Land Application of Sulfate Salts for Enhanced Natural Attenuation of Benzene in Groundwater: A Case Study

Sulfate reducing conditions are widely observed in groundwater plumes associated with petroleum hydrocarbon releases. This leads to sulfate depletion in groundwater which can limit biodegradation of hydrocarbons (usually benzene, toluene, ethylbenzene, xylenes [BTEX] compounds) and can therefore result in extended timeframes to achieve groundwater cleanup objectives by monitored natural attenuation. Under these conditions, sulfate addition to the subsurface can potentially enhance BTEX biodegradation and facilitate enhanced natural attenuation. However, a delivery approach that enables effective contact with the hydrocarbons and is able to sustain elevated and uniform sulfate concentrations in groundwater remains a key challenge. In this case study, sulfate addition to a groundwater plume containing predominantly benzene by land application of agricultural gypsum and Epsom salt is described. Over 4 years of groundwater monitoring data from key wells subjected to pilot‐scale and site‐wide land application events are presented. These are compared to data from pilot testing employing liquid Epsom salt injections as an alternate sulfate delivery approach. Sulfate land application, sulfate retention within the vadose zone, and periodic infiltration following ongoing precipitation events resulted in elevated sulfate concentrations (>150 mg/L) in groundwater that were sustained over 12 months between application events and stimulated benzene biodegradation as indicated by declines in dissolved benzene concentration, and compound‐specific isotope analysis data for carbon in benzene. Long‐term groundwater benzene concentration reductions were achieved in spite of periodic rebounds resulting from water table fluctuations across the smear zone. Land application of gypsum is a potentially cost‐effective sulfate delivery approach at sites with open, unpaved surfaces, relatively permeable geology, and shallow hydrocarbon impacts. However, more research is needed to understand the fate and persistence of sulfate and to improve the likelihood of success and effectiveness of this delivery approach.     

Carbon Isotope Analysis to Evaluate Nanoscale Fe(O) Treatment at a Chlorohydrocarbon Contaminated Site

Remediation of groundwater contaminated by chlorinated hydrocarbons via in situ technologies such as direct injection of nanoscale zero valent iron (ZVI, Fe(O)) particles is increasingly common. However, assessing target compound degradation by abiotic processes is difficult because (1) the injection may displace the contaminant plume so that concentration measurements alone are often inconclusive and (2) biodegradation may also occur, making it challenging to identify and evaluate the abiotic degradation component. In this study, trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA) were treated in a highly heterogeneous hydrogeologic setting. The purpose of this study was to evaluate the potential for compound-specific stable isotope analysis (CSIA) to monitor the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA degradation. Prior to ZVI injection, carbon isotope measurements demonstrated biodegradation of TCE by native microorganisms. This in situ biodegradation was quantified by measuring the enrichment of ¹³C in TCE samples downstream of the suspected source. When ZVI was injected through only two injection wells, no changes in TCE and 1,1,1-TCA isotope signatures were detected compared to preinjection values. In contrast, when ZVI was injected through 11 wells covering a greater portion of the contaminated area, 5 out of 10 monitoring wells showed further enrichment of ¹³C in either TCE or 1,1,1-TCA, indicating additional target compound transformation. The abiotic nature of this TCE transformation was confirmed through temporal trends in carbon isotope values of the putative transformation products cis-dichloroethylene (cis-DCE), ethene and ethane. This demonstrates the usefulness of CSIA in distinguishing abiotic vs. biotic transformation in the field.     

Benzene Dynamics and Biodegradation in Alluvial Aquifers Affected by River Fluctuations

The spatial distribution and temporal dynamics of a benzene plume in an alluvial aquifer strongly affected by river fluctuations was studied. Benzene concentrations, aquifer geochemistry datasets, past river morphology, and benzene degradation rates estimated in situ using stable carbon isotope enrichment were analyzed in concert with aquifer heterogeneity and river fluctuations. Geochemistry data demonstrated that benzene biodegradation was on‐going under sulfate reducing conditions. Long‐term monitoring of hydraulic heads and characterization of the alluvial aquifer formed the basis of a detailed modeled image of aquifer heterogeneity. Hydraulic conductivity was found to strongly correlate with benzene degradation, indicating that low hydraulic conductivity areas are capable of sustaining benzene anaerobic biodegradation provided the electron acceptor (SO₄^2–) does not become rate limiting. Modeling results demonstrated that the groundwater flux direction is reversed on annual basis when the river level rises up to 2 m, thereby forcing the infiltration of oxygenated surface water into the aquifer. The mobilization state of metal trace elements such as Zn, Cd, and As present in the aquifer predominantly depended on the strong potential gradient within the plume. However, infiltration of oxygenated water was found to trigger a change from strongly reducing to oxic conditions near the river, causing mobilization of previously immobile metal species and vice versa. MNA appears to be an appropriate remediation strategy in this type of dynamic environment provided that aquifer characterization and targeted monitoring of redox conditions are adequate and electron acceptors remain available until concentrations of toxic compounds reduce to acceptable levels.     

Methane Production and Isotopic Fingerprinting in Ethanol Fuel Contaminated Sites

Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ¹³C = −11.1‰) is more enriched in ¹³C, with δ¹³C values ranging from −20‰ to −30‰, while the methane from toluene (δ¹³C = −28.5‰) had a carbon isotopic signature of −55‰. The field samples had δ¹³C values varying over a wide range (−10‰ to −80‰), and the δ¹³C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded.     

Effect of Biofuels on Biodegradation of Benzene and Toluene at Gasoline Spill Sites

The risk that benzene and toluene from spills of gasoline will impact drinking water wells is largely controlled by the natural anaerobic biodegradation of benzene and toluene. Benzene and toluene, as well as ethanol and other biofuels, are degraded under anaerobic conditions to the same pool of degradation products. Biodegradation of biofuels may produce concentrations of degradation products that make the thermodynamics for degradation of benzene and toluene infeasible under methanogenic conditions and produce larger plumes of benzene and toluene. This study evaluated the concentrations of fuel alcohols that are necessary to inhibit the anaerobic degradation of benzene and toluene under methanogenic conditions. At two ethanol spill sites, concentrations of ethanol greater ≥42 mg/L inhibited the anaerobic degradation of toluene. The pH and concentrations of acetate, dissolved inorganic carbon, and molecular hydrogen were used to calculate the Gibbs free energy for the biodegradation of toluene. In general, the anaerobic biodegradation of toluene was not thermodynamically feasible in water with ≥42 mg/L ethanol. In a microcosm study, when the concentrations of ethanol were ≥14 mg/L or the concentrations of n‐butanol were ≥16 mg/L, the biodegradation of the alcohols consistently produced concentrations of hydrogen, dissolved inorganic carbon, and acetate that would preclude natural anaerobic biodegradation of benzene and toluene by syntrophic organisms. In contrast, iso‐butanol and n‐propanol only occasionally produced conditions that would preclude the biodegradation of benzene and toluene.     

Geochemical Indicators of Intrinsic Bioremediation

A detailed field investigation has been completed at a gasoline-contaminated aquifer near Rocky Point, NC, to examine possible indicators of intrinsic bioremediation and identify factors that may significantly influence the rate and extent of bioremediation. The dissolved plume of benzene, toluene, ethylbenzene, and xylene (BTEX) in ground water is naturally degrading. Toluene and o-xylene are most rapidly degraded followed by m-, p-xylene, and benzene. Ethylbenzene appears to degrade very slowly under anaerobic conditions present in the center of the plume. The rate and extent of biodegradation appears to be strongly influenced by the type and quantity of electron acceptors present in the aquifer. At the upgradient edge of the plume, nitrate, ferric iron, and oxygen are used as terminal electron acceptors during hydrocarbon biodegradation. The equivalent of 40 to 50 mg/I of hydrocarbon is degraded based on the increase in dissolved CO₂ relative to background ground water. Immediately downgradient of the source area, sulfate and iron are the dominant electron acceptors. Toluene and o-xylene are rapidly removed in this region. Once the available oxygen, nitrate, and sulfate are consumed, biodegradation is limited and appears to be controlled by mixing and aerobic biodegradation at the plume fringes.     

Sulfur isotope ratios of Icelandic lava incrustations and volcanic gases

Sulfur isotope ratios were measured in eight lava incrustations and three volcanic gas samples and their corresponding lava flows. The lava incrustations of sulfate composition are from five recent eruptions and occur as thenardite or as aphtitalite-thenardite mixtures, with abundant trace elements. The incrustations show small sulfur isotope fractionation of 1–2‰ compared with corresponding lavas and the volcanic gas samples. The sulfate incrustations are formed through oxidation of SO₂ from the emitted volcanic gas and subsequent reaction with metal halides. The volcanic gas samples show a distribution of decreasing δ³⁴S through time from +3.4 to −1.8‰; sulfate was preferentially degassed compared to sulfide. The data indicate that sulfate incrustations serve as a late-stage volcanic gas sample with respect to sulfur isotopes.     

Enhancing Microbial Sulfate Reduction of Hydrocarbons in Groundwater Using Permeable Filled Borings

At a service station closed in 1993, groundwater contained benzene that persisted above the cleanup goal of 1 mg/L in zones depleted of background sulfate. The benzene and other petroleum hydrocarbons (PHCs) were present as much as 36 feet (11 m) below the water table and therefore remediation of a thick saturated zone interval was required. Microcosms using site sediments demonstrated that anaerobic benzene biodegradation occurred only if sulfate was added, suggesting sulfate addition as a remediation approach. Twenty-four boreholes (9.1″ diameter and 56′ deep) were drilled around four monitoring wells, in which benzene concentrations exceeded 1 mg/L. The boreholes were backfilled with a mixture of gravel and 15,000 pounds of gypsum (which releases sulfate as it dissolves) to create “Permeable Filled Borings” (PFBs). Concurrently, nine high pressure injections (HPIs) of gypsum slurry were conducted in other site locations (312 pounds of gypsum total). PFBs were expected to release sulfate for up to 20 years, whereas HPIs were expected to produce a short-lived plume of sulfate. Concentrations of benzene and sulfate in groundwater were monitored over a 3-year period in six monitoring wells. In two wells near PFBs, benzene concentrations dropped below the cleanup goal by two to three orders of magnitude; in one well, sulfate concentrations exceeded 500 mg/L for the most recent 18 months. Benzene concentrations in two other PFB monitoring wells declined by a factor of 2 to 4, but remained above 1 mg/L, presumably due to high-dissolved PHC concentrations and possibly greater residual PHC mass in adjacent sediments, and therefore greater sulfate demand. However, hydrogen and sulfur isotopic enrichment in benzene and sulfate, respectively, confirmed biodegradation of benzene and stimulation of sulfate-reducing conditions. Thus, it is hypothesized that the PHC mass in adjacent sediments will decline over time, as will dissolved PHC concentrations, and eventually benzene concentrations will decrease below the cleanup goal. Benzene in two HPI monitoring wells was below the cleanup goal for all but one sampling event before HPIs were conducted and remained below the cleanup goal after HPIs; there was no stimulation of sulfate-reducing conditions. It is concluded that sulfate released from PFBs contributed to declining benzene concentrations.     

Massive barite deposits and carbonate mineralization in the Derugin Basin, Sea of Okhotsk: precipitation processes at cold seep sites

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (∼1%) in the barite fabric imply the presence of H₂S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative δ¹³C values of these carbonates (>−43.5‰ PDB) indicate methane as major carbon source; δ¹⁸O values between 4.04 and 5.88‰ PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with ¹⁴C-ages ranging from 20?680 to >49?080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO₄^2- concentrations and a parallel increase of H₂S with depth. Additionally, S and O isotope data of barite sulfate (δ³⁴S: 21.0-38.6‰ CDT; δ¹⁸O: 9.0-17.6‰ SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with ‘normal’ seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49?000 yr.     

Enhancement of In Situ Bioremediation of BTEX-Contaminated Ground Water by Oxygen Diffusion from Silicone Tubing

A field study of oxygen-enhanced biodegradation was carried out in a sandy iron-rich ground water system contaminated with gasoline hydrocarbons. Prior to the oxygen study, intrinsic microbial biodegradation in the contaminant plume had depleted dissolved oxygen and created anaerobic conditions. An oxygen diffusion system made of silicone polymer tubing was installed in an injection well within an oxygen delivery zone containing coarse highly permeable sand. During the study, this system delivered high dissolved oxygen (DO) levels (39 mg/L) to the ground water within a part of the plume. The ground water was sampled at a series of monitors in the test zone downgradient of the delivery well to determine the effect of oxygen on dissolved BTEX, ground water geochemistry, and microbially mediated biodegradation processes. The DO levels and Eh increased markedly at distances up to 2.3 m (7.5 feet) downgradient. Potential biofouling and iron precipitation effects did not clog the well screens or porous medium. The increased dissolved oxygen enhanced the population of aerobes while the activity of anaerobic sulfate-reducing bacteria and methanogens decreased. Based on concentration changes, the estimated total rate of BTEX biodegradation rose from 872 mg/day before enhancement to 2530 mg/day after 60 days of oxygen delivery. Increased oxygen flux to the test area could account for aerobic biodegradation of 1835 mg/day of the BTEX. The estimated rates of anaerobic biodegradation processes decreased based on the flux of sulfate, iron (II), and methane. Two contaminants in the plume, benzene and ethylbenzene, are not biodegraded as readily as toluene or xylenes under anaerobic conditions. Following oxygen enhancement, however, the benzene and ethylbenzene concentrations decreased about 98%, as did toluene and total xylenes.     

The hydrothermal system of Mendeleev Volcano,Kunashir Island,Kuril Islands: The geochemistry and the transport of magmatic components

This paper reports a detailed geochemical study of thermal occurrences as observed in the edifice and on the flanks of Mendeleev Volcano, Kunashir Island in August and September 2015. We showed that three main types of thermal water are discharged there (neutral chloride sodium, acid chloride sulfate, and acid sulfate types); these waters exhibit a zonality that is typical of volcano-hydrothermal island arc systems. Spontaneous and solfataric gases have relatively low ³He/⁴He ratios, ranging between 5.4Ra and 5.6Ra, and δ¹³C-CO₂ between –4.8‰ and –3.1‰, and contain a light isotope of carbon in methane (δ¹³C ≈ –40‰). Gas and isotope geothermometers yield relatively low temperatures around 200°C. The isotope compositions in all types of water are similar to that of local meteoric water. The distribution of microcomponents varies among different types. The isotope composition of dissolved Sr varies considerably, from 0.7034 as observed in Kunashir rocks on an average to 0.7052 in coastal springs, which may have resulted from admixtures of seawater. The total hydrothermal transport rates of magmatic Cl and SO₄, as observed for Mendeleev Volcano, are 7.8 t/d and 11.6 t/d, respectively. The natural outward transport of heat by the volcano’s hydrothermal system is estimated as 21 MW.     

Quantifying the sources of dissolved inorganic carbon within the sulfate-methane transition zone in nearshore sediments of Qi’ao Island,Pearl River Estuary,Southern China

The significance of the various biogeochemical pathways that drive carbon cycling and the relative fractions of dissolved inorganic carbon(DIC) produced by these reactions within the sulfate-methane transition zone(SMTZ) are still being debated. Unraveling these processes is important to our understanding of the benthic DIC sources and their contributions to the global carbon cycle. Here, we measure pore water geochemistry(chlorine, sulfate, methane, Ca~(2+), Mg~(2+), DIC and δ~(13)C-DIC) as well as solid geochemistry(sedimentary organic carbon(SOC) and δ~(13)C of SOC) in nearshore sediments from Qi'ao Island in the Pearl River Estuary of the Southern China Sea. Our analysis indicates that SOC originates from the mixing of carbon from terrestrial and marine sources, and that terrestrial materials dominate the net loss of SOC during the degradation of organic matter, especially at sites located near the river outlets. Sulfate reduction via SOC degradation is not appreciable in the upper sediment layer due to conservative mixing-dilution by freshwater. However, below this layer, the anaerobic oxidation of methane(AOM) and methanogenesis occur. Within the SMTZ, the δ~(13)C mass balance shows that the proportions of DIC derived from organoclastic SO_4~(2-) reduction(OSR) and AOM are 50.3% to 66.7% and 0.1% to 17.9%, respectively, whereas methanogenesis contributes 17.0% to 43.9%. This study reveals that the upward diffusion of DIC from ongoing methanogenesis significantly influences carbon cycling within the SMTZ in these estuarine sediments. As a result, we suggest that the plots of the ratio of change in sulfate to change in DIC in pore water should be used with caution when discriminating between sulfate reduction pathways in methane-rich sediments.     

Stable isotope fractionation of fatty acids of Daphnia fed laboratory cultures of microalgae

We tested a comparatively new method of tracing of natural food webs, compound-specific isotope analysis (CSIA) of fatty acids (FA), using laboratory culture of Daphnia galeata fed Chlorella vulgaris and Cryptomonas sp. In general, Daphnia had significantly lighter carbon stable isotope composition of most fatty acids, including essential, than those of their food, microalgae. Thus, our results did not support the pivotal premise of the FA-CSIA application for food web analysis, i.e., transmitting the isotope ‘signal’ of essential FAs to consumers from their food without any modification. Moreover, the values of isotope fractionation of particular FAs in the consumer relative to its food were not constant, but varied from 1.35‰ to 7.04‰. The different isotope fractionation (depletion) values of diverse FAs in consumer were probably caused by different processes of their synthesis, catabolism and assimilation. More work is evidently to be done for correct interpretation of results of FA-CSIA during field studies for tracing of natural food webs.     

Methan- und Sauerstoffhaushalt im mesotrophen Lungernsee

Prealpine Lake Lungern shows in spite of low primary production rates (120 g C/m². year) and full winter overturns a complete oxygen depletion in the deepest hypolimnion (65–70 m below surface) towards the end of summer stagnation. Periodical examinations of O₂- and CH₄-concentrations, CH₄-oxidation rates and temperature in the water column during 1975/76 enabled an O₂-balance of Lake Lungern. The direct measurement of the CH₄-flux at the sediment-water-interface and of the CH₄-concentrations in sediment cores as well as the determination of the age of methane bubbles lead to the conclusion, that the hypolimnic oxygen depletion is partly due to the oxidation of fossile methane penetrating the lake from below.      

Biodegradation of Petroleum Hydrocarbons by Pseudomonas putida Strain MHF 7109

Pseudomonas putida MHF 7109 has been isolated and identified from cow dung microbial consortium for biodegradation of selected petroleum hydrocarbon compounds – benzene, toluene, and o‐xylene (BTX). Each compound was applied separately at concentrations of 50, 100, 250, and 500 mg L^?1 in minimal salt medium to evaluate degradation activity of the identified microbial strain. The results indicated that the strain used has high potential to degrade BTX at a concentration of 50 mg L^?1 within a period of 48, 96, and 168 h, respectively; whereas the concentration of 100 mg L^?1 of benzene and toluene was found to be completely degraded within 120 and 168 h, respectively. Sixty‐two percent of o‐xylene were degraded within 168 h at the 100 mg L^?1 concentration level. The maximum degradation rates for BTX were 1.35, 1.04, and 0.51 mg L^?1 h^?1, respectively. At higher concentrations (250 and 500 mg L^?1) BTX inhibited the activity of microorganisms. The mass spectrometry analysis identified the intermediates as catechol, 2‐hydroxymuconic semialdehyde, 3‐methylcatechol, cis‐2‐hydroxypenta‐2,4‐dienoate, 2‐methylbenzyl alcohol, and 1,2‐dihydroxy‐6‐methylcyclohexa‐3,5‐dienecarboxylate, for BTX, respectively. P. putida MHF 7109 has been found to have high potential for biodegradation of volatile petroleum hydrocarbons.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

Differences in stable isotope compositions of freshwater snails from surface sediments of two Polish shallow lakes

The study reports and discusses the differences in δ¹³C and δ¹⁸O values of shells between several species of freshwater snails. Shells were derived from sediment samples collected from depths of 0.5, 1, 2 and 3 m along transects in two shallow eutrophic lakes located in mid-western Poland. Mean δ¹³C values of the shells ranged between −7.5 and −3.8‰ in Lake Jarosławieckie and between −8.1 and −5.2‰ in Lake Rosnowskie Duże, whereas mean δ¹⁸O values ranged between −2.2 and −0.2‰ and between −2.2 and 0.4‰ respectively in the studied lakes. A similar order of species in terms of shell isotope values, from least to most ¹³C and ¹⁸O-depleted was observed in both lakes and seems to indicate constancy of the factors controlling the stable isotope compositions of snail shells. We postulate that the nearly 4‰ difference in the mean carbon stable isotope values between the species was primarily controlled by the amount of metabolic carbon incorporated into the shells and the δ¹³C values of the snail food. Different growth cessation temperatures and microhabitats of the species studied result in temporally and spatially varied DIC δ¹³C values, water δ¹⁸O values and water temperature of shell precipitation, and may thus differentiate the δ¹³C and δ¹⁸O values of shells. The range of δ¹³C and δ¹⁸O values of individual shells from a sediment sample (mean 2.35 and 2.15‰, respectively) is interpreted as reflecting an intraspecific variability of isotope compositions in shells from a population and changes of the ambient conditions during the accumulation of the sediment layer. The species-specificity and intraspecific variability in C and O isotopic compositions of shells allow concluding that in palaeolimnological studies, stable isotope analyses should be performed on a set of mono-specific shells representing mean isotope compositions of the species for the interval studied rather than single shells or multispecific bulk shell material.     

Environmental Factors Associated With Natural Methane Occurrence in the Appalachian Basin

The recent boom in shale gas development in the Marcellus Shale has increased interest in the methods to distinguish between naturally occurring methane in groundwater and stray methane associated with drilling and production operations. This study evaluates the relationship between natural methane occurrence and three principal environmental factors (groundwater redox state, water type, and topography) using two pre‐drill datasets of 132 samples from western Pennsylvania, Ohio, and West Virginia and 1417 samples from northeastern Pennsylvania. Higher natural methane concentrations in residential wells are strongly associated with reducing conditions characterized by low nitrate and low sulfate ([NO₃^?] < 0.5 mg/L; [SO₄^2?] < 2.5 mg/L). However, no significant relationship exists between methane and iron [Fe(II)], which is traditionally considered an indicator of conditions that have progressed through iron reduction. As shown in previous studies, water type is significantly correlated with natural methane concentrations, where sodium (Na) ‐rich waters exhibit significantly higher (p<0.001) natural methane concentrations than calcium (Ca)‐rich waters. For water wells exhibiting Na‐rich waters and/or low nitrate and low sulfate conditions, valley locations are associated with higher methane concentrations than upland topography. Consequently, we identify three factors (“Low NO₃^? & SO₄^2?” redox condition, Na‐rich water type, and valley location), which, in combination, offer strong predictive power regarding the natural occurrence of high methane concentrations. Samples exhibiting these three factors have a median methane concentration of 10,000 µg/L. These heuristic relationships may facilitate the design of pre‐drill monitoring programs and the subsequent evaluation of post‐drill monitoring results to help distinguish between naturally occurring methane and methane originating from anthropogenic sources or migration pathways.     

Use of Hydrogeochemistry and Isotopes for Evaluation of Groundwater in Qilian Coal Base of China

The Jiangcang Basin is an important mining area of the former Qilian Mountain large coal base in Qinghai Province, and understanding the groundwater circulation mechanism is the basis for studying the hydrological effects of permafrost degradation in alpine regions. In this study, hydrogeochemical and multiple isotope tracer analysis methods are used to understand the chemical evolution and circulation mechanisms of the groundwater in the typical alpine region of the Jiangcang Basin. The diversity of the groundwater hydrochemistry in the study area reflects the complexity of the hydrogeochemical environment in which it is located. The suprapermafrost water and intrapermafrost water are recharged by modern meteoric water. The groundwater is closely hydraulically connected to the surface water with weak evaporation overall. The high δ³⁴S value of deep groundwater is due to SO₄ reduction, and SO₄²⁻-rich snow recharge with lixiviated sulfate minerals are the main controlling factor for the high SO₄²⁻ concentration in groundwater. According to the multivariate water conversion relationships, it reveals that the river receives more groundwater recharge, suprapermafrost water is recharged by the proportion of meteoric water, which is closely related to the mountainous area at the edge of the basin, while intrapermafrost water is mainly recharged by the shallow groundwater. This study provides a data-driven approach to understanding groundwater recharge and evolution in alpine regions, in addition to having significant implications for water resource management and ecological environmental protection in coal bases of the Tibetan Plateau.