Economic Geology

Vol. 98, 2003, pp. 1397–1411

Origin of Ore-Forming Brines in Sediment-Hosted Zn-Pb Deposits of

the Basque-Cantabrian Basin, Northern Spain
FIDEL GRANDIA,† ÀNGELS CANALS,
Departament de Cristal lografia, Mineralogia i Dipòsits Minerals, Universitat de Barcelona, Martí i Franquès s/n, 08028 Barcelona, Spain

ESTEVE CARDELLACH,
Departament de Geologia, Universitat Autònoma de Barcelona, Edifici C, UAB, 08193 Bellaterra, Spain

DAVID A. BANKS,
School of Earth Sciences, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, United Kingdom

AND JOAQUIM PERONA

Departament de Geologia, Universitat Autònoma de Barcelona, Edifici C, UAB, 08193 Bellaterra, Spain

Abstract
Fluid inclusion data (microthermometry and Na-K-Li-Cl-Br chemistry) from Mississippi Valley-type Zn-Pb
deposits in the Basque-Cantabrian basin, north Iberian Peninsula, indicate that fluid mixing occurred during
mineralization. Cl/Br ratios of the ore-forming brines suggest that the high salinity was primarily acquired by
evaporation of seawater. Only in deposits near salt domes (Orduña and Murgía diapirs) do the ore-forming
brines have halogen signatures indicative of halite dissolution.
Mixing of fluids frequently cannot be detected using only microthermometry or halogen data, although mi-
crothermometric data can indicate mixing where one of the end members is fresh water or a highly diluted
fluid. Combining the two allows both the recognition of mixing and an estimation of the relative proportion of
the different fluids involved. The effects of mixing on the salinity and halogen ratios of the resulting mixture
have been calculated using four types of fluids: (1) seawater, (2) evaporated seawater before the onset of halite
precipitation, (3) seawater evaporated past the point of halite precipitation, and (4) a halite-saturated brine at
25ºC derived from halite dissolution. The calculated Cl/Br-Na/Br mixing curves have been compared to data
from the Zn-Pb deposits of the Basque-Cantabrian basin and show that mixing between a residual brine and a
halite-dissolution brine can account for the deposits in the Western Biscay district (Txomin, Matienzo, Baram-
bio). Most of the ore-forming brines from the studied deposits around the Orduña and Murgía salt domes (Al-
tube, Monteleón, Jugo) originated by halite dissolution, although there is also significant contribution (20–50
wt %) from a highly evaporated brine.

Introduction vicinity of salt diapirs is there evidence of salinity acquired by

HALOGEN (Cl, Br, and to a lesser extent I) concentrations and dissolution of evaporites (Posey and Kyle, 1988). However,
ratios have been used as tracers of fluid movement and indi- Chi and Savard (1997) suggested that the brines derived from
cators of the origin of salinity in fluids in sedimentary basins seawater evaporation and halite dissolution are not mutually
(Carpenter, 1978; Land and Prezbindowski, 1981; Stoessell exclusive and that mixing can occur in sedimentary basins.
and Moore, 1983; Walter et al., 1990; Banks and Yardley, According to these authors, data plotted on the seawater
1992; Kesler et al., 1995, 1996). Their usefulness lies in the evaporation trajectory in a Cl/Br versus Na/Br diagram can be
fact that they behave conservatively in solution, as they do not explained by mixing of evaporated seawater with a halite-dis-
readily exchange with rocks during water-rock interactions. solution fluid, and brines having Cl/Br and Na/Br ratios
Brines formed by dissolution of evaporites and by seawater higher than seawater could have a contribution from evapo-
evaporation have very different Na-Cl-Br systematics (Fig. 1). rated seawater. They concluded that Cl/Br versus Na/Br dia-
During seawater evaporation, Br is concentrated in the resid- grams could not be used to distinguish between evaporated
ual brine, as it cannot be accommodated in the halite crystal seawater and halite-dissolution fluid.
lattice. Conversely, when halite is dissolved, the resulting The aim of this paper is to provide new insights concerning
brine will have low Br concentration and the Cl/Br and Na/Br the role of mixing in the interpretation of data in Na/Br ver-
ratios of the resulting fluids will be distinctly higher. sus Cl/Br diagrams. Microthermometric and halogen data ob-
Halogen data from fluids related to Mississippi Valley-type tained in sphalerite, dolomite, quartz, barite, and calcite from
deposits worldwide are interpreted by using Cl/Br versus Mississippi Valley-type deposits in the Basque-Cantabrian
Na/Br diagrams, and most indicate that basinal brines ac- basin, northern Iberian Peninsula, are presented and com-
quired their salinity by seawater evaporation (Kesler et al., pared with several theoretical mixing scenarios. The results
1996; Viets et al., 1996; among others). Only in areas in the extend the utility of the Na/Br versus Cl/Br diagrams for the
interpretation of fluid inclusion data, brine sources, and fluid
† Corresponding author: e-mail, [email protected] movement in sedimentary basins.

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by Society of Economic Geologists, Cesar Ricardo Vargas
 1398 GRANDIA ET AL.

26000
Basque-Cantabrian
22000 Basin

18000 Halite
1200 PYREN
EAN RIF
14000 T SYSTE
M

1000 10000

IB
ER
N

IA
A
6000

N
OCE
Barcelona

RI
FT
6000 10000 14000 18000 22000 26000
molar

800

SY
NTIC
Maestrat Basin

ST
Halite Seawater Madrid

EM
(Cl/Br)

ATLA
600 precipitation
IBERIAN MASSIF

Seawater evaporation
400 N
ST
EM
TERTIARY BASINS
trajectory SY
IFT
R MESOZOIC RIFT SYSTEMS
TIC
BE
200 HERCYNIAN BASEMENT
Mg-K salts precipitation
0
FIG. 2. Schematic geological map of the Iberian Peninsula, showing the
0 200 400 600 800 1000 1200 location of the rifting systems during the Mesozoic. The boundary between
the Iberian and European plates is shown by a dashed line along the Pyre-
(Na/Br) molar nean rift system.
FIG. 1. Cl/Br versus Na/Br ratios of halite, seawater, and residual fluids
precipitated from the progressive evaporation of seawater. Data for the evap-
oration seawater trajectory are taken from Fontes and Matray (1993). Data this period, the basin was divided into several sub-basins. In
for halite are from McCaffrey et al. (1987).
the central and eastern regions of the Basque-Cantabrian
basin, the Urgonian facies are essentially made up of terrige-
nous sediments (e.g., Bilbao Formation), whereas reefal car-
Zn-Pb Deposits in the Basque-Cantabrian Basin bonates are predominant in the west (e.g., Reocín and Ra-
(North Iberian Peninsula) males formations: García-Mondéjar et al., 1996). Sediments
directly overlying the Urgonian facies are commonly silici-
Geologic setting
clastic (Utrillas and Valmaseda formations) and were de-
Mesozoic basins in the north Iberian Peninsula contain Zn- posited in continental, delta, and talus environments. Upper
Pb Mississippi Valley-type mineralization primarily in the Cretaceous-Paleocene rocks range from continental clastics
Basque-Cantabrian basin (Herrero, 1989; Velasco et al., to platform limestones to flysch-type marls.
1994), and in the Maestrat basin (Michel, 1974; Grandia et
al., 2003). These basins are associated with rift systems that Mineralization
developed during the Mesozoic between the Iberian and Eu- Zn-Pb mineralization in the Basque-Cantabrian basin is
ropean plates (Fig. 2; see reviews in Vergés and García-Senz, found in five districts (Fig. 3A; Velasco et al., 1994): (1) the
2001; Salas et al., 2001). After the extensional stages, collision Santander district, which includes the largest epigenetic Zn-
of the two plates occurred during the Alpine orogeny in the Pb deposit in the Iberian Peninsula (Reocín mine, ~60 Mt at
Tertiary. 8% Zn: Abajo and Piret, 1989); (2) the Western Biscay dis-
The Mesozoic stratigraphic record in the Basque-Cantabrian trict; (3) the Bilbao district, where the mineralization consists
basin includes sedimentary rocks from the Triassic up to the mainly of iron carbonates; (4) the Guipúzcoa district, with
Upper Cretaceous. The Triassic series, deposited during the some important syngenetic deposits (e.g., Troya mine); and
first rifting stages, shows the characteristic germanic-type (5) the Northern Biscay district. Although no absolute dating
succession, with red clastic sediments (Buntsandstein and of mineralization in these districts is available, it is believed
Middle Muschelkalk facies), platform carbonates (Lower and that most deposits could have been formed in a relatively
Upper Muschelkalk facies), and evaporite-rich shale units short period of time, between the Late Cretaceous and the
(Keuper facies). Jurassic rocks typically consist of platform Tertiary.
limestones and marly facies. The intense fault activity during This study is mainly concerned with mineralization in the
a second rifting event that began in the Late Jurassic led to Santander and Western Biscay districts, where the main Zn-
the deposition of a very thick succession of sedimentary rocks, Pb epigenetic deposits occur. In the Santander district (Fig.
mainly during the Early Cretaceous. The initial sedimenta- 3B), mineralization is enclosed within dolomitized platform
tion, from Kimmeridgian to Barremian, was clastic (Purbeck limestones of Aptian age (Reocín Formation). Morphologi-
and Weald facies: Rat, 1983). The Aptian to Albian period is cally, sulfides are characteristically stratiform or irregular re-
characterized by the deposition of the Urgonian facies (Rat, placements and vug fillings (Barbanson, 1987; Velasco et al.,
1959), which typically consists of shallow-platform limestones 1994). Sphalerite is usually the major sulfide, commonly pre-
with abundant rudist-rich reefs. Their accumulated thickness cipitating as colloform and banded growths. Galena is com-
may be up to 4,000 m in the western and central parts of the monly present as skeletal or dendritic growths, evidence of
Basque-Cantabrian basin (García-Mondéjar, 1985). During rapid precipitation. Carbonate gangue is usually dolomite; at

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 ORE-FORMING FLUIDS OF THE BASQUE-CANTABRIAN BASIN, SPAIN 1399

Santander Western Biscay Cantabrian Sea

A District District Northern B N 43°30'

Santander Bilbao Biscay Cantabrian Sea

District District 5 km
Bilbao San San Vicente
Sebasti n Comillas
de la Barquera
liva Novales
Mine
Udías
Orduña & Murgía Guipúzcoa
Vitoria
District Cabezón Reocín Torrelavega
Tertiary N salt domes de la Sal
Mesozoic La Florida
Triassic salt domes Ebro
Basin 43°15'
Paleozoic
50 km
4°15' 4°00'
Paleozoic Early Cretaceous Main towns
Triassic Late Cretaceous Faults
Jurassic Tertiary Zn-Pb deposits

5 km
C D N
Amurri Barambio
43°16'
Ramales Orduña
de la Diapir
Victoria Ambasaguas
Matienzo Monteleón
43º00
Orduñ Altube
Matienzo 43°14'
Treto Murgí
Txomin Concha Paúl
Lanestosa Iturlum
N La Antigua Beluntza
Jugo
Murgía
3 km 43°12' Diapir 42º55
Aperregui Mina de Vila
3°30' 3°25' 3°20' 3º00' 2º50'
Early Cretaceous Triassic
Triassic Main towns (with embedded Jurassic blocks) Zn-Pb deposits
(siliciclastic rocks)
Jurassic Latest Albian- Aptian Late Cretaceous Faults
Faults
Early Cretaceous Cenomanian Albian- Early
Zn-Pb deposits Miocene Main towns
(carbonate rocks) Cenomanian

FIG. 3. A. Geological map of the Basque-Cantabrian basin, with the main Zn-Pb districts (modified from García-Mondé-
jar et al., 1996). B. Geological map of the Santander district, showing the location of the major Zn-Pb deposits (after Insti-
tuto Geológico y Minero de España, 1970). C. Geological map of the Western Biscay district, showing the location of the
major Zn-Pb deposits (after Instituto Geológico y Minero de España, 1970). D. Geological map of the Orduña and Murgía
salt domes and the surrounding area (after Instituto Geológico y Minero de España, 1970). Peridiapiric Zn-Pb-Ba deposits
are indicated. Although the Barambio vein is close to these salt domes, its geological features are comparable to veins in the
Western Biscay district, and therefore, this deposit is considered to belong to this district (see text).

Reocín, several precipitation stages of this carbonate have Mineralization in the Txomin mine consists of a stratiform
been recognized (Velasco et al., 2000). Marcasite is locally unit of up to 1.5 m in thickness, developed in the platform-
very abundant in this deposit. Other similar but smaller de- talus transition facies. The hypogene assemblage consists of
posits are found at the Novales, Udías, and La Florida mines. sphalerite, galena, pyrite, dolomite, calcite, and quartz. The
Zn-Pb occurrences in the Western Biscay district (Fig. 3C) Matienzo vein system is located 5 km to the east of the Txo-
are hosted by three distinct lithologic units: dolomitized Apt- min mine and fills a fracture zone in the talus facies. Vein
ian-Albian platform carbonate rocks (Ramales Formation), thicknesses can reach up to 3 m, and the veins are filled by
platform-talus transition rocks, and basinal marls (Herrero, sphalerite, galena, fluorite, and calcite. Authigenic K feldspar
1989). Most mineralization consists of sulfide replacement is found in country rocks near the veins. Based on isotopic
and dissemination, although some veins cementing north- data and cathodoluminescence petrography, Simón and
west-southeast–trending fractures also occur. The most im- Grandia (1998) showed that a clear genetic link between the
portant deposits in this area are the Txomin and Matienzo Txomin and Matienzo deposits could be established and con-
mines, with a total tonnage of about 3 Mt at 11 percent Zn. cluded that the differences in morphology were caused by the

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 1400 GRANDIA ET AL.

permeability of the particular enclosing rocks. Other mineral- Na, K, Li, Cl, and Br in inclusion fluids were analyzed fol-
ized fracture systems include the Treto vein, located near the lowing the method of Banks and Yardley (1992). 1- to 2-mm
Matienzo and Txomin area, and the Barambio vein, located mineral grains were cleaned by boiling and washing three
close to salt domes of Triassic evaporites farther south (Fig. times in milli-Q water. The dried samples (about 2 g) were
3D). Some of these domes contain vein-type and strata- crushed in an agate mortar, and the powder was transferred
bound Zn-Pb mineralization. The most significant deposits to a 7-ml Sterlin container. Approximately 6 ml of milli-Q
are in the Orduña (Monteleón and Paúl) and Murgía (Altube, water was added to redissolve the dried salts. The samples
Aperregui, and Jugo) diapirs, which are hosted by rocks of were filtered through 0.2-µm nylon filters prior to analysis for
Jurassic to Turonian age (Perona et al., 2002). The paragene- Cl and Br by ion chromatography (Dionex 4500i). Na, K, and
sis consists of sphalerite, galena, pyrite, barite, dolomite, cal- Li were analyzed by flame emission spectrometry on the
cite, and bitumen. same leach solutions. The analytical precision was usually bet-
Numerous Zn-Pb deposits are also found in Paleozoic rocks ter than 10 percent (2σ error) for the Cl and Br, about 10 per-
at the margins of the Basque-Cantabrian basin. There is a cent (2σ) for the K and Na at low concentrations (less than
general consensus that many of the deposits are post-Paleo- 200–300 ppb), and about 5 percent (2σ) above these values.
zoic in age. Samples from the Áliva mine have been included Calcium was not determined because many of the samples
in this study for comparison. The Áliva mine (0.6 Mt, 13% Zn) were carbonate (one fluorite), and because of the small
is located at the western margin of the Basque-Cantabrian amount of sample material available for multi-acid leaching.
basin (the Picos de Europa region, Cantabrian zone, Hercyn- Aqueous, two-phase primary fluid inclusions in sphalerite
ian Massif), near some of the deposits in the Santander dis- from the Reocín deposit (Fig. 4A) have similar homogeniza-
trict (Fig. 3A), and is hosted by dolomitized limestones of tion temperatures (54º–110ºC) to those reported by Bustillo
Carboniferous age. and Ordóñez (1995). However, ice-melting temperatures, the
last phase to melt in most inclusions, range from –32.3º to
Fluid Inclusions –28.6ºC, resulting in salinities from 25 to 26 wt percent NaCl
equiv, which are much higher than those reported by these
Previous data authors (Figs. 5A and 6A). Data from similar inclusions in
Little data relating to fluid composition in deposits from sphalerite from the Udías area indicate salinities of about 23
the Santander district exist. Moderate salinity (15–20 wt % wt percent NaCl equiv. In both cases, selected samples con-
NaCl equiv) and low homogenization temperatures tained a few secondary fluid inclusions that were not studied
(60º–80ºC) were obtained in fluid inclusions in dolomite from due to their small size (less than 5 µm). Data from sphalerite
Reocín (Bustillo and Ordóñez, 1995). Fluid inclusion studies and quartz of the Barambio vein indicate that ore-forming
in most deposits of the Western Biscay district show broad brines had salinities from 9.2 to 15.9 wt percent NaCl equiv,
ranges in both the salinity and temperature of the ore- with homogenization temperatures from 150º to 180ºC. Many
forming brines. In the Txomin mine, a progressive dilution inclusions contained an opaque solid that likely derived from
through the paragenetic sequence is observed, ranging from maturation of an organic compound after trapping (Fig. 4B).
~17 wt percent NaCl equiv in sphalerite to less than 5 wt In such inclusions, homogenization temperatures were con-
percent NaCl equiv in late quartz (Ente Vasco de la Energía, sidered invalid.
1997; Simón et al., 1999). This salinity drop does not In the Altube, Aperregui, and Jugo deposits (Murgía salt
correspond to a temperature decrease, which ranges from dome), the salinity of primary inclusions in sphalerite ranges
145º to 225ºC. Brines with similar salinities and temperatures from ~10 to more than 25 wt percent NaCl equiv, with tem-
have been found in fluorite and sphalerite from the Matienzo peratures between 150º and 250ºC (Figs. 5B and 6B). Barite
veins (~15–16 wt % NaCl equiv, 150º–170ºC; Velasco et al., from the same area (Iturlum occurrence) hosts inclusions
1994; Simón et al., 1999). Secondary fluids with moderate with a lower salinity (as low as 5.4 wt % NaCl equiv; mean
salinity have also been reported in Matienzo (up to 7 wt % value of 14.7 wt %). Similar salinities have been found in the
NaCl equiv; Herrero et al., 1988). Orduña salt dome (Figs. 5C and 6C), as seen in fluid inclu-
In the Áliva mine, the origin of the mineralization has been sions from Monteleón, with 15 to 25 wt percent NaCl equiv,
related to migration of fluids with moderate salinity, from 6.4 and from Paúl, with 12.7 to 25 wt percent NaCl equiv. All
to 23.6 wt percent NaCl equiv, and temperatures from 95º to studied fluid inclusions were two phase and liquid rich (Fig.
175ºC (Gómez-Fernández et al., 2000). 4C, D). In fluid inclusions from Altube, Aperregui, and Mon-
teleón, CH4 clathrate was the last phase to melt (Fig. 4D),
New data whereas hydrohalite melts before ice in most other inclusions.
In the present study, 49 samples of ore and gangue miner- In sample 40.90 ALT-3 (sphalerite) from the Altube deposit,
als from the deposits described above and from salt domes the last phase to melt in all inclusions was hydrohalite (Tmh
were selected for fluid inclusion analysis (Table 1). Samples from –19.7º to –17.6ºC), resulting in higher salinities on aver-
were collected from surface outcrops, underground works, age (25 wt % NaCl equiv). As the salinity deduced from hy-
and drill cores. Doubly polished sections of 14 samples were drohalite and ice melting is more than 15 wt percent NaCl
studied for microthermometry, which was performed on a equiv and the content of volatile components is low (no sepa-
Linkam THMS-600 heating-freezing stage, calibrated with dis- rate phase is observed at room temperature), errors in the cal-
tilled water and pure CO2 fluid inclusions. The reproducibility culated salinity due to clathrate formation are insignificant.
of the measurements below 0ºC was ±0.2ºC and ±2ºC for the In the Áliva mine, measurements in primary fluid inclu-
homogenization temperatures. The relative concentrations of sions (Fig. 4E) in sphalerite yielded salinities from 15 to 15.9

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 ORE-FORMING FLUIDS OF THE BASQUE-CANTABRIAN BASIN, SPAIN 1401

A T=-113 ºC B T=+25 ºC

Ice
Bitumen ?
Vapor
Hydrohalite

50 µm 50 µm
Vapor

C T=+25 ºC D T=+25 ºC T=-28 ºC

CH4 clathrate

Vapor
20 µm 20 µm

E T=+25 ºC F T=+25 ºC

180 µm 50 µm

FIG. 4. Fluid inclusions from the studied deposits in the Basque-Cantabrian basin. A. Primary, aqueous fluid inclusion in
sphalerite from the Reocín deposit (Santander district). The picture is taken at –113ºC, and a hexagonal crystal of hydro-
halite, which is the last phase to melt in this inclusion, is clearly observed close to the vapor bubble. B. Aqueous, primary
fluid inclusion in sphalerite from the Barambio mine (Western Biscay district). Black shadow to the left-hand side of the in-
clusion is a solid of unknown composition, likely of organic origin. As most inclusions in the sample contained this solid phase,
it is not considered to be trapped during inclusion growth. C. Aqueous, two-phase fluid inclusion in sphalerite from the Paúl
deposit (Orduña salt dome). Fluid inclusions in this deposit record the lowest homogenization temperatures in the Triassic
salt domes of the Basque-Cantabrian basin. D. Primary fluid inclusion in sphalerite from the Aperregui deposit (Murgía salt
dome). This inclusion is two phase at room temperature (aqueous liquid and vapor bubble); at low temperatures, a CH4
clathrate is seen. Fluid inclusions with small amounts of CH4 have been observed in almost all deposits around the Triassic
salt domes in the Basque-Cantabrian basin. E. Large, primary fluid inclusion in sphalerite from the Áliva deposit (western
Paleozoic margin of the Basque-Cantabrian basin). F. Secondary fluid inclusions in fluorite from the Matienzo mine. Due to
their moderate salinity (up to 7 wt % NaCl equiv; Herrero et al., 1988), these inclusions may have significant influence on
the leachate composition during the crush-leach analysis of the sample.

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 TABLE 1. Fluid Inclusion Data for Samples from Zn-Pb Mineralization in the Basque-Cantabrian Basin
1402
Sample no. Mineral Locality Host rock Ore type Microthermometry Leachate data

Thomogenization wt % NaCl equiv (Cl/Br)molar (Na/Br)molar (Na/Li)molar (Na/K)molar

Min. Mean Max. n Min. Mean Max. n

Santander district

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FL-1 Sphalerite La Florida Dolostone (Aptian) Replacement 631 411 1,620 26
FL-2 Dolomite La Florida Dolostone (Aptian) Replacement 574 412 1,863 38

by Society of Economic Geologists, Cesar Ricardo Vargas

RE-1 Sphalerite Reocín Dolostone (Aptian) Replacement 638 452 1,638 67
RE-2 Dolomite Reocín Dolostone (Aptian) Replacement 597 463 3,090 50
RE-3 Sphalerite Reocín Dolostone (Aptian) Replacement 55 77 110 42 25 25.5 26 33 192 60 288 9
NOV-1 Sphalerite Novales Dolostone (Aptian) Replacement 345 114 475 7
UD-1 Sphalerite Udías Dolostone (Aptian) Replacement 125 1 22 22.5 23.5 3 408 312 386 7

Western Biscay district

TX-1 Sphalerite1 Txomin Dolostone (Aptian) Replacement 125 162 215 92 15.7 17.1 18.2 13 52 52 23
TX-2 Calcite1 Txomin Dolostone (Aptian) Replacement 15 1 334 324 106
TX-3 Dolomite1 Txomin Dolostone (Aptian) Replacement 195 202 212 9 16.1 1 591 392 517 71
TX-4 Quartz1,2 Txomin Dolostone (Aptian) Replacement 99 176 225 33 4.2 5.7 7.3 17 181 153 24
C-98-1 Sphalerite Treto Marls (Aptian) Vein 28 26 79 20
MAT-1 Sphalerite3 Matienzo Marls (Aptian) Vein 95 15.5 206 137 83 156
MAT-2 Fluorite2 Matienzo Marls (Aptian) Vein 148 154 160 7 15 16 17.8 7 161 124 225 143
MAT-3 Calcite Matienzo Marls (Aptian) Vein 142 101 193 1,173

1402
BA-1 Sphalerite Barambio Sandstone (Albian) Vein 180 1 12.8 15 15.9 11 906 699 18 10
BA-2 Quartz Barambio Sandstone (Albian) Vein 140 160 182 4 9.2 9.5 10 3 937 818 27 38

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GRANDIA ET AL.

Salt domes

Murgía diapir

198.30 ALT-2 Sphalerite Altube Sandstone (Albian) Replacement 1,292 1,054 26 26

35.20 ALT-3 Calcite Altube Limestone (Albian) Replacement 402 321 160 79
36.70 ALT-3 Sphalerite Altube Limestone (Albian) Vein 1,043 825 75 10
40.90 ALT-3 Sphalerite Altube Sandstone (Albian) Vein 264 1 24.5 25 25.5 4 7,368 7,569 8 12
40.90 ALT-3 Calcite Altube Sandstone (Albian) Vein 16.6 19.8 20.5 10 1,941 1,569 119 79
111.80 ALT-5 Sphalerite Altube Sandstone (Albian) Vein 2,037 1,733 99 63
126.00 ALT-5 Calcite Altube Sandstone (Albian) Replacement 1,418 986 81 23
144.00 ALT-6 Calcite Altube Limestone (Albian) Replacement 1,749 1,368 90 68
198.50 ALT-6 Sphalerite Altube Limestone (Albian) Vein 1,417 1,272 18 17
209.00 ALT-6 Sphalerite Altube Sandstone (Albian) Replacement 145 217 295 8 11.9 23.5 25 18 2,178 1,970 30 13
206.40 ALT-7 Sphalerite Altube Sandstone (Albian) Replacement 1,362 1,030 26 12
233.10 ALT-7 Sphalerite Altube Sandstone (Albian) Vein 179 199 217 4 21 24 24.5 11 3,852 3,588 15 10
233.20 ALT-7 Sphalerite Altube Sandstone (Albian) Vein 1,861 1,632 31 20
233.20 ALT-7 Calcite Altube Sandstone (Albian) Vein 1,877 1,483 74 54
307.50 ALT-7 Sphalerite Altube Limestone (Albian) Replacement 740 467 15 0.6
312.75 ALT-7 Quartz Altube Sandstone (Albian) Replacement 120 148 196 41 17.8 21 24 47 2,356 1,810 116 29
DM-03-5 Sphalerite Jugo Sandstone (Albian) Vein 126 153 173 6 10.9 16.9 20.1 7 500 305 64 9
DM-03-5 Barite Jugo Sandstone (Albian) Vein 894 704 42 27
DM-04-1 Barite Vila Dolostone (Jurassic) Replacement 2,032 1,711 167 56
DM-02-1 Barite Iturlum Dolostone (Jurassic) Replacement 160 204 240 7 5.4 14.7 24 28 514 346 12 7
DM-05-1 Sphalerite Aperregui Dolostone (Jurassic) Breccia cement 150 182 202 17 22 23.5 24.7 33 1,638 1,429 47 16
 TABLE 1. (Cont.)

Sample no. Mineral Locality Host rock Ore type Microthermometry Leachate data

Thomogenization wt % NaCl equiv (Cl/Br)molar (Na/Br)molar (Na/Li)molar (Na/K)molar

Min. Mean Max. n Min. Mean Max. n

Orduña diapir

0361-0128/98/000/000-00 $6.00
DO-03-bloc Sphalerite Monteleón Dolostone (Jurassic) Replacement 2,600 2,241 69 68

by Society of Economic Geologists, Cesar Ricardo Vargas

DO-03-4 Sphalerite Monteleón Dolostone (Jurassic) Replacement 175 180 184 2 15.1 23.5 25 15 3,537 2,939 29 13
DO-03-1 Dolomite Monteleón Dolostone (Jurassic) Replacement 2,472 2,059 222 120
DO-03-bloc Calcite Monteleón Dolostone (Jurassic) Replacement 1,987 1,389 118 77
DO-03-5 Sphalerite Monteleón Dolostone (Jurassic) Replacement 179 192 204 2 21 23 23 9 2,503 2,374 75 79
DO-04-1 Sphalerite Paúl Black shales (Turonian) Vein 84 135 196 40 12.7 21.5 25 53 2,468 2,146 190 87
DO-04-1 Dolomite Paúl Black shales (Turonian) Vein 2,348 1,891 398 133
Paul n. Inf. Sphalerite Paúl Black shales (Turonian) Dissemination 80 101 118 12 15.9 21.5 25 13 911 673 3 1
DO-02-7 Calcite La Antigua Limestone (Turonian) Vein 2,728 2,332 53 127
ALI-1 Sphalerite Áliva Dolostone (Carboniferous) Replacement 153 162 170 12 15 15.6 15.9 11 791 613 329 46.1
ALI-2 Sphalerite Áliva Dolostone (Carboniferous) Replacement 812 725 414 62.9

1 Microthermometric data from Ente Vasco Energía (1997)

2 Microthermometric data from Simón et al. (1999); leachate data for samples TXO-4 and MAT-2 were obtained from the same specimens studied by Simón et al. (1999)
3 Microthermometric data (mean value) from Velasco et al. (1994)

1403

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N
0
2
4
6
N 8

0
2
4
6
8
10
12
14
16
20

10
0
2
4
6
8
N 10
12
14
16
18

B
A

60

C
60

60

domes, respectively.
100
100

100
140
ORE-FORMING FLUIDS OF THE BASQUE-CANTABRIAN BASIN, SPAIN

140

140
Th (°C)

Th (°C)
Th (°C)
180
180

180
RE-1

TX-4
UD-1

MAT-2

220

220
220

DO-03- 5
DO-03- 4
DM-05-1
DM-02-2
Biscay districts

260

260
Paul n. Inf.
260
BA-2
BA-1

ALI-1

DO-04-1 sph
Orduña salt dome
Santander and Western

DM-03-5 sph
312.75 ALT-7
233.10 ALT-7
209.00 ALT-6
40.9 ALT-3 sph
Murgía salt dome
300

300
300

(A). Histograms (B) and (C) show the data from the Murgía and Orduña salt
studied samples. See Table 1 for location of the samples. Data from the Mis-

cluding the Áliva mine hosted by Paleozoic rocks) are shown in the histogram
FIG. 5. Homogenization temperatures of primary fluid inclusions in the

sissippi Valley-type deposits in Western Biscay and Santander districts (in-

1403
 1404 GRANDIA ET AL.

30 wt percent NaCl equiv and homogenization temperatures

A Santander and Western from 153º to 170ºC (Figs. 5A and 6A). These data are within the
Biscay districts
25 range of values reported by Gómez-Fernández et al. (2000).
RE-1 BA-1 The broad ranges in both homogenization temperatures
UD-1 BA-2 and salinity in many deposits (Fig. 7) suggest that mixing of
20 TX-4 ALI-1 fluids occurred during ore formation. Inclusion fluids in sam-
MAT-2 ples from the Western Biscay district are typically less saline
N
15 than those found in the deposits around salt domes, although
a continuous spectrum from high to low salinity is observed.
10 Data from the Reocín deposit does not plot in this trend be-
cause of the very low homogenization temperatures.
Leachate data show wide ranges in Cl/Br ratios (Table 1),
5
plotting above and below the seawater value (Cl/Brmolar ~660:
Fontes and Matray, 1993). Most leachates from the Matienzo
0 and Txomin mines (Western Biscay district) and one from the
-32 -28 -24 -20 -16 -12 -8 -4 0 Reocín mine (Santander district) have ratios consistent with
Tmi highly evaporated brines (past the point of halite precipita-
tion, Cl/Brmolar ~200). The other samples from Reocín and
35 from other deposits in the Santander district have intermedi-
B Murgía salt dome
ate values between those of seawater and highly evaporated
30 40.9 ALT-3 cc brines. Cl/Br ratios slightly higher than that of seawater are
40.9 ALT-3 sph found in samples from Áliva (~800) and Barambio (~900). In
25 209.00 ALT-6 contrast, the samples from deposits close to Triassic salt
312.75 ALT-7 domes show a broad range of values, with ratios consistent
20 233.10 ALT-7
N with evaporated, halite-saturated fluids to ratios associated
DM-02-1
with halite dissolution. This variation is observed at a local
15 DM-03-5 sph
scale in the Altube mine (Murgía salt dome), where
DM-05-1
10
(Cl/Br)molar values range from 402 to 7,368 in samples col-
lected from the same drill core.
5
The Na/Br ratio in all samples is in accordance with the de-
gree of evaporation or halite dissolution deduced from the
0 Cl/Br ratios (Fig. 8). Na/K and Na/Li ratios in samples from
deposits hosted by Cretaceous dolostones (Txomin and San-
-32 -28 -24 -20 -16 -12 -8 -4 0
tander district deposits) also reflect the degree of evaporation
Tmi indicated by the Cl/Br ratios (Na/Kmolar of 7–71; Fig. 9;
16 Na/Limolar of 23–3,090). In contrast, the samples from marl-
hosted veins in Western Biscay district (Matienzo and Treto)
14 C Orduña salt dome
typically have much higher Na/K ratios (as high as 1,173).
DO-03- 4 Moreover, many samples near salt domes have Na/K and
12 DO-03- 5 Na/Li ratios (Na/Kmolar of 0.6–133; Fig. 9; Na/Limolar of 3–398)
DO-04-1 sph much lower than expected for a fluid dissolving halite
10 Paul n. Inf. (Na/Kmolar > 300: Dean, 1978, Herut et al., 1998; Na/Limolar >
N 8 50,000: Pueyo, pers. commun., 2001).
As the “crush-leach” technique is a bulk sample analysis,
6 the presence of secondary fluid inclusions may influence the
ratios above reported. In those cases in which secondary fluid
4 inclusion salinity is known, the changes in the primary Cl/Br
2 ratios of the brines could be estimated in a Cl/Br versus Cl
plot. However, primary fluid inclusions predominate in the
0 samples analyzed in this study, and only in samples from the
Santander district and from the Matienzo vein may the influ-
-32 -28 -24 -20 -16 -12 -8 -4 0
ence of secondary fluids be significant (Fig. 4F).
Tmi
Discussion: Cl vs. Cl/Br vs. Na/Br Diagrams
and Mixing Lines
FIG. 6. Ice-melting temperatures of fluid inclusions in the studied sam-
ples. See Table 1 for location of the samples. Data from the Mississippi Val- Theoretical cases
ley-type deposits in Western Biscay and Santander districts (including the
Áliva mine hosted by Paleozoic rocks) are shown in the histogram (A). His-
Mixing of fluids has been invoked in most Mississippi Val-
tograms (B) and (C) show the data from the Murgía and Orduña salt domes, ley-type deposits to explain mineral precipitation. The main
respectively. evidence for the mixing is based on microthermometric data

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 ORE-FORMING FLUIDS OF THE BASQUE-CANTABRIAN BASIN, SPAIN 1405

300

260

220

T homogenization (ºC) 180

140

100

60

20
-34 -32 -30 -28 -26 -24 -22 -20 -18 -16 -14 -12 -10 -8 -6 -4 -2 0

Tmelting ice (ºC)

FIG. 7. Homogenization–versus–ice-melting temperature plot for fluid inclusions from some Zn-Pb deposits in the
Basque-Cantabrian basin and in its western Paleozoic margin. (●●) = Santander district deposits, (●) = Áliva mine, () = Tx-
omin mine, () = Matienzo-Treto veins, () = Barambio vein, () = Murgía salt dome deposits, ( ) = Orduña salt dome de-
posits. Note the broad ranges in both ice-melting and homogenization temperatures of fluid inclusions from the Murgía and
Orduña salt domes. Data in quartz from the Txomin mine are from Ente Vasco de la Energía (1997) and Simón et al. (1999).
Data in fluorite from the Matienzo mine is from Simón et al. (1999).

8000
1000
Seawater evaporation
800 trajectory
7000
600
400 SW
6000
200
0
5000
(Cl/Br) molar

0 200 400 600 800 1000

(ºC)
4000

3000

2000

1000

0
0 1000 2000 3000 4000 5000 6000 7000 8000
(Na/Br) molar
FIG. 8. (Cl/Br)molar versus (Na/Br)molar plot of fluids from the Basque-Cantabrian basin. (● ●) = Santander district deposits,
(●) = Áliva mine, () = Txomin mine, ( ) = Matienzo-Treto veins, () = Barambio vein, () = Murgía salt dome deposits,
( ) = Orduña salt dome deposits. Inclusion fluids in the deposits from the Western Biscay district typically have very low ra-
tios, consistent with highly evaporated brines (past the point of halite precipitation, Cl/Brmolar ~200). Most samples from de-
posits in the Santander district have intermediate values between those of seawater and highly evaporated brines. Samples
from deposits close to Orduña and Murgía salt domes show a broad range of values, with ratios consistent with evaporated,
halite-saturated fluids to ratios associated with halite dissolution. Data for the evaporation seawater trajectory are taken from
Fontes and Matray (1993).

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 1406 GRANDIA ET AL.

8000
8000
7000 7000 Mixing model
curve
6000
6000 5000
Na loss?
4000
3000
5000 2000
(Cl/Br)molar

0.2
1000 0.6
0.8 0.4
0
4000
0 100 200 300 400 500 600 700 800

3000

2000
Mixing model curve
SW
1000
Seawater evaporation trajectory
0
0 50 100 150 200
(Na/K) molar
FIG. 9. (Cl/Br)molar versus (Na/K)molar plot of fluids from the Basque-Cantabrian basin. A model curve of the mixing trend
between a seven-times diluted, highly evaporated seawater and a halite-dissolution brine is shown. This mixing model is also
used in Figure 12. Weight fractions of the evaporated brine are indicated. See Figure 6 for legend and Table 2 for end-mem-
ber compositions of the model curve. Data for the evaporation seawater trajectory are taken from Fontes and Matray (1993).

(see Wilkinson, 2001, and references therein). Halogen data four types of fluids (Table 2): (1) seawater, (2) an evaporated
may also help to identify mixing processes in cases where the seawater before the onset of halite precipitation, (3) a highly
end-member fluids acquired their salinity by different mech- evaporated seawater, and (4) a halite-saturated brine at 25ºC de-
anisms (i.e., halite dissolution or seawater evaporation). How- rived from halite dissolution. Fluids 3 and 4, diluted five times
ever, Chi and Savard (1997) suggest that, in some cases, the by fresh water, have also been used in the modeling. These flu-
proportion of the end members in a mixture is difficult to ids have been selected because they are common in present-day
constrain solely on the basis of halogen ratios, and values of sedimentary basins and they are thought to be involved in ore
Cl/Br lower than the seawater value may result from mixtures formation processes (e.g., Hanor, 1994). Cl/Br and cation (Na/K
with major contribution of a halite-dissolution brine. and Na/Li) ratios of fluids 1, 2, and 3 have been taken from
In order to test the effect of mixing on the salinity and halo- Fontes and Matray (1993). For fluid 4, a (Cl/Br)molar ratio of
gen ratios, four mixing scenarios have been evaluated using 20,000 has been used, a value typical of a fluid dissolving halite.

TABLE 2. Element Concentrations and Ratios of the End-Member Fluids Used in the Mixing Models

2: Evaporated 3: Highly evaporated 3: Highly evaporated seawater 4: Halite- 4: Halite-

seawater at seawater at at carnallite saturation dissolution dissolution brine
Fluid 1: Seawater halite saturation carnallite saturation (5 times diluted) brine (5 times diluted)

Cl (ppm) 19,354 145,847 229,887 45,977 159,457 31,891

Br (ppm) 67 480 5,570 1,114 18 4
Na (ppm) 10,763 78,987 6,151 1,230 103,543 20,709
Ca (ppm) 410 373 45 9 350 70
K (ppm) 399 2,990 649 130 350 70
Mg (ppm) 1,291 11,130 82,113 16,423 350 70
TDS (ppm) 32,284 239,807 324,415 64,883 264,063 52,814

(Cl/Br)molar 650 684 93 93 19,938 19,938

(Na/Br)molar 558 572 4 4 19,983 19,983
(Na/K)molar 46 45 16 16 502 502

Data for seawater (fluid 1) and for fluids derived from seawater evaporation (fluids 2 and 3 ) are from Fontes and Matray (1993); concentrations of fluid
2 correspond to a halite-saturated brine and of fluid 3 to a carnallite-saturated brine; fluid 4 concentrations correspond to a halite-saturated brine at 25 ºC
from halite dissolution
TDS = Total dissolved salts

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 ORE-FORMING FLUIDS OF THE BASQUE-CANTABRIAN BASIN, SPAIN 1407

Although (Cl/Br)molar ratios as low as 6,000 have been found in evaporation trajectory. Also, salinity changes rapidly as the
the latest halites crystallizing during seawater evaporation (Fig. mixing proceeds, whereas Cl/Br and Na/Br ratios are almost
1; McCaffrey et al., 1987), and recrystallization of halite may constant, resembling a simple dilution of fluid 3. Only accu-
generate Br-rich brines (Stoessell and Moore, 1983), relatively rate information about the slope of the Cl/Br versus [Cl]
low (Cl/Br)molar ratios (6,000–10,000) in the halite-dissolution curve for different mixture proportions indicates the involve-
fluid do not significantly change the results of the modeling. ment of a halite-dissolution brine (Fig. 11). For contributions
The curves are constructed from linear mixing equations, as- of fluid 3 lower than 10 wt percent, very small variations in
suming a conservative behavior of each dissolved element (i.e., salinity are expected (less than 2 wt %) and, thus, mixing is
no mineral precipitation occurs). The curves are represented in not detected by microthermometry. In this case, significant
two types of diagrams: Cl/Br versus Na/Br ratios and Cl/Br ra- variations of Cl/Br and Na/Br merely represent small changes
tios versus Cl concentrations (Figs. 10 and 11). in the proportion of fluids in the mixture.
Case 1, mixing of fluid 1 with fluid 4: This model illustrates Case 2b, mixing of diluted fluid 3 with fluid 4: Highly evap-
the effects of adding increasing amounts of an ordinary sea- orated brines may mix with low-salinity fluids (e.g., fresh
water to a halite-dissolution brine, such as the brines associ- water) prior to the mixing with fluids dissolving evaporites,
ated with salt diapirs. In this model, all data plot above Cl/Br reducing their salinity but not the Cl/Br ratios. If the salinity
and Na/Br seawater values, and small changes in the propor- of fluid 3 is, for instance, lowered by a factor of five, a pro-
tions of end-member fluids in the mixing produce large vari- portion of fluid 4 greater than 65 wt percent in the mixture is
ations of these ratios. Since the end-member fluids have con- needed to produce Cl/Br ratios higher than the value for sea-
trasting salinities, variations of the Cl/Br and Na/Br ratios are water. As in case 2, salinity changes are not detected by mi-
coupled with large variations of salinity. crothermometry at contributions of fluid 3 smaller than 10 wt
Case 2, mixing of fluid 3 with fluid 4: This model tests the percent; conversely, contributions greater than 10 wt percent
effects of adding a highly evaporated seawater to a halite-dis- result in significant changes in salinity, but the Cl/Br and
solution brine. Although the salinity of both fluids is different Na/Br ratios are almost constant, as would be predicted by di-
(about 6 wt %), a contribution of fluid 3 greater than 10 wt lution with fresh water. Again, by coupling microthermomet-
percent in the mixture is enough to reduce the Cl/Br and ric and halogen data, it is possible to detect the presence of an
Na/Br ratios to values below those of seawater, and in a Cl/Br evaporated brine with part of the salinity being related to
versus Na/Br diagram, the mixtures plot on the seawater halite dissolution (Fig. 11).

8000
800 0.4
SW 0.6
Seawater evaporation
trajectory
7000 600 0.4
Case 3b
Case 1
400 0.2
6000 Case 2b 0.4
0.6
200 0.8 0.4
0.6 Case 2
1
5000 0
molar

0 200 400 600 800

(Cl/Br)

4000
Case 3
0.6
0.2
3000

2000 0.8
0.2 0.4
0.6 0.2
1000

0
0 1000 2000 3000 4000 5000 6000 7000 8000
(Na/Br) molar
FIG. 10. (Cl/Br)molar versus (Na/Br)molar ratios of the mixtures in the theoretical mixing scenarios. The mixing is calculated
by addition of increasing amounts (in grams) of one brine into the other. The weight of each element in a certain mixture
will depend on the salinity of both fluids, the concentration of the element in the end members, and the degree of mixing.
The final Cl/Br and cation ratios are obtained by dividing the weight of both elements corresponding to the mixture. The
fluid fractions indicated in the plot are the weight fraction of one fluid in the mixture. Case 1 (●): in this model, increasing
amounts of an ordinary seawater are added to a halite-dissolution brine. Case 2 (● ●): this model tests the effects of adding a
highly evaporated seawater to a halite-dissolution brine. Case 2b (●): the same scenario as case 2, but the highly evaporated
brine is diluted by a factor of five prior to the mixing with a fluid dissolving evaporites. Case 3 (): an evaporated seawater
before the onset of the halite precipitation is added to a brine dissolving halite. Case 3b (): the same scenario as case 3, but
the fluid dissolving halite is diluted by a factor of five prior to the mixing with seawater.

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 1408 GRANDIA ET AL.

8000

7000 Case 1

Case 3b
6000 0.4

5000
(Cl/Br) molar

Case 2b

4000
0.6
0.2
3000 Case 3

Seawater evaporation
2000 0.8 trajectory
0.2 0.4 Case 2
SW
0.2 0.6
0.4 0.6 Onset of halite precipitation
1000 1 0.2 0.8 0.8
0.6 1 0.2 0.4
Case 4 1 0.8 0.4 0.6 0.4 0.6 0.8 1
0
0 50000 100000 150000 200000 250000
[Cl] ppm
FIG. 11. (Cl/Br)molar versus [Cl] of the mixtures in the theoretical mixing scenarios (see Fig. 10 for mixing calculations and
●) = case 2, (●) = case 2b, () = case 3, ( ) = case 3b, () = case 4.
explanations of cases 1, 2, 2b, 3, and 3b). (●) = case 1, (●
Case 4 illustrates the addition of seawater-evaporation fluids (before halite precipitation) to fresh water or seawater.

Case 3, mixing of fluid 2 with fluid 4: In this case, an evap- Microthermometric data will reveal salinity variations, al-
orated seawater before the onset of the halite precipitation is though they will be unable to distinguish the origin of the
added to a brine dissolving halite. In a Cl/Br versus Na/Br plot, end-member fluids.
the mixing of fluid 4 with an evaporated seawater is similar to
that in case 1, but the ratios decrease more steeply; for exam- Basque-Cantabrian basin data
ple, a contribution of 40 wt percent of fluid 2 results in a mix- Microthermometry suggests that the fluid mixing was com-
ture with (Cl/Br)molar = 1,709, whereas in case 1, the ratio was mon in deposits from the Basque-Cantabrian basin (Velasco
6,190. Since both fluids have a similar salinity, a very narrow et al., 1994; Simón et al., 1999; and present work). Although
range of salinity in the mixture results and no significant vari- widespread Triassic evaporite (mainly gypsum and minor
ations are detected by microthermometric studies. Therefore, halite) deposits occur in the Basque-Cantabrian basin, most
halogen ratios provide clear evidence for mixing, but the rela- inclusion fluids from Mississippi Valley-type ores are consis-
tive proportions of the end-member fluids are only observed tent with evaporated seawater rather than halite-dissolution
by plotting the data in a Cl/Br versus [Cl] diagram. fluids, according to the Cl/Br versus Na/Br plots (Fig. 8).
Case 3b, mixing of fluid 2 with diluted fluid 4: Like case 2b, Only in the deposits near the salt domes do the ore-forming
dilution of a halite-dissolution brine by fresh water prior to fluids have a halogen signature that suggests the involvement
the mixing with fluid 2 reduces its salinity but does not of brines from the dissolution of halite. However, the nature
change the Cl/Br ratio. Here, an arbitrary dilution factor of of the end-member fluids and the relative proportions of end
five has been chosen. As the diluted fluid 4 has a low salinity members involved in mixing are not well constrained. Com-
(~50,000 ppm total dissolved salts), Cl/Br and Na/Br ratios bining the salinity with the halogen ratios in a Cl/Br versus
are mainly controlled by fluid 2. In mixtures with more than [Cl] plot, the mixing between fluids of different origin and
80 wt percent of diluted fluid 4, small changes in the relative salinity is better defined and the end-member fluids are bet-
proportions of fluids will produce broad ranges in both ratios. ter constrained (Fig. 12).
In contrast, mixtures with less than 80 wt percent of fluid 4 Data from deposits near salt domes define a high-Cl/Br,
will have similar Cl/Br and Na/Br ratios, and so, small changes high-salinity to low-Cl/Br, low-salinity trend from a mixture
in such ratios could indicate major changes in the relative where one of the end members is a brine generated by halite
proportions of the end members. In this case, large variations dissolution (e.g., fluid 4) and the other is a highly evaporated
in salinity are always observed unless the proportion of di- fluid that underwent dilution prior to mixing (fluid 3 diluted
luted fluid 4 is greater than 80 wt percent. about seven times). This trend defines a curve similar to that
Case 4, mixing of fluid 1 with fluid 2: Addition of seawater- explained for case 2b in Figure 11, where significant changes
evaporation fluids (before halite precipitation) to fresh in salinity (i.e., >5 wt % NaCl equiv) of the mixture are not
water or seawater, which may occur in many evaporative en- observed until the proportion of the low-salinity fluid reaches
vironments, also does not change the Cl/Br and Na/Br ratios. ~20 wt percent, whereas the Cl/Br ratio decreases by a factor

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 ORE-FORMING FLUIDS OF THE BASQUE-CANTABRIAN BASIN, SPAIN 1409

8000

7000

6000

5000
(Cl/Br) molar

4000

3000

2000 0.2
SW Onset of halite precipitation
1000 0.4 Seawater evaporation
trajectory
0.8
0.6
0 1
0 50000 100000 150000 200000 250000
[Cl] ppm
FIG. 12. (Cl/Br)molar versus [Cl] plot of fluids from the Basque-Cantabrian basin. Bars show the [Cl] range determined by
microthermometry. Symbols are averages: (● ●) = Santander district deposits, (●) = Áliva mine, () = Txomin mine, (
) = Ma-
tienzo-Treto veins, () = Barambio vein, () = Murgía salt dome deposits, ( ) = Orduña salt dome deposits. Solid line shows
the addition of a highly evaporated brine that underwent dilution by a factor of seven to a fluid-dissolving halite. This model
curve allows the explanation of the broad ranges of Cl/Br ratios in samples from an individual deposit (e.g., Altube deposits)
or from the same district (e.g., Murgía salt dome). The mixing model also shows a possible link between ore-forming brines
around Triassic diapirs and fluids in Mississippi Valley-type deposits in the Basque-Cantabrian basin. Dashed line represents
the addition of seawater or fresh water to a previous mixture formed by ~25 wt percent of highly evaporated brine and ~75
wt percent of a halite-dissolution brine. This sort of mixing allows the explanation of the data of Áliva and Barambio mines.

of 10. This mixing curve may explain the large changes in the comparable to the fluids found in other areas of the Western
Cl/Br ratios observed in leachates from the Altube mine Biscay district, such as those in the late stages of mineraliza-
(Murgía salt dome) in samples having a narrow range in mean tion in the Txomin mine, where highly evaporated brines had
salinity values (within 5 wt % NaCl equiv). Mixtures domi- been diluted (Simón et al., 1999)
nated by the low-salinity fluid in the Altube mine are also sug- The interpretation of the data in the Txomin-Matienzo area is
gested, as some samples have low Cl/Br ratios (as low as 402). not straightforward, and no well-defined trends are observed.
The broad ranges in salinity in some samples indicate differ- The presence of secondary fluids with a moderate salinity (up to
ent degrees of mixing and mineral precipitation. 7 wt % NaCl equiv; Herrero et al., 1988; Fig. 4F) could account
Although the theoretical mixing lines explained above are for the Cl/Br in some samples. It is clearly observed that the flu-
based on fluids with present-day Na-K-Cl-Br ratios, we be- ids were diluted prior to ore deposition (Fig. 12).
lieve that they can be used to interpret the fossil fluid data. The leachates from the Barambio vein, despite having
Differences in these ratios in Phanerozoic seawater (Lowen- Cl/Br ratios higher than seawater, do not fit well with mixing
stein et al., 2001) are likely smaller than analytical errors of curves involving a halite-dissolution brine. These halogen ra-
crush-leach analyses. tios and salinities could be explained by the presence of a
From the mixing model curve (Fig. 12), it is deduced that third fluid (e.g., seawater or fresh water) that mixed with a
mineralization in most deposits around the Murgía and Or- previously formed mixture of a highly evaporated brine and a
duña salt domes precipitated from mixtures dominated by halite-dissolution brine (dashed line in Fig. 12).
greater than 75 wt percent of fluids dissolving halite, with a The scarcity of microthermometric data in most deposits
significant contribution of a diluted, evaporated brine. In this from the Santander district does not allow a mixing curve to
model curve, the theoretical end member dissolving halite be defined. Also, the effect on the Cl/Br ratio by the sec-
had a salinity of around 26 wt percent NaCl equiv, in accor- ondary fluid inclusions cannot be assessed because their salin-
dance with a halite-saturated fluid at 25ºC. Because homoge- ity is not known. However, fluid mixing could have occurred
nization temperatures measured in the deposits are up to as shown by the presence of samples with different Cl/Br ra-
290ºC, and halite solubility increases with temperature, either tios distributed along the seawater evaporation trajectory. In
the end member did not reach halite saturation or it was this case, one of the end-member fluids could have been a
saturated and subsequently diluted prior to the mixing related highly evaporated brine and the second fluid could have been
to mineralization. The low-salinity end member could be either an evaporated brine that was not halite saturated or a

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 1410 GRANDIA ET AL.

diluted halite-dissolution brine. The Áliva data, with a behav- Conclusions

ior similar to Barambio, could also be related to a diluted Microthermometric data can indicate mixing if one of the
halite-dissolution brine. end members is fresh water or highly diluted fluid, but they
As Na/K and Na/Li ratios in halite are much higher than in cannot identify mixing between fluids with a high proportion
seawater or in any residual fluid after seawater evaporation, of brine. In contrast, halogen data can be used to identify mix-
large variations in these ratios are expected when small pro- ing between brines, potentially allowing for the distinction of
portions of a highly evaporated fluid are added to a brine dis- solute sources from water sources. Combining these data can
solving halite. Consequently, mixing processes can also be provide a quantitative estimate of the relative proportions of
traced by using such ratios. However, unlike Cl/Br, the ratios a variety of different fluids that may be involved in mixing.
involving cations such as Na, K, and Li may be more sensitive Previous microthermometric studies of fluid inclusions in
to fluid-rock interaction. This is evident in some samples from ore and gangue minerals of Mississippi Valley-type deposits
deposits around Murgía and Orduña salt domes, which have from the Basque-Cantabrian basin determined that at least
Na/K and Na/Li ratios orders of magnitude lower than those two fluids were involved in the mineralization. One of them
expected based on the mixing scenarios discussed above (Fig. was highly saline, ca. 25 wt percent NaCl equiv, and the other
9). The mixing model curve used in the plot of Cl/Br versus had a lower but unknown salinity. In this study, the combina-
[Cl] indicates that mixing alone cannot explain the Na/K ra- tion of microthermometric and halogen data has shown that
tios of samples from the salt domes (Fig. 9). Dissolution of K- brines of different origin were involved in the mineralizing
rich salts also cannot account for these low ratios, since they processes: brines derived from seawater evaporation with
are absent in the stratigraphy of the area (Serrano and variable degrees of evaporation, brines dissolving halite from
Martínez del Olmo, 1990). Therefore, other mechanisms salt domes, and low-salinity fluids (seawater or fresh water)
such as halite precipitation or interaction with siliciclastic that acted as dilutants. Data from the Western Biscay district
rocks (Chan et al., 2002) must be invoked. Perona et al. (Txomin, Matienzo, and Barambio deposits) can be ac-
(2002) reported albite precipitation in host rocks from the counted for by mixing between a residual brine and a halite-
Monteleón (Orduña diapir), Aperregui, and Jugo (Murgía di- dissolution brine. On the other hand, most of the ore-forming
apir) deposits, suggesting that the low Na/K ratio could be brines from the studied deposits around Orduña and Murgía
caused, at least in part, by precipitation of autigenic albite salt domes (Altube, Monteleón, Jugo) originated by halite dis-
from the ore-forming fluids. On the other hand, the fluids in solution, although a significant contribution (20–50 wt %)
the Matienzo area show wide ranges in the Na/K ratio, with from a highly evaporated brine was recognized.
all values higher than those for highly evaporated brines (up
to 1,173, beyond the scale of the Fig. 9). These values may be Acknowledgments
explained by the loss of K by absorption and/or precipitation
of a K-rich phase in the sediments. It is interesting to notice This work is part of the Ph.D. thesis of the senior author at
that autigenic K feldspar was recognized in country rocks the Universitat Autònoma de Barcelona. We thank Sarah
near the veins (Simón and Grandia, 1998). Samples from de- Gleeson and an anonymous reviewer for their constructive
posits hosted by carbonate rocks do not show major Na-K-Li comments. Also, we wish to thank Luís Muñoz and Álex
exchange, indicating either differences in the reactivity of the Franco (Ente Vasco de la Energía) for providing samples
rock and/or differences in the water/rock ratio. from Mississippi Valley-type deposits in the Basque-
Although the involvement of highly evaporated brines has Cantabrian basin, and Joachim Beck (Outokumpu Minera
been accepted as an explanation for the Cl/Br ratios of most Española) and Juan García (Ente Vasco de la Energía) for the
Mississippi Valley-type, ore-forming brines (Wilkinson, 2001, use of geological data from the Murgía and Orduña salt
and references therein) with implications for fluid migration domes. This work has been financed through the DGESIC
paths (Leach et al., 2001), the proposed mixing models in this PB98-0901 Project (Spanish Ministry of Education and Cul-
study provide additional information, and possible alternative ture).
explanations for the origin of the halogen ratios. Kesler et al. February 6, 2002; May 28, 2003
(1995) noted similar Na-Cl-Br systematics of fluid inclusions
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