A Middle Ordovician Age For The Laisvall Sandstone-Hosted PB-ZN Deposit, Sweden: A Response To Early Caledonian Orogenic Activity

©2015 Society of Economic Geologists, Inc.
Economic Geology, v. 110, pp. 1779–1801
A Middle Ordovician Age for the Laisvall Sandstone-Hosted Pb-Zn Deposit, Sweden:
A Response to Early Caledonian Orogenic Activity*
Nicolas J. Saintilan,1,†** Jens Schneider,2 Michael B. Stephens,3,4 Massimo Chiaradia,1 Kalin Kouzmanov,1
Marküs Wälle,5 and Lluís Fontboté1
1 Section of Earth and Environmental Sciences, University of Geneva, Rue des Maraîchers 13, 1205 Geneva, Switzerland
2 Department of Mineralogy, Technische Universität Bergakademie Freiberg, Brennhausgasse 14, 09596 Freiberg, Germany
3 Geological Survey of Sweden (SGU), Box 670 SE-751 28 Uppsala, Sweden
4 Department of Civil, Environmental and Natural Resources Engineering, Division of Geosciences,
Luleå University of Technology, SE-971 87 Luleå, Sweden
5 Institute of Geochemistry and Petrology, ETH Zürich, Clausiusstrasse 25, CH-8092 Zürich, Switzerland
Abstract
Ten sphalerite separates isolated from mineralized samples in proximal and distal positions relative to the
proposed main feeder fault systems at the Laisvall deposit were used to obtain an absolute age determina-
tion of this world-class Pb-Zn deposit hosted by autochthonous Ediacaran to Lower Cambrian sandstone and
located currently along the erosional front of the Scandinavian Caledonides in northern Sweden. Residue and
leachate fractions of each separate were obtained using the crush-leaching technique. All samples correspond
to sphalerite formed using reduced sulfur derived from thermochemical sulfate reduction, three of them from
disseminated ore in the Lower Sandstone, two from the disseminated ore in the Upper Sandstone, and five
from steeply dipping galena-sphalerite-calcite veinlets interpreted in previous works as remobilization of dis-
seminated ores. The isotope dilution-thermal ionization mass spectrometry (ID-TIMS) data yield an overall
complex Rb-Sr isotope pattern with two distinct trends in the 87Sr/86Sr vs. 87Rb/86Sr isochron diagram. The three
sphalerite residues of disseminated mineralization from the Lower Sandstone orebody show Rb-Sr isotope sys-
tematics indicative of undisturbed primary precipitates, and yield an isochron model age of 467 ± 5 Ma (mean
square weighted deviation, MSWD, 1.4). Since the isochron is based on three points, the obtained age is to be
considered as preliminary. Yet, the obtained age is fully consistent with geologic evidence reported by previous
authors and pointing to Middle Ordovician timing of ore formation.
The ID-TIMS data were complemented by laser ablation-inductively coupled plasma mass spectrometry
(LA-ICPMS) analyses on the same sphalerite samples. The data support the hypothesis that the measured
ID-TIMS Rb and Sr contents in these sphalerite residues are held in the sphalerite structure itself and are not
related to micro-inclusions. The most viable hypothesis, in agreement with published work, is that during rapid
growth, sphalerite may incorporate Rb and Sr ions from the hydrothermal fluids in its structure, most probably
in octahedral voids.
By contrast, the second trend in the 87Sr/86Sr vs. 87Rb/86Sr space defined by most other sphalerite residues and
corresponding inclusion fluid leachates from the Upper Sandstone orebody and the veinlet samples is too steep
to account for a realistic isochron age determination. This steep linear trend is interpreted to represent a post-
mineralization disturbance involving fluids rich in Sr. This disturbance of the Rb-Sr isotope system is consistent
with the presence of the steeply dipping galena-sphalerite-calcite veinlets and the fact that the Upper Sandstone
is, in places, tectonically disrupted because of its proximity to the basal Caledonian décollement. The attempt to
date the Granberget deposit, located in tectonically disrupted allochthonous units inside the Caledonian orogen,
failed because the Rb-Sr isotope systematics of the three analyzed sphalerite samples are also disturbed.
The obtained Middle Ordovician (467 ± 5 Ma) mineralization age at Laisvall can be interpreted as a far-field
foreland response to an early Caledonian arc-continent collision and the subsequent development of a foreland
basin. Basinal brines formed in the foredeep of the orogen could be conveyed cratonward, interact with per-
meable Baltica crystalline basement rocks, and resurge as metal-bearing fluids in sandstone at Laisvall along
reactivated Paleoproterozoic crystalline basement faults. Mixing of metal-bearing brines with hydrocarbon and
H2S-rich fluids in Ediacaran to Lower Cambrian sandstone may explain the initial Sr isotope signature (87Sr/86Sr
= 0.715900 ± 60) of the isochron intersect.
Introduction Ag), currently located along the erosional front of the Scandi-
The sandstone-hosted Pb-Zn deposit at Laisvall (64.3 navian Caledonides in northern Sweden (Fig. 1A), was discov-
million metric tons of ore at 4.0% Pb, 0.6% Zn, and 9.0 g/t ered in 1939. Mining operations started in 1941 (Grip, 1954)
and lasted until its closure in 2001. The timing of this Pb-Zn
mineralization has been discussed with some controversy (cf.
† Corresponding author: e-mail, [email protected] Rickard et al., 1979, 1981; Rickard, 1983; Bjørlykke and Sang-
*A digital supplement of Appendices to this paper is available at http://
economicgeology.org/ and at http://econgeol.geoscienceworld.org/.
ster, 1981; Bjørlykke et al., 1991; Romer, 1992; Kendrick et
**Present address: University of Alberta, 126 Earth Sciences Building, al., 2005) and geochronological work had not been carried out
Edmonton, AB, Canada T6G 2E3. prior to the current study.
Submitted: September 3, 2014
0361-0128/15/4349/1779-23 1779 Accepted: April 17, 2015
Downloaded from https://pubs.geoscienceworld.org/segweb/economicgeology/article-pdf/3472950/1779-1801.pdf

by Society of Economic Geologists, Cesar Ricardo Vargas
1780 SAINTILAN ET AL.
Var.
70 ºN A P. Barents
Sea
Norwegian
Sea V.
Laisvall G. J.
P.
Storuman
Ko nsu
Pe
d
la la
Torneträsk
ni
an
vein district
nl
Fi
R
.F
Åkerlandet Granberget
ed
66 ºN
.
vein district (Dorotea district)
Caledonian orogen
(0.5 – 0.4 Ga), including
Atlantic windows with uncertain
Ocean Fig tectonostratigraphic status
ure
1B Timanian orogen
(0.62 – 0.55 Ga)
Autochthonous sedimentary
62 ºN
cover rock & Oslo Rift
(Cryogenian to Paleogene)
Vassbo
Precambrian crystalline
+Boda basement (continent Baltica)
Osen Sandstone-hosted Pb-Zn
deposit in Ediacaran to
ay
Sweden Lower Cambrian

w
or
autochthonous cover rock

N
Sandstone-hosted Pb-Zn
58 ºN
deposit in lowermost
allochthonous units inside
North the Caledonian orogen
Sea Calcite-fluorite-Zn±Pb
sulfide vein in Archean or
0 100 Paleoproterozoic basement
km
10ºE
15ºE
20º E
W Norway Sweden E
0 0
Baltica basement
0 50 100 150 km
Middle and Upper Allochthons

Lower Allochthon and Autochthon
Köli Nappe Complex (outboard terranes)
Seve Nappe Complex (schist, paragneiss, Baltoscandian sedimentary cover
amphibolite) (allochthonous & autochthonous)
Baltica basement (allochthonous &
Särv Nappe (feldspathic sandstone, dolerite)
autochthonous)
Mylonitic granite, feldspathic sandstone
B
Fig. 1. A. Simplified geologic map of Scandinavia (modified after Roberts and Siedlecka, 2002; Gee et al., 2008; and
Bergman et al., 2012). The locations of (i) sandstone-hosted Pb-Zn deposits in Ediacaran to lower Cambrian siliciclastic sedi-
mentary rock, both in the autochthonous cover rocks to the crystalline basement and in the lowermost allochthonous units in
the Caledonian orogen (after Zachrisson, 1980; Stephens, 1986), (ii) calcite-fluorite-Zn ± Pb sulfide vein-type mineralization
in Paleoproterozoic crystalline basement in the Åkerlandet and Storuman areas, northern Sweden, (iii) similar vein-type
mineralization in Paleoproterozoic basement rocks in northern Norway (e.g., G. = Gurrogaissa), in Archean basement rocks
in northern Norway and Russia (e.g., J. = Jakobselv, P.: Peuravuono), and in rocks of the Timanian orogen in Russia (e.g., V.
= Vaitolahti) (after Gee, 1972; Sundblad, 1990) are shown. Abbreviations: R. Fed. = Russian Federation; Var. P. = Varanger
Peninsula. B. Cross section through the central part of the Scandinavian Caledonides in Sweden and Norway (modified after
Gee et al., 2010).
Rickard et al. (1979) characterized the Laisvall deposit as Kendrick et al. (2005), who provided evidence for extensive
epigenetic mineralization in sandstone, resulting from the mix- fluid-basement interaction before mineralization. Kendrick et
ing of migrating metal-rich brines with H2S-rich fluid hosted al. (2005) also suggested that the mineralizing process involved
in porous sandstone. This epigenetic model was supported by basinal brine-dominated fluids influenced by subsequent fluid

A MIDDLE ORDOVICIAN AGE FOR THE LAISVALL DEPOSIT, SWEDEN 1781
interaction with organic-matter in the subsurface. Recently, Representative sphalerite samples were selected from the
Saintilan et al. (2015) proposed that Paleoproterozoic base- following mineralization types (Fig. 1A): (1) the two strata-
ment faults at Laisvall were reactivated during Ediacaran bound orebodies in the autochthonous Lower Sandstone
to Lower Cambrian sedimentation and subsequently acted (Pb-Zn) and Upper Sandstone (Zn-Pb) at Laisvall; (2) the
as feeders of the metal-bearing fluids, providing support to strata-bound Granberget Zn-Pb mineralization in sandstone
Romer (1992) who invoked fluid migration through base- of the lowermost allochthonous units inside the Caledonian
ment structures in the genesis of Laisvall and similar mineral orogen, located about 200 km south of Laisvall; and (3) the
deposits presently located along the erosional front of the Åkerlandet calcite-fluorite-Zn ± Pb sulfide vein deposit,
Scandinavian Caledonides (e.g., Osen, Vassbo; Fig. 1A). By located in the Paleoproterozoic basement about 35 km to the
contrast, Bjørlykke and Sangster (1981) proposed an early east of the erosional front of the Scandinavian Caledonides.
diagenetic model based on groundwater transport of metals The latter is part of a group of calcite-galena vein depos-
from the underlying basement under stable tectonic condi- its that were proposed to be cogenetic with strata-bound
tions although, subsequently, Bjørlykke et al. (1991) placed sandstone-hosted Pb-Zn deposits of the Laisvall type (e.g.,
the formation at a later stage involving sedimentary brines. Johansson and Rickard, 1984). Additionally, whole-rock Sr
The lack of absolute age determinations for Laisvall-type isotope geochemistry and X-ray fluorescence analyses were
mineralization has markedly contributed to the genetic con- performed on crystalline basement and unconformably
troversy. Grip (1960) proposed a genetic relationship between overlying siliciclastic rocks from the autochthonous stratig-
epigenetic mineralization and Caledonian overthrusting with raphy at Laisvall.
mineralizing solutions derived from the “inner part of the This paper will be complemented soon by two companion
Caledonian range” (p. 158). Geologic and geochemical evi- articles that, respectively, explain the role of organic matter
dence led Gee (1972) and Rickard et al. (1975, 1979) to pro- in mineralization and refine a genetic model for the Laisvall
pose that mineralization at Laisvall probably occurred after deposit, and propose a reevaluation of the source(s) of metals
the deposition of the Middle Cambrian to Lower Ordovician in mineralization at Laisvall and in basement-hosted calcite-
Alum Shale Formation that represents an impermeable cap galena vein deposits.
rock above the strata-bound mineralization in sandstone.
Rickard et al. (1979) related mineralization at Laisvall to Geologic Setting
Caledonian tectonics and suggested that mineralization pre-
dated the “great Caledonian nappes emplacement” (p. 1277) Geologic framework
during the early Devonian. Rickard et al. (1979) maintained In the central and northern parts of Sweden, the crystal-
that some sets of joints “related to the Caledonian trend” (p. line basement is composed of Paleoproterozoic and Archean
1278) were filled at the same time as the disseminated strata- rocks belonging to a 2.0 to 1.8 Ga orogenic system (Sveco-
bound mineralization in sandstone, possibly in early Silu- karelian orogen), and subordinate late Paleoproterozoic to
rian time. Rickard (1983) later suggested that basinal brines early Neoproterozoic (1.7–0.9 Ga) sedimentary, volcanic, and
might have been supplied to the depositional site at Laisvall intrusive rocks. The basement is overlain unconformably by a
during the “beginning of the Caledonian orogeny” (p. 456), thin cover of Ediacaran to Lower Cambrian, locally through
which, based on the polyphase Caledonian orogenic evolu- Lower Ordovician, autochthonous sedimentary rocks that
tion proposed by Gee (1972) and Sturt (1978), was placed by were deposited on the western (present-day coordinates)
Rickard (1983) during “Upper Cambrian to Lower Ordovi- stable platformal margin of the Baltica continent (Bergman
cian” time (p. 456). et al., 2012; Fig. 1A). Along the northeastern (present-day
The hypothesis of ore formation driven by early Caledonian coordinates) continental margin of Baltica, in the Varanger
tectonic activity receives additional support by the similarity and Kola Peninsulas along the Barents Sea parts of Norway
of the lead isotope signature of galena in disseminated miner- and Russia (Fig. 1A), sedimentation onto Archean and Paleo-
alization hosted by Lower Ordovician limestone in the Boda proterozoic crystalline basement rocks commenced in the
area (Fig. 1A) and Laisvall-type mineralization (Wickman et al., early Cryogenian and continued in the Ediacaran (Roberts
1963; Gee, 1972). This geochemical evidence led Gee (1972) to and Siedlecka, 2002). Sedimentation occurred in an elongate
propose that epigenetic Pb mineralization was of Middle Ordo- basin controlled by important NW–SE faults along pre-exist-
vician age or younger. Kesler (1994) concluded that epigenetic ing, deep-seated anisotropies in the basement (Roberts and
mineralization at Laisvall had already been emplaced prior to Siedlecka, 2002). These sedimentary rocks are tectonically
the end of Ordovician time, i.e., before the dismantling of the juxtaposed against folded and metamorphosed rocks belong-
hydrological system related to Caledonian thrust tectonics. ing to the ca. 620 to 550 Ma Timanian orogen (Roberts and
The aim of the current study is to present an absolute age Siedlecka, 2002; Pease et al., 2008; Fig. 1A).
for the Laisvall deposit by using sphalerite Rb-Sr isotope To the west, rocks belonging to both continental margins
dilution thermal ionization mass spectrometry (ID-TIMS) and the Timanian orogen are overlain by thrust sheets belong-
systematics. In order to better constrain the siting of Rb and ing to the ca. 500 to ca. 400 Ma Caledonian orogen (Gee, 1975;
Sr in sphalerite and to strengthen the viability of Rb-Sr iso- Roberts and Gee, 1985; Bergman et al., 2012; Fig. 1A, B). In
tope geochronology age determination in this mineral, we the present study, the term “Caledonian” is used to character-
use a multidisciplinary approach that combines Rb-Sr isotope ize tectonic events that took place during the time interval
determinations with laser ablation-inductively coupled mass between late Cambrian (ca. 500 Ma) and Middle Devonian
spectrometry (LA-ICPMS) analyses of the Rb and Sr contents (ca. 395 Ma); the term “pre-Caledonian” is used for events
in inclusion-free and inclusion-bearing sphalerite. that occurred prior to 500 Ma.

The Caledonian orogen in present-day Scandinavia resulted autochthonous sequences beneath the Caledonian thrust
from a polyphase orogenic evolution (Gee, 1972; Sturt, 1978; nappes includes the Osen, Vassbo, Laisvall, and Tornesträsk
Dallmeyer and Gee, 1986). A foreland basin developed as a deposits and related minor occurrences (Fig. 1A; Christof-
response to the collision of Baltica with an outboard island ferson et al., 1979; Rickard et al., 1979; Zachrisson, 1980;
arc, with the collision producing a mountain belt comprising Bjørlykke and Sangster, 1981; Stephens, 1986). Similar sand-
mixed accreted Neoproterozoic continental rocks and oceanic stone-hosted mineralization occurs in the lowermost alloch-
material. These continental supracrustal rocks, preserved thonous units inside the Caledonian orogen and includes the
ca. 10 km northwest of Laisvall in the allochthonous nappes Granberget, Bellviksberg, and Lövstrand deposits in the Dor-
referred to as the Seve Nappe Complex, contain eclogites otea district (Fig. 1A; Årebäck, 2003; Ayrault, 2008; Chelle-
that were exhumed to high crustal levels at ca. 490 to 460 Ma Michou, 2008; Saintilan, 2010).
(Dallmeyer and Gee, 1986; Santallier, 1988; Stephens, 1988; At Laisvall (Fig. 2A), the autochthonous stratigraphy (Fig.
Kullerud et al., 1990; Gromet et al., 1996; Greiling and Gar- 2B) overlying the Paleoproterozoic (1.8 Ga) granite basement
funkel, 2007; Root and Corfu, 2012). This early continent-arc (Skiöld, 1988; Bergman et al., 2012) is approximately 100 m
collision and foreland basin development preceded the clo- thick and is preserved underneath the main Caledonian
sure of the Iapetus Ocean and terminal continent-continent décollement in the Alum Shale Formation and the overlying
(Laurentia-Baltica) collision, which probably began at ca. allochthonous thrust sheets. The sequence of autochthonous
450 Ma during the latest part of the Ordovician, and continued sedimentary cover rocks comprises the 35- to 40-m-thick
through the Silurian into Devonian time with final emplace- Ediacaran to Lower Cambrian Laisberg Formation (Willdén,
ment of the Caledonian thrust nappes (Gee, 1975; Stephens, 1980; Nielsen and Schovsbo, 2011) passing upward into the
1988; Gee et al., 2010; Root and Corfu, 2012). Lower Cambrian Grammajukku Formation and the lower-
most part of the Middle Cambrian to Lower Ordovician Alum
Strata-bound sandstone-hosted Pb-Zn deposit in autochthonous Shale Formation (Ljungner, 1950; Rickard et al., 1979; Will-
sedimentary cover rocks and lowermost allochthonous units dén, 1980; Thickpenny, 1984).
Strata-bound Pb-Zn sulfide mineralization hosted by Edia- The Laisberg Formation (Fig. 2B) represents a transgres-
caran to Lower Cambrian siliciclastic sedimentary rocks in sive, sandstone-dominated sequence (Willdén, 1980; Nielsen
A Middle Alum Shale Formation Stratigraphy at Laisvall B

Cambrian (organic-rich shale)
Grammajukku Formation
Laisvall (shale and siltstone,
~40 m)
Lower Cambrian
* phosphorite conglomerate so-called “Assjatj Member” (0.5 m)

Upper Sandstone-ore
horizon (6-8 m)
Middle Sandstone
Laisberg Formation
(6-8 m)
Lower Sandstone-ore
Ai
horizon (~25 m)
sja
ur
e
Lais
?
Ediacaran
Pebble shale (~12 m)

an R
Proterozoic
Feldspathic sandstone
iver
and conglomerate,~10 m)
Ediacaran
Paleoproterozoic
Pre-
granitic basement
Caledonian thrust nappes (allochthon)

Thrust (symbols towards the overlying unit)
Middle Cambrian to Lower Ordovician Alum Shale Formation (partly in allochthon)
Ediacaran to Lower Cambrian sandstone, shale and siltstone (autochthon)
Granite (1.8 Ga Sorsele granite, autochthon)
Mineralization in autochthonous Ediacaran to Cambrian sandstone at Laisvall (projected to
ground surface)
Fault (Lilljequist, 1973)
0 2 4
Fault in autochthonous sedimentary cover rocks close to the Laisvall deposit, rooting downwards
kilometers in the crystalline basement (projected to ground surface; Saintilan et al., 2015)
Fig. 2. A. Geologic map of the Caledonian allochthons, autochthonous sedimentary cover rocks, and Paleoproterozoic
crystalline basement in the Laisvall area (modified after Lilljequist, 1973; Bergman et al., 2012). The projection of the Laisvall
orebodies to ground surface is also shown. B. Stratigraphic column of the autochthonous sedimentary cover sequence above
Paleoproterozoic basement at Laisvall (modified after Rickard et al., 1979; Willdén, 1980; Nielsen and Schovsbo, 2011). The
age of the Sorsele granite at Laisvall is after Skiöld (1988).

and Schovsbo, 2011). Epigenetic, disseminated, mottled or contrast to the autochthonous stratigraphy at Laisvall. In
banded galena-sphalerite cement mineralization is hosted places, the Alum Shale Formation occurs in direct contact
in two sandstone paleoaquifers, the Lower and Upper Sand- with Paleoproterozoic basement (Gee et al., 1978; Thick-
stones (Rickard et al., 1979; Willdén, 1980; Saintilan et al., penny, 1984; Saintilan, 2010). Mineralization, not observed
2015). Calcite, quartz, barite, K-feldspar, and fluorite occur as in the autochthonous rocks, occurs in clay-matrix, clast-
accessory to locally dominant premineralization cements (Rick- supported, coarse-grained feldspathic sandstone/arkose and
ard et al., 1979; Lindblom, 1986; Saintilan et al., in press). A conglomerate in the lowermost allochthonous units formed
detailed paragenetic sequence of Pb-Zn sulfide mineralization during the Caledonian orogeny. It consists mainly of sphaler-
at Laisvall and Raman spectrometry studies of solid and fluid ite and galena cementing quartz and feldspar detrital grains,
inclusions in sphalerite indicates the local presence of fluorapa- similar to that at Laisvall. Fluorapatite is not observed. Dis-
tite inclusions in sphalerite (Saintilan et al., in press). Early dia- seminated mineralization is tectonically disrupted by subver-
genetic fluorapatite, in places abundant, is found in cements of tical faults, cut by steeply dipping galena-sphalerite-calcite
the Upper Sandstone. In addition, a new generation of aggre- veinlets, and all these structures are in turn cut by low-angle
gated euhedral to subhedral fluorapatite has been found to be thrusts (Årebäck, 2003; Saintilan, 2010).
cogenetic within sphalerite (Saintilan et al., in press). Organic
compounds (i.e., solid bitumen) are intergrown with sphalerite Calcite-galena vein deposits in the basement
or included in barite (Saintilan et al., in press) and hydrocar- Moorbath and Vokes (1963), Wickman et al. (1963), Grip
bons were optically recognized in fluid inclusions in sphalerite (1967, 1973), Gee (1972), Johansson and Rickard (1984), Lin-
(Lindblom, 1986). These observations are consistent with the dahl and Bjørlykke (1988), and Sundblad (1990) report the
results of the work by Rickard et al. (1975), suggesting that the existence of several calcite-galena vein deposits in the Paleo-
mineralizing fluids contained petroleum-like compounds. proterozoic and Archean basement of Baltica. Several of these
In places, steeply dipping galena-sphalerite-calcite vein- vein deposits occur 10 to 35 km east of the current erosional
lets cut through both the Lower Sandstone and Upper Sand- front of the Scandinavian Caledonides in Sweden and Norway
stone orebodies (Rickard et al., 1979; Saintilan et al., 2015). (Fig. 1A). In addition, veins comprising either quartz-calcite-
At Laisvall, parts of the mineralization in the autochthonous barite-galena-sphalerite or only calcite-galena (Sundblad, 1990)
sedimentary cover rocks were affected by reverse faults and are found along the shoreline of the Kola Peninsula in Norway
some mineralization has been incorporated in the lowermost and Russia (Fig. 1A). In all cases, lead isotope studies suggest
allochthonous thrust sheets (Rickard et al., 1979; Saintilan that Pb in galena was derived from local Precambrian base-
et al., 2015). These observations suggest that the mineraliza- ment rocks (Johansson, 1983a; Johansson and Rickard, 1984;
tion predated the Middle Silurian to Lower Devonian (post- Lindhal and Bjørlykke, 1988; Sundblad, 1990; Romer and
430 and pre-397 Ma) emplacement of the Caledonian thrust Wright, 1993; Billström et al., 2012).
nappes (Stephens, 1988; Gee et al., 2008; Corfu et al., 2014). Along the erosional front of the Scandinavian Caledonides,
Similar observations were made at the Vassbo deposit (Christ- calcite-fluorite Zn ± Pb sulfide vein deposits in the Storuman
offerson et al., 1979; Saintilan et al., 2015). and Åkerlandet districts (Fig. 1A) are hosted by Paleoprotero-
The Grammajukku Formation (Willdén, 1980) overlies a zoic (1.9 Ga) metasedimentary rocks intruded by Revsund
thin phosphorite pebble conglomerate horizon at the top of granite (1.8 Ga), and Paleoproterozoic (1.9 Ga) migmatitic
the Laisberg Formation (Fig. 2B). It consists of shale and silt- paragneiss and homogeneous leucocratic granite, respectively
stone with subordinate sandstone intercalations. The overlying (Bergman et al., 2012). The vein deposits are located in brittle
Alum Shale Formation (Fig. 2B) comprises mainly black and structures along shear zones with N-S to NE-SW trends and
gray, laminated, organic matter rich mudstone and shale with both strike-slip and dip-slip components of movement (Bill-
high total organic carbon (TOC) contents (1 to 22 wt %) that ström et al., 2012; Saintilan et al., 2012). Johansson (1983b,
could have constituted hydrocarbon source rocks (Thickpenny, 1984) and Billström et al. (2012) proposed that these vein
1984). This formation builds a regionally extensive cap-rock deposits formed by the mixing of a hot (160°–200°C) saline
sealing the hydrodynamic system above the sandstone paleoa- hydrothermal fluid with a cooler (<70°C), less saline fluid.
quifers that host the Laisvall deposit. Early diagenetic calcite
concretions within the black shales of the Alum Shale Forma- Sample Selection and Analytical Procedures
tion in southern Sweden were dated at 509.8 ± 5.1 Ma using
U-Pb geochronology (Israelson et al., 1996), an age proposed Sample selection for Rb-Sr isotope systematics and
for the Upper Cambrian (Cohen et al., 2013) and in line with characterization
the proposed time of deposition of the Alum Shale Forma- Sphalerite samples from the orebodies at Laisvall were
tion from Middle Cambrian to locally Lower Ordovician using taken from the two distinct types of mineralization at the
paleontological data (cf. Andersson et al., 1985). Deposition of deposit: disseminated sphalerite mineralization as cement in
≥200 m Lower Ordovician limestone (Gee et al., 2013) caused sandstone, referred to hereafter as disseminated samples; and
the “final stage of sediment compaction of the semi-consoli- steeply dipping galena-sphalerite-calcite veinlets discordant
dated Alum Shale Formation” and “significant changes in the to the disseminated mineralization, referred to hereafter as
pore water regime of shale” (Israelson et al., 1996, p. 158). veinlet samples. The sampling included the following: (1) two
These limestones are not preserved at Laisvall. disseminated and three veinlet samples from the Upper Sand-
At Granberget in the Dorotea district (Fig. 1A), the autoch- stone orebody; (2) three disseminated and two veinlet samples
thonous stratigraphy is less than 10 m thick, comprises shale from the Lower Sandstone orebody (Table 1). Several sphal-
and siltstone, and lacks porous sandstone units, in sharp erite generations have been distinguished petrographically

1784
Table 1. Location and Geologic Setting of Disseminated and Veinlet Sphalerite Samples from the Orebodies at Laisvall and at the Granberget Deposit, and
the Sphalerite Sample from the Basement-Hosted Åkerlandet Vein Deposit Selected for Rb-Sr Isotope Geochemistry
Deposit Sample no. Mineral phase (δ34S VCDT) Type Location and geologic setting

Laisvall, Upper Sandstone orebody 12 LAI 12 Sphalerite δ34S = 29.0‰ Disseminated Beige, disseminated sphalerite in borehole 1647 ~20 m to the
north of the northern segment of the Kautsky fault (distal,
NW of the Nadok fault)
12 LAI 52 Sphalerite δ34S = 29.2‰ Disseminated Mottled mineralization with different colors of sphalerite
(yellow and orange) in borehole 280 on the Nadok fault
Laisvall, Lower Sandstone orebody 12 LAI 03 Sphalerite δ34S = 31.5‰ Disseminated Typical interstitial mottled mineralization; located ~50 m to the
SE of the northern segment of the Kautsky fault in borehole
1610 (distal, NW of the Nadok fault)
12 LAI 53 Sphalerite δ34S = 29.1‰ Disseminated Located on the Nadok fault in borehole 280; typical mottled
mineralization
11 LAI 33 Sphalerite δ34S = 28.2‰ Disseminated Located in borehole 1580, a few meters to the north of the
densely fractured area in the Lower Sandstone, where the
mineralization makes an inflection point changing direction
from NE-SW to NW-E (distal, east of the Nadok fault)
Laisvall, veinlets in Upper Sandstone orebody 12 LAI 43 Sphalerite δ34S = 28.3‰ Veinlet Steeply dipping galena-sphalerite-calcite veinlets in borehole

258, ~25 m north of the small fault between the Niepsurt and
Kramaviken faults (Central Malm)
12 LAI 44-1 & -2 Sphalerite δ34S = 29.8‰ Veinlet Several veinlets at same location as 12 LAI 43
SAINTILAN ET AL.
Laisvall, veinlets in Lower Sandstone orebody 12 LAI 14 Sphalerite δ34S = 29.4‰ Veinlet Steeply dipping galena-sphalerite-calcite veinlet on the northern
segment of the Kautsky fault
12 LAI 84 Sphalerite δ34S = n. a. Veinlet Steeply dipping galena-sphalerite-calcite veinlet on the northern
segment of the Kautsky fault
Granberget BRB 50 Sphalerite δ34S = 17.2‰ Disseminated Main mineralized lens (Saintilan, 2010)
BRB 56 Sphalerite δ34S = 14.1‰ Disseminated Mineralization in secondary lenses above a low-angle thrust
above the main lens (Saintilan, 2010)
BRB 58 Sphalerite δ34S = 19.3‰ Disseminated
Åkerlandet vein deposit 12 AKE 01 Sphalerite δ34S = 0.1‰ Basement- Calcite-fluorite vein with brecciated sphalerite-quartz-adularia
hosted vein clasts
Note: The δ34S VCDT isotope compositions (±0.3‰) of the sphalerite aliquots are after Saintilan et al. (in press); n.a. = not analyzed; the fault system at Laisvall is described in Saintilan et al. (2015)
and by means of sulfur isotope data (Saintilan et al., in press). Table 2. Whole-Rock Samples Selected in the Stratigraphy at
All samples belong to the main sphalerite generation char- Laisvall (Fig. 2B) for Major, Minor, and Trace Element Geochemistry
as well as Radiogenic Sr Isotope Geochemistry
acterized by heavy δ34S values from 27.0 to 34.0‰, indicat-
ing H2S produced by thermochemical sulfate reduction (cf. Sample no. Rock type
Rickard, 1983; Saintilan et al., in press) involving hydrocar-
bons (cf. Rickard et al., 1975; Lindblom, 1986; Saintilan et 11LAI16-2 Black shale with pyrite in the Alum Shale Formation
11LAI45 Gray shale with organic matter in the Alum Shale
al., in press). The sampling procedure avoided earlier-stage Formation
generations that formed by replacement of early diagenetic 11LAI26 Green shale in the Grammajukku Formation
framboidal pyrite and euhedral diagenetic pyrite (δ34S values 11LAI03-1 Phosphorite polymictic conglomerate, poorly
for these pyrite generations: from –11.0 to –6.0‰, and from galena-mineralized
21.0 to 31.0‰, respectively; Saintilan et al., in press). The 11LAI03-2 Phosphorite polymictic conglomerate with interstitial
sphalerite
samples were collected from drill cores stored at the Geo- 11BAS01 Granite (1.8 Ga) in the crystalline basement
logical Survey of Sweden (SGU) in Malå and at the Boliden 11BAS02 Granite (1.8 Ga) in the crystalline basement
AB core archive in Boliden, Sweden. The 10 samples were 11BAS03 Granite (1.8 Ga) in the crystalline basement
selected in profiles in proximal and distal positions relative 11BAS04 Granite (1.8 Ga) in the crystalline basement
11BAS05 Granite (1.8 Ga) in the crystalline basement
to the Nadok fault and Central Malm fault systems (Table 1), 11BAS06 Granite (1.8 Ga) in the crystalline basement
which are interpreted as having been main feeder systems for
mineralization (Saintilan et al., 2015).
In addition, three disseminated samples from the Gran-
berget deposit were taken from drill core archived in Boliden Whole-rock X-ray fluorescence (XRF) analyses were per-
(Table 1). Furthermore, one intensely mineralized sphalerite- formed for major, minor, and trace elements (including Rb
rich calcite-fluorite-sulfide vein sample was selected at Åker- and Sr) on these samples, using an Axios Advanced 4.0 kW
landet for analysis from the old adit in a previously operated X-ray fluorescence spectrometer at the University of Laus-
small-scale quarry within the main mineralized area along a anne, Switzerland.
shear zone. Given the close proximity between the Granber-
get deposit and the basement-hosted Åkerlandet vein deposit Mineral chemistry of sphalerite
(Fig. 1A), the original goal was to combine the Rb-Sr system- Major and minor elements in sphalerite (S, Zn, Fe, Mn,
atics of these samples in a regression to study the possible Cu, Se, Ag, Cd, and In) were quantified in the thick sections
genetic link between these two deposits. by electron microprobe analysis (EMPA, JEOL 8200 elec-
Thin sections of all samples were studied by transmitted tron Superprobe) at the University of Lausanne, Switzerland.
and reflected light microscopy. The paragenetic sequence and Operating conditions were set to an acceleration voltage of
the relationships between the pre-sphalerite stage cements, 20 kV, a beam current of 40 nA, and a counting time of 20 sec-
the accessory mineral phases, and the sphalerite-stage min- onds (s) for peak and 2 × 10 s for background. Se, Ag, and In
eral associations have been established for Laisvall and pre- were systematically below detection limit in all samples, and
sented elsewhere (Saintilan et al., in press). Carbon-coated, Cu was detected and quantified only rarely. Data for S, Mn,
polished thick sections of two representative disseminated Fe, Cu, Zn, and Cd were averaged using the geometric mean
samples from both the Lower and Upper Sandstone orebod- per sample and reported with 1σ standard deviation.
ies at Laisvall (~100 µm thick) and of the sample from Åker- LA-ICPMS analyses of trace elements in sphalerite were
landet (~30 µm thick) were utilized for electron microprobe conducted using a 193 nm ArF Excimer laser with an energy-
and subsequent LA-ICPMS analyses. homogenized beam profile coupled with the ELAN 6100
Portions of all samples (Table 1) were crushed using a DRC ICP quadrupole mass spectrometer (QMS) at ETH
hydraulic press and sieved. Following heavy liquid separation Zürich, Switzerland (Günther et al., 1997; Heinrich et al.,
of the 315- to 125-µm-size fractions, the heavy mineral frac- 2003). Table 3 provides a summary of the elements analyzed
tions were handpicked under a binocular microscope to obtain and the analytical conditions and data acquisition parameters.
about 75 mg sphalerite aliquots for Rb-Sr isotope analysis. The ablation rate for sphalerite was between 0.1 and 0.2 µm/
Table 2 lists the samples selected from key stratigraphic pulse. By adjusting an aperture in the laser beam path, the
units at Laisvall for whole-rock and Sr isotope geochemical optical imaging system permits visual positioning of ablation
analyses. Samples of granite, collected from drill core pieces or points and the use of different pit diameters (30–60 µm) at
basement outcrops in the field, were crushed and milled using constant energy densities. The samples were loaded, along
an automated grinder with a built-in agate mortar. Other drill with the synthetic polymetallic sulfide standard MASS-1 (Wil-
core samples include black (11LAI16-2) and dark-gray shale son et al., 2002) and the SRM 610 glass NIST standard, in a
(11LAI45) from the Alum Shale Formation, and a green shale 1 cm3 ablation cell on a modified Zeiss petrographic micro-
(11LAI26) from the Grammajukku Formation. In addition, scope. P, Rb, and Sr were quantified using the SRM 610 glass
a sphalerite-mineralized sample (11LAI03-2) was taken from NIST external standard; for quantification of all other ele-
the lower part of the phosphorite conglomerate at the contact ments, the MASS-1 standard was used. Data reduction was
with the underlying sphalerite ± galena-mineralized Upper carried out using the SILLS software (Guillong et al., 2008)
Sandstone orebody (Fig. 2B), and a poorly galena mineral- and using the Zn content, known from electron microprobe
ized sample (11LAI03-1) was collected from the upper part analyses, as an internal standard.
of this conglomerate in contact with green shale belonging to Si was used to monitor inclusions of hydrothermal quartz
the Grammajukku Formation. in sphalerite, while P was used to monitor the presence of

Table 3. LA-ICPMS Machine and Data Acquisition Parameters SEM-CL imaging with transmitted and reflected light micros-
copy (Fig. 3). However, such inclusions may not have been
Excimer 193 nm
ArF laser Compex 110I Sphalerite avoided in all instances. Representative single-spot spectra
chosen from the complete dataset, showing both smooth
Output energy 20 mJ and irregular profiles, are shown in Figure 4. Since the spot
Homogeneous energy ~5 J/cm2 sizes used for LA-ICPMS analyses were greater than many
density on sample
Repetition rate 5 Hz
of these inclusions, the ablation profiles are not invariably
Ablation mode Single hole homogeneous at the scale of the ablation spots (Fig. 4A, B).
Crater sizes 30-60 µm Aside from such inclusions, the analyzed samples show rather
Ablation cell In-house built glass chamber with homogeneous ablation profiles for other elements.
antireflection coated silica glass window
Rb-Sr isotope analysis of sphalerite and whole-rock samples
Perkin Elmer ELAN 6100 DRC
The sphalerite separates were leached in 2 N HCl and 2 N
Rf-power 1550 W HF (15 min each) to remove carbonate, phosphate, or silicate
Detector mode Dual (cf. Schneider et al., 1999). The separates were then repeat-
Quadrupole setting time 3 ms
Nebulizer gas flow 0.79 l/min Ar
edly washed and ultrasonified in deionized water. The wet sep-
Auxiliary gas flow 0.85 l/min Ar arates were crushed using a precleaned boron carbide mortar
Plasma gas flow 15.5 l/min Ar and pestle for 2 to 5 min and ~1.5 ml of deionized water was
Carrier gas flow 1.1 l/min He added after crushing in order to sample the liberated fluid
Additional gas flow 5 ml/min H2 inclusions. Care was taken to grind the aliquots thoroughly to
Data acquisition parameters minimize the possibility of contributions from unopened fluid
inclusions (Pettke and Diamond, 1996). The leachate (L) was
Sweeps per reading 1 recovered from the residual sphalerite, hereafter referred to
Readings per replicate 300 as residue or R, by repeated centrifuging. The first supernate
Replicates 1
Dwell time per isotope 30 ms for Ga, Rb, Sr
was kept as the fluid inclusion leachate sample, and a known
10 ms for all others weight of a mixed tracer containing highly enriched 87Rb and
Points per peak 1 per measurement 84Sr was added to these solutions.
Oxide production rate tuned to <0.5 % ThO The residual sphalerite powders were again leached
Isotopes analyzed 28Si, 31P, 32S, 55Mn, 57Fe, 65Cu, 66Zn, 69Ga,
and sonified in 2 N HCl and 2 N HF (15 min each), with
77Se, 85Rb, 88Sr, 109Ag, 111Cd, 115In, 118Sn,
121Sb, 208Pb repeated water washes in between until neutral reaction of
the supernate. All washes were discarded. The residues were
transferred to preweighed Teflon vials and dried overnight.
Subsequently, the sample containers were allowed to cool and
fluorapatite inclusions in sphalerite or of fluorapatite lining reweighed to obtain the sample weights. The sphalerite resi-
sphalerite crystals along contacts with detrital quartz and dues were then totally spiked using a mixed 87Rb-84Sr tracer
quartz overgrowths in the host sandstone at Laisvall (Fig. 3). solution and dissolved in 6 N HCl on a hot plate.
In order to optimize the LA-ICPMS analyses using ablation Rubidium and strontium were separated with 3 N HNO3
crater diameters of 30 to 60 mm, an effort was made to pre- using EICHROM Sr resin on 50 µl Teflon microcolumns, fol-
select sphalerite volumes free of obvious fluorapatite, quartz, lowing the methods of Deniel and Pin (2001). The first 600 µl
galena, or other solid and fluid inclusions by combining of HNO3 wash were collected for Rb collection. The Rb cuts
detrital quartz
galena
rowth
v erg
zo
art Ba-mica
qu
qtz ovg
quartz sphalerite
fluorapatite
Ba-K-fds
A 10 μm
B detrital quartz
10 μm
10.0 kV SEM-CL WD 16.4 mm 10.0 kV SEM-CL WD 16.4 mm
Fig. 3. Scanning electron microscope, cathodoluminescence mode (SEM-CL) images of galena-mineralized (A) and
sphalerite-mineralized (B) sandstone at Laisvall, showing details of diagenetic quartz overgrowth (qtz ovg) on detrital quartz
grains, as well as later cogenetic Ba-mica and Ba-bearing K-feldspar inclusions in galena, and cogenetic fluorapatite inclusions
in sphalerite.

108
Zn
A 107
B
Zn
107
106
Sr-rich Sr-Rb-rich
fluorapatite Mn
Counts per second

fluid inclusion
Counts per second
106 inclusion Cd
Cd
Mn 105
Fe
105 Fe
Cu
P 104
Cu
104
Sr
103
103 Rb
Sr
Rb 102
102
101 101
0 50 100 150 0 50 100
Time (seconds) Time (seconds)
Fig. 4. Representative single-spot LA-ICPMS spectra for Rb, Sr, P, and major elements (previously determined by
EMPA) in sphalerite in the Upper Sandstone orebody at Laisvall. A. The spectrum is composed of two successive single-spot
analyses within the same sphalerite crystal. Note the presence of Sr-rich fluorapatite inclusion at the beginning of the second
analysis. B. Sphalerite with representative heterogeneous distribution of Sr and Rb in sphalerite. Note the presence of an
Sr- and Rb-rich fluid inclusion in the central part of the spectrum (see text for discussion). Spectra similar to Figure 4B exist
for sphalerite in the Lower Sandstone orebody.
from sphalerite residues were further purified using standard the age calculations was λ87Rb = 1.42 × 10–11a–1 (Steiger and
cation-exchange procedures (Birck, 1986), whereas no addi- Jäger, 1977), and errors on Rb-Sr model ages are quoted at
tional Rb separation was necessary for the fluid inclusion liq- the 2σ level. The goodness of fit of linear and planar regres-
uids. Sr was stripped from the columns with 1 ml of deionized sions has been tested by means of the mean square weighted
water. For ID-TIMS analysis of spiked sphalerite Rb and Sr, deviation (MSWD) parameter (Wendt and Carl, 1991).
Sr was loaded with a TaCl5-HF-H3PO4 solution (Birck, 1986)
onto W single filaments. Rb was loaded with 2 N HNO3 onto Results
the evaporation ribbon of a Ta double-filament assemblage.
Between 100 and 150 mg of powdered whole-rock sam- Minor and trace element distribution in sphalerite from
ples were prepared and dissolved following the procedure disseminated samples
described in Chiaradia et al. (2011). Strontium was separated Major and minor element concentrations of sphalerite sam-
from the rock matrix using EICHROM Sr resin before being ples are provided in Appendix 2. The full LA-ICPMS dataset
converted into 5 ml solutions of 2% HNO3. of minor and trace elements in sphalerite, including 60 single-
All isotopic measurements of the Rb and Sr cuts from spot analyses in the Laisvall samples and 31 single-spot analyses
sphalerite residues and leachates were performed on Thermo in the Åkerlandet sample, is reported in Appendix 3. Apatite
Fisher TRITON (ID-TIMS), while Sr isotope ratios of whole- inclusions were identified by P and Sr peaks in the ablation pro-
rock samples were determined by multicollector ICP-MS files (Fig. 4A). The presence of parts of the ablated samples rich
(NEPTUNE) in static mode using the virtual amplifier mode in or devoid of Rb- and Sr-rich fluid inclusions in sphalerite
at the University of Geneva, Switzerland. Details relative to is readily identified in ablation profiles (Figs. 4B). In ablated
procedural blank corrections and in-run and external fraction- samples devoid of fluid inclusion, Sr and Rb contents in sphal-
ation corrections are given in Appendix 1. A 87Sr/86Sr ratio of erite do not correlate with the distribution of the principal trace
0.721269 ± 1.4 × 10–5 (2σ) is reported as 0.721269 ± 14. metals (e.g., Zn, Mn, Fe, Cu, and Cd; Fig. 4A, B).
Rb-Sr model isochron regressions were calculated after
Ludwig (2003) using the ISOPLOT/Ex version 3.00 program. Rb-Sr isotope systematics of sphalerite
For iterative planar paleomixing line regressions according to The results of Rb and Sr isotope analyses for sphalerite
Schneider et al. (2003), an internal FORTRAN subroutine samples are shown in Table 4. The Rb and Sr elemental con-
“MIXING LINE 3 D” was used. The decay constant used for centrations of the sphalerite residues (R) obtained in the three

Table 4. Rb-Sr Isotope Composition of Residues and Corresponding Leachates of Sphalerite Samples from the
Lower Sandstone and Upper Sandstone Orebodies (disseminated samples) and Remobilization Veinlets (veinlet samples) at
the Laisvall Deposit, from the Sandstone-Hosted Granberget Deposit and from the Basement-Hosted Åkerlandet Vein Deposit
87Rb/86Sr 2σ 87Sr/86Sr 2σ Rb [ppm] 2σ Sr [ppm] 2σ
Crushed-leached sphalerite residues (R)

Laisvall Upper Sandstone
12 LAI 12 R 0.2572 0.0038 0.726134 2.0E-06 0.1339 0.0017 1.5090 0.0197
12 LAI 52 R 1.3499 0.0193 0.727203 4.0E-06 0.1677 0.0021 0.3600 0.0047
Laisvall Lower Sandstone
12 LAI 03 R 0.4946 0.0071 0.719191 4.0E-06 0.0973 0.0012 0.5695 0.0074
11 LAI 33 R 4.9872 0.0715 0.748900 1.7E-05 0.3194 0.0041 0.1860 0.0024
12 LAI 53 R 7.2453 0.1173 0.764457 6.0E-06 2.6007 0.0364 1.0443 0.0136
Veinlet in Laisvall Upper Sandstone
12 LAI 43 R 0.1570 0.0025 0.726391 2.0E-06 0.1149 0.0016 2.1211 0.0277
12 LAI 44 R (1) 0.2600 0.0038 0.726294 2.4E-05 0.1025 0.0013 1.1426 0.0149
12 LAI 44 R (2) 0.1699 0.0024 0.725305 3.0E-06 0.1624 0.0021 2.7714 0.0363
Veinlet in Laisvall Lower Sandstone
12 LAI 14 R 0.4654 0.0520 0.739143 1.0E-05 0.0303 0.0026 0.1892 0.0025
12 LAI 84 R 0.2626 0.0038 0.737266 8.0E-06 0.0323 0.0004 0.3568 0.0047
Granberget
BRB 50 R 0.4991 0.0074 0.746848 8.9E-05 0.2243 0.0029 1.3051 0.0173
BRB 56 R 0.1416 0.0020 0.729805 5.0E-06 0.0154 0.0002 0.3144 0.0041
BRB 58 R 0.2667 0.0038 0.744350 1.4E-05 0.2771 0.0035 3.0170 0.0394
Åkerlandet
AKE-1 R 1.1129 0.0158 0.723380 8.0E-06 0.0274 0.0004 0.0713 0.0009
Fluid inclusion leachates (L)*

Laisvall Upper Sandstone
12 LAI 12 L 0.1025 0.0015 0.723846 4.0E-06 - - - -
12 LAI 52 L 0.1290 0.0019 0.722199 3.0E-06 - - - -
Laisvall Lower Sandstone
12 LAI 03 L 0.1265 0.0018 0.717892 3.0E-06 - - - -
11 LAI 33 L 1.2249 0.0229 0.727581 2.0E-05 - - - -
12 LAI 53 L 1.1512 0.0165 0.732624 5.0E-06 - - - -
Veinlet in Laisvall Upper Sandstone
12 LAI 43 L 0.0959 0.0014 0.727287 6.0E-06 - - - -
12 LAI 44 L (1) 0.2635 0.0038 0.722985 4.0E-06 - - - -
12 LAI 44 L (2) 0.1130 0.0016 0.725883 3.0E-06 - - - -
Veinlet in Laisvall Lower Sandstone
12 LAI 14 L 0.1736 0.0025 0.740630 3.0E-06 - - - -
12 LAI 84 L 0.1508 0.0022 0.738577 3.0E-06 - - - -
Granberget1
BRB 50 L 0.1133 0.0017 0.745676 2.4E-05 - - - -
BRB 56 L 0.1177 0.0017 0.733489 4.0E-06 - - - -
Åkerlandet
AKE L 0.1424 0.0020 0.720009 4.0E-06 - - - -
Note: *Rb and Sr concentrations of fluid inclusions are not reported since the total amount of trapped fluid in the samples is not known; 1 = leachate
BRB 58 L was lost, - = no data
analyzed deposits display wide ranges (0.015–2.6 ppm Rb and et al., 1995a, b; Yang and Zhou, 2001). See also Rb and Sr
0.071–3.017 ppm Sr). Except for one sample from the Lower concentrations found in sphalerite and other sulfides in Mis-
Sandstone orebody at Laisvall, which has a high Rb content sissippi Valley-type (MVT) deposits, e.g., from Pine Point,
of 2.601 ppm, Rb contents remain below 0.4 ppm, whereas Northwest Territories, Canada (Medford et al., 1983) and
Sr shows greater variations, with several Laisvall sphalerite from the Immel mine-Coy mine, Mascot-Jefferson MVT dis-
residues showing high contents of Sr (2.121–3.017 ppm). In trict, eastern Tennessee (Nakai et al., 1990; 1993). Rb and Sr
general, the Rb and Sr elemental concentrations of the sphal- concentrations of fluid inclusion leachates are not reported
erite residues obtained in the three analyzed deposits are because the total amount of trapped fluid in the samples can-
consistent with other published Rb-Sr data for sulfides (see not be determined.
Reesman, 1968; Medford et al., 1983; Nakai et al., 1990, 1993; The sphalerite samples have 87Rb/86Sr ratios between 0.141
Brannon et al., 1991, 1992; Nelson et al., 2002, Christensen and 7.25, with most ratios being lower than 0.6. All sphalerite

samples show moderately radiogenic 87Sr/86Sr ratios between the deposits. Schneider et al. (2003) successfully evaluated a
0.7191 and 0.7645 (Table 4). On a 87Sr/86Sr vs. 87Rb/86Sr corre- method that enables the dating of Sr isotope disequilibrium
lation (isochron) diagram including the three studied deposits in hydrothermal alteration assemblages by reconstruction of
(Fig. 5A), the sphalerite residues scatter widely and do not hypothetical two-component paleomixing lines in 87Sr/86Sr vs.
define an all-sample Rb-Sr isochron. Remarkable internal con- 1/86Sr space from Rb-Sr analytical data, using an iterative pla-
trasts in the Rb-Sr isotope systematics are found between the nar regression approach. However, application of this method
two following groups of samples: (1) the three disseminated to the sphalerite residues analyzed in this study does not yield
samples from the Lower Sandstone orebody at Laisvall, one statistically robust binary paleomixing lines for any realistic age
disseminated sample (12LAI52 R) from the Upper Sandstone (calculated ages are in excess of 3.0 Ga). As discussed below,
orebody, and the Åkerlandet vein sample; (2) the other sphal- this trend probably reflects postmineralization event(s) that
erite samples from the Upper Sandstone orebody, the veinlet affected and disturbed the Rb-Sr systems of both the inclusion
samples from the Lower Sandstone orebody at Laisvall, and fluids and their host minerals in most samples from the Upper
the disseminated samples from the Granberget deposit. Sandstone, in the veinlet samples of the Lower Sandstone ore-
In a 87Sr/86Sr vs. 87Rb/86Sr diagram, the three disseminated bodies, and in all samples from Granberget.
residues from the Lower Sandstone orebody plot along a line
of moderate slope which can be interpreted to represent a Geochemistry and Sr isotope composition of the
three-point isochron (Fig. 5B); the slope corresponds to an crystalline basement and the autochthonous sedimentary
age of 467 ± 5 Ma (MSWD = 1.4, with an initial 87Sr/86Sr ratio cover sequence at Laisvall
of 0.715900 ± 60). Since the isochron is based on three points, X-ray fluorescence (XRF) analyses of oxides and trace ele-
the obtained age is to be considered preliminary. These resi- ments in dark-gray shale from the Alum Shale Formation,
dues do not plot as a mixing array but remain scattered in in green shale from the Grammajukku Formation, and in
a 87Sr/86Sr vs. 1/86Sr diagram (Fig. 6A). The results suggest variably mineralized polymictic phosphorite conglomerate
that the original Rb-Sr system in the disseminated sphalerite beneath the Grammajukku Formation are given in Appen-
mineralization in the Lower Sandstone orebody has been pre- dix 4. Dark-gray and green shales have relatively high K2O
served. The three corresponding fluid inclusion leachates plot (2.1 and 5.6 wt %, respectively) and P2O5 contents (0.2 and
slightly above this model isochron, reflecting limited postmin- 0.3 wt %, respectively). The P2O5 enrichment is probably
eralization disturbance. The disseminated residue 12LAI52 linked to numerous phosphorite pebble horizons present in
(R) from the Upper Sandstone orebody also plots slightly green shale in the Grammajukku Formation (Nielsen and
above this model isochron. Schovsbo, 2011; Saintilan et al., 2015), whereas high K2O con-
For the given number of sphalerite residues from the tents are probably related to feldspar-rich silt inliers (cf. Will-
Lower Sandstone orebody (n = 3) and considering their true dén, 1980). Both shale samples are characterized by rather
and limited analytical errors (Table 4), the goodness of fit in high Rb and Sr contents. The Rb content of dark-gray shale
terms of MSWD indicates that these sphalerite residues are is about three times lower than that of green shale (111 and
age concordant in the sense of the isochron model. This inter- 372 ppm, respectively), whereas Sr contents are similar in
pretation is supported by leachate sample 12LAI03 (L), which both shale units (40 and 50 ppm, respectively). The samples
has the least radiogenic 87Sr/86Sr ratio (0.717892 ± 3) of the of poorly mineralized subhorizons in polymictic phosphorite
entire sample set and, therefore, most probably represents pebble conglomerate have Sr contents of 122 and 77 ppm and
the pristine isotopic fluid composition. Rb contents of 10 and 30 ppm, respectively. The sphalerite-
The sphalerite residue from the Åkerlandet calcite-galena mineralized sample has three times the Rb content of the
basement-hosted vein also plots close to the above-men- galena-mineralized sample, but much lower Sr content.
tioned line of moderate slope and would fall on the three- The strontium isotope data and the Rb and Sr concentra-
point model isochron defined by the sphalerite residues from tions of the rock units that underlie and overlie the miner-
the Lower Sandstone orebody at Laisvall (cf. Fig. 5B, C). A alized sandstone units in the stratigraphy at Laisvall are
combined four-point model isochron (Fig. 5C) would yield an presented in Table 5. Black shale with pyrite and gray shale
age of 468 ± 5 Ma with an essentially identical MSWD and have present-day 87Sr/86Sr ratios of 0.721269 ± 14 and
initial 87Sr/86Sr ratio as those of the three-point isochron for 0.739333 ± 14, respectively, whereas underlying green shale
the Lower Sandstone disseminated mineralization. The Åker- has an 87Sr/86Sr ratio of 0.764182 ± 16. Correction of these
landet fluid inclusion leachate plots close to leachate 12LAI03 87Sr/86Sr ratios for radiogenic growth back to the presumed
(L), and similarly, slightly above this model isochron, reflect- depositional age yields unrealistically low values <0.7020
ing limited postmineralization disturbance. These results are (even for 200–300 Ma).
intriguing when taking into account the different geologic set- The samples of poorly mineralized phosphorite pebble
tings and the distance between the Åkerlandet and Laisvall conglomerates have 87Sr/86Sr ratios of 0.720336 ± 14 and
deposits, as discussed in more detail below. 0.724978 ± 14, respectively. Due to their low Rb/Sr ratios,
All other fluid inclusion leachates and the corresponding these radiogenic values cannot be explained solely by decay
residues (i.e., from the Upper Sandstone orebody at Laisvall, of the original Rb, which would have yielded 87Sr/86Sr values
from the Granberget deposit, and from two veinlet samples around 0.715 when corrected for a presumed sedimentation
in the Lower Sandstone orebody are positively correlated (r = age of ~530 Ma. For this reason, it is proposed that both sam-
0.785) and plot along a steep linear trend with MSWD >10,000 ples have experienced hydrothermal overprints.
(Fig. 5A). The slope of this line corresponds to an unreal- Two granite samples with chlorite-altered amphibole have
istic age (2.65 Ga), far in excess of the age of rocks hosting comparable, moderately radiogenic present-day 87Sr/86Sr

0.770
87
Sr
A 12LAI53 R 86
Sr Data-point error ellipses are 2σ
0.770 B
0.760
11LAI33 R
12LAI53 R
Mixing trend
11LAI33 R 0.750
0.750
Sr/86Sr
0.740 0.730
12LAI12 R Age = 467 ± 5 Ma
87
Initial 87Sr/86Sr = 0.715900 ± 0.000060

12LAI53 L
MSWD = 1.4
0.730 11LAI33 L 0.710
12LAI03 R 87
Rb
12LAI52 R
0 2 4 6 8 86
Sr
sphalerite leachate (L) sphalerite residue (R)
0.720
12LAI03 R
12LAI03 L
0.710
0 2 4 6 8
87
Rb/86Sr 0.800
87
Sr In addition, two data points for Paleoproterozoic granite
86
Sr
0.770
0.790 with 87Sr/86Sr ratios > 0.800 are outside D
the present diagram
Data-point error ellipses are 2σ 0.780
C 12LAI53 R
0.770
11LAI33 R
0.760
Sr/86Sr
0.750
0.750
87
0.740
0.730
0.730 12AKE01 R
0.720
Age = 468 ± 5 Ma
+
+
Initial 87Sr/86Sr = 0.715900 ± 0.000063 0.710
MSWD = 1.4
0.710
12LAI03 R 87
Rb
0.700
0 2 4 6 8 86
Sr 0 5 10 15 20
sphalerite leachate (L), Laisvall sphalerite leachate (L), Åkerlandet
87
Rb/86Sr
sphalerite residue (R), Laisvall + sphalerite residue (R), Åkerlandet
Legend to Figures 5A and 5D

Disseminated sphalerite residue, Granberget, Lower Allochthon, Caledonides Sphalerite leachate, Granberget, Lower Allochthon, Caledonides
Disseminated sphalerite residue, Upper Sandstone orebody, Laisvall Sphalerite leachate, Upper Sandstone orebody, Laisvall
Disseminated sphalerite residue, Lower Sandstone orebody, Laisvall Sphalerite leachate, Lower Sandstone orebody, Laisvall
Sphalerite leachate, galena-sphalerite-calcite vein in Upper Sandstone
Veinlet sphalerite residue, galena-sphalerite-calcite vein in Upper Sandstone
orebody, Laisvall
orebody, Laisvall
Sphalerite leachate, galena-sphalerite-calcite vein in Lower Sandstone
Veinlet sphalerite residue, galena-sphalerite-calcite vein in Lower Sandstone orebody, Laisvall
orebody, Laisvall
Sphalerite leachate, Åkerlandet vein deposit in Paleoproterozoic basement
Sphalerite residue, Åkerlandet vein deposit in Paleoproterozoic basement
Addtional legend to Figure 5D
Gray shale, Alum Shale Formation, Laisvall Sphalerite-mineralized phosphorite pebble conglomerate,
Green shale, Grammajukku Formation, Laisvall Laisberg Formation, Laisvall
Poorly galena-mineralized phosphorite pebble conglomerate, Paleoproterozoic granite, basement at Laisvall
Laisberg Formation, Laisvall
Fig. 5. A. 87Sr/86Sr vs. 87Rb/86Sr diagram for sphalerite disseminated residues and complementary leachates from the
Lower Sandstone and Upper Sandstone orebodies, from remobilization veinlets at the Laisvall deposit, from the sandstone-
hosted Granberget deposit, and from the Åkerlandet vein deposit in Paleoproterozoic basement. B. Rb-Sr isochron diagram
for disseminated sphalerite samples (n = 3) from the Lower Sandstone orebody at Laisvall. 2σ values are provided in Table 4.
C. Rb-Sr isochron diagram for disseminated sphalerite samples from the Lower Sandstone orebody at Laisvall and the sphal-
erite residue from the Åkerlandet vein deposit in Paleoproterozoic basement (n = 4); 2σ values are provided in Table 4. D.
87Sr/86Sr vs. 87Rb/86Sr diagram for sphalerite disseminated residues from the Lower Sandstone and Upper Sandstone orebod-
ies, from remobilization veinlets at the Laisvall deposit, and from the sandstone-hosted Granberget deposit. Data points with
the Rb-Sr isotopic composition of granite (1.8 Ga) in the Paleoproterozoic basement, in the phosphorite pebble conglomerate
of the Laisberg Formation, in the green shale of the Grammajukku Formation, and in the gray shale of the overlying Alum
Shale Formation at Laisvall are also shown. Two data points for Paleoproterozoic granite with 87Rb/86Sr ratios above 20 and
87Sr/86Sr ratios between 1.2 and 1.4 plot outside the present diagram but define a statistically robust regression line with the
other granite samples. See text for further discussion.

0.770 70
12LAI53 R A B
0.760 60
combined loss of Rb
and gain of Sr Rb loss
50
0.750
11LAI33 R
40
Sr/86Sr
1/Rb
0.740
12LAI84 R
12LAI14 R 30
87
Sr gain
0.730
20
12LAI52 R
12LAI12 R
0.720 12LAI12 R
10
12LAI03 R 12LAI52 R
0.710 0
0 10 20 30 40 50 60 0 2 4 6 8
1/86Sr 87
Rb/86Sr
10
C Disseminated sphalerite residue, Granberget, Lower Allochthon
12LAI12 R Disseminated sphalerite residue, Upper Sandstone orebody, Laisvall

Sr (ppm)
1 Disseminated sphalerite residue, Lower Sandstone orebody, Laisvall

Veinlet sphalerite residue, galena-sphalerite-calcite vein in Upper Sandstone
orebody, Laisvall
12LAI52 R Veinlet sphalerite residue, galena-sphalerite-calcite vein in Lower Sandstone
orebody, Laisvall
0.1
0.01 0.1 1 10
Rb (ppm)
Fig. 6. A. 87Sr/86Sr vs. 1/86Sr diagram for residues of disseminated sphalerite samples from the Lower Sandstone and
Upper Sandstone orebodies, from remobilization veinlets at the Laisvall deposit, and from the sandstone-hosted Granberget
deposit; 2σ values are provided in Table 4. B. 1/Rb vs. 87Rb/86Sr diagram for the same residues of sphalerite as shown in Figure
6A. The alignment of the residues of disseminated sphalerite samples from the Lower Sandstone orebody is a consequence
of isochronism identified in Figure 5B; 2σ values are provided in Table 4. C. Sr vs. Rb diagram showing the ppm contents of
these elements in the same residues of sphalerite as included in Fig. 6A. 2σ values are provided in Table 4.
ratios of ~0.774 as well as 87Rb/86Sr ratios and elemental the discrepancies in certain ore districts between Rb-Sr ages
concentrations. By contrast, reddened granite samples with (e.g., Schneider et al., 2002; Heijlen et al., 2003) and paleo-
hematite veinlets have highly radiogenic strontium ratios magnetic ages (e.g., Symons et al., 1995), Bradley and Leach
(87Sr/86Sr of 1.188594 ± 20 and 1.286898 ± 20) whereas rela- (2003) and Bradley et al. (2004) raised doubts around the
tively fresh granite samples have relatively low 87Sr/86Sr ratios Rb-Sr dating of sphalerite and were concerned by the possi-
(0.743031 ± 14 and 0.755376 ± 16). A best-fit line (MSWD ble contamination by carbonate and clay inclusions present in
= 35, apparent initial 87Sr/86Sr = 0.72) defined by the gran- sphalerite. On the other hand, Kesler et al. (2004) questioned
ite data points in 87Sr/86Sr vs. 87Rb/86Sr space (Fig. 5D) yields the validity of paleomagnetic ages, which are often similar to
a slope corresponding to an apparent age of 1330 ± 70 Ma, or younger than Rb-Sr isotope ages, potentially reflecting late
which may indicate an alteration event. Applying calculated fluid events which may have reset paleomagnetic ages.
Rb/Sr ratios for the 1.8 Ga granite samples, all analyzed gran- Recent studies provide examples of concordance between
ite samples of the Paleoproterozoic basement progressively Rb-Sr ages and the ages determined by using other geochro-
arrive at unrealistically low 87Sr/86Sr ratios. nologic isotopic systems. For instance, Re-Os geochronometry
on bitumen coatings on sulfide mineralization at the Polaris
Discussion Zn-Pb deposit yielded an age in agreement with Rb-Sr sphal-
erite and paleomagnetic ages for the mineralization (Selby et
Siting of Rb and Sr in sphalerite and implications for al., 2005, and references therein). Schneider et al. (2007) pre-
Rb-Sr isochron geochronology sented concordant Re-Os and Rb-Sr ages from direct dating
Benchmark studies (e.g., Christensen et al., 1996; Pettke of sulfide phases at the Kipushi deposit, DR Congo. Chesley
and Diamond, 1996) explained in detail why Rb-Sr direct dat- et al. (1994) has also presented Sm-Nd ages on fluorite in the
ing of sphalerite is significant and identified the main analytical Illinois-Kentucky fluorite district in agreement with Rb-Sr
pitfalls to be avoided. However, the connection between some ages on sphalerite from the possibly related Upper Mississippi
MVT mineralization and orogenic phases based on Rb-Sr ages Valley district (Brannon et al., 1992).
on sphalerite, e.g., the East Tennessee MVT district and the The critical issue of the siting of Rb and Sr in sphaler-
Acadian orogeny (Kesler and Carrigan, 2002, and references ite, i.e., in its lattice or hosted by fluid and/or solid inclu-
therein), has been questioned (Leach et al., 2001, 2002). Given sions, was discussed in detail in the 1990s by Nakai et al.

Table 5. Rb and Sr Contents (ppm), and Sr Isotope Composition of Whole-Rock Samples Selected in the Stratigraphy at Laisvall
Sample no. Stratigraphy Alteration Rb Sr 87Rb/86Sr 2σ 87Sr/86Sr 2σ
(ppm) (ppm)
11LAI16-2 Black shale with pyrite in the Alum Shale - - - - 0.721269 1.4E-05
Formation
11LAI45 Gray shale with organic matter in the Alum 111 40 8.05 0.24 0.739333 1.4E-05
Shale Formation
11LAI26 Green shale in the Grammajukku Formation 372 50 21.64 0.65 0.764182 1.6E-05
11LAI03-1 Phosphorite polymictic conglomerate, poorly 10 122 0.24 0.01 0.720336 1.4E-05
galena-mineralized
11LAI03-2 Phosphorite polymictic conglomerate with 30 77 1.13 0.03 0.724978 1.4E-05
interstitial sphalerite
11BAS01 Granite (1.8 Ga) in the crystalline basement Chlorite alteration 149 148 2.93 0.09 0.773616 1.6E-05
11BAS02 Granite (1.8 Ga) in the crystalline basement Reddened, hematite veins 245 31 23.94 0.72 1.188594 2.0E-05
11BAS03 Granite (1.8 Ga) in the crystalline basement Chlorite alteration 153 150 2.97 0.09 0.774925 1.6E-05
11BAS04 Granite (1.8 Ga) in the crystalline basement Reddened, hematite veins 217 22 30.15 0.90 1.286898 2.0E-05
11BAS05 Granite (1.8 Ga) in the crystalline basement Slightly altered (reddened) - - - - 0.743031 1.4E-05
11BAS06 Granite (1.8 Ga) in the crystalline basement Slightly altered (reddened) 134 221 1.76 0.05 0.755376 1.6E-05
Note: - = not available
(1990, 1993), Brannon et al. (1991, 1992), Christensen et sphalerite in the Lower Sandstone was preserved whereas
al. (1996), and Pettke and Diamond (1996). Brannon et that in the Upper Sandstone was disturbed.
al. (1991) showed that Rb/Sr ratios of sphalerite in several A diagram of Sr vs. P contents in “inclusion-free” sphaler-
MVT deposits were similar to those of associated K-feldspar ite data (Fig. 7C) shows that there is no apparent correlation
or clay minerals. Their investigations showed that sparse between Sr and P in the analyzed samples from the Lower
K-feldspar inclusions constituted less than 0.1% of their Sandstone orebody at Laisvall and from the Åkerlandet vein
host sphalerite. On the basis of Rb and Sr geochemical data deposit. About half the data for sphalerite from the Upper
on K-feldspar, they concluded that sphalerite isochronism Sandstone orebody at Laisvall do not show an apparent cor-
is not an artifact of leaching of K-feldspar, and that mixing relation between Sr and P; however, other data for high P
between K-feldspar and other components with lower Rb/ contents (>~50 ppm) show a moderate positive correlation.
Sr ratios could not have produced the sphalerite isochrons The absence of a correlation between Sr and P in sphaler-
obtained in their studies. ite from the Lower Sandstone orebody at Laisvall and from
Ablation profiles for sphalerite analyzed in this study (Fig. the Åkerlandet vein deposit, and in places in sphalerite from
4A, B) show that Rb and Sr concentrations are two orders of the Upper Sandstone orebody suggests that, in these samples,
magnitude higher in the analyzed volume of sphalerite con- Sr contents are not related to micrometer-scale inclusions of
taining micrometer-scale fluid inclusions than in inclusion- fluorapatite or another P-bearing mineral phase but rather
free sphalerite. These in situ analyses confirm the findings originate from the sphalerite lattice itself. Conversely, the
by Pettke and Diamond (1996) that Rb-Sr isotope analyses of moderate positive correlation between Sr and P in sphaler-
sphalerite residues are highly sensitive to minute amounts of ite with P contents above ~50 ppm in the Upper Sandstone
unopened fluid inclusions, given that trapped hydrothermal orebody suggests that some Sr might be contributed by
fluids may have high Sr and high Rb contents. The relative micrometer-scale P-bearing phases (e.g., fluorapatite). Rb-Sr
similarity of Rb and Sr contents in sphalerite residues deter- systematics in sphalerite mineralization with cogenetic fluor-
mined by ID-TIMS (Table 4) and Rb and Sr contents of inclu- apatite is not understood yet. However, the failure to obtain
sion-free sphalerite determined by LA-ICPMS (Appendix 3) an absolute date for mineralization in the Upper Sandstone
favors the hypothesis that the obtained Rb and Sr values in orebody is apparently not related to the presence of this fluor-
sphalerite residues correspond to the contents of these ele- apatite cogenetic with sphalerite, but to the later disturbance
ments in inclusion-free parts where they are held within the of the Rb-Sr system, as discussed below.
crystalline sphalerite structure. Nakai et al. (1993), Pettke and Diamond (1996), and Chris-
Similarly, LA-ICPMS data for inclusion-free sphalerite tensen et al. (1996) argued that it is unlikely that Rb and Sr
in the Lower Sandstone orebody define a straight line with occupy a zinc site in the sphalerite crystal structure, given
a slope of 0.020 ± 0.002 (2σ) on an Rb vs. Sr diagram (Fig. the much higher ionic radii of Rb and Sr relative to Zn. Sb
7A). This positive correlation is interpreted to be intrinsic to concentrations in sphalerite in the Lower Sandstone orebody
sphalerite in which the Rb-Sr was not disturbed by postmin- at Laisvall, determined by LA-ICPMS in the present study
eralization processes. By contrast, the data for inclusion-free (Appendix 3), show a weak positive correlation with Rb con-
sphalerite in the Upper Sandstone orebody show greater scat- tents, whereas the correlation is very weak or absent in the
ter, in particular at low values of Rb or Sr, and only part of Upper Sandstone (data in Saintilan, 2015). Sn contents show
the data points define a straight line with a slope of 0.045 ± no correlation with Rb in either orebody at Laisvall. Similarly,
0.018 (2σ) on an Rb vs. Sr diagram (Fig. 7B). This scatter may Rb does not correlate with Ga in any of the orebodies (Appen-
be an additional indication that the Rb-Sr isotope system in dix 3). These results suggest that the proposed charge-coupled

0.7 1.8
Lower Sandstone Upper Sandstone
1.6
0.6
1.4
0.5
1.2
Rb (ppm)
Rb (ppm)
0.4 1.0
0.3 0.8
0.6
0.2
0.4
0.1
A 0.2
B
0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
Sr (ppm) Sr (ppm)
100
10 Upper Sandstone orebody, Laisvall

Lower Sandstone orebody, Laisvall
Åkerlandet vein deposit
Sr (ppm)
0.1
0.01
C
1 10 100 1000
P (ppm)
Fig. 7. A. Rb vs. Sr diagram for the ppm contents of these elements in sphalerite in the Lower Sandstone orebody at the
Laisvall deposit, determined by LA-ICPMS analyses. B. Rb vs. Sr diagram for the ppm contents of these elements in sphal-
erite in the Upper Sandstone orebody at the Laisvall deposit, determined by LA-ICPMS analyses. C. Sr vs. P diagram for the
ppm contents of these elements in sphalerite in the Lower Sandstone and Upper Sandstone orebodies at the Laisvall deposit,
and in sphalerite at the Åkerlandet vein deposit, determined by LA-ICPMS analyses.
substitution 2 Zn2+ ↔ Rb+ + Me3+ (e.g., Me: Sb, Sn, Ga; Pettke
and Diamond, 1996) is not a likely mechanism for the incor- Legend
poration of Rb in the analyzed sphalerite. Sulfur atom
In conclusion, the LA-ICPMS and ID-TIMS data are con- Zinc atom Rb+
sistent with the hypothesis that Rb and Sr are held in the or
Sr-rich fluorapatite
sphalerite structure. Our data suggest also that fluorapatite Sr2+
1-10 μm Sr-Rb-rich fluid inclusion
inclusions and the coupled substitution cannot explain the
observed Rb and Sr contents in fluid inclusion-free sphalerite.
At the present state of knowledge, the most viable explanation
could be that Rb and Sr are located in octahedral voids in the ab
sp lat Octahedral void
ot ion
sphalerite structure itself (Fig. 8), as proposed by Pettke and si
ze
Diamond (1996).
Christensen et al. (1996) emphasized that fine-grained
colloform sphalerite (e.g., at Pine Point: Nakai et al., 1993; at
Polaris: Christensen et al., 1995b) characterized by elevated
87Rb/86Sr ratios of up to 10 had a higher potential to be suc-
spha
cessfully dated. Pettke and Diamond (1996) and Christensen lerite
et al. (1996) invoked disequilibrium kinetics during crystal

qu
ar
growth, favoring partitioning of low-concentration trace ele-

tz
ov
ments, which have Dcrystal/liquid <<1 (e.g., Rb and Sr), to explain

er
gr
the possible concentration of Rb and Sr during rapid precipi-

o
detrital quartz
w
th
tation of colloform or fine-grained sphalerite. At Laisvall, evi-

dence for rapid crystal growth of sphalerite was documented 50 μm
by Lindblom (1986). Indeed, fine-grained sphalerite dissemi-
nated residues in the orebodies at Laisvall, in particular the Fig. 8. Sketch of typical epigenetic sphalerite mineralization with H2S
three disseminated residues from the Lower Sandstone, have derived from thermochemical sulfate reduction at Laisvall. The sphalerite
cement was precipitated in sandstone, interstitially to partly dissolved etched
elevated 87Rb/86Sr ratios of up to 7 (Table 4). These petro- detrital quartz and diagenetic quartz overgrowths. The types of solid and fluid
graphic and geochemical evidences offer additional explana- inclusions in sphalerite are shown, complemented by a sketch of sphalerite
tions for why an isochron could be obtained for these samples. crystal structure with the proposed siting of Rb and Sr in octahedral voids.

Interpretation of the results from the Åkerlandet vein deposit obtained from the four-point Rb-Sr isochron is justified.
The original Rb-Sr systematics in the sphalerite sample According to hypothesis no. 1, the Laisvall, Åkerlandet, and
from the Åkerlandet vein deposit also seems to have been Granberget deposits could all have formed as a response to
preserved. The data can be interpreted in at least two ways the tectonic event discussed below (in the section devoted to
(Fig. 9A), both being geologically meaningful. The regional- the age determination of the Laisvall deposit). Furthermore,
scale implications of the alternative hypotheses no. 1 and 2 are the Åkerlandet vein system could represent an equivalent to
discussed further below. feeders of metal-rich brines for Laisvall-type mineralization,
Hypothesis no.1: As indicated above, a four-point isochron as has been proposed by previous authors (e.g., Johansson
defined by the disseminated residues from the Lower Sand- and Rickard, 1984).
stone orebody at Laisvall and the residue from the Åker- Hypothesis no. 2: An alternative hypothesis is that the
landet vein deposit yields an age of 468 ± 5 Ma (Fig. 5C), Åkerlandet residue lies along the three-point isochron of dis-
similar to the age of 467 ± 5 Ma from the three-point iso- seminated sphalerite mineralization in the Lower Sandstone
chron defined by the disseminated residues from the Lower because of a fortuitous coincidence. If so, the following pos-
Sandstone orebody. At a first view, it may appear surprising sibility merits some exploration.
that data from the Åkerlandet and Laisvall deposits, sepa- Billström et al. (2012) presented a tentative four-point
rated by a distance of 250 km (Fig. 1A), lie along the same Rb-Sr isochron age of 531 ± 6.5 Ma (Lower Cambrian; initial
87Sr/86Sr = 0.716560 ± 660) for sphalerite residues (MSWD
regression line. However, the Åkerlandet mineralization is
located only 35 km east of the Granberget deposit (Fig. 1A) = 2.4) from the basement-hosted Ersmarksberget, Svärtträsk,
that, in turn, shares many similarities with the disseminated and Gubbträsk vein deposits in the Storuman district, 100 km
mineralization at Laisvall. Given our working hypothesis north of Åkerlandet (Fig. 1A). These authors described cal-
stated above that the Laisvall and Granberget deposits were cite-fluorite-Zn-Pb sulfide mineralization at Ersmarksberget
formed coevally by fluids driven during the same large-scale and Gubbträsk along brittle structures partly discordant to the
tectonic event, it is geologically plausible that the Laisvall regional ductile fabric. Given the similarities in mineralogy,
and Åkerlandet deposits, despite the distance between texture, and tectonic structures in the host basement rocks
them, are also coeval and that the model age of 468 ± 5 Ma at the Ersmarksberget, Gubbträsk, and Åkerlandet deposits
0.810 87
Sr
86
Sr Figure 9B
A 87
Sr
86
Sr
0.790
Age = 544 ± 4 Ma
0.810 Initial 87Sr/86Sr = 0.71477 ± 0.00015
MSWD = 1.9
0.790
0.770 Gubbträsk
0.770
Ersmarksberget
0.750
0.750 0.730 Åkerlandet
0.710
Data-point error crosses are 2σ B 87
Rb
Figure 5C 0 2 4 6 8 10 12 86
Sr
+ Sphalerite residue, all deposits
0.730
Sphalerite leachate, Åkerlandet vein deposit
Sphalerite leachate, Ersmarksberget vein deposit
Sphalerite leachate, Gubbträsk vein deposit
0.710
87
Rb
0 2 4 6 8 10 12 86
Sr
Sphalerite residue, Åkerlandet deposit Sphalerite residue, Gubbträsk deposit
Sphalerite leachate, Åkerlandet deposit Sphalerite leachate, Gubbträsk deposit
Sphalerite residue, Ersmarksberget deposit Sphalerite residue, Lower Sandstone
Sphalerite leachate, Ersmarksberget deposit orebody, Laisvall
Fig. 9. A. 87Sr/86S vs. 87Rb/86Sr diagram for sphalerite residues and complementary leachates from several samples of
calcite-fluorite-Zn ± Pb sulfide vein-type mineralization in Paleoproterozoic basement along the erosional front of the Scan-
dinavian Caledonides: (i) the Ersmarksberget and Gubbträsk deposits in the Storuman district (data after Billström et al.,
2012), (ii) the Åkerlandet deposit (this study). The sphalerite residues from the Lower Sandstone orebody at Laisvall are
shown for reference. The dashed lines represent the model isochron (n = 4) combining disseminated residues from the
Lower Sandstone orebody at Laisvall and the data from Åkerlandet (black dashed line; Fig. 5C), and the model isochron (n
= 4) for only the basement-hosted vein deposits (gray dashed line; Fig. 9B). See text for further explanation. B. Recalculated
isochron model age diagram (n = 4) for residues and corresponding leachates of sphalerite samples from the basement-hosted
Ersmarksberget and Gubbträsk vein deposits and the basement-hosted Åkerlandet vein deposit.

(Billström et al., 2012; Saintilan et al., 2012), it seems rea- the precipitation of the outer rims around some K-feldspar
sonable to try to combine our Åkerlandet data with those grains. As discussed in the section on geologic setting above,
published for the Ersmarksberget and Gubbträsk deposits by the period defined by the in situ 40Ar-39Ar ages of 453 ± 8 to
Billström et al. (2012). 403 ± 6 Ma is characterized by continuous tectonic conver-
The regression of the sphalerite residue aliquots from the gence related to the terminal continent-continent (Laurentia-
Ersmarksberget and Gubbträsk deposits with our aliquot from Baltica) collision, as well as subsequent orogenic collapse and
Åkerlandet yields a recalculated four-point isochron model age the formation of intra-orogenic basins. This fluid migration
of 544 ± 4 Ma (late Ediacaran; Fig. 9B; MSWD = 1.9, initial may have also caused the postmineralization disturbance of
87Sr/86Sr = 0.714770 ± 150). One fluid inclusion leachate cor- the Rb-Sr systems by Sr-rich fluids, the nature of which is
responding to the Ersmarksberget vein deposit has an 87Sr/86Sr described below.
ratio close to the obtained initial 87Sr/86Sr ratio of our recalcu- All disseminated and veinlet residues from the Upper
lation, whereas the other leachate from Ersmarksberget and Sandstone orebody (excluding the relatively undisturbed dis-
those from the Gubbträsk and Åkerlandet vein deposits plot seminated residue 12LAI52 R) and the veinlet samples from
slightly above this model isochron, reflecting limited second- the Lower Sandstone orebody (12LAI14 R and 12LAI84 R)
ary disturbance (Fig. 9B). According to hypothesis no. 2, an define an array in the 87Sr/86Sr vs. 1/86Sr diagram (Fig. 6A)
age of 544 ± 4 Ma could be proposed, which is close to the in which the Upper Sandstone orebody sphalerite residues
Rb-Sr isochron age of 531 ± 6.5 Ma of Billström et al. (2012). are biased toward high contents of common Sr. The same
samples in the 1/Rb vs. 87Rb/86Sr diagram (Fig. 6B) system-
Nature and origin of the disturbance of the Rb-Sr systematics atically show very low 87Rb/86Sr ratios. An Sr vs. Rb diagram
in sphalerite in the Upper Sandstone at Laisvall and at the (Fig. 6C) shows that the disseminated residues in the Upper
Granberget deposit Sandstone have rather similar Rb contents, but the disturbed
As discussed above, all analyzed samples except three dis- residue 12LAI12 contains four times more Sr than the rela-
seminated samples from the Lower Sandstone orebody, one tively undisturbed residue 12LAI52 and falls in the field of
disseminated sample from the Upper Sandstone orebody at the veinlet samples in the Upper Sandstone orebody (Tables
Laisvall, and the Åkerlandet vein sample are disturbed in the 1 and 4). In addition, the disturbed residue 12LAI12 has a
Rb-Sr isotope systematics and plot on a strikingly different iso- low 1/86Sr ratio, a slightly lower 87Sr/86Sr, but a markedly lower
topic trend in the 87Sr/86Sr vs. 87Rb/86Sr space (Fig. 5A). This 87Rb/86Sr ratio than residue 12LAI52. The Rb and Sr budget
trend indicates various degrees of disturbance of the original of the disturbed residue 12LAI12 being similar to that of the
Rb-Sr system, both in residues and leachates of these samples veinlets, it can be suggested that this isotopic composition was
(Fig. 5A), that prevented isochron model age determination acquired through an input of Sr during remobilization that
for the Upper Sandstone disseminated samples, the Upper produced the steeply dipping galena-sphalerite-calcite vein-
Sandstone and Lower Sandstone veinlet samples, and for the lets in the Upper Sandstone. The Granberget disseminated
Granberget disseminated samples. Taking into account that residues appear to have been affected by a similar input of Sr
disseminated mineralization in the Upper Sandstone orebody (Figs. 5A, 6B, C).
appears to have been remobilized in steeply dipping galena- These results and steep linear disturbance trend discussed
sphalerite-calcite veinlets (cf. Rickard et al., 1979; Saintilan et above are compatible with a gain of Sr during postmineraliza-
al., 2015) and that the Upper Sandstone is close to the basal tion event(s). Figure 5D shows the isotopic composition of
Caledonian décollement, it is not surprising that the Rb-Sr possible Sr sources in the stratigraphy at Laisvall that could be
system in disseminated samples in the Upper Sandstone has responsible for the disturbance of the Rb-Sr system with the
been disturbed during postmineralization events. Failure to mixing of (1) very radiogenic Sr (87Sr/86Sr >0.750), probably
determine the age of the disseminated Granberget mineral- mobilized from the Paleoproterozoic crystalline basement;
ization is also not surprising, bearing in mind that the miner- and (2) less radiogenic Sr, released from a sedimentary source
alization is tectonically disrupted by subvertical faults, cut by with a Sr composition close to that of galena-poor phosphorite
steeply dipping galena-sphalerite-calcite veinlets, and that all pebble conglomerate deposited on top of the Upper Sand-
of these structures are cut, in turn, by low-angle thrusts (Åre- stone paleoaquifer (87Sr/86Sr ~ 0.725: Table 5). The Sr isotope
bäck, 2003; Saintilan, 2010). composition of the two samples of shale overlying the Laisvall
Linear trends, defined by sphalerite fluid inclusion leach- sandstone paleoaquifers (Table 5, Fig. 5D) is not compatible
ates plotting steeper than or deviating from isochrons of with these shales having been an Sr reservoir involved in this
corresponding sphalerite residues, were observed by, for steep mixing trend.
example, Christensen et al. (1995b), Schneider et al. (1999,
2007), and Nelson et al. (2002), and have generally been Early Caledonian foreland basin evolution and the age of
interpreted to reflect mixtures of “primary and secondary” strata-bound and disseminated mineralization in the
fluids (e.g., ore-bearing fluids and later fluids). Sherlock et al. Lower Sandstone at Laisvall
(2005) documented certain detrital K-feldspar grains in sand- A 467 ± 5 Ma (Middle Ordovician) age for mineralization
stone paleoaquifers at Laisvall that show outer rims with in at Laisvall is geologically plausible (Fig. 10A). Logically, the
situ 40Ar-39Ar ages of 453 ± 8 to 403 ± 6 Ma (Upper Ordovi- same applies for the combined four-point model isochron
cian to Early Devonian). These ages are younger than our 467 with an age of 468 ± 5 Ma, using hypothesis no. 1 above.
± 5 Ma Rb-Sr sphalerite age for disseminated mineralization In details, a tectonic response to the development of the
in the Lower Sandstone at Laisvall. Sherlock et al. (2005) sug- early Caledonian foreland basin could have involved the reac-
gested that tectonically induced fluid flow was responsible for tivation of faults in the Paleoproterozoic crystalline basement

Nanisivik Zn-Pb MVT deposit,

461 ± 3 Ma (Sherlock et al., 2004)
A. Middle Ordovician ~467 Ma B. Ediacaran ~580 Ma
(foreland response to
early Caledonian orogenic activity) Sediment transport Timanian
orogen
Iap
etu
sO
Laurentia ce
an
Eq
ua
Volcanic island arc tor
Baltica
Laurentia
30ºS
an
ce
B
O
s
in
tu
bas South pole

pe
nd
Ia
ela B’
For
Baltica
C. Late Ediacaran ~550 Ma

Erosion
B B’ (foreland response to late Timanian orogenic
Foredeep Forebulge Foreland
sea level
Laisvall
activity)
sandstone-hosted Laurentia A Tim
Pb-Zn deposit
s
or ania
in
as
(467 ± 5 Ma) og
en n
tb
ean
rif
0 ~250 km ~500 m
Oc
s
us
tu
et
pe
H2S-rich fluid in sandstone (Rickard et al., 1979; Lindblom, 1986; Saintilan et al., 2015, in press) Iap Pl
Ia
A’ atf
e-
Hydrocarbon-aqueous fluid system (Rickard et al., 1979; Lindblom, 1986; Saintilan et al., in press) or
Pr
Tim m
Metal-bearing fluid (Rickard et al., 1979; Bjørlykke et al., 1991; Saintilan et al., in press), coming up an in th al s
0 200 km ian e he
along reactivated basement structures (Romer, 1992; Kendrick et al., 2005; Saintilan et al., 2015) for lf
ela
Mixed accreted continental margin (Neoproterozoic) and Baltica n d
oceanic material (Cambrian to Lower Ordovician)
Caledonian foreland basin sedimentation
A Erosion A’
Turbidite and shale (Lower to Middle Ordovician)
Stable platformal continental margin sedimentation
Timanian Foreland basin Foreland
Limestone and shale (Lower to Middle Ordovician)
orogen
Black and gray laminated, organic-rich mudstone and shale Calcite-fluorite-
(Middle Cambrian to Lower Ordovician) Zn±Pb sulfide
vein deposits
Sandstone, shale and glacial sediment (Ediacaran to Lower Cambrian) 0 100
km
(544 ± 4 Ma)
Rifted continental margin sedimentation
Arkose, feldspathic sandstone and conglomerate (Tonian to Cryogenian)
Fig. 10. Cartoons showing the series of tectonic events between Ediacaran and Middle Ordovician time, with focus on
Baltica. The paleogeography of Laurentia is shown for reference. A. Middle Ordovician (~467 Ma). The proposed ~467 Ma
age for mineralization at Laisvall is coeval with the deepening of the foreland basin during the Middle Ordovician. See text for
further discussion. It is interesting that the Nanisivik Zn-Pb Mississippi Valley-type deposit is suggested to have formed at 461
± 3 Ma in Mesoproterozoic sedimentary rock in the basement of Laurentia beneath Cambrian to Ordovician transgressive
sedimentary rock sequences (Sherlock et al., 2004). The general structural framework and the paleogeography of Laurentia
and the Iapetus Ocean are drawn after Mac Niocaill et al. (1997), whereas the structural framework and paleogeography of
Baltica are drawn after Stephens (1988) and Mac Niocaill et al. (1997). B. Ediacaran (~580 Ma). Continental drift between
Baltica and Laurentia and opening of the Iapetus Ocean, development of a platformal shelf over much of Baltica, and forma-
tion of a foreland basin to the Timanian orogen (~620 to 550 Ma; after Svenningsen, 2001; Remizov and Pease, 2004; Kirkland
et al., 2011; Andresen et al., 2014). Paleogeography is drawn after Pease et al. (2008). C. Late Ediacaran (~550 Ma). Waning
stage of the Timanian orogeny with proposed basement-hosted calcite-fluorite-Zn±Pb vein-type mineralization at 544 ± 4
Ma. Paleogeography is drawn after Pease et al. (2008).
(Gee, 1972; Saintilan et al., 2015) in the vicinity of the foreb- et al., 1999). This initial high Sr isotope composition can be
ulge (Fig. 10A), i.e., the so-called “hinge-zone” of Gee (1972). explained as having resulted from the mixing of brines with
Basinal brines in the foredeep to the northwest could have hydrocarbon and H2S-rich fluids in sandstone (Rickard et al.,
been conveyed cratonward to the southeast and resurged 1975, 1979; Lindblom, 1986; Saintilan et al., in press). The
as metal-bearing fluids along reactivated basement faults at brines would have acquired metals during cratonward migra-
Laisvall (Rickard et al., 1979, Romer, 1992; Saintilan et al., tion and interaction with permeable Baltica basement rocks
2015). The initial Sr isotope signature (Fig. 5B) indicated by (Wickman et al., 1963; Rickard et al., 1981; Romer, 1992;
the three-point isochron (87Sr/86Sr = 0.715900 ± 60) is much Kendrick et al., 2005; Saintilan et al., 2015). A link between
higher than the Sr isotope composition of Cambrian-Ordovi- MVT mineralization and reactivation of large-scale basement
cian seawater that ranged between 0.707 and 0.709 (Veizer structures during the development of a foreland basin in

connection with collisional tectonics has also been proposed Reevaluation of the relationship between the
in the case of the Ellesmerian orogen and the Polaris MVT Laisvall deposit and calcite-galena vein mineralization in
deposit and for the Ouachita orogen and the southeastern the Baltica basement
Missouri MVT district (Bradley and Leach, 2003, and refer- Hypothesis no. 1: A possible genetic link between the
ences therein). Laisvall deposit and basement-hosted calcite-galena veins.
Remnants of the early Caledonian foreland basin are now The 468 ± 5 Ma age derived from the four-point isochron
preserved in the lower allochthonous Caledonian nappes in defined by the disseminated residues from the Lower Sand-
Sweden and Norway and this >260-km-wide foreland basin stone orebody at Laisvall and the residue from the Åkerlandet
can be traced with a NNE–SSW trend for at least 500 km vein deposit suggests that these deposits are coeval, supporting
along the Caledonian orogen (Gee, 1972; Stephens, 1988; the hypothesis of Johansson and Rickard (1984) that certain
Karis, 1998; Greiling and Garfunkel, 2007; Gee et al., 2013). vein deposits may represent feeder traces of metal-bearing
The basin had a well-defined eastern external margin that fluids in the crystalline basement for Laisvall-type mineraliza-
moved progressively toward the foreland during Lower to tion. If this hypothesis is correct, it also implies that there are
Middle Ordovician time (Garfunkel and Greiling, 2002; several phases of basement-hosted vein-type mineralization
Greiling and Garfunkel, 2007). Greiling and Garfunkel (2007) in the Baltica basement, given the significantly older age of
proposed a location for this external margin ~20 km west from ca. 531 Ma for the calcite-galena vein deposits in Paleopro-
the present-day location of the Laisvall deposit during the terozoic basement in the Storuman district (Billström et al.,
Lower Ordovician. This margin ceased to migrate toward the 2012). Moorbath and Vokes (1963), Wickman et al. (1963),
foreland and the basin deepened instead during the Middle and Johansson and Rickard (1984) documented that all these
Ordovician (Greiling and Garfunkel, 2007); the proposed age basement-hosted calcite-galena vein deposits are character-
for Laisvall mineralization at 467 ± 5 Ma suggests a possible ized by radiogenic lead in galena. A hypothesis of diachron-
link with this basin deepening. ous and polyphase hydrothermal vein-type activity would be
Estimates for the depth and sediment thickness within the in accordance with the mobilization of radiogenic lead at the
basin are difficult to assess (Greiling and Garfunkel, 2007). scale of the Fennoscandian Shield, coinciding with multiple
Turbidite sedimentation in Lower to Middle Ordovician time tectonic reactivation of old fault zones in the foreland of sev-
documents basin subsidence that, in turn, implies increased eral orogens (including the ~0.5–0.4 Ga Caledonian orogen,
orogenic load (Greiling and Garfunkel, 2007). The over- the ~1.1–0.9 Ga Sveconorwegian orogen, and the ~2.0–1.8 Ga
all tectonic evolution resulted in shallow-marine carbonate Svecokarelian orogen) or rifts (e.g., the Oslo rift at ~280 Ma).
sedimentation along the forebulge during the Middle Ordovi- Polyphase hydrothermal vein-type activity has been docu-
cian, with these strata being progressively overstepped subse- mented, for instance, in the Black Forest in southwestern Ger-
quently by a turbidite and shale sequence to the northwest. many, where five generations of hydrothermal veins in Variscan
Increased turbidite and shale sedimentation continued and basement with ages between Permian and Miocene have been
prevailed laterally northwestward in the deepening basin. distinguished (Staude et al., 2009 and references therein).
The sediment fill amounted to ~500 m, and several hundred Hypothesis no. 2: A possible late Timanian origin for some
meters of water depth were reached between shallow carbon- basement-hosted calcite-galena vein deposits.
ate intervals (Fig. 10A; Karis, 1998; Greiling and Garfunkel, The recalculated four-point isochron for calcite-galena
2007). This tectonic setting and the upward-deepening sedi- vein-type mineralization in the Paleoproterozoic basement,
mentary succession are similar to the conditions described obtained by combining our Åkerlandet data with those for the
by Bradley and Leach (2003, their fig. 3) in their sequential Ersmarksberget and Gubbträsk deposits in the Storuman dis-
model for an arc-passive margin collision and the foredeep- trict (Billström et al., 2012), yields a late Ediacaran age of 544
forebulge-foreland situation of the Ouachita orogen in North ± 4 Ma. This age is close to the original Lower Cambrian age
America. This “arc-passive margin collision provides all of the of 531 ± 6.5 Ma obtained by Billström et al. (2012). Migration
key ingredients for MVT mineralization in a single chain of of hydrothermal fluids in the basement in the 525 to 548 Ma
events” (Bradley and Leach, 2003, p. 664). range could be related to a far-field tectonic response to the
According to the model in the present study, the passive Timanian orogeny (Fig. 10B, C; cf. Roberts and Siedlecka,
margin of Baltica with organic-rich shale in the regionally 2002; Roberts and Olovyanishnikov, 2004; Pease et al., 2008).
extensive Alum Shale Formation and underlying Ediacaran According to this hypothesis, hydrothermal vein mineraliza-
to Cambrian siliclastic rocks was already buried in the fore- tion could have taken place in the Timanian foreland (cf.
land basin during the Lower Ordovician and overlain by the Remizov and Pease, 2004; Pease et al., 2008; Andresen et al.,
additional load of the orogenic wedge (Karis, 1998; Greiling 2014) as a consequence of tectonic activity along the north-
and Garfunkel, 2007). For this reason, it is proposed that the eastern margin of Baltica.
burial in the foredeep provided conditions for hydrocarbon
generation from organic-rich shale. Subsequently, hydrocar-
bon migration (Rickard et al., 1975; 1979; Lindblom, 1986; Conclusions
Saintilan et al., in press) could have taken place from the basin This study provides the first absolute age determination of
in the northwest, southeastward toward the forebulge. Hydro- the Pb-Zn Laisvall deposit hosted by autochthonous Edia-
carbon accumulation in sandstone paleoaquifers contributed caran to Lower Cambrian sandstone. Ten crushed and leached
to the generation of reduced sulfur via thermochemical sul- sphalerite separates were obtained from mineralized sand-
fate reduction (Rickard et al., 1975; Rickard, 1983; Saintilan stone samples in proximal and distal positions relative to the
et al., in press). proposed main feeder fault systems at the Laisvall deposit.

All separates correspond to sphalerite that precipitated using compatible with two hypotheses, both of which are geologi-
reduced sulfur derived from thermochemical sulfate reduction, cally meaningful. A four-point isochron combining data from
the main reduced sulfur source at Laisvall. A Rb-Sr isochron the Lower Sandstone orebody at Laisvall and the residue from
model age of 467 ± 5 Ma was obtained from three sphalerite the Åkerlandet vein deposit would yield an age of 468 ± 5 Ma,
residues sampled from the Lower Sandstone sphalerite dis- similar to the proposed 467 ± 5 Ma age for mineralization
seminated mineralization. Yet, the obtained age is consistent in the Lower Sandstone orebody at Laisvall. This hypothesis
with geologic evidence reported by previous authors pointing would give credit to the suggestion by Johansson and Rickard
to a Middle Ordovician timing of ore formation. (1984) that, for Laisvall-type mineralization, this vein deposit
LA-ICPMS analyses on the same sphalerite samples sup- may represent traces of metal-bearing fluids guided by feeders
port the hypothesis that the measured ID-TIMS Rb and Sr in the crystalline basement. Bearing in mind the age of sphal-
contents in these sphalerite residues are held in the sphalerite erite mineralization of 531 ± 6.5 Ma obtained by Billström et
structure itself and are not related to micro-inclusions. The al. (2012) for the Storuman vein district, this difference in age
most viable explanation, in agreement with Pettke and Dia- of sphalerite precipitation would imply that basement-hosted
mond (1996) and Christensen et al. (1996), is that Rb and Sr vein-type mineralization in the Baltica basement is polyphase.
ions from hydrothermal fluids may be incorporated into the Alternatively, regression of sphalerite data for the Åkerlandet
structure of sphalerite, possibly in octahedral voids, during vein deposit with the geologically and mineralogically simi-
rapid crystal growth. lar basement-hosted Ersmarksberget and Gubbträsk vein
Dating of samples from the Laisvall Upper Sandstone ore- deposits in the Storuman district would yield a recalculated
body probably failed due to postmineralization disturbance of Rb-Sr isochron model age of 544 ± 4 Ma, which is close to the
the Rb-Sr isotope systematics. The Upper Sandstone miner- Rb-Sr isochron age of 531 ± 6.5 Ma of Billström et al. (2012).
alization is located close to the basal Caledonian décollement According to this second hypothesis, mineralization could be
(ca. 430–397 Ma, i.e., Middle Silurian to Lower Devonian a far-field tectonic response to the Timanian orogeny along
time) and was therefore more probably disrupted tectonically the northeastern margin of Baltica.
than the Lower Sandstone mineralization. Postmineraliza-
tion disturbance may also explain the failure to date steeply Acknowledgments
dipping galena-sphalerite-calcite veinlets in the Upper and This research has been financially supported by Boliden AB
Lower Sandstone orebodies, which are interpreted to be in (Sweden) and the Swiss National Science Foundation (SNF,
part remobilization of disseminated mineralization. Most data Switzerland, FN 146 353). The Geological Survey of Sweden
obtained from sphalerite residues and corresponding inclu- (SGU) also provided financial and logistical support for much
sion fluid leachates from these samples define a trend in the of the fieldwork in Sweden, and the staff at SGU in Malå is
87Sr/86Sr vs. 87Rb/86Sr diagram too steep to account for a real- thanked for their help at the national core archive. The authors
istic isochron age determination. The pattern in a 1/Rb vs. are grateful to Boliden AB including Hans Årebäck (former
87Rb/86Sr diagram and LA-ICPMS analyses of Rb and Sr con- exploration manager) and Rodney L. Allen (Manager Geology
tents in sphalerite suggest that the disturbance of the Rb-Sr Research and Development) for financial and logistical sup-
isotope systematics involved an admixture of Sr-rich fluids. port for the work carried out in Boliden and also stimulating
Similarly, the attempt to date disseminated sandstone- discussions. We acknowledge the help of the staff working at
hosted mineralization at the Granberget deposit in the lower the core archive in Boliden in the supply of drill cores. Cyril
allochthonous units in the Caledonian orogen was not success- Chelle-Michou (University of Geneva) is acknowledged for
ful. At Granberget, mineralization is tectonically disrupted by constructive discussions concerning hydrothermal fluid circu-
subvertical faults cut by steeply dipping galena-sphalerite- lation and orogenic systems in general. A. Bjørlykke and D.T.
calcite veinlets. All of these structures are cut in turn by low- Rickard are thanked for their reviews and helpful comments
angle thrusts. This tectonic setting can explain the observed toward clarifying many aspects of the manuscript. We would
disturbance of the Rb-Sr isotope systematics of the three ana- also like to acknowledge the thorough and pertinent reviews
lyzed sphalerite samples. of associate editor Alex Brown and the editorial work of Edi-
A mineralization age for Laisvall at 467 ± 5 Ma corresponds tor Larry Meinert.
to a far-field foreland response to an early Caledonian arc-
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A Middle Ordovician Age For The Laisvall Sandstone-Hosted PB-ZN Deposit, Sweden: A Response To Early Caledonian Orogenic Activity

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©2015 Society of Economic Geologists, Inc.

Economic Geology, v. 110, pp. 1779–1801

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Sweden Lower Cambrian

autochthonous cover rock

Middle and Upper Allochthons

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A Middle Alum Shale Formation Stratigraphy at Laisvall B

* phosphorite conglomerate so-called “Assjatj Member” (0.5 m)

Pebble shale (~12 m)

Caledonian thrust nappes (allochthon)

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by Society of Economic Geologists, Cesar Ricardo Vargas

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Counts per second

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87Rb/86Sr 2σ 87Sr/86Sr 2σ Rb [ppm] 2σ Sr [ppm] 2σ

Crushed-leached sphalerite residues (R)

Fluid inclusion leachates (L)*

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Initial 87Sr/86Sr = 0.715900 ± 0.000060

Legend to Figures 5A and 5D

other granite samples. See text for further discussion.

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C Disseminated sphalerite residue, Granberget, Lower Allochthon

12LAI12 R Disseminated sphalerite residue, Upper Sandstone orebody, Laisvall

1 Disseminated sphalerite residue, Lower Sandstone orebody, Laisvall

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Sample no. Stratigraphy Alteration Rb Sr 87Rb/86Sr 2σ 87Sr/86Sr 2σ

Note: - = not available

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10 Upper Sandstone orebody, Laisvall

et al. (1996) invoked disequilibrium kinetics during crystal

growth, favoring partitioning of low-concentration trace ele-

ments, which have Dcrystal/liquid <<1 (e.g., Rb and Sr), to explain

the possible concentration of Rb and Sr during rapid precipi-

tation of colloform or fine-grained sphalerite. At Laisvall, evi-

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0.750 0.730 Åkerlandet

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Nanisivik Zn-Pb MVT deposit,

bas South pole

C. Late Ediacaran ~550 Ma

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