Palaeohydrodynamics of fluids in the Brent Group (Oseberg Field,Norwegian North Sea) from chemical and isotopic compositions of formation waters

Generally, the history of past sub-surface fluid movements is difficult to reconstruct. However, the composition of oil-field waters characterizes the origins and mixing processes that allow such a reconstruction. We have investigated present-day formation waters from Brent Group sedimentary rocks of the Oseberg Field in order to assess both their geochemical variations, and their origin(s). Water samples (sampled at the separator) produced from immediately above the oil–water contact and from the aquifer (water-saturated zone below the oil–water contact) were taken from 11 wells across the field. In addition, 3 trace water samples were extracted from oil produced from higher up in the oil column. The water samples were analysed for their chemical components and isotopic compositions. Conservative tracers such as Cl, Br, δD, and δ¹⁸O were used to evaluate the origin of the waters. All formation waters can be characterised as Na–Cl-brines. The separator samples are of aquifer origin, indicating that aquifer water, drawn up by the pressure reduction near the well, is produced from the lower few tens of metres of the oil-zone. By defining plausible endmembers, the waters can be described as mixtures of seawater (60–90%), meteoric water (10–30%), evaporated seawater (primary brines) (3–5%), and possibly waters which have dissolved evaporites (secondary brines). Alternatively, using multidimensional scaling, the waters can be described as mixtures of only 3 endmembers without presupposing their compositions. In fact, they are seawater, very dilute brine, and a secondary brine (confirming the power of this approach). Meteoric water was introduced into the reservoir during the end-Brent and early-Cretaceous periods of emergence and erosion, and partially replaced the marine pore fluids. Lateral chemical variations across the Oseberg Field are extremely small. The waters from closer to the erosion surfaces show slightly stronger meteoric water isotopic signatures. The primary and secondary brines are believed to come from Permian and Triassic evaporitic rocks in the deeply buried Viking Graben to the west, and to have been modified by water–rock interactions along their migration path. These primary basinal brines have not been detected in the oil–zone waters, suggesting that the brines entered the reservoir after the main phase of oil-migration. There are indications that these external fluids were introduced into the reservoir along faults. Present-day aquifer waters are mixtures of waters from different origins and hardly vary at a field-scale. They are different in composition to the water trapped in the present oil-zone. One of the oil-zone samples is a very dilute brine. It is thought to represent a simple mixture of seawater and meteoric water. Due to oil-emplacement, this geochemical signature was preserved in the waters trapped within the oil-zone. Another oil-zone water shows a very similar chemical signature to the aquifer waters, but the chlorine isotopic signature is similar to that of the dilute oil-zone water. This water is interpreted to represent a palaeo-aquifer water. That is, it was within the aquifer zone in the past, but was trapped by subsequent emplacement of more oil. These vertical differences can be explained by two features: (i) emergence of the Brent Group sedimentary rocks in the Early Cretaceous allowed ingress of meteoric water; (ii) subsequent rapid burial of Viking Graben rocks caused migration of petroleum and aqueous fluids into the adjacent, less deeply buried Oseberg Field.     

Brines in the Carboniferous Sydney Coalfield,Atlantic Canada

Formation waters within Upper Carboniferous sandstones in the sub-sea Prince and Phalen coal mines, Nova Scotia, originated as residual evaporative fluids, probably during the precipitation of Windsor Group (Lower Carboniferous) salts which underlie the coal measures. Salinity varies from 7800 to 176,000 mg/l, and the waters are Na–Ca–Cl brines enriched in Ca, Sr and Br and depleted in Na, K, Mg and SO₄ relative to the seawater evaporation curve. Br:Cl and Na:Cl ratios suggest that the brine composition corresponds to an evaporation ratio of as much as 30. The brines lie close to the meteoric line on H/O isotopic plots but with a compositional range of δ¹⁸O from −4.18 to −6.99 and of δD from −42.4 to −23.5, distant from modern meteoric or ocean water. Mine water composition contrasts with that of nearby salt-spring brines, which are inferred to have originated through dissolution of Windsor Group evaporites by modern meteoric waters. However, a contribution to the mine waters from halite dissolution and from Br in organic matter cannot be ruled out. Present concentrations of several elements in the brines can be explained by water–rock interaction. The original Windsor brines probably moved up into the overlying coal-measure sandstones along faults, prior to the Late Triassic. The high salinity and irregular salinity distribution in the Phalen sandstones suggests that the brines have undergone only modest dilution and are virtually immobile. In contrast, Prince waters show a progressive increase in salinity with depth and are inferred to have mixed with surface waters. Basinal brines from which these modern formation fluids were derived may have been important agents in base-metal and Ba mineralisation from the mid-Carboniferous onwards, as saline fluid inclusions are common in Zn–Pb sulphide deposits in the region.     

A strontium, oxygen and hydrogen isotopic composition of brines, Michigan and appalachian basins, Ontario and Michigan

⁸⁷Sr/⁸⁶Sr ratios of brine from samples from the Michigan and Appalachian Basins, in Ontario and Michigan, covering the stratigraphic interval from the Cambrian to Mississippian, vary from 0.708 to 0.711. With the exception of the salt units of the Salina Formation (Silurian), most values are greater than seawater for the time in question, indicating water-rock interaction. The sources of the radiogenic Sr has not been identified. All samples plot below the GMWL in δ¹⁸O−δ²H space, with the Cambrian and Ordovician samples closest to the line. Mixing of brines meteoric and glacial (Pleistocene) water is indicated in some cases. The more concentrated brines from each stratigraphic unit show a very narrow spread in values. All the Ordovician brines show a narrow range over a 200 km area for Sr, O and H isotopes, indicating extensive lateral migration of the fluids.Strontium in the brine has not equilibrated isotopically with its host rock. In some cases the late-stage minerals saddle dolomite, calcite and anhydrite have the same ⁸⁷Sr/⁸⁶Sr ratios as the brine, indicating that they precipitated from the brine in isotopic equilibrium.     

Metal sources of the Navan carbonate-hosted base metal deposit, Ireland: Nd and Sr isotope evidence for deep hydrothermal convection

Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial ⁸⁷Sr/⁸⁶Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest ¹⁴³Nd/¹⁴⁴Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial ⁸⁷Sr/⁸⁶Sr ratios (maximum 0.7105) and lower initial ¹⁴³Nd/¹⁴⁴Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The ¹⁴³Nd/¹⁴⁴Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.     

Genetic Aspects of the Manto-type Copper Deposits Based on Geochemical Studies of North Chilean Deposits

Recent studies on mineralogy, geochronology, fluid inclusion and stable isotope (Pb, Os, S, C, O, Sr) characteristics were reviewed to determine constraints for genetic models of the Chilean manto‐type copper deposits. The Chilean manto‐type deposits are divided into the two geologic categories of the northern areas (Arica–Iquique, Tocopilla–Taltal) and the central areas (Copiapó, La Serena, Santiago). The former is distributed in the coastal range composed of Jurassic andesite‐dominated volcano‐sedimentary piles and younger plutonic intrusions, and yields chalcocite (‐digenite) and bornite as the principal hypogene copper sulfides. The latter is hosted mostly in Lower Cretaceous volcano‐sedimentary sequences, and has chalcopyrite‐rich mineral associations. The fluid inclusion data indicate that the primary copper mineralization was commonly generated in the temperature range 150–360°C under low‐pressure conditions near the boiling curve, mediated with relatively saline brines. Generally, homogeneous Pb and S isotope compositions for primary copper minerals imply direct magma source or leaching of igneous rocks. Pb and Os isotope data published for some deposits, however, suggest that ore‐forming metals were derived mainly from the volcano‐sedimentary host rocks. The noticeably negative isotope ratios of primary sulfide sulfur and hydrothermal calcite carbon of some central area deposits indicate influx of sedimentary rock components, and the high ⁸⁷Sr/⁸⁶Sr initial ratios of hydrothermal calcite from the Tocopilla–Taltal area deposits imply contribution of the contemporaneous seawater or marine carbonates. These isotopic constraints imply a formation mechanism in which the Chilean manto‐type copper deposits formed epigenetically in the process of hydrothermal interaction of non‐magmatic surface‐derived brine with the volcano‐sedimentary host rocks, which is inferred to have been induced by a deep‐seated plutonic complex as the possible heat source.     

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (～50–140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0–25 wt.% NaCl eq.), low fluid δ¹⁸O values (?10 to +2 ‰ V-SMOW), low fluid δ¹³C values (?9 to ?15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO₄/Cl, NO₃/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na–Ca–Cl basinal brines or shield brines, (3) SO₄–NO₃–Cl–(H)CO₃ playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.     

Messinian Ca–Cl Brines from Mediterranean Basins: Tracing Diagenetic Effects by Ca/Mg Versus Ca/Sr Diagram

In natural resource exploration, Ca–Cl basinal brines are important for understanding the origin and spatial and temporal distribution of hydrocarbons and sedimentary ore deposits. Little attention has been paid to the possible connection between fossil basinal brines and paleo-seawaters and to the implications for reconstructing paleo-seawater compositions. Secular variations of Ca/Mg and Ca/Sr ratios in seawater have been documented mainly using fluid inclusions in halite, calcareous fossils and mineral analyses. However, brines and other sedimentary records connected to paleo-seawater or its evaporated residues may be chemically affected by burial diagenesis or the effects of continental waters of meteoric origin, thus complicating interpretations of the analytical results. To investigate these effects on fluids and minerals related to the Messinian salinity crisis of the Mediterranean basin, we re-evaluate published data from: (1) brackish-to-brine waters from onshore (Northern Apennine foredeep; Levantine basin) and offshore (porewaters from the Deep Sea Drilling Project); (2) Messinian parental seawater deduced from calcareous fossils, fluid inclusions and sulfate minerals; (3) meteoric waters dissolving evaporites. The compositional trends related to seawater evaporation, diagenesis and mixing that affect the Ca/Mg and Ca/Sr molar ratios of the basinal brines are effectively discriminated on a binary plot depicting the proper fields for seawater and meteoric-derived fluids. Brines showing stronger dolomitization start from Ca/Mg and Ca/Sr molar ratios of Messinian seawater deduced from the published analysis of fluid inclusions and open ocean fossils, that are therefore here validated ex post.     

The origin of reservoir fluids in the geothermal field of Los Azufres,Mexico — isotopical and hydrological indications

The calculation of hydrological balance resulted in a potential, average annual infiltration rate of 446±206 mm/m² for the Los Azufres geothermal area, which corresponds to a total of 82×10⁶ m³ per a. Due to the highly fractured and faulted structure of the volcanic formations, a considerable potential for the infiltration of recent meteoric water into deeper sections of the volcanic formations can be assumed. Isotopic data indicate the minor importance of recent meteoric water for the recharge of the geothermal reservoir. Very negative δ¹³C values can be explained by the input of organic C from the surface, but the lack of ¹⁴C in the deep fluids reflects a pre-historic age for the infiltration event of fossil meteoric water. The dilution of the meteoric water by ¹⁴C-free CO₂ gas from a shallow magma chamber complicates the exact age determination of the infiltration event, which probably occurred during the Late Pleistocene or Early Holocene glacial period. Strong water–rock interaction processes, such as sericitization/chloritization, caused the primary brine composition to be camouflaged. A preliminary hydrological model of the reservoir can be postulated as follows: the fossil hydrodynamic system was characterized by the infiltration of meteoric water and mixing with andesitic and/or magmatic water. Strong water–rock interaction processes in the main part of the production zone prove the existence of former active fluid circulation systems. Due to changes in pressure and temperature, the rising fluids get separated into liquid and vapour phases at a depth of 1500 m. After cooling, the main portions of both phases remain within the convective reservoir cycle. Isotope analyses of hot spring waters indicate the direct communication of the reservoir with the surface at some local outcrops. A recent reactivation of the hydrodynamic system is caused by the geothermal production, as indicated by the detection of lateral communication between some production and reinjection wells.     

Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano,Italy

This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and ⁸⁷Sr/⁸⁶Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and ⁸⁷Sr/⁸⁶Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water–rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average ⁸⁷Sr/⁸⁶Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704–0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher ⁸⁷Sr/⁸⁶Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO₄ and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites).     

Origin of salinity in produced waters from the Palm Valley gas field,Northern Territory,Australia

The chemical composition and evolution of produced waters associated with gas production in the Palm Valley gas field, Northern Territory, has important implications for issues such as gas reserve calculations, reservoir management and saline water disposal. The occurrence of saline formation water in the Palm Valley field has been the subject of considerable debate. There were no occurrences of mobile water early in the development of the field and only after gas production had reduced the reservoir pressure, was saline formation water produced. Initially this was in small quantities but has increased dramatically with time, particularly after the initiation of compression in November 1996.The produced waters range from highly saline (up to 300,000 mg/L TDS), with unusual enrichments in Ca, Ba and Sr, to low salinity fluids that may represent condensate waters. The Sr isotopic compositions of the waters (⁸⁷Sr/⁸⁶Sr = 0.7041–0.7172) are also variable but do not correlate closely with major and trace element abundances. Although the extreme salinity suggests possible involvement of evaporite deposits lower in the stratigraphic sequence, the Sr isotopic composition of the high salinity waters suggests a more complex evolutionary history.The formation waters are chemically and isotopically heterogeneous and are not well mixed. The high salinity brines have Sr isotopic compositions and other geochemical characteristics more consistent with long-term residence within the reservoir rocks than with present-day derivation from a more distal pool of brines associated with evaporites. If the high salinity brines entered the reservoir during the Devonian uplift and were displaced by the reservoir gas into a stagnant pool, which has remained near the reservoir for the last 300–400 Ma, then the size of the brine pool is limited. At a minimum, it might be equivalent to the volume displaced by the reservoired gas.     

On the origin of saline fluids in the KTB (Continental Deep Drilling Project of Germany)

Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m³ Ca–Na–Cl brines with about 68 g l⁻¹ total dissolved solids (TDS) and some 270 m³ associated gases, mainly N₂ and CH₄ were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water–rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous–Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high ³⁶Cl/Cl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in U–Th, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes, capable of supplying sufficient neutron flux for considerable subsurface production of ³⁶Cl. The Na–Cl–(K-, SO₄) precursor fluids of the Ca–Na–Cl brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.     

Strontium isotopic composition of oil-field and gas-field waters,Japan

The⁸⁷Sr/⁸⁶Sr ratios of 10 formation waters in petroleum and natural gas reservoirs along the western coast of northeastern Honshu, Japan, ranged from 0.7052 to 0.7084, and are distinctly lower than the ratio in seawater. This forms a marked contrast to oil-field brines from the U.S.A. which have higher⁸⁷Sr/⁸⁶Sr ratios. Taking into consideration that petroleum and natural gas in Japan accumulate in volcanic rocks derived from intense submarine volcanism in the Middle Miocene, the⁸⁷Sr/⁸⁶Sr ratios of the water samples are explained in terms of the isotope exchange between waters containing seawater Sr and reservoir rocks with lower ratios.     

Geology and ore genesis of the late Paleozoic Heijianshan Fe oxide–Cu (–Au) deposit in the Eastern Tianshan,NW China

The Heijianshan Fe–Cu (–Au) deposit, located in the Aqishan-Yamansu belt of the Eastern Tianshan (NW China), is hosted in the mafic–intermediate volcanic and mafic–felsic volcaniclastic rocks of the Upper Carboniferous Matoutan Formation. Based on the pervasive alteration, mineral assemblages and crosscutting relationships of veins, six magmatic–hydrothermal stages have been established, including epidote alteration (Stage I), magnetite mineralization (Stage II), pyrite alteration (Stage III), Cu (–Au) mineralization (Stage IV), late veins (Stage V) and supergene alteration (Stage VI). The Stage I epidote–calcite–tourmaline–sericite alteration assemblage indicates a pre-mineralization Ca–Mg alteration event. Stage II Fe and Stage IV Cu (–Au) mineralization stages at Heijianshan can be clearly distinguished from alteration, mineral assemblages, and nature and sources of ore-forming fluids.Homogenization temperatures of primary fluid inclusions in quartz and calcite from Stage I (189–370 °C), II (301–536 °C), III (119–262 °C) and V (46–198 °C) suggest that fluid incursion and mixing probably occurred during Stage I to II and Stage V, respectively. The Stage II magmatic–hydrothermal-derived Fe mineralization fluids were characterized by high temperature (>300 °C), medium–high salinity (21.2–56.0 wt% NaCl equiv.) and being Na–Ca–Mg–Fe-dominated. These fluids were overprinted by the external low temperature (<300 °C), medium–high salinity (19.0–34.7 wt% NaCl equiv.) and Ca–Mg-dominated basinal brines that were responsible for the subsequent pyrite alteration and Cu (–Au) mineralization, as supported by quartz CL images and H–O isotopes. Furthermore, in-situ sulfur isotopes also indicate that the sulfur sources vary in different stages, viz., Stage II (magmatic–hydrothermal), III (basinal brine-related) and IV (magmatic–hydrothermal). Stage II disseminated pyrite has δ³⁴S_fluid values of 1.7–4.3‰, comparable with sulfur from magmatic reservoirs. δ³⁴S_fluid values (24.3–29.3‰) of Stage III Type A pyrite (coexists with hematite) probably indicate external basinal brine involvement, consistent with the analytical results of fluid inclusions. With the basinal brines further interacting with volcanic/volcaniclastic rocks of the Carboniferous Matoutan Formation, Stage III Type B pyrite–chalcopyrite–pyrrhotite assemblage (with low δ³⁴S_fluid values of 4.6–10.0‰) may have formed at low fO₂ and temperature (119–262 °C). The continuous basinal brine–volcanic/volcaniclastic rock interactions during the basin inversion (∼325–300 Ma) may have leached sulfur and copper from the rocks, yielding magmatic-like δ³⁴S_fluid values (1.5–4.1‰). Such fluids may have altered pyrite and precipitated chalcopyrite with minor Au in Stage IV. Eventually, the Stage V low temperature (∼160 °C) and low salinity meteoric water may have percolated into the ore-forming fluid system and formed late-hydrothermal veins.The similar alteration and mineralization paragenetic sequences, ore-forming fluid sources and evolution, and tectonic settings of the Heijianshan deposit to the Mesozoic Central Andean IOCG deposits indicate that the former is probably the first identified Paleozoic IOCG-like deposit in the Central Asian Orogenic Belt.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

Geochemical evolution of groundwater in the Cambrian–Vendian aquifer system of the Baltic Basin

The shallowly buried marginal part of the Cambrian–Vendian confined aquifer system of the Baltic Basin is characterised by fresh and low δ¹⁸O composition water, whereas the deeply settled parts of the aquifer are characterized by typical Na–Ca–Cl basinal brines. Spatial variation in water geochemistry and stable isotope composition suggests mixing origin of the diluted water of three end-members—glacial melt water of the Weichselian Ice Age (115 000–10 000 BP), Na–Ca–Cl composition basin brine and modern meteoric water. The mixing has occurred in two stages. First, the intrusion and mixing of isotopically depleted glacial waters with basinal brines occurred during the Pleistocene glacial periods when the subglacial melt-water with high hydraulic gradient penetrated into the aquifer. The second stage of mixing takes place nowadays by intrusion of meteoric waters. The freshened water at the northern margin of the basin has acquired a partial equilibrium with the weakly cemented rock matrix of the aquifer.     

On the origin of saline fluids in the KTB (continental deep drilling project of Germany)

Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m³ CaNaCl brines with about 68 g l⁻¹ total dissolved solids (TDS) and some 270 m³ associated gases, mainly N₂ and CH₄ were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water-rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous-Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high ³⁶ClCl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in UTh, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes capable of supplying sufficient neutron flux for considerable subsurface production of 36C1. The NaCl(K, SO₄) precursor fluids of the CaNaCI brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.     

Oxygen isotopes in the Cretaceous-Paleogene granites of Primorye and some problems of their genesis

The Cretaceous-Paleogene granites of the Eastern Sikhote Alin volcanic belt (ESAVB) and Late Cretaceous granitoids of the Tatibin Series (Central Sikhote Alin) are subdivided into three groups according to their oxygen isotope composition: group I with δ¹⁸O from +5.5 to +6.5‰, group II with δ¹⁸O from +7.6 to +10.2‰, and group III with less than +4.5‰. Group I rocks are similar in oxygen isotope composition to that of oceanic basalts and can be derived by melting of basaltic crust. Group II (rocks of the Tatibin Series) have higher δ¹⁸O, which suggests that their parental melts were contaminated by sedimentary material. The low ¹⁸O composition of group III rocks can be explained by their derivation from ¹⁸O-depleted rocks or by subsolidus isotopic exchange with low-¹⁸O fluid or meteoric waters. The relatively low δ¹⁸O and ⁸⁷Sr/⁸⁶Sr in the granitoids of Primorye suggest their derivation from rocks with a short-lived crustal history and can result from the following: (1) melting of sedimentary rocks enriched in young volcanic material that was accumulated in the trench along the transform continental margin (granites of the Tatibin Series) and (2) melting of a mixture of abyssal sediments, ocean floor basalts, and upper mantle in the lithospheric plate that subsided beneath the continent in the subduction zone (granites of the ESAVB).     

Comparison of the Sr isotopic signatures in brines of the Canadian and Fennoscandian shields

A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L⁻¹ below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L⁻¹ below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of ⁸⁷Sr/⁸⁶Sr ratios for the deep brines in different selected sites. All sites show a specific ⁸⁷Sr/⁸⁶Sr signature and the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the ⁸⁷Sr/⁸⁶Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained ⁸⁷Sr/⁸⁶Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.     

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemical Evidence of 13C,18O and 87Sr/86Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and 87Sr/86Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than ?5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate-derived, with the δ13C generally more than ?2.0‰PDB, δ18O less than ?10.0‰PDB, Z value more than 120 and 87Sr/86Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid (including possibly a little mantle-derived fluid or meteoric water), with the δ13C generally ranging from ?2.0‰ to ?8.0‰PDB, δ18O from ?10.0‰ to ?18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to ?10.0‰PDB, δ18O less than ?8.0‰PDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.     

Formation of magnesite and siderite deposits in the Southern Urals—evidence of inclusion fluid chemistry

World-class deposits of magnesite and siderite occur in Riphean strata of the Southern Urals, Russia. Field evidence, inclusion fluid chemistry, and stable isotope data presented in this study clearly proof that the replacement and precipitation processes leading to the formation of the epigenetic dolomite, magnesite and hydrothermal siderite were genetically related to evaporitic fluids affecting already lithified rocks. There is, however, a systematic succession of events leading to the formation of magnesite in a first stage. After burial and diagenesis the same brines were modified to hot and reducing hydrothermal fluids and were the source for the formation of hydrothermal siderite. The magnesites of the Satka Formation as well as the magnesites and the siderites of the Bakal Formation exhibit low Na/Br (106 to 222) and Cl/Br (162 to 280) ratios plotting on the seawater evaporation trend, indicating that the fluids acquired their salinity by evaporation processes of seawater. Temperature calculations based on cation exchange thermometers indicate a formation temperature of the magnesites of?~?130 °C. Considering the fractionation at this temperature stable isotope evidence shows that the magnesite forming brines had δ¹⁸O_SMOW values of?~?+1 ‰ thus indicating a seawater origin of the original fluid. Furthermore it proves that these fluids were not yet affected by appreciable fluid-rock interaction, which again implies magnesite formation in relatively high crustal levels. In contrast to the magnesites, the siderite mineralization was caused by hydrothermal fluids that underwent more intense reactions with their host rocks in deeper crustal levels compared to the magnesite. The values of ⁸⁷Sr ^/86Sr in the siderites are substantially higher compared to the host rock slates. They also exceed the ⁸⁷Sr ^/86Sr ratios of the magnesites and the host rock limestones indicating these slates as the source of iron as a consequence of water-rock interaction. The siderites were formed at temperatures of?~?250 °C indicating a relatively heavy fluid in equilibrium with siderite of 13 ‰ δ¹⁸O_SMOW, which is in the range of diagenetic/metamorphic fluids and reflects the?±?complete equilibration with the host rocks. Carbon isotope evidence shows that the fluid forming the siderites underwent a much higher interaction with the host rocks resulting in a lowering of the δ¹³C numbers (?3,3 to ?3,7 ‰). The light carbon was most probably derived from decaying hydrocarbons in the Riphean sediments. In a very early stage after sedimentation of the Satka Formation (~1,550 Ma) magnesite was formed by seepage reflux of evaporitic bittern brines at the stage of riftogenic activity in the region (1,380–1,350 Ma). Sedimentation of the Bakal Formation (~1,430 Ma) and intrusion of diabase dykes (1,386?±?1,4 Ma) followed. Diagenetic/epigenetic mobilization of these buried fluids at?~?1,100 Ma resulted in the formation of hydrothermal siderite bodies.