Tracing the decomposition of dissolved organic carbon in artificial groundwater recharge using carbon isotope ratios

Reducing the concentration of dissolved organic C (DOC) in water is one of the main challenges in the process of artificial groundwater recharge. At the Tuusula waterworks in southern Finland, surface water is artificially recharged into an esker by pond infiltration and an equal amount of groundwater is daily pumped from the aquifer. This groundwater study was conducted to consider the role of redox processes in the decomposition of DOC. The isotopic composition of dissolved inorganic C (δ¹³C_DIC) in the recharged water was used as a tracer for redox reactions. The isotopic composition of O and H in water was determined in order to calculate mixing ratios between the local groundwater and the infiltrated surface water. Three distinct processes in the reduction of the DOC content were traced using isotopic methods and concentration analyses of DIC and DOC: (1) the decomposition of DOC, (2) adsorption of DOC on mineral matter, and (3) the dilution of artificially recharged water by mixing with local groundwater. The largest decrease (44%) in the DOC content occurred during the early stage of subsurface flow, within 350 m of the infiltration ponds. The reduction of DOC was accompanied by an equal increase in DIC and a significant drop in δ¹³C_DIC. This change is attributed to the oxidative decomposition of DOC. A further 23% decrease in DOC is attributed to adsorption and a final drop of 14% to dilution with local groundwater.     

Tracing dissolved O2 and dissolved inorganic carbon stable isotope dynamics in the Nyack aquifer: Middle Fork Flathead River, Montana, USA

The geochemistry and microbiology of shallow groundwater aquifers is greatly influenced by the concentration of dissolved oxygen gas (DO); however, the mechanisms that consume DO in groundwater (e.g., biotic or abiotic) are often ambiguous. The use of stable isotopes of molecular O₂ (δ¹⁸O-DO), in conjunction with stable isotopes of dissolved inorganic carbon (δ¹³C-DIC), has potential to discriminate between the various mechanisms causing DO depletion in subsurface waters.Here we report the results of spatial and seasonal changes in δ¹⁸O-DO and δ¹³C-DIC at the Nyack floodplain aquifer along the Middle Fork of the Flathead River near West Glacier, Montana, USA. Over a short, well constrained flow path (∼100 m) near a main recharge zone of the floodplain, the δ¹⁸O-DO consistently increased as DO concentrations decreased with distance from the recharge source. Concurrently, DIC concentrations increased and δ¹³C-DIC values decreased. These observations are explained by community respiration coupled with dissolution of calcite from cobbles in the aquifer matrix. When these results are compared to data from wells distributed over the entire floodplain (several km) a much less predictable relationship was observed between DO concentration and δ¹⁸O-DO. Many wells with low DO concentrations (e.g., <125 μmol L⁻¹ or 4 mg L⁻¹) had anomalously low δ¹⁸O-DO values (e.g., <20‰). Mass balance calculations show that approximately equal amounts of O₂ may be contributed to the aquifer by diffusion from the vadose zone and by advection from the river recharge. Calculations presented here suggest that diffusion across a narrow air-water interface can contribute isotopically light δ¹⁸O-DO to the saturated zone. Possible contributions of light δ¹⁸O-DO from other processes, such as isotopic exchange and radial oxygen loss from plant roots in or near the water table, are compared and evaluated.     

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.     

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.     

Lithium isotopes in foraminifera shells as a novel proxy for the ocean dissolved inorganic carbon (DIC)

Past ocean pH and pCO₂ are critical parameters for establishing relationships between Earth's climate and the carbon cycle. Previous pCO₂ estimates are associated with large uncertainties and are debated. In this study, laboratory cultures of the foraminiferan genus Amphistegina were performed in order to examine the possible factors that control the Li isotope composition (δ⁷Li) of their shells. δ⁷Li is insensitive to temperature and pH variations but correlates positively with the Dissolved Inorganic Carbon (DIC) of seawater. Li/Ca ratio in the shells shows negative correlation with δ⁷Li, consistent with published data for planktonic foraminifera from core tops and from short periods during the Cenozoic. We propose that the sensitivity of δ⁷Li and Li/Ca ratio to DIC is a biological phenomenon and is related to biomineralization mechanisms in foraminifera. We used the published foraminiferal δ⁷Li records, and our experimental results, to determine the paleo-ocean DIC and pH for the last glacial–interglacial cycle. The results are consistent with published estimates of pH and pCO₂ based on boron isotopes and ice cores. We suggest Li and its isotopes may serve as a new complementary proxy for the paleo-ocean carbonate chemistry.     

Evaluation of petroleum hydrocarbon biodegradation in shallow groundwater by hydrogeochemical indicators and C, S-isotopes

Biodegradation is one of the main natural attenuation processes in groundwater contaminated with petroleum hydrocarbons. In this work, preliminary studies have been carried out by analyzing the concentrations of total petroleum hydrocarbons (TPH), dissolved inorganic carbon (DIC), dominant terminal electron accepters or donors, as well as δ ¹³C_DIC and δ ³⁴S_SO4, to reveal the biodegradation mechanism of petroleum hydrocarbons in a contaminated site. The results show that along groundwater flow in the central line of the plume, the concentrations of electron acceptors, pH, and E _h increased but TPH and DIC decreased. The δ ¹³C_DIC values of the contaminated groundwater were in the range of ?14.02 to ?22.28 ‰_PDB and ?7.71 to 8.36 ‰_PDB, which reflected a significant depletion and enrichment of ¹³C, respectively. The increase of DIC is believed to result from the non-methanogenic and methanogenic biodegradation of petroleum hydrocarbon in groundwater. Meanwhile, from the contaminated source to the downgradient of the plume, the ³⁴S in the contaminated groundwater became more depleted. The Rayleigh model calculation confirmed the occurrence of bacterial sulfate reduction as a biodegradation pathway of the petroleum hydrocarbon in the contaminated aquifers. It was concluded that stable isotope measurements, combined with other biogeochemical measurements, can be a useful tool to prove the occurrence of the biodegradation process and to identify the dominant terminal electron-accepting process in contaminated aquifers.     

Interaction between shallow and deep aquifers in the Tivoli Plain (Central Italy) enhanced by groundwater extraction: A multi-isotope approach and geochemical modeling

In the Tivoli Plain (Rome, Central Italy) the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using isotopic and chemical tracers. A conceptual model of the groundwater flowpaths has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as DIC/Cl⁻, Ca/(Ca + Mg)/SO₄/(SO₄ + HCO₃), and environmental isotopes (δ¹⁸O, δ²H, ⁸⁷Sr/⁸⁶Sr, δ³⁴S and δ¹³C) was carried out in order to determine the sources of recharge of the aquifer, the origin of solutes and the mixing processes in groundwater of Tivoli Plain. Multivariate statistical methods such as principal component analysis and Cluster analyses have confirmed the existence of different geochemical facies and the role of mixing in the chemical composition of the groundwater.     

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.     

Hydrological characteristics of karstic groundwater in the northeast Viet Nam as studied by isotopic techniques

The stable water isotopic composition (δ²H and δ¹⁸Ο), tritium (³H) activity, dissolved organic carbon, alkalinity, as well as the composition of carbon 13 (δ¹³C) in dissolved inorganic carbon (DIC) of 36 water samples taken from 16 resurgences in the northeast provinces of Viet Nam in the dry (Mar 2008) and rainy (June 2008) seasons were analyzed to elucidate hydrological characteristics of the karstic aquifers in the area. The stable water isotopic composition of the water samples collected clearly demonstrated that the karstic groundwater in the region was recharged from the local meteorological water. The tritium activity in the samples was found to be in between 3 and 4 TU, falling in the range of the ³H activity in the local precipitation and thus meaning that the traveling of recharge water to the resurgences was very short. Concentrated and diffuse allogenic recharges seem to be important sources of karstic groundwater in the study region. Water in the karstic aquifers could be classified into three types as: (a) water from karstic areas with dense vegetation cover that causes DIC be depleted in carbon 13 (¹³δ<?12‰ vs. Pee Dee Belemnite standard of Vienna, VPDB); (b) water from karstic areas with poor vegetation cover that originates DIC with carbon 13 composition ranging from ?11 to ?12‰; and (c) surface water from lakes, springs and rivers that has DIC with enriched carbon 13 (δ¹³C >?10‰). This implies that there are several sources of carbon dioxide contributing to the DIC in water of the karstic aquifers in the study region. Among other potential sources, the atmospheric CO₂, CO₂ from carbonate rock dissolution, biomineralization of soil organic matters and plant roots respiration seem to be important sources of the DIC in the waters of this region. The results show high vulnerability towards anthropogenic contaminants of karstic groundwater in the study region.     

The fate of nitrogen and sulfur in hard-rock aquifers as shown by sulfate-isotope tracing

Stable SO₄ isotopes (δ³⁴S_-SO4 and δ¹⁸O_-SO4), and more occasionally δ¹⁵N_-NO3 were studied in groundwater from seven hard-rock aquifer catchments. The sites are located in Brittany (France) and all are characterized by intensive agricultural activity. The purpose of the study was to investigate the potential use of these isotopes for highlighting the fate of both SO₄ and NO₃ in the different aquifer compartments. Nitrate-contaminated groundwater occurs in the regolith; δ³⁴S fingerprints the origin of SO₄, such as atmospheric deposition and fertilizers, and δ¹⁸O_-SO4 provides evidence of the cycling of S within soil. The correlation between the δ¹⁸O_-SO4 of sulfates and the δ¹⁵N_-NO3 of nitrates suggests that S and N were both cycled in soil before being leached to groundwater. Autotrophic and heterotrophic denitrification was noted in fissured aquifers and in wetlands, respectively, the two processes being distinguished on the basis of stable SO₄ isotopes. During autotrophic denitrification, both δ³⁴S_-SO4 and δ¹⁸O_-SO4 decrease due to the oxidation of pyrite and the incorporation of O from the NO₃ molecule in the newly formed SO₄. Within wetlands, fractionation occurs of O isotopes on SO₄ in favour of lighter isotopes, probably through reductive assimilation processes. Fractionation of S isotopes is negligible as the redox conditions are not sufficiently reductive for dissimilatory reduction. δ³⁴S_-SO4 and δ¹⁸O_-SO4 data fingerprint the presence of a NO₃-free brackish groundwater in the deepest parts of the aquifer. Through mixing with present-day denitrified groundwater, this brackish groundwater can contribute to significantly increase the salinity of pumped water from the fissured aquifer.     

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.     

Hydrochemical and isotopic characterisation of the Bathonian and Bajocian coastal aquifer of the Caen area (northern France)

This paper describes the geochemical evolution of groundwater in the Bathonian and Bajocian aquifer along its flowpath. Since this aquifer represents one of the main sources of fresh water supply in the Caen area and has been subjected to a Holocene marine intrusion, its management requires a sound knowledge of (1) the primary conditions and (2) the potential influence of either natural or anthropogenic pressures. Groundwater vertical sampling validity is discussed with the contribution of high resolution temperature logging. The main processes of geochemical evolution along a groundwater flow line and the sea-water intrusion characteristics are discussed using ionic concentrations (Br⁻, F⁻ and major elements) and isotopes (water δ²H and δ¹⁸O, TDIC δ¹³C and A¹⁴C, sulphate δ¹⁸O and δ³⁴S). As the ¹³C content of TDIC is used as a tracer of water-rock interaction, it shows evidence of specific chemical and isotopic evolutions of groundwater within the aquifer, both related to water-rock interaction and mineral equilibria in groundwater. All the above-mentioned tracers evolve downflow: cation concentrations are modified by exchange with clay minerals allowing a high F⁻ concentration in groundwater, whereas Br⁻ and SO²⁻₄ concentrations appear to be redox condition dependant. Superimposed on these geochemical patterns, δ¹⁸O and δ²H compositions indicate that aquifer recharge has varied significantly through time. The chemical evolution of groundwater is locally affected by a salty water intrusion that is characterised by mixing between Flandrian fresh water and sea-water which has interacted with peat as evidenced by a high Br⁻/Cl⁻ ratio and SO²⁻₄ reduction.     

Assessment of nitrate contamination risk: The Italian experience

The purpose of this study is to show the results of the Italian research project of national interest (PRIN) launched in 2006 and finished in 2008, concerning the “assessment of groundwater contamination risk by nitrates assessment”. The project verified the IPNOA method for nitrate groundwater contamination risk assessment in four test-sites of Italy. The IPNOA is a parametric index which assesses the potential hazard of nitrate contamination originating from agriculture on a regional scale. The method integrates two categories of parameters: the hazard factors (HF), which represent all farming activities that cause, or might cause, an impact on soil quality in terms of nitrate (use of fertilisers, application of livestock and poultry manure, food industry wastewater and urban sludge), and the control factors (CF) which adapt the hazard factors to the characteristics of the site (geographical location, climatic conditions and agronomic practices). Finally, the Potential Risk Map is obtained by coupling the potential hazard of nitrate pollution (IPNOA) and the aquifer Contamination Vulnerability Map. The project was carried out by five Research Units (RU) from the Politecnico di Torino, Universities of Piacenza, Florence, Naples and Palermo. The geochemistry of groundwaters from the four test-sites was studied to determine the distribution of nitrate, and to evaluate groundwater chemical facies. All the study areas are affected by groundwater nitrate contamination and often by hydrogeochemical peculiarities. In some cases isotopic study, δ¹⁸O–NO₃δ¹⁵N–NO₃, allowed to differentiate nitrates of chemical fertilisers from those of biological origin, as well as denitrification processes.     

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.     

Development of climatic and vegetation conditions and the geochemical and isotopic composition in the Franconian Albvorland aquifer system

The impact of climatic and vegetation conditions over the past 15 Ka on the chemical composition and ¹⁴C dating of groundwater from the Franconian Albvorland aquifer system is discussed. Seven groundwaters over a flow distance of 25.5 km are investigated. Groundwater dating is made by ¹⁴C of dissolved inorganic carbon (DIC) and aqueous fulvic acid as well as ¹⁸O. ¹⁴C dating via fulvic acid gives groundwater ages consistent with climatic and vegetation records and variations in the groundwater composition. No correction for geochemical processes is required, since under these geochemical conditions fulvic acid remains stable over this time period and flow-distance. On the other hand, ¹⁴C dating via DIC requires correction of the ¹⁴C value due to perturbation by different geochemical processes. Up to a groundwater flow distance of approximately 17 km and an age of about 10 Ka, the ¹⁴C dating by DIC shows considerable dependence on the ¹⁴C-correction model applied. Beyond this groundwater age, ¹⁴C-DIC dating results in an overestimation by two to three ¹⁴C half-lives (T_1/2=5730 a). This deviation may result from different groundwater recharge conditions at the end of the past glaciation and geochemical processes acting on DIC that cannot be adequately characterized. The present study has implications for humic substance mediated transport of pollutants in natural aquatic systems over long time periods.     

Deciphering interaction of regional aquifers in Southern Tunisia using hydrochemistry and isotopic tools

Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO₂ entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO₂ in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ¹⁸O and from −60 to −25‰ for δ²H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ¹⁸O and from −68.2‰ to −45.7‰ for δ²H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.     

The geochemistry of dissolved inorganic carbon in a surficial groundwater aquifer in North Inlet, South Carolina, and the carbon fluxes to the coastal ocean

We report measurements of pH, total dissolved inorganic carbon (DIC), total or titration alkalinity (TAlk), Ca²⁺, Mg²⁺, sulfate, and sulfide data at the seawater-freshwater interface in a shallow groundwater aquifer in North Inlet, South Carolina. These measurements and a diagenetic modeling analysis indicate that the groundwaters at North Inlet are mixtures of seawater and freshwater end-members and are seriously modified by carbon dioxide inputs from organic carbon degradation via SO₄²⁻ reduction across the entire salinity range and fermentation and CaCO₃ dissolution in the low-salinity region. DIC and TAlk are several times higher than the theoretical dilution line, whereas Ca²⁺ is slightly higher and SO₄²⁻ is somewhat lower than the dilution line. Partial pressure of CO₂ in the groundwater is extremely high (0.05 to 0.12 atm). These deviations are consistent with theoretical predictions from known diagenetic reactions. Estimated groundwater DIC fluxes to the South Atlantic Bight from either the surficial aquifer (via salt marshes) or the Upper Floridan Aquifer (direct input) are significant when compared to riverine flux in this area.     

The sources and budget for dissolved sulfate in a fractured carbonate aquifer,southern Sacramento Mountains,New Mexico,USA

Climate change in the SW USA is likely to involve drier conditions and higher surface temperatures. In order to better understand the evolution of water chemistry and the sources of aqueous SO₄ in these semi-arid settings, chemical and S isotope compositions were determined of springs, groundwater, and bedrock associated with a Permian fractured carbonate aquifer located in the southern Sacramento Mountains, New Mexico, USA. The results suggest that the evolution of water chemistry in the semi-arid carbonate aquifer is mainly controlled by dedolomitization of bedrock, which was magnified by increasing temperature and increasing dissolution of gypsum/anhydrite along the groundwater flow path. The δ³⁴S of dissolved SO₄ in spring and groundwater samples varied from +9.0‰ to +12.8‰, reflecting the mixing of SO₄ from the dissolution of Permian gypsum/anhydrite (+12.3‰ to +13.4‰) and oxidation of sulfide minerals (−24.5‰ to −4.2‰). According to S isotope mass balance constraints, the contribution of sulfide-derived SO₄ was considerable in the High Mountain recharge areas, accounting for up to ∼10% of the total SO₄ load. However, sulfide weathering decreased in importance in the lower reaches of the watershed. A smaller SO₄ input of ∼2–4% was contributed by atmospheric wet deposition. This study implies that the δ³⁴S variation of SO₄ in semi-arid environments can be complex, but that S isotopes can be used to distinguish among the different sources of weathering. Here it was found that H₂SO₄ dissolution due to sulfide oxidation contributes up to 5% of the total carbonate weathering budget, while most of the SO₄ is released from bedrock sources during dedolomitization.     

Carbon isotope systematics of the Cambrian–Vendian aquifer system in the northern Baltic Basin: Implications to the age and evolution of groundwater

Groundwater in the Cambrian–Vendian aquifer system has a strongly depleted stable isotope composition (δ¹⁸O values of about −22‰) and a low radiocarbon concentration, which suggests that the water is of glacial origin from the last Ice Age. The aim of this paper was to elucidate the timing of infiltration of glacial waters and to understand the geochemical evolution of this groundwater. The composition of the dissolved inorganic C (DIC) in Cambrian–Vendian groundwater is influenced by complex reactions and isotope exchange processes between water, organic materials and rock matrix. The δ¹³C composition of dissolved inorganic C in Cambrian–Vendian water also indicates a bacterial modification of the isotope system. The corrected radiocarbon ages of groundwater are between 14,000 and 27,000 radiocarbon years, which is coeval with the advance of the Weichselian Glacier in the area.