Origin and evolution of oilfield brines from Tertiary strata in western Qaidam Basin: Constraints from <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, δ¹⁸O and δ³⁴S of brines were measured from Tertiary strata and Quaternary salt lakes in the western Qaidam Basin. The water chemistry data show that all oilfield brines are CaCl₂ type. They were enriched in Ca²⁺, B³⁺, Li⁺, Sr²⁺, Br⁻, and were depleted in Mg²⁺, SO₄ ²⁻, which indicated that these brines had the characteristics of deeply circulated water. The relationship between δD and δ¹⁸O shows that all data of these brines decline towards the Global Meteoric Water Line (GWL) and Qaidam Meteoric Water Line (QWL), and that the intersection between oilfield brines and Meteoric Water Lines was close to the local spring and fresh water in the piedmont in the western Qaidam Basin. The results suggest that oilfield brines has initially originated from meteoric water, and then might be affected by water-rock metamorphose, because most oilfield brines distribute in the range of metamorphosing water. The ⁸⁷Sr/⁸⁶Sr values of most oilfield brines range from 0.71121 to 0.71194, and was less than that in salt lake water (>0.712), but close to that of halite in the study area. These imply that salt dissolution occurred in the process of migration. In addition, all oilfield brines have obviously much positive δ³⁴S values (ranging from 26.46‰ to 54.57‰) than that of salt lake brines, which was caused by bacterial sulfate reduction resulting in positive shift of δ³⁴S value and depleteed SO₄ ²⁻ in oilfield brines. Combined with water chemical data and δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, δ³⁴S values, we concluded that oilfield brines mainly originate from the deeply circulated meteoric waters, and then are affected by salt dissolution, water-rock metamorphose, sulfate reduction and dolomitization during the process of migration. These processes alter the chemical compositions of oilfield brines and accumulate rich elements (such as B, Li, Sr, Br, K and so on) for sustainable utilization of salt lake resources in the Qaidam Basin.     

柴达木盆地西部古近系和新近系油田卤水资源水化学特征及化学演化

在柴达木盆地西部一些背斜构造单元的古近系-新近系中,赋存储量巨大的油田卤水,有望成为第四系盐湖卤水的后续利用资源。通过对小梁山、南翼山、油泉子、开特米里克、油墩子、油砂山等典型构造区石油钻孔自喷的油田卤水以及地表盐湖卤水、晶间卤水取样分析,讨论了其水化学特征及资源分布,重点通过与海水、青海湖水蒸发曲线对比,分析了油田卤水的化学演化特征。结果表明,油田卤水中K、B、Li资源远超工业开采品位,Br、Sr等也达到工业开采品位,有优越的高品位综合开发利用前景;油田卤水资源元素富集规律表现为平面上以中部南翼山背斜最为富集,向北、向南相对降低,垂向上深部油田卤水比浅层晶间卤水、湖表卤水资源元素相对更为富集;油田卤水的化学演化主要受控于水岩反应、深部水的混合以及蒸发浓缩和盐岩的溶解作用,这些作用为卤水分异演化、富集成矿提供了良好的地球化学条件。     

Isotopic composition (H,O, Cl,Sr) of ground brines of the Siberian Platform

New data on the geochemistry and isotopic composition of chloride brines of the Siberian Platform are presented. The distribution of stable isotopes (²H, ¹⁸O, and ³⁷Cl) in brines of the Tunguska, Angara-Lena, western part of the Yakutian and Olenek artesian basins and ⁸⁷Sr/⁸⁶Sr in brines of the western part of the Olenek artesian basin was studied in the context of the problem of genesis of highly mineralized groundwaters. Results of the study and comparative analysis of the geochemical and isotopic peculiarities of the Siberian Platform brines conform to the theory of brine formation through the interaction of connate waters with enclosing rocks.     

柴达木盆地西部尕斯库勒油田E_3~1油藏成藏条件与机制

柴达木盆地西部原油为盐湖相未成熟—低成熟原油,属于典型的原油成因类型。尕斯库勒油田是柴达木盆地西部最大的油田。从油气生成运移、聚集成藏诸方面,较为系统地研究了该油田中E13 油藏的形成条件,动态地探讨了油藏的形成机制,为该油藏的成因认识和进一步勘探开发提供了科学依据。     

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.     

柴达木盆地西部尕斯库勒油田E31油藏成藏条件与机制

柴达木盆地西部原油为盐湖相未成熟-低成熟原油,属于典型的原油成因类型。尕斯库勒油田是柴达木盆地西部最大的油田。从油气生成运移、聚集成藏诸方面,较为系统地研究了该油田中E1₃ 油藏的形成条件,动态地探讨了油藏的形成机制,为该油藏的成因认识和进一步勘探开发提供了科学依据。     

察尔汗盐湖物质来源的研究

柴达木盆地察尔汗盐湖是一个以氯化物为主的盐湖,然而今天补给该盐湖的水是碳酸盐和硫酸盐型的。所以,该盐湖的物质来源问题是研究其成因的根本问题,也一直是中外学者感兴趣。同时又感到非常棘手的问题,他们提出了各种假说。本文综合了六化学、岩相古地理、Sr和Br的地球化学、古生态、同位素和构造方面的资料,对前人提出的各种假说逐一进行了论证,最后的结论是,察尔汗盐湖的盐类物质有三个来原:通过河流补给的地表化学风化淋滤物质、通过断层补给的油田水和柴达木古湖的遗留物质。否定了海水来源和第三纪含盐系风化淋滤来源的假说。 中更新世末,察尔汗湖从柴达木古湖中完全蚀立出来,并继承了部分从古湖遗留下来的盐类物质。在察尔汗湖蚀立过程中和独立后早期,构造运动比较强烈,通过断层补给的油田水较多,后来随着构造运动的减弱,油田水补给量逐渐减少,而地丧化学风化淋滤物质的补给一直是比较稳定的。     

Fossil brines preserved in the St-Lawrence Lowlands, Québec, Canada as revealed by their chemistry and noble gas isotopes

Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Bécancour, Québec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na-Ca-Cl type, possibly derived from halite dissolution. ⁸⁷Sr/⁸⁶Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2-3% contribution of mantle ³He and large amounts of nucleogenic ²¹Ne^∗ and ³⁸Ar^∗ and radiogenic ⁴He and ⁴⁰Ar^∗. ⁴He/⁴⁰Ar^∗ and ²¹Ne^∗/⁴⁰Ar^∗ ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of ⁴⁰Ar^∗ in brines constrain the residence time of Bécancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian-Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian-Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic ⁴⁰Ar^∗ into the brines. The last thermal event that could have facilitated the liberation of ⁴⁰Ar^∗ into fluids and contributed to mantle ³He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Bécancour brines.     

Fluid-rock interactions in a geothermal Rotliegend/Permo-Carboniferous reservoir (North German Basin)

Comprehensive data on the chemical composition of reservoir rocks and geothermal brines from the geothermal well doublet Groβ Schönebeck (North German Basin) drilled into a Rotliegend sedimentary and Permo-Carboniferous volcanic rock reservoir were sampled over the past years. They were characterized with respect to their major and minor elemental composition including various isotope ratios. The study considered the impact of drilling and reservoir operations on fluid composition and aimed at determining fluid–rock interactions to gain information on fluid origin and hydraulic pathways.The highly saline fluids (up to 265 g/L TDS) show δ ¹⁸O and δD of water (2.7–5.6 and −3.1–15, respectively) as well as δ ³⁴S of sulfate (3.6–5), and ⁸⁷Sr/⁸⁶Sr ratios (0.715–0.716) that resemble Rotliegend brines from an area located around 200 km in the west (the Altmark). Halogen ratios indicated that brines developed predominantly by evaporation of meteoric water (primary brine) together with halite dissolution brine (secondary brine). Indication for mixing with Zechstein brine or with younger meteoric water was not found.No geochemical distinction was possible between fluids deriving from different rock formations (dacites or sedimentary rocks, respectively). This is due to the evolution of the sediments from the effusive rocks resulting in a similar mineralogical and chemical composition and due to a hydraulic connectivity between the two types of rock. This connection existed probably already before reservoir stimulation as indicated by a set of faults identified in the area that could connect the Rotliegend formation with both, the volcanic rocks and the lower units of the Zechstein. Additional geochemical indication for a hydraulic connectivity is given by (1) the very high heavy metal contents (mainly Cu and Pb) in fluids and scaling that derive from the volcanic rocks and were that were also found in increased amounts up at the Zechstein border (Kupferschiefer formation). (2) The ⁸⁷Sr/⁸⁶Sr isotope ratios of fluid samples correspond to the ratios determined for the sedimentary rocks indicating that initially the fluids developed in the sedimentary rocks and circulated later, when faults structures were created by tectonic events into the volcanic rocks.     

Elemental dispersion and stable isotope fractionation during reactive fluid-flow and fluid immiscibility in the Bufa del Diente aureole,NE-Mexico: evidence from radiographies and Li,B, Sr,Nd, and Pb isotope systematics

The 31.6±0.3 Ma old Bufa del Diente alkali-syenite (NE Mexico) intruded a sequence of Cretaceous limestones with intercalated sub-horizontal chert layers. The cherts acted as aquifers that facilitated transport of brines and pegmatitic melts within the shallow-level (<1 kbar) contact-metamorphic aureole. Fluid-driven reactions between chert and marble wallrock, and the influx of late melts and various fluids gave rise to distinct chemical and isotopic signatures within the aquifer and across the zones of infiltration and fluid-driven reaction. Aqueous brines of magmatic origin produced thick wollastonite mantles around the chert layers. Wollastonite formation occurred at the expense of limestone and chert and generated CO₂. This CO₂-induced fluid unmixing into an aqueous brine and a low-density CO₂-rich fluid, which was lost to the overlying marble where it oxidized organic matter and caused ¹³C and ¹⁸O shifts in a zone some 5–10 cm wide. After wollastonite formation, the chert aquifers were locally intruded by pegmatite veins carrying alkali feldspar, quartz, aegirine-augite, eudialyte, zircon, and apatite. Aqueous fluids that exsolved during crystallization of the pegmatite veins escaped along late cross-fractures and migrated along the inner and outer borders of the wollastonite margins. Chemical dispersion patterns of U, Al, Na + K, P, S, Fe, and REE across the chert-to-marble boundary and its metasomatic rims are shown by autoradiography and neutron-induced radiography. Scavenging of cations at mineralogical contacts and cation transport into the marbles occurred only on the mm to cm scale. Isotopic data for Pb and Sr across a simple metachert-marble boundary and for Pb, Sr, Nd, B, and Li across a metachert-pegmatite-marble sequence demonstrate the following: (1) The Pb and Sr isotopic signature of early fluids was buffered by the carbonate wallrock. Only late fluids, shielded from wallrock interaction by a wollastonite mantle, variably preserved a memory of their initial magmatic signature. (2) Since the Nd isotope signature of marble and chert is bound to calcite and clay minerals, systematic shifts to unradiogenic Nd in marble reflect loss of carbonate-bound Nd as the wollastonite margin is approached. Nd in the wollastonite margin is dominated by Nd originally bound to clay minerals. The later emplacement of the pegmatite, which carried the Nd isotope signature of its alkali-syenite source, had little effect on the Nd isotopic composition of the wollastonite rim. (3) Although the Li and B isotopic compositions reflect the alkali-syenite source, they are also affected by isotopic fractionation and partitioning between melt, fluid, and solids.Editorial responsibility J. Hoefs     

Geochemistry of deep formation waters in the Canning Basin,Western Australia,and their relationship to Zn‐Pb mineralization

The Canning Basin contains several Mississippi Valley‐type Zn‐Pb sulphide prospects and deposits in Devonian carbonate reef complexes on the northern edge of the Fitzroy Trough, and in Ordovician and Silurian marine sequences on the northern margin of the Willara Sub‐basin. This study uses the ionic composition and 5D, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr isotopic data on present‐day deep formation waters to determine their origin and possible relationship to the Zn‐Pb mineralizing palaeofluids.

The present‐day Canning Basin formation waters have salinity ranging from typically less than 5000 mg/L up to 250 000 mg/L locally. The brines are mixtures of highly saline water, formed by seawater which evaporated beyond halite saturation (bittern water), with meteoric water ranging in salinity from low (<5000 mg/L) to hypersaline water (up to about 50 000 mg/L) formed by re‐solution of halite and calcium sulphate minerals. The original marine chemical composition of the bittern‐dominated brines was changed to that of a Na‐Ca‐Cl water by addition of Ca and removal of Mg and SO₄, initially by bacterial sulphate reduction and later by dolomitization of carbonate. Other reactions with terrigenous components of the sediment have provided additional Ca and Sr, including a small proportion of ⁸⁷Sr‐rich material. The δ³⁴S values of the bittern‐containing waters are within the range over which marine sulphate has fluctuated from the Ordovician to the Holocene, although one of the hypersaline waters has a value of +6.8%, indicating SO₄ of non‐marine origin. The pH of the bittern‐containing waters is low (about 5) and they contain significant concentrations of dissolved Fe (up to 120 mg/L).

The Canning Basin bitterns appear similar in origin and chemical composition to highly saline marine brines in the Mississippi Salt Dome Basin, USA, which are known to be either metal or sulphide‐rich depending on the organic content of the host rock. In the Canning Basin, mixing of the bittern water with the various types of meteoric water has resulted in decreases in salinity, Na, Ca, Mg, K, Sr, Li and Fe, and increases in HCO₃, SO₄ and pH.

Mixing of the bitterns with other types of metalliferous fluids and/or with sulphate‐containing hypersaline meteoric waters formed from the same marine evaporite sequence should produce ore‐precipitating fluids which are relatively hot and saline, and the resulting ore deposit should be of high grade and contain abundant sulphate minerals. In the southern Canning Basin, this type of mixing and the corresponding style of ore deposit is evident in the evaporite‐associated areas of Zn‐Pb mineralization near the Admiral Bay Fault. If the bitterns mix with low salinity HCO₃‐waters in near‐surface environments, then the ore‐precipitating fluids should have relatively low salinities and carbonate minerals would precipitate during later stages of mixing. In the Lennard Shelf, the present‐day formation waters, the style of the Zn‐Pb deposits, and range of salinity and temperature of the ore‐forming palaeofluids are consistent with this type of mixing.     

Trace-element and Sr–Nd isotopic evidence for the origin of the Sardinian fluorite mineralization (Italy)

The fluorite-bearing hydrothermal mineralization in Sardinia mainly occurs within Paleozoic volcanic and metasedimentary rocks. Only 3 occurrences are located in volcanic and siliciclastic Cenozoic rocks. Most Sardinian fluorites exhibit relatively high rare earth and Y (REY) contents, strong positive Y anomalies, slightly negative Ce and generally positive Eu anomalies. These features indicate that the REY were mobilized mainly from non-carbonate rocks. Neither Sr nor Nd isotopes can be used to date radiometrically the Sardinian fluorites. However, the measured Sr-isotope ratios of the fluorites hosted by Paleozoic rocks fit mixing lines in the 1000/Sr versus ⁸⁷Sr/⁸⁶Sr plot once recalculated at 280 Ma, suggesting that the age inferred for the correction probably represents that of the formation of the fluorite mineralization. Mixing likely occurred between diluted surficial waters and brines circulating mainly through the Lower Paleozoic metasedimentary basement. The Cenozoic fluorites exhibit chemical and isotopic features similar to those of the Paleozoic fluorites, except the Nuraghe Onigu fluorite displaying a possible contribution of Sr from Cenozoic magmatic rocks. The initial ε_Nd values of the Paleozoic fluorites fit the age proposed for the formation of the deposits. Moreover, the values suggest that radiogenic Nd was provided to the fluids from the Ordovician siliciclastic basement, except for 3 deposits where the potential source rocks of Nd were mainly Ordovician acidic magmatic rocks. The initial ε_Nd values of the Cenozoic fluorites suggest a provenance of Nd essentially from the leaching of Variscan granitoids.     

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.     

Geochemistry and Petrogenesis of Intracontinental Basaltic Volcanism on the Northwest Arabian Plate,Gaziantep Basin,Southeast Anatolia,Turkey

Volcanism along the northwest boundary of the Arabian Plate found in the Gaziantep Basin, southeast Turkey, is of Miocene age and is of alkaline and calc-alkaline basic composition. The rare earth element data for both compositional series indicates spinel–peridotite source areas. The rare earth and trace elements of the alkaline lavas originate from a highly primitive and slightly contaminated asthenospheric mantle; those of the calc-alkaline lavas originate from a highly heterogeneous, asthenospheric, and lithospheric mantle source. Partial melting and magmatic differentiation processes played a role in the formation of the petrological features of these volcanics. These rocks form two groups on the basis of their ~(87) Sr/~(86) Sr and ~(143) Nd/~(144) Nd isotopic compositions in addition to their classifications based on their chemical compositions(alkaline and calc-alkaline). These isotopic differences indicate a dissimilar parental magma. Therefore, high Nd isotope samples imply a previously formed and highly primitive mantle whereas low Nd isotope samples may indicate comparable partial melting of an enriched heterogeneous shallow mantle. Other isotopic changes that do not conform to the chemical features of these lavas are partly related to the various tectonic events of the region, such as the Dead Sea Fault System and the Bitlis Suture Zone.     

Insights to magmatic-hydrothermal processes in the Manus back-arc basin as recorded by anhydrite

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REE_N patterns measured in anhydrite from mid-ocean ridge deposits. The REE_N patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. ⁸⁷Sr/⁸⁶Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ³⁴S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ³⁴S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO₂ degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.     

Massive dolomitization of a late Miocene carbonate platform: a case of mixed evaporative brines with meteoric water,Nijar, Spain

Late Miocene platform carbonates from Nijar, Spain, have been extensively dolomitized. Limestones are present in the most landward parts of the platform, in stratigraphically lower units and topographically highest outcrops, suggesting that dolomitizing fluids were derived from the adjacent Nijar Basin. The dolomite crystals range from <10 to ≈100 μm existing as both replacements and cements. Na, Cl and SO₄ concentrations in the dolomites range from 200 to 1700 p.p.m., 250–650 p.p.m., and 600–7000 p.p.m., respectively, comparable with other Tertiary and modern brine dolomite values, and also overlapping values from mixing-zone dolomites. Sr concentrations range between 50 and 300 p.p.m., and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 7× seawater brine to freshwater ratios. The δ¹⁸O and δ¹³C of the dolomites range from ?1·0 to +4·2‰ PDB, and ?4·0 to +2·0‰ PDB, respectively. ⁸⁷Sr/⁸⁶Sr values (0·70899–0·70928) of the dolomites range from late Miocene seawater to values greater than modern seawater. Mixtures of freshwater with seawater and evaporative brines probably precipitated the Nijar dolomites. Modelled covariations of molar Sr/Ca vs. δ¹⁸O and Na/Ca vs. δ¹⁸O from these mixtures are consistent with those of the proposed Nijar dolomitizing fluids. Complete or partial dolomite recrystallization is ruled out by well preserved CL zoning, nonstoichiometry and quantitative water–rock interaction modelling of covariations of Na vs. Sr and δ¹⁸O vs. δ¹³C. The possibility of multiple dolomitization events induced by evaporative brines, seawater and freshwater, respectively, is consistent with mineral-mineral mixing modelling. The basin-derived dolomitizing brines probably mixed with freshwater in the Nijar Basin or mixed with fresh groundwater in the platform, and were genetically related either to deposition of the Yesares gypsum or the Feos gypsum. Dolomitization occurred during either the middle Messinian or the early upper Messinian. Nijar dolomitization models may be applicable to dolomitization of other late Miocene platform carbonates of the western Mediterranean. Moreover, the Nijar models may offer an analogue for more ancient evaporite-absent platform carbonates fringing evaporite basins.     

Dolomitization of the Devonian Swan Hills Formation, Rosevear Field, Alberta, Canada

The Swan Hills Formation (Middle-Upper Devonian) of the Western Canada Basin is host to several NW-SE-trending gas fields developed in massive replacement dolostone. One of these, the Rosevear Field, contains two major dolostone trends along opposing margins of a marine channel that penetrates into a platform-reef complex. Dolostones consist predominantly of branching and bulbous strdmatoporoid floatstones and rudstones with well-developed moldic and vuggy porosity. Replacement dolomite is coarsely crystalline (100-600 μm), inclusion-rich, composed of euhedral through anhedral crystals and has a blotchy to homogeneous red cathodoluminescence. Geochemically, replacement dolomite is characterized by (i) nearly stoichiometric composition (50.1-51.1 mol% CaCO₃), (ii) negative δ¹⁸O values (mean=-7.5‰, PDB) and (iii) variable ⁸⁷Sr/⁸⁶Sr ratios ranging from values similar to Late Devonian-Early Mississippian seawater (～0.7082) to radiogenic compositions comparable to saddle dolomite cements (>0.7100). Dolomitization began after widespread precipitation of early, equant calcite spar and after the onset of pressure solution, implying that replacement dolomite formed in a burial environment. Oxygen isotope data suggest that dolomite formed at 35-75°C, temperatures reached during burial in Late Devonian through Jurassic time, at minimum depths of 450 m. The linear NW-SE orientation of most dolomite fields in the Swan Hills Formation is suggestive of fault control on fluid circulation. Two models are proposed for fault-controlled circulation of dolomitizing fluids at the Rosevear Field. In the first, compaction-driven, updip fluid migration occurred in response to basin tilting commencing in the Late Palaeozoic. Deep basinal fluids migrating updip were focused into channel-margin sediments along fault conduits. The second model calls upon fault-controlled convective circulation of (i) warm Devonian-Mississippian seawater or (ii) Middle Devonian residual evaporitic brines. The overlap in ⁸⁷Sr/⁸⁶Sr and δ¹⁸O compositions, and similar cathodoluminescence properties between replacement and saddle dolomites provide evidence for neomorphism of some replacement dolomite. Quantitative modelling of Sr and O isotopes and Sr abundances suggests partial equilibration of some replacement dolomite with hot radiogenic brines derived during deep burial of the Swan Hills Formation in the Late Cretaceous-Palaeocene. Interaction of replacement dolomite with deep brines led to enrichment in ⁸⁷Sr while leaving δ¹⁸O similar to pre-neomorphism values.     

He,Ne, Ar,and C isotope systematics of geothermal emanations in the Lesser Antilles Islands Arc

We present He, Ne, Ar, and C isotope analyses of hydrothermal brines and gases from fumaroles, hot springs, mofettes and hydrothermal exploration drillings on the major islands of the Lesser Antilles Arc. The origin of hydrothermal brines, which have been analyzed also for O and H isotopes, is essentially meteoric-hydrothermal. Air-corrected isotope compositions of helium (2.2 Rc/Ra < ³He/⁴He < 8.6 Rc/Ra) and carbon (−20 < δ¹³C_PDB < +0.5) are variable and require a variety of crustal and magmatic sources. The diversity of δ¹³C_PDB and ³He/CO₂ ratios within individual volcanic centres suggests that crustal sources (e.g., limestone) contaminate magmatic CO₂ en route from high-level magma reservoirs (depth < 15 km) to the surface. A similar contamination may be found for magmatic helium on distal springs. The ³He/⁴He signature of summit fumaroles, thought to reflect the ³He/⁴He signature of high-level magmas, shows a remarkable systematic variation along the arc. In addition, there is a correlation throughout the arc between published Sr, Pb, and Nd isotope signatures of lavas and the ³He/⁴He signatures of summit fumaroles. On the northern islands (Nevis, Montserrat, Guadeloupe, and Dominica) summit fumaroles have the N-MORB signature (³He/⁴He = 8 ± 1 R/Ra), and the isotope signature of lavas is not dissimilar from comparable intra-oceanic arc tholeiites elsewhere. Variable enrichments in radiogenic Sr and Pb have been reported for lavas of individual volcanic centres of the Southern Islands (Martinique, St.Lucia, and Grenada), and summit fumaroles on these centres match these variations by variable radiogenic He-enrichments, i.e., lower ³He/⁴He ratios. This correlation suggests that radiogenic Sr and Pb enrichments of lavas and low ³He/⁴He signatures on summit fumaroles have a common origin, i.e., a terrigenous contaminant derived from the Orinoco depositionary fan. Crustal assimilation is thought to decouple the He isotope system from any other radiogenic isotope system and, therefore, we argue that the observed correlation of He, Sr, Pb, and Nd isotope systems is related to a terrigenous contaminant derived from subducted sediments. Support for this scenario also comes from the matching of low ³He/⁴He ratios and tectonic features of the forearc thought to favor the subduction of forearc sediments.The present study offers a first clue that, under suitable conditions, crustal helium from oceanic sediments might be subducted to the depth of arc magma sources and, possibly, even recycled into the deeper mantle.     

Genesis of the Jinding Zn-Pb deposit,northwest Yunnan Province,China: Constraints from rare earth elements and noble gas isotopes

The giant sediment-hosted Jinding zinc-lead deposit is located in the Lanping Basin, northwestern Yunnan Province, China. The genesis of the deposit has long been debated and the sources of the ore-forming fluids and metals are controversial. This study presents rare earth element (REE) and noble gas isotope data that constrain the origins of the ore fluids and the heat source driving the hydrothermal circulation. The early-stage sulfides are enriched in light REEs and have high ∑REE values (30.8–94.8 ppm) and weakly negative Eu (δEu 0.85–0.89) and Ce anomalies (δCe 0.84–0.95), suggesting that the fluids were likely derived from dissolution of Upper Triassic marine carbonates with input of REEs from aluminosilicate rocks in the basin. In contrast, the late-stage sulfides have irregular REE patterns, generally low ∑REE values (0.24–10.8 ppm) and positive Eu (δEu 1.22–10.9) and weakly negative Ce anomalies (δCe 0.53–0.90), which suggest that the ore-forming fluids interacted with evaporite minerals. The ³He/⁴He (0.01–0.04 R_a) and ⁴⁰Ar/³⁶Ar values (301–340) of the ore-forming fluids indicate crustal and atmospheric origins for these noble gases. These findings are in agreement with the published fluid inclusion microthermometry data and the results of H, O, C, S, Pb and Sr isotope studies. Our data, in combination with published results, support a two-stage hydrothermal mineralization model, involving early-stage basinal brines and late-stage meteoric water that acquired metals and heat from crustal sources.