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.     

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.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

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.     

Seasonal water-column dynamics of dissolved inorganic carbon stable isotopic compositions (δCDIC) in small hardwater lakes in Minnesota and Montana

The carbon stable isotopic value of dissolved inorganic carbon (δ¹³C_DIC) was measured over several years at different depths in the water column in six carbonate-precipitating temperate lakes. δ¹³C_DIC behavior in three of these lakes departed from the conventional model wherein epilimnetic waters are seasonally enriched relative to all hypolimnetic waters, and in general δ¹³C_DIC values in the water column were not readily correlated to parameters such as lake stratification, algal productivity, hydraulic residence time, or water chemistry. Additionally, the processes implicated in generating the δ¹³C_DIC values of individual lakes differ between lakes with similar δ¹³C_DIC compositions. Each lake thus initially appears idiosyncratic, but when the effects of carbonate mineral equilibria, microbial activity, and lake residence time are viewed in terms of the magnitude of distinct DIC pools and fluxes in stratified lakes, generalizations can be made that allow lakes to be grouped by δ¹³C_DIC behavior. We recognize three modes in the relationship between δ¹³C_DIC values and DIC concentration ([DIC]) of individual lakes: (A) δ¹³C_DIC values decreasing with increasing [DIC]; (B) δ¹³C_DIC values increasing with increasing [DIC]; (C) δ¹³C_DIC values decreasing with increasing [DIC] but increasing again at the highest [DIC]. This approach is useful both in understanding δ¹³C_DIC dynamics in modern hardwater lakes and in reconstructing the environmental changes recorded by sedimentary δ¹³C components in the lacustrine paleorecord.     

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.     

Mixing of magmatic CO2 into volcano groundwater flow at Aso volcano assessed combining carbon and water stable isotopes

To understand deep groundwater flow systems and their interaction with CO₂ emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ¹³C_DIC) and DIC concentrations of the sampled waters show that magma-derived CO₂ mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ¹³C_DIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ¹⁸O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ¹³C_DIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO₂ is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO₂ mixes into deeper groundwater flowing nearer the magma conduit or chamber.     

Chemical Dynamics and Evaluation of Biogeochemical Processes in Alpine River Kamniška Bistrica, North Slovenia

Biogeochemical processes were investigated in alpine river—Kamni?ka Bistrica River (North Slovenia), which represents an ideal natural laboratory for studying anthropogenic impacts in catchments with high weathering capacity. The Kamni?ka Bistrica River water chemistry is dominated by HCO₃ ^?, Ca²⁺ and Mg²⁺, and Ca²⁺/Mg²⁺ molar ratios indicate that calcite weathering is the major source of solutes to the river system. The Kamni?ka Bistrica River and its tributaries are oversaturated with respect to calcite and dolomite. pCO₂ concentrations were on average up to 25 times over atmospheric values. δ¹³C_DIC values ranged from ?12.7 to ?2.7 ‰, controlled by biogeochemical processes in the catchment and within the stream; carbonate dissolution is the most important biogeochemical process affecting carbon isotopes in the upstream portions of the catchment, while carbonate dissolution and organic matter degradation control carbon isotope signatures downstream. Contributions of DIC from various biogeochemical processes were determined using steady state equations for different sampling seasons at the mouth of the Kamni?ka Bistrica River; results indicate that: (1) 1.9–2.2 % of DIC came from exchange with atmospheric CO₂, (2) 0–27.5 % of DIC came from degradation of organic matter, (3) 25.4–41.5 % of DIC came from dissolution of carbonates and (4) 33–85 % of DIC came from tributaries. δ¹⁵N values of nitrate ranged from ?5.2 ‰ at the headwater spring to 9.8 ‰ in the lower reaches. Higher δ¹⁵N values in the lower reaches of the river suggest anthropogenic pollution from agricultural activity. Based on seasonal and longitudinal changes of chemical and isotopic indicators of carbon and nitrogen in Kamni?ka Bistrica River, it can be concluded that seasonal changes are observed (higher concentrations are detected at low discharge conditions) and it turns from pristine alpine river to anthropogenic influenced river in central flow.     

C and O stable isotope variability in recent freshwater carbonates (River Krka, Croatia)

Three types of recent carbonate precipitates from the River Krka, Croatia, were analysed: (1) bulk tufa from four main cascades in a 34 km long section of the river flow through the Krka National Park; (2) a laminar stromatolite‐like incrustation formed in the tunnel of a hydroelectric power plant close to the lowest cascade; and (3) recent precipitates collected on artificial substrates during winter, spring and summer periods. Stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in the carbonate and organic carbon (δ¹³C_org) were determined and compared with δ¹⁸O of water and δ¹³C of dissolved inorganic carbon (DIC). The source of DIC, which provides C for tufa precipitation, was determined from the slope of the line ([DIC]/[DIC₀]?1) vs. (δ¹³C‐DIC × ([DIC]/[DIC₀])) ( Sayles & Curry, 1988 ). The δ¹³C value of added DIC was ?13·6‰, corresponding to the dissolution of CO₂ with δ¹³C between ?19·5 and ?23·0‰ Vienna Pee Dee Belemnite (VPDB). The observed difference between the measured and calculated equilibrium temperature of precipitation of bulk tufa barriers indicates that the higher the water temperature, the larger the error in the estimated temperature of precipitation. This implies that the climatic signals may be valid only in tufas precipitated at lower and relatively stable temperatures. The laminar crust comprising a continuous record of the last 40 years of precipitation shows a consistent trend of increasing δ¹³C and decreasing δ¹⁸O. The lack of covariation between δ¹³C and δ¹⁸O indicates that precipitation of calcite was not kinetically controlled for either of the elements. δ¹³C and δ¹⁸O of precipitates collected on different artificial substrates show that surface characteristics both of substrates and colonizing biota play an important role in C and O isotope fractionation during carbonate precipitation.     

Controls on dissolved inorganic carbon and δC in cave waters from DeSoto Caverns: Implications for speleothem δC assessments

Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ¹³C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ¹³C_DIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ¹³C_DIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ¹³C_DIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ¹³C_DIC = −2.49[DIC] + 0.64, r² = 0.84). A shallow pool fed by multiple drips shows a bimodal δ¹³C_DIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO₂ fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ¹³C_DIC variability. Measured values of high [DIC] and low δ¹³C_DIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ¹³C_DIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO₂ and precipitated CaCO₃(1000lnα_{[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2}) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of ¹⁴C mass balance and paired ¹⁴C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from ¹⁴C-dead dolomite cap while the remainder of ∼77% is derived from ¹⁴C-live biomass. δ¹³C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ¹³C values calculated using the shallow pool summer/early fall data thus confirming the δ¹³C seasonality in both drips and coeval aragonite. δ¹³C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ¹³C records of stalagmites at DeSoto Caverns with resolving power >10⁻¹ year will likely carry the imprints of drip annual means that record climate-driven δ¹³C seasonal biases.     

The origins and behaviour of carbon in a major semi-arid river,the Murray River,Australia, as constrained by carbon isotopes and hydrochemistry

δ¹³C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ¹⁸O and δ²H values of water, δ³⁴S values of dissolved SO₄, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ¹³C_DIC values in the Murray River vary between −9.5 and −4.7‰ with a range of <3‰ within any sampling round. δ¹³C_DIC values of the tributaries are −11.0‰ to −5.1‰. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45–55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6–0.7 in the headwaters to ∼0.2–0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO₂; this interpretation is consistent with pCO₂ values that are in the range 550–11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ¹³C_DIC values are similar to those that would be produced by the weathering of marine limestone (δ¹³C ∼ 0‰). However, the lack of marine limestones cropping out in the Murray–Darling Basin and the relatively uniform δ¹³C_DIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO₂ values and δ¹³C_DIC values are best explained by a combination of mineralisation of low δ¹³C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ¹³C values.     

Isotopic and Chemical Constraints on the Biogeochemistry of Dissolved Inorganic Carbon and Chemical Weathering in the Karst Watershed of Krka River (Slovenia)

The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ¹³C_DIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO₃ ^?, Ca²⁺ and Mg²⁺ originating from carbonate dissolution. The Mg²⁺/Ca²⁺ and Mg²⁺/HCO₃ ^? molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO₂ concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO₂ downstream. The δ¹³C values in river water range from ?15.6 to ?9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO₂, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO₂ has minor influence on the inorganic carbon pool in the Krka River.     

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.     

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.     

Brine formation recorded by stable isotopes of Recent benthic foraminifera in Storfjorden,Svalbard: palaeoceanographical implications

We discuss water oxygen isotopes (δ¹⁸O_w) and carbon isotopes of dissolved inorganic carbon (δ¹³C_DIC) of brine‐enriched shelf water (BSW) from Storfjorden (southern Svalbard) in comparison to Recent benthic foraminiferal δ¹⁸O_c and δ¹³C_c calcified in the same water. We determined relatively high δ¹⁸O_w values of 0.15±0.03‰ VSMOW in BSW below sill depth at temperatures below ?1.8 °C, and high δ¹⁸O_c values of 3.90±0.18‰ VPDB. Such high BSW δ¹⁸O_w cannot significantly deplete ¹⁸O_w contents of Arctic Ocean deep water; furthermore, such high δ¹⁸O_c cannot be distinguished from δ¹⁸O_c values of 3.82±0.12‰, calcified in warmer Arctic and Nordic seas intermediate and deeper waters. Today, in Storfjorden low benthic δ¹³C_c and high δ¹⁸O_c reflect the low δ¹³C_DIC and relatively high δ¹⁸O_w of BSW. High benthic δ¹⁸O_c is in contrast to expected low δ¹⁸O_c as brine rejection is widely thought to predominantly take place in surface water diluted by meteoric water with very low δ¹⁸O_w. Low epibenthic δ¹³C_c values of 0.50±0.12‰ partly reflect low δ¹³C_DIC caused by enhanced uptake of atmospheric low δ¹³C_CO2 decreased by anthropogenic activities. An adjustment for preindustrial higher values would increase δ¹³C_c by about 0.6‰. Therefore, in Storfjorden brine formed before the industrial era would be characterized by both high δ¹³C_c as well as high δ¹⁸O_c values of benthic foraminiferal calcite. Our data may cast doubt on scenarios that explain negative excursions in benthic foraminiferal stable isotope records from the Atlantic Ocean during cold stadials in the last glacial period by enhanced brine formation in Nordic seas analogously to modern processes in Storfjorden.     

Strontium and carbon isotope stratigraphy of the Late Jurassic shallow marine limestone in western Palaeo-Pacific,northwest Borneo

Strontium and carbon isotope stratigraphy was applied to a 202 m-thick shallow marine carbonate section within the Late Jurassic Bau Limestone at the SSF quarry in northwest Borneo, Malaysia, which was deposited in the western Palaeo-Pacific. Strontium isotopic ratios of rudist specimens suggest that the SSF section was formed between the latest Oxfordian (155.95 Ma) and the Late Kimmeridgian (152.70 Ma), which is consistent with previous biostratigraphy. The δ¹³C_carb values of bulk carbonate range from −0.10 to +2.28‰ and generally show an increasing upward trend in the lower part of the section and a decreasing upward trend in the upper part of the section. A comparable pattern is preserved in the δ¹³C_org isotope record. Limestone samples of the SSF section mainly preserve the initial δ¹³C_carb values, except for the interval 84–92 m, where an apparent negative anomaly likely developed as a result of meteoric diagenesis. Comparing with the Tethyan δ¹³C_carb profile, a negative anomaly in the lower SSF section can be correlated with the lowered δ¹³C values around the Oxfordian/Kimmeridgian boundary. In addition, δ¹³C_carb values of the Bau Limestone are generally ∼1‰ lower than the Tethyan values, but comparable with the values reported from Scotland and Russia, located in Boreal realm during the Late Jurassic. This suggests that either the Tethyan record or the other records have been affected by the δ¹³C values of regionally variable dissolved inorganic carbon (DIC). The Late Jurassic δ¹³C_DIC values are thought to have been regionally variable as a result of their palaeoceanographic settings. This study shows that δ¹³C chemostratigraphy of the Palaeo-Pacific region contributes to an improved understanding of global carbon cycling and oceanography during this time period.     

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.