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.     

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO₃-N (74–83 mg L^?1). The δ¹⁵N-NO₃ values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ¹⁵N-NO₃ values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ¹⁵N-NO₃ and δ¹⁸O-NO₃ values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between ?4.8 and ?7.9‰ and O isotope enrichment factors varying between ?3.8 and ?4.9‰. Similar δD and δ¹⁸O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10–20 years) than in the north (20–30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

Multi-isotope (Ba,C, O) partitioning during experimental carbonatization of a hyper-alkaline solution

Carbonates formed from hyperalkaline aqueous solutions at the Earth?s surface are known to bear the most extreme disequilibrium isotope signatures reported so far in nature. We present here the results for stable carbon (C), oxygen (O), and barium (Ba) isotope fractionation during the precipitation of witherite (BaCO₃) induced by the chemical absorption of atmospheric carbon dioxide (CO₂) into an aqueous hyper-alkaline solution (at 4° and 21?°C; 1?atm total pressure). Independent from temperature, the barium carbonate formation was associated with a substantial enrichment of the lighter C and O isotopes in the solid compared to the atmosphere (C, O), close to previous results found in experiments and nature. A new approach is introduced to explain oxygen isotope fractionation upon hydroxylation of CO₂. With Ba isotope enrichment factors between ?0.45 and ?0.53‰ (^138/134ε) or ?0.34 and ?0.40‰ (^137/134ε), respectively, the synthesized BaCO₃ displays the highest kinetic enrichment of the light Ba isotope in the carbonate solid reported so far.     

Assessment of MTBE biodegradation in contaminated groundwater using C and C analysis: Field and laboratory microcosm studies

Radiolabelled assays and compound-specific stable isotope analysis (CSIA) were used to assess methyl tert-butyl ether (MTBE) biodegradation in an unleaded fuel plume in a UK chalk aquifer, both in the field and in laboratory microcosm experiments. The ¹⁴C-MTBE radiorespirometry studies demonstrated widespread potential for aerobic and anaerobic MTBE biodegradation in the aquifer. However, δ¹³C compositions of MTBE in groundwater samples from the plume showed no significant ¹³C enrichment that would indicate MTBE biodegradation at the field scale. Carbon isotope enrichment during MTBE biodegradation was assessed in the microcosms when dissolved O₂ was not limiting, compared with low in situ concentrations (2 mg/L) in the aquifer, and in the absence of O₂. The microcosm experiments showed ubiquitous potential for aerobic MTBE biodegradation in the aquifer within hundreds of days. Aerobic MTBE biodegradation in the microcosms produced an enrichment of 7‰ in the MTBE δ¹³C composition and an isotope enrichment factor (ε) of −1.53‰ when dissolved O₂ was not limiting. However, for the low dissolved O₂ concentration of up to 2 mg/L that characterizes most of the MTBE plume fringe, aerobic MTBE biodegradation produced an enrichment of 0.5-0.7‰, corresponding to an ε value of −0.22‰ to −0.24‰. No anaerobic MTBE biodegradation occurred under these experimental conditions. These results suggest the existence of a complex MTBE-biodegrading community in the aquifer, which may consist of different aerobic species competing for MTBE and dissolved O₂. Under low O₂ conditions, the lower fractionating species have been shown to govern overall MTBE C-isotope fractionation during biodegradation, confirming the results of previous laboratory experiments mixing pure cultures. This implies that significant aerobic MTBE biodegradation could occur under the low dissolved O₂ concentration that typifies the reactive fringe zone of MTBE plumes, without producing detectable changes in the MTBE δ¹³C composition. This observed insensitivity of C isotope enrichment to MTBE biodegradation could lead to significant underestimation of aerobic MTBE biodegradation at field scale, with an unnecessarily pessimistic performance assessment for natural attenuation. Site-specific C isotope enrichment factors are, therefore, required to reliably quantify MTBE biodegradation, which may limit CSIA as a tool for the in situ assessment of MTBE biodegradation in groundwater using only C isotopes.     

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 possible sulfate sources in karst groundwater in Chongqing, China

Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are affected by both natural environment and people. Therefore, the study of karst groundwater hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. This paper focused on the major ion chemistry and sulfate isotope of karst groundwater in Chongqing for tracing the sulfate sources and related hydrochemical processes. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO₃ type or Ca(Mg)-HCO₃ type. However, some hydrochemical types were the K + Na + Ca-SO₄ type (G25 site) or Ca-HCO₃ + SO₄ type (G26 and G14 sites), indicating that the hydrochemistry of these sites may be strongly influenced by anthropogenic activities or unique geological characteristics. The δ³⁴S-SO₄ ^2? of collected karst groundwater sample fell into a range of ?6.8 to 21.5 ‰, with a mean value of 5.6 ‰. In dolomite aquifer, the δ³⁴S-SO₄ ^2? value ranges from ?4.3 to 11.0 ‰, and in limestone aquifer, it ranged from ?6.8 to 21.5 ‰. The groundwater samples from different land use types showed distinctive δ³⁴S-SO₄ ^2? value. The δ³⁴S-SO₄ ^2? value of groundwater samples had range of ?6.8 to 16.7 ‰ (mean 4.0 ‰, n = 11) in cultivated land areas, 1.5–21.5 ‰ (mean 7.2 ‰, n = 20) in forested land areas, and ?4.3 to 0.8 ‰ (mean ?1.7 ‰, n = 2) in coalmine areas. The δ³⁴S-SO₄ ^2? values of groundwater samples collected from factory area and town area were 2.2 and 9.9 ‰, respectively. According to the δ³⁴S information of potential sulfate sources, this paper discussed the possible sulfate sources of collected karst groundwater samples in Chongqing. The variations of both δ³⁴S and 1/SO₄ ^2? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sulfide mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) contributed to sulfate in karst groundwater. The influence of oxidation of sulfide mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread. For protecting, sustaining, and utilizing the groundwater resources, the sewage possibly originating from urban, mine or industrial area must be controlled and treated, and the use of fertilizer should be limited.     

Anatomy of a large Ag–Pb–Zn deposit in the Great Xing'an Range,northeast China: metallogeny associated with Early Cretaceous magmatism

The Bairendaba vein-type Ag–Pb–Zn deposit, hosted in a Carboniferous quartz diorite, is one of the largest polymetallic deposits in the southern Great Xing'an Range. Reserves exceeding 8000 tonnes of Ag and 3 million tonnes of Pb?+?Zn with grades of 30 g/t and 4.5% have been estimated. We identify three distinct mineralization stages in this deposit: a barren pre-ore stage (stage 1), a main-ore stage with economic Ag–Pb–Zn mineralization (stage 2), and a post-ore stage with barren mineralization (stage 3). Stage 1 is characterized by abundant arsenopyrite?+?quartz and minor pyrite. Stage 2 is represented by abundant Fe–Zn–Pb–Ag sulphides and is further subdivided into three substages comprising the calcite–polymetallic sulphide stage (substage 1), the fluorite–polymetallic sulphide stage (substage 2), and the quartz–polymetallic sulphide stage (substage 3). Stage 3 involves an assemblage dominated by calcite with variable pyrite, galena, quartz, fluorite, illite, and chlorite. Fluid inclusion analysis and mineral thermometry indicate that the three stages of mineralization were formed at temperatures of 320–350°C, 200–340°C, and 180–240°C, respectively. Stage 1 early mineralization is characterized by low-salinity fluids (5.86–8.81 wt.% NaCl equiv.) with an isotopic signature of magmatic origin (δ¹⁸O_fluid = 10.45–10.65‰). The main ore minerals of stage 2 precipitated from aqueous–carbonic fluids (4.34–8.81 wt.% NaCl equiv.). The calculated and measured oxygen and hydrogen isotopic compositions of the ore-forming aqueous fluids (δ¹⁸O_fluid = 3.31–8.59‰, δD_fluid?=??132.00‰ to??104.00‰) indicate that they were derived from a magmatic source and mixed with meteoric water. Measured and calculated sulphur isotope compositions of hydrothermal fluids (δ³⁴S_∑S?=??1.2–3.8‰) indicate that the ore sulphur was derived mainly from a magmatic source. The calculated carbon isotope compositions of hydrothermal fluids (δ¹³C_fluid?=??26.52‰ to??25.82‰) suggest a possible contribution of carbon sourced from the basement gneisses. The stage 3 late mineralization is dominated (1.40–8.81 wt.% NaCl equiv.) by aqueous fluids. The fluids show lower δ¹⁸O_fluid (?16.06‰ to??0.70‰) and higher δD_fluid (?90.10‰ to??74.50‰) values, indicating a heated meteoric water signature. The calculated carbon isotope compositions (δ¹³C_fluid?=??12.82‰ to??6.62‰) of the hydrothermal fluids in stage 3 also suggest a possible contribution of gneiss-sourced carbon. The isotopic compositions and fluid chemistry indicate that the ore mineralization in the Bairendaba deposit was related to Early Cretaceous magmatism.     

Further stable isotope investigations of human urinary stones: comparison with other body components

Carbon and sulphur isotope investigations of human urinary stones have been expanded to relate such data to various body components and to diet. Techniques include isotopic determinations for various body components, for example, hair and urine, as well as trace sulphate and sulphide in apatite-struvite stones.Hair from individuals in Calgary was found to be, on average, about 3‰ depleted in¹³C in comparison to samples from Hawaii. Uric acid stones from both locations were found to be 1 to 3‰ enriched in¹³C, compared to hair. Oxalate stones from Calgary had δ¹³C values very close to those of hair. In contrast, oxalate stones from 31 patients from Honolulu fit the regression lineδ¹³C_oxalate= 0.8 δ¹³C_hair− 4.4‰, with a correlation coefficient of 0.77. It remains debatable as to whether the isotopic differences between the stones and hair reflects preferential incorporation of dietary components or kinetic isotope effects during biochemical conversions. There was no evidence in the data from Honolulu that ethnic background significantly influenced the carbon isotope composition of hair or kidney stones. There was a suggestion that recent arrivals had hair and stones slightly depleted in¹³C as compared to longer residents.The δ³⁴S values of cystine stones from Calgary were markedly consistent, near 0‰, and isotopic variations among different body components of individuals were of the order of 1‰.The trace sulphate content of a bladder stone from Papua New Guinea, was 300ppm S, whereas the sulphide content was negligible (determined by in vacuo Kiba extraction). The total S content of three samples from Calgary averaged 250 ppm, whereas 150 ppm was found for two stones each from Quito, Ecuador and Honolulu, Hawaii. For stones other than the speciment from Papua New Guinea, the sulphate-to-sulphide ratio varied from 1 to 4. The source of sulphide is uncertain but degradation of organic S could contribute to this fraction during Kiba extraction. The small range of δ³⁴S values (+3.5 to +7.4‰) for trace total S in the phosphate-containing urinary stones is believed to reflect only a fraction of the global variation of these materials. Trace sulphate was variably enriched in³⁴S (0 to 9‰) as compared to sulphide. Neither these enrichments, nor the sulphate-to-sulphide ratio, could be related to the struvite-to-apatite ratio.There were no significant differences in the carbon and sulphur isotope compositions of hair from patients and non-stone formers. Both the carbon and sulphur isotope variations can be attributed to the isotopic compositions of diets and the superposition of small kinetic isotope effects during biochemical conversions.     

Isotope and chemical composition of gases from mud volcanoes in the Taman Peninsula and problem of their genesis

Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ¹³C values in CH₄ and CO₂ vary from ?59.5 to ?44.0‰ (δ¹³C_av = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ¹³C_av = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO₂-HCO₃ system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO₃ ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy ¹³C isotope. The δ¹³C_TDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO₂, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ¹³C_TDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO₃ varies from 1–4 to 36–50 wt %. The δ¹³C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO₂ forms.     

Geochemical characteristics of methane from sediments of the underwater high Posolskaya Bank (Lake Baikal)

The component and carbon isotope compositions were studied in the hydrocabon gases from sediments of the underwater high Posolskaya Bank (Lake Baikal). It was established that sediments of this Baikal area contain methane of microbial (C₁/C₂ >16000; δ¹³C 70 ± 3‰) and thermocatalytic (C₁/C₂ <100; δ¹³C–46 ± 3‰) origin. Some samples represent a gas mixture of thermocatalytic and microbial origin. This gas is characterized by δ¹³C of methane varying from–60 to–70‰ and contains a significant amount of ethane. The main homolog of methane in the thermocatalytic and mixed gas is ethane. Owing to biodegradation, propane and butanes are present in trace amounts.     

Observation of CO2 degassing in Tianshuihai Lake Basin of the Qinghai-Tibetan Plateau

A large volume of underground gas in the permafrost region of the Qinghai-Tibetan Plateau has been identified. Although many studies were performed to investigate the soil organic carbon dynamics and Earth degassing in volcanic areas, this is the first report of a large amount of non-volcanic CO₂ contained in permafrost. The gas was mostly CO₂ (81.76 vol. %) and nitrogen (14.59 vol. %). The gas composition and the evidence from carbon stable isotope values (?23.9 ‰, PDB) suggested that the gases possibly had a deep origin. The gas emissions may be triggered by permafrost degradation, which means mitigation of the barrier effect of permafrost for the gas. In addition, plate tectonic processes may also lead to gas emissions, as the tectonic activity is strong in the area. Therefore, particular attention should be paid to the underground gases in the study of global change and permafrost degradation.     

Sulphur isotopes in carbonatites and associated silicate rocks from the Superior Province, Canada

Thirty-five S isotope analyses obtained from six carbonatite complexes from the Superior Province, Canadian Shield, ranging in age from 1,897 Ma to 1,093 Ma, have δ³⁴S_CDT values of between ?4.5‰ and +3.4‰. Pyrrhotite, chalcopyrite and pyrite mineral separates were used. Each complex possesses its own distinct range and mean S isotope composition. The range for Schryburt Lake is: ?4.5‰ to ?3.4‰ ( mean?=??3.9‰), for Big Beaver House: ?3.6‰ to ?1.5‰ (mean?=??2.2‰), for Cargill: ?1.5‰–+0.5‰ (mean?=??0.7‰), for Spanish River: ?0.1‰–+0.1‰ (mean?=?0.0‰), and for Firesand River: +1.3‰–+3.4‰ (mean?=?+1.7‰). A single sample from Carb Lake yielded a δ³⁴S_CDT value of +2.8‰. Differences in isotope compositions can be related to isotope effects brought about during melt generation and emplacment, such as variations in fo₂ and temperature. The different S and C isotope data for most complexes, however, suggest that the parental melts could have been generated from a heterogeneous mantle source, although process-driven changes cannot be completely ruled out.     

Carbon isotopes and geochemical processes in CO2-rich cold mineral water,N-Portugal

This paper summarizes a new outlook on the conceptual model of Melgaço–Messegães CO₂-rich cold (≈18 °C) mineral water systems, issuing in N of Portugal, based on their isotopic (²H, ³H, ¹³C, ¹⁴C and ¹⁸O) and geochemical features. Stable isotopes indicate the meteoric origin of these CO₂-rich mineral waters. Based on the isotopic fractionation with the altitude, a recharge altitude between 513 up to 740 m a.s.l. was estimated, corroborating the tritium results. The lowest ³H content (0 TU) is found in the groundwater samples with the highest mineralization. The mineral waters circulation are mainly related to a granitic and granodioritic environment inducing two different groundwater types (Ca/Na–HCO₃ and Na/Ca–HCO₃), indicating different underground flow paths. Calcium dissolution is controlled by hydrolysis of rock-matrix silicate minerals (e.g. Ca-plagioclases) and not associated to anthropogenic sources. The shallow dilute groundwaters exhibit signatures of anthropogenic origins (e.g. NO₃) and higher Na/Ca ratios. The stable isotopes together with the geochemistry provided no indication of mixing between the regional shallow cold dilute groundwater and mineral water systems. The heavy isotopic signatures identified in the δ¹³C data (δ¹³C = 4.7 ‰, performed on the total dissolved inorganic carbon (TDIC) of CO₂-rich mineral waters) could be derived from a deep-seated (upper mantle) source or associated to methanogenesis (CH₄ source). The negligible ¹⁴C content (≈2 pmC) determined in the TDIC of the mineral waters, corroborates the hypothesis of a mantle-derived carbon source to the mineral groundwater systems or dissolution of carbonate layers at depth.     

Trace element contents and C-O isotope geochemistry of the different originated magnesite deposits in Lake District (Southwestern Anatolia), Turkey

Vein-stockwork magnesite in the Madenli area, sedimentary huntite-magnesite in the A?a??t?rtar area, and lacustrine hydromagnesite in the Salda Lake area are located in the Bey?ehir-Hoyran and Lycian nappe rocks around Isparta and Burdur, Southwest Anatolia. The aim of this study is to understand trace element contents and carbon-oxygen isotope ratios in different originated magnesite, magnesite bearing huntite, and hydromagnesite deposits. Also, the element contents and isotope ratios of the magnesite occurrences are to compare with each other and similar magnesite occurrences in Turkey and world. It is found that the Madenli magnesite occurrences in the ?arkikaraa?aç ophiolites, A?a??t?rtar magnesite bearing huntite deposits in the lacustrine rocks of the Miocene-Pliocene, and the Salda hydromagnesite deposits in lacustrine basin on the Ye?ilova ophiolites. The paragenesis contains a common carbonate mineral magnesite, less calcite, serpentine, smectite, dolomite, and talc in the Madenli magnesite occurrences, mostly huntite and locally magnesite, dolomite, calcite, illite, quartz, and smectite in the A?a??t?rtar huntite-magnesite occurrences, and only hydromagnesite mineral in the Salda Lake hydromagnesite occurrences. Vein and stockwork Madenli magnesite deposits were recognized by higher total iron oxide concentrations (mean 1.10 wt%) than sedimentary A?a??t?rtar magnesite bearing huntite (mean 0.13 wt%) and lacustrine Salda hydromagnesite (mean 0.22 wt%) deposits. It is suggested that high Fe content (up to 5%) in the magnesite associated with ultramafic rocks than those from sedimentary environments (≤1% Fe). Based on average Ni, Co, Ba, Sr, As and Zr contents in the magnesite deposits, average Ni (134.63 ppm) and Co (15.19 ppm) contents in the Madenli magnesite and Salda hydromagnesite (36.85 ppm for Ni, 3.15 ppm for Co) have higher values than A?a??t?rtar huntite + magnesite (7.67 ppm for Ni and 0.89 ppm for Co). Average Ni-Co contents of these deposits can have close values depending on ophiolite host rock. Average Ba values of the Madenli (108.09 ppm) and A?a??t?rtar (115.88 ppm) areas are higher than those of Salda hydromagnesite (13.15 ppm). Sediment-hosted A?a??t?rtar magnesite-huntite deposits have the highest Sr contents (mean 505.81 ppm) as reasonably different from ultrabasic rock-related Madenli magnesite (mean 38.76 ppm) and Salda hydromagnesite (mean 36.70 ppm). The highest Sr content of sedimentary A?a??t?rtar deposits reveals that Sr is related to carbonate rocks. As and Zr contents have the highest average values (As 52.76 ppm and Zr 9.67 ppm) in the A?a??t?rtar deposits different from Madenli magnesite (As 0.54 ppm and Zr 1.67 ppm) and Salda hydromagnesite (As 0.5 ppm and Zr 2.58 ppm) deposits. High As and Zr concentrations in the A?a??t?rtar magnesite-huntite deposits may come from volcanic rocks in near country rocks. The δ ¹³C (PDB) isotope values vary between ?10.1 and ?11.4‰ in the Madenli magnesite, 7.8 to 8.8‰ for huntite, 1.7 to 8.3‰ for huntite + magnesite and 4.0‰ for limestone + magnesite in the A?a??t?rtar huntite-magnesite deposits, and 4.4 to 4.9‰ for Salda Lake hydromagnesite. The sources of the CO₂ are hydrothermal solutions, meteoric waters, groundwater dissolved carbon released from fresh water carbonates and marine limestone, soil CO₂, and plant C3 in the Madenli magnesite, and may be deep seated metamorphic reactions in limestone and shales of rich in terms of organic matter. The sources of CO₂ in A?a??t?rtar huntite and Salda hydromagnesite were meteoric water, groundwater dissolved inorganic carbon, fresh water carbonates, and marine limestone. The δ ¹⁸O (SMOW) isotope composition ranges from 26.8 to 28.1‰ in the Madenli magnesite, 30.4 to 32.4‰ for huntite and 29.8 to 35.5‰ for huntite + magnesite and 26.9‰ for limestone + magnesite in the A?a??t?rtar area, and 36.4 to 38.2‰ in the Salda Lake hydromagnesite. The Salda Lake hydromagnesite has heavier oxygen isotopic values than others. The sources of oxygen in the Madenli magnesite deposits are hydrothermal solutions, meteoric water, freshwater carbonates, and marine limestone, but the sources of oxygen of the A?a??t?rtar magnesite-huntite are meteoric water, fresh water carbonates, and marine limestone. The Salda Lake hydromagnesite has very high δ¹⁸O isotope values indicating a strong evaporitic environment. Magnesium (Mg⁺²) and silica are released by disintegration of very weathered-serpentinized ultrabasic rocks of all magnesite deposits and from partly dolomite and dolomitic limestone in the A?a??t?rtar magnesite bearing huntite deposits. In the A?a??t?rtar area, calcium (Ca⁺²) for huntite mineralization is provided by surrounding carbonate rocks. Based on isotopic data, host rocks, petrographic properties of the Madenli magnesite can be described as an ultramafic-associated hydrothermal vein mineralization corresponding to “Kraubath type” deposits, but A?a??t?rtar ve Salda Lake deposits are sedimentary mineralization (lacustrine/evaporitic) corresponding to “Bela Stena type” deposits. The estimated temperature using average δ¹⁸O isotope values is about 33.51 °C for Madenli magnesite, 48.33 °C for A?a??t?rtar huntite-magnesite, and 25 °C for Salda hydromagnesite. Based on isotope data, we can be say that the Madenli magnesite, A?a??t?rtar magnesite-huntite, and Salda hydromagnesite occur at low to moderate-low temperature water and alkaline (pH 8.5–10.5) under surface or near-surface conditions.     

Reconstruction of Holocene paleohydrological and sedimentological characteristics of Umm Ar-Rimam basin (northern Kuwait)

The paleohydrological and sedimentological characteristics of a playa lake in northern Kuwait (Arabian Gulf) are reconstructed using sedimentological, geochemical, and isotopic techniques. The sequence consists of up to 8 cycles of S-poor, alluvial sediments capped by a thin organic soil interbedded with gravity-fall calcrete sediments. The succession is locally derived from mainly Quaternary sediments and is regressive with upsection filling of the subsiding basin by cycles of sheetwash flow in response to climatic change. There is no natural, open-water lake water as indicated by low total organic carbon (TOC) data, but the presence of incised calcrete yardangs suggests that more extensive open-water conditions were operative in the past. Stable isotope (δ¹⁸O‰ and δ¹³C‰) values of the authigenic carbonates indicate the following three distinct processes: evaporation, meteoric fluid infiltration, and rapid per-descensum flow (rapid downward movement of water and playa sediment through pipes) through a porous, clastic sequence. Because evaporites are scarce, other factors besides evaporation action control chemical and isotopic compositions of the per-decensum lake fluids. Consequently, the isotopic composition cannot be interpreted exclusively as an indicator of salinity or evaporation ratio. The degassing of CO₂ during groundwater discharge may explain the enriched carbon isotope values for the authigenic carbonates precipitated in the sediments. Hydrologically closed lake water bodies tend to show low negative carbonate oxygen and carbon isotopic signatures. Isotopically negative δ¹³C values imply a strong input of soil-zone carbon to the groundwater of the top 60 cm of the sediment. Lakes that are hydrologically closed and evaporate or equilibrate with atmospheric CO₂ will tend to have low negative δ¹⁸O and δ¹³C values in the carbonates as reported by Talbot (Chem Geol: Isotope Geosci Sect 80(4):261–279, 1990). Biologically active lakes will tend toward lower δ¹³C of dissolved carbon due to the photosynthetic effects of ¹²C withdrawal as reported by Dunagan and Driese (J Sed Res 69:772–783, 1999). Increased biological activity during sedimentation may account for low carbon isotope values where plants were abundant, but in shrinkage-dominated systems (those of clay-rich soil subjecting to wet-dry conditions), carbon isotopes will be largely inherited from the calcretic limestones in the land extending landward of the coast and not influenced by coastal processes (known as hinterland), such as Umm Ar-Rimam depression. This basin does not fit the classic shallow playa-type basins of the Arabian Peninsula but rather the recharge playas of the southwestern USA.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

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.     

Variation characteristics of CO2 in a newly-excavated soil profile,Chinese Loess Plateau: Excavation-induced ancient soil organic carbon decomposition

Soils of the Chinese Loess Plateau(CLP)contain substantial amounts of soil inorganic carbon(SIC),as well as recent and ancient soil organic carbon(SOC).With the advent of the Anthropocene,human perturbation,including excavation,has increased soil CO₂ emission from the huge loess carbon pool.This study aims to determine the potential of loess CO₂ emission induced by excavation.Soil CO₂ were continuously monitored for seven years on a newly-excavated profile in the central CLP and the stable C isotope compositions of soil CO₂ and SOC were used to identify their sources.The results showed that the soil CO₂ concentrations ranged from 830μL·L^-1 to 11190μL·L^-1 with an annually reducing trend after excavation,indicating that the human excavation can induce CO₂ production in loess profile.Theδ¹³ C of CO₂ ranged from–21.27‰to–19.22‰(mean:–20.11‰),with positive deviation from top to bottom.The range of δ¹³CSOC was–24.0‰to–21.1‰with an average of–23.1‰.Theδ¹³ C-CO₂ in this study has a positive relationship with the reversed CO₂ concentration,and it is calculated that 80.22%of the soil CO₂ in this profile is from the microbial decomposition of SOC and 19.78%from the degasification during carbonate precipitation.We conclude that the human excavation can significantly enhance the decomposition of the ancient OC in loess during the first two years after perturbation,producing and releasing soil CO₂ to atmosphere.     

Groundwater Discharge as a Source of Dissolved Carbon and Greenhouse Gases in a Subtropical Estuary

Groundwater may be highly enriched in dissolved carbon species, but its role as a source of carbon to coastal waters is still poorly constrained. Exports of deep and shallow groundwater-derived dissolved carbon species from a small subtropical estuary (Korogoro Creek, Australia, latitude ?31.0478°, longitude 153.0649°) were quantified using a radium isotope mass balance model (²³³Ra and ²²⁴Ra, natural groundwater tracers) under two hydrological conditions. In addition, air-water exchange of carbon dioxide and methane in the estuary was estimated. The highest carbon inputs to the estuary were from deep fresh groundwater in the wet season. Most of the dissolved carbon delivered by groundwater and exported from the estuary to the coastal ocean was in the form of dissolved inorganic carbon (DIC; 687 mmol m^?2 estuary day^?1; 20 mmol m^?2 catchment day^?1, respectively), with a large export of alkalinity (23 mmol m^?2 catchment day^?1). Average water to air flux of CO₂ (869 mmol m^?2 day^?1) and CH₄ (26 mmol m^?2 day^?1) were 5- and 43-fold higher, respectively, than the average global evasion in estuaries due to the large input of CO₂- and CH₄-enriched groundwater. The groundwater discharge contribution to carbon exports from the estuary for DIC, dissolved organic carbon (DOC), alkalinity, CO₂, and CH₄ was 22, 41, 3, 75, and 100 %, respectively. The results show that CO₂ and CH₄ evasion rates from small subtropical estuaries surrounded by wetlands can be extremely high and that groundwater discharge had a major role in carbon export and evasion from the estuary and therefore should be accounted for in coastal carbon budgets.