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1.
The Korba aquifer on the east coast of Cape Bon has been overexploited since the 1960s with a resultant reversal of the hydraulic gradient and a degradation of the quality due to seawater intrusion. In 2008 the authorities introduced integrated water resources planning based on a managed aquifer recharge with treated wastewater. Water quality monitoring was implemented in order to determine the different system components and trace the effectiveness of the artificial recharge. Groundwater samples taken from recharge control piezometers and surrounding farm wells were analyzed for their chemical contents, for their B isotopes, a proven tracer of groundwater salinization and domestic sewage, and their carbamazepine content, an anti-epileptic known to pass through wastewater treatment and so recognized as a pertinent tracer of wastewater contamination. The system equilibrium was permanently disturbed by the different temporal dynamics of continuous processes such as cation exchange, and by threshold processes linked to oxidation–reduction conditions. The B isotopic compositions significantly shifted back-and-forth due to mixing with end-members of various origin. Under the variable contribution of meteoric recharge, the Plio-Quaternary groundwater (δ11B of 35–40.6‰, a mean B concentration of 30 μmol/L, no carbamazepine, n = 7) was subject to seawater intrusion that induced a high δ11B level (δ11B of 41.5–48.0‰, a mean B concentration of 36 μmol/L, and n = 8). Fresh groundwater (δ11B of 19.89‰, B concentration of 2.8 μmol/L, no carbamazepine) was detected close to the recharge site and may represent the deep Miocene pole which feeds the upper Plio-Quaternary aquifer. The managed recharge water (δ11B of 10.67–13.8‰, n = 3) was brackish and of poor quality with a carbamazepine content showing a large short term variability with an average daily level of 328 ± 61 ng/L. A few piezometers in the vicinity of the recharge site gradually acquired a B isotopic composition close to the wastewater signature and showed an increasing carbamazepine content (from 20 to 910 ng/L). The combination of B isotopic signatures with B and carbamazepine contents is a useful tool to assess sources and mixing of treated wastewaters in groundwaters. Effluent quality needs to be greatly improved before injection to prevent further degradation of groundwater quality.  相似文献   

2.
This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ34SSO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ18OSO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ34SSO4 and δ18OSO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II1) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ34SSO4 and δ18OSO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II2) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ34SSO4 and δ18OSO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II3) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ34SSO4 and δ18OSO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ34SSO4 = 10–35‰ and δ18OSO4 = 7–20‰), soil sulfate (δ34SSO4 = 5.9‰ and δ18OSO4 = 5.8‰) and sewage water (δ34SSO4 = 10.0‰ and δ18OSO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II3), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ34SSO4 and δ18OSO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.  相似文献   

3.
Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH4 gas content and its C isotopes (δ13CCH4), and select isotope tracers (δ11B, 87Sr/86Sr, δ2H, δ18O, δ13CDIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH4/L. The δ13CCH4 of dissolved CH4 ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH4. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ13CCH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO3 dominated, (3) TDS > 100 mg/L and Na–HCO3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (87Sr/86Sr = 0.7097–0.7166), C (δ13CDIC = −21.3‰ to −4.7‰), and B (δ11B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO3, and higher-mineralized Na–HCO3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.  相似文献   

4.
Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of Th values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (Tmf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H2O during mineralization. The relatively higher average Th at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ18O values indicate that ore-forming hydrothermal fluids in the study area had δ18OH2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly 18O-enriched compared with present-day hydrothermal meteoric water in the area (δ18O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ34S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.  相似文献   

5.
《Applied Geochemistry》2004,19(11):1655-1686
Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N2, Ar, O2, CH4) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O2 reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka (14C) B.P. near the water table to 12.8 ± 0.9 ka (14C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO3 in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO3 in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N2 derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10−3 μmol N L−1 a−1), indicating this process would require >10 ka to reduce the average NO3 concentration in recent recharge to the Holocene background concentration.  相似文献   

6.
《Sedimentary Geology》2006,183(1-2):51-69
The Chicxulub Sedimentary Basin of the northwestern Yucatan Peninsula, Mexico, which was formed because of the largest identified Phanerozoic bolide impact on Earth, became a site of deposition of dominantly marine carbonate sediments during most of the Cenozoic Era. This is a study of the filling and diagenetic history of this basin and surrounding areas. The study makes use of lithologic, biostratigraphic, petrographic, and geochemical data obtained on core samples from boreholes drilled throughout the northwestern Yucatan Peninsula.The core sample data indicate that: 1) The Chicxulub Sedimentary Basin concentrated the deposition of pelagic and outer-platform sediments during the Paleocene and Eocene, and, in places, during the Early Oligocene, as well, and filled during the Middle Miocene, 2) deeper-water limestone also is present within the Paleocene and Lower Eocene of the proposed Santa Elena Depression, which is located immediately south of the Basin, 3) shallow-water deposits are relatively more abundant outside the Basin and Depression than inside, 4) the autigenic and allogenic silicates from the Paleogene formations are the most abundant inside the Depression, 5) sediment deposition and diagenesis within the Basin also were controlled by impact crater topography, 6) the abundance of the possible features of subaerial exposure increases upward and outward from the center of the Basin, and 7) the formation of replacive low-magnesium calcite and dolomite, dedolomitization, dissolution, and precipitation of vug-filling calcite and dolomite cement have been more common outside the Basin than inside.δ18O in whole-rock (excluding vug-filling) calcite from core samples ranges from − 7.14‰ to + 0.85‰ PDB. δ13C varies from − 6.92‰ to + 3.30‰ PDB. Both stable isotopes correlate inversely with the abundance of subaerial exposure features indicating that freshwater diagenesis has been extensive especially outside and at the edge of the Chicxulub Sedimentary Basin.δ18O and δ13C in whole-rock (excluding vug-filling) dolomite ranges from − 5.54‰ to + 0.87‰ PDB and − 4.63‰ to + 3.38‰ PDB, respectively. Most dolomite samples have negative δ18O and positive δ13C suggesting that replacive dolomitization involved the presence of a fluid dominated by freshwater and/or an anomalously high geothermal gradient.Most dolomite XRD-determined mole percent CaCO3 varies between 51 and 56. Replacive dolomite is larger, more euhedral, and less stoichiometric inside the Chicxulub Sedimentary Basin than outside.  相似文献   

7.
Concentrations and isotopic compositions of Hg and Pb were measured in a sediment core collected from Lake Ballinger, near Seattle, Washington, USA. Lake Ballinger has been affected by input of metal contaminants emitted from the Tacoma smelter, which operated from 1887 to 1986 and was located about 53 km south of the lake. Concentrations and loadings of Hg and Pb in Lake Ballinger increased by as much as three orders of magnitude during the period of smelting as compared to the pre-smelting period. Concentrations and loadings of Hg and Pb then decreased by about 55% and 75%, respectively, after smelting ended. Isotopic compositions of Hg changed considerably during the period of smelting (δ202Hg = −2.29‰ to −0.38‰, mean −1.23‰, n = 9) compared to the pre-smelting period (δ202Hg = −2.91‰ to −2.50‰, mean −2.75‰, n = 4). Variations were also observed in 206Pb/207Pb and 208Pb/207Pb isotopic compositions during these periods. Data for Δ199Hg and Δ201Hg indicate mass independent fractionation (MIF) of Hg isotopes in Lake Ballinger sediment during the smelting and post-smelting period and suggest MIF in the ore smelted, during the smelting process, or chemical modification at some point in the past. Negative values for Δ199Hg and Δ201Hg for the pre-smelting period are similar to those previously reported for soil, peat, and lichen, likely suggesting some component of atmospheric Hg. Variations in the concentrations and isotopic compositions of Hg and Pb were useful in tracing contaminant sources and the understanding of the depositional history of sedimentation in Lake Ballinger.  相似文献   

8.
Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε18OSO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent εSO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. δ34SSO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ34SSO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.  相似文献   

9.
This study demonstrates the value of targeted pump and treatment (PAT) to enhance the in situ biodegradation of organic contaminants in groundwater for improved restoration. The approach is illustrated for a plume of phenolic compounds in a sandstone aquifer, where PAT is used for hydraulic containment and removal of dissolved phase contaminants from specific depth intervals. Time-series analysis of the plume hydrochemistry and stable isotope composition of dissolved species (δ34S-SO4, δ13C-CH4, δ13C-TDIC (TDIC = Total Dissolved Inorganic Carbon)) in groundwater samples from high-resolution multilevel samplers were used to deduce changes in the relative significance of biodegradation processes and microbial activity in the plume, induced by the PAT system over 3 years. The PAT system has reduced the maximum contaminant concentrations (up to 6800 mg L−1 total phenols) in the plume by 50% to ∼70% at different locations. This intervention has (i) stimulated in situ biodegradation in general, with an approximate doubling of contaminant turnover based on TDIC concentration, which has increased from <200 mg L−1 to >350 mg L−1, (ii) enhanced the activity of SO4-reducing microorganisms (marked by a declining SO4 concentration with corresponding increase in SO4-δ34S to values >7–14‰V-CDT relative to background values of 1.9–6.5‰V-CDT), and (iii) where the TDIC increase is greatest, has changed TDIC-δ13C from values of −10 to −15‰V-PDB to ∼−20‰V-PDB. This indicates an increase in the relative importance of respiration processes (including denitrification and anaerobic methane oxidation, AMO) that yield 13C-depleted TDIC over fermentation and acetoclastic methanogenesis that yield 13C-enriched TDIC in the plume, leading to higher contaminant turnover. The plume fringe was found to be a zone of enhanced biodegradation by SO4-reduction and methanogenesis. Isotopically heavy methane compositions (up to −47.8‰V-PDB) and trends between δ13C-TDIC and δ13C-CH4 suggest that AMO occurs at the plume fringe where the contaminant concentrations have been reduced by the PAT system. Mass and isotope balances for inorganic carbon in the plume confirm the shift in spatial dominance of different biodegradation processes and significant increase in contribution of anaerobic respiration for contaminant biodegradation in zones targeted by the PAT system. The enhanced in situ biodegradation results from a reduction in organic contaminant concentrations in the plume to levels below those that formerly suppressed microbial activity, combined with increased supply of soluble electron acceptors (e.g. nitrate) into the plume by dispersion. An interruption of the PAT system and recovery of the dissolved organic contaminant concentrations towards former values highlights the dynamic nature of this enhancement on restoration and relatively rapid response of the aquifer microorganisms to changing conditions induced by the PAT system. In situ restoration using this combined engineered and passive approach has the potential to manage plumes of biodegradable contaminants over shorter timescales than would be possible using these methods independently. The application of PAT in this way strongly depends on the ability to ensure an adequate flux of dissolved electron acceptors into the plume by advection and dispersion, particularly in heterogeneous aquifers.  相似文献   

10.
A large number of Paleoproterozoic borate deposits are hosted by the lower units of a volcanic-sedimentary sequence in Liaoning Province, northeastern China, and are a major source of boron in China. The ore-bearing wall rocks in the deposits are serpentinized ultrabasic rocks and carbonates, with layered leptynites, leptites, amphibolites, and migmatites adjacent to the ore. Both the borate ores and country rocks contain tourmaline, although the country rocks have much lower abundances of the mineral. Based on in situ boron isotope measurements using laser ablation–multi-collector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS), boron isotope data show that: (1) δ11B values of borate ores range from + 6.8‰ to + 13.9‰ (mean + 10.8‰); (2) tourmalines from the borate ores have δ11B values from + 9.5‰ to + 12.7‰; and (3) the wall rocks within the borate ores yield slightly lower δ11B values ranging from + 5.7‰ to + 7.6‰, and those outside the deposits from − 9.9‰ to − 5.9‰. Positive δ11B values in borates as well as in tourmalines inside the mining area indicate that boron in these Paleoproterozoic borate deposits was derived from marine evaporites. δ34SV-CDT (where V-CDT is Vienna Canyon Diablo Troilite) values of borate ores, serpentinized marbles, and anhydrites range from + 16.1‰ to + 24.7‰, whereas δ13CV-PDB (where V-PDB is Vienna Pee Dee Belemnite) values of marbles range from + 3.2‰ to + 5.9‰. These isotopic characteristics are interpreted to reflect formation in a marine evaporative environment. LA–MC–ICP–MS zircon weighted207Pb/206Pb ages of leptite and serpentinized olivine basalt from the hanging wall of the borate deposits are 2139 ± 13 Ma and 2130 ± 19 Ma, respectively. Therefore, the (~ 2.2 Ga) borate deposits may have originated from marine evaporative boron-bearing sediments, which were interbedded within bimodal volcanic rocks during the early stages of development of the Liaoji rift.  相似文献   

11.
《Applied Geochemistry》2005,20(4):789-805
Mineralogical, hydrochemical and S isotope data were used to constrain hydrogeochemical processes that produce acid mine drainage from sulfidic waste at the historic Mount Morgan Au–Cu mine, and the factors controlling the concentration of SO4 and environmentally hazardous metals in the nearby Dee River in Queensland, Australia. Some highly contaminated acid waters, with metal contents up to hundreds of orders of magnitude greater than the Australia–New Zealand environmental standards, by-pass the water management system at the site and drain into the adjacent Dee River.Mine drainage precipitates at Mt. Morgan were classified into 4 major groups and were identified as hydrous sulfates and hydroxides of Fe and Al with various contents of other metals. These minerals contain adsorbed or mineralogically bound metals that are released into the water system after rainfall events. Sulfate in open pit water and collection sumps generally has a narrow range of S isotope compositions (δ34S = 1.8–3.7‰) that is comparable to the orebody sulfides and makes S isotopes useful for tracing SO4 back to its source. The higher δ34S values for No. 2 Mill Diesel sump may be attributed to a difference in the source. Dissolved SO4 in the river above the mine influence and 20 km downstream show distinctive heavier isotope compositions (δ34S = 5.4–6.8‰). The Dee River downstream of the mine is enriched in 34S (δ34S = 2.8–5.4‰) compared with mine drainage possibly as a result of bacterial SO4 reduction in the weir pools, and in the water bodies within the river channel. The SO4 and metals attenuate downstream by a combination of dilution with the receiving waters, SO4 reduction, and the precipitation of Fe and Al sulfates and hydroxides. It is suggested here that in subtropical Queensland, with distinct wet and dry seasons, temporary reducing environments in the river play an important role in S isotope systematics.  相似文献   

12.
《Applied Geochemistry》2005,20(11):2017-2037
The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH4, thermogenic C2+ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH4 is bacteriogenic (Calculated δ13CC1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH4. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ13CC1–C = −35.80‰; Hamitabat Field) and Group-3 (δ13C1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C2+ gases. The Group-2 C2+ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ13C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C2+ gases, produced from one field, were generated from isotopically light marine kerogen (δ13C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C2+ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ13C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (Req = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.  相似文献   

13.
Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in 13C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C1 in C1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C2/C3) vs. δ13C2–δ13C3 and δ13C1 vs. δ13C2–δ13C3, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of 13C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.  相似文献   

14.
《Applied Geochemistry》2005,20(1):23-39
Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (Tmi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (Th)  = 325 ± 5 °C. The boiling zone shows Th = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO2. Positive clathrate melting temperatures (fusion) with Th = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO2 (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ18O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ18O is due to the rock–water interaction at relatively high temperatures. δ13C stable isotope data show a magmatic source with a minor meteoric contribution for CO2. The initial isotopic value δ34SRES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ34S (FeS2) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ18O.  相似文献   

15.
《Organic Geochemistry》2012,42(12):1269-1276
This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ13C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C3 photosynthesis and indicate a wide range of CAM use, with δ13C values ranging from −33.01‰ to −18.54‰ (C27–C33 n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ13Cbulk and δDC31 values with R2 = 0.60 (δ13CC31 and δDC31 values with R2 = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.  相似文献   

16.
This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shellE. desertorum were analyzed for carbonate composition and isotopic composition (δ18O, δ13C). The plants and organic matterE. desertorum were analyzed for organic carbon content and δ13C. The soil carbonate, consisting of calcite plus minor dolomite, has δ18O values from −3.19 to −1.78‰ and δ13C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ13C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shellE. desertorum is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ18Omean = −0.28 ± 0.22‰; δ13Cmean = −4.46 ± 0.58‰). Most of the δ18O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matterE. desertorum varies only slightly in bulk organic carbon δ13C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ13C values (−17.32‰) observed between shellE. desertorum carbonate and organic matterE. desertorum exceeds the value expected for vegetation input, and implies that 30% of carbon in the shellE. desertorum carbonate comes from the consumption of limestone material.  相似文献   

17.
《Applied Geochemistry》2005,20(9):1626-1636
Isotopic composition of NO3 (δ15NNO3 and δ18ONO3) and B (δ11B) were used to evaluate NO3 contamination and identify geochemical processes occurring in a hydrologically complex Basin and Range valley in northern Nevada with multiple potential sources of NO3. Combined use of these isotopes may be a useful tool in identifying NO3 sources because NO3 and B co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The principal cause of elevated NO3 concentrations in residential parts of the study area is wastewater and not natural NO3 or fertilizers. This is indicated by some samples with elevated NO3 concentrations plotting along δ15NNO3 and NO3 mixing lines between natural NO3 from the study area and theoretical septic-system effluent. This conclusion is supported by the presence of caffeine in one sample and the absence of samples with elevated NO3 concentrations that fall along mixing lines between natural NO3 and theoretical percolate below fertilized lawns. Nitrogen isotopes alone could not be used to determine NO3 sources in several wells because denitrification blurred the original isotopic signatures. The range of δ11B values in native ground water in the study area (−8.2‰ to +21.2‰) is large. The samples with the low δ11B values have a geochemical signature characteristic of hydrothermal systems. Physical and chemical data suggest B is not being strongly fractionated by adsorption onto clays. δ11B values from local STP effluent (−2.7‰) and wash water from a domestic washing machine (−5.7‰) were used to plot mixing lines between wastewater and native ground water. In general, wells with elevated NO3 concentrations fell along mixing lines between wastewater and background water on plots of δ11B against 1/B and Cl/B. Combined use of δ15N and δ11B in the study area was generally successful in identifying contaminant sources and processes that are occurring, however, it is likely to be more successful in simpler settings with a well-characterized δ11B value for background wells.  相似文献   

18.
Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCleqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ18OH2O SMOW = 0.2‰ to 4.2‰; δDH2O SMOW = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO32− or CO2 in ore-forming fluid (δ13CPDB = −6.9‰ to −5.7‰, δ18OSMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ34SVCDT = 8.8–14.2‰ and 206Pb/204Pb = 17.156–17.209, 207Pb/204Pb = 15.532–15.508, 208Pb/204Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ18OH2O and δDH2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ18OH2O and δDH2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.  相似文献   

19.
The Hukeng tungsten deposit, located in the Wugongshan area in central part of Jiangxi province, South China, is a large-scale quartz-vein wolframite deposit. It is hosted in the Hukeng granitic intrusion. Based on the mineral assemblage and crosscutting relationship of the veins, three mineralization stages are identified, including: (1) quartz–wolframite stage, (2) quartz–fluorite–wolframite stage, and (3) quartz–pyrite–sphalerite–wolframite stage.The homogenization temperatures of fluid inclusions in vein quartz vary from 220 to 320 °C, and the salinities are from 0 to 10 wt.% NaCl equiv.; corresponding densities range from 0.7 to 1 g/cm3. These features indicated that the ore-forming fluids in the Hukeng tungsten deposit have medium temperature, low density and low salinity.The δ18OSMOW values of quartz range from 10.8‰ to 14.4‰, with corresponding δ18Ofluid values of 3.7‰ to 7.7‰, and δD values of fluid inclusions of between ? 70‰ and ? 55‰. The combined isotopic data indicate that the ore-forming fluids of the Hukeng tungsten deposit were mainly derived from magmatic water, with some minor input from meteoric water.We have carried out molybdenite Re–Os and muscovite 40Ar/39Ar dating to constrain the timing of mineralization. Re–Os dating of six molybdenite samples yielded model ages ranging from 149.1 ± 2.0 to 150.7 ± 3.7 Ma, with an average of 150.0 Ma. The Re–Os analyses give a well-defined 187Re/187Os isochron with an age of 150.2 ± 2.2 Ma (MSWD = 0.60). Hydrothermal muscovite yields a plateau 40Ar/39Ar age of 147.2 ± 1.4 Ma. 40Ar/39Ar age is in good agreement with the Re–Os age. These ages show that the timing of tungsten mineralization occurred at about 150 Ma. Our new data, when combined with published geochronological results from the other major deposits in this region, suggest that widespread W mineralization occurred in the Late Jurassic throughout South China.  相似文献   

20.
Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ74Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ74Ge. Spex and Merck standard solutions yield mean δ74Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ74Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ74Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ74Gepyrite < δ74Gesphalerite < δ74Gegalena, which may be controlled by the kinetic or Rayleigh fractionation.  相似文献   

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