the
[Na2Ca(SO4)2], 20 % magnesite, 15 % talc and <10 % com- lower three carbonate units. For example, in drill hole 76Y-4,
bined gypsum and anhydrite. Strauss (1993) consider these the richest Cu intersections are in bed 2a (0.15 m @ 5.5 %
evaporites to be time-equivalent to the upper evaporite level, Cu) and bed 3 (1.16 m @ 1.18 % Cu), both occurrences are
the Killian Formation, in the Amundsen Embayment At this tied to preserved beds of nodular anhydrite (Ruelle 1982).
time the significance of this sulphate-evaporite-rich residue In well 77Y-3, the sulphide minerals are zoned vertically
assemblage in relation to the overlying sulphate evaporites with bornite and chalcocite in the lower portion, passing up
and to focusing a redox front with any metal-transporting into a chalcopyrite-bornite interval, upwards into
brines is neither well documented nor understood. At the chalcopyrite-pyrite and finally into pyrite (Fig. 15.37b).
time of mineralisation there may have been a much thicker, Sphalerite and galena occur at the uppermost part of the
possibly halokinetic, halite mass. If so then the Transition Transition Zone in contact with the overlying carbonates of
Zone copper beds are suprasalt with affinities to the Lisbon the Coppercap Fm (Chartrand et al. 1989). The relatively
Valley and possibly the Dzhezkazgan deposits. Without pub- high silver content coincides with high copper contents in
lic domain detail beyond what was published in the 1980s, it the base of the Transition Zone and, according to Ruelle
is difficult to say. A map of the brecciation geometries in the (1982), indicates the silver is entrained within bornite.
Redstone Formation would be informative. Like the Kupferschiefer and Lisbon deposits, mineralisa-
The largest and most economically promising Cu deposit tion in Redstone Copper Belt deposits show a pronounced
in the Redstone Copper Belt is situated within the Coates mineral zonation, with the Cu:Fe ratio in the sulphides
Lake embayment and covers an area greater than 12 km2. It decreasing upsection through the Transition Zone and toward
occupies a bed 1 m thick and contains drill-indicated reserves the embayment margins (Fig. 15.37c). The copper sulphides
occur as partial to complete diagenetic replacements of dissolution of the halite also drives the enrichment of CaSO4
anhydrite nodules in the cryptalgal-laminated units and as at the site of dissolution. What is also obvious from the lit-
disseminations of anhedral to euhedral grains in the inter- erature of SSC deposits is that salt residues are under-
tidal mud flat facies. Bladelike anhydrite crystals are also appreciated or not even recognised. Yet they are indicators of
partially to completely replaced by chalcopyrite. Preserved former substantial salt masses which played significant roles
anhydrite nodules are ellipsoidal in cross section and up to as chloride brine sources and metal precipitation foci. We
several centimetres in diameter, although most are less than shall return to this notion of halokinesis supplying subsalt
1 cm. Mineralisation of these nodule layers creates a laminar cupriferous brines and suprasalt/weld stability after we con-
fenestral fabric to the mineralisation. Further away from the sider some of the larger Pb-Zn deposits in the same salty
Cu mineralisation front, pyrite with chert replaces the anhy- framework.
drite nodules (Ruelle 1982).
Metals were leached and transported as metal-chloride
complexes from volcaniclastic/redbeds that were derived tratiform Sediment Hosted Pb-Zn Deposits
S
from Cu-bearing mafic lavas in the Redstone River and (Salt-Related)
Thundercloud formations (Fig. 15.37c). As slightly acidic
and weakly oxidised basinal brines moved up and outward Current economic geology literature typically considers
from the basin sediment pile, they were focused into the SedEx (sedimentary exhalative) and MVT (Mississippi
basin margins by the presence of overlying evaporite aqui- Valley Type) deposits as related responses to the flow of
cludes. Near the margins, where the evaporite aquicludes basinal fluids. SedEx deposits are typically a mineralised
were dissolved, had pinched out, or welded, the solutions response to basinal fluid flow in deeper water mostly silici-
seeped up section to encounter redox fronts associated with clastic sediment hosts and MVT deposits the updip responses
the organic-rich cryptalgalaminites of the Transition Zone. mostly hosted in carbonates (Fig. 15.38; Emsbo 2009; Leach
This interaction then fixed the metals on the reduced side of et al. 2010).
the redox front with a sulphide zonation identical to that Exact definitions of what constitutes a SedEx versus an
found in the Kupferschiefer ore zones. In each of the cycles MVT deposit vary, according to the syngenetic verses epi-
of the host stratigraphy the positions of oxidation reducing genetic inclination of the writer. For SedEx deposits, a good
fronts are still preserved as the red to grey-green colour tran- definition is that of Goodfellow and Lydon 2007. They define
sition. Hematite is still visible in the red-coloured intervals sedimentary exhalative (SedEx) deposits as typically tabular
and the proportion of Cu in the grey-green intervals is much bodies, composed predominantly of Zn, Pb, and Ag, bound
higher (Rose et al. 1986). in sphalerite and galena, which occur interbedded with iron
sulphides and basinal sedimentary rocks. Deposition was on
ummary of SSC Deposits Tied to Evaporites
S the seafloor and associated with sub-seafloor vent complexes
Clearly, stratabound copper accumulations in sediments can fed by hydrothermal fluids seeping into mostly reduced sedi-
be related to redox fronts set up between saline, highly mentary basins in continental rifts. In the vicinity of the brine
reducing pore waters and somewhat less saline, slightly vent tract, SedEx deposits are typically zoned, with the pro-
acidic oxidising waters. The importance of the redox inter- portion of Pb, baryte and Mn decreasing away from the
face in diagenetic precipitation of copper was well known in feeder/vent zone, which is typically centred on one or more
the economic geology community since the 1970s (e.g. Rose extensional faults (Fig. 15.74).
1976). and has been an integral part of the interpretive para- For MVT deposits a widely accepted definition is that of
digm for redbed copper since that time. What is less appreci- Leach and Sangster (1993). They define MVT deposits as a
ated is the role that evaporites both bedded and halokinetic varied family of epigenetic ores, precipitated from dense
can play in setting up and maintaining the position of the basinal brines at temperatures ranging between 75° and
redox interface in earth space, so that substantial accumula- 200 °C, typically in platform carbonate sequences and
tions or copper can occur in a single buildups, such as in the lacking genetic affinities to igneous activity. That is, in con-
Kupferschiefer-Lubin, or bed associated buildups as in the trast to the basinal sediment host of SedEx deposits, MVT
Dzhezkazgan district. deposits tend to be hosted in dolomitised platform carbon-
The redox interface is better maintained when the reduc- ates or more rarely in sandstone interbeds. Such miner-
ing side of the interface is supplied by dissolution of a halo- alised systems are sometimes located at or near the
kinetic salt mass rather than an individual salt bed. This is high-energy fault-defined platform edge, as defined by the
because in a halokinetic system the salt is thick enough so rock matrix character of the host (Fig. 15.38). And some-
that it will continue to flow into the site of dissolution until times they are located adjacent to the dissolution edge of
the conduit to the mother salt mass is lost either by salt weld- platform evaporites where the three features (fault, shelf
ing or by the complete dissolution of the salt mass. Fractional edge, saltern edge) may coincide to focus ore precipitation,
Stratiform Sediment Hosted Pb-Zn Deposits (Salt-Related) 1525
Fluid source
Distal expressions of mineralisation Large shallow evaporitic platform (>105 km2)
Metalliferous black shales Seawater evaporation (dolomite & salt)
Ba, PO4, Mn Fluid drive
Density-driven reflux hydrothermal dolomitization
Contemporaneous evaporite and shale
Reflux dolomite Rift-sag sequence (1–4 km)

McArthur River Hydrothermal dolomite MVT/Cadjebut type Limestone, shale, calcareous shale, siltstone
Century, Meggen MVT/Irish type
Metal trap Dolostone Dolostone
K+Na mineralisation
Howards Pass
Anoxic/euxinic in bathymetric lows
Tom, Jason
black shales with > 1 % TOC
e
s
ston
nate
Dolo
o
carb
Mg -
Red Dog
K+Na alteration
Rift fill sequence (4-10 km thick, >3 km deep)
Coarse, oxidized continental clastic rocks. Conglomerates,
redbeds, sandstones, turbidites, with some siltstones and
Alkali alteration
Fe/Mn carbonate evaporites, commonly volcanic felsic and mafic sequence
Plumbing system 100 km

Long-lived basin faults
Synsedimentary faulting (facies, isopach, breccias, slumps)
Platform carbonates Coarse continental clastic ricks with some volcanic felsic and mafic sequences
Shale, calcarous shale, siltstone Crystalline basement

MVT - Mississippi Vallet type
TOC - Total organic carbon
Fig. 15.38 Geologic setting and geologic assessment criteria for important SedEx deposits relative to the shallow-water platform
SedEx Zn-Pb-Ag deposits emphasising relationship between SedEx margin are indicated and may reflect the structural architecture of
and MVT deposits as deduced by USGS worldwide synthesis the basin or the maturity of the rift cycle (Figure based in part on
(Emsbo 2009 and references therein). Likely locations of several Emsbo 2009)
as in the Cadjebut and San Vicente deposits. Other times Evaporite Associated MVT Deposits
they form in thrusted platform carbonates with a fluid flow
system tied to evaporite-focused décollements, as in the Much like we have already seen in redbed Cu-evaporite asso-
Gays River/Ainslie deposit/prospects. MVT deposits often ciations, for MVT Pb-Zn deposits associated with evapo-
occur in fluid-defined clusters made up of a number of rites, there are two fabric/structure styles: (1) Halokinetic
smaller deposits. edges, with the metalliferous brine interactions typically tied
In contrast to the clustered nature within an ore district of to fluid interfaces within the sulphate fringe (caprock or car-
MVT deposits, individual SedEx deposits tend to be larger apace), which defines the dissolutional periphery of a diapir
stratiform deposits, spaced some distance apart. Russell et al. crest or stem, a salt allochthon periphery, or below a salt-
(1981) tied the larger separation of SedEx deposits to the size lubricated decollement plane, and; (2) Bedded sulphate
of convective fluid cells in thick sedimentary basin fills. As we interactions typically located where fault-controlled metal-
shall see, whenever SedEx deposits can be tied syndeposition- liferous fluids intersected with, and interacted with, one or
ally to the presence of former evaporites they tend to be typified more platform sulphate beds (salina or saltern). For SedEx
by orehosting sedimentary laminites deposited within deeper deposits there is a third evaporite type, a suprasalt allochthon
water anoxic seafloor lows filled with hypersaline brine structuration that creates fault-fed, metal-prone, seafloor
(DHALs), with their seafloor positions controlled by a combi- brine lakes. Thus we can target exploration in a predicative
nation of halokinetic focusing of fluid flows and extensional fashion for those MVT Pb-Zn deposits with an evaporite
feeder faults. association: the targeting is based on identifying favourable
By the end of the chapter we will add an understanding of intersections where fault structures (extensional faults or
the importance of flowing and dissolving evaporites in a thrust planes) intersect units of dissolving bedded or haloki-
basin fills when SedEx and MVT deposits are forming. Once netic evaporites (now marked by residues and other “salt that
again, let me emphasise that evaporites do not form miner- was” textures, as detailed in Chap. 7).
alised Pb-Zn deposits, rather as they dissolve and alter in the
subsurface, evaporite masses focus and stabilise the position eridiapiric Diagenesis and Zn-Pb
P
in earth-space of brine flow conduits and redox/thermal For many years, the edges of diapirs or salt domes have been
interfaces, within the diagenetic mineralising milieu of viewed as potential targets for petroleum, salt and sulphur
faults, vents and brine sumps that drives the creation of larger accumulations. Lately, they have also come to be viewed as
MVT districts and SedEx deposits. potential targets, or at least process analogs, for Pb and Zn
Peridiapiric Pb-Zn
Spanish allochthons
Triassic salt
Peridiapiric Pb-Zn
Tunisian allochthons
Caprock Pb-Zn Triassic salt
Gulf Coast
Jurassic salt
Peridiapiric Pb-Zn
Neoproterozoic salt
Rauhwacke terrance
Adelaide foldbelt
Fig. 15.39 Occurrences of documented MVT Pb-Zn occurrences related to diapirs or allochthons as discussed in text (Plot extracted from
Saltwork GIS database version 1.6)
deposits (Wang et al. 1998a). Peridiapiric mineralised Pb-Zn halite (see Chap. 6). To form the calcite portion from this
systems can be divided into two types (Figs. 15.38 and anhydrite/gypsum precursor requires the presence of organ-
15.39): (1) Caprock/carapace hosted deposits, where the host ics/hydrocarbons and sulphate-reducing bacteria in the
rock consists of the anhydrite and bacteriogenic limestone region of the calcium sulphate cap (Fig. 15.40a). Such a situ-
carapace to the dissolving crest of a salt structure; (2) Diapir/ ation exists subseafloor, as well as in zones of continental
allochthon proximal deposits, where the bulk of the miner- meteoric circulation. The anhydrite carapace that makes up
alisation resides in laminar organic-rich sediment hosts, the greater volume of a diapir caprock is not just a meteoric
located adjacent to the diapir/allochthon or its residual cara- product, it is forming today on deep seafloor sites in zones of
pace. Examples of both these deposit styles tend to be rela- seawater driven fractional dissolution atop shallow salt dia-
tively small in volume and limited in extent. pirs and allochthonous salt sheets in the present day Gulf of
Mexico (Kennicutt II et al. 1985; Roberts et al. 1990). These
Caprock-Hosted Pb-Zn, Gulf Coast & North Africa sites are coincident with petroleum seeps, so that the calcite
Small deposits of Pb-Zn with a diapir association were rec- cap, including that in entrained mollusc shells, has isotopic
ognised in northern Africa more than 100 years ago, but it signatures indicating a crude petroleum source.
was not until the geology of diapir-hosted subeconomic Pb-Zn sulphides begin forming as soon as an anhydrite
deposits in the Gulf of Mexico (Kyle 1991), and economic cap rock carapace encrusts a developing salt structure. This
north African diapir- and peridiapir-hosted deposits, such as can happen during the earliest phases of salt flow and con-
Bou Grine and Oued Jebs (Rouvier et al. 1985; Orgeval tinue, perhaps episodically, as long as the structure’s crest is
1994; Bejaoui et al. 2013), were fully understood, that the bathed in nearsurface halite-undersaturated waters and oil-
significance of diapirism in controlling this style of small- or methane-bearing basinal fluids continue to circulate in the
scale Pb-Zn was fully appreciated (Fig. 15.39). vicinity of the diapir. Some of the earliest minerals to form in
Mineralogically, the diapir-associated mineral deposits are the caprock are sulphides precipitated in equilibrium with
similar to many other carbonate and shale-hosted mineral anhydrite, where they often form laminar sulphide-anhydrite
deposits. They all contain pyrite, marcasite, sphalerite, textures controlled by the morphology of the dissolution
galena and baryte; many deposits also contain high concen- interface (Kyle and Posey 1991). Biogenic calcite forms as a
trations of pyrrhotite and celestite. byproduct of bacterial sulphate reduction as crude oil and
thermogenic methane migrates up a diapir’s margin to come
Caprock Pb-Zn Accumulations into contact with anhydrite/gypsum in a low temperature
Caprock sulphates and bacteriogenic limestones created environment (≈80 °C) (Fig. 15.40a). Sulphides, baryte and
during caprock formation are important ore hosts in this style celestite can precipitate at the same time, or postdate, the
of deposit. All that is required to form the anhydrite portion calcite. Gypsum caprock continues to form after anhydrite
of a caprock is that the top of the diapiric salt stem or sheet and calcite caprock interfaces are well established, typically
be bathed in a solution that is undersaturated with respect to via the ongoing infiltration of undersaturated nearsurface
a Caprock mineralisation Peridiapiric mineralisation

surface
b
Calcite
Fault Gypsum Ba
Fault
Pb-Zn
Ba
Ba
Anhydrite
Hanging Ore body Footwall

Pb-Zn wall
Pb-Zn
Mudstone Deep seafloor

Ag Former salt muds and silts
allochthon
Sandstone Triassic - Rauhwacke breccias, marls, evaporite residues
Salt Paleocene - Marls, locally elevated TOC
Oxide zone - Smithsonite and cerussite

Sulphide minerals - sphalerite, galena, pyrite, marcasite &
chalcopyrite with gangue of barite, celestite, calcite, dolomite
Fracture Breccia
Impregnation ore - galena
Fig. 15.40 Peridiapiric mineralisation. (a) Caprock rock -hosted model, based on the USA Gulf Coast as seen in the Winnfield, Hockley and Tatum
salt diapir crests (After Kyle 1991). (b) Salt allochthon m
argin mineralisation, as seen in Ain Allega deposit, Tunisia (After Abidi et al. 2012)
waters that ultimately will rehydrate any remaining a nhydrite caprock also forms first at its bottom, but it does so via the
(Werner et al. 1988). progressive bacteriogenic replacement of the underlying cal-
Thus, iron sulphides typically form early at any particular cium sulphate (Light and Posey 1992). Metal sulphides that
site in a caprock/carapace deposit, even as the first laminar precipitate syngenetically within either the anhydrite or the
anhydrite residues accrue on the diapir periphery; galena and calcite cap rocks show isotopic compositions and major ele-
sphalerite form later; and baryte, celestite and sulphur are ment compositions that vary with depth. This range in isoto-
generally the last phases to precipitate. Banded or colloform pic values may record chemical changes in upward migrating
textures, consisting of finely crystalline aggregates, are the metal-bearing brines or changes in local chemical conditions
most common textures exhibited by the iron sulphides and relating to bacteriogenic overprints during sulphide precipi-
sphalerite. These base metal sulphides occur as; inter- tation (e.g. Fig. 9.72). The range in metal concentrations
anhydrite crystal cements, open-space fills in anhydrite, as most likely reflects changes in brine composition due either
carbonate/sulphate replacements, and as open-space (vug/ to brine mixing or to evolution of brine composition.
cavity) fills. Most of the anhydrite-hosted mineralisation A detailed record of episodic basin dewatering events is
formed during anhydrite caprock accumulation, whereas documented in mineralised anhydrite-rich cap rocks of two
most of the sulphides hosted in biogenic calcite formed prior Gulf Coast salt domes: the Hockley Dome and the Winnfield
to, or during, calcite precipitation, as seen in Hockley Dome Dome (Fig. 15.41; Kyle and Price 1986a, b; Hallager et al.
caprock (Fig. 15.41; Kyle and Price 1986a, b). 1990). There the majority of the highgrade mineralisation
In general, an anhydrite caprock accretes or thickens by occurs as massive laminar sulphide lenses. The lenses are
growth along its underbelly by a process of underplating typically vuggy, fractured and brecciated. At Hockley, the
(Fig. 6.111). As diapiric salt dissolves from the uppermost highest sulphide concentrations occur in the periphery of the
portions of the underlying halite stem/sheet, it leaves behind cap rock at depths ranging from 120 to 365 m (Fig. 15.41a).
the entrained anhydrite as a residue (Fig. 15.40a). Calcitic Elevated sulphide levels occur in both calcite and anhydrite
Fig. 15.41 Sulphides in caprock HH-1 HH-2 HH-3

of Hockley Dome, Texas. 0
Surface
(a) Structure contour map TEXAS
showing depth (metres) to top Location
caprock. (b) Geologic Miocene-Pleistocene
cross-section in caprock based Siliciclastic Strata
on wells HH-1 to HH-3.
Intersections of Zn + Pb in wells
are plotted on well trajectories 100 Gypsum
(After Kyle and Price 1986a, Salt
Kyle 1991) mine
Depth (m)
Gypsum
200
Calcite
Hockley 50
oil field HH-3
HH-2
HH-2 0 2 4%
100 Pb-Zn
200 300 Anhydrite
500 m Combined
Salt
a b
caprock hosts, are somewhat higher in the bacteriogenic cal- vugs in the anhydrite cap rock. Sulphide layers generally are
cite, with sulphide-rich zones between adjacent wells appear- less than one millimetre to several centimetres thick and can
ing laterally consistent in same-lithology units (Fig. 15.41b). be traced laterally for tens of meters. The principal sulphide
Marcasite, pyrite, sphalerite, and galena range from trace is monoclinic pyrrhotite, but sphalerite, galena, pyrite, and
components to local massive sulphide zones; significant marcasite are abundant locally. A nearsurface overhanging
Zn + Pb drill intercepts include 5.5 m of 7.1 % and 12 m of caprock helped focus escaping metalliferous fluid into the
4.2 %. Sphalerite is the dominant economic mineral, with an zone of salt dissolution between the top of salt and the over-
overall Zn/Pb ratio of about 3:l. Metal distribution studies lying residual anhydrite cap rock. Iron, lead, and zinc sul-
suggest that there is a trend of increasing zinc/lead down- phides saturations were exceeded in this zone, possibly in
ward in the anhydrite cap rock (Kyle and Agee 1988). response to H2S generation related to periodic dissolution
The Winnfield Dome diapir is roughly circular in outline and biogenic reduction of the caprock sulphates.
with a diameter of about 1.1 km at the −180 m structural In general, it seems that episodes when metalliferous
elevation. The top of the salt is 76–80 m below sea level, is brine entered accreting diapir caprocks are recorded as rela-
horizontal, and is directly overlain by anhydrite cap rock. tively thin bands of sulphide sandwiched between thicker
The salt/anhydrite cap rock contact is marked by a brine cav- bands of anhydrite. Continued dissolution of salt and under-
ity zone as much as a few meters thick. The anhydrite/calcite plating of residual anhydrite caused the sulphide bands to be
caprock interface at Winnfield is highly irregular and a gyp- displaced upward relative to the base of the cap, leading to an
sum zone as much as 12 m thick occurs locally. The calcite inverted stratigraphic record of basin dewatering events.
zone varies in areal extent and in thickness from about a Palaeomagnetic data from the Winnfield salt dome suggest
meter to over 90 m. Sulphide layers in the caprock consist that sulphide-producing basin dewatering events and anhy-
mostly of iron sulphides, with vugs and fractures lined with drite caprock accumulation occurred between 157 and
sphalerite, galena, baryte and calcite. The sulphide precipi- 145 Ma, and that widespread sulphide precipitation in the
tates had their origins in deep metal-rich basinal brines that cap is no longer active.
were intermittently expelled from geopressured zones deeper The paragenetic relationships among the metallic miner-
in the stratigraphic section. Brines were channelled upward als and host caprocks at Hockley, Winnfield and other Gulf
along permeable escape structures bounding the diapir stems. Coast salt domes are complex (Kyle 1991). Generally, iron
Sulphides at Winnfield mostly occur as laminar zones sulphide minerals appear to have been the first sulphide pre-
parallel to the tightly intergrown, layered anhydrite grains or cipitates, followed by sphalerite and galena, with the more
as coarse euhedral crystals growing in open space within oxidized sulphur species, such as elemental sulphur,
Fig. 15.42 Diapir-related
France North
mineralisation in the Triassic
Ita
Cap Serrat
allochthon region known as
ly
Spain
Domes district in the Maghreb, Ain Allega Bizerte
Be lif
Tunisia (After Rouvier O.
et al. 1985)
Zouza
Maghreb
ine
ne sar
e zo
dil Lan
He
Nap
p
s zone
e hibar TUNIS
Dom
Ghardimaou
T
Fej-El Medjez El Bab
SoukAhras
-Adoum
iet
Sak Teboursouk
Ouenza Pb-Zn
Le Kef
g h
rou
Fe-carbonate
Me
slo
ula
Bou
ia nt (sideritic)
nis
Guern
Grine Triassic outcrop
Tu
Halfaya
(Halokinetic breccia)
dr a Bou Lorbeus Associated with continental Neogene
Kha Jaber
Bou Sh sediments
elf
zon Possible mineralisation association
e with Neogene volcanism
Diapir-caprock hosted mineralisation

(transitional deposits)
Djebissa Peridiapiric, hosted in Middle Cretaceous neritic
50 km
carbonate, may or may not lie directly adjacent to
Triassic outcrop
anganese sulphides, and the sulphate minerals, forming

m making them stratiform peridiapiric ore deposits
later. This mineralisation sequence happened more than once (Fig. 15.40b). The highly reduced, organic-rich, nature of
in any dome cap. laminated peridiapiric brine-pool sediments means that
Thus, stratiform laminar sulphide textures within the pyrite easily forms as a syndepositional precipitate in any
anhydrite cap rock are believed to represent mineralization adjacent DHAL laminite and its fault-fed surrounds (see
at the salt/ cap rock interface (Ulrich et al. 1984) and are Chap. 9). As this pyrite is buried deeper into the brine/
therefore syngenetic with regard to the enclosing host cap- hydrothermal system it is bathed and altered by escaping
rocks but epigenetic with respect to the encasing sediments. metalliferous basinal brines. Examples of this brine pool
In addition, euhedral sulphide crystals can form simple or DHAL style of mineralisation are typically small to
open-space fillings of late fractures or vugs within the cal- medium scale Pb-Zn accumulations, such as Bou Grine,
cite cap rock; in other cases, earlier generations are brecci- Quern Halfaya and Ain Allegra in the Maghreb, North
ated and cemented by later sulphides or calcite (Kyle and Africa and the Orduña and Murgía domes in Spain
Price 1986a). Calcite may also be intimately intergrown (Fig. 15.39; Bechtel et al. 1996; Jemmali et al. 2011, 2013;
with sulphide minerals. Therefore, calcite precipitation, i.e. Grandia et al. 2003).
calcite cap rock formation, can pre-date, be contemporane- The eastern part of the Maghrebides fold–thrust belt in
ous with, or post-date local sulphide precipitation. The the southern Tunisian Atlas is perhaps the type area for out-
complex textural relationships among sulphide minerals crops of this style of deposit. The region is made up of the
and their host rocks is a function of an evolving geochemi- Nappe zone, which was formed by the stacking of Numidian
cal system in which earlier mineral products are over- flysch along south-verging Tellian thrust sheets and more
printed by pressurized fluids re-entering a zone of earlier importantly for this type of deposit, is the Domes region to
sulphides with entry driven by later halokinetic and fluid the east and at the front of the Nappe zone (Fig. 15.42). This
events. NE–SW trending, roughly 50-km-wide and 300-km-long
zone comprises the Mejerda valley and is characterized by
llochthon-Edge Stratiform Pb-Zn (Sr-F)
A surface exposures of Triassic evaporitic lithologies related to
As well as forming in the diapiric caprock, Pb-Zn deposits the emergence of major thrusts and anticlines core with halo-
can be hosted in organic-rich pyritic and sideritic laminites kinetic salt and its associated breccias and residues
located centripetal to salt sheets or halokinetic breccias, so (Perthuisot et al. 1999).
Fig. 15.43 Peridiapiric Bou a b

Grine Pb-Zn deposit in plan (a)
and section (b) views (After
Bechtel et al. 1998)
100 m
100 m
Cretaceous
“Bahloul Formation”
Bou Grine Triassic (allochthon residues)
s
rbeu
Lo
Mineralisation
Lenticular bodies in cap transition zone
Minor ore in Turonian
5 km Stratiform mineralisation in Bahloul
Semi-massive ore body in Cretaceous sediments
Quaternary Cretaceous Minor ore in Cenomanian
Neogene Triassic
Eocene
The Domes region covers almost 8,000 km2 with a large s eafloor highs created by diapir and salt allochthon emplace-
number of Triassic diapirs and allochthons piercing the ment; and (4) Vein-type deposits (Fig. 15.43).
Cretaceous cover rocks and aligned parallel to the regional The Bou Grine Zn-Pb deposit is situated at the edge of
folding. During the Early Cretaceous the area was a seafloor the Lorbeus diapir, in the Domes region of the Maghreb
trough much like the modern slope and rise of the Gulf of (Table 15.2 and Fig. 15.43a; Rouvier et al. 1985; Charef and
Mexico and was then caught up in the subsequent Alpine Sheppard 1987, 1991; Orgeval 1991, 1994; Bechtel et al.
Orogeny related to the collision of the African and Eurasian 1996, 1998; Jemmali et al. 2013; Bejaoui et al. 2013;
plates. Today remnants of the salt allochthon outcrops and Masrouhi et al. 2014). Bou Grine mineralisation belongs
subcrops are covered by pelagic Cretaceous sediments and in mostly to the first and second groupings, that is, lenticular
places are overlain by a variety of Tertiary sediments, includ- and stratiform (Fig. 15.43b). In this, the Bou Grine deposit
ing phosphates. All these postsalt sediments are variably differs from caprock sulphides in the Gulf of Mexico in that
pierced by diapirs and salt sheets, along with entrained sands, much of the Pb-Zn mineralisation resides not in diapir cap-
carbonate lenses and mottled clays with distributions con- rock but in the adjacent organic-rich limestone laminites of
trolled by highs and troughs related to salt flow. The the DHAL successions in the Bahloul Fm adjacent to the
Cretaceous cover includes a major discontinuity in the upper diapir. As well, in Bou Grine a semi-massive ore body
Albian strata that divides it into two megasequences: (1) an (hanging wall orebody) cuts the Cretaceous series in the
Early Cretaceous to Late Albian succession, and (2) a termi- second megasequence in the Cenomenian-Turonian Bahloul
nal Albian to Palaeocene sequence. There are strong facies Formation. The geologic reserves, with a cutoff value of
and thickness variations in the Cretaceous sediments located 4 % Pb + Zn, are estimated at 7.3 million tonnes of ore at
close to the diapirs, indicating that halokinesis was active in 2.4 % Pb and 9.7 % Zn, equivalent to 880,000 tonnes of
the Aptian and continued into the Tertiary. metal (Orgeval et al. 1989). Mining of Pb-Zn ore at Bou
Pb-Zn (Ba, Sr, F) mineralisation in the Domes area occurs Grine ceased in September 2005.
mainly in Cretaceous cover rocks near the edges of the The zinciferous laminites in the Bahloul Fm in the Bou
Triassic diapirs in deposits such as Bou Grine, Oud Edeboua Grine deposit are made up of mineralised bioclastic clayey-
(Guern Halfaya), Jebel Hamra and Fej-el-Adoum. There are carbonaceous calcimicrites, whose major features are: (1) A
four main mineralisation types in these deposits: (1) regular, in places laminar, bedded structure implying low
Lenticular Pb-Zn-(Ba-Sr)-Fe bodies in the zone of transition energy, subwavebase bottom conditions; (2) Numerous for-
from the Triassic to the Cretaceous host sediment (caprocks); aminifera and other bioclastic components showing open
(2) Stratiform Pb-Zn mineralisation in calcareous laminites, marine affinities; (3) Mineralisation that is in part affected
which are typically rich in organic matter (DHAL deposits in by early diagenetic structures, especially ferroan and cal-
the Bahloul Formation); (3) Pb-Zn-Ba-F and Fe-Pb deposits, citic cements. Sphalerite is present as microcrystals dissem-
with vug-fill features similar to Mississippi Valley Type inated along the bedding planes, or as coalescent flattened
deposits, in the Aptian reef formations that formed atop nodules; it also appears to have been remobilised as
concentrations along fissures and later fractures. Galena in the subsurface by large amounts of anhydrite with a halite
occurs in euhedral crystals along the bedding planes and as core (Hatira and Zouari 1997). Lower Cretaceous strata,
scattered crystals in later fractures associated with calcite which outcrop in the western part of the area, include Aptian–
and schalenblende1. Calcite is observed in fissures that were Lower Albian rocks, which encompass strongly iron-
deformed during compaction, as well as in all the later frac- mineralized (oxidized siderite) micritic limestones and sandy
tures; it also pseudomorphs occasional sulphate crystals clays overlain by thick Orbitolina-bearing limestones. Those
(baryte and anhydrite). limestones are covered by the Albian micrites and marls that
The early nature of mineralisation at Bou Grine is reflected can enclose lenses of coarse-grained platform limestones.
in: (1) Convoluted mineralised laminar beds deformed by The Upper Cretaceous is composed of Cenomanian marl–
intraformational slip, with flow structures; (2) Compaction limestone alternations overlain by yellowish limestones. The
structures around rigid cores of pyrite nodules and galena Upper Cenomanian– Lower Turonian consists of laminated
crystals; (3) Deformed infilled fissures. Sphalerite developed gray to black organic-rich limestones of the Bahloul
as: (1) Early regularly disseminated microsphalerite crystals Formation, with 3–7.5 % TOC. The while the overlying
in a slightly compacted sediment; (2) As almost simultane- Turonian includes marls and banded limestones. The Upper
ous concentrations along sedimentary structures, textures Turonian–Eocene series are made up of the following forma-
and discontinuities; (3) As later concentrations and deforma- tions, all of which outcrop in the SSW part of Jebel Oum
tions of the mineralisation due to compaction and subsequent Edeboua and form the vast syncline of Guern Halfaya. The
fracturing; and (4) As diagenetic remobilised cements that Coniacian–Santonian Aleg Formation is primarily marly.
were either passive infills or provoked by circulation of min- The Upper Campanian–Lower Maastrichtian Abiod
eralising fluids. Formation consists of marl–limestones and limestones. The
Laminites of the Bou Grine region also show high total Paleocene–Lower Eocene El Haria Formation is a series of
organic carbon contents (4–5 % TOC), low organic maturity clays with marl, gypsum and rare limestone intercalations.
(Tmax = 423 °C) and a marine (Type II) phytoplankton origin The Ypresian Metlaoui Formation is a nummulite-bearing
(Bechtel et al. 1996). Hydrocarbon enrichment at particular limestone forming the core of the Guern Halfaya syncline.
levels suggests possible former hydrocarbon reservoirs in The Miocene series starts with coarse conglomerates and
some of the sediments adjacent to the diapirs. Montacer et al. carbonates and continues with micro-conglomerates, which
(1988) showed that sulphate reduction in the laminite facies are well represented at the northern foot of Koudiat el Hamra,
was bacterially mediated, with evolution of the organic mat- and ends with sandstones and sandy clays. The Quaternary
ter probably occurring by in situ maturation of the laminite consists of alluvium and clayey sand aureoles on Miocene
source rock. Their isotope studies support the notion of a conglomerates.
close relationship between the initial metal stock and the The Guern Halfaya Pb-Zn deposit is composed of the
sedimentological/diagenetic setting. Sulphur isotopes also Koudiat el Hamra Oum Edeboua orebodies, which are dis-
indicate development of mineralisation in a closed sulphur tributed around the periphery of NE–SW trending evaporite-
system. Along with Sr and Pb isotopes, they also show the bearing Triassic rocks and closely associated with the
deposit, and its aureole, formed under the influence of an NE–SW and N–S trending normal faults (Fig. 15.44; Bejaoui
organic-rich diagenetic paleocirculation, with Pb derived et al. 2013). The deposits exhibit three styles of mineraliza-
from a single source. tion within the contact Triassic–Upper Cretaceous series,
The Guern Halfaya deposit occurs comprises the perched particularly in the Cenomanian marl–limestone alternations
Guern Halfaya syncline in the east and a tight anticline in the and in the Bahloul Formation and show strong affinites to
west (Figs. 15.42 and 15.44a, b; Jemmali et al. 2013). In the mineralisation styles at Bou Grine, namely: (1) lenticular
northwestern part, there are two longitudinal Triassic out- mineralization in the Cenomanian marl–limestone alterna-
crops defining the Koudiat el Hamra–Jebel Oum Edeboua tions consisting of abundant pyrite with marcasite, sphaler-
zone. The northern–northwestern parts are cut by NE–SW ite, galena and celestite, hosted in halokinetically induced
and N–S trending normal faults, which are at places invaded dolostone breccias as impregnations, substitutions and
by Triassic evaporites. The lithologic succession at Guern replacements of the clayey-dolostone matrix. (2) Stratiform
Halfaya is composed of Mesozoic and Cenozoic sedimen- mineralization in the Bahloul Formation consisting of fram-
tary rocks. boidal and cubic pyrite, disseminated sphalerite and galena.
The Triassic outcrop consist of chaotic gypsiferous clays, (3) Veins, disseminations and stockworks in breccias of
sandstones, black dolomitic-limestones, which are underlain Cenomanian–Turonian limestones and of pyrite, galena and
sphalerite.
Various workers in the Maghreb – Domes Pb-Zn deposits
Compact sphalerite and wurtzite masses of a pale brown colour, occur-
1
ring in concentric layers with reniform surfaces, which also may con- have found that sulphur isotope determinations in the host
tain pyrite and galena. rocks and ores and gangues are consistently indicative of a
a b
X Guern Halfaya Oum Edeboua
X X´
Oum Edeboua Mostly

residues
Koudiat
el Hamra
Salt at
depth
100 m
North 1,000 m
X´
1 km
Quaternary terraces of lacustrine limestones conglomerates and Turonian: Black banded limestones and marl-limestone alternations
coarse sands
Miocene sandstone with calcareous cement and variegated clays Cenomanian: Marls and and marl-limestones
Early Eocene Nummulitic limestones (Metlaoui Fm.) Albian: micritic limestones and black marls
Paleocene- Early Eocene: Marls with black gypsum and limestones Aptian: Sandy clays and carbonates
(El Haria Fm)
Campanian-Maastrichtian marl-limestone and limestones (Abiod Fm.) Triassic: halite and anhydrite, breccia, sandy-clays, gypsum, carbonate
Coniacian-Santonian marls with intercalations of limestones (Aleg Fm.) Transitional contact (brecciated residuals and lateral caprocks
± rauhwacke)
Fig. 15.44 Geological map (a) and schematic NW–SE cross-section (b) of the Guern Halfaya area where the Oum Edeboua mine and Jebel Guern
Halfaya are located (After Jemmali et al. 2013)
bacterial sulphate reduction set of processes acting on sul- d iagenetic pyrite from the Bahloul Formation, with higher
phate evaporites, organics and hydrocarbons in the vicinity concentration in laminites, which were deposited in parts of
of the various Triassic salt structures (Jemmali et al. 2013; the Bahloul deep seafloor that were Cretaceous DHALS.
Bejaoui et al. 2013 and references therein) For example, More positive δ34S values in base-metal sulphides from
gypsum, celestite and baryte in Triassic rocks at Oum the Oum Edeboua and Bou Grine mines may suggest an
Edeboua have δ34S values ranging from 12.8 to 15.0 ‰, additional sulphur input during abiotic thermally-driven sul-
whereas anhydrite in Triassic evaporite (from drill core) at phate reduction (TSR) of Triassic sulphates at depth. But,
Tabbet Lahsan (Fej-el-Adoum district) yielded δ34S values given the likelihood of lower temperatures at mineralisation,
ranging from 14.2 to 15.6 ‰ (Fig. 15.45). These data are as documented in inclusion studies, it is less likely that TSR
similar to typical δ34S values of (a) about 16 ‰ obtained was a significant supplier of sulphur. TSR typically requires
from anhydrite and celestite in Tunisian Triassic evaporite temperatures well in excess of 120–130 °C and produces sul-
diapirs, (b) about 15 ‰ obtained from regional Tunisian sulphate–sulphide fractionations that typically range from ~0 to
phates and (c) 11–17 ‰ in Triassic marine sulphates 10 ‰ (Chap. 9). Documented homogenization temperatures
(Fig. 15.45a). This consistency implies Triassic evaporites for mineralizations at Oum Edeboua and Bou Grine are
are likely sources of sulphur that can be associated with sul- 95–130 °C (Kassaa 1998) and 75–100 °C (Orgeval 1994).
phate minerals in Triassic strata. Bacterial sulphate reduction (BSR) typically occurs at tem-
Galena in mineralized Triassic–Upper Cretaceous rocks peratures lower than 110 °C and produce sulphate–sulphide
at Oum Edeboua yielded δ34S values of 3.3–9.5 ‰, whereas fractionations that typically range from 15 to 60 ‰ with
galena and sphalerite in mineralized Cenomanian–Turonian respect to seawater sulphur. Thus, both the sulphur isotope
and Turonian rocks at Bou Grine yielded δ34S values of 2.6– ranges and mineralisation temperatures favour BSR over
9.4 ‰. Such sulphur isotope compositions overlap sulphur TSR, with marine-derived sulphates and pyrite as the likely
isotope values of orebodies at Bou Grine (Fig. 15.45b). This sulphur sources. The significance of BSR is further sup-
implies the same or similar source of sulphur in the base- ported by the presence of bacterial relics in the Oum Edeboua
metal sulphide deposits in both the Oum Edeboua and Bou mine (Kassaa 1998) and the Bou Grine mine (Orgeval 1994).
Grine with Triassic seawater brines and associated evapo- In addition, pyrite associated with galena in the Oum
rites as likely ultimate sources of sulphur. In addition, Edeboua mine exhibits framboidal texture, which is
Fig. 15.45 Sulphur δ34S isotope

a
values in the Domes region of the Cretaceous seawater
Maghreb. (a) Spread of sample Triassic seawater
fields mostly collected from sites
in Bou Brine, Guern Halfaya and Guern Halfaya sulphates
Jebel Hamra regions. (b) Tabbet Lahsan anhydrite
Distribution (frequency) plot of
Bou Grine organic matter
site specific values of sulphides Bou Grine
(galena + sphalerite) and sulphates sulphates
(gypsum + baryte + celestite +
Celestite caprock
anhydrite) from the Oum
Edeboua, Bou Grine and Tabbet Anhydrite caprock
Lahsan deposits (After Jemmali Regional sulphates
et al. 2013 and Bejaoui
et al. 2013)
Jebel Hamra galena

Jebel Hamra sphalerite
Guern Halfaya sulphide
Guern Halfaya sulphide
Bou Grine F3
Bou Grine F2
Bou Grine F1
Fedj-el-
Adoum
−5 0 5 10 15 20 25 30 35
δ34Sv-CDT (‰)
b
Galena-sphalerite at Bou Grine
4 Galena-sphalerite at Oum Edeboua (Guern Halfaya)
Gypsum at Oum Edeboua (Guern Halfaya)
Baryte-celestite at Oum Edeboua (Guern Halfaya)
Anhydrite at Tabbet Lahsan (Fej-el-Adoum)
3
Frequency
0
0 2 4 6 8 10 12 14 16
δ34Sv-CDT (‰)
characteristic of BSR-linked galena at several Pb–Zn 15.667–15.685 and 38.806–38.889, respectively (Jemmali
deposits such as in Bleiberg, Austria and Navan, Ireland. et al. 2013). This suggests a single source reservoir of Pb at
But, was the ultimate source of the metals local or more some depth in the upper crust. The syn-diagenetic mineraliza-
distal? The present Pb isotope data are homogeneous with tion in the Bahloul Formation and the calculated age from the
206
Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of 18.723–18.783, Pb isotopic data suggest an Upper Cretaceous age for the Pb-Zn
deposits in the Guern Halfaya and Bou Grine areas. During this The Domes region, at its halokinetic Cretaceous begin-
period, NE-SW to ENE-WSW trending regional extensional nings, was a submarine slope at the edge of a structural
tectonic structures likely favoured migration of mineralizing high. At that time, other than near a few local diapirs and
fluids and eventual deposition at Guern Halfaya and Bou Grine salt allochthons, this area never seemed to have shoaled
in metal-rich brine conduits in redox positions controlled by a sufficiently for a true shallow water carbonate platform to
combination of salt focusing and associated faulting. have developed. The organic-rich sediments probably
Across the Domes region a Pb-Zn deposit’s locality and accumulated in this region only in the deeper areas of rim
host rock geometry was controlled by a feedback between synclines about the active diapirs and salt sheets, hence the
salt flow and the creation of Cretaceous deep seafloor brine localisation of the mineralisation to laminites in the peridi-
sumps in response to synkinematic movement of the sea- apiric areas. Throughout the metal evolution history the
floor. Thus halokinesis and the associated allochthons con- salt was halokinetic, first in an extensional and then in a
trolled: (1) Local deposition of conglomerates and breccias compressional (squeezed-diapir salt thrust) tectonic asso-
adjacent to the highs atop the growing salt allochthons, (2) ciation. Only later with the withdrawal of the seaway did
Local deposition of organic-rich pyritic laminites in areas of arid Cenozoic sabkha and salina deposition come to
brine ponding (DHAL) on locally deepened seafloor, (3) dominate.
Tilting of panels of sediments by listric faults activated by
the emplacement of allochthons and diapirs, (4) Overlapping vaporite-Cored Thrusts and MVT’s
E
of sedimentary bodies by shoal/shelf progradation or trunca- in the Maritimes Basin, Canada
tion. Halokinesis also led to marked thickness variations of Beyond the very obvious evaporite-related and Cretaceous
the various facies across the regions via the repetitious puls- hosted peridiapiric Pb-Zn deposits of the Domes region
ing of the active diapir and its ongoing dissolution. and the Tertiary-hosted Gulf of Mexico caprocks, there are
In addition to Pb and Zn, recent work by Dill et al. (2014) a number of other older carbonate platform-hosted MVT
has related significant accumulations of Sr and F to the accumulations in compressional traps, which are tied to
peripheries of salt structures in the Domes Region and their salt allochthons or salt-cored thrust décollements. One of
associated brines. Shallow halokinetic units create a basin- most obvious of these occurs in the Maritimes thrust belt
and-swell topography in any landscape and so provided the of Canada, tied to the strike-slip system centred on the
local and regional unconformities to which many of the Sr Minas Geofracture and subsidiary thrusts (Fig. 15.46;
and F mineral deposits are related. Syndiapiric salt dissolu- Waldron et al. 2013). These various metal accumulations
tion and welding also created carrier brines and focused their include the well known Gays River and Jubilee/Ainslie
upwelling. Dill et al. argue that there are five mineralizing and Walton deposits (Fig. 15.46a) Gays River and Jubilee
processes or stages, each with characteristic sedimentary ore in most current ore deposit classifications are typically
textures related to subsurface salt movement and ore pigeonholed as type examples of MVT (Mississippi Valley
emplacement: (1 +
2) Early- and late-stage replacement Type deposits; e.g. Paradis et al. 2007; Taylor et al. 2009).
(“zebra rocks”), (3) hydraulic fracturing (“fitting breccia”), Siderites and barytes of the Walton-Magnet baryte deposit
(4) remobilization (“spinifex structures”), and (5) open- are also part of this halokinetic Maritimes association, but
space filling (“caves and vein-like deposits”). All can be were discussed earlier as an examples of baryte accumula-
related to the coming and going of evaporite beds and flows. tion in fault-related halokinetic alteration haloes (Fig.
Basinal brines from Mesozoic aquifers delivered Pb, Zn, 7.95a) and so will not be considered in detail in this metals
Cd, REE, Y, Hg, and Se, while Sr, Cs, Be, Li, Cu and Co were chapter.
perhaps derived from Cenozoic salinas across the Neo-Tethyan Because this tie of the Pb-Zn mineralisation to an evapo-
basin (Dill et al. 2014). Mixing of Mesozoic and Cenozoic rite allochthon décollement is so obvious in Gays River and
brines between 28 and 19 Ma drove emplacement of Sr–F Jubilee (Fig. 15.46b), I now discuss them the current sec-
minerals at temperatures below 200 °C, under strongly alka- tion dealing with undeniable peridiapiric-salt allochthon
line conditions. Epigenetic polyphase Sr–F deposits bearing Pb-Zn associations. But, under all current definitions of
base-metals which are closely related to salt domes (Tunisian- MVT deposits, they definitively belong also to the MVT
Type) can also be traced into epigenetic monophase Sr depos- pigeonhole. We shall come back to classifications of vari-
its within bioherms (Cyprus-Type) largely devoid of Pb, Zn ous low- temperature ore deposits at the end of this
and F. Moving eastward in the Domes region, syndiagenetic chapter.
monophase Sr deposits in biostromes (Gulf of Mexico-Type)
herald the beginning of Sr concentration in Miocene sabkhas ays River, Nova Scotia
G
of the Neo-Tethys. Dill et al. (2014) argue their work bridges The Gays River Zn-Pb deposit of southern Nova Scotia,
the knowledge gap between epigenetic carbonate-hosted Canada has reserves ca. 2.4 million tonnes at 14.3 % Zn and
MVT and syndiagenetic evaporite deposits. 6.3 % Pb of either massive or disseminated ore. The deposit
Fig. 15.46 Pb-Zn in the a

Maritimes Basin, Canada (a)
Map of Nova Scotia showing North
Highlands massif
Carboniferous sub-basins, major Cape
thrust fault traces and the Breton
Maritimes sub-basins
Antigosh, Cape Breton and highland
Cobequid highlands. (b) Fault trace
Schematic cross-section showing River Denys sub-basin
relationships between regional Major base metal deposits
stratigraphy, mineralisation and
the position of the Ainslie Antigosh
Detachment (After Lynch et al. Cumberland sub-basin
1998). Note that the timing of the sub-basin
detachment is indicated by a gap Jubilee
in the Windsor Group
stratigraphy in the Gays River
region created by the presence of highland
a salt unit and salt flow. The thick Cobequid
salt, when it was formerly present Cobequid-Chedabucto fault system
at the level of the detachment, Walton
acted as a focus for the up-dip Minas
channelling of escaping basinal geofracture
Kennetcook
fluids sub-basin
Gays river Antigosh ean
Oc
highland tic
Shubenacadie
Atlan
sub-basin
Mubquodoboit
Halifax
sub-basin 50 km
b NW SE
Present erosion
Pictou Broad cove formation surface
group Un am
Inverness formation e d r ed
Morto b ed
n grou s in
p o ff sh
Cumberland Port hood formation o re
group
e
Pomquet formation Ainsli nt
Mabou
e t a c hme
group d
Hastings formation
Upper
Windsor Middle Gays river
group Jubilee formation
Lower
setting (gays river setting)
Macumber Pre-carboniferous
Horton formation rocks
group
Escaping metalliferous Thick halokinetic salt of lower
basinal fluids Windsor Group feeding halite into
Ainslie detachment/décollement.
Its dissolving underbelly acts as
Fisset Bk.
the focus for escaping basin fluids.
formation
is located in the Meguma Terrane of southern Nova Scotia hydrocarbons, and not the adjacent permeable dolomitised
and is hosted by Windsor Group (Visean) carbonate/evapo- Carboniferous carbonate buildup, that controlled the locality
rites that were deposited in several sub-basins of the larger and the process of mineralisation. The massive ore zone is
Maritimes Basin of eastern Canada (Fig. 15.46a; Kontak and directly adjacent to the sulphate evaporite bed and is made up of
Jackson 1995; Sangster et al. 1998a, b). fine-grained, beige coloured sphalerite and medium to coarse-
In terms of ore focusing, it was the adjacent dissolving and grained galena. The massive ore is only found along the
sealing evaporite units, along with associated entrapped carbonate-evaporite contact (Fig. 15.47a). Disseminated ore,
a b δ34S (‰)
Galena Sphalerite
River alluvium 8 10 12 14 8 10 12 14
Quaternary
Glacial
Sand till
Sand and
gravel Glacial till Massive ore
Gays river
Altered Dolomite formation
Karstic
gypsum Low-grade
Massive ore
zinc ore
(carboniferous)
Windsor group
Massive ore
Disseminated ore Disseminated &
Anhydrite net-textured
“Trench” sediment (karst fill)
Breccia ore
Basal breccia
Sedimentary breccia
Not to scale (former evaporite)
Basal breccia
Fig. 15.47 Gays River Deposit, Nova Scotia (see Fig. 15.46a for loca- gypsum-anhydrite residue as an indication of the position of former salt
tion). (a) Schematic cross section showing intimate relationship allochthon/décollement (in part after Kontak et al. 1994). (b) Sulphur
between Pb-Zn mineralisation, ore textures, and the position of the isotopes classified using ore textures (After Sangster et al. 1998a, b)
a b
10
4 Pyrite-marcasite
Cm
Ore-related calcite Dm Sm
Pre-ore Sphalerite
(gangue)
0 dolomite
8 Galena
Gays River
Siderite Baryte
−4 Theoretical ore-
related siderite Walton
Ore-stage
−8 6
Frequency
δ13CPDB
−12 Ore-related
anhedral
calcite 4
−16 Pre-ore
Jubilee
−20 2
Post-ore
−24 Pre-ore
fibrous calcite
0
−16 −12 −8 −4 0 −8 −6 −4 −2 0 2 4 6 8 10 12 14 16 18
δ18OPDB δ34S(‰)
Fig. 15.48 Isotopes in selected Pb-Zn deposits of the Maritimes Basin oxygen values indicate higher burial temperature). (b) Sulphur isotopes
(a) Carbon and oxygen plot-fields of pre-ore dolomite (Dm), calcite of pre-ore, ore and post-ore stage mineral precipitates in Gays River
(Cm) and siderite (Sm) as well as ore-gangue calcites (more negative (After Sangster et al. 1998a, b)
adjacent to the massive ore and its evaporite seal, is hosted by (Fig. 15.47b). When carbon oxygen values in the associated ore
Visean-age, dolomitised carbonate rocks that are part of a series gangue calcite are plotted and compared with C-O plotfield of
of carbonate banks within the Gays River Formation. Both the the earlier carbonate cements it is obvious that the fluids carry-
galena and sphalerite show similar sulphur isotope values indi- ing the metals and gangue calcite are hotter and separate to the
cating they come from a similar, if not the same, sulphur source authigenic carbonate cements in the host dolomites (Fig. 15.48a).
Jubilee Walton
200 Gays river 80 60
150 Calcite 60 Calcite

40
Sphalerite Sphalerite
Frequency
Frequency
Frequency
100 40
20
50 20
0 0 0
80 120 160 200 240 280 320 80 120 160 200 240 280 320 80 120 160 200 240 280 320
Homogenisation T (°C) Homogenisation T (°C) Homogenisation T (°C)
120 25 80
100 20 60
80
Frequency
Frequency
15
Frequency
60 40
10
40
20
20 5
0 0
0 4 8 12 16 20 24 28 32 0 4 8 12 16 20 24 28 32 0 4 8 12 16 20 24 28 32
Salinity (wt % eq. NaCl) Salinity (wt % eq. NaCl) Salinity (wt % eq. NaCl)
Fig. 15.49 Summary of fluid inclusion temperature and salinity in the three main deposits; Gays River, Jubilee and Walton (After Sangster
et al. 1998a, b)
The Carboniferous sediments that host lower percentages indefinitely on August. 15, 1981, as a result of continuing
of mineralisation than the evaporite contact initially grew on problems with ore grade continuity and underground water.
fault-controlled paleotopographic highs that were underlain So today, the Gays River mine is now abandoned and flooded.
by Lower Palaeozoic meta-turbidites of the Meguma Group, The mine was only operational for 4 years from 1978 to
sometimes with local intervening breccia units (Horton 1981. This was more than three decades ago, in a time prior
Group). The breccias contain fragments (centimetre to metre to our current understanding of diagenetic significance of
scale) of Meguma Group lithologies within a dolostone various evaporite textures.
matrix and are likely rauhwacke units (Figs. 15.46b and In the context of likely evaporite associations, the deposi-
15.47a). The disseminated, lower-grade mineralisation infill- tional setting of the carbonate banks hosting low-grade min-
ing porosity in the dolomitised carbonate banks consists of eralisation and located adjacent to the main ore body is
yellow to orange, millimetre-scale sphalerite and euhedral interesting. In the 1970s and 80s these banks were inter-
galena coating the walls of larger pores and cavities. Trace preted as shoalwater carbonate platform build-ups. But the
amounts of Fe and Cu sulphides as well as fluorite and baryte abundance and perfection of preservation of filter-feeding
are also present. brachiopods and bryozoans in many of the mounds was puz-
To generate improved predictive exploration models zling in a supposed shoal water photic community. The Gays
based on a Gays River analog, requires that the evaporites at River mounds were reinterpreted as vent-fed chemosynthetic
the mineralised contact are characterised in a basinal diage- mounds by von Bitter et al. (1992). Such an origin is more
netic context in as much, if not more, detail than the carbon- consistent with the distribution of the massive ore and with
ates that host the lower ore grades in adjacent strata. the obvious peridiapiric/allochthon distribution of the evapo-
Construction of surface plant and mill processing facilities rite facies.
commenced in 1978, and the mine was further developed to The main ore-hosting authigenic dolomite replaced its
support an intended production rate of 1,350 t per day. Mill limestone precursor prior to the mineralisation event (pre-ore
production commenced in October 1979, and by mid- dolomite as seen in Fig. 15.48; Savard 1996). Dolomitization
summer of 1981 a total of 554,000 t of ore and 272,000 t of played a role in ground preparation, but was not directly tied
waste had been mined. Throughout this period, efforts to to the Zn- and Pb-rich basinal fluids that mineralised the
achieve the full production rate, as well as efforts to mine Gays River deposit. Stable isotopes show clearly that the
areas of higher grade mineralization were continually main dolomite in carbonate buildups predates the minerali-
thwarted by the combination of an extremely complex geo- sation at Gays River (Fig. 15.48a). Fluid inclusion work on
logical setting and severe hydrological problems. Throughout the coarse-grained sphalerites, and rare earth element pro-
the life of the mine, water influx from karst piping tied to files in late stage carbonate cements associated with the min-
aquifers in the glacial overburden was an ongoing problem. eralisation, indicate that the mineralising fluids were warm
Production operations at Gays River Mine were suspended (<120–140 °C), saline brines (>20–24 wt% NaCl)
a b c
Cobequid Bay Ore Ore R std. dev.
80 Smectite 2.0 °
60
R
° 1.5
Relative fraction (<2µm)

40
Shubenacadie sub-basin 20 Kaolinite & R mean
°
corrensite 1.0
C A B C A B C
D
A B Ore Ore R std. dev.
80 2.0 °
Mubquodobott 60 R
Smectite
° 1.5
sub-basin 40
Gay river 0 15 Kaolinite & R mean
20 °
mine corrensite
E 1.0
km
D B E D B E
Fig. 15.50 Clay mineral and vitrinite reflectances as indicators of (b) Relative abundance of authigenic kaolin ± corrensite versus smectite
elevated temperatures associated with focused fluid flow in the Gays River in the vicinity of the orebody. (c) Variation in the mean reflectance and its
Pb-Zn deposit. (a) Map showing position of sections ABC and DBE. standard deviation with respect to the orebody (After Heroux et al. 1996)
(Fig. 15.49; Akande and Zentilli 1984; Chi and Savard 1995; Inclusion studies in sphalerite and pre- and post-ore cal-
Kontak and Jackson 1995; Sangster et al. 1998a, b). 40Ar/39Ar cite also indicate that the mineralising fluids were hypersa-
dating places the mineralisation event at 300 Ma, while other line basinal brines with locally elevated temperatures
isotopic data (Sr, C, O, Pb) indicate that the mineralising flu- (Fig. 15.49; Chi and Savard 1997, 1998). The Nadeficit- Caexcess
ids were derived by fluid flushing of the underlying plot shows the mineralizing brines were not tied to meteoric
meta-turbidites of the Meguma Group or of the derived detri- waters, rather they were a product of mixing of halite-
tus that resides in the Devonian-Carboniferous Horton Group dissolution fluid and evaporated seawater (indicated by lines
and carried to the sulphate-rich precipitation site by saline a and b in Fig. 15.51, respectively).
basinal brines (Kontak 1998; Kontak et al. 1994). Rock matrix relationships, and the salt-décollement-
Heroux et al. (1994, 1996) found that the elevated tem- adjacent position of the massive and disseminated ore zones
peratures and hydrocarbon contents of the mineralising brines in the Gays River deposit (Figs. 15.46b and 15.47) imply
also altered the clay mineralogy and organic maturity profiles evaporite impermeability and the fractionated base-salt
of the adjacent carbonate/claystone matrix (Fig. 15.50a, b). sulphate-dissolution residuum position controlled the pre-
The Gays River deposit is associated with smectite replace- cipitation position of the metal sulphides. That is, the pres-
ment of well crystallised detrital illite and chlorite. This forms ence of massive ore at the host-evaporite (anhydrite) contact
a diagenetic halo around the main ore zone, while authigenic is a response to the focusing effect of the impervious evapo-
kaolinite and chlorite-corrensite typify the alteration halo in rites, and that the basal anhydrite along the underbelly of the
the immediate vicinity of the ore zone (Fig. 15.50b). Vitrinite thick evaporite package was probably the major source of
reflectance (Ro) values and their absolute variability increase sulphur. It is highly likely that halokinetic evaporites once
in the host rocks toward the ore zone (0.8–1.88 %) and show covered the Gays River carbonate buildup and formed a
a relatively low Ro within the ore zone. That is, the Ro exhibits regional focus and likely seal at the time of ore emplace-
an anomalous suppressive effect with respect to depth of ment. The allochthonous salt mass stabilized the precipita-
burial at the mine site, suggesting a chemical alteration of the tion interface and allowed mineralising solutions to pond at
organic matter in the mineralised zone. the contact with the permeable dolomite host rocks beneath
Alternatively, as in other oil-generating basins in the it (Fig. 15.47a).
world, vitrinite suppression can indicate overpressuring or Later the evaporite seal was breached by meteoric disso-
the occurrence of H-enriched liptinites. The highest Ro val- lution, perhaps in the Cretaceous, and the karst system is still
ues are associated with mosaic (recrystallised) textures in the active today (McKee and Hannon 1985). The effect of this
host carbonates and outline a thermal anomaly in the region, breaching clearly has a surface expression in the present gla-
probably related to the evaporite-focused escape of basinal cial landsurface in the presence of numerous collapse dolines
brines. Heroux et al.’s work suggests that rock matrix rela- in the tills and related lithofacies thicknesses and distribution
tionships between clay mineralogies, organic anomalies and above the deposit. These Pleistocene sediments infilled an
the mineralisation as defined at the Gay River Mine at the evaporite karst landscape. Fluid temperatures in excess of
mine can be used as sedimentological guides in the explora- 120 °C seen in the ore sphalerite and galena inclusions
tion for base-metal sulphides in this area and elsewhere. implies thermochemical sulphate reduction occurred much
Fig. 15.51 Nadeficit -Caexcess plot 2,500

of inclusion fluids from
sphalerite and syn- to post-ore Sphalerite
calcite in the Gays River MVT ge
2,000 Syn- to post-ore calcite han
deposit (Data from Savard and exc
Chi 1998; assumed Na
2
salinity = 24 wt%). Lines a and b for
indicate the predicted position of 1,500 Ca
1
Ca-excess (meq / l)
a
a fluid with a [Cl] = 150 g/l
originating from halite-
dissolution and seawater 1,000 b
evaporation, respectively
2,500
0 SW
Seawater evaporation
olution
Halite diss
−500
−1000 −500 0 500 1,000 1,500 2,000 2,500
Na-deficit (meq/l)
earlier than telogenesis, perhaps during or slightly later than interstratified limestone and anhydrite, with a massive anhy-
the main thrust décollement and well prior to karst develop- drite unit capping the sequence. The deposit extends over
ment. That is, all mineralisation and associated gangue cal- 2.75 km2, and contains 0.9 million tonnes of 5.2 % Zn and
cite precipitation was mesogenetic and not telogenetic 1.4 % Pb, and is hosted in the laminated limestones and brec-
(Figs. 15.48a and 15.49). Ore was precipitated as a passive cias of Macumber Formation (basal Windsor Group). The
infill in whatever porosity was available at the time in the Macumber Formation is the lateral equivalent to the Gays
periodically overpressured subsurface TSR mixing zone River Formation that hosts the Gays River deposit.
(Chi et al. 1995; Heroux et al. 1996). The Macumber Formation in the Jubilee deposit is made
It was the evaporite-organic-sulphate TSR interface (not up of three main lithofacies: (1) A micritic lithofacies that
BSR) that focused the mineralising fluids. Pre-ore dolomiti- locally contains ooids, oncolites and pellets, (2) A finely
sation of the matrix was likely a response to the crossflow of laminated lithofacies, and (3) A mineralised breccia facies
the same evaporite-focused plumbing that later focused hot- (Fallara et al. 1998). The facies transition between the first
ter mineralising hydrothermal brines. Dolomitisation is not a two lithofacies is gradational and concordant, whereas the
direct indicator of metal emplacement. The main economic contact between the finely laminated lithofacies and the min-
role of dolomitised carbonate in the Gay’s River deposit was eralised breccia is sharp. The breccia is conformable at the
that of passive host to the mixing of mineralising solutions, top of the Macumber Formation and never crosscuts it
entrained hydrocarbons, and the thermochemically reduced (Fig. 15.46b). The deposit is located near two faults inter-
sulphur derived from the dissolving evaporites. Prior dolo- preted as normal synsedimentary faults. Armstrong et al.
mitisation events, likely related to less evolved escaping (1993) suggested the mineralisation was a low temperature
basinal brines, or even syndepositional brine reflux, may sulphide system related to the former presence of
well have enhanced the aquifer properties of the ore host in hydrocarbons.
the vicinity of the evaporite aquiclude. Overlying the breccia at the base of the Carrols Corner
Formation is a transitional zone of interbedded limestone
J ubilee Zn-Pb Deposit, Nova Scotia and evaporite. Some of the limestone is replaced by anhy-
The Jubilee Zn-Pb prospect, Nova Scotia, is located 2 km drite in the basal part of the transition zone. The overlying
southeast of Little Narrows village, near the quarry of the Carrols Corner Formation is a thick sequence of anhydrite
Little Narrows Gypsum Co. (Fallara et al. 1998). Like Gays and gypsum, up to 300 m thick. The breccia that hosts the ore
River, it is one of many lead and zinc shows in Early has been variably interpreted as: (1) An evaporite solution
Carboniferous limestones of the Maritime region, eastern collapse breccia, (2) A tectonic breccia that was the result of
Canada (Fig. 15.46a; Armstrong et al. 1993; Coron 1982). At normal faulting and magmatic intrusions that created a horst
Jubilee, a laminated limestone is overlain by transitional, structure, and (3) A collapse breccia produced by the
Table 15.11 Characteristics of the three breccia styles that constitute the various breccias that occur in the basal Windsor Formation, aka
Pembroke Breccia sensu lato
Early Late
Early (synsedimentary) Tectonic Karstic
% clasts 60–95 % 40–75 % 40–90 %
Nature Laminite Laminite Laminite, breccia, red mudstone,
various siliciclastics (siderite in
Walton)
Rounding Some None Some for mudstone
Size <1 mm–10 cm >1 mm–5 cm 1 mm–50 cm
Matrix cement Crushed fragments and lime mud Crushed fragments and fibrous Carbonate fragments, red
calcite cement siliciclastics, lime mud, calcite
cement
Sedimentary structures Soft sediment deformation, Jig-saw puzzle like textures Coarsening and fining upward,
concave upward shear failure (crackle breccias) graded matrix
planes, Cyclic pattern
Diagenetic elements Pre stylolite, prior to secondary Post secondary dissolution Dissolution surfaces on clasts.
dissolution Oxidised rims and matrix.
Post-stylolite (post siderite) and
post sulphides
Timing of formation Pre-burial and hydrocarbon Syn-burial and hydrocarbon Post-burial and other breccias
migrations (Pre-Visean) migration (locally) (Namurian (Westphalian or younger?)
Westphalian)
Unit Macumber Macumber Pembroke (sensu strictu)
After Lavoie et al. (1995, 1998)
s ubsurface dissolution of evaporite during the circulation of equant sparry, or locally radiaxial fibrous calcite, together
the mineralising fluid. with sulphides. Liquid hydrocarbons and solid bitumens are
Work on breccias in the lower part of the Windsor Group abundant, particularly within sulphide-rich domains, and
by Lavoie et al. (1995, 1998) and has shown that all three also occur as inclusions within sphalerite and baryte crystals.
origins are correct. What previously was loosely called the Stable isotope data clearly show the metals in the miner-
Pembroke Breccia (sensu lato), and considered a single unit, alised matrix breccia were derived from escaping basinal
does in part host the ore. The problem is that the Pembroke brines (Armstrong et al. 1993).
Breccia is a term that is used to describe all breccias in the In contrast, the evaporite solution breccia that forms via
region, when in reality it does not describe a single l ithofacies surface related dissolution of the evaporites is a classic rock
or a formation specific unit. Rather, the term Pembroke matrix collapse breccia; it contains clast-supported, chaoti-
Breccia has been applied to three temporally and genetically cally distributed, centimetre-sized, subrounded to angular
distinct breccia bodies (Table 15.11). There is a pre-ore syn- fragments of the Macumber Formation. Most of the clasts
sedimentary carbonate slope breccia, a syn-ore tectonic brec- retain their original laminated texture and have not been
cia related to the Ainslie Detachment, and a modern karstic extensively recrystallised. According to Hein et al. (1991),
post-ore evaporite solution collapse breccia related to the the clasts in the breccia fell into open spaces created by dis-
modern groundwater system. The formation of the syn-ore solving evaporite interbeds and interlaminae. The interclast
breccia was aided by pressure buildup and hydrofracturing matrix is made up of finely comminuted rock fragments of
beneath the regional evaporite cap; processes which also the overlying Macumber Formation. This rock matrix brec-
facilitated the formation of the regional subsalt detachment cia can be present in cored intervals that also intersect miner-
(Ainslie Detachment) at the base of the Windsor Group alised intervals, hence the earlier confusion in separating the
(Fig. 15.46b). two styles of breccia.
The main ore host is this syntectonic hydraulic breccia; it The NNW-trending faults that cut the Jubilee deposit have
is a mineralised-matrix breccia is that contains pyrite, marca- been shown by Hein et al. (1991) to be synsedimentary and
site, sphalerite, galena and baryte, in addition to burial cal- continued to be active solution conduits after they were over-
cite and siderite. Its clasts have been extensively recrystallised thrust by a thick evaporite seal. In the early stages, prior to
and commonly retain finely disseminated sulphides. the thrust emplacement of the evaporite, the faults supplied
Anhydrite is absent, as is true sedimentary interclast matrix. nutrient-rich waters that vented on to the sea floor. This
Instead, the recrystallised breccia fragments are cemented by allowed enhanced carbonate sedimentation on the deep sea
Fig. 15.52 Sulphur isotope ranges for various mineral

phases in the Walton deposit and its evaporitic sulphate δ34S(‰)
surrounds, shaded central panel shows sulphide range for
−20 −10 0 +10 +20 +30
the sphalerite and galena in the Gays River mine (After
Sangster et al. 1998a, b)
Sulphur in Country Rocks
Pyrite, Horton Bluff Fm.
Anhydrite in evaporites Windso
Gypsum in evaporites Groupr
Sulphur in epigenetic deposits

Anhydrite veins near evaporites Sulphur in Country Rocks
Gypsum veins near evaporites
Baryte in veins & pods
Massive baryte
Pyrite
Galena
ore sulphides
Chalcopyrite Walton
Gays River
Tennanite deposit
Proustite-pearcite
Galena (late)
−20 −10 0 +10 +20 +30

34
δ S(‰)
floor in the vicinity of the vents, where chemosynthetic c omposition of 0.3 % Cu, 2.5 % Pb, 0.2 % Zn, and 31.2 %
communities of fossil tubes, serpulid and spirorbid worms, BaSO4, comprises baryte and variable sulfide contents. Type
conularids, brachiopods, bryozoa and ostracods flourished II, comprised of sulphides only, has a composition of 0.5 %
(von Bitter et al. 1990). Later, during burial diagenesis, and Cu, 0.5 % Pb, 0.1 % Zn, 51 g/t Ag, and no baryte. Type I ore
after thrust emplacement of the evaporite cap, the faults forms a roughly conformable sheet which straddles the upper
acted as conduits that carried metalliferous basinal fluids up Macumber-lower Macumber contact and contains lenses of
into the base of the anhydrites where the sulphides then Pb- and Cu-rich ore. Type II ore is most commonly associ-
precipitated. This explains why, even though it is syn-ore ated with the upper Macumber mounds where it forms large
tectonic breccia, the mineralised breccia unit is thickest and pods which cut the type I ore zone. Type II ore also occurs
most heavily mineralised adjacent to the Jubilee Fault. within the underlying Horton Group sandstones but only
The Walton Ba-Cu-Pb-Zn-Ag deposit produced some 4.5 where the upper Macumber mounds have developed. There
million metric tons (Mt) >90 % BaSO4 and 412,850 t @ is also a stratigraphic zonation in metal content in as much as
0.52 % Cu, 4.28 % Pb, 1.29 % Zn, and 350 g/t Ag (Sangster all metals are higher, on average, in the lower Macumber
et al. 1998a). It is hosted by Visean age carbonate rocks of the relative to the upper Macumber.
Macumber Formation and its associated breccia (Fig. 7.95a). The host stratigraphy is steeply dipping and faulted and
The Macumber Formation in the Walton area is divided into both features are considered to be post-ore events. Karsting,
two units, the lower Macumber, a laminated carbonate unit which also postdates mineralization and probably folding,
9–12 m thick and the upper; Macumber, a synsedimentary car- has removed portions of the stratigraphic upper parts of the
bonate breccia that forms two mounds up to 21 m thick. deposit. The cavities produced by this process are now par-
Outside the immediate mine area the carbonate is either tially filled with sand and limestone breccia. This work by
limestone or dolostone; the Macumber Formation surround- Sangster et al. considers the ore host breccias to be deposi-
ing the deposit has been altered to manganiferous siderite. tional carbonate slumps and did not consider the possibility
Although three textural types of siderite are recognized, little that the prepared ground could have been a response to halo-
variation in bulk chemical composition is evident among kinesis and salt dissolution (Fig. 7.95a)
them. Minerals were deposited in the sequence: baryte, Gays River, Jubilee and Walton deposits are part of a
pyrite-marcasite, sphalerite, galena, tennantite, chalcopyrite, larger regional scale Zn-Pb-baryte-evaporite association,
and (para)rammelsbergite. Each mineral replaces earlier with consistent sulphur isotope, carbon-oxygen isotope and
minerals to varying degrees. Sulphur isotope data from the fluid temperature ranges, related to evaporite focused out-
deposit are given in Fig. 15.52. flow interfaces. These were active during dewatering and
Based on baryte and metal content, two main ore types salt-lubricated thrusting as the various tectonic sub-basins of
are defined (Sangster et al. 1998a). Type I, with a bulk the Maritimes Basin of eastern Canada were created
(Lynch et al. 1998; Sangster et al. 1998a, b, Waldron et al. ississippi Valley Type (MVT) Deposits
M
2013). Throughout central Nova Scotia, Pb-Zn and baryte and Bedded Platform Sulphates?
deposits are tied to faults and salt structures responding to In addition to the relatively small evaporite focused Pb-Zn
compression of the once laterally continuous saline giant deposits discussed so far, many of the larger carbonate-
that defined the original salt distribution in the Maritimes hosted Pb-Zn deposits within the MVT group of deposits are
Basin fill. Deposits are generally tied to features at the associated with salt-sourced hypersaline ore fluids. The
Touraisian-Visean (Mississippian) clastic carbonate-evapo- hypersaline affinity is based on fluid inclusion studies that
rite disconformity, and overlie Cambrian to Devonian indicate most MVT sulphides are precipitated from highly
metasedimentary and granitic rocks, which likely acted as saline basinal fluids at temperatures within the normal range
sources for the metals. for diagenetic brines (80–150 °C; Anderson and MacQueen
In addition to Gays River and Jubilee, other significant 1990). Many of the larger MVT examples listed are also tied
deposits of this association include: the Southvale baryte to dissolving evaporites as a source of the chloride-rich
occurrence, the Pembroke Pb deposit, the Smithfield Pb-Zn- basinal waters carrying the metals and many to sulphur
Cu-Ba deposit, the middle Stewiacke baryte occurrence, the sources that are either at or near the precipitation site as bed-
Brookfield baryte deposit, the Hilden baryte occurrence, the ded platform sulphates or as H2S in the pore waters derived
Walton-Magnet Cove Ba-Pb-Zn-Cu-Ag deposit and the Lake by sulphate reduction (bacterial and thermogenic), typically
Fletcher baryte deposit. All these deposits occur on the from CaSO4 sources. The setting is much like the deposits
southern margin of the >10 km thick Carboniferous discussed so far but not a metal precipitation setting that is
Maritimes (Fundy-Magdalen) Basin. Regional isotope and necessarily directly adjacent to thick current, or former, salt
inclusion studies show the deposits all formed from basinal masses.
brines, which were derived from >5 km depths in catabaric In what follows we shall focus on some of those MVT
sediments that lay beneath the Visean evaporites (Figs. 15.47a, deposits located on the platform and tied to bedded cal-
15.48, and 15.52; Ravenhurst and Zentilli 1987). According cium sulphate units (Fig. 15.53). In an accompanying
to Sangster et al. 1998b, the isotopic evidence suggests that plot of grade versus ore tonnage I have indicated some of
the Walton, Gays River and Jubilee deposits were derived the MVT deposits known to be associated with evaporites
from the same brine source, probably deeply circulating sul- or derived brines (Fig. 15.54). This includes some very
phate-rich brines, as noted by Boyle et al. (1976), these sul- large deposits, such as Polaris and Admiral Bay, as well
phur signatures in these brines are virtually identical to an as the small Pb-Zn deposits discussed in the preceding
evaporite source. sections. My approach in the remainder of section is not
Regional salt-lubricated detachment surfaces such as the to attempt to define an all encompassing Pb-Zn/MVT
Ainslie Detachment, controlled and focused the escaping model, this has been done in excellent papers by Leach
basinal fluids, were probably first created by lateral “into-the- et al. (2010) and Emsbo (2009). Rather, as in the preced-
basin” gravity sliding or displacements along the sole of the ing sections, I shall restrict my discussion to those Pb-Zn
regional salt thick in a foreland basin setting not too dissimi- MVT deposits that have an intimate association with
lar to the Maghreb. The remaining salt now resides in the evaporite beds or their residues, so as to develop a spe-
lower Windsor Group and, away from the dissolution edges to cific understanding that can give predictive exploration
the various tectonic sub-basins, is today made up of some paradigms for those MVT deposits created by their asso-
350 m + evaporites of the Carrols Corner Formation and its ciation with evaporites.
equivalents (Waldron et al. 2013). During regional compres-
sion, the impervious underside of the salt and its allochthons adjebut Region, Lennard Shelf, Australia
C
and detachments focused the flow and periodic trapping of Bedded calcium sulphate evaporites, and their lateral disso-
escaping metalliferous brines. Prior to reaching the sulphates lutional equivalents, have been cored in the area around the
of the salt base, these same fluids had circulated through the Cadjebut mine on the Lennard Shelf and they pass into mine
Tournisian clastic rocks and the immediately adjacent tec- sulphides in the mine and its immediate surrounds
tonic breccias of the detachments. Rising metalliferous brines (Figs. 15.55 and 15.56). The details of Cadjebut Pb-Zn ore
mixed with shallower basinal fluids across breach points in system and ore textures at the mine scale were discussed in
the evaporite aquiclude, which are now accessible for mining detail in Chap. 7 as an example of hydrothermal karst devel-
mostly about the basin margin (Fig. 15.46a). Thermochemical opment in a platform saltern and so are only mentioned here.
sulphate reduction was the main metal fixing reaction of the Evaporite solution breccias (rock matrix breccias) are the
various deposits, with the sulphur/sulphate supplied by the lateral equivalents of the mineralised sequence in the
adjacent evaporites and the organics from the migrating Cadjebut mine The deposit undoubtedly represents one of
hydrocarbons (Savard et al. 1996; Sangster et al. 1998b; the best documented examples of in situ burial replacement
Lynch et al. 1998; Lynch and Keller 1998). of a number of evaporite beds by Pb-Zn sulphides on a one
Polaris Pavlovshoye
Nanisivek
Navan
Jubilee La Calamine
Reocin Largiente
Gays River
Buick
Toussit-Bou Bek Mesloula
Winnfield Tatum Daliangzi
Salt Dome Salt Dome Fankou
Benue
Trough
San Vicente
Admiral Bay Cadjebut
Elura
Flinders
Fig. 15.53 Plot of some of the documented MVT deposits with known ties to evaporites, as detailed in the text
Fig. 15.54 Grade-tonnage plot of 100

MVT deposits (Replotted from Cadjebut
10
10
Polaris
10
1,
00
,0
0,
,0
USGS data). H indicates (H+E) (H+E)
00
00
00
0,
00
,0
0
hypersaline ore fluids, E indicates
00
San Vicente 0 Gayna
evaporites or indications of its Fankou (H+E?)
(H+E) River (H)
former presence
Reocin (H)
Navan (H+E)
10 Admiral Bay
1,
Pb +Zn grade
00
(H+E)
0
to
nn
es
Jubilee
Mehdiabad
of
(H+E)
Pb
(H+aridity)
+Z
Nanisivik
n
(H+E) Pavlovskoye (?)

m
et
Buick
al
1 Bou Grine (H+E)

10
0
(H+E)
Gays River
Walton
(H+E)
(H+E)
0.1 1 10 100 1,000

Ore (million tonne)
for one basis (Tompkins et al. 1994a, b; Warren and Kempton n odular evaporite textures (Tompkins et al. 1994a, b versus
1997). That is, the pre-existing platform saltern beds are Warren and Kempton 1997).
directly replaced by Pb-Zn sulphides and these saltern sul- More broadly, the Cadjebut ore deposit is a Mississippi
phates were the sulphur source. The sulphate to sulphide Valley Type (MVT) deposit hosted within the Givetian anhy-
replacement process occurred across cm- to metre- sized drite entraining Lower Dolomite unit of the Cadjebut Fm.
cavities, and so the banded and breccia replacement textures ramp. This sand-shoal-rimmed ramp was the depositional
are layered, sometimes forming “zebra” textures. This cavity setting that immediately preceded the reef-rimmed Pillara
infill replacement process means the ore textures are not Limestone platform, which defines the Lennard Shelf
necessarily a direct mimicry of the precursor laminar to (Fig. 15.55). Regionally, the Givetian depositional setting
Fitzroy trough Lennard shelf

Winjana Lst. Fairfield group
system
Meteoric or marine
pore fluids Low salinity fluids,
Non-mineralised
1 Nullara Lst.
Piker Hills Fm. Bacterial sulphate
Pinnacle fault
reduction,
Virgin Hills Fm. Sour gas reservoirs
Estimated burial depth (km)
Pillara Lst.
Gogo Fm.
Sadler Lst.
Pb-Zn sulphide
2
mineralisation
Basinal brines and hypersaline
Mineralised depths
Cadjebut mine
Compactional basinal brine
Cadjebut Fm.
flow Breccia Pb-Zn CaSO4 beds interactions
Devonian rimmed-shelf Sour gas Hydrocarbon

Hydrocarbon Basinal calcareous shales Hydrocarbons generation and
3 hypersaline brine
generation Basinal brines Pb-Zn sulphides
migration
Fig. 15.55 Conceptual model for MVT sulphide precipitation on the largely fed by Givetian saltern CaSO4 evaporites (Cadjebut Formation)
eastern Lennard Shelf. At around 350 Ma, sediments of the Fitzroy and H2S-rich reservoirs higher in the stratigraphy form in a variety of
Trough expelled metalliferous basinal brines and mature hydrocarbons traps (faults, antiforms, and stratigraphic traps). Sulphides are precipi-
by compactional flow. In shallow subsurface environments with low tated when basinal brines interact directly with evaporites or invade
salinity and low temperature (60–70 °C) fluids, bacterial sulphate intervals of trapped H2S-rich (Modified from Playford and Wallace
reduction occurred in and around saltern evaporite seals and hydrocar- 2001; Wallace et al. 2002; Warren and Kempton 1997; Kerans and
bon reservoirs within the Devonian platform. Sulphate reduction was Harris 2008)
N 4
Ca
dj 2
eb
ut
δ13OPDB
)
fa ng T
ul
t increasi
1
Bu rial ( Devonian
marine
dolomite
0
Cadjebut mine
5 km
–1
Oolite shoals Pinn Limestone Regional med-crse dolomite (replacive)

acle –2
fault Mimetic dolomite Mine coarse dolomite (replacive)
Lagoonal mudstones
Salina and sabkha sulphates a –12 –10 –8 –6 –4 –2

b
δ OPDB
18
Fig. 15.56 Cadjebut Mine geological evolution. (a) Givetian paleogeo- dolomitised lagoonal wackestone and siltstone in back shoal area. A slight
graphic reconstruction based on logged core intersections across the mine fall in relative sealevel created a sulphate mudflat complex in the vicinity
and its surrounds. Grey line defines the outline of the Emmanuel Ranges. of Cadjebut Mine. (b) Plot of δ18OPDB versus δ13CPDB for various dolomites
Oolite shoals developed in vicinity of Cadjebut and Pinnacle faults, with in the Cadjebut mine and its surrounds (After Warren and Kempton 1997)
can be divided into two zones (Fig. 15.56a): (a) a higher times evaporitic, lagoonal setting laid down in a series of
energy shoal region in the vicinity of the mine and Cadjebut shoaling carbonate cycles. The upper portion of each cycle
Fault and, (b) a landward more restricted, lower energy, at is characterized by an evaporitic cap of laminar dolomitic
siltstone and mudstone with associated nodular anhydrite Some workers (Tompkins et al. 1994a, b) did not realise that
that formed a laterally extensive facies mosaic of sabkhas the current gypsum textures in relict anhydrite beds recov-
and salinas across an evaporitic mudflat. This originally shal- ered in cores are replete with such telogenetic rehydration
low subaqueous or sabkha mudflat gypsum converted to features (tertiary evaporites).
nodular anhydrite during shallow burial and was subse- Such gypsum rose and cannonball textures should not be
quently replaced by Pb-Zn sulphides in the mine area. compared to possible primary depositional textures (errone-
Three petrographically distinct forms of dolomite occur ous assignment to a sabkha for massive sulphate units), nor
in the lower dolomite unit across the Cadjebut region to cavity fill and layered textures in the metal sulphides that
(Fig. 15.56b): (a) a regional finer-grained non ferroan formed in the mesogenetic realm. Ore evolution models that
mimetic form with δ18OPDB of −2 to −4 ‰ – this dolomite and do not remove the effect of modern gypsum overprints, or
(b) a ferroan medium to coarsely crystalline form with any assumption that gypsum textures in recovered cored
δ18OPDB -4 to −7 ‰ that is best developed about major growth could be primary (has survived kilometres of burial and
faults. This dolomite overprints and replaces the finer grained uplift) are erroneous. Respective precipitative processes for
stratabound mimetic dolomites as well as other carbonate anhydrite rehydration and metal sulphide textures at Cadjebut
facies. The finer grained ferroan dolomite formed by synde- are totally unrelated in terms of time and space (Warren and
positional brine reflux associated with the deposition of Kempton 1997).
evaporites, while the coarser more ferroan dolomite formed The now depleted Cadjebut deposit is the largest and most
during burial from escaping basinal fluids. These same fluids concentrated of a number of MVT accumulations in the
later carried metalliferous fluids from the Fitzroy Trough Lennard Shelf Pb-Zn province, mostly hosted in Devonian
into sites of ore formation. Post-ore coarse replacement and shelf carbonates, although the Cadjebut is deposited in ramp
saddle dolomites from the Cadjebut mine constitute the third dolomites of the Givetian Cadjebut Fm, which immediately
dolomite type and are further depleted in δ18OPDB (−10 to underlies the Frasnian-Famennian rimmed-margin domi-
−12 ‰) and likely indicate localized somewhat elevate ther- nated by the Willara and Pillara platforms (Fig. 15.55;
mal conditions related to sulphide mineralization. Hocking et al. 1996). The rimmed-margin Frasnian-
Interaction of a metalliferous basinal brine with sulphate Famennian platform-hosted deposits include hydrothermal-
that was derived from the dissolving anhydrite beds precipi- karst dominated deposits (Goongewa and Bloodwood), and
tated the various ore lenses at Cadjebut mine. Sulphide- fault or fracture-hosted deposits (e.g. Pillara (aka Blendevale),
mineralised horizons in the Cadjebut mine can be correlated Kapok, Fossil Downs). Fault and fracture hosted mineraliza-
on a one to one basis with fine-rock matrix breccia horizons tion style dominates Frasnian and Famennian platform host
in the immediate area around the mine and with remnant across the Lennard Shelf (Wallace et al. 2002).
bedded sulphate units well away from the mine. The precur- The Goongewa deposit is situated in the hanging wall of a
sor host lithology to the various ore horizons at Cadjebut are normal fault (Cadjebut Fault). Stratigraphically, the miner-
massive to bedded nodular anhydrite beds. The stratabound alisation occurs around a Givetian platform margin and also
linear nature of the Cadjebut deposit reflects a time when occurs at the boundary between dolomitised and undolomi-
metalliferous basinal fluids encountered bedded stratiform tised carbonates. MVT sulphides there are largely present as
nodular anhydrites causing them to precipitate lead and zinc cavity-filling cements within large hydrothermal karst cav-
sulphides. This process locked in place a mineralization erns. The nearby Kutarta mineralisation (close to the old
event at the stratigraphic position of each evaporite bed in the Price’s Creek prospect) has a quite different style again, with
lower dolomite unit. Conduits for the metalliferous basinal much of the base-metal sulphide mineralisation being a
fluids were the basin-margin-defining faults such as the replacement of dolomitised and brecciated back-reef carbon-
Cadjebut and Pinnacle Faults (Fig. 7.71a). Fine-matrix brec- ates (Pittari 1999).
cias define subsurface evaporite dissolution both prior to and The timing of MVT sulphide precipitation is well con-
after the sulphide mineralization event. Today the remnant strained by a number of techniques. Using carbonate
nodular anhydrite beds are rehydrating to satin-spar and poi- cement stratigraphic relationships in host rock primary
kilotopic gypsum as modern groundwaters seep into the porosity, McManus and Wallace (1992) suggested that a
units. single, widespread sulphide precipitation event (pyrite,
One of the problems with comparing nodular calcium sul- sphalerite, galena, marcasite) occurred during early burial
phate and open-space filling zinc and lead sulphide textures diagenesis during latest Devonian–earliest Carboniferous
in the Cadjebut region occurs when modern telogenetic time (350 ± 15 Ma) within the reef complexes of the
effects go unrecognised. Much of the shallow anhydrite that Lennard Shelf. This mineralisation age has since been con-
was cored in the 1980’s and 1990’s is converting to porphy- firmed by both Rb-Sr dating of sphalerite at Blendevale and
roblastic gypsum down to depths of hundreds of metres as it U-Pb dating of ore-stage calcites from Goongewa (Wallace
is flushed by modern meteoric waters (telogenetic alteration). et al. 2002). Further south in the basin, the giant saltern
evaporite sealed Admiral Bay Pb-Zn deposit was discov- dolomitised carbonate rocks of the Upper Ordovician
ered as part of an oil exploration program, but it is too deep Thumb Mountain Formation. The now-depleted Polaris
to be exploited by conventional mining techniques Mine exploited one of the largest single Mississippi Valley-
McCracken et al. 1997). type ore deposits in the world (Reid et al. 2013).
Reinforcing the notion of ongoing fault focused fluid Dimensions of the Polaris deposit are: 800 m strike length,
evolution controlling mineralisation in the Canning basin 300 m at its widest point and a thickness ranging from 20 m
are the various stromatolite-baryte-sulphide mounds that in the west to 100 m in the central portion (Dewing et al.
constitute outcrops at a number of localities on the eastern 2005). The deposit is blind, with the topmost ore lying 50 m
Lennard Shelf. They are interpreted as fault-fed synsedi- below surface on the west and up to 160 m below surface on
mentary exhalative deposits on the Devonian deep basin- the east side. It forms a continuous sulphide body broken
margin seafloor (Playford and Wallace 2001). For example, down based on grade, position and textures into a number of
such stromatolite mounds occur near the Gogo Formation– units; P1 -P2 and K1 to K3 (Table 15.12; Dewing et al. 2005).
base Virgin Hills Formation contact and are associated Of the five ore types recognized: two occur in the upper
with extensive gossans in outcrop. In drill core, iron sul- Thumb Mountain and three in the lower Thumb Mountain
phides (marcasite and pyrite) are dominant, with base- Formation (Fig. 15.59).
metal sulphides only occurring as later stage cross-cutting P1 ore was the economically most important and formed a
veins. 10–30 m thick, high grade Zn-Fe-Pb, tabular unit hosted in
The varying ore style geometries reflect the simple fact
that no bedded evaporites were deposited in the Frasnian-
Famennian backreef, only in the Givetian back-shoal region. Little Cornwallis
And so, when the basinal fluid pulses of metalliferous fluids Island
Cornwallis Island
moved up along faults at the basin margin and through the
various carbonate hosts, it precipitated well bedded ore units
where metal-carrying fault conduits intersected anhydrites in
the Cadjebut Formation and fault/ hydrothermal karst geom-
etries where faults encountered mixtures of hydrocarbons
and other reductants in the Frasnian-Famennian platform
hosts. Once again, dissolving evaporites do not necessarily
make ore deposits, when they do, they tend to focus the pre-
cipitative process and so make a more concentrated
accumulation.
Polaris Zn-Pb Mine, Nanavut, Canada

The Mine, near the coast of Little Cornwallis Island, is
hosted by the Ordovician Thumb Mountain Formation and
located on the northeast flank of a large NW–SE oriented
salt-cored antiform that formed in the Ellesmerian
Foldbelt, during the Late Silurian to the Middle Devonian 20 km
(Figs. 15.57 and 15.58; Thorsteinsson and Uyeno 1980
Dewing and Copper, 1991). Based on paleomagnetism
Rb-Sr and Re-Os dates from ore sphalerites and bitumens, Polaris Mine
respectively, the mineralisation is known to have occurred Zn-Pb show Ordovician carbonate and evaporite
at 366 ± 15 Ma and so is co-occurrent with tilting and com- Cu show Silurian and Devonian strata
pression that formed the Ellesmerian (Parry Island) fold- Antiformal axis
belt and the Boothia Uplift (Symons and Sangster 1992; Graben
Selby et al. 2005; Jober et al. 2007). The mine commenced
Fig. 15.57 Map of the Cornwallis Island region showing positions of
operation in 1981 and closed in July 2002, When in opera- salt-cored antiforms on the Boothia Uplift in the Ellesmerian foldbelt,
tion, the mine had a reserve of over 20 Mt of sphalerite the Polaris Mine on Little Cornwallis Island and a number of Zn-Pb and
(ZnS) and galena (PbS) and was hosted in brecciated and Cu shows (After Reid et al. 2013)
Cambrian Ordovician Silurian Devonian
Upper mbr
Lower Cass Fjord
nomenclature
Upper mbr
Lower mbr
Upper Cass Fjord
Change in
nomenclature
nomenclature
Change in
Change in
Upper Turner Cliffs
Lower Turner Cliffs
shale, gypsum, locally with redbeds
Sandstone, siltstone, carbonate,
Formation name
Facies/member contact
Formation contact
Sandstone
Conglomerate, sandstone
Sandstone, siltstone, shale, redbeds
nomenclature
Change in
nomenclature
Change in
Bathurst Is
Polaris mine Greenland
Carbonate, known from drill-holes and seismic
Chert, carbonate
Shale, chert, carbonate, olistostromes
Bioturbated and locally fossiliferous carbonate
Boundstone, rudstone, grainstone
Oolitic grainstone
Carbonate, locally abundant clastics
Carbonate, locally with gypsum and mudrock
Carbonate, gypsum (anhy-halite precursor, shale
Melville
Is.
Nanisivik mine
Baffin Is.
nomenclature
Change in
Parry Is. fold belt
Fig. 15.58 Time-stratigraphic diagram showing a south to north transect in outcrop is after halokinetically overprinted anhydrite and that this halite
from northwestern Baffin Island to northern Bathurst Island (see inset). The was once present in the region. It is still present in surface equivalents, for
chart is after Dewing et al. 2005 and references therein. Importantly the example, the star indicates gypsum/halite remnant breccias, in Bay Fiord
cited chart is based on outcropping mineralogies and does not consider that Fm. as illustrated Fig. 15.59
textural evidence throughout the region indicates that much of the gypsum
the basal part of the upper Thumb Mountain Formation. P1 Pb + Zn and 1–2 % Fe. The lowermost ore unit is K1 ore com-
ore consisted of massive, carbonate replacement, breccia-fill posed of fracture-filling and vein sulphides, discontinuous
and vein sulphide averaging 4–5 % Fe with up to 30 % Fe and lower grade (10–15 % Pb + Zn, 1 % Fe). This ore unit
(Table 15.12). Overlying the P1 ore, above the major N-S follows either the N-S (mine grid) axis of mineralization or a
structures defining the boundaries of the Keel graben, are NE-SW trend and is centred on lower stratigraphic horizons
blocks designated as P2 ore. This ore is composed of numer- around a green marker bed in the lower Thumb Mountain
ous thin to 1 m thick veins of sphalerite, marcasite and galena Formation (Fig. 15.59). To the east and west of the orebody,
oriented vertically, sub-perpendicular to bedding. Marcasite sulphide mineralization dies out rapidly within 15 m of the
halos surround most P2 veins. Directly underlying the P1 ore boundaries. Sulphide feathers out into small, scattered
tabular body is the high grade K3 ore, composed of complex, lenses and sulphide vein systems to the north and south of
cross-cutting veins along with massive to disseminated metal the orebody and further out transitions into a breccia unit,
sulphides replacing Tetradium beds containing 3–5 % Fe called pseudobreccia, in the mine terminology
(Fig. 15.59). Diagenesis of the mine series is indicated by extensive
Differentiation between K3 and P1 ore was based mainly hydrothermal alteration, including sequential dolomitisation,
on lower iron contents of K3 versus the P1 ore. K2 ore under- marcasite and baryte precipitation events (Figs. 15.60 and
lies the K3 unit and is composed of fracture filling and vein 15.61; Savard et al. 2000; Reid et al. 2013). There are three
sulphides with lesser replacement of carbonate, with local paragenetic stages: (1) Early replacement dolomites and
pods of mineralized brecciation carrying grades of 8–20 % marcasite; (2) Main stage sulphide and hydrothermal
coarsely-crystalline (saddle) dolomite; and (3) Late calcite,
marcasite and baryte. Ore mineral textures range from dis-
Table 15.12 Ore grade divisions in the Polaris Mine (Dewing crete crystals to massive crystal aggregates and formed as
et al. 2005)
replacements of the dolomite host rock or as fracture- and
Zone Pb + Zn Fe Zn/Pb open space-filling mineralization. Zinc concentration is
P2 16.5 4.6 3.1 highest in the core of the deposit where open-space fill and
P1 22.4 4.5 3.5 botryoidal aggregates predominate. Locally elevated Th val-
K3 19.1 3.1 5.6 ues ≈ 100 °C are associated with nearby organic-rich strata
K2 17.3 1.7 4.3 and bitumens, while the ore carries a geochemical signature
K1 15.5 0.8 8.1 that includes in situ sulphur fractionation. Detailed isotope
600E 800E 1000E 1200E 1400E 1600E 1800E
Crozier
strait
−200 m
Cape Phillips formation - Cape Phillips formation - Thumb Mountain formation - Bay Fiord formation- Ore body
memner B ridge-forming member dol upper Chert Marker dol upper
P2
Cape Phillips formation - Thumb Mountain formation - Geological contact P1
Irene Bay formation
memner A dol lower Green Marker K3 Panhandle
Fault K2
Keel
K1
Fig. 15.59 Section through Polaris Mine on mine grid 2,100 N showing the outline of the ore and dolomitisation. P denotes Panhandle Zone ore,
and K denotes Keel Zone ore; see text and Table 15.12 for descriptions and grades of the P2, P1, K3, K2, and K1 ore types (After Dewing et al. 2005)
Fig. 15.60 Paragenetic-diagenetic Earlier Main Later

sequence in the Polaris Mine
stage stage stage
(After Savard et al. 2000; Reid
et al. 2013) Calcite microspar (SC)
Replacive calcite (RC)
Solution seams
Fe-rich dolomite fine x´line (RD1)
Fe poor dolomite in mudstone (RD2)

Fe poor dolomite in grainstone (RD3)
Carbonate-evaporite dissoution/brecciation
Pyrite/Marcasite
Sphalerite
Galena
Pore filling dolomite Fe-poor (PD1)
Pore filling dolomite Fe-rich coats PD1 in ore zone (PD2)

Hydrocarbons/bitumens
Stylolitites
Silica
Coarse pore filling calcite (PC)
Baryte
study tied to petrography clearly shows that replacive dolo- analysis of these same fluid inclusions indicates low concen-
mite predates and is synchronous with ore emplacement. As trations of hydrocarbons (<0.06 mol%).
in other MVT deposits so far, dolomitisation is associated There are no regular spatial variations for fluid inclusion
with emplacement of sulphide minerals, but is not the con- and isotope data during metal sulphide emplacement, indi-
trolling process for mineralisation. cating an overall geochemical homogeneity in the hydrother-
Five types of dolomite were distinguished by Savard et al. mal system at that time. Sulphur isotopes show slightly
(2000), including three replacement (RD) and two pore- different groupings for galena and sphlarite, with sphalerite
filling dolomites (PD). The paragenetic order is RD1, RD2, tending toward somewhat more negative δ34S values
RD3, PD1, and PD2. Pore-filling calcite (PC) postdates all (Fig. 15.61c). Some samples close to the fracture zones in
other minerals. Baryte and silica are late-stage precipitates. the orebody show slightly elevated TH and 87Sr/86Sr values
In most cases, sulphides and dolomite did not co-precipitate, and more depleted δ18O values, suggesting that the fracture
but sphalerite and galena largely overlap with RD3 and PD1. zone was the likely conduit for warm metalliferous brines.
Various dolomites are dissolved or replaced by sulphide- Based on the geological and geochemical characteristics
precipitating fluids; sulphides in turn can be overgrown by of the deposit, Savard et al. (2000) propose that sulphide pre-
dolomites. Colloform texture in sphalerite is widespread. cipitation at Polaris was caused by the mixing at the site of
Early calcite, both microspar replacement (SC) and early mineralization of a reduced, metal-rich, sulphur-poor fluid
replacive calcite spar (RC) have C-O stable isotope values with a reduced, metal-poor, sulphur-rich fluid. The metal-
closest to ambient seawater, as does early fine-grained dolo- carrying fluid ascended along fractures from below the
mite (RD1). The isotopic values of RD2, RD3, PD1, and deposit and was hotter than the host rocks, whereas the
PD2 cluster tightly and form largely overlapping domains reduced sulphur-carrying fluid was delivered to the site of
(Fig. 15.61a). With respect to the host limestone, they are mineralization laterally from dissolving sulphate beds and
depleted in 18O, similar in δ13C, and slightly enriched in 87Sr. was in thermal equilibrium with the host rocks (Savard et al.
Fluid inclusions were studied by Savard et al. (2000) in RD3, 2000). This model can explain the dissolution of dolomite/
PD1, PD2, sphalerite, and PC. The overall ranges of homog- evaporite during sulphide precipitation and the abundance of
enization temperatures (TH) for non-stretched fluid inclu- colloform sphalerite, as well as the low concentrations of
sions in dolomites and sphalerites range from 67° to 110 °C, hydrocarbons in fluid inclusions.
indicative of warm basinal brines with high salinities and An alternative model for the Polaris deposit is that sul-
elevated Ca/Na ratios (Fig. 15.61b). Gas chromatographic phate was supplied by dissolution of anhydrites of the under-
32
5
30
Salinity (Wt %)
28
0
26
–5 24
80 85 90 95 100 105 110 115
δ3CPDB
TH (°C)
6
–10 Sphalerite
Galena
Frequency
–15
2
–20 0
–25 –20 –15 –10 –5 1 2 3 4 5 6 7 8 9 10 11
δ OPDB
18
δ SCDT
34
Early calcite microspar SC Dolomite fine-x´line Fe-rich rhomb RD1 Dolomite pore filling Fe-poor PD1
Early replacive calcite RC Dolomite Fe-poor in mudstone RD2 Dolomite pore-filling Fe-rich PD2
Late fracture filling calcite PC Dolomite Fe-poor in grainstone RD3 Sphalerite
Fig. 15.61 Isotopes and temperatures in the Polaris Mine. (a) Carbon- inclusions of selected carbonate phases and sphalerite. (c) Sulphur iso-
oxygen isotope crossplot in various carbonate phases in the Polaris tope determinations in sphalerite and galena (From Savard et al. 2000;
mine. (b) Salinities (wt%) and homogenisation temperatures (TH) in Reid et al. 2013)
lying Bay Fiord Formation, while the organic-rich shales of precipitation of crystalline sphalerite as the gas cap is
the Irene Bay formation acted as both seal and as a source of depleted and gas slowly produced by ongoing BSR.
organics in the fault focused zone of sulphate reduction that Any model for the Polaris deposit (Fig. 15.61) must
drove the mineralisation (Fig. 15.62a; Reid et al. 2013; invoke a source of metal ions within the stratigraphic col-
Dewing et al. 2005). umn, since strontium or lead isotopes show no indication of
TSR is unlikely to have been the dominant precipitative basement involvement. The likely metal source was units
mechanism in either model, since: (i) the temperatures are beneath the dissolving and deforming Bay Fiord salt seal
too low (>120 °C is needed), (ii) there is no blocky calcite where metals were convectively flushed by chloride-rich
with strongly negative δ13C values that is typically produced saline brines and were carried toward the basin edges through
during TSR, (iii) there is fractionation of the sulphur iso- aquifers deep in the stratigraphic column. Driven by the Late
topes, a process that does not occur during TSR (Machel Devonian Ellesmerian Orogeny, the fluids rose along faults
et al. 1995), and (iv) the δ34S in individual sphalerite masses until they encountered the organic-rich, permeable Thumb
is inhomogeneous, typically showing a variation from 8 ‰ in Mountain Formation limestone overlain by the impermeable
the colloform centre of the sphalerite mass to 12 ‰ at the Irene Bay Formation shale.
outer crystalline rim which is somewhat similar to the galena. Bacterial sulphate reduction (BSR) likely reduced sul-
Presumably this reflects pulses of fluid activity, with BSR phate to H2S utilising the abundant algal organic matter in
producing a gas cap with strongly fractionated H2S, followed the upper Thumb Mountain Formation as a reductant. The
by the introduction of metal-rich brine, rapid precipitation of resulting H2S explains a shift in δ34S values of −15 ‰
amorphous colloform sphalerite, followed by slower (Fig. 15.62a). The H2S reacts inorganically with zinc, lead,
Fig. 15.62 Polaris Mine. a Baryte

(a) Mineralisation model δ34S = 40−60 ‰
showing the halite dissolution
origin of metal and sulphate-rich
fluids in the sedimentary pile.
Transport was as a single saline
fluid to site of ore precipitation,
where reduction and fractionation
was driven by bacterial sulphate Aq
reduction, in combination with uita
δ 34S rd
isotopically light H2S and metal =5
−15
ions to form ore and create acidic BSR ‰
fluids that created hydrothermal 60−80°C Org
karst cavities and associated ani
c-r
open-space collapse textures. The ich
H2S
expulsion of isotopically heavy
sulphate produces a characteristic
baryte halo. Refer to Fig. 15.59
for lithology legend (Adapted
SO4 + metals
from Dewing et al. 2005). (b).
Model of detailing the δ34S = 25 ‰
Bay
distribution of breccia types Fio
rd
relative to massive sulphide
Anh
mineralisation (After Reid ydr
et al. 2013) Chloride-rich metalliferous brines ite
from halite dissolution – alteration
during Ellesmerian orogeny and carrying
Pb, Zn, Fe at temperatures < 140 °C
b Ore body keel

Country rock Transitional ore
Massive
sulphides
Mineralized collapse Dolomite Cobble breccia

breccia
Mineralized crackle Pseudobreccia Crackle breccia
breccia
Megabreccia
and iron ions to produce sulphides with a δ34S value of about Cornwallis Island), (iii) the heavy sulphur isotope values,
10 ‰. Released hydrogen ions dissolve carbonate resulting and iv) co-occurrence of baryte with late stage marcasite.
in dissolution breccias and other open-space dissolution fab- Temperatures measured from fluid inclusions in the sphal-
rics. Excess sulphate was expelled from the system and pro- erite and inferred from the thermal maturity data from kero-
duced a halo of baryte up to 10 km from the deposit, with gens in the mine series indicate a range of 80–105 °C (Reid
δ34S of +40 to +60 ‰ (Dewing et al. 2005). Evidence of a et al. 2013; Dewing et al. 2005). This is the appropriate range
temporal link between baryte and ore is based on the follow- for bacterial sulphate reduction. Thermochemical sulphate
ing; (i) a sample from the 930–124 stope at Polaris that has reduction (TSR) is unlikely to have been active since; (1)
sphalerite, which pre- and post-dates baryte, (ii) the proxim- The temperatures are too low (>140 °C is needed), (2) There
ity of baryte to Polaris (baryte is common on southern Little is no blocky calcite with strongly negative δ13C values that is
typically produced during TSR, (3) There is fractionation of LITHOLOGY

the sulphur isotopes, a process that typically does not occur
Upper
during TSR (Machel et al. 1995), and (4) the δ34S in indi- Bay Fiord
SONIC
vidual sphalerite masses is inhomogeneous, typically show- Formation
Thickness LOG
ing a variation from 8 ‰ in the colloform centre of the mass −3396 m
to 12 ‰ at the outer crystalline rim. Presumably this reflects 521 m
pulses of fluid activity, with BSR producing a gas cap with 500 m
strongly fractionated H2S, followed by the introduction of
metal-rich brine, rapid precipitation of amorphous colloform
sphalerite, followed by slower precipitation of crystalline
sphalerite as the gas cap is depleted and gas slowly produced
by ongoing BSR.
400 m
Given this paragenesis, let us once again step away from
the Polaris deposit look more broadly at its regional evaporite
association. As Davies (1974) notes, there are two significant
evaporite units that lie beneath the Thumb Mountain
Formation, the Early Ordovician Baumann Fiord Formation
and the Middle Ordovician Bay Fiord Formation (Figs. 15.58 300 m Lower
and 15.62). The Baumann Fiord is exposed on eastern and Bay Fiord
southern Ellesmere Island, and extends southwestward to Formation
Cornwallis Island (Thorsteinsson and Kerr 1968), where it
forms the exposed Ordovician core of a large central dome.
The Baumann Fiord Formation is about 750 m thick in the 200 m
type area on eastern Ellesmere Island; about 600 m of this cur-
rent thickness is anhydrite with cyclically-interbedded carbon-
ates, some stromatolitic (Mossop 1972, 1973). The anhydrite
grades westward into shallow-water shelf carbonates, while to
eastward it thins, becomes sandier, and may pass to an uncon- 100 m
formity close to the shelf-craton margin. Mossop (1972) inter-
prets the Baumann Fiord evaporite-carbonate units to be a
succession of sabkha cycles. Halite in the Baumann Fiord is
not exposed at the surface. I would interpret it as a series of −4461 m
stacked sulphate salterns in an intracratonic sag basin. 0m
The next youngest and most extensive Ordovician evapo-
Eleanor
rite unit is the Bay Fiord Formation (Kerr 1977) of Middle River
Ordovician age (Fig. 15.63). It lies immediately below the Formation
Thumb Mountain Formation and constitutes the basal forma-
tion of the Cornwallis Group. The Bay Fiord is exposed in
eastern and southern Ellesmere Island, and can be traced Limestone
southwestward to Cornwallis Island and Bathurst Island. In Anhydrite Marl
the type area on eastern Ellesmere Island (Kerr 1968), the Salt (halite) Dolostone
Bay Fiord Formation contains gypsum and anhydrite in the
lower part of a 500 m thick section of argillaceous and dolo- Fig. 15.63 Interpreted lithostratigraphy and sonic log trace showing
mitic limestone, siltstone and shale. The Bay Fiord are the anhydrite – halite distribution in the Lower Bay Fiord Formation in
Sabina Bay A-07 well on Melville Island (Harrison 1995) (See inset in
thought to lie within the carbonate-dominant shelf succes- Fig. 15.58 for location)
sion that extends southeastward of the Franklinian trough,
approximately co-extensive with the older Baumann Fiord
Formation. The thickness an purity of the sulphate units in On Cornwallis Island, carbonate breccias in the Bay Fiord
the Bay Fiord once again indicates they are salterns within an exposures are interpreted as solution-collapse breccias
intracratonic sag (Warren 2010). But more significantly (Thorsteinsson and Kerr 1968) due to removal of halite.
away from their leached outcrop positions there are halite More than 1,000 m of halite apparently equivalent to the
units in the Bay Fiord, and some are extensively thrusted and exposed Bay Fiord sulphate residues on Cornwallis Island
folded (Fig. 15.63; Chap. 6; Harrison 1995) occur in the subsurface of eastern Bathurst Island (Fig. 15.63;
Davies 1974; Harrison 1995); the km thickness on eastern of visible shortening (0–1 %), deformation is manifested by
Bathurst may be in part an expression of tectonic thickening the buckling of the competent carbonate and black shale for-
and associated diapirism that occurred during the formation mations (upper Bay Fiord, Thumb Mountain, and Cape
of the Ellesmerian foldbelt. The Bay Fiord is the key haloki- Phillips formations and age-equivalent strata). Evaporites in
netic stratum caught up in the Ellesmerian orogeny. Diapiric the lower Bay Fiord ductile zone, already weakened and
capstones to the Bay Fiord evaporites are exposed anhydrite buoyed up by the influence of high pore fluid pressures,
carapaces on Bathurst Island. The Bay Fiord evaporites simultaneously migrate into the axial region of each anti-
played an important role as a detachment zone and the cre- cline. The shortening is redistributed through the upper duc-
ation of antiformal welts during mid-Palaeozoic Ellesmerian tile zone of the Cape de Bray Formation by thinning of shale
folding and the development of the Parry Island and over the crestal regions of the anticline.” They go on to note
Cornwallis Foldbelts structural junction (Harrison 1995). that there are significant thrust detachment levels in the
The possibility of salt/thrust weld fluid focusing and a Thumb Mountain formation, as well as significant tectonic
more localised anhydrite source is not considered in any of wedging of the upper Bay Fiord and Thumb Mountain for-
the current published models. In current Polaris models the mations (p. 318, Harrison and Bally 1988)
Bay Fiord is typically offered as the sulphur source and that The various breccias at Polaris are still enigmatic meso-
is the only evaporite association discussed (Fig. 15.62a). In genetic units in their variably-thrusted platform carbonate
the context I would like to note that there is anomalous clas- host. The geological focus of most of the work at Polaris was
tic matrix dominant carbonate clast unit called the cobble on the ore and its paragenesis. A sedimentological study of
conglomerate that is only found in the immediate mine area “pseudo breccia” the “mega-breccia” and the “cobble con-
(Fig. 15.62b). “Cobbles” are 1 to 3 cm in size, usually of glomerate” (Fig. 15.62b) and an understanding of “the salt
slightly elliptical shape, packed in a dark muddy terrigenous that was” would likely have improved our understanding of
matrix that looks somewhat like a cobble-supported con- the deposit’s diagenetic evolution. Whatever the origin of the
glomerate (Randell and Anderson 1997). Earlier workers various non-mineralised breccias, all workers agree that the
described this unit as “transported and re-deposited cobble sulphur source for Polaris was anhydrite, with BSR as the
conglomerate” as meteoric cave-fill and argued this jumble dominant precipitative mechanism (Reid et al. 2013). Halite/
of cobble conglomerate clastics as completely incompatible sulphate units of the Bay Fiord did not directly drive the for-
with the environment of deposition of the Thumb Mountain mation of the Polaris MVT deposit. Rather, through their
Formation. It was attributed to the choking of meteoric karst ongoing dissolution and deformation, they drove regional
by transgressive conglomerates advancing across the early suprasalt structuration and hypersaline brine flows that sup-
Devonian unconformity. plied metalliferous brines and evaporite-derived sulphate to
But as noted by Randall and Anderson (1997) cobble con- the structurally-focused trap configurations known as the
glomerate has gradational contacts with normal Upper Polaris deposit.
Thumb Mountain Formation; occurs exclusively in Upper
Thumb Mountain Formation; carries remnants of galena Nanisivik Baffin Island, Canada
veinlets and dolomite veinlets exclusively in the cobbles, not The Zn-Pb-Ag ore at Nanisivek, near the north end of Baffin
in the “matrix”; is extensively riven by stylolites and, most Island, consists of massive sulphides hosted in dolomite of
tellingly, commonly exhibits whole fossils in place: many the platform/ramp carbonates of Middle-Upper Proterozoic
Receptaculitids, many Cateniporids and Halysitids, and the Society Cliffs Formation (Fig. 15.64a; Clayton and Thorpe
large solitary rugose coral Bighornia. Likewise, microfossils 1982). The mine first opened on 15 October 1976 and perma-
recovered from this rock match those of the usual Upper nently closed in September 2002. Textural and mineralogical
Thumb Mountain Formation. Cobble clasts preserved bur- variations divide the Main orebody into three vertical and
row structures, and the “matrix” an insoluble residue. four horizontal ore zones (Arne et al. 1991). The upper lens
“Cobble conglomerate” is not evidence for cave-fill, karsting of the Main orebody can be further subdivided into six tex-
or the exposure of Thumb Mountain cited by Kerr (1977). turally distinct, laterally extensive mine units. Pyrite is the
Randell and Anderson (1997) interpret the cobble conglom- main sulphide mineral in the region, but in places sphalerite
erate as a hydrothermal karst fill. and galena are present in ore-grade proportions. Most of the
In my mind, I wonder if it and the other non-mineralised known sulphides are in horizontal lenses about 10 m thick.
breccias could not be the remnants of a halokinetic salt The Main Ore Zone is 3,000 m long and, on average, about
tongue or salt lubricated thrusts with a now mineralized and 100 m wide. This body is estimated to contain 11 million
replaced fault feeder sourced in the Bay Fiord (a remnant of tonnes of sulphides, of which 6.5 million tonnes are ore-
a squeezed weld or diapir). In a key paper on salt-lubricated grade, averaging 12 % Zn, 1.5 % Pb and 50 g Ag/tonne
thrusting in the Parry Island foldbelt, located south of Polaris, (McNaughton and Smith 1986). There are also sulphides
Harrison and Bally (1988) noted that… “In the earliest phase below the main lenses, either in horizontal lenses or in
Kumulu Trend
Area-14
b
Ocean View
N South South S
Main Ore
Shale Hill
Eskimo Beach Pyrite Pyrite
STRA Zone Boundary
THCO 500
NA SO
UND NORTH North Pyrite
Elevation (m-msl)
400 Zone
Eskimo Beach
300
Shale Hill North
Pyrite Ocean View 200
Zone
Kumulu Trend 100
Main Ore Zone
Key n 0
s t o n e Grabe 500 m
South Kumulu
Pyrite Area Lake
Zone 14 37
c 37 Crosscut Central zone
Upper lens Western
West zone
Keel zone
Twin Lake Sulphide body Cut-off Eastern zone
sulphide ore Keystone
Gabbro Dyke Lower lens fault
1 km 20 m Main ore zone 500 m
Fault
Fig. 15.64 Nanisivik region, Baffin Island. (a) Map of the major bodies. (c) Cross section of Main Ore Zone showing upper and lower
sulphide bodies and structural features in the Nanisivik Region.
lenses connected by keel zone at crosscut 37 and the plan view of upper
(b) Schematic N-S cross section howing major faults and sulphide lens, Main ore zone (After Ghazban et al. 1990; Arne et al. 1991)
n ear-vertical vein-like structures. The host dolomite has been Mapped extent of
extensively block-faulted. Sulphide bodies pass laterally stratabound breccia North
through some of these faults and appear to be confined to the in Society Cliffs Fm.
upper half of the formation, which is mostly constructed of

W
laminated algal dolomite that has been extensively brecci- hit
eB
ated and recrystallised. Crosscutting relationships shows the ay
Fa
deposits are clearly diagenetic, not syngenetic. ult
Zo
The orebodies are characterised by well-banded ore tex- ne
73°N
tures, interpreted by Arne et al. (1991) as progressive replace- Nanisivik
ment of the carbonate wall rock. In contrast, Ghazban (1988)
noted the obvious knife-sharp contacts between the massive
pyrite and the adjacent host dolostone, and the presence of Arctic Bay
unaltered relict “fins” of the host dolostone. Ghazban et al.
(1992) use this relationship to argue for a more passive fill of Cen
tral
hydrothermal karstic caves, with ore precipitating as the Bor
den
matrix was dissolving. There is a third possibility, namely Fau
lt Z
50 km one
the precipitation of ore in cavities adjacent to or within dis-
solving sulphate bodies, in a manner akin to that characteris- 73°N
86°W 84°W 82°W 80°W
ing the Cadjebut ores where similar “fins” and other
equivalent ore textures are present (Warren and Kempton Fig. 15.65 Extent of brecciation mainly within the upper part of the
1997). A study of the solution breccias in the Nanisivik Society Cliff Formation in the western Borden Peninsula (After Jackson
deposit and listing of the presence or absence of evaporite et al. 1978)
indicators would help in resolving which of the three possi-
ble mechanisms is the most viable. Ghazban et al. 1990, 1992) Kah et al. (2001) noted that the
In this context, it is interesting to note that the sphalerite 1.2 Ga Society Cliffs Formation (Bylot Supergroup, northern
-galena body is dominantly stratabound and lies within the Baffin Island) today consists of some 720 m of peritidal car-
dolostones of the Society Cliffs Formation, which dips bonates, evaporites, and minor siliciclastic rocks. Evaporites
10–20° to the north (Fig. 15.64b, c). Gypsum outcrops in the occur predominantly in the lowermost 300 m of the Society
Society Cliffs Formation near Arctic Bay (25 km west of Cliffs Formation, where gypsum beds (1–250 cm thick) con-
Nanisivik) and in the southeastern Borden Basin (Fig. 15.65; stitute up to 15 % of the exposed strata. Stratigraphic and
a 5 b
10
Sphalerite
Frequency
5
0
0
Pyrite
δ CPDB
Frequency
13
–5
Borehole dolomite with
sedimentary structures 0
Microsparry replacive
dolomite Galena
–10
Frequency
5
Coarse zebra-texture
dolomite
0
–18 –16 –14 –12 –10 –8 –6 –4 –2 20 22 24 26 28 30 32
18 δ34SCDT
δ OPDB
Fig. 15.66 Isotopes in the Nanisivik ore deposit. (a) Carbon-oxygen isotope crossplot of the various dolomites associated with the Nanisivik
deposit. (b) Sulphur isotope values of metal sulphides in the Nanisivik deposit (Replotted from data tables in Ghazban 1988)
sedimentologic constraints, as well as isotopic (C, O, Sr) and minerals (Fig. 15.65). The breccia zones are stratabound
elemental (Ca, Sr, Na, K, Ba) compositions of evaporites and appear to be stratigraphically controlled, they bear no close
associated carbonates, indicate a initial marine origin for or obvious relationships to faults and folds within the forma-
Society Cliffs gypsum. However it must have experienced a tion (Olson 1984). The association of secondary CaSO4 and
significant degree of mineralogical alteration during its pas- stratiform brecciation implies the karstic brecciation is asso-
sage through the mesogenetic and telogenetic environments ciated with, and perhaps controlled by, evaporite solution
to where no more than relicts of the original beds outcrop collapse (Jackson et al. 1978).
today. Three distinct stages of dolomitisation can be distin-
There are also red beds with halite casts and associated guished by their petrographic, cathodoluminescence, and
with gypsum-bearing mudflat sequences within the lower isotopic characteristics (Fig. 15.66): (1) Massive fine-
Society Cliffs Formation on Bylot Island, some 150 km east medium crystalline dolomitisation of precursor carbonates
of Nanisivek (Jackson and Cumming 1981). Outcrops pat- preserving sedimentary features, and (2) Microsparry
terns on Bylot Island show high levels of deformation and replacive dolomite, (3) Coarse latestage dolomite cementa-
evaporite-related folding in the Society Cliffs Formation tion forming “zebra” dolomites (Fig. 15.66a; Ghazban et al.
(Jackson and Cumming 1981). The documented extent of 1992). The massive dolomites in the sulphate-bearing facies
such salty features in the Society Cliffs formation for may of the lower member of the Society Cliffs Formation and
kilometres east and west of Nanisivik suggests that at least laminated algal stromatolitic to massive dolostones of the
portions of the Society Cliff succession once contained a upper member are isotopically similar. Covariant C-O iso-
much greater volume of halite and that the unit, at least in tope signatures imply later dolomite cements was precipi-
some regions was halokinetic. tated from warmer pore fluids, along with ongoing
Closer to the Nanisivik deposit, a thin bed of relict gyp- replacement and isotopic re-equilibration of some of the ear-
sum (5–10 cm thick) was encountered at the same strati- lier dolomite precipitates. Such rock-fluid interactions with
graphic level as the ore zone in two boreholes immediately increasing fluid temperatures typify mesogenetic textures in
west of the main ore zone. In addition, gypsum (satin spar) fold and thrust belts worldwide (Warren et al. 2014).
commonly fills fractures in the dolostones surrounding the Dolomitising fluids responsible for later fracture and vug
ore zones in the mine area. Much of the Society Cliffs filling zebra dolomite cements may have been released by
Formation outcrop is extensively brecciated, particularly in compaction of the underlying Arctic Bay Shale, which also
the western Borden Peninsula, with interfragment spaces appear to have been the source of the base metals (Ghazban
filled with sparry dolomite and less frequently with sulphide et al. 1992).
Heavy δ34S values of sulphides, ranging from 21.5 to Tarma granodiorite. In the San Vicente area, the Tarma
31.2 ‰, suggest complete reduction of marine evaporitic sul- granodiorite and Precambrian metamorphic basement rocks
phate, with no isotopic difference between sulphate and sul- have been thrust over the Pucará carbonate rocks from west
phides. Isotopic temperatures from intersulphide
fractionations range from 90 to 270 °C. Plots of fractionation 75°25´ 75°20´
versus δ34S show that the sulphur source was heavy through- La Merced
out sulphide precipitation, and was also consistent with total 11°05´
in situ thermochemical sulphate reduction (Fig. 15.66b;
Ghazban et al. 1990). The likely reductant was organic mat-
ter, traces of which remain as pyrobitumen, although meth-
ane and volatile hydrocarbons may also have been involved. San Ramon
SP
Striking evidence for the role of organic derivatives is found
in δ13C values of the white sparry ore dolomite, which varies
between +6 and −12 ‰ (Fig. 15.66a; Ghazban et al. 1992). PJ
Whatever the fine-scale paragenetic detail, overall ore
formation at Nanisivik reflects processes involving in situ PA
reduction of calcium sulphate in the presence of hydrocar-
bons and derived H2S at the site of ore deposition. The loca- AR MA Vitoc
tion and configuration of the orebodies was probably
San Vicente Mine
controlled by the former position of near horizontal fluid
redox interfaces. The question to be resolved by future US
North AC
matrix characterisation is: was that interface there because of 11°15´
a now-dissolved evaporite seals? AY
San Vicente, Peru 5 km

QU UT
The San Vicente Zn-Pb deposit is the largest of a number of
similar Pb-Zn-Ag accumulations hosted in the Upper Triassic YS
Lower Jurassic Pucará Group in central Peru (Fig. 15.67) RO
and situated 300 km east of Lima, in central Peru. It is part of Pucará Group
an outcrop belt that defines the eastern part of the NNW- Lower Paleozoic QP
trending Pucará Basin at the margin of the Brazilian Shield. Tectonic lineament
In the San Vicente district, evaporitic platform carbonates of Closed mine
the Pucará Group constitute a thrust prism that overlies mag- MVT ore occurrence
matic and continental siliciclastic rocks of the Upper
Permian – Lower Triassic Mitu Group. Phyllites of the Fig. 15.67 San Vicente, Central Peru. (a) Map of San Vicente MVT
Lower to Middle Palaeozoic Excelsior Group occur region- district. QP Quebrada Pifion, RO Rondayacu, YS Yanachuro Sur, UT
below the Mitu Group (Fig. 15.68; Badoux et al. 2001). Utcuyacu, QU Quebrada Uteuyacu, AY Aynamayo, CH Chilpes, US
Uncush Sur, AC Afloramiento Campana, SV San Vicente mine, AR
During Late Permian – Early Triassic time, various intru- Arcopunco, MA Machuyacu, PA Palmapata, PJ Puntayacu Junior, PS
sions were emplaced, such as the San Ramon granite and the Pichita Sur
Precambrian basement rocks

West t East
us
thr
y atu San Vicente
cu orebodies
Ut Mitu Group
(Late Permian-Early Triassic)
Fig. 15.68 Schematic cross-section Tarma
of the San Vicente district, Bolivia. Granodiorite
The Pucará Group has been
overthrust by the Tarma
Granodiorite along the Utcuyatu San Ramon
fault. The Pucará Group is a variably Granite
dolomitic and evaporitic sequence Pu Excelsior
(Upp
er Tria cara Grou Group 1 km
undergoing shearing along a ssic-L p
westerly plane dipping ~25–30° ower
Juras
sic)
(After Badoux et al. 2001)
Platform Edge
Open Basin
Continental
Tidal Flat
Lagoon
% detr.
Barrier
Slope
quartz
Arama Condor
-chay -singer
1 5 20 40
Alfonso Dolomite: Medium to very coarsely crystalline
Hettangian
dolomite with abundant white sparry dolomite (WSD)

1,200 m Breccia
Unoush Limestone: Bituminous laminated black
limestone with shale/silt intercalations Breccia
San Vicente Dolomite: Main ore bearing unit. Fine to Evaporite
1,000 m Evaporite
very coarse dolomite. Abbundant WSD with evaporite
pseudomorphs. Subtidal oolitic barrier facies with
Evaporite
lagoonal and supratidal intercalations Evaporite
Evaporite
Neptuno Limestone: Dolomite layers in part de- 800 m
dolomitised and karstied. Shaly intercalations.
Rhaetian
Breccia
Chambara
San Judas Dolomite: Fine to very coarse dolomite.

Triassic
Abundant WSD and evaporite pseudomorphs. Subtidal 600 m

oolitic barrier facies with lagoonal and supratidal
intercalations Evaporite
Breccia
400 m Breccia
Basal series: Limestone and dolomite. Up to 35 %

detrital material, mostly at base. Facies: mostly open 200 m
marine shelf with intercalations of shallower facies
Norian
0m
Red sandstone: Clastic facies consisting of red silt
and sandstone with massive lenses of gypsum
Horizon with diagenetic rhythmites

Ore horizon
Fig. 15.69 Stratigraphy of part of the Pucará Group in the San Vicente Mine area (In part after Fontboté and Gorzawski 1990)
to east along the Utcuyacu thrust. Minor thrust zones also Sphalerite and galena are the main ore minerals, with
occur in the Pucará Group. The thrusts are located along a accessory pyrite and traces of marcasite, chalcopyrite and
major Andean thrust zone, which is probably Miocene in age sulphosalts. The gangue consists predominantly of dolomite
(Badoux et al. 2001). with accessory calcite. Different generations of hydrother-
The first written records of mining activity in the San mal carbonates can be distinguished: (1) early, dark
Vicente region are from 1820, when the area was named the replacement dolomite; (2) open-space filling, white sparry
Guernica Mine. Various operations continued, at times sporadi- dolomite; (3) late stage void-filling dolomite and calcite; and
cally, since then and operations continue today. Production dur- (4) dolomite and calcite replacing sulphates in evaporitic
ing the past 20 years, plus present reserves, exceeds 12 million units. Most of the sphalerite occurs in the same paragenetic
tonnes of ore assaying about 12 % Zn and 1%Pb. Sphalerite position as the hydrothermal dolomite. Fine-grained, dark
and galena, the only ore minerals, occur as lens-shaped bodies brown sphalerite accompanies early, dark replacement dolo-
generally parallel to the bedding. There are three ore-bearing mite, and coarse-grained brown to yellow sphalerite is asso-
dolomites that lie within the 1,400 m thick Pucará sequence ciated with white sparry dolomite. Galena precipitated
(Figs. 15.68 and 15.69). The San Vicente dolomite is the main mainly with late stage void-filling dolomite (Fontboté and
ore-bearing unit and hosts the exploited part of the San Vicente Gorzawski 1990).
mine. Other ore occurrences are located in the San Judas Three major types of gangue structures can be at the San
Dolomite and the Alfonso Dolomite. Individual ore lenses are Vicente mine (Fig. 15.69): (1) rhythmic, inter-layering of
hosted in dolomitised tidal flat and lagoon facies characterised dark replacement and white sparry dolomite, defining typical
by cryptalgal laminae and evaporite moulds after former sul- zebra structures; (2) breccia with clasts of dark replacement
phate evaporites (including gypsum). dolomite in a matrix of white sparry dolomite; and (3) veins
4 According to Fontboté and Gorzawski (1990), such burial

Ore stage dolomites temperatures would have been attained when sediments
A
2 reached at a burial depth of ≈ 2–3 km and indicative of burial
100 °C depths reached by the end of the Jurassic. However, the tim-
ing of the ore emplacement is controversial. Fontboté and
0 120 °C
Gorzawski (1990) suggested that brine circulation was
related to uplift of the Marañon geoanticline at the end of the
−2 100 °C
Jurassic, and Moritz et al. (1996) proposed that the San
Vicente deposit was contemporaneous with the Incaic phase
δ CPDB (‰)
−4
B 150 °C of the Andean orogeny at ~40 Ma. Underground mine exten-
sions in recent years have revealed abundant ore-bearing
120 °C
structures suggestive of a syntectonic origin for the San
13
−6 Vicente deposit (Badoux et al. 2001). Thus, the deposit might

be as young as the host thrust zone, which is probably
−8 Miocene in age.
Whatever the emplacement age, ores were emplaced by
Uncush limestone
the thermochemical reduction of evaporite-derived sulphates
−10
Late void filling calcite at or near the ore site and the introduction of a zinc- and lead-
Calcite replacing evaporite bearing basinal brine (Fontboté and Gorzawski 1990). After
−12 the low temperature sulphide ore emplacement stage, the
150 °C C
replacement of the evaporites continued with the precipita-
12 14 16 18 20 22 24 26 tion of calcite replacing evaporites with isotope characteris-
18
δ OSMOW
(‰) tics indicating fluid temperatures in excess of 150 °C
(Fig. 15.70).
Fig. 15.70 δ13C vs. δ18O for various calcites from the San Vicente Interestingly, San Vicente ore zones are associated not
mine. Also plotted are theoretical temperature curves for calcites indi-
just with sulphate evaporites, but with well developed strat-
cated by mixing of fluids (A, B, C). Shaded field indicates plot field
occupied by ore-stage dolomites (Based on analyses listed and interpre- abound breccia layers. Historically, these breccias were
tation by Fontboté and Gorzawski 1990) interpreted as depositional slope deposits by Fontboté and
Gorzawski (1990). Their interpretation was done 25 years
ago, before there was a widespread understanding of evapo-
filled with white sparry dolomite. These structures are recog- rite solution breccia textures. More broadly, the Pucará group
nised in both economic and barren areas of the mine. In ore- was deposited in an extensive system of Traissic rift-to-drift
bearing areas, brown to yellow sphalerite generally occurs grabens that constitute the Oriente-Ucayali-Ene Basin. In
between dark dolomite and white, sparry dolomite, whether northeast Peru the Pucará Group depositional system con-
it is zebra, breccia or vein-type ore (Fontboté and Gorzawski tains thick halites at the level of the Mitu Group. This same
1990). Ore lenses tend to occur as stratabound units adjacent salt level is now the mother salt horizon for a number of dia-
to oolitic grainstones of former barrier-shoal facies. All three piric structures, such as the Huallaga diapirs, which have
ore-hosting dolomite units were deposited in a peritidal car- seen seismically imaged and drilled by the petroleum indus-
bonate platform that comprised: (1) the inner margin of the try (Alemán an Marksteiner 1995, 1997). The same salt is
lagoon (tidal flat), (2) the lagoon sensu stricto and (3) the also caught up in thrusts and other Andean deformation fea-
outer margin of the lagoon (barrier subenvironment). tures. If the same halite level once extended as far south as
Strontium, carbon, oxygen, and sulphur isotope geo- the San Vicente area is not known, but the evaporitic condi-
chemistry was carried out on consecutive crystallisation tions certainly did, as evidenced by the gypsum beds in the
generations in the San Vicente region (Spangenberg et al. Alfonso dolomite, the San Vicente dolomite and the San
1996; Moritz et al. 1996). The results obtained display sys- Judas Dolomite.
tematic trends that all show San Vicente lead-zinc deposit
formed during burial diagenesis via the mixing of incoming Largentière, Ardèche, France
hot saline, slightly acidic, radiogenic (Pb, Sr) basinal fluids The Largentière Pb–Zn deposit is located at the boundary
and local sulphate-rich formation waters derived from cal- between the sedimentary cover and the Massif Central block
cium sulphate beds. The temperatures indicated by sulphur and belongs to the Cévennes Pb–Zn MVT province
isotope geothermometry and carbon and oxygen ore stage (Fig. 15.71a; Aquilina et al. 2011; Leach et al. 2006; much of
dolomites are consistent with temperatures of 75–92 °C the following is based on these references). Since it is not in
(Fig. 15.70). limestone, the sandstone-hosted Largentière deposit lies
a Massif b Malm
Central Post Jurassic
Largentiére cover FRANCE
Dogger
Jurassic cover
Liassic
Causse Triassic cover
s
ne
Triassic
ult
basin
n
ve
Fa
Cé
er
Pre-Triassic Largentiére Upper
Uz
basement
FRANCE Carboniferous
MM1 well
lt
Fault
au
Tréves Southeast Mine BA1 well
ult
Basement
ef
Massif basin area
Fa
éch
Central > 400,000 t
Les Malines
llet
of Pb-Zn Fault
Ad
04°30´
Ma
2 km
< 400,000 t Fault
20 km of Pb-Zn 44°30´ paleosurface
c Largentiére Pb-Zn deposits

MM1 BA1
NW
SE
Uz
er
Fa
u
Mallet fault
lt
Liassic carbonates
Carbon
Hettangian fractured dolomite ife rous dé
colleme
nt
Triassic evaporitic formations (continental?)
Permian and Stephanian formations 1 km
Crystalline basement
Fig. 15.71 Largentiére Pb-Zn, SW France. (a) Regional geological map showing Pb-Zn occurrences in the Cevenne District. (b) Local geology
of the Largentiére region. (c) Cross section of the Largentiére region, position of section indicated on Fig. 15.71b (After Aquilina et al. 2011)
outside the typical carbonate platform host assumed for a fluid-driven set of processes tied to a chemistry and hydrol-
MVT Zn-Pb mineralisation deposit (Sverjensky 1986). ogy driven by dissolving evaporites; it is an precipitative
Largentière is considered to be part of a broader sandstone- interaction between evaporitic sulphate, chloride brines and
hosted Pb-Zn association, mostly related to saline basinal- hydrocarbons/ organic matter. “MVT” style precipitation can
brine metal carriers (Schrijver 1992). In addition, there are be independent of the ore matrix, although sulphate evaporites
many Zn-Pb deposits along the same Cévennes margin, are more typically found in platform carbonates. In Largentiére,
hosted in platform carbonates. Hence, the area is also consid- sulphates reside in redbed sandstones, not salterns or carbon-
ered an MVT district, made up of numerous small deposits, ate hosted evaporitic mudflats. Locally, the precipitation pro-
including those with sandstone ore hosts. cess (in this case TSR) can be independent of the matrix
Independent of host lithology there is clearly a common lithology (sandstone or carbonate). The commonality between
genetic origin to the Pb-Zn deposits of the Cévennes district the two matrices (carbonate versus siliciclastic) is in the pres-
that ties them to a combination of chloride-rich fluids, struc- ence of calcium sulphate on the reducing (greenbed) side of
ture and calcium sulphate. The Cévennes district is structur- the redbed/greenbed diagenetic front.
ally related to the Mesozoic Southeast Basin to the east as well Ores in the Cévennes MVT district occur in various geo-
as the Triassic and Jurassic cover of the Causse basin to the logical contexts: Cambrian and Jurassic carbonates, fault-
west (Fig. 15.71a). The fact that the host is a sandstone is why related or massive deposits, vug fillings in carbonates, etc.
I will describe these deposits in a fair degree of detail. I use as well as in various types of mineralogical sequences
Largentière to illustrate that Pb-Zn precipitation a ssociation is (Aquilina et al. 2011). Most of the economic precipitates are
hosted in platform carbonate rocks and consist of sphalerite, in the Volpilliare region, along with galena in fibrous veins
galena, pyrite and baryte (and fluorite). On a larger scale, (satin-spar) crosscutting the marls. The possible significance
they can be related to the MVT deposits of Mesozoic sedi- of satinspar texture as a likely indicator of former more
mentary basins in western Europe associated with the break- widespread halite is not considered in the existing literature.
up of Pangea (Heijlen et al. 2001; Muchez et al. 2005). The coincidence between sedimentary facies, faulting and
There are numerous mining sites along the Cévennes chain the location of mineralization implies a lithologic/structural
(Fig. 15.71a). The deposits of Les Malines include massive control to the ore deposit. Regionally Pb-Zn mineralization
sulphide bodies in Bathonian karst cavities (40 % of the appears along the Hercynian faults of the Mallet horst but is
total tonnage) and ore bodies within Triassic karstic infills also controlled by synsedimentary faults in some Triassic
of cavities developed in Cambrian dolomites (35 % of the beds (Fig. 15.71c). Mixing of hot basinal chloride brines
total tonnage). (high metal content) derived in part from dissolving downdip
The Cévennes is one of the most important Pb–Zn dis- Permian evaporite masses and cooler meteoric fluids leaching
tricts in Europe, with a total metal content of 2 Mt of Pb and of Triassic sulphates (high sulphur content) is proposed for
Zn (Aquilina et al. 2011). Largentière, the northernmost the Trèves deposit located close to Largentière (Fig. 15.71a;
deposit, was estimated as hosting 350,000 t of Pb and Leach et al. 2006).
70,000 t of Zn (9.6 Mt of ore mined) and 710 t of Ag. The The key to the interpretation of the mineralisation para-
most recent mine at Largentiére operated as France’s largest genesis at Largentiére comes from placing the isotopic and
Pb mine from 1953 to 1984, but silver was mined in the petrographic signatures of this and other nearby Pb-Zn
region as early as the 14th and 15th centuries. The mine site deposits in into a more regional diagenetic and structural
at Largentiére is on the western edge of the Cévennes is context, as was done by Aquilina et al. 2011 (Fig. 15.72).
Trèves, with an estimated 80,000 t of Zn and 20,000 t of Pb Their synthesis shows that a major fluid circulation event
(3,600 t Zn and 817 t Pb produced, respectively) (Fig. 15.71b). occurred across the Alpine margin of Tethys during the Early
Largentière Pb-Zn mineralization covers an area some Jurassic (Hettangian–Bathonian). It produced a general
1.5–3 km across, where precipitates include galena, sphaler- cementation of the rock porosity, through precipitation of
ite, pyrite and baryte (Fig. 15.71b). Mineralisation occurs dolomite, burial anhydrite and baryte. Fracture fillings yield
mostly within Lower Triassic sandstones and arkoses (30– isotopic signatures distinct from the matrix cements
50 m thick), less frequently in about 20 m of overlying (Fig. 15.72; sedimentary sulphate versus fluid-related sul-
Middle Triassic dolomite, and rarely in Upper Triassic argil- phate plot field). Matrix cements have particular characteris-
laceous sandstones (Bouladon 1984). Ore at Largentière tics, i.e. δ34S and δ13C values that indicate a marine-brine
occurs either as fracture fillings, as disseminated sulphides, hypersaline source. The δ34S values of Permo-Carboniferous
or as fracture controlled massive sulphide ore. Whilst pyrite to Triassic sulphides from fracture cements likely indicate
appears in the mineralized area associated with quartz, anhy- thermo-chemical reduction of sulphates. Fracture sulphates
drite is observed in the western part of the district. At the in the same geological formations yield δ34S values that
scale of the Southeast basin, the ore deposits always appear define a relatively homogeneous end-member, with compo-
at the contact between the sandstone and the sedimentary sitions similar to fluid-related calcium sulphates in the
anhydrite facies (Fig. 15.71b, c; Debrand-Passard 1984). Largentière Pb–Zn ore deposit. The source of S and the met-
For example, Bed 5 ore at Largentiére formed as a cement alliferous chloride-rich brines is attributed to dissolving
within coarse-grained sandstones at the base of the Triassic evaporite masses in the Permo-Carboniferous succession.
section and is located less than 15 m above the Permian con- The extensional geometries so obvious in Fig. 15.71c show
tact. There is not always a single mineralised horizon, but structural similarities it the updip salt-withdrawal basin-edge
stratiform character is the rule at Largentiére. Local ore grabens in the Gulf of Mexico, onshore Texas.
enrichments are related to shear zones, the general connec- The borehole fracture fillings are attributed to a major
tion between mineralisation and faults in bed 5 ore is not fluid circulation stage compatible with the Early Jurassic
always clear, but the tie to the redbed-green bed (CaSO4) stage. The formation of the Largentière deposit is considered
contact is. About 10 m above bed 5, the redbed sandstones as resulting from the mixing of Early Jurassic fluids with
change to dolomite-cemented greenbeds and green argilla- hydrothermal fluids circulating in a basement horst, along
ceous, gypsum-bearing lagoonal siltstones appear (the the basement high that constitutes the up-dip margin of the
reduced facies). The Pb-Zn mineralisation in beds 1, 2 and 3 sedimentary basin (Fig. 15.71c). Other nearby Pb–Zn depos-
(termed the “upper mineralised horizon”) is consistently tied its are also related to fluid migration along the basement/
to the presence of gypsum within the mineralised intervals sedimentary cover interface in the eastern and western parts
(Bouladon 1984). In this upper interval, mineralisation is of the Massif Central. According to Aquilina et al. (2011),
associated with faults, and “fissure ore” dominates in dolo- this regional fluid circulation event is a likely geodynamic
mitic sandstones and marls. Gypsum has been reprecipitated marker of the Jurassic extensional phase.
Fig. 15.72 Sulphur isotope

4
frequency histograms from Fissure anhydrite
samples collected in the MM1
and BA boreholes. Largentiére
2
region (Replotted for data tables
in Aquilina et al. 2011)
0
1
Fissure gypsum
2
Fissure baryte
2 Matrix anhydrite
Frequency
1
Fissure pyrite
Matrix pyrite
0
– 40 – 30 – 20 – 10 0 10 20 30
δ34S (‰)
CDT
In the Palaeozoic formations in the Largentiére region, sul- biological reduction of sulphate followed in both cases by
phur from sulphates and sulphides shows a relatively narrow precipitation of pyrite and other metal sulphide via interac-
range of isotopic variation (−10 ‰ to +5 ‰, except for two tion with H2S. Both the TSR and BSR mechanisms lead to
pyrite values), similar to the Largentière Pb–Zn deposits stable isotope fractionation plot fields of pyrite sulphur that
(−10 ‰ to +6 ‰). Such values are different from the marine can overlap (−20 ‰ to −10 ‰ at 200–100 °C and −15 ‰ to
sedimentary signature (Fig. 15.72). They likely indicate the −30 ‰ at ambient temperature). Biological reduction is
thermal sulphate reduction of calcium sulphates to sulphur or unlikely at Largentiére because (1) Excessively high
Fig. 15.73 Carbonate and 30

Sulphate stable isotope plot
fields indicating the diagenetic BA1
Sedimentary Hettangian
nature of the calcium sulphate in
25 carbonates
the BA 1 and MM wells in the
Largentiére region. See
Fig. 15.71b for location (After
Aquilina et al. 2011) Sedimentary
20 sulphates
δ18O(‰)
15
Fluid-related
carbonates MM1
10 Hettangian
Fluid-related
5 sulphates
Carbonates Sulphates
0
−20 −10 0 10 20 30
δ C(‰)
13
δ S(‰)
34
Fissure minerals in BA1 Matrix minerals in BA1

Fissure minerals in MM1 Matrix minerals in MM1
Hettangian fissure sulphates Hettangian fissure sulphates
in BA1 in MM1
t emperatures are indicated in fissure cements in the Palaeozoic already mentioned, the S isotope signature of the sedimen-
(about 100–200 °C), (2) δ34S are higher (more positive) than tary anhydrites is too low to be a diagenetically unmodified
the values found in matrix sulphides related to biological sul- calcium sulphate source. (2) Hypersaline brine migration
phate reduction and (3) lower fractionation differences at the from the eastern part of the basin: fluid migration related to
relatively high temperatures produced by thermo-reduction, Triassic diapirs has been identified from fluid inclusion stud-
compared with biological reduction, fits better with the data ies in the deeper eastern part of the southeast basin, but simi-
(e.g., note the strong overlap between fluid-related sulphates lar fluid inclusions (NaCl type) were not identified in cements
and the sulphide pyrite values in Fig. 15.72). in the BA1 and MM1 boreholes. Furthermore, the isotopic
The δ34S values in the fissure sulphates from Palaeozoic signature of the calcium sulphates of these fluids should be
and Triassic formations vary from +13 ‰ to +22 ‰ similar to those of the Triassic evaporites in BA1 and MM1,
(Fig. 15.72). This is interpreted by Aquiliana et al. (2011) as since the evaporitic formations in the Southeast basin are
the result of mixing between the sedimentary sulphate pool contemporaneous. (3) Palaeozoic calcium sulphates: Permian
of the Triassic middle sulphate unit and sulphate with a and Carboniferous evaporitic formations attain a great thick-
higher δ34S signature. The Triassic sulphate signature is par- ness over the whole margin (about 1,000 m), representing a
ticularly marked at the base of the middle calcium sulphate large source of S with a marine isotopic signature. Burial of
unit in the well MM1 and immediately below the equivalent these Permian formations to a depth close to 1,000 m at the
unit in the BA1 well. The high δ34S population observed in end of the Triassic, and reaching 2,500–4,000 m during the
the calcium sulphates of the Triassic, and even more clearly Jurassic, along with ongoing dissolution of the Permian
in the Palaeozoic formations, is in the range +17 ‰ to +20 ‰. halites created early conditions for fluid expulsion.
This range is similar to that observed in the Largentière Pb– The link of the Uzer fault with intra-Carboniferous décol-
Zn deposits (+17 ‰ to +22 ‰). This very narrow range of lement led to Permo-Carboniferous derived fluid moving up
δ34S for the sulphate deposits across the region in a sedimen- along the Uzer and other related extensional faults
tary pile about 800 m thick, as seen in the two boreholes, (Fig. 15.71c). As observed for the sulphate δ34S values in the
requires a large-sized and homogeneous sulphate pool. anhydrite cements, the δ13C of the fissure carbonates is rela-
Three potential sulphur sources are considered by tively homogeneous across the Palaeozoic and Triassic, with
Aquilina et al. (2011): (1) Triassic evaporitic units: but, as a narrow range of −5 ‰ to −10 ‰ (Fig. 15.73). Such values
do not represent marine sedimentary carbonates and cannot v ariety of tectonic settings, after we consider what happens
be attributed to simple C-isotope fractionation between cal- to saline fluids from the haloes of halokinetic salt masses that
cite and CO2 or HCO3. This is because, at 100 °C, calcite is pass vertically to seafloor rather than migrating to the basin
enriched in 13C by about 1.5 ‰ compared with these fluid margin. We touched on this type of ore deposit in the discus-
species. These low carbon isotope signatures imply the con- sion of the Atlantis II Deep sulphides and brine pools at the
tribution of low-δ13C organic carbon, a common feature that edge of dissolving salt allochthons in a salt-covered rift-
has already been observed under similar burial conditions in induced basinal brine sump, and so we come to a discussion
other Pb-Zn deposits (Aquilina et al. 2011). Indeed, organic of evaporite-associated SedEx deposits
matter is present in this context, as well as CO2 accumula-
tions with negative δ13C (−2.7 ‰ to −3.2 ‰). Furthermore,
this carbon signature represents a relatively homogeneous Evaporite-Associated SedEx Deposits
‘crustal’ carbon, even though it originates from both a marine
and an organic source. As such, it provides another indica- Associated with a hydrothermal vent-related origin for vari-
tion of fluid transfer at the margin scale, including density ous sediment-hosted exhalative (SedEx) deposits, most
and thermal-driven convective circulation within the margin authors currently accept there are two laminite endmember
basement (See Chap. 8). models, namely, SedEx deposits that are; (1) Vent-proximal
The fissure sulphates in the Hettangian interval can have laminites formed by rain-out of a metalliferous plume
high δ34S and high Sr isotope ratios in both the boreholes, spreading in the water column, considered by some to tied to
which could indicate a different fluid circulation stage and/or VMS black-smoker or Cyprus-style vent deposits (see Chap.
slightly different source or conditions of evolution for higher 16) versus, (2) Vent-distal laminites formed in a bottom-
value cements. However, as observed in Fig. 15.73, this hugging saline pond in a sea-bottom brine sump or lake,
mainly applies to cements the Hettangian in BA1, but is less much like the Atlantis II deep discussed earlier (Fig. 15.74).
clear for MM1, which yields δ34S overlapping values than The matrix within many Pb-Zn laminite deposits typically
the Triassic fluid carried sulphates. Although affected by the contains little or no carbonate. Within this classification
same generalized fluid circulation event at a geological scale, framework, additional subtypes, typically listed by economic
the Hettangian hosted cements in well BA1 may represent a geologists as SedEx in the broader sense can include; Broken
different regime with higher temperatures lower fluid/rock Hill type (BHT) deposits and those Pb-Zn deposits that
ratios and slightly different fluids. Such a difference between formed below, but near, a seafloor vent system (e.g., Irish-
the two geological formations may be linked to the Uzer type Navan deposits; Goodfellow and Lydon 2007). The
fault. The very high initial porosity of the Triassic upper Irish type of SedEx deposit is hosted predominantly in car-
sandstone unit (and, to a lesser extent, the lower sandstone bonate rocks and these deposits, either individually or col-
unit) may have channelled the fluid circulation, whilst more lectively (district-wide), may show characteristics of saline
limited fluid flow could have occurred in the Hettangian. brines involved in both seafloor deposition (seep-related che-
Largentiére and all the other Pb-Zn deposits discussed in mosynthetic communities) and in epigenetic/hydrothermal
this section illustrate what happens when metalliferous karst settings, which many geologists consider more typical
chloride-rich saline fluid climbs into basin margin sediments, of Mississippi Valley-type deposits.
where they precipitate Pb-Zn sulphides at a chemical interface, Irish-type deposits are considered to have formed by ore-
which is typically a redox front tied to either bacterial or ther- forming processes similar to those of seafloor SedEx depos-
mogenic sulphate reduction. The sulphur that ends up in the its. But, because carbonate platforms are highly soluble in
metal sulphide is typically evaporite-derived; it may be locally mildly acidic ore fluids, the ores were typically deposited
sourced in saltern beds or nodule sulphate in evaporitic mud- subsurface rather than at-surface, as passive precipitates in
flats, it may be a burial anhydrite cement in a sandstone, or it open porosity in a carbonate host that commonly formed by
may be a residual carapace or caprock to a salt structure. hydrothermal karsting (e.g., mineralisation in hypogene dis-
Alternatively sulphur may be carried to the final site of precipi- solution voids, collapse breccias; stylolite replacements;
tation (trap) in solution as sulphate or as H2S, depending on the Reed and Wallace 2004). Broken Hill Type deposits are
chemical state of the carrier fluid. Much of the time the carrier characterized by higher metamorphic grade, elevated base
bed geometries are tied to combinations of dissolving salt metal to sulphur ratios, a spatial and temporal association
masses, permeable beds and fault foci. Much of the faulting, with Fe-Si-Mn oxide exhalites, and bimodal felsic-mafic
either suprasalt or updip is related to structural accommodation volcanic/intrusive and fine- to coarse-grained, mostly clastic
driven by flowing and dissolving downdip salt masses. Such sedimentary host rocks (Figs. 14.64 and 15.38; Conor and
fault and salt mass focused fluid flow and mixing can occur in Preiss 2008).
either extensional or compressional tectonic settings. A plethora of overlapping characteristics and poorly
We shall come back to this notion of regional salt-related defined associations to particular analogs typifies the current
controls to low temperature diagenetic ore deposits in a state of classification of low temperature Pb-Zn SedEx
Sedimentary-hydrothermal facies: sphalerite, galena, pyrite, pyrrhotite,

chalcopyrite, interbedded with baryte, chert, and pelagic/clastic
a
sedimentary rocks (laminites)
Distal sedimentary facies: baryte, carbonates, Fe-oxides, phosphates, pyrite,
minor sphalerite, etc. Post-ore
sedimentary rocks
Thin beds of hydrothermal minerals: baryte, apatite, pyrite, minor sphalerite
in post-ore sediments
Vent complex: bedded sulphides brecciated, veined and variably replaced by

one or a combination of chalcopyrite, tetrahedrite, arsenopyrite, pyrrhotite,
galena and sphalerite
Feeder Zone: footwall sedimentary rocks brecciated, infilled and replaced by
Syn
combinations of quartz, carbonate, chlorite, sericite, tourmaline and
sulphides
sed
Stratabound infilling, replacement and alteration of permeable sedimentary Pb:Zn decreases
units. (In northern Australia it is mostly sparry ferroan carbonate and Ba:Zn increases
ime
magnesite)
ntar lt
Hydrothermal alteration zone in post-ore sedimentary rocks (albite,
fau
chlorite, carbonates, minor sulphides)
Pre-ore
y
sedimentary rocks
Fault scarp: fragmental and sedimentary breccias (Are they all
nonevaporitic? Or are some horizons related to former layers of mobile
salt?) Vent complex Bedded Distal hydroth.
Representative scale Ore grade decreases

m 100 Pb:Zn ratio decreases
0
Sedimentary exhalitive Ba:Zn ratio decreases
m
(sedex) lithofacies 20
Mn increases
Thickness decreases
b O2
c
distal hydrothermal Bouyant vent plume H2S

sediments (in water mass) O2
H2 S
Brine lake on Venting into sumps
deep seafloor
Vent
complex
Bedded
sulphides Feeder Deeper water Bedded sulphides
Zone muds
Alteration Alteration
halo halo
Hydrothermal
alteration
Dispersed Proximal Distal Proximal
Fig. 15.74 Sedimentary exhalative (SedEx) deposit model. (a) from the brine lake. Venting brines are dense and hug the seafloor as
Schematic cross section of SedEx mineralisation showing zonation and they flow toward the deep-seafloor brine sump (After Goodfellow et al.,
accompanying lithofacies. (b) SedEx in proximal position with brine 1993; Goodfellow and Lydon 2007; Warren 1999, 2000b)
plume dispersal. (c) Brine lake style with brines venting some distance
deposits (as noted by Groves et al. 2005, 2010). In the eco- ocean basalt ridges. At continent -continent promixal young-
nomic geology literature it is generally argued, especially at oceanic ridges, the halite must be halokinetic – as in the ther-
the deposit scale, that, no matter what criteria are used to mal Atlantis II deep, (3) solution chemistry and characteristics
define a SedEx deposit, there is a continuum of characteris- of sulphide and non-sulphide cements in the associated brec-
tics between SedEx and VMS (volcanogenic massive sul- cias in the immediate vicinity of ore lenses [either warm as in
phide) deposits on the one hand, and SedEx and MVT diagenetic (<200–250 °C; versus hot >250–300 °C] in igneous
deposits on the other hand. VMS associations. The differences in these three factors are
I disagree, the following sedimentologic/diagenetic/meta indicators of the specific ore system; as is the nature of the sur-
evaporite criteria clearly separate the three deposit styles, rounding non-ore matrices, as well as the type and geometry of
namely; (1) the nature of the associated CaSO4 (depositional the alteration residues. In addition, differences in ionic propor-
beds versus burial diagenetic verses hydrothermal in an tions seen in the hydrochemical details, captured in fluid inclu-
igneous-rich matrix), (2) tectonic settings that facilitate thick sions, are pointers to the ultimate brine source. In combination,
bedded halite deposits, thick halite cannot precipitate at open all these factors can be used to separate the three deposit styles.
Fig. 15.75 Resource plot for 100 10 10

10 8 Giant and supergiant
sedimentary exhalative deposits. 7 to 9
to Rampura-
to nn nn Agucha (E)
Halokinetic association indicated nn e
Century (H?)
Red Dog
by H, bedded evaporite e e Hilton-George Fisher (H)
Mt Isa (H)
association by B and metamorphic
evaporite association by M Broken Hill (E)
(Plotted data values were HYC (H)
10 10 Sullivan (E)
extracted from, integrated with the
Pb + Zn grade (%)
6
to Kholodninskoye
SedEx evaporite association GIS nn
base and classification extracted e Howards Pass
from the SaltWork database Dongshengmiao (H)
version 1.6) Gamsberg
Changba-
10 Lijiagou
1 6
to
nn
e
0.1
0.1 1 10 100 1,000
Ore (millions of tonnes)
SedEx and MVT deposits tend to occur within slope than 10 metric tons (Mt) combined Pb + Zn. In order of
deposits of thick sedimentary basin fills or in platform car- decreasing endowment these six are; Mt. Isa–McArthur
bonates, respectively. Both are the result of the upward and basins (7 deposits totalling 112 Mt of Zn + Pb metal), Selwyn
lateral migration of slightly acidic basinal chloride-rich met- basin (17 deposits totalling 55 Mt), Brooks Range (3 depos-
alliferous somewhat lower-temperature saline fluids. Updip its totalling 40 Mt), Rajasthan (5 deposits totalling 20 Mt),
fluid movements often enhanced or focused by fault and Belt-Purcell (1 deposit totalling 19 Mt), and the Rhenish
fracture-related conduits, which are related to halite flow Basin (2 deposits totalling 11 Mt) (Figs. 15.75 and 15.76).
(diapirism and gravity gliding) and salt dissolution. And, as Distribution of SedEx deposits is not equally spread
we shall see, the strength of the ore-depositing SedEx system across geological time (Fig. 15.77; Lyons et al. 2006). SedEx
can be enhanced by the dissolution of basinal or platform Zn-Pb-sulphide mineralization first occurred on a large scale
evaporites. during the late Paleoproterozoic with only a few small dubi-
In contrast, VHMS deposits occur in submarine volcanic- ous set of examples in the Archaean, most of which are better
sedimentary host sequences (associated with Kuroko-style pigeonholed in a VMS setting. Because free oceanic sulphate
anhydrites), which host hot convective hydrothermal flows ions and resulting sulphate evaporites are produced mostly
of seawater and/or magmatic fluids, mostly through igneous through weathering of the continents in the presence of oxy-
basement, driven by the heatflow from a subvolcanic magma gen, a lack of calcium sulphate beds in the Archaean and the
body. Typically, no sedimentary evaporites are involved in beginnings of sulphate bedded deposits in the early
the metal transport or precipitative portions of a Volcanic Proterozoic implies a transition into more oxygeneated
Hosted Massive Sulphide (VHMS) deposit, although rem- ocean surface waters. Sulphate (not H2S) typified ocean
nant textures from hydrothermal-seawater anhydrites can be waters at that time and since. This event was biogenically
a common gangue phase. VHMS deposits are discussed in driven and is called the first “Great Oxidation Event.”
the next chapter. Colloquially, it is known as the time when the oceans rusted
Using Goodfellow and Lydon’s (2007) definition, SedEx and widespread oceanic banded iron formation (BIF) pre-
deposits encompass a broad range of tonnages and grades cipitation largely ceased (Chap. 2). The subsequent period
(Fig. 15.75). They account for more than 50 % of the world’s (≈1,800–800 Ma) was typified by relatively low oxygen con-
zinc and lead reserves and furnish more than 25 % of the centrations, when atmospheric levels lay between the abun-
world’s production of these two metals (Emsbo 2009). More dances of the Phanerozoic and the deficiencies of the
than 130 deposits of this type have been recognized in sedi- Archaean, as indicated by the Precambrian sulphur isotope
mentary basins around the world (Leach and others 2005; record (Chap. 2).
Goodfellow and Lydon 2007). A compilation based on Given the limited availability of atmospheric oxygen,
Sangster and Hillary (2000) shows that the largest 65 depos- deepwater anoxia may have persisted well into the
its occur in 25 sedimentary basins, six of which contain more Proterozoic in the presence of a growing sulphate reservoir,
Brooks Range (Red Dog)

Selwyn Basin (Howards Pass. Jason)
Rhenish Basin (Meggen, Rammelsberg) Kholodninskoye
Belt Purcell Basin (Sullivan) Dongshengmiao
Rajasthan Basin
(Saladipura) Changba-Lijiagou
Mt Isa-McArthur Basins
(also George-Fisher, Century, Cannington)
Broken Hill
Fig. 15.76 Location of the world’s larger SedEx deposits and the sedimentary basins in which they occur (Replotted from Pb-Zn module in
SaltWork database, version 1.6)
Fig. 15.77 Age distribution of a 180
Pb + Zn million
SedEx mineralization as (a) tons
of tonnes
of Zn and Pb per 100 m.y. 120
interval and, (b) number of
60
deposits per 100 m.y. interval
(After Lyons et al. 2006) 0
20
b
Number of
15
deposits
10
5
0
(Ma) 2,000 1,600 1,200 800 400 0
Widespread oceanic
anoxia/euxinia in
stratied oceans
G.O.E. (≈2.3 Ga) Disappearance Second major

increasing SO4 of BIFs oxidation event
availability (H2S>Fe) in world oceans
Increasing O2 in world atmosphere and oeeans
which promoted prevalent euxinia. Collectively, these of banded iron formations—marking the transition from an
observations suggest that the mid-Proterozoic maximum in early iron-dominated ocean to one more strongly influenced
SedEx mineralization and the absence of Archaean deposits by sulphide availability. By contrast, the generally more
indicate a critical threshold in the accumulation of oceanic oxygenated Phanerozoic ocean may have only locally and
sulphate and thus sulphide within anoxic bottom waters and intermittently favoured the formation and preservation of
pore fluids—conditions that favoured both the production exhalative mineralization in brine-floored sumps, and most
and preservation of sulphide mineralization at or just below Phanerozoic deposits formed from reduced fluids that car-
the seafloor. Consistent with these evolving global condi- ried some sulphide to the site of ore precipitation.
tions, the appearance of voluminous SedEx mineralization Within this worldscale breakdown it is also worthwhile
around 1,800 Ma coincides generally with the disappearance noting the number of large SedEx deposits in the Proterozoic
and Phanerozoic that are located above, or lateral to, a cArthur River Basin and the HYC Deposit,
M
present or former halite mass in the same sedimentary basin Northern Territory
(indicated by E in Fig. 15.75). In my mind this regional asso- The McArthur River (aka HYC) zinc-lead deposit is one of
ciation with a thick dissolving salt bed in the basin stratigra- the largest in the world and is one of a number of Proterozoic
phy is more than fortuitous and once again illustrates the Pb-Zn deposits in northeastern Australia, south of the Gulf of
principle that evaporites do not form sulphide accumula- Carpentaria (Figs. 15.78 and 15.79). Current mineral
tions. Rather, ongoing salt flow and dissolution tends to sta- resources at the HYC McArthur River deposit are estimated
bilise the metal precipitation interface in a particular position at 157 Mt @ 11.3 % Zn, 4.9 % Pb and 49 g/t Ag. The ore is
in earthspace, so sediment-hosted deposits associated with made up of laminites dominated by fine-grained galena and
disappearing evaporites tend to be larger and richer. sphalerite, with pyrite and pyrrhotite. There is either a iron-
To illustrate the significance of this evaporite association I manganese or a silicate alteration halo to the ore zones,
will focus on Proterozoic examples in Australia that I have which show combinations of synsedimentary and replace-
worked during consultancy projects over the past 30 years. ment ore textures. The McArthur River (HYC) deposit com-
These and all the other examples I will discuss in this section are prises 50 % of the world’s current zinc and lead reserves and
SedEx deposits tied to present or former dissolving halokinetic some 20–25 % of world zinc and lead production. The HYC
salt masses. They are chosen to illustrate how salt dissolution, (“Here’s Your Chance”) deposit occurs at or near the base of
and associated brine flow, can aid in the formation of sulphide the HYC Pyritic Shale Member and the deposits proximity to
precipitates in seafloor brine lakes (Fig. 15.74c). Broader SedEx feeder faults (e.g. Western and Emu faults) is regarded as
compilations are published in excellent papers by Leach et al. being an important factor in understanding the genesis of
(2010), Goodfellow and Lydon (2007) and Lyons et al. (2006). HYC and nearby Ridge Cooley deposits (Fig. 15.80; Ireland
We have already looked at the best documented active et al. 2004; Large et al. 2005).
SedEx brine system in a metalliferous halokinetic associa- Current consensus is that the HYC deposit is a SedEx
tion, namely the modern Atlantis II Deep. There metal sul- deposit, which accumulated in an anoxic seafloor brine
phides are accumulating in a deep seafloor saline brine lake, basin, adjacent to a set of feeder faults that supplied brine
mostly sourced from an adjacent basalt-volcaniclastic aqui- and metals to the deep seafloor sump. Likely formative
fer, with outflow focused about the thinned and faulted edges mechanisms are detailed in an excellent paper by Large et al.
of a thick halokinetic salt mass. In the remainder of this (2005) and associated papers by Davidson (1999), Bull
chapter, we shall look at some older examples of a similar set (1998), Walker et al. (1977a, b). I will not repeat the details
of salt-dissolution brine focusing processes, but where the here other than to note the proximity of the deposit to the
dissolution brines are partially suprasalt and have passed Western Fault, its alteration halo and the association of the
along leaky fault conduits through a substantial thickness of Cooley Dolomite breccia unit to the deposit and the overly-
passive margin sediments. Unlike the Atlantis II deep, they ing HYC Pyritic Shale (Fig. 15.80a). The Western Fault and
do no sit atop or adjacent to seafloor basalts. Differences in the adjacent Emu Fault acted as a source of the debris and
source-feeder mineralogies explain why the Atlantis II Deep hydrothermal fluids, as noted by Ireland et al. 2004
is a Cu-Pb association (leaching Cu from the subsalt basalt- (Figs. 15.79 and 15.80b, c). The source of hypersaline fluids
redbed understory), while most SedEx deposit are Pb-Zn, seeping into the basin sump appears to change from a more
largely leaching their metals from the suprasalt sediment pile northerly source during the deposition of ore lenses 1–4, to a
(Sverjensky 1989). more easterly source for the upper ore lenses 5–8
To understand how the system operates we will also need (Fig. 15.80b). Throughout the time metalliferous laminites
to look through a veil of textural confusion in the economic accumulated in the lower part of the HYC pyritic shale, the
geology community, especially what constitutes a replaced depositional setting was a deep seafloor sump where
or altered evaporite association in Precambrian successions noncarbonate laminites accumulated, surrounded by shoal-
where the evaporites are typically long gone or represented water carbonate platform sediments and separated across a
by recrystallised anhydrites. There is also a widespread deep-basin bounding fault (Fig. 15.80c).
problem where some Proterozoic carbonate successions Beyond this consensus, which is also consistent with the
dominated by early marine cementstone textures on the floor brine pool model of Goodfellow and Lydon (Fig. 15.74c),
of a CO2 -saturated shallow ocean floor have been misinter- there is the question of the deposit’s regional significance
preted as evaporitic. I will do this in detail for the McArthur with respect to future exploration and exploitation for similar
Basin where I have some experience of the geology, both in SedEx laminites, both within the basin and elsewhere. That
the field as well as in core study. A study of the literature is, what drove and maintained the intraplatform sumps or
base in other SedEx basins makes it clear that similar analy- lows where the metalliferous sediments accumulated? At the
sis and refinement of possible evaporite indicators is needed broad scale, the deposit sits in an intracontinental sag known
in many Precambrian basins worldwide. as the Batten Fault zone (Fig. 15.78). But, more locally, what
Fig. 15.78 Proterozoic Pb-Zn 132° 00´ 141° 30´

SedEx deposits in northeastern
Australia 11° 00´
ARAFURA SEA GULF OF CARPENTARIA
Arnhem Inlier
Batten Fault
Zone
Pine Creek
McArthur
Inlier
River (HYC)
McArthur Basin
Walford
Creek
Murphy Inlier
Mt Isa
Basin
Century
Dugald
Lady Loretta River
Pre-Mesoproterozoic basement
Hilton &
Meso- to Paleo-proterozoic George Fisher
Intracontinental basin
Mt Isa
Phanerozoic cover
Cannington 22° 30´
drove and maintained the anoxic brine ponds where the met- Creek Formation. Table 15.14 lists the characteristics of
alliferous sediment has accumulated? The lack of a pervasive evaporite occurrence in some other major “SedEx” deposits
metamorphic overprint makes the McArthur Basin a suitable hosted in the Proterozoic sediments of northeastern Australia.
place to study mineralising characteristics in syndepositional In studies conducted in the McArthur Basin across the
and early burial settings. These determinations can then be 1960s through the 1980s, evaporites were interpreted as
used to better understand other similar but more heavily occurring throughout much of the Proterozoic stratigraphy in
metamorphosed SedEx successions, such as the Mt Isa, the McArthur Basin (see Walker et al. 1977a, b); Wells 1980
Dugald River, Hilton and Century deposits. and Jackson et al. 1987b for a good summaries of this litera-
With this question of regional controls to mineralisation ture). The ubiquitous and pervasive nature of inferred evapo-
in mind, what I want to explore is the broader depositional rite indicators across large portions of the stratigraphic
association of the McArthur River (HYC) deposit, with ties column, immediately arouses suspicions as to its validity. In
to possible salt flow, withdrawal and related diagenesis, in a all basins with significant evaporites, thick sequences of
framework of evaporite indicator distribution in the basin evaporite salts, especially halite, are typically confined to
stratigraphy. This has not been done before in the public particular tectonically-controlled positions in the stratigra-
realm, and to do so in a reliable way requires a relook at the phy (see Chap. 5 and Warren 2010).
nature and distribution of evaporites and their indicators in My field work, as part of a number of consultancy con-
the McArthur Basin sediments. Table 15.13 and Fig. 15.81 tracts, including walking out and mapping of contacts of key
list the distribution of evaporite indicators in the basin stra- units in the McArthur Basin, shows that the “siderite mar-
tigraphy in the units that overlie and underlie the McArthur bles” of Jackson et al. (1987), one of the most ubiquitous
River (HYC) Zn-Pb deposit, which is hosted in the Barney indicators of former evaporites across the stratigraphy, were
Fig. 15.79 McArthur River 136°07´ b

(m) Orebody
Mine (HYC Pb-Zn-Ag deposit), a 136°05´ 136°06´

Reward Dolomite
Northern Territory, Australia. 80 8 (normal marine
platform cementstone)
(a) Deposit location within Su 7
the Barney Creek graben and rpr
ise
the position of metalliferous fluid Cr 70
ee 16°25´
flow in the graben. Dashed line k r
ve
Barney Creek Formation

Ri
6
indicates approximate position of thur HYC
schematic section in Fig. 15.80a. Ar 60 5
Mc
Pyritic
Shale
(b) McArthur Basin stratigraphy k Member
ee
in the ore interval with an y Cr 50
(intrashelf
rne 4 sump deeper)
expanded view of the HYC Ba Western
e
in
deposit showing Fault Block
icl
16°26´
nt
the eight ore bodies (Based on
ll A
40 Ore zone (deep
seafloor brine)
Hi
Williford et al. 2011). Dashed 3
e y
W-fold shale
line indicates approximate rn
Ba
position of schematic section 30

in Fig. 15.80a
Teena Dolomite
2 (normal marine
20 platform)
16°27´
Emu Fault Zone 100 m

10
1
0
Unmineralized dolomitic shale

Direction of fluid flow Sedimentary breccia
16°28´ Tuff
Position of mine pit Mineralized shale
0 1 km Dolomite
Dolomitic, tuffaceous siltstone
Pyritic shale
incorrectly interpreted as gypsum pseudomorphs clastic and peloidal wackestones, grainstones and rudstones.
(Fig. 15.82). Rather, “siderite marbles” are fault-controlled They do not, as reported in earlier work, define former beds
diagenetic brine haloes made up of sparry hydrothermal fer- composed of lenticular gypsum. A nonstratiform facies
roan replacements in marine platform sediments (Warren expression of the “siderite marbles” can be clearly seen when
1999). “Siderite marbles” occur along and adjacent to faults, the edges, and not the permeability-parallel tops, of these
fractures, salt welds and joints that were fed by subsurface stratiform ferroan bodies are walked out and mapped. The
FeCl2-rich basinal brines. Away from their transtratal feeder margins of the replaced regions are typically pinolitic and
faults, the “siderite marbles” show a tendency to become facies transgressive. The edges of a “sideritic marble” unit do
bedding parallel and then pass laterally into non-replaced not parallel bedding but, at the broad scale, follow faults or
sediments. This reflects preferential fluid entry along beds pass laterally into unaltered carbonate. These textures clearly
that were more permeable at the time the Fe-Cl rich basinal do not indicate a replaced CaSO4 bed.
brines were ascending the feeder faults. Thus, at the time of At the mesoscale, replaced ferroan intervals can some-
fluid crossflow, such coarser grained beds (grainstones and times be seen to nucleate off joint planes (e.g. Figs. 74, 75 in
floatstones), along with joint planes, show a propensity to be Jackson et al. 1987 and Plate 1 in Pietsch et al. 1991).
replaced first and most effectively by ferroan carbonate. Less Similarly, bedding planes and chert nodule horizons in adja-
permeable micritic intervals tend not to be fully replaced and cent unaltered carbonates can be traced into the sparry fer-
so retain less pervasive overprints of ferroan carbonate pre- roan carbonate replacement zones without any loss in
cipitates, such as cm-sized isolated lozenges of ferroan car- vertical spacing of the bedding indicators. This clearly
bonate with pinolitic2 textures (Fig. 15.82). shows that the sparry replacement did not form as a replace-
These sparry lozenge-shaped crystals originally formed ment of a bedded evaporite unit, nor of its solution breccia.
as diagenetic replacements in dolomitic, open marine, intra- Likewise, the chert nodules that are encased in the “siderite
marble” zones are smooth-walled nodules with normal
marine affinities. There are no knobbly-surfaced cauliflower
Pinolitic describes crystal splay textures made up of elongate lenticu-
2
cherts after anhydrite, gypsum or trona in any of the “sider-
lar crystals of ferroan to magnesian carbonate (siderite, ankerite, brun-
nerite, magnesite) with outlines in two dimensions that resemble the
ite marble” units in the McArthur Basin. Historically some
patterning along the outside of a closed or partially closed pine-cone these smooth-walled cherts, which internally retain uncom-
(Pinus pinea). pacted marine peloids and no evaporite pseudomorphs, have
Fig. 15.80 HYC Geology. West East

(a) Schematic E-W cross section a Ridge II Cooley II
see Fig. 15.79a for approximate HYC deposit deposit deposit
position. (b) Combined plot
Emmerugga
showing up-section change in the HYC pyritic dolomite
orientation of metal zonation W-fold shale shale
within the deposit, and the Cooley Myrtle shale
Tee
ULT
contours of the ratio 100×Zn/ na d dolomite Toonganine Fm
ault
olom breccia
RN FA
(Zn + Pb) for the lowermost and ite
EMU F
uppermost ore lenses. Arrows
WESTE
depict the interpreted direction Concordant Pb-Zn Em
mineralisation mer
of fluid flux through the ugg
a do
mineralising system during Discordant Pb-Zn Myr lom
Too tle s ite
formation of each ore lens (c) mineralisation nga hale
nine
Schematic plan view showing Fm
likely synsedimentary spatial 500 m
relationship between pyritic
siltstones, nodular carbonates,
and base metal-mineralized b c HYC mass flow “fanglomerate”
(reworked halokinetic
Lower
McArthur
siltstones in the HYC subbasin. 1 2 3 breccia?) Group
Ore lens 1 contours Direction of
Fault control of the eastern basin 4
Ore lens 2 contours fluid flux
margin and impingement of a (by ore lens)
Emu fa
fanglomerate wedge in the north 3000
(Adapted from Walker et al. 3000 5
12.5
re)
g str Zone
Limit of strongly
1977b; Ireland et al. 2004)
uctu
16.7 pyritic siltstones Laminated
ult zone
6
ld
(con tern Fo
(oxic zone- sphaleritic
25 siltstone
trollin
25 mixing zone
Cooley
Wes
boundary
50 16.7
rop
breccia contact Local depocentre:

outc
12.5 with seafloor) warmest, most acidic

7 part ot the anoxic zone
face
8 1000
Sur
Nodular carbonate
2000 50 12.5 Salt withdrawal cooler, more alkaline
16.7 sink? part of the anoxic zone
16.7
25
Western fault
50
Pyritic siltstone
uppermost parts of the
anoxic & mixing zones
100 x Zn/(Zn+Pb) Salt weld?
7000 8000 Shallow water
1000 sediments
7000
been misinterpreted as replacements of anhydrite nodules in fabrics, which were the dominant textures in the precursor
gypsum beds. open-marine platform carbonates and are not evaporite indi-
XRD analysis shows “siderite marbles” of the McArthur cators. Likewise, the lenticular outlines of individual ferroan
Basin are not composed solely of siderite but of a range of fer- crystals (e.g. Fig. 74 in Jackson et al. 1987) do not mimic
roan carbonates dominated by sparry ferroan magnesites. In lenticular bird-beak gypsum or axe-head anhydrite (Chap.
many sampled outcrops siderite was not present in the coarse 1). Rather, the crystals show the characteristic blunt-ended or
spar facies. The mineralogy of the replacing sparry carbonates stubby lozenge-shaped outlines of pinolitic ferroan carbon-
is in large part dependent on what lithology was replaced. ates (especially, sparry ferroan magnesite and siderite;
Ferroan magnesites tend to dominate where platform dolomite Fig. 15.82).
was replaced. Siderite tends to occur where a calcitic precur- The notion of a “sideritic marble” being a replacement of
sor mineralogy dominated, or in more localised limestone a syndepositional gypsum mush bed, means the presence of
regions that were flushed by large volumes of bathyphreatic siderite lozenges were used incorrectly by some authors to
FeCl2 brine. In outcrop, ferroan carbonate phases ultimately assign and evaporite depositional setting to outcrops of a
weather to fine powdery to massive goethite/hematite, and so number of formations in the McArthur Group cross cut by
reliable analysis of the ferroan carbonate parent is best con- feeder faults, such as the Amelia Dolomite, Reward Dolomite,
ducted on samples from core or in mine workings. Teena Dolomite, Emmerugga Dolomite that were actually
Thin sections of the “siderite marbles” retain poikilotopi- normal-salinity epeiric marine carbonates (Table 15.13).
cally enclosed ghost textures of peloidal carbonate grain Elsewhere, in other Proterozoic basins of the Northern
Table 15.13 Re-interpreted evaporite occurrence chart in the McArthur Basin stratigraphy, emphasising the overinterpretation of evaporites in
the stratigraphy by some earlier studies (e.g., Jackson et al. 1987 and references therein)
Formation Member Dominant lithologies Thickness (m) Evaporite indicators Significance
Looking Glass Chert; chert breccia; 25–230 None noted Coarse dolospar in the
Formation (Amos minor dolomite Caranbirini Member is
Fm) a possible late stage
dolomitisation
overprint
Stretton Sandstone Flaggy quartz 30–245 None noted
sandstone
Yalco Formation Chert; chert breccia; 130 C, LD, DBH Non-evaporitic shallow
minor dolomite carbonate platform
Lynott Formation Donnegan Member Dolomitic siltstone; 50–300 N, Co, DBH? Non-evaporitic shallow
Hot Spring chert; chert breccia; carbonate platform
Member minor dolomite
Caranbirini
Member
Reward Dolomite Dolomite with chert 210–760 LD, C, DBH? Non-evaporitic shallow
pellets; minor dolomite carbonate platform
Barney Creek HYC Pyritic Shale Pyritic carbonaceous 0–490 Non-noted; breccias are Infill of deeper
Formation Mbr (basinal) dolomitic shale; commonplace; possible intraplatform
W-fold Shale Mbr. dolomite, dolomitic DBH depressions on a
(basinal) Cooley breccia; HYC deposit shallow carbonate
Dolostone member platform. Tectonism
(platform). possibly associated
with halokinesis.
Teena Dolomite Coxco Dolomite Massive and laminated 57 H, N, Co, DBH, SM Non-evaporitic shallow
Member stromatolitic dolomite carbonate platform
Emmerugga Mitchell Yard Massive and laminated 500 H, LD, N, Co, DBH, Non-evaporitic shallow
Dolomite Massive Dolomite Mara stromatolitic dolomite SM carbonate platform
and laminated Dolomite Member
Significant interstratal and transtratal evaporite dissolution breccia layer mostly at or near Mara/Myrtle contact; likely indicative of former
allochthonolayer.
Myrtle Shale Thin evaporitic red bed 30–100 H, DBH Transitional restricted
unit terrigenous evaporitic
platform (?lacustrine in
part)
Leilia Sandstone Coarse-grained and 20–30 None noted
crossbedded dolomitic
sandstone
Tooganinie Stromatolitic dolomite; 800 H, LD, SM Non-evaporitic marine
Formation dolomitic shale; dolomites and cherts
quartzarenite; overprinted by coarsely
dolomitic siltstone crystalline diagenetic
magnesite (not primary
evaporite).
Tatoola Sandstone Quartz arenite; 140 LD
dolomitic siltstone
Amelia Dolomite Laminated and 90–240 H, LD, C, DBH, false Ferro-magnesite haloes
stromatolitic dolomite, SM near fault zones that
(passive gypsum were incorrectly
pseudomorphs in beds) interpreted using
SM. These are fault
-fed diagenetic ferroan
carbonate haloes that
crosscut primary bed
contacts
(continued)
Table 15.13 (continued)
Formation Member Dominant lithologies Thickness (m) Evaporite indicators Significance
Mallapunyah Purple dolomitic 30–750 H, LD, C, DBH, SM Diagenetic anhydrite
Formation siltstone; minor nodules perhaps
dolomite; quartz formed by post-
arenite depositional brine
reflux (evaporites are
possibly arid lacustrine,
but not sabkha)
Masterson Sandstone Coarse braided 30–350 H, LD, in uppermost Post-depositional halite
sandstone, ferruginous beds growth in an alluvial
and siliceous cement fan/fluvial uppermost
sandstone beds. Indicates reflux
rather than evaporitic at
deposition
KEY H Halite casts, LD Euhedral and discoidal gypsum and/or anhydrite pseudomorphs, not all are syndepositional, N Acicular gypsum pseudo-
morphs, C Cauliflower chert nodules, SM Sideritic “marble” (incorrectly interpreted as after bedded gypsum?), DBH Dissolution breccia horizon
“Coxco” (cock’s-comb) structures incorrectly interpreted as gypsum pseudomorphs, actually marine aragonite cement splays in cementstone units
SM is not siderite but ferro-magnesite under XRD (brunnerite) and is a diagenetic hydrothermal precipitate. It is not a replacement of a primary
gypsum bed (incorrect earlier interpretation). LD is mostly displacive and replacive late stage ferroan carbonate associated with “SM” haloes. N
is a Proterozoic seafloor carbonate cement, no association with a gypsum precursor. Some DBH units are halokinetic residue layers
Territory, the same lenticular texture in sparry ferroan car- Mg-calcite, which were subsequently dolomitised. The crys-
bonates was applied inappropriately as an indicator of evapo- tal splays, locally know as Coxcos3, because of their resem-
rite pseudomorphs. For example. Muir (1987) makes an blance in two-dimensions to a “cock’s-comb,” were used,
early diagenetic lenticular gypsum interpretation of what are like occurrences of siderite marbles, in studies in the 1960s
hydrothermal pinolitic structures in fault-fed metasomatic through 90s, to indicate former evaporites. A predominance
magnesites in the Pine Creek Inlier. Work by Bone (1983), of replaced splays in one particular unit gave that formation
and later by Aharon (1988), on the same Pine Creek magne- its name, the Coxco Dolomite. But as with siderite marbles,
sites correctly interprets them as indicators of epigenetic “Coxcos” are a process indicator and so are not formation
replacement of a dolomite precursor by throughflushing of specific. Rather they indicate the predominance of aragonite
hot basinal brines. Interestingly, Muir (p.8 opp. cit.) quotes cements in the carbonate-saturated tropical normal-marine
the misinterpreted “sideritic marbles” of the Amelia Dolomite seaways of the Proterozoic when CO2 levels in the atmo-
in the McArthur Basin as her main argument that the Pine sphere and oceans was much higher than today (Grotzinger
Creek magnesites are low temperature replacements of an 1995). They define widespread cementstone layers and typ-
earlier evaporite bed and so erroneously concludes the mar- ify shallow marine hardgrounds in a number of formations in
bles cannot be hydrothermal replacements. the basin, and are found numerous cores from wells in the
Sideritic marbles in the McArthur Basin, and other simi- basin, including the shoal water platforms that surround and
lar fabrics worldwide, are not formation or precursor specific underlie the mineralised zones of the Barney Creek forma-
but process specific; they indicate diagenetic replacement of tion (Table 15.13)
platform carbonates by ferruginous chloride-rich basinal When occurrences of “siderite marbles” are plotted in the
waters, supplied via hydrothermal feeder zones, located near McArthur Group stratigraphy, the “siderite marbles” are not
active faults or salt welds. The ultimate source of these found deeper in the stratigraphy than the Wollogorang
chloride-rich waters was from convecting basinal brines, Formation, implying the ultimate source of the ascending
with their high levels of chloride supplied by thick dissolving chloride-rich brines was at this level in the stratigraphy. In
halite units buried deeper in the basin. The dissolving and the McArthur Basin the primary salt weld was probably at
flowing salt mass focused leaching of iron as the brines cir- the level of the Wollogorang Formation (Fig. 15.81).
culated through subsalt sediments during passage to the salt Multiple layers of evaporite dissolution breccias, as in the
edge and/or the basin margin. well DD91RC18 (Fig. 15.83), indicate the former presence
The other major misinterpretation of an evaporite indica- of a number of thick intervals of now dissolved bedded halite
tor, leading to inappropriate evaporite distribution maps in within the Mesoproterozoic Wollogorang Formation. This
the McArthur Basin stratigraphy, was that of dolomite-
replaced splays of aragonite cement as being indicators for
The coxco features were correctly interpreted as marine aragonite
3
replaced gypsum (Table 15.13). Terminations of many of the splay pseudomorphs Brown et al. (1978), then misidentified as pseudo-
crystal outlines suggest the precursor was dominated by morphs after radiating gypsum splay in subsequent studies; e.g. Walker
grasslike cementstone layers and botryoids of aragonite or et al. 1977; Jackson et al. 1987)
Fig. 15.81 Stratigraphy of the

McArthur Basin in the vicinity of McArthur basin stratigraphy Reinterpreted evaporite
the McArthur (HYC) mine, (after duffet et al. 2005) distribution
Batten Trough, Northern
Territory, Australia (After Duffett Looking glass FM Amos formation
et al. 2005) and the interpreted Stretton sandstone
Subgroup
evaporite distribution, based on Yalco formation
Batten
discussion in this chapter Lynott Donnegan member
formation Hot spring member
Caranbirini member
Reward dolostone
Barney Creek HYC pyritic shale member Cooley
Formation W-fold shale member dolostone member
Mcarthur group Coxco dolostone member Open marine carbonate platform

(not saltern)
Teena dolostone
Emmerugga Mitchell Yard dolostone member
Umbolooga subgroup
dolostone Mara dolostone member Allochthon
salt tier Saline Mudflat
Myrtle shale
Leila sandstone
Tooganinie formation Open marine carbonate platform

(not saltern)
Tatoola sandstone
Amelia dolostone
Mallapunyah formation Diagenetic burial anhydrite - not sabkha
Masterton sandstone
Tanumbirini rhyolite Nyanantu formation
Mother salt bed
GCV Formation
Wollogorang
SCV
Wununmantyala sandstone
Aquarium formation
Sly Creek sandstone

Tawallah group
Seigal volcanics
Yiyintyi sandstone
Scrutton volcanics
core, and many Wollogorang breccia outcrops, show charac- organic-rich laminites (locally known as the “ovoid beds”),
teristic salt dissolution features, such as smooth breccia while the Cu peaks occur mostly in dissolution-effected
bases that are overlain by thin beds of insoluble residues, breccia intervals. Cu migration through this sequence is
along with commonplace radial quartz micronodules and clearly later diagenetic and postdates salt solution. In con-
length-slow quartz euhedra preserved within the breccia trast, the Zn and Pb anomalies show an early diagenetic (pos-
matrix. The breccia beds at each former halite level pass up sibly syngenetic) control.
through rubble breccia into mosaic to crackle-brecciated bed Work by Williford et al. (2011) on organic signatures in
tops (see Chap. 4). extractable hydrocarbons from the mineralized shales of the
When public-domain base-metal data are replotted against HYC deposit further reinforces the importance of the evapo-
same scale sedimentological log, the utility of an applied ritic brines sourced at the Wollogorang level in the stratigraphy.
sedimentological approach in the economic geology of the δD of n-alkanes, branched alkanes and bulk aromatic fractions
region is obvious (Fig. 15.83). The plot clearly shows that were measured, and δ13C of n-alkanes, polynuclear aromatic
the Pb and Zn anomalies are suprasalt and centred on dark hydrocarbons (PAHs) and bulk kerogen were measured to
Table 15.14 Characteristics of relatively low temperature (subgreenschist to greenschist grade) Proterozoic SedEx deposits, Australia
1574
Host, its age and Tonnes Metamorphic

Deposit Age (Ma) Characteristics depositional setting (Mt) Grade Ore grade Model References
Mount Isa 1,653 30 stacked lenses, most Urquhart Shale 150 7 %Zn Bedding-parallel Greenschist Both sedimentary Neudert and
of which occur in the (1,652 Ma): 6 %Pb bands of galena exhalative and diagenetic Russell et al.
upper 650 m of the carbonaceous, 150 g/t Ag and sphalerite; fine models; overprint during (1981),
Urquhart Shale; deposit pyritic, and (248Mt @ grained pyrite, the Isan orogeny has McGoldrick and
is located to the east of dolomitic siltstones; 3.3 % Cu) pyrrhotite, and resulted in remobilization Keays (1990),
the Mount Isa fault zone tuffaceous horizons. minor of the Pb-Zn Forrestal (1990),
and in the hanging wall Neudert and Russell chalcopyrite, mineralization; Painter et al.
of the syn-extensional (1981) and Neudert arsenopyrite, and remobilized ore has been (1999), Wilde
Paroo fault; intense (1986) favour marcasite. At Mt used to argue for (2011)
overprinting during the deposition in a Isa the orebodies synorogenic epigenetic
Isan orogeny sabhka setting, are on one limb of mineralization (Perkins
Hilton 1,653 7 stacked ore lenses in whereas Domagala 120 10.2 % Zn a plunging Greenschist and Bell 1998). Sulphur Forrestal (1990),
the upper Urquhart Shale, et al. (2000) 5.5 % Zn anticline and are isotopes indicate sulphur Valenta (1994)
complicated by intense interpret the 100 g/t Ag extensively source was local sulphate
shortening associated Urquhart Shale to be faulted. Also in evaporites, pseudomorphs
with the Isan orogeny turbidite and/or the Mt Isa mine is of which are present
tempestite sediments a Cu ore zone, throughout the Urquhart
George 1,653 11 stacked ore lenses in 108 11.1 % Zn Sub- to lower Chapman (2004)
related to a hosted in the Shale (i.e., gypsum,
Fisher the upper Urquhart Shale 5.4 % Pb greenschist
submarine fan. A epigenetic anhydrite, and baryte).
93 g/tAg
halokinetic silica-dolomite Deep-burial diagenetic
association favors a halokinetic unit replacement of these
deepwater (preserves a evaporites resulted in
interpretation. massive anhydrite sulphate-bearing basin
unit) waters which migrated
parallel to bedding. Were
the sulphates primary, or
halokinetic dissolution
residue layers sourced
above or below the
mineralisation level?
Lady 1,650 Approximately Lady Loretta 8.3 18.4 % Zn Sphalerite, galena, Sub-greenschist Interpreted as a Hancock and
Loretta 50-m-thick single ore Formation (1,647+ 8.5 % Pb and pyrite, combination of Purvis (1990),
horizon; the ore horizon 4 Ma): carbonaceous 125 g/t Ag baryte-chert- sedimentary exhalative McGoldrick
is preserved within a pyritic, dolomitic, sulphide, minor and diagenetic processes et al. (1996),
regional syncline and is and sideritic, chalcopyrite, in which hydrothermal Domagala et al.
bounded to the north and siltstone and shale. quartz, siderite, brines were transported (2000)
west by inverted Deep water laminite tetrahedrite, and along extensional faults
extensional faults freibergite during the deposition of
the Lady Loretta
Formation
15 Lower Temperature Metals in an Evaporitic Framework
Century 1,575 Mineralized 40-m Lawn Hill Formation 118 10.2 % Zn Sphalerite Sub-greenschist Epigenetic mineralization Broadbent et al.
interval with 2 ore (1,595 + 6 Ma): 1.5 % Pb dominated; in which hot basinal (1998), Large
horizons; preserved in an siliciclastic, 36 g/t Ag bedding-parallel, brines (120–180 °C) et al. (2005),
open fault-bounded carbonaceous (TOC finegrained caused maturation of Polito et al.
syncline; stylolitic 1–5 %), sideritic, sphalerite, galena, organic material (2006),
layering in ore succession shale and siltstone, and pyrite; siderite (pyrobitumen) leading to Kawasaki et al.
focused mineralization, with tuffaceous is the main Fe sulphate reduction and (2010)
mineralization horizons. Deposited gangue phase and base metal precipitation;
transgresses bedding at in a deep water is developed in deposit is interpreted to
deposit scale; deposit is laminate setting siderite siltstone have formed at a depth
proximal to intersection (sea-bottom brine and siderite between 800 and 3,000 m;
of the Termite Range lake). carbonaceous fluid flow is interpreted to
fault and a buried normal mudstone layers have been tectonically
fault. Mineralisation ≈ that separate the driven, occurring during
1,558 ± 4 Ma mineralized basin inversion, and it has
horizons been compared with
Mississippi Valley-type
ore-forming environments
HYC 1,640 8 ore lenses in 70-m Barney Creek 240 9.2 % Zn Pyrite, galena, and Sub-greenschist Sedimentary exhalative Williams (1978),
interval; deposit located Formation 4.1 % Pb sphalerite, finely (e.g., Large et al. 1998) Eldridge et al.
Stratiform Sediment Hosted Pb-Zn Deposits (Salt-Related)
in unmetamorphosed (1,640 + 3 Ma): ~41 g/tAg disseminated vs. early diagenetic (e.g., (1991, 1993),
successions and dolomitic siltstone, throughout the Rye and Williams 1981; Hinman (1995,
preserved in the hanging coarse sedimentary siltstone Eldridge et al. 1993; 1997), Bull
wall of inverted breccias, tuffaceous interlayered with Hinman 1995; Logan (1998), Large
(strikeslip?) Emu fault horizons, pyritic poorly mineralized et al. 2001) models et al. (1998,
near its intersection with shale; pyritic shale is siltstone, fine proposed; in 2000), Logan
a normal fault organic rich (7 % sandstone, breccia, synsedimentary exhalative et al. (2001)
TOC). Deposited in and mudstone model the formation of
a deep water horizons numerous ore lenses when
laminate setting metalliferous brines were
(sea-bottom brine exhaled during several
lake). pulses of mineralization,
related to episodic fault
movements; in diagenetic
model fewer pulses of
mineralization are
envisaged, with epigenetic
mineralization occurring
through lateral flow of
metalliferous fluids via the
Emu fault zone
1575
depleted compared to n-alkanes, typical for Precambrian

sediments (Fig. 15.84b, c). PAHs are more 13C-depleted with
increasing molecular weight and aromaticity, strengthening
the case for a negative isotopic effect associated with aroma-
tization in ancient sediments. According to Williford et al.
(2011) these data are consistent with an ore deposition model
in which fluids originated in an evaporitic deposit lower in
the basin and interacted with metals and organic matter in the
Tawallah Group at temperatures above 250 °C and a depth
of ~ 6 km, before ascending conduits associated with the
Emu Fault and cooling to 200 ± 20 °C before reaching Barney
Creek sediments.
In summary, if ancient fine-grained or sparry ferroan
replacements in sedimentary hosts in the McArthur Basin
are interpreted as possible palaeoplumbing indicators, rather
than as ubiquitous pseudomorphed primary evaporite beds,
they become useful indicators of fluid conduits, which typi-
cally can be traced back to extensional feeder faults. This
reinterpretation of evaporite textures defines an evolving dia-
genetic hydrology where metalliferous FeCl2 -rich basinal
brines have ascended from depth. The lowest occurrence of
the “siderite marbles” in the stratigraphy, at the Wollogorang
Fm. level, likely defines the level of the former thick mother
salt bed that, as it flowed and dissolved, supplied the high
chloride content and metal carrying capacity to the basinal
2 cm brine. Before the mother salt level and its allochthon tiers
were halokinetically breached and evolved into welds, it also
acted as an overpressured seal, facilitating hydrothermal
Fig. 15.82 Pinolitic texture from a scanned black and white field pho- convection and metal enrichment in density-fed brines flush-
tograph of a siderite marble (brunnerite) halo. This texture was incor- ing the underlying marine shales. The flow and breaching of
rectly interpreted in the 1960s and 70s as replaced gypsum beds, as
were some baryte rosettes. A few hours of walking out contacts of this the same mother salt also facilitated the formation of various
diagenetic units clearly shows that although it is locally stratiform, on structures that acted as conduits for the escape of the Fe-rich
the broader scale it is mostly transtratal and ties back to feeder-fault basinal brine. During their subsequent ascent along focused
haloes conduits (faults, fractures, joints and salt welds), the brines
leaked into adjacent permeable sediments to form character-
assess the isotopic effects of a varying degree of hydrothermal istic pinolitic and massive ferroan replacement fabrics.
alteration on different components of HYC organic matter When evaporite textures are correctly interpreted, then a
(Fig. 15.84a–c respectively). Relative to n-alkanes in Barney depositional model for the McArthur River (HYC) deposit
Creek Formation sediments that did not undergo mineraliza- HYC becomes a fault-bound hydrographically closed intra-
tion, HYC n-alkanes are enriched in deuterium (D) by shelf anoxic deep atop salt withdrawal seafloor sumps within
50–60 ‰. This is likely to be a result of equilibrium hydrogen a typical Proterozoic normal marine platform carbonate suc-
exchange during ore genesis with a highly D-enriched fluid that cession. Relogging of a number of relevant cores and mapping
originated in an underlying evaporitic unit. of the stratigraphy below the Pb-Zn laminites of the HYC
Trends with distance along the sample transect are ambig- mine region, from an evaporite-aware perspective, shows that
uous, but from the northernmost to southernmost point, feeder faults intersect underlying breccias that entrain indica-
n-alkanes are less D-enriched, and PAHs are less abundant tors of former evaporite beds and allochthons. These feeder
and less 13C-enriched (Fig. 15.84). This could be due to faults have hydrothermal haloes of diagenetic ferroan carbon-
decreasing hydrothermal alteration effects, decreasing deliv- ate cements that replace adjacent platform carbonate.
ery of highly altered OM by the mineralizing fluid, or both, The stratigraphy of most wells in the McArthur Basin that
hence the fluid flow path illustrated in Fig. 15.79. The carbon pass through the equivalents of the Barney Creek Formation,
isotopic composition of HYC PAHs is inconsistent with a host to HYC deposit, clearly show a deepening (gradational)
Barney Creek Fm source, but consistent with an origin in the profile upward from the platform cementstones of the Teena
underlying Wollogorang Formation. PAHs are 13C-depleted and Coxco dolomites, and equivalents, into the deepened
relative to n-alkanes, reflecting a kerogen source that was 13C waters of the Barney Creek mass flows and laminites
Fig. 15.83 Log of the mother
Granule
Breccia
salt level in the Wollogorang
Sand
Mud
Depth Composition
Silt
Formation in the DD91RC 18
(m)
borehole in the McArthur Basin.
See text for detail
240
250
260
Wollogorang formation
270
possible level of former megahalite

280
290
Salt solution freccia indicates
300
Cu
310
Pb
s s
s
s s
s s
320 s s Zn
v v v v
v v v
Settlement Creek
v v
v v v v v
v v 0 50 100 150 200 250 300
v v v v
volcanics
v v v
v
v
v
v v v ppm
Borehole DD91RC18
(Fig. 15.85). Units in almost all wells through the Barney p latform sediments of the same age and is indicative of a
Creek Formation and its equivalents can be broken down into CO2-enriched Proterozoic atmosphere (e.g. Grotzinger 1995;
three facies belts (A, B, C; Figs. 15.85 and 15.86). Grotzinger and Knoll 1995).
Facies A is now dolomitised; it was originally deposited Facies B is a layered to laminated dolomitised siltstone
on the floor of a shallow normal-marine tropical ocean as with interbedded packstones. It is usually slumped or cross-
cementstones interlayered with micritic intraclast packstones laminated and was deposited as some form of intrabasin
and rudstones. Terminations of many of the crystal outlines slope deposit. Its lack of cementstone layers implies it was
suggest it was dominated by grasslike cement layers and bot- deposited in deeper, but still oxygenated, shelf waters. It too
ryoids of aragonite and perhaps Mg-calcite that were subse- is now extensively dolomitised, although the occasional
quently dolomitised. This facies, with its abundant normal siliceous interval is still cemented by calcite not dolomite.
marine cements, is identical to other tropical carbonate The dolomitising mechanism for the region was relatively
Fig. 15.84 Organic Distance from HYC Pit 1 (m)

characteristics in the HYC 0 200 400 600 800 WFS/BCF
deposit (After Williford et al. −50
2011). (a) δD of four n-alkanes
δD (‰ VSMOW)
and bulk aromatic fractions with −70 n-C18 WFS b-C19-21
distance from Pit 1 (S 16° 25′
53.3742″ E 136° 6′ 1.0368″) n-C19 WFS b-C18-21
−90
along a northeast–southwest n-C20 BCF b-C18-20
transect in the HYC deposit. Also −110 n-C21 BCF b-C18-21
plotted are n-alkane and
branched (b-) alkane values for Bulk aromatics
−130 a
the W-Fold Shale (WFS) below
the HYC deposit and previously
reported n-alkane values for
bitumen recovered from the
Barney Creek Formation (BCF) −26
(Sessions et al. 2004). (b) δ13CPDB n-C18 Phenanthrene
for four n-alkanes and four PAHs −28 n-C19
δ13C (‰ VPDB)
Pyrene
with distance south from Pit 1.
(c) δ13CPDB of n-alkanes n-C20 Triphenylene
−30
recovered from five samples in n-C21 Benzo(E)pyrene
the HYC deposit. Note; Size of
data points in (a) and (b) and (c) −32 Bulk kerogen
indicates analytical uncertainty
(±1σ) for replicate measurements −34
of indicated compounds averaged 0 200 400 600 800 WFS/BCF
across all samples
Distance from HYC Pit 1 (m)
−25
1 (0 m)
−26
2 (104 m)
δ13C (‰ VPDB)
−27
3 (372 m)
−28
4 (553 m)
−29
5 (710 m)
c
−30
15 16 17 18 19 20 21 22 23 24 25 26 27 28
Carbon number
early and driven by hydrological processes that were most level of the Wollogorang Formation (Fig. 15.81), suggests an
active in platform sediments (e. g. epeiric brine reflux). alternative salt-floored halokinetic model of formation for
Facies C is a finely laminated organic-rich siltstone. Its SedEx deposits in the McArthur Basin and other SedEx
inherently higher levels of organics and framboidal pyrite entraining basins in Northern Australia. This model can only
imply it accumulated under anoxic bottom conditions. Of the be applied to sedimentary basins with evidence of former
three platform facies it was deposited in the deepest waters in thick salt units below the ore level, located regionally in an
intrashelf basins that were too anoxic and acidic on the bot- extensional passive margin tectonic setting at the time of
tom to accumulate significant carbonate, even hemipelagic mineralisation.
carbonate mud did not survive on this H2S-enriched deeper Analysis of underlying evaporite solution breccias and
seafloor. This is the facies style that hosts the HYC ore. vertical changes in sedimentation style in the vicinity of the
The presence of an evaporite solution breccia (possible for- McArthur Deposit, and its equivalents in other nearby sedi-
mer allochthon tier) at the Myrtle-Mara contact immediately ment thicks such as the Glyde sub-basin, suggests the vari-
below the level of the Barney Creek Formation (Table 15.13), ous intraplatform deepwater pyritic thicks in the Barney
and evidence of a major thick regional mother salt bed at the Creek Formation where metalliferous basinal brines seeped
Contact
Contact
Colour
Facies
Brecc.
Carb.
Facies
class
Gran.
Brecc.
Sand
Gran.
Mineral Mineral
to brown Buff to light grey Colour

Sand
Mud
Comments Comments
Carb.
Mud
class
Silt
Silt
composition composition
Reward Dolomite 310 S
Dark grey
W/M
B? (shoaling marine platform) Barney Creek Formation
10 Massive to bedded dolomitic siltstone
with some disrupted laminae B
(intraplatform shoaling basin fill)
T Finely laminated siltstone (<1 mm
M/W
Barney Creek Formation
Green
planar laminae) grading upward into more
T (intraplatform shoaling basin fill)
finely laminated siltstone (<1 mm competent bedded coarser siltstone
320
Green/brown
C indicating a shoaling environment
planar laminae) grading upward into more T
M/W
20
Brown
competent bedded siltstone
HYC Shale Member (deep intraplat. basin)

S C HYC Shale Member (deep intraplat. basin)
Teena Dolomite
Dark
grey
330
(transitional platform to deepening
intraplatform slope) T Barney Creek Formation
30
Green/brown
B (intraplatform basin fill)
Mostly massive to bedded impure

Light grey to buff
W/M
340 calcareous siltstone. Some ripple cross
Mostly massive to bedded impure
W/M
B laminae and thin breccia horizons.

dolomitic siltstone. Some ripple cross Clay impurities and laminations increase
40 laminae and thin breccia horizons. up section indicating a deepening
Light grey/buff
Clay impurities and laminations increase depositional environment
up section indicating a deepening
depositional environment
350
T
50
Depth (m)
Teena Dolomite
(transitional platform to deepening
B intraplatform slope)
T Coxco Dolomite Member
(marine cementstone with interlayered Mostly massive to bedded impure
360
Light grey/buff
sandflats) dolomitic siltstone increasingly calcareous
upward. Some ripple cross
60
Light grey
W/P
Massive to bedded impure dolomitic

to green
laminae and thin breccia horizons.
W/M
A2 siltstone to sandstone with numerous
Clay impurities and laminations increase
cementstone horizons (coxcos) composed up section indicating a deepening
of subvertically aligned crystal splays depositional environment
(former aragonite) 370
Float breccia: clasts of buff-brown dolomitic Cm-layered dolomitic siltstone to sandstone.
70 grey FBx siltstone in a clayey dark-grey dolomitic Massive at base becoming more bedded up
matrix (possible former salt allochthon debris) T section. Shows increasing proportion of fines
Light grey
to green
W/P
A2
A1 Coxco Dolomite member
Buff / light grey

T Dolomitic siltstone to sandstone. Massive 380 (marine cementstone with interlayered
sandflats)
P/W
at base becoming more bedded (cm-scale)
toward top. Numerous aragonite
80 cementstone layers (coxcos). Some slumps 376 to 383.6 m: Numerous horizons of aragonite
in bedded dolostone horizons. Top of cement (coxcos)
member defined by last well developed Myrtle Basin 5
cementstone horizon
P/W
Buff to light grey
90 Cementstone horizons (coxcos) composed P = Packstone

A1 of subvertically aligned crystal splays
(former aragonite) W = Wackestone
Cross-laminated sediment M = Mudstone
100 Numerous fractures at base in lled with

early marine (former aragonite) cements
Slumped sediment
S = Sharp contact
and geopetal sediment
Syndepositional cement-filled fractures, T = Transitional
including sub-vertical Neptunian dykes
Berjaya 1
Fig. 15.85 Facies and depositional setting in the Berjaya 1 and Myrtle Basin 5 wells, McArthur Basin, Northern Territory, Australia. Facies belts
are illustrated in Fig. 15.86
into local brine-filled anoxic deeps. The subsurface passage controlling seafloor positions of ore-hosting pyritic shales.
of the halite-dissolution-derived Fe-chloride rich brines that The halokinetic scenario outlined in Fig. 15.87 is one
fed these pools is indicated by Fecarbonate haloes along possible halokinetic scenario that can explain the regional
faults and glide shears, such as portions of the Emu fault setting of the HYC deposit. It uses a five stage model of a
zone in the vicinity of the HYC deposit. deforming salt allochthon in a salt entraining basin that is
However, as in the peridiapiric North African deposits undergoing extensional deformation and is based upon a
discussed earlier (Fig. 15.42), these ferroan carbonate haloes typical extensional margin undergoing raft tectonics (see
are not deposit or formation specific, and can be found over Chaps. 6 and 9 for a full discussion of the relevant haloki-
much wider areas than the immediate region of metalliferous netic and raft tectonics mechanisms that can form local
laminites of the McArthur deposit. The accumulation of sub- organic-rich deeps and depopods). Salt flow settings, other
stantial sulphides, especially pyrite framboids formed in the than the salt-hinged platform-edge raft tectonic model
early stages of sulphide accumulation, requires the presence given in Fig. 15.87, are also possible. Which of the various
of stable anoxic bottom brines in the deeper portions (brine halokinetic deformation styles was the most likely requires
sumps) of isolated depressions on the shelf floor. a detailed sedimentological analysis of breccias, both
Sedimentological analysis of public domain cores and beneath and within the ore deposit, to be tied to a back-
well exposed outcrops in the vicinity of the HYC deposit stripped regional structural analysis. This requires access to
suggests allochthonous salt sheets, such as those that define proprietary company-held core and the permission to pub-
the Myrtle Mara contact (disconformity), played a role in lish the results.
Cooley Creek Dolostone Member Cooley Creek

Barney Creek Formation Dolostone
similar open marine textures to
Reward Dolomite and Member
Teena Dolomite Fm. (occasional
exposure)
Shallow carbonate platform Intraplatform slope Intraplatform basin
Oxic seawater, saturated with respect to CaCO3
>50−100 m deep
Widespread aragonite cements
in wackestones and Fluctuating oxygen levels
cementstones,
early induration, fracturing.
Slumped and syn-faulted Anoxic brine
interbedded dolomitic sands pool
FACIES A and siltstones.
Organic-rich mm-laminated
FACIES B siltstone, can be slumped,
rarely dolomitic.
FACIES C Alteration halo

Metalliferous Fe-chloride-rich basinal brines (”siderite marble”)
with flow focused by various allochthonous
salt tiers, with ultimate mother salt level in
the Woologorang Formation (now a breccia).
Fig. 15.86 Interpreted intra-platform deep setting for mineralised portions of the lower Barney Creek Formation. Seafloor low formed atop salt
withdrawal sinks adjacent to active basin -edge fault (Based on author’s work in the basin in the 1990s)
Pyritic anoxic shale in brine lled deep

Sealevel
Fault
weld
Seafloor locally deepened by salt withdrawal (feeder)
Sealevel
Salt glacier on seafloor
Salt weld
Sealevel
Break in salt sheet allows convecting metalliferous

Salt sheet basin water to escape via fault conduit (brine pool
or bed Sub-salt density/thermal convection near vent along with hydrothermal anhydrite and
generates chloride brines that leach metals ferroan carbonate halo about fault feeder)
Sub-salt density/thermal convection No break (weld) in salt sheet Time 3: Moderate diapir fall (preraft stage)
generates chloride brines that leach metals.
Time 2: Initial diapir fall
No break (weld) in salt sheet
Time 1: Passive diapir rise
Subsidence slows as mother
salt thins and subsiding block
Aggraded oxygenated Aggrading into oxygenated founders on sub-salt basement
sea floor surface Sealevel sea oor surface
Sealevel
Salt solution breccia Future salt solution

and salt weld
Complete loss of salt pressure seal as bottom of block breccia/salt weld
is defined by salt weld. Ascending uids are no Hydrothermal venting continues and buried pyrite
longer focused into feeder fault. Extension is no longer framboids are replaced by lead and zinc sulphides
active and fault activity has ceased (buried hydrothermal anhydrite as possible extra
Time 5: Salt unit completely dissolved into weld sulphur source) 0 km 5
Time 4: Extreme diapir fall (raft stage)
Fig. 15.87 Salt-floored extensional basin model explaining the formation of localised intraplatform brine-pool laminites in the HYC (McArthur
River) deposit
For the purposes of this discussion, I will only use the salt deeps (facies C). The anoxic acidic bottom conditions mean
tectonic style shown in Fig. 15.87, for the HYC deposit, it that little or no carbonate matrix survives in the pelagic shale
does explain: intervals.
By the end of time 3, the subsidence of the down-hinged
• Underlying and syndeformational halokinetic solution structural block is slowing as the mother salt bed is thinning
breccias; to where the bottom of the block begins to founder on the
• Ongoing soft sediment extensional faulting, which breaks sub salt basement. Throughout time 3 and time 4, the dis-
up the continuity of individual ore layers in the HYC solution feather-edge of the mother salt continues to focus
deposit; the ascending hydrothermal brines into the main set of basin
• Pyritic and organic-rich nature of the ore host; defining faults. The burial of the pyritic ore-host laminites
• Localised syndepositional thickening of the Barney Creek means hotter ascending brines now have access to the pyritic
Formation within an otherwise shallower water setting laminites. The early diagenetic replacement of the pyrite
(compare Time 3 scenario with depositional setting based and other early sulphides by coarser hotter Zn and Pb sul-
on sedimentological analysis shown in Fig. 15.86); phides begins.
• Ferroan carbonate halo distribution about faults, espe- As long as the withdrawal edge of the mother salt bed
cially along the intrashelf basin edge; and continues to focus ascending hydrothermal brines, the feeder
• Syndepositional extensional graben structuring seen in fault continues to act a focus for the ongoing subsurface
the regional structure of HYC the deposit. influx of metalliferous basinal brine into the now shallow-
buried pyritic laminites. The elevated burial temperatures
Time 1 encapsulates a typical passive diapir scenario, associated with ongoing brine flushing facilitate the nearsur-
where the upper portion of the diapir is near, or at, the sea- face replacement of earlier formed pyrite by Pb and Zn sul-
floor. The underlying source salt bed or allochthon is intact phides, driven by BSR at lower pore temperatures and TSR
and acting as a pressure seal to deep basinal brines. Ongoing at higher temperatures. Any hydrothermal anhydrite initially
dissolution along its underbelly is continually supplying formed near the brine vent will now redissolve and may act
dense chloride-rich basinal brines into active hydrothermal as an extra source of sulphur for newly forming metal sul-
convection cells. These convecting brines are leaching phides. Once the mother salt mass is completely dissolved or
metals from sediments and volcanics below the salt sheet. drained from the system, then its focusing effect on fluid
At the surface, periodic dissolution and slumping of the flow is lost and the mineralisation process becomes inactive
allochthon carapace is creating monomict and occasional (time 5).
polymict sedimentary breccias atop the surrounding sea- At the surface, this cessation of salt-induced subsidence,
floor (facies A). or a lessening in the rate of supply of brine, means the brine
Time 2 is the falling diapir stage, where ongoing exten- pool sediment surface can now aggrade back into oxic set-
sion causes the diapir crest to fall, with the formation of a tings (facies C to B in Figs. 15.85 and 15.86). Ultimately,
local deep atop the falling diapir crest (the bicuspidate diapir pyrite accumulation on the seafloor ceases as shallower, oxy-
stage). The deepening of the seafloor is indicated in core by genated seafloor sediments cover pyrite-rich laminites for
the transition from the shoal water platform carbonates of the last time (Time 5 in Fig. 15.87).
facies A to the deeper water carbonate slope deposits of
facies B. Hydrothermal circulation continues unabated edEx Deposits Within Fe-carbonate Haloes/
S
beneath the source salt unit (Fig. 15.86). Hosts in the Mt Isa Inlier, Australia
By time 3, ongoing basin extension has created a breach In terms of zinc, lead, and silver metal endowment, the
in the mother salt unit (a salt weld), which allows pressured Proterozoic sedimentary basins of northern Australia, espe-
hot Fe-rich basinal waters to escape across the weld. Their cially those in the Mt Isa Inlier, rank number one in the world
subsequent upward passage is focused into the still active (Fig. 15.75; Large et al. 2005; Murphy et al. 2011). In total
zone of extension associated with the growth fault. The sub- the Mt. Isa-McArthur basin system hosts five supergiant,
surface passage of these rising and cooling Fe-rich hydro- stratiform, sedimentary rock-hosted Zn-Pb-Ag deposits
thermal waters along the feeder fault creates replacement (McArthur River, Century, Mt. Isa, Hilton, and George
haloes of ferroan carbonate cement in the adjacent sedi- Fisher) at or below greenschist grade and one supergiant
ments. Cooling of these ascending waters means copper is strata-bound Ag-Pb-Zn deposit (Cannington) at amphibolite
not carried far above the level of the sealing salt bed and so grade (Table 15.14). As well as some of the largest Pb–Zn
does not make it to the seafloor at this early diagenetic stage stratiform deposits in the world (e.g., Mount Isa, HYC,
of burial (see copper transport discussion in next chapter). Century), the Mount Isa Inlier hosts and also several IOCG
Where these brines vent and pond as a seafloor brine pool it (Iron Oxide Copper Gold) deposits (e.g., Ernest Henry,
facilitates the formation of pyritic shales in anoxic closed Eloise, Starra) that are discussed in the next chapter.
a 138°40´ E b
Sandstone and regional seal
H5
H4s
18°40´ S
Lawn Hill Fm.

Regional siderite precipitation
via decrease in T, P, Eh-pH during
hydrothermal fluid interaction
H4
Century H3
H2
Termite range Fm.

H1
Te
Termite range formation

rm
(upper part includes H1-shales and

ite
H2 - tuffaceous sandstones)
ra
ng
Watson’s Termite range

e
18°50´ S
fa
Lode 200 m faults

ul
t
Upward migrating
2 km
0 10 warm basinal brines
km
Cambrian limestone Post-faulting fold Mn-Ankerite alteration Laminated sulphides

Lawn Hill Fm. (Prot.) Pb-Zn lode deposits
Mn-Siderite alteration Siltstone and sandstone facies
Termite range Fm. (Prot.) Dome structure
Major syncline Mn-Carbonate alteration Shale facies
Major anticline
Fig. 15.88 Century deposit, Queensland. (a) Map view showing proximity to domal structure (interpreted as astrobleme or diapiric sag).
(b) Model of mineralisation emphasizing fault focus to metalliferous fluid supply (After Kawasaki et al. 2010; Large et al. 2005; Pirajno 2009)
Common to almost all these economic deposits are: (1) ineralisation that is Century continues unabated across the
m
ties to highly saline evaporitic brines, (2) the proximity of edge of the circular structure. Likewise the widespread breccia
deposits and prospects to faults that were active during basin textures are as easily interpreted as evaporite dissolution fea-
evolution (Neudert and McGeough 1996; Betts and Lister tures as due to an astrobleme. If so, it is an indicator of the
2002) and, (3) a thick, now dissolved and altered halite unit former presence of a salt-cored anticlinal dome, with the salt
that deformed halokinetically and gave a strong structural now dissolved. The co-occurrence of a domal feature and a
focus to the various mineralising events, both synsedimen- fault intersection better explains the association with the min-
tary and syntectonic (see also Chap. 16 and Betts et al. 2004). eralisation and the subsequent weathering also explains the
The Century deposit, Queensland, with its mineralisation Cambrian sag fill. Stewart (1999) discusses criteria that can be
hosted in deepwater sideritic siltstones, like the HYC deposit used to interpret various circular structures preserved in the
is a structurally and hydrothermally focused metal trap and rock record. A new look at how hydrothermally altered brec-
like the HYC shows textures that have not been obliterated cias formed in Century, starting with the capping breccia in the
by subsequent metamorphism (Table 15.14; Waltho and mine pit, perhaps as possible salt allochthon and rauhwacke
Andrews 1993; Broadbent et al. 1998). It is located close to residues, would help refine the deposit’s genesis.
the Termite Range Fault, which was probably the major con- Century has a higher Zn:Pb ratio (6.8) than other major
duit for ore fluids. Australian SedEx deposits (1.2–2.9), with a geologic
Century Zn-Pb deposit is located on the west side of an resource of 167.5 Mt (8.2 wt % Zn, 1.2 % Pb. and 33 g/t Ag),
interesting 20-km-diameter circular structure (Fig. 15.88a). including a higher grade mining resource of 105 Mt (12.1 wt
This structure has been interpreted as a possible meteorite % Zn, 1.75 % Pb, and 46 g/t Ag; Large et al. 2005). Although
impact feature (Shoemaker and Shoemaker 1996; Salisbury the Century Deposit’s hosting laminite has many deposi-
et al. 2008) and is outlined by a brecciated Cambrian Thortonia tional similarities to the synsedimentary McArthur River
Limestone fill. The notion of an impact crater has not been deposit, it’s Zn-Pb mineralisation likely has a different,
accepted by most geologists in the companies working the deeper diagenetic replacement origin, synchronous with
deposit (Salisbury et al. 2008). In my mind this circular fea- fault-focused metalliferous fluid crossflows, perhaps driven
ture, if it is an astrobleme, is unlikely to be associated with the by an episode of compression and basin inversion (Broadbent
mineralisation event as the Termite Range Fault and the et al. 1998, 2002).
Galena
50 HYC Early burial Later burial
n = 441 (biogenic) (thermochemical) Sphalerite
40 Pyrite
30 Pyrrhotite
20
Chalcopyrite
10
0
−20 −10 0 10 20 30 40 50
15
Century
10 n = 57
5
0
−20 −10 0 10 20 30 40 50
15
10 Mt Isa (Zn-Pb)
n = 145
5
0
−20 −10 0 10 20 30 40 50
30
20 Mt Isa (Cu)
10 n = 144
0
−20 −10 0 δ34S (‰) 10 20 30 40 50
Fig. 15.89 δ34S values for sulphide minerals from McArthur HYC, Century and Mount Isa Zn-Pb and Mt Isa Cu ores after Pirajno (2009) and
references therein
Ore-hosting siderites were likely emplaced earlier via fluids was driven by phases of basin inversion and regional
predominantly subsurface seepage during extension, fol- compression. Hot fluids reacted with organic-rich sideritic
lowed by compression driven, fault-focused metalliferous shales, producing gas and liquid hydrocarbons. This led to
basinal brine crossflows that were focused into anticline the thermochemical reactions, which resulted in the precipi-
traps in their ferroan carbonate-rich deepwater sediment tation of sulphides. Sulphur isotope systematics revealed
hosts (Fig. 15.88b; Broadbent et al. 1998; Large et al. 2005). progressively higher δ34S values, from 5–10 % to 20–25 %,
That is, the Zn-Pb mineralisation at Century transgresses the reflecting a closed-system hydrothermal reservoir with
stratigraphy, in that the higher grade zones are associated enrichment in heavy sulphur over the life of the mineralisa-
with thicker black shale host rocks (Fig. 15.88b). The deposit tion event reflecting the passage from biogenic to thermo-
is spatially associated with regional-scale lode mineralisa- chemical sulphate reduction with increasing burial
tion, mainly veins and breccias within fault zones. The main (Fig. 15.89). Illite and chlorite crystallinity variation across
ore mineral is sphalerite, of which two varieties are present: the Lawn Hill Platform suggest the southern part of the plat-
one porous and associated with abundant pyrobitumen, the form experienced higher temperatures (up to 300 °C) than
other is non-porous and with a low pyrobitumen content. The similar stratigraphic horizons in the north. Much of the more
intergrowth of the sphalerite with hydrocarbons, suggests intense thermal alteration is focused by fault conduits, which
that thermochemical sulphate reduction (reaction of deeper were active a number of times in their tectonic history
sulphate and metal-bearing fluids with liquid and gaseous (Golding et al. 2006).
hydrocarbons), took place in a burial setting and perhaps not There is also the obvious burial-related bimodal isotope
syndepositionally (Fig. 15.88b; Pirajno 2009). signature of the Mt Isa Zn-Pb sulphides and the clear later
Broadbent et al. (1998) argues that the sulphate-bearing burial origin of the copper sulphides there (Fig. 15.89). The
hydrothermal solutions originated from the deeper more sulphate bearing fluids in Century were likely derived from
saline parts of the basin stratigraphy and were channelled up evaporitic rocks in the deeper parts of the basin (Broadbent
along faults (Termite Range Fault system). The movement of et al. 1998, 2002; Pirajno 2009). What is not considered in
the existing literature in the origin of the various Proterozoic notite (K2(UO2)2(VO4)2 · 3H2O). Uranium-rich secondary
SedEx deposits of Australia is the strong likelihood of halo- silica is also important locally in the mineralised zones
kinetic focusing to the fluid flow from early to later burial (Fig. 15.90b). Carnotite deposits occur along the drainage
and the importance of now dissolved salt in the extensional systems throughout the Yilgarn region and include the world
welds and décollements, similar to the various halokinetic class Yeelirrie deposit (Fig. 15.91a). Other potential
examples discussed earlier in this chapter and also explains U-resources on the Yilgarn craton are the Lake Maitland,
the ore distributions in SedEx deposits with host matrices Centipede and Lake Way prospects (Table 15.15; Carlisle
now in the metamorphic realm (see Chap. 14 for a discussion et al. 1978; Noble et al. 2011).
of Mt Isa and the eastern foldbelt – Mary Kathleen meta- Uranium in the Yilgarn groundwater is sourced from granite
evaporite deposits). weathering, and vanadium from greenstones and alluvial sedi-
ments (Mann and Deutscher 1978; Morgan 1993; Noble et al.
2011). Groundwater moves down gradient into the channels
rid-Zone Diagenetic Uranium
A (Figs. 15.90 and 15.91a), where capillary evaporation occurs
and Copper Associations (both in channels and playas) and, as a result, carbonate and
apatite (if PO4 is present) precipitates. This is important for two
As well as the low temperature base metal evaporite associa- reasons (Noble et al. 2011): (i) carbonate-rich zones will have
tions that benefit from the presence of dissolving and flowing a high-pH groundwater; and (ii) the formation of carbonate and
evaporites in their burial evolution there are other economic apatite will result in the loss of P and HCO3 from the ground-
accumulations that benefit from the brine concentrating water. Both of these conditions force the reaction of the aque-
effects in near surface waters in arid evaporitic climates. ous species of U, V and K and so form carnotite.
They include low temperature secondary enrichment phases Although apatite precipitation could drive this reaction, it
in uranium and porphyry copper deposits. is a minor contributor to the carbonate formation in the
Yilgarn. The role of PO4 in the solubilisation of U is hypoth-
esised by Noble et al. (2011) to be most important where
uricrusts: Yilgarn Australia
D groundwater pH is more acidic, such as the active weather-
and Namibe, Africa ing uplands (closer to the breakaway crests). Apatite precipi-
tation is more likely near these zones and away from the
In the arid desert zone that is the northern Yilgarn of West carnotite mineralisation. This process will shift the pH to
Australia, U deposits occur in playa and paleochannel cal- more alkaline and change the dominant U-bearing aqueous
cretes, with an intermediary third type occurring geomor- species from UO2HPO4 to UO2(CO3)2. The arid association
phologically between the two settings, typically designated of the uraniferous calcretes in Australia means gypsum is
as platform or delta calcretes, often located where channel often present as a gangue mineral and this can create pro-
drainages enter playas (Table 15.15 and Fig. 15.90a; Noble cessing problems (Pownceby and Johnson 2014). The pres-
et al. 2011). All deposits are at or near the land surface and ence of gypsum is a processing hindrance when an alkaline
have a similar capillary-driven genesis and ore mineralogy. leach solution is used as it reacts to precipitate calcium car-
They are responses to concentrative changes in shallow bonate and forms sodium sulphate in solution. A gypsum
groundwater redox interfaces, with circulations driven by content of more than 4 % in a surficial calcrete uranium ore
evaporation, and U-precipitates typically dominated by car- leads to excessive reagent consumption and sufficiently
Table 15.15 Size of major valley channel and playa calcretehosted U deposits in the Yilgarn area, including the worldclass Yeelirrie Deposit
(After Noble et al. 2011). Delta deposits are transitional between channel and playa types
Deposit Type U3O8 t Grade cutoff (ppm) Grade U3O8 (ppm)
Yeelirrie Channel 52,500 ? 1,500
Lake Maitand Playa 11,420 370 370
Lake Way Delta 5,710 200 540
Centipede Delta 5,355 200 550
Lake Austin Playa ? ? ?
Lake Raeside Playa 1,700 250 200
Lake Mason Playa 2,700 ? 350
Hillview Channel 3,720 2,150 180
Little Well Channel ? ? 350
Dawson Well Channel 4,700 150 228
Arid-Zone Diagenetic Uranium and Copper Associations 1585
Breakaway
1 1 Paleochannel Playa
3 deposit 1 deposit
2 Sandplain 5 5
UO2HPO4 2 2
1 5 Dunes
UO2CO3 6
K 6
4 7
3 3 KUO2VO4
VO2 UO2HPO4
3
UO2CO3
10 km K
Processes Granite U mineralisation

1 Precipitation 5 Evaporation, evapotranspiration Water table
Greenstone
2 Infiltration, CO2 equilibrium 6 Carbonate, phosphate, silicate ppts.
Alluvial/colluvium Saprolite
3 Weathering from primary source 7 Playa zone evaporation, precipitation
4 Lateral groundwater movement Calcrete
A
R R R R
Fossil B
mound Salt pan clays
Capillary
spring
S
E E E evaporites Trunk valley sand & clay
S I E
Salt lake
Si Si Calcrete (partly remobilised)
Opaline silica (Si)/silcrete
Contemporary alluvial fill

Oxidising Reducing Fill & valley fill
Bicarbonate waters Chloride and sulphate
Fresh-brackish alkaline Saline alkaline Hypersaline neut.-acid Basement & saprolite
500-5000ppm 5,000−20,000 ppm 20,000−200,000+ ppm
R Rainfall I Intake
Surface replacement Dolomite
Solution Solution Colloidal clay
of Ca with SiO2 S Surface runoff E Evaporation
Ca Mg HCO3 fixing evaporites
Deposition of Calcrete/calcite (uranium, gold, metals)
Mn fixing SiO2 Fe Mn Fluid flux
carb.replace Fe hydroxides
Fig. 15.90 Uraniferous calcrete. (a) Location and mechanisms Mann and Deutscher 1978). (b) General model of water–rock interac-
involved in formation of channel and playa secondary U deposit formation, processes and hydrogeochemistry in regions of uraniferous cal-
tion in the northern Yilgarn Craton (Modified from Noble et al. 2011; crete (After Morgan 1993)
affects processing costs to rule out the use of relatively cheap claystone (Princep and Hutson 2010). The mineralisation
sodium carbonate-based leach solutions. occurs as an undulating 1–30 m thick layer, which is shaped
As well as the Australian calcrete examples listed in like a subterranean meandering river. At intervals down the
Table 15.15, significant uraniferous calcrete accumulations valley, thick “pond-like” pods of higher-grade uranium have
have been identified at the northern margin of the Namibe formed. These are generally located immediately upstream
Erg, south-west Africa and include Langer Heinrich, Tubas of a narrowing of the valley edges. Carnotite occurs prefer-
Grant, and Klein Spitkoppe (Carlisle et al. 1978). The Langer entially in less cemented sections of the ore but shows no
Heinrich deposit became an operational uranium mine in relationship to any rock type in the alluvial matrix. Nor does
2007 (Fig. 15.91b). Mineralisation at Langer Heinrich con- it occur within any of the detrital clasts, whether boulder,
sists of sub-horizontal carnotite that has been precipitated sand, or silt size.
within clastic valley-fill rock units, which vary from con- The uraniferous calcrete and gypcrete-hosted deposits in
glomerates through grits and sands to micaceous claystone. Namibia differ from the Australian calcrete deposits in the
In a general way, ore becomes finer grained with depth and following ways: (1) A likely Late Tertiary age with uplift-
hence ore from beneath the watertable is mainly micaceous related erosion of the upper parts of some deposits, (2) An
a b
Yeelirrie deposit
Langer Heinrich mine
1 km 1 km
Fig. 15.91 Arid zone uraniferous calcretes. (a) Yeelirrie deposit, West Australia. (b) Langer Heinrich Mine, Namibia
abundance of coarse detrital fragments in a braidplain host, Interestingly, the Langer Heinrich mine, the richest of the
which constitute the skeletal framework of the uraniferous various known Namib examples, is located in a definite val-
calcrete. Radiogenic carbonate cement typically making up ley constriction. First and foremost is the required combina-
around 15 % of the rock volume, (3) This carbonate cement tion of groundwater and aridity to drive capillary
is predominantly sparry calcite, with neither dolomite nor concentration of the uraniferous salts, and the co-
opaline silica as co-precipitates, (4) The presence of abun- precipitation of evaporitic capillary salts. Lateral transport
dant gypsum in the upper parts of profile in occurrences of uranium in brackish to increasingly saline groundwater in
within 60 km of the Atlantic and the gypsum is probably the outflow sump is essential to ore deposition in both
marine saltspray derived (Chap. 2), and (5) A vertical grada- regions, as is the presence of bedrock barriers or constric-
tion upward into pedogenic sheet calcrete and gypcrete (per- tions in order to narrow the channel of subsurface flow, and
haps indicative of the greater age compared to the Yilgarn act as sills. This forces the groundwater to pond and so
deposits). move closer to the land surface, where it is subject to evapo-
Reasons for the coarse detritus host in Namibe are: (1) the ration and loss of dissolved CO2. In both regions the larger
very appreciable relief between the Great Western Escarpment, part of all valley calcretes and gypcretes are unmineralized.
with hinterland elevations in excess of 2,000 m in the Khomas Ore-grade mineralization is roughly horizontal in attitude
Hochland, and the broad coastal platform (lowland) of the and related to capillary concentration of shallow past or
central Namib Desert and, (2) the relatively modest degree of present groundwater tables. Source rocks in both regions are
chemical weathering in the basement compared to the deep weathered Proterozoic to Archaean migmatites, pegmatites,
sapropelic weathering in Australia. Namibian calcretes do not alaskites, and granites; many are “hot” sources, that is, they
typically develop abundant dehydration or shrinkage cracks, are already appreciably enriched in uranium. Lastly and
and unlike the Australian calcrete hosts, the lack of current most significantly, deposits in both areas could not form
microporosity means they today are not as permeable aqui- without evaporitic ground conditions. The uranium salts in
fers, though locally there can be appreciable permeability. In both regions are true evaporite salts in the same way that
several places, irregular open solution tubules and replace- capillary anhydrite and capillary halite are true evaporite
ment bodies about the size of a finger, but sometimes much salts.
larger, have developed in the calcrete. Commonly, the tubules
have a shell of impure calcite and a sandy porous filling,
which, under some conditions, is richly mineralized with car- orphyry Copper, Supergene Enrichment
P
notite. Owing to the higher gradient setting of the local and and Aridity
regional hydrology draining toward the coast, Namibian ura-
niferous-calcretes do not seem to occur preferentially in playa Porphyry copper deposits are well developed in the in the
or saline delta settings. Atacama Desert of northern Chile, where supergene enrich-
When comparing deposits between the two regions, the ment is considered to be the principal factor in making this
marked process similarities are obvious (Fig. 15.90). region the greatest producer of Cu in the world. Classic
Arid-Zone Diagenetic Uranium and Copper Associations 1587
Lithocap remnant
Vadose 10-Ma ignimbrite

WT
Exotic 14-Ma pa
leosurface
chalcocite Andes
ite volc
Phreatic enrichment anic ro
cks
Outer limit of pyrite halo Gravel-bedrock

Porphyry stock contact
Hypogene alteration Supergene profile Post mineralization units

500 m
Advanced argillic Hematitic Leached Ignimbrite/airfall tuff
Sericitic Jarositic capping Piedmont gravel
Potassic Oxidized zone Exotic copper mineralization
Enriched zone in gravel and bedrock
Propylitic
500 m
Anhydrite front 0
Fig. 15.92 Mature supergene profile based on porphyry copper depos- outer potassic and inner propylitic alteration zones. Position and con-
its in northern Chile (After Sillitoe 2005). Position and configuration of figuration of exotic chalcocite enrichment and exotic copper oxide min-
leached capping (patterned) and the enriched sulphide ore zone (dark eralization in gravel and bedrock are controlled by the pyrite halo and
green) are controlled by relatively unreactive advanced argillic and ser- paleo-watertable. Anhydrite front defines depth above which anhydrite
icitic alteration. Copper oxide ore is stabilized by higher pH fluid in has been leached
odels argue that supergene enrichment was driven by the

m time. If this is so then, as suggested by Clarke (2006), super-
exposure of Cu sulphides to the effects of oxidative gene enrichment is tied to periods of landscape uplift and
weathering during times of moderate precipitation
dissection, not to landscape stability. Such periods of uplift
(Fig. 15.92; Sillitoe 2005; Sillitoe and McKee 1996). Thus, in the Andes would drive a relative fall in the watertable and
the development of porphyry copper “giants” in the Atacama vadose (supergene) mineral cycling independent of the tran-
Desert is strongly coupled to climatic evolution. Isotopic dat- sition to hyperaridity.
ing of supergene minerals, principally alunite group miner- It seems that in the hyperarid sediments of the Atacama
als, has shown that supergene enrichment in the Atacama desert the distribution of copper minerals is controlled by a
occurred over a long period from ~45 to 9–5 Ma, possibly combination of evaporatively driven “per ascendum and per
reaching a maximum at 14–21 Ma (Reich et al. 2009). descendum” hydrologies. The first stage of supergene oxida-
Supergene enrichment is traditionally believed to have tion peaked between 21 and 15 Ma as the result of percolat-
ceased when semi-arid conditions in the Atacama, with sig- ing oxygenated meteoric waters in a semi-arid setting. This
nificant pluvial precipitation periods, changed to hyperarid. was followed by a second stage of supergene oxidation
However, there is no consensus about the onset of hyperarid- where atacamite formed from uprising basinal brines and
ity, which may have commenced as early as 25 Ma and even subsequently preserved under hyper-arid conditions for at
extend back to the Triassic (Clarke 2006). If this is so, then least the last 2 Ma.
Cu enrichment may not be driven solely by periods with rela- Evaporitic high-altitude low-temperature conditions are
tively abundant fresh meteoric waters. There may be as not directly involved in the formation of porphyry copper
aspect of Cu concentration in the Atacama that is associated accumulations, which are formed by a combination of igne-
with more saline groundwaters. ous emplacement and hydrothermal circulation (John et al.
Recent geochemical and isotopic studies reveal that ata- 2010). But the transition from semi-arid to hyperarid cli-
camite (Cu2Cl(OH)3), a major constituent of supergene mates in Chile were responsible, first for supergene enrich-
Cu-oxide zones in Chilean deposits and co-associated with ment and then for preservation of the resulting deposits,
capillary gypsum, formed within the last few million years along with ongoing deposit enrichment. Understanding the
(Palacios et al. 2011; Reich et al. 2009). Atacamite is a prod- history of Neogene aridity, responding to uplift/adiabatic cli-
uct of the upward flow of saline basement waters through the mate is a significant component in understanding ore distri-
pre-existing oxide zones, focused along active faults and has bution in high-altitude arid-zone porphyry copper deposits
been preserved in the hyperarid climate prevailing since that (Fig. 15.92).
Bedded stratabound ores (not illustrated in this figure) Peri-allochthon or Allochthon associated ores (extens. and compress.)
Kupferschiefer-style, Lubin Poland (Cu-Permian - Fig. 9.46) peridiapir brine lake Atlantis II Deep, Red Sea (Cu-Zn, modern)
Gays River, Nova Scotia (Pb-Zn, Carboniferous) Dzhezkazgan, Kazakhstan (Cu-Pb, Carboniferous)
Ceta, Oklahoma, USA (Cu, Permian) Lisbon Valley, Utah USA ( Cu, Cretaceous)
Corocoro, Bolivia (Cu, Tertiary) Caprock . . . . .. . . Dongchuan, China (Cu, Mesoproterozoic)
. . . ..
Redstone River, Canada (Cu, Neoproterozoic) . . .. .. ... .. . Bou Grine, Tunisia (Zn-Pb, Cretaceous)
. . .. .
San Vincente, Peru (Zn-Pb, Triassic-Jurassic) Gulf Coast caprock (Zn-Pb, Cretaceous)
Cadjebut, Australia (Zn-Pb, Devonian - Fig. 7.51) Flowing salt
Zone of base metal Jubilee, Nova Scotia (Zn-Pb, Carboniferous)
(may be
replacement of organic- HYC, Century, Mt Isa, Australia (Zn-Pb, Cu, Mesoprot.)
adjacent to,
rich pyritic laminites
or deep below,
Fe-carbonate
the brine pool)
halo indicates
supply conduits Upwelling of mixed
of rising Fe-Cl brines hydrothermal/basinal
Mineralised laminites first deposited in seafloor brine metalliferous Cl-rich brine
pool that then evolve (replaced) with burial
Salt allochthon (primary or secondary salt tiers - with
Roho and counter-regional geometries) actively
flows through and over post-rift sediments. Red Sea Deep Style-stratified waters
Owing to water-rock interaction in chloride brines Cu-Pb laminite
circulating beneath any allochthon tier (90° view to section below)
the resulting metalliferous brines are
Flowing salt typically rich in Pb-Zn if subsalt brine
convection is high in the post-rift
stratigraphy or Cu if salt is primary
weld and circulation was at
Salt raft focused synrift level of the
mineralisation.
This style can form atop synrift sediments at the level of the
primary weld(Cu-rich) or atop gravity glide salt tongues
emplaced in post rift sediments as secondary salt tiers (Pb-Zn)
Salt
Post-rift canopy
Subsalt focused brine flow into a sediment
zone of organic-rich mesohaline ore
host is important in forming Salt allochthon
Kupferschiefer-Lubin (Cu) Syn-rift
and Gays RIver or Jubilee evaporites
(Pb-Zn) styles of gravity gliding
mineralisation. Syn-rift Salt allochthon flowing
Salf allochthon flowing over synrift sediments atop redbeds and basalts
Pre-rift Continental redbeds (Cu source)
sediments at the level of the
basement (Cu source) Seafloor basalts
mother salt bed (becomes primary weld)
(Cu source)
Lithology hosting subsalt convecting chloride brines (water-rock interaction) controls whether the resulting chloride-transported brine is Cu or Pb-Zn rich.
Cu tends to be derived from a subsalt (Lubin) or suprasalt (Dzhezkazgan) redbed or volcaniclastic source , while Zn-Pb tends to be
leached from passive-margin shelf sediment beneath allochthon tiers higher in the stratigraphy (MacArthur Basin-HYC-Century brine pool styles)
Fig. 15.93 Base metal associations in the context of a salt allochthon terrane (After Warren 2000b)
ase Metals, Evaporites and Diagenetic

B stable redox front, now indicated by the facies of the Rote
Accumulations: A Summary Faule. The Dzhezkazgan deposits (as well as smaller scale
Lisbon-Valley style deposits) are suprasalt and formed where
Many low-temperature base metal deposits in evaporite a dissolving halite-dominated salt structure maintained a
entraining sedimentary basins can be related to the presence structural focus to a regional redox interface. It also drove
of preserved evaporites or indicators of the former presence the circulation system whereby metalliferous saline brines
of evaporites, such as bedded and halokinetic breccias, chert leached adjacent redbeds. In both scenarios the resulting sul-
nodules and other indicators of “the evaporite that was” phides are zoned and arranged in the order Cu, Pb, Zn as one
(Fig. 15.93). The link is either direct, with metal accumula- moves away from the zone of salt-solution supplied brines.
tion at the site of the present or former evaporites, especially This redox zonation can be used as a regional pointer to both
calcium sulphate beds; or indirect, from ascending hypersa- mineralisation and, more academically, to the position of a
line fluids supplied from a dissolving mother salt bed via a former salt bed. In the fault-fed suprasalt accumulations the
single or a series of feeder faults. Thus mineralisation can be feeder faults were typically created and maintained by the
subsalt, intrasalt, or suprasalt and the salt, or its breccia, can jiggling of brittle overburden blocks atop a moving and dis-
be bedded or halokinetic. In many cases the H2S that causes solving salt unit. A similar mechanism localises many of the
the ore to precipitate at the redox interface is derived from caprock replacement haloes seen in the diapiric provinces of
bacteriogenic or thermochemical reduction of nearby evapo- the Gulf of Mexico and Northern Africa.
ritic sulphate in combination with organics supplied by Evaporite-associated Pb-Zn deposits, like Cu deposits,
hydrocarbons ponded beneath an evaporite seal (Table 15.2). can be associated with both bedded and halokinetic salt units
The diagenetic evaporite-base metal association includes or their residues. Stratiform deposits such as Gays River,
world class Cu deposits, such as the Kupferschiefer-style Cadjebut and Nanisivek, have formed immediately adjacent
Lubin deposits of Poland and the large accumulations in the to or within the bedded salt body, with the bedded sulphate
Dzhezkazgan region of Kazakhstan. The Lubin deposits are acting as a sulphur source. In diapiric deposits the Pb-Zn
subsalt and occur where longterm dissolution of salt in con- mineralisation can occur both within a caprock or adjacent to
junction with upwelling metalliferous basin brines created a the salt structure as replacements of peridiapiric organic-rich
Base Metals, Evaporites and Diagenetic Accumulations: A Summary 1589
pyritic sediments. In the latter case the conditions of bottom • There is a redox interface where these metalliferous chlo-
anoxia that allowed the preservation of pyrite were created ride rich waters mix with anoxic waters within a pore
by the presence of brine springs and seeps fed from the dis- fluid environment that is rich in organics and sulphate/
solution of nearby salt sheets and diapirs. The deposits in the sulphide/H2S.
peridiapiric group tend to be widespread; but, in Phanerozoic • There is a salt-induced focusing mechanism that allows
strata, the individual deposits are relatively small and mostly for a stable, longterm maintenance of the redox front, e.g.
subeconomic. However, the fluid flow and brine pool mecha- the underbelly of the salt bed (subsalt deposits), a dissolu-
nisms, as well as models of replacement haloes in bottom tion or halokinetically maintained fault activity, the over-
brine sediments, can be used to model larger counterparts burden (suprasalt deposits), a stratiform intrabed evaporite
within Proterozoic settings for which there are no modern dissolution front (intrasalt deposits).
analogs. This notion is developed further in the next
chapter. Most important is the notion that the sulphide orebodies
In all the deposits discussed in this chapter there are four that form at the redox interfaces can remain long after the
common factors that can be used to recognise suitably pre- actual salt units have dissolved or evolved into meta-
pared ground and so improve exploration models: evaporites. To an explorationist trained in the recognition of
former salts, the indicators remain visible and act as pointers
• A dissolving evaporite bed acts either as a supplier of to zones of structural or diagenetic foci for the
chloride-rich basinal brines capable of leaching metals, or mineral-depositing redox system. When such zones are rec-
as a supplier of sulphur and organics that can fix metals. ognised, and placed within the regional framework or basin
• Where the dissolving bed is acting as a supplier of chlo- architecture, then particular zones or lithologies of interest
chloride-rich brines, there is a suitable nearby source of are quickly defined and suitable for more intense
metals that can be leached by these basinal brines. exploration.

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Lower Temperature Metals

Introduction chapter we will focus on stratabound Cu, Pb-Zn and U asso-

© Springer International Publishing Switzerland 2016 1469

a Orogenic-convergent margin settings b Anorogenic or continental-basin settings

Cyprus-type (HA) Uranium in weathered

Abitibi-type (HA) Kiruna-type

Orogenic gold (HA) Lead-zinc in clastic

and placer gold Lead-zinc in carb-

Porphyry Cu (HA) Copper in clastic

(Tertiary) economic halokinesis alteration in association with reservoired hydrocarbons

0 basin. Thick beds of dissolving halite (the most common

(E) matrix in nearby beds modifies overall brine chemistry (see

a 2,000 evaporites, are chloride-rich, somewhat acidic and in some

fluid must contain on the order of 1 mg/l or more of the

Prezbindowski 1981; Sverjensky 1986; Kharaka et al. 1987).

Fig. 15.7 Influence of flushed McArthur River, Australia

Fig. 15.8 Average base metal

Carribuddy mudstone GoGo mudstone

CuCl32+ CuO favorable to

10–1 100 101 102 103

a Table 15.6 Widely accepted models for transportation and precipita-

Eut′′ other is metal-rich

Halite Sulphate reduction models Reduction of sulphate by reactions

Base metals transported with organic matter or hydrocarbons,

5 P4 PS4b (FIA 09)

P5 PS5 methane (e.g. Anderson 1983; Powell and MacQueen

Fig. 15.13 Metal sulphide a

The variably metalliferous seafloor deeps or deepsea

the next chapter. I offer it as our first example of the impor-

tance of nearby dissolving evaporites in stabilising the min-

The Red Sea is a young intracratonic basin atop a region of

NWB SEB? Heatflow

SP:5800 6000 6200 6400

Volcanic extrusion Line 99-081 Salt

SW Brine lake in deep

Fig. 15.17 Temperature and In situ temperature (°C) Salinity (psu)

Red Sea deep water 24°C

W Basin (core 684) SW Basin (core 683)

entraining sulphide minerals.

occurs both as at-surface nodular hydrothermal beds

composed of 20–50 μm plates and laths of anhydrite, typi-

of nodular sekko-oko ore in a Kuroko deposit, except that 23,000 years

Sapropel (12 ka)

Fig. 15.22 Resource plot for 10

Fig. 15.23 Distribution of the 16°E 18°E 20°E

Central basin 53°N

Lubin-Sieroszowice area (Cu >20 kg/m2)

b Sieroszowice Rudna mine region

Dolomite with occasional anhydrite (Werra)

Silty dolomite (residues?)

Bituminous dolomite (Kupferschiefer)

Fig. 15.25 Organic character in a OI (mg CO2/gCorg) b

Fig. 15.26 Highly schematic

Table 15.8 Stratigraphic column of the Dzhezkazgan copper district

her rad m Lisbon Valley fault zone

Warm saline metaliferous

Fig. 15.28 Geological map Panzhihua

Slate cias, lenses, and veins around fluid-venting centres tied to

114 000 27° 14′ 118 000

Kipushi town Salt weld (?)

Introduction chapter we will focus on stratabound Cu, Pb-Zn and U asso-

anganese sulphides, and the sulphate minerals, forming