Stable Carbon Isotope Variations in Cave Percolation Waters and their Implications in Four Caves of Guizhou, China

Monitoring and sampling of main plants,soil CO2,soil water,bedrock,spring water,drip water and its corresponding speleothem were performed at four cave systems of Guizhou,Southwest China,from April 2003 to May 2004,in order to understand stable carbon isotope ratios variations of dissolved inorganic Carbon(DIC) in cave percolation waters(δ13CDIC) and their implications for paleoclimate.Stable carbon isotopic compositions and ions(Ca,Mg,Sr,SO4,Cl etc.) were measured for all samples.The results indicate that there are significant differences among the δ13CDIC values from inter-cave,even inter-drip of intra-cave in the four caves.The δ13CDIC values from the Liangfeng Cave(LFC) is lightest among the four caves,where vegetation type overlying the cave is primary forest dominated by tall trees with lighter average δ13C value(–29.9‰).And there are remarkable differences in δ13CDIC values of different drip waters in the Qixing Cave(QXC) and Jiangjun Cave(JJC),up to 6.9‰ and 7.8‰,respectively.Further analyses show that the δ13CDIC values in cave drip waters are not only controlled by vegetation biomass overlying the cave,but also hydro-geochemical processes.Therefore,accurate interpreting of δ13C recorded in speleothems cannot be guaranteed if these effects of the above mentioned factors are not taken into consideration.     

Stable carbon isotope biogeochemistry of a shallow sand aquifer contaminated with fuel hydrocarbons

Ground-water chemistry and the stable C isotope composition (δ¹³C_DIC) of dissolved inorganic C (DIC) were measured in a sand aquifer contaminated with JP–4 fuel hydrocarbons. Results show that ground water in the upgradient zone was characterized by DIC content of 14–20 mg C/L and δ¹³C_DIC values of −11.3‰ to −13.0‰. The contaminant source zone was characterized by an increase in DIC content (12.5 mg C/L to 54 mg C/L), Ca, and alkalinity, with a significant depletion of ¹³C in δ¹³C_DIC (−11.9‰ to −19.2‰). The source zone of the contaminant plume was also characterized by elevated levels of aromatic hydrocarbons (0 μg/L to 1490 μg/L) and microbial metabolites (aromatic acids, 0 μg/L to 2277 μg/L), non-detectable dissolved O₂, NO₃ and SO₄. Phospholipid ester-linked fatty acid analyses suggest the presence of viable SO₄-reducing bacteria in ground water at the time of sampling. The ground-water chemistry and stable C isotope composition of ground-water DIC are interpreted using a chemical reaction model involving rainwater recharge, contributions of CO₂ from soil gas and biodegradation of hydrocarbons, and carbonate dissolution. The major-ion chemistry and δ¹³C_DIC were reconciled, and the model predictions were in good agreement with field measurements. It was concluded that stable C isotope measurements, combined with other biogeochemical measures can be a useful tool to monitor the dominant terminal electron-accepting processes in contaminated aquifers and to identify mineralogical, hydrological, and microbiological factors that affect δ¹³C of dissolved inorganic C.     

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

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 δ¹³C_DIC 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 δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC 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 δ¹³C_DIC 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.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

Stable isotope geochemical characteristics of dissolved inorganic carbon in the Jiulong River Estuary,Fujian Province,China

The isotopic composition of dissolved inorganic carbon （DIC） in estuarine environments has been studied for its significant role in determining the isotopic composition of inorganic/organic matter and its applications to the study of various natural processes. In this paper, based on the stable isotope geochemical characteristics of dis- solved inorganic carbon in the Jiulong River Estuary, the following conclusions are drawn： （1） δ13CDIC values are mainly controlled by the mixing ratio of fresh water and sea water; （2）δ13Cphytoplankton values are linearly related to the δ13CDIC values; （3） δ13CpoM values for the Jiulong River Estuary are affected by anthropogenic pollution signifi- cantly; and （4） the comprehensive analysis of δ13Cphytoplankton, δ13CpoM and δ13CDIc shows that along with increasing salinity, the proportion of POM derived from the degradation of phytoplanktons gradually increases.     

Dissolved inorganic carbon (DIC) and hydrologic mixing in a subtropical riverine estuary,southwest Florida,USA

Physical and chemical parameters were measured in a subtropical estuary with a blind river source in southwest Florida, United States, to assess seasonal discharge of overland flow and groundwater in hydrologic mixing. Water temperature, pH, salinity, alkalinity, dissolved inorganic carbon (DIC), δ¹⁸O, and δ¹³C_DIC varied significantly due to seasonal rainfall and climate. Axial distribution of the physical and chemical parameters constrained by tidal conditions during sampling showed that river water at low tide was a mixture of freshwater from overland flow and saline ground-water in the wet season and mostly saline groundwater in the dry season. Relationships between salinity and temperature, δ¹⁸O, and DIC for both the dry and wet seasons showed that DIC was most sensitive to seawater mixing in the estuary as DIC changed in concentration between values measured in river water at the tidal front to the most seaward station. A salinity-δ¹³C_DIC model was able to describe seawater mixing in the estuary for the wet season but not for the dry season because river water salinity was higher than that of seawater and the salinity gradient between seawater and river water was small. A DIC-δ¹³C_DIC mixing model was able to describe mixing of carbon from sheet flow and river water at low tide, and river water and seawater at high tide for both wet and dry seasons. The DIC-δ¹³C_DIC model was able to predict the seawater end member DIC for the wet season. The model was not able to predict the seawater end member DIC for the dry season data due to secondary physical and biogeochemical processes that altered estuarine DIC prior to mixing with seawater. The results of this study suggest that DIC and δ¹³C_DIC can provide additional insights into mixing of river water and seawater in estuaries during periods where small salinity gradients between river water and seawater and higher river water salinities preclude the use of salinity-carbon models.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

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 δ¹³C_CARB 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 (δ¹⁸O_H2O), hydrogen (δD_H2O) 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. δ¹³C_DIC 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 %.     

13C Record of benthic foraminifera in the last interglacial ocean: Implications for the carbon cycle and the global deep water circulation

The ¹³C/¹²C ratios of Upper Holocene benthic foraminiferal tests (genera Cibicides and Uvigerina) of deep sea cores from the various world ocean basins have been compared with those of the modern total carbon dioxide (TCO₂) measured during the GEOSECS program. The δ¹³C difference between benthic foraminifera and TCO₂ is 0.07 ± 0.04‰ for Cibicides and ?0.83 ± 0.07‰ for Uvigerina at the 95% confidence level. δ¹³C analyses of the benthic foraminifera that lived during the last interglaciation (isotopic substage 5e, about 120,000 yr ago) show that the bulk of the TCO₂ in the world ocean had a δ¹³C value 0.15 ± 0.12‰ lower than the modern one at the 95% confidence level, reflecting a depletion, compared to the present value, of the global organic carbon reservoir. Regional differences in δ¹³C between the various oceanic basins are explained by a pattern of deep water circulation different from the modern one: the Antarctic Bottom Water production was higher than today during the last interglaciation, but the eastward transport in the Circumpolar Deep Water was lower.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

Isotope geochemistry (O, C, S, Sr) and Rb-Sr age of carbonatites in central Tuva

The Rb-Sr isochron age of igneous ankerite-calcite and siderite carbonatites in central Tuva is estimated at 118 ± 9 Ma. The following ranges of initial values of O, C, Sr, and sulfide and S isotopic compositions were established: δ¹⁸O_carb = +(8.8?14.7)‰, δ¹³C_carb = ?(3.6?4.9)‰, δ¹⁸O_quartz = +(11.6?13.7)‰, δ³⁴S_pyrite = +(0.3?1.1)‰, and (⁸⁷Sr/⁸⁶Sr)_i =0.7042?0.7048 for ankerite-calcite carbonatite and δ¹⁸O_sid = +(9.2?12.4)‰, δ¹³C_sid = ?(3.9?5.9)‰, δ¹⁸O_quartz = +(11.2?11.4)‰, δ³⁴S_pyrite = ?(4.4–1.8)‰, δ³⁴S_sulfate = +(8.6?14.5)‰, and (⁸⁷Sr/⁸⁶Sr)_i = 0.7042?0.7045 for siderite carbonatite. The obtained isotopic characteristics indicate that both varieties of carbonatites are cognate and their mantle source is comparable with the sources of Late Mesozoic carbonatites in the western Transbaikal region and Mongolia. The revealed heterogeneity of isotopic compositions of carbonatites is caused by their contamination with country rocks, replacement with hydrothermal celestine, and supergene alteration.     

Controls on the δ13CDIC and alkalinity budget of a flashy subtropical stream (Manoa River,Hawaii)

Hawaiian streams are flashy in nature because watersheds are small and steep and receive intense and unevenly distributed rainfall. As a result, stream chemistry is characterized by considerable spatiotemporal variability. To examine how rainfall and streamflow affect the solute content of the Manoa River in Hawaii, time-series geochemical data collected during 17 sampling campaigns in spring-fall of 2010 were evaluated in a coupled δ¹³C_DIC/major ion inversion model. Spatially, the stream is characterized by a distinct shift from a low HCO₃ (43 mg/L), low pCO₂ (3760 ppmv) and heavy δ¹³C_DIC (−6.5‰) fingerprint in the upper reaches to a high HCO₃ (91 mg/L), high pCO₂ (8961 ppmv) and light δ¹³C_DIC (−11.7‰) signature in the lowlands. These trends are attributed to (1) progressive weathering of exposed aluminosilicates, and (2) downstream enrichment in CO₂ from organic matter decay in the soil zone. Solute (i.e., nitrate) yields from nitric acid weathering are generally low (<1% of TDS), even in the developed lowlands, where runoff of nitrate-enriched urban effluent has historically been documented. Data furthermore indicate a significant positive correlation between δ¹³C_DIC and rainfall rates in the mid-stream section of the river which is consistent with an atmospheric CO₂ dilution effect during high rainfall events. This dilution effect needs to be accounted for to reliably describe the role of volcanic island river systems in global assessments of silicate weathering and CO₂ degassing.     

Hydrogen and Oxygen Isotope Study on the Water-Rock Interaction of the Yinshan (Cu-) Pb-Zn-Ag Ore Deposit, Jiangxi Province

The δ18O values of vein quartz of different stages from the Yinshan ore deposit are constant around 16‰ and the calculated δ18OH2O values attain 8‰± ; the δDH2O values of fluid inclu-sions in vein quartz are constant at about-60‰. From the surface down to 1200 m below the δ18O values of altered rocks gradually decrease from 15‰± to 11‰± . Various water-rock inversion calculations indicate that the ore fluids were formed by the interaction between meteoric water and phyllite at 350℃ and the effective W/ R value of around 0.1. When the water-rock exchange in the upper mineralization system took place, the effective W / R value increased to 5.0 or more. As a result, an evolution and mineralization model of a buffered open system with two-stage water-rock interactions is proposed in this study.     

Application of carbon isotopes to detect seepage out of coalbed natural gas produced water impoundments

Coalbed natural gas (CBNG) production from coal bed aquifers requires large volumes of produced water to be pumped from the subsurface. The produced water ranges from high quality that meets state and federal drinking water standards to low quality due to increased salinity and/or sodicity. The Powder River Basin of northeastern Wyoming is a major coalbed natural gas producing region, where water quality generally decreases moving from the southeastern portion of the basin towards the center. Most produced water in Wyoming is disposed into impoundments and other surface drainages, where it may infiltrate into shallow groundwater. Groundwater degradation caused by infiltration of CBNG produced water holding impoundments into arid, soluble salt-rich soils is an issue of immense importance because groundwater is a major source for stock water, irrigation, and drinking water for many small communities in these areas. This study examines the potential of using stable C isotope signatures of dissolved inorganic C (δ¹³C_DIC) to track the fate of CBNG produced water after it is discharged into the impoundments. Other geochemical proxies like the major cations and major anions were used in conjunction with field water quality measurements to understand the geochemical differences between CBNG produced waters and ambient waters in the study area. Samples were collected from the CBNG discharge outfalls, produced water holding impoundments, and monitoring wells from different parts of the Powder River Basin and analyzed for δ¹³C_DIC. The CBNG produced waters from outfalls and impoundments have positive δ¹³C_DIC values that fall within the range of +12‰ to +22‰, distinct from the ambient regional surface and groundwaters with δ¹³C_DIC values ranging from −10‰ to −14‰. The results from the study demonstrate that these contrasting δ¹³C_DIC signatures can be used to trace seepage out of CBNG produced water impoundments into shallow groundwaters.     

Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

热液体系氩同位素示踪研究

 采用分阶段加热爆裂法测定了不同成因热液矿床脉石英流体包裹体的氩同位素,计算出各温度段内大气氩的相对含量,从而,总结出大气降水热液矿床、再平衡岩浆水热液矿床等成矿流体的氩同位素组成特征及其演化规律。典型的大气降水热液矿床,其成矿流体以具有高大气Ar组分(约95%-100%)为特征;再平衡岩浆水热液矿床成矿流体的Ar同位素组成特征取决于与其有成因关系的初始岩浆水的Ar同位素组成及矿源层和围岩的性质,产于古老变质岩中的,一般以具有低大气Ar组分(约6%-20%)为特征,其它的再平衡岩浆水热液矿床在主成矿温度范围内一般为50%-60%左右。     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

Paleoproterozoic positive δ13Ccarb excursion in the northeastern Sino-Korean craton: Evidence of the Lomagundi Event

The 2.33–2.06 Ga positive δ¹³C_carb excursion, associated with environmental change and the breakup of the Kenorland or Superia supercontinent, is called the Lomagundi or Jatulian Event or Great Oxidation Event, and has been reported in many Early Precambrian cratons, but not yet in the Sino-Korean craton. The Guanmenshan Formation of the Liaohe Group occurs in the northeastern part of the Sino-Korean craton. δ¹³C_carb and δ¹⁸O values in 42 samples from this formation range from 3.5–5.9‰ (V-PDB), and 15.4–24.8‰ (V-SMOW), respectively, showing a clear positive δ¹³C_carb excursion that characterizes the Lomagundi Event. Thirty-five of the 42 samples with less hydrothermal alteration have higher δ¹³C_carb and δ¹⁸O_carb values than the other 7 samples obviously affected by fluid flow, confirming that it was fluid flow that reduced the δ¹³C_carb and δ¹⁸O_carb values. This positive δ¹³C_carb excursion places deposition of the Guanmenshan Formation within the age range of 2.33–2.06 Ga.     

Damming effects on dissolved inorganic carbon in different kinds of reservoirs in Jialing River,Southwest China

To assess the effects of river damming on dissolved inorganic carbon in the Jialing River, a total of 40 water samples, including inflow, outflow, and stratified water in four cascade reservoirs (Tingzikou, Xinzheng, Dongxiguan, Caojie) were collected in January and July, 2016. The major cations, anions, and δ¹³C_DIC values were analyzed. It was found that the dissolved compositions are dominated by carbonate weathering, while sulfuric acids may play a relatively important role during carbonate weathering and increasing DIC concentration. Different reservoirs had variable characteristics of water physiochemical stratification. The DIC concentrations of reservoir water were lower in summer than those in winter due to the dilute effects and intensive aquatic photosynthesis, as well as imported tributaries. The δ¹³C_DIC values in Tingzikou Reservoir were higher during summer than those in winter, which indicated that intensive photosynthesis increased the δ¹³C_DIC values in residual water, but a similar trend was not obvious in other reservoirs. Except for in Xinzheng Reservoir, the δ¹³C_DIC values in inflow and outflow reservoir water were lower than those in the surface water of stratified sampling in summer. For stratified sampling, it could be found that, in summer, the Tingzikou Reservoir δ¹³C_DIC values significantly decreased with water depth due to the anaerobic breakdown of organic matter. The significant correlation (p < 0.01 or 0.05) between the DIC concentrations, the δ¹³C_DIC values and anthropogenic species (Na⁺+K⁺, Cl^–, \({\text{SO}}_{4}^{2 - }\)and \({\text{NO}}_{3}^{ - }\)) showed that the isotope composition of DIC can be a useful tracer of contaminants. In total, Tingzikou Reservoir showed lacustrine features, Xinzheng Reservoir and Dongxiguan Reservoir had “transitional” features, and Caojie Reservoir had a total of “fluvial” features. Generally, cascade reservoirs in the Jialing River exhibited natural river features rather than typical lake features due to characteristics of reservoir water in physiochemical stratification, spatiotemporal variations of DIC concentrations and isotopic compositions. It is evident that the dissolved inorganic carbon dynamics of natural rivers had been partly remolded by dam building.