Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin,Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO₄ (δ³⁴S and δ¹⁸O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ³⁴S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO₄/Cl ratios, as well as relatively low δ¹⁸O_SO4 values, suggest that vertical input of biogenically derived SO₄ via diffuse recharge is the predominant source of dissolved SO₄ to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ³⁴S values in the unconfined Murray Group Aquifer increase, and SO₄/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO₄/Cl and high δ³⁴S (14.9–56.4‰). Relatively positive δ³⁴S and δ¹⁸O_SO4 values, and low SO₄/Cl in the Renmark Group Aquifer is typical of SO₄ removal by bacterial reduction. The S isotope fractionation between SO₄ and HS⁻ of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ³⁴S and SO₄/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.     

Identifying sources of salinization using hydrochemical and isotopic techniques, Konarsiah, Iran

Konarsiah salt diapir is situated in the Simply Folded Zone of the Zagros Mountain, south Iran. Eight small permanent brine springs emerge from the Konarsiah salt body, with average total dissolved solids of 326.7 g/L. There are numerous brackish to saline springs emerging from the alluvial and karst aquifers adjacent to the diapir. Concerning emergence of Konarsiah diapir in the study area, halite dissolution is the most probable source of salinity in the adjacent aquifers. However, other sources including evaporation and deep brines through deep Mangerak Fault are possible. The water samples of the study area were classified based on their water-type, salinity, and the trend of the ions concentration curves. The result of this classification is in agreement with the hydrogeological setting of the study area. The hydrochemical and isotopic evaluations show that the groundwater samples are the result of mixing of four end members; Gachsaran sulfate water, Sarvak and Asmari carbonate fresh waters, and diapir brine. The molar ratios of Na/Cl, Li/Cl, Br/Cl, and SO₄/Cl; and isotopic signature of the mixed samples justify a groundwater mixing model for the aquifers adjacent to the salt diapir. The share of brine in each adjacent aquifer was calculated using Cl mass balance. In addition, concentrations of 34 trace elements were determined to characterize the diapir brine and to identify the possible tracers of salinity sources in the mixed water samples. B, Mn, Rb, Sr, Cs, Tl, and Te were identified as trace elements evidencing contact of groundwater with the salt diapir.     

The integrated impacts of natural processes and human activities on groundwater salinization in the coastal aquifers of Beihai,southern China

Salinization in coastal aquifers is usually related to both seawater intrusion and water–rock interaction. The results of chemical and isotopic methods were combined to identify the origin and processes of groundwater salinization in Daguansha area of Beihai, southern China. The concentrations of the major ions that dominate in seawater (Cl^?, Na⁺, Ca²⁺, Mg²⁺ and SO ₄ ^2– ), as well as the isotopic content and ratios (²H, ¹⁸O, ⁸⁷Sr/⁸⁶Sr and ¹³C), suggest that the salinization occurring in the aquifer of the coastal plain is related to seawater and that the prevailing hydrochemical processes are evaporation, mixing, dissolution and ion exchange. For the unconfined aquifer, groundwater salinization has occurred in an area that is significantly influenced by land-based sea farming. The integrated impacts of seawater intrusion from the Beibuwan Gulf and infiltration of seawater from the culture ponds are identified in the shallowest confined aquifer (I) in the middle of the area (site BBW2). Leakage from this polluted confined aquifer causes the salinization of groundwater in the underlying confined aquifer (II). At the coastal monitoring site (BBW3), confined aquifer I and lower confined aquifer II are heavily contaminated by seawater intrusion. The weak connectivity between the upper aquifers, and the seaward movement of freshwater, prevents saltwater from encroaching the deepest confined aquifer (III). A conceptual model is presented. Above all, understanding of the origin and processes of groundwater salinization will provide essential information for the planning and sustainable management of groundwater resources in this region.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.     

Groundwater origins and mixing pattern in the multilayer aquifer system of the Gafsa-south mining district: a chemical and isotopic approach

Major ion geochemistry and environmental isotopes were used to identify the origins and the mineralisation processes of groundwater flowing within the three aquifer levels of the multilayer system of the Gafsa-south mining district (Southwestern Tunisia). It has been demonstrated that groundwaters are characterised by a Ca–Mg–SO₄ water type. Geochemical pattern is mainly controlled by the dissolution of halite, gypsum and/or anhydrite as well as by the incongruent dissolution of dolomite. δ¹⁸O and δ²H values are much lower than the isotopic signature of regional precipitation and fall close to the meteoric water lines, indicating that groundwaters have not been significantly affected by evaporation or mineral–water reactions. The distribution of stable and radiogenic isotopes (δ¹⁸O, δ²H, δ¹³C and ¹⁴C) within the aquifer levels suggests that the deep confined aquifer receives a significant modern recharge at higher altitudes, while, the shallow unconfined aquifer has been mainly recharged under cooler paleoclimatic condition, likely during Late Pleistocene and Early Holocene humid periods. However, waters from the intermediate confined/unconfined aquifer have composite isotopic signatures, highlighting that they are derived from a mixture of the two first end-members.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Groundwater recharge and chemical evolution in the southern High Plains of Texas, USA

The unconfined High Plains (Ogallala) aquifer is the largest aquifer in the USA and the primary water supply for the semiarid southern High Plains of Texas and New Mexico. Analyses of water and soils northeast of Amarillo, Texas, together with data from other regional studies, indicate that processes during recharge control the composition of unconfined groundwater in the northern half of the southern High Plains. Solute and isotopic data are consistent with a sequence of episodic precipitation, concentration of solutes in upland soils by evapotranspiration, runoff, and infiltration beneath playas and ditches (modified locally by return flow of wastewater and irrigation tailwater). Plausible reactions during recharge include oxidation of organic matter, dissolution and exsolution of CO₂, dissolution of CaCO₃, silicate weathering, and cation exchange. Si and ¹⁴C data suggest leakage from perched aquifers to the High Plains aquifer. Plausible mass-balance models for the High Plains aquifer include scenarios of flow with leakage but not reactions, flow with reactions but not leakage, and flow with neither reactions nor leakage. Mechanisms of recharge and chemical evolution delineated in this study agree with those noted for other aquifers in the south-central and southwestern USA. Electronic Publication     

Assessing hydrochemical evolution of groundwater in limestone terrain via principal component analysis

This paper describes the use of multivariate statistical analysis to trace hydrochemical evolution in a limestone terrain at Zagros region, Iran. The study area includes a deep confined aquifer, overlaid by an unconfined aquifer. The method involves the use of principal component analysis (PCA) to assess and evaluate the hydrochemical evolution based on chemical and isotope variables of 12 piezometers drilled in both the unconfined and confined aquifers. First PCA on all variables shows that water–rock interaction under different conditions with respect to the atmospheric CO₂ is the main process responsible for chemical constituents. As a result, combinations of several ratios such as Ca/TDS, SO₄/TDS and Mg/TDS with physico-chemical and isotope variables reveal different hydrochemical evolution trend in the aquifers. Second PCA on the selective samples and variables reveals that displacement of the unconfined samples from dry to wet season follows a refreshing trend towards river samples that is characterized by reducing electrical conductivity and increasing sulphate and tritium contents. However, the refreshing trend cannot be traced in the confined aquifer samples suggesting no recharge from river to the confined aquifer. Third PCA reveals that, chemical composition of water samples in the unconfined aquifer tends to have considerable difference from each other in the end of recharge period. In contrast, the confined aquifer samples have a tendency to show similar chemical composition during recharge period in comparison to end of dry period. This difference is caused by different mechanism of recharge in the unconfined aquifer (through the whole aquifer surface) and the confined aquifer (through the limited recharge area).     

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County,Pennsylvania, USA

Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ¹³C_DIC) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in ¹³C due to enhanced carbonate dissolution associated with the release of H₂SO₄ from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ³⁴S_SO4 and δ¹⁸O_SO4 isotopic signatures of the mine drainage and the presence of presumptive SO₄-reducing bacteria suggest that SO₄ reduction activity also contributes C depleted in ¹³C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased_, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H₂SO₄ dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO₂ outgassing.     

Tracing sources of carbon in urban groundwater using δ<Superscript>13</Superscript>C<Subscript>TDIC</Subscript> ratios

Total dissolved inorganic carbon (TDIC) and its stable isotope ratio δ¹³C_TDIC are used to trace the evolution of the carbon system of groundwater in three UK Permo-Triassic sandstone aquifers. Samples were collected from multilevel piezometers, open boreholes and sewer sampling points in the British Midlands (Nottingham, Birmingham and Doncaster) to evaluate both local and regional variations in δ¹³C_TDIC. δ¹³C samples of matrix and pore water have also been analysed in each aquifer to further constrain the interpretations. Combining δ¹³C_TDIC ratios with measurements of TDIC and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Triassic sandstone aquifers, where processes can be both natural (e.g. carbonate dissolution) and anthropogenic (sewer-derived recharge). The paper shows that δ¹³C_TDIC resolves ambiguities that arise from the interpretation of TDIC and pH measurements in isolation. Field measurements demonstrate that, under natural conditions, the carbonate system evolves similarly in each aquifer. An open-system evolution during recharge largely saturates the groundwater with carbonate depending upon its availability in the sandstone matrix. The contribution of sewer exfiltration to urban recharge is readily distinguished by lower pH and higher TDIC values without significant changes in δ¹³C_TDIC.     

Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain,USA

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ～300 km long. The hydrochemical facies evolves from Ca-HCO₃ upgradient to Na-HCO₃ downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO₄ ^2? reduction to methanogenesis. In particular, decreasing SO₄ ^2? and increasing δ³⁴S of SO₄ ^2? along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO₄ ^2? reduction. Values of δ¹³C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH₂O oxidation, and dissolution of amorphous Fe(OH)₃, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.     

S- and O-isotopic character of dissolved sulphate in the cover rock aquifers of a Zechstein salt dome

Sulfur and O isotope analyses of dissolved SO₄ were used to constrain a hydrogeological model for the area overlying the Gorleben–Rambow Salt Structure, Northern Germany. Samples were collected from 80 wells screened at different depth-intervals. The study area consists of a set of two vertically stacked aquifer systems. Generally, the isotope data show a good spatial correlation, outlining well-defined groundwater zones containing SO₄ of characteristic isotopic composition. Highly saline waters from deeper parts of the lower aquifer system are characterized by rather constant SO₄ isotopic compositions, which are typical of Permian Zechstein evaporites (δ³⁴S=9.6–11.9‰; δ¹⁸O=9.5–12.1‰). Above this is a transition zone containing ground waters of intermediate salinity and slightly higher isotopic values (average δ³⁴S=16.6‰; δ¹⁸O=15.3‰). The confined groundwater horizon on the top of the lower aquifer system below the low permeable Hamburg Clays is low in total dissolved solids and is characterized by an extreme ³⁴S enrichment (average δ³⁴S=39.1‰; δ¹⁸O=18.4‰), suggesting that bacterially mediated SO₄ reduction is a dominant geochemical process in this zone. Two areas of distinct isotopic composition can be identified in the shallow ground water horizons of the upper hydrogeological system. Sulfate in groundwaters adjacent to the river Elbe and Löcknitz has a typical meteoric isotopic signature (δ³⁴S=5.2‰; δ¹⁸O=8.2‰), whereas the central part of the area is characterized by more elevated isotopic ratios (δ³⁴S=12.7‰; δ¹⁸O=15.6‰). The two major SO₄ pools in the area are represented by Permian seawater SO₄ and a SO₄ of meteoric origin that has been mixed with SO₄ resulting from the oxidation of pyrite. It is suggested that the S-isotope compositions observed reflect the nature of the SO₄ source that have been modified to various extent by bacterial SO₄ reduction. Groundwaters with transitional salinity have resulted from mixing between brines and low-mineralized waters affected by bacterial SO₄ reduction.     

Using stable isotopes (δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) to identify sources of water in abandoned mines in the Fengfeng coal mining district,northern China

With depleted coal resources or deteriorating mining geological conditions, some coal mines have been abandoned in the Fengfeng mining district, China. Water that accumulates in an abandoned underground mine (goaf water) may be a hazard to neighboring mines and impact the groundwater environment. Groundwater samples at three abandoned mines (Yi, Er and Quantou mines) in the Fengfeng mining district and the underlying Ordovician limestone aquifer were collected to characterize their chemical and isotopic compositions and identify the sources of the mine water. The water was HCO₃·SO₄-Ca·Mg type in Er mine and the auxiliary shaft of Yi mine, and HCO₃·SO₄-Na type in the main shaft of Quantou mine. The isotopic compositions (δD and δ¹⁸O) of water in the three abandoned mines were close to that of Ordovician limestone groundwater. Faults in the abandoned mines were developmental, possibly facilitating inflows of groundwater from the underlying Ordovician limestone aquifers into the coal mines. Although the Sr²⁺ concentrations differed considerably, the ratios of Sr²⁺/Ca²⁺ and ⁸⁷Sr/⁸⁶Sr and the ³⁴S content of SO₄^2? were similar for all three mine waters and Ordovician limestone groundwater, indicating that a close hydraulic connection may exist. Geochemical and isotopic indicators suggest that (1) the mine waters may originate mainly from the Ordovician limestone groundwater inflows, and (2) the upward hydraulic gradient in the limestone aquifer may prevent its contamination by the overlying abandoned mine water. The results of this study could be useful for water resources management in this area and other similar mining areas.     

A study on the hydrogeology and hydrogeochemistry of groundwater from different depths in a coastal aquifer: Annamalai Nagar,Tamilnadu, India

Chemical characterization of groundwater is essential to bring out its nature and utility. Samples from shallow and deep ground water of the same location were collected and studied for their geochemical characteristics following standard procedures (APHA 1998). Sediment samples from different depths were collected and analysed for minerals using FTIR and SEM. Resisitivity logging was carried out in the bore well to understand the variations in depth to fresh water potential. The shallow ground water is dominated by Na–Cl–HCO₃–SO₄ and deeper groundwater by Na–HCO₃–SO₄–Cl types. It is observed that there is a significant ionic variation with depth. The ionic strength of the deeper samples is lesser than in the shallower samples. Wide pH variations in the shallow water samples are due to ion exchange process. Thermodynamic stability plot was used to identify the state of stability. It is inferred that there is no major significant difference in the thermodynamic state of stability in the shallow and the deeper aquifers as the aquifer matrix for the shallow and deeper aquifers are almost similar. Saturation index of Gibbsite, Kaolinite, Calcite, Dolomite and anhydrite, were studied for shallow and deep aquifers, to identify the difference in hydro chemical signatures. The Si/Al ratios of shallow samples are less when compared with the deeper samples. Leaching of secondary salts was the chief mechanism controlling the ground water chemistry of the region.     

Twenty years of groundwater evolution in the Triassic sandstone aquifer of Lorraine: Impacts on baseline water quality

The Lorraine Triassic Sandstone Aquifer (LTSA), which has already been the subject of a chemical and radioisotopic study (1979), is used to investigate the impacts of 20 a of large scale pumping on baseline water quality. In parallel, new sampling of the aquifer (2001) provides new inorganic geochemical data (including trace elements) that allow improving the knowledge of baseline conditions and hydrochemical functioning of a major sandstone aquifer. The good correlation between ¹⁴C activities, temperature and depth along the main flow line indicate regular downgradient trends and possible water stratification. Unreactive tracers, mainly stable isotope ratios ¹⁸O and ²H, as well as C isotopes are used to define a timescale for the aquifer, showing two groups of groundwater, namely of modern and Holocene age, and late Pleistocene age, with a mixing zone. Baseline quality is then represented by a wide range of concentrations, mainly the result of time-dependent water–rock interaction, as already observed elsewhere in Triassic sandstone aquifers. Some trace elements such as Li, Rb, Cs, which are not limited by solubility constraints, show linear trends. During saturated flow downgradient, the chemistry is also specifically characterised by a regular increase in Na and Cl (and locally SO₄) as a result of evaporite dissolution related to overlying or basement limits. The aquifer is mostly oxidising with a redox boundary marked by U decrease, some 40 km from outcrop.     

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.     

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.     

Hydrogeochemistry and dissolved inorganic carbon isotopic composition on karst groundwater in Maolan, southwest China

The forest ecosystem in the Maolan karst forest, southwest China is the only concentrated, intact, and relatively stable karst forest ecosystem which has survived in the area at the same latitude in the world, and is a valuable karst forest plant resource as well. Groundwater samples from Maolan karst forest were collected from wells and springs during summer; and concentrations of major ions and dissolved inorganic carbon (DIC) isotopic compositions were measured. The pH values range from 7.2 to 8.3 results from the dissolution of carbonate, HCO₃ ⁻ is the dominant species of DIC in groundwater. Calcium and HCO₃ ⁻, followed by Mg²⁺ and SO₄ ²⁻ dominate the chemical composition of major ions in the groundwaters. Groundwater samples have δ¹³C values in the range from −8.1‰ to −16.6‰, which are lower than that of the other karst city groundwaters in the southwest China. Combining δ¹³C_DIC ratios with measurements of HCO₃ ⁻ and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Carboniferous carbonate aquifers, where processes can be both degradation of organic matters in the soil and the carbonate dissolution.