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1.
Thirty-five S isotope analyses obtained from six carbonatite complexes from the Superior Province, Canadian Shield, ranging in age from 1,897 Ma to 1,093 Ma, have δ34SCDT values of between ?4.5‰ and +3.4‰. Pyrrhotite, chalcopyrite and pyrite mineral separates were used. Each complex possesses its own distinct range and mean S isotope composition. The range for Schryburt Lake is: ?4.5‰ to ?3.4‰ ( mean?=??3.9‰), for Big Beaver House: ?3.6‰ to ?1.5‰ (mean?=??2.2‰), for Cargill: ?1.5‰–+0.5‰ (mean?=??0.7‰), for Spanish River: ?0.1‰–+0.1‰ (mean?=?0.0‰), and for Firesand River: +1.3‰–+3.4‰ (mean?=?+1.7‰). A single sample from Carb Lake yielded a δ34SCDT value of +2.8‰. Differences in isotope compositions can be related to isotope effects brought about during melt generation and emplacment, such as variations in fo2 and temperature. The different S and C isotope data for most complexes, however, suggest that the parental melts could have been generated from a heterogeneous mantle source, although process-driven changes cannot be completely ruled out.  相似文献   

2.
Brine extremely rich in potassium, boron and bromine has been discovered from the Middle Triassic Leikoupo Formation at a depth of 4300 m in Sichuan Province. It contains ～50 g/L of K+, >92 g/L of Na+, >12 g/L of B2O3, >2.36 g/L of Br? and ～0.030 g/L of I+. The solid precipitates during evaporation at 25°C include KB5O8·4H2O, K2B4O7·3H2O, MgCl2·6H2O and KMgCl3·6H2O. The brine ranges from 2.2‰ to 2.8‰ (SMOW) in δ18O, ? 38‰ – ? 53‰ (SMOW) in δD, 15.6‰ in δ34S, and 13.5‰–15.1‰ in δ11B. These data, particularly the isotopic composition of boron, indicate that the brine has a composite derivation from marine and nonmarine brines and dissolved marine evaporites in the Triassic system.  相似文献   

3.
《Applied Geochemistry》1995,10(4):447-460
Brines in the Miocene formations of the Upper Silesian Coal Basin have isotopic composition close to SMOW, which identifies them as the connate marine water. However, controversies exist on the origin of brines in the Carboniferous formations. Isotopic and hydrochemical data exclude any relationship to marine water and enrichment by evaporation. The most common brine which occurs at great depths can be identified as the oldest infiltration in a very hot climate (δ18O ⋟ −2‰, δD ⋟ −20‰, Cl− content 34 to 140 g/L). This brine is free of SO42− and U, and rich in Ba2+ and226Ra. Its salinity is probably related to the leaching of evaporites and intensive weathering of rocks during the Rotliegendes.Other brines are difficult to identify because their isotopic contents are within the range of mixing between the oldest brine and the Quaternary waters (δ18O ⋟ 10‰, δD ⋟ 70‰). Isotopic and hydrochemical data allow identification of several occurrences of brine formed by meteoric water of a warm Tertiary climate, after the last marine transgression in the Tortonian. That brine is rich in SO42− and contains moderate contents of226Ra and U. Its salinity is thought to result from leaching of Miocene evaporites. Two other identified types of brines can be related to some infiltration periods before the last marine transgression. The sources in salinity of these 2 types remain unknown. Mining activity results in a common occurrence of mixed brines. When the Quaternary component dominates, its identification is easy from the isotopic composition, whereas the end brine component can ususally be identified by chosen ion ratios and the presence or lack of sulphates.  相似文献   

4.
Abstract

The Upper Triassic Chang 8 Member, the eighth member of the Yanchang Formation, is a key reservoir interval in the Jiyuan area of the Ordos Basin. The reservoir quality of the Chang 8 Member tight sandstones is extremely heterogeneous owing to the widespread distribution of carbonate cements. The carbonate cements commonly develop near sandstone–mudstone interfaces and gradually decrease away from the interfaces to the centres of the sand bodies. However, the content of carbonate cements (≤6%) has a positive correlation with the visual porosity in the Chang 8 Member sandstone, revealing that the carbonate cements contribute to the compaction resistance and the residual primary pores of reservoirs during the diagenetic process. Three main types of carbonate cement are identified: type I (calcite), type II (calcite and ferrocalcite), and type III (dolomite and ankerite). The type I calcite is characterised by enriched δ13C (mean –3.41‰) and δ18O (mean –15.17‰) values compared with the type II (mean δ13C?=?–7.33‰, δ18O?=?–18.90‰) and type III (mean δ13C?=?–10.0‰, δ18O?=?–20.2‰) cements. Furthermore, the mean δ18O value (–4.7‰) of the type I pore fluids is 1.5‰ and 0.9‰ lower than the type II (mean –3.2‰) and type III (mean –3.8‰) pore fluids, respectively. This indicates that the evolving pore fluids experienced some relative strong water–rock interactions that provided the original materials (e.g. Ca2+, Fe3+, and Mg2+) for the carbonate cements during the diagenetic process. The highly saline lake water directly provided the primary material for the type I calcite precipitation, which also provided the material necessary for the precipitation of the type II and type III carbonate cements, causing enriched δ18O values of the pore fluids during the precipitation of the type II and type III carbonate cements. Although the earlier dissolved pores were filled with ferrocalcite, dolomite and ankerite in the middle–late diagenetic stages, some residual pores and fractures remained to become the potential reservoir storage spaces for the oil and gas exploration in the Jiyuan area.  相似文献   

5.
An investigation using environmental isotopes (δ18O and δD) was conducted to gain insight into the hydrological processes of the Ganga Alluvial Plain, northern India. River-water, shallow-groundwater and lake-water samples from the Gomati River Basin were analyzed. During the winter season, the δ18O and δD compositions of the Gomati River water ranged from ?1.67 to ?7.62 ‰ and ?25.08 to ?61.50 ‰, respectively. Deuterium excess values in the river water (+0.3 to ?13 ‰) and the lake water (?20 ‰) indicate the significance of evaporation processes. Monthly variation of δ18O and δD values of the Gomati River water and the shallow groundwater follows a similar trend, with isotope-depleted peaks for δ18O and δD synchronized during the monsoon season. The isotopically depleted peak values of the river water (δ18O?=??8.30 ‰ and δD?=??57.10 ‰) can be used as a proxy record for the isotopic signature of the monsoon precipitation in the Ganga Alluvial Plain.  相似文献   

6.
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.  相似文献   

7.

This study contributes to identifying and spatializing the different types of nitrate sources by combining hydrogeochemical and isotopic data with principal component analysis (PCA) and t-distributed stochastic neighbor embedding (t-SNE) multicriteria statistical methods. The methodology is applied to the strategic Mons Basin chalk aquifer (Belgium). The results are based on a whole dataset containing 72 water samples with analyses of the hydrogeochemical parameters (temperature, pH, electrical conductivity (EC), redox potential, dissolved O2), alkalinity, total organic carbon (TOC), silica (SiO2), major and minor ions (NO3–, NH4+, Ca2+, dissolved Fe and Mn, K+, Mg2+, Na+, Sr2+, Cl–, F–, SO4–, B) and multiple stable isotope ratios (δ11B, δ15N–NO3–, δ18O–NO3–). Compared to classical PCA, the recently developed t-SNE method, which considers nonlinear relationships between variables and preserves local-scale similarities in a low-dimensional space, showed much better performance in discriminating different groups of samples and related zones in the aquifer. t-SNE results combined with isotope ratios highlighted four zones in the aquifer (grouped as A–D) and the presence of denitrification fronts. Group A presents a manure signature (δ15N–NO3– – mean (μ) +12.78‰, standard deviation (σ) 6.48‰; δ11B – μ 29.96‰, σ 6.91‰). Group B exhibits both manure and inorganic fertilizer signatures (δ15N–NO3– – μ 6.27‰, σ 2.55‰; δ11B – μ 15.86‰, σ 9.69‰). Group C shows a contamination by sewage (δ15N–NO3– – μ 12.67‰, σ 5.60‰; δ11B – μ 9.97‰, σ 7.08‰). Group D presents a mixed signature (δ15N–NO3– – μ 9.25‰, σ 2.94‰; δ11B – μ 20.00‰, σ 6.70‰).

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8.
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.  相似文献   

9.
The chemical and isotopic characteristics of the water and suspended particulate materials（SPM） in the Yangtze River were investigated on the samples collected from 25 hydrological monitoring stations in the mainsteam and 13 hydrological monitoring stations in the major tributaries during 2003 to 2007. The water samples show a large variation in both δD（ 30‰ to 112‰） and δ18O（ 3.8‰ to 15.4‰） values. Both δD and δ18O values show a decrease from the river head to the Jinsha Jiang section and then increase downstream to the river mouth. It is found that the oxygen and hydrogen isotopic compositions of the Yangtze water are controlled by meteoric precipitation, evaporation, ice（and snow） melting and dam building. The Yangtze SPM concentrations show a large variation and are well corresponded to the spatial and temporal changes of flow speed, runoff and SPM supply, which are affected by the slope of the river bed, local precipitation rate, weathering intensity, erosion condition and anthropogenic activity. The Yangtze SPM consists of clay minerals, clastic silicate and carbonate minerals, heavy minerals, iron hydroxide and organic compounds. From the upper to lower reaches, the clay and clastic silicate components in SPM increase gradually, but the carbonate components decrease gradually, which may reflect changes of climate and weathering intensity in the drainage area. Compared to those of the upper crust rocks, the Yangtze SPM has lower contents of SiO2, CaO, K2 O and Na2 O and higher contents of TFe2 O3 and trace metals of Co, Ni, Cu, Zn, Pb and Cd. The ΣREE in the Yangtze SPM is also slightly higher than that of the upper crust. From the upper to lower reaches, the CaO and MgO contents in SPM decrease gradually, but the SiO2 content increases gradually, corresponding to the increase of clay minerals and decrease of the carbonates. The δ30SiSPM values（ 1.1‰ to 0.3‰） of the Yangtze SPM are similar to those of the average shale, but lower than those of the granite rocks（ 0.3‰ to 0.3‰）, reflecting the effect of silicon isotope fractionation in silicate weathering process. The δ30SiSPM values of the Yangtze SPM show a decreasing trend from the upper to the middle and lower reaches, responding to the variation of the clay content. The major anions of the river water are HCO 3, SO 4 2, Cl, NO 3, SiO 4 4 and F and the major cations include Ca2＋, Na＋, Mg2＋, K＋ and Sr2＋. The good correlation between HCO3-content and the content of Ca2＋may suggest that carbonate dissolution is the dominate contributor to the total dissolved solid（TDS） of the Yangtze River. Very good correlations are also found among contents of Cl, SO4 2, Na＋, Mg2＋, K＋and Sr2＋, indicating the important contribution of evaporite dissolution to the TDS of the Yangtze River. High TDS contents are generally found in the head water, reflecting a strong effect of evaporation in the Qinghai-Tibet Plateau. A small increase of the TDS is generally observed in the river mouth, indicating the influence of tidal intrusion. The F and NO3 contents show a clear increase trend from the upstream to downstream, reflecting the contribution of pesticides and fertilizers in the Chuan Jiang section and the middle and lower reaches. The DSi shows a decrease trend from the upstream to downstream, reflecting the effect of rice and grass growth along the Chuan Jiang section and the middle and lower reaches. The dissolved Cu, Zn and Cd in the Yangtze water are all higher than those in world large rivers, reflecting the effect of intensive mining activity along the Yangtze drainage area. The Yangtze water generally shows similar REE distribution pattern to the global shale. The δ30SiDiss values of the dissolved silicon vary from 0.5‰ to 3.7‰, which is the highest among those of the rivers studied. The δ30SiDiss values of the water in the Yangtze mainsteam show an increase trend from the upper stream to downstream. Its DSi and δ30SiDiss are influenced by multiple processes, such as weathering process, phytolith growth in plants, evaporation, phytolith dissolution, growth of fresh water diatom, adsorption and desorption of aqueous monosilicic acid on iron oxide, precipitation of silcretes and formation of clays coatings in aquifers, and human activity. The δ34SSO4 values of the Yangtze water range from 1.7‰ to 9.0‰. The SO4 in the Yangtze water are mainly from the SO4 in meteoric water, the dissolved sulfate from evaporite, and oxidation of sulfide in rocks, coal and ore deposits. The sulfate reduction and precipitation process can also affect the sulfur isotope composition of the Yangtze water. The87Sr/86Sr ratios of the Yangtze water range from 0.70823 to 0.71590, with an average value of 0.71084. The87Sr/86Sr ratio and Sr concentration are primary controlled by mixing of various sources with different87Sr/86Sr ratios and Sr contents, including the limestone, evaporite and the silicate rocks. The atmospheric precipitation and anthropogenic inputs can also contribute some Sr to the river. The δ11B values of the dissolved B in the Yangtze water range from 2.0‰ to 18.3‰, which is affected by multifactors, such as silicate weathering, carbonate weathering, evaporite dissolution, atmospheric deposition, and anthropogenic inputs.  相似文献   

10.
Cation and anion concentrations and oxygen and hydrogen isotopic ratios of brines in the Asmari Formation (Oligocene–early Miocene) from the Marun oil field of southwest Iran were measured to identify the origin of these brines (e.g. salt dissolution vs. seawater evaporation) as well as the involvement of water–rock reaction processes in their evolution. Marun brines are characterized by having higher concentrations of calcium (11 000–20 000 mg/L), chlorine (120 000–160 000 mg/L) and bromide (600–1000 mg/L) compared to modern seawater. Samples are also enriched in 18O relative to seawater, fall to the right of the Global Meteoric Water Line and local rain water, and plot close to the halite brine trajectory on the δD versus δ18O diagram. Geochemical characteristics of Marun brines are inconsistent with a meteoric origin, but instead correspond to residual evaporated seawater modified by water–rock interaction, most significantly dolomitization. In addition, anhydrite precipitation or sulphate reduction appears to be important in chemical modification of the Marun brines, as indicated by lower sulphate contents relative to evaporated seawater. Extensive dolomitization, the presence of anhydrite nodules and high salinity fluid inclusions in the upper parts of the Asmari Formation fit a model whereby the Marun brines likely originated from the seepage reflux of concentrated seawater during the deposition of the overlying Gachsaran Formation evaporites in the Miocene. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

11.
The paper presents the results of determinations of stable S and O isotopes of dissolved sulfates and O and H stable isotopes of waters from three ponds, that is, Marczakowe Do?y acid pond, Marczakowe Do?y fish pond and Podwi?niówka acid pit pond, located in the Holy Cross Mountains (south-central Poland). The δ34SV-CDT and δ18OV-SMOW of SO4 2? in waters of three ponds (n = 14) varied from ?16.2 to ?9.5 ‰ (mean of ?13.6 ‰) and from ?8.1 to ?3.2 ‰ (mean of ?4.8 ‰), respectively. The mean δ34S–SO4 2? values were closer to those of pyrite (mean of ?25.4 ‰) and efflorescent sulfate salts (mean of ?25.6 ‰), recorded previously in the Podwi?niówka quarry, than to sulfates derived from other anthropogenic or soil and bedrock sources. The SO4 2? ions formed by bacterially induced pyrite oxidation combined with bacterial (dissimilatory) dissolved sulfate reduction, and presumably with subordinate mineralization of carbon-bonded sulfur compounds, especially in both Marczakowe Do?y ponds. In addition, the comparison of δ18O–SO4 2? and δ18O–H2O values indicated that 75–100 % of sulfate oxygen was derived from water. Due to the largest size, the Podwi?niówka acid pit pond revealed distinct seasonal variations in both δ18O–H2O (?9.2 to ?1.6) and δD–H2O (?29.7 to ?71.3) values. The strong correlation coefficient (r 2 = 0.99) was noted between δ18O–H2O and δD–H2O values, which points to atmospheric precipitation as the only source of water. The sediments of both acid ponds display different mineral inventory: the Marczakowe Do?y acid pond sediment consists of schwertmannite and goethite, whereas Podwi?niówka acid pit pond sediment is composed of quartz, illite, chlorite and kaolinite with some admixture of jarosite reflecting a more acidic environment. Geochemical modeling of two acid ponds indicated that the saturation indices of schwertmannite and nanosized ε-Fe2O3 (Fe3+ oxide polymorph) were closest to thermodynamic equilibrium state with water, varying from ?1.44 to 3.05 and from ?3.42 to 6.04, respectively. This evidence matches well with the obtained mineralogical results.  相似文献   

12.
Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ18O, δD, δ11B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ18O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ11B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ18O = 12.4 ‰, δD = ?29.5 ‰, and δ11B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ18O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ11B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on 18O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ18O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ18O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ18O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.  相似文献   

13.
《Applied Geochemistry》2001,16(1):35-55
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.  相似文献   

14.
Twenty-four brine samples from the Heletz-Kokhav oilfield, Israel, have been analyzed for chemical composition and Li isotope ratios. The chemical composition of the brines, together with geological evidence, suggests derivation from (Messinian) seawater by evaporation that proceeded well into the gypsum stability field but failed to reach the stage of halite crystallization. The present salinity of the samples (18-47 g Cl/L) was achieved by dilution of the original evaporitic brine by local fresh waters. Like brines from other sedimentary basins, the Li/Cl ratios in the Heletz-Kokhav samples show a prominent Li enrichment (five-fold to eight-fold) relative to modern seawater. The isotopic ratios of Li, expressed in the δ 6Li notation, vary from −26.3 to −17.9‰, all values being significantly higher than that of modern seawater (−32‰) irrespective of their corresponding Li concentration (1.0-2.3 mg/L). The isotopic composition of Li and the Li/Cl ratio in the oilfield brines were acquired in two stages: (a) The original evaporated seawater gained isotopically light Li during the diagenetic interaction between the interstitial Messinian brine and the basin sediments. A parent brine with an elevated Li/Cl ratio was formed. The brine was later diluted in the oilfields. (b) The δ 6Li values of the final brines were determined during epigenetic interaction with the Heletz-Kokhav aquifer rocks. At the same time, the Li/Cl ratio inherited from stage (a) remained largely unchanged. This work represents the first use of lithium isotopic composition to elucidate the origin and evolution of formation waters in sedimentary basins.  相似文献   

15.
《Applied Geochemistry》2004,19(6):937-946
Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ18O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ13CDIC ranged from −7.4 to −17.4‰. SO42, Ca2+ and Mg2+ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ13CDIC indicate both open and closed system carbonate evolution. Combined δ13CDIC and Ca2+, Mg2+, and SO42− suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO42−content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ18O, δD and δ13CDIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.  相似文献   

16.
In this study, nineteen brine samples from the Qarhan Salt Lake (QSL) in western China were collected and analyzed for boron (B) and chlorine (Cl) concentrations, total dissolved solids (TDS), pH values and stable B isotopic compositions. The B concentrations and δ11B values of brines in the QSL range from 51.6 mg/L to 138.4 mg/L, and from +9.32‰ to +13.08‰, respectively. By comparison of B concentrations and TDS of brines in QSL with evaporation paths of brackish water, we found that B enrichment of brines primarily results from strong evaporation and concentration of Qarhan lake water. Combining with comparisons of B concentrations, TDS, pH values and δ11B values of brines, previously elemental ratios (K/Cl, Mg/Cl, Ca/Cl, B/Cl) and δ11B values of halite from a sediment core (ISL1A), we observe good correlations between B concentrations and TDS, TDS and pH values, pH and δ11B values of brines, which demonstrate that higher B concentrations and more positive δ11B values of halite indicate higher salinity of the Qarhan paleolake water as well as drier paleoclimatic conditions. Based on this interpretation of the δ11B values of halite in core ISL1A, higher salinity of the Qarhan paleolake occurred during two intervals, around 46–34 ka and 26–9 ka, which are almost coincident with the upper and lower halite-dominated salt layers in core ISL1A, drier climate phases documented from the δ18O record of carbonate in core ISL1A and the paleomoisture record in monsoonal central Asia, and a higher solar insolation at 30°N. These results demonstrate that the δ11B values of halite in the arid Qaidam Basin could be regarded as a new proxy for reconstructing the salinity record of paleolake water as well as paleoclimate conditions.  相似文献   

17.
Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ13C of CH4, C2, C3, and CO2, and δD of CH4. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH4 (29.7–98.6 mol% of total gas volume), N2 (0.8–66.2 mol%), Ar + O2 (0.2–3.4 mol%), and CO2 (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH4. The relatively low δ13C values of CH4 (−89.9‰ to −57.3‰), covariance of δD values of CH4 and H2O, positive correlation between δ13C values of CH4 and CO2, and lack of higher chain hydrocarbons (C3+) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO3, SO4), in addition to organic substrates, controls the occurrence of microbial CH4 in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH4 (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H2O).  相似文献   

18.
The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ13CCARB value of +2.2 ‰. The major groundwater geochemical composition is HCO3 ? > Ca2+ > Mg2+. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg2+/Ca2+ ratios and low Na+, K+ and Si values. Trace element and nutrient concentrations (SO4 2?, NO3 ?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO2 was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ18OH2O), hydrogen (δDH2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ18O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ13CDIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.  相似文献   

19.
The Huize Zn-Pb- (Ag-Ge) district is a typical representative of the well-known medium-to large-sized carbonate-hosted Zn-Pb- (Ag-Ge) deposits, occurring in the Sichuan-Yunnan-Guizhou Pb-Zn Ore-forming Zone. Generally, fluid inclusions within calcite, one of the major gangue minerals, are dominated by two kinds of small (1-10 um) inclusions including pure-liquid and liquid. The inclusions exist in concentrated groups along the crystal planes of the calcite. The ore-forming fluids containing Pb and Zn, which belong to the Na+-K+-Ca2+-Cl--F--SO42- type, are characterized by temperatures of 164-221℃, medium salinity in 5-10.8 wt% NaCl, and medium pressure at 410×105 to 661×105 Pa. The contents of Na+-K+ and C1--F-, and ratios of Na+/K+-Cl-/F- in fluid inclusions present good linearity. The ratios of Na+/K+ (4.66-6.71) and Cl-/F- (18.21-31.04) in the fluid inclusions of calcite are relatively high, while those of Na+/K+ (0.29-5.69) and Cl-/F- (5.00-26.0) in the inclusions of sphalerite and pyrite are rela  相似文献   

20.
The Hoshbulak Zn–Pb deposit is located in South Tianshan, Xinjiang, China. The Zn–Pb orebody is tabular and stratoid in form and it is hosted in calcareous rocks of the Upper Devonian Tan'gaitaer Formation which were thrust over the Carboniferous system. The ores are mineralogically simple and composed mainly of sphalerite, galena, pyrite, calcite, dolomite and exhibit massive, banded, veinlets, colloidal, metasomatic, eutectic, concentric ring and microbial-like fabrics. The Co/Ni ratios of pyrite in the ores range from 0.46 to 0.90 by electron microprobe, which suggested that the Hoshbulak Zn–Pb mineralization was formed in a sedimentary environment. The REE patterns of the hydrothermal calcite coincide well with those of recrystallized micritic limestones, suggesting that the Hoshbulak Pb–Zn mineralization was closely genetically related to limestones of the Tan'gaitaer Formation. The C-, H- and O-isotopic compositions of hydrothermal calcite and dolomite in the ores yield δ13C(VPDB) values ranging from − 1.9‰ to + 2.6‰ (mean 0.79‰), δ18O(VSMOW) values from 22.41‰ to 24.67‰ (mean 23.04‰) and δD values from − 77‰ to − 102‰ for fluid inclusions. It is suggested that the ore-forming fluids, including CO2, were derived from the calcareous strata of the Tan'gaitaer Formation in association with hydrocarbon brines. The δ34S(VCDT) ranges from − 22.3‰ to − 8.5‰ for early ore-stage sulfides and from 5.9‰ to 24.2‰ with a cluster between 14.4‰ and 24.2‰ for the sulfides (pyrite, sphalerite, galena) in the main ore-stage. The ore sulfur may have been derived from evaporite rocks by thermochemical sulfate reduction (TSR) as the predominant mechanism for H2S generation. The Pb-isotopic compositions of the sulfide minerals from the Hoshbulak ores yield 206Pb/204Pb ratios from 17.847 to 18.173, 207Pb/204Pb ratios from 15.586 to 15.873 and 208Pb/204Pb ratios from 37.997 to 38.905, which indicate that the metals were sourced mainly from the Tan'gaitaer Formation. We conclude that the genesis of the Hoshbulak Mississippi Valley-type deposit was closely related to thrust faulting in the South Tianshan orogen of China.  相似文献   

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