Stable isotope fractionation during bacterial sulfate reduction is controlled by reoxidation of intermediates

Bacterial sulfate reduction is one of the most important respiration processes in anoxic habitats and is often assessed by analyzing the results of stable isotope fractionation. However, stable isotope fractionation is supposed to be influenced by the reduction rate and other parameters, such as temperature. We studied here the mechanistic basics of observed differences in stable isotope fractionation during bacterial sulfate reduction. Batch experiments with four sulfate-reducing strains (Desulfovibrio desulfuricans, Desulfobacca acetoxidans, Desulfonatronovibrio hydrogenovorans, and strain TRM1) were performed. These microorganisms metabolize different carbon sources (lactate, acetate, formate, and toluene) and showed broad variations in their sulfur isotope enrichment factors. We performed a series of experiments on isotope exchange of ¹⁸O between residual sulfate and ambient water. Batch experiments were conducted with ¹⁸O-enriched (δ¹⁸O_water = +700‰) and depleted water (δ¹⁸O_water = −40‰), respectively, and the stable ¹⁸O isotope shift in the residual sulfate was followed. For Desulfovibrio desulfuricans and Desulfonatronovibrio hydrogenovorans, which are both characterized by low sulfur isotope fractionation (ε_S > −13.2‰), δ¹⁸O values in the remaining sulfate increased by only 50‰ during growth when ¹⁸O-enriched water was used for the growth medium. In contrast, with Desulfobacca acetoxidans and strain TRM1 (ε_S < −22.7‰) the residual sulfate showed an increase of the sulfate δ¹⁸O close to the values of the enriched water of +700‰. In the experiments with δ¹⁸O-depleted water, the oxygen isotope values in the residual sulfate stayed fairly constant for strains Desulfovibrio desulfuricans, Desulfobacca acetoxidans and Desulfonatronovibrio hydrogenovorans. However, strain TRM1, which exhibits the lowest sulfur isotope fractionation factor (ε_S < −38.7‰) showed slightly decreasing δ¹⁸O values.Our results give strong evidence that the oxygen atoms of sulfate exchange with water during sulfate reduction. However, this neither takes place in the sulfate itself nor during formation of APS (adenosine-5′-phosphosulfate), but rather in intermediates of the sulfate reduction pathway. These may in turn be partially reoxidized to form sulfate. This reoxidation leads to an incorporation of oxygen from water into the “recycled” sulfate changing the overall ¹⁸O isotopic composition of the remaining sulfate fraction. Our study shows that such incorporation of ¹⁸O is correlated with the stable isotope enrichment factor for sulfur measured during sulfate reduction. The reoxidation of intermediates of the sulfate reduction pathway does also strongly influence the sulfur stable isotope enrichment factor. This aforesaid reoxidation is probably dependent on the metabolic conversion of the substrate and therefore also influences the stable isotope fractionation factor indirectly in a rate dependent manner. However, this effect is only indirect. The sulfur isotope enrichment factors for the kinetic reactions themselves are probably not rate dependent.     

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S⁰ was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H₂S. At the shelf stations, on the other hand, pyrite was significantly depleted in ³⁴S relative to its potential precursors FeS and S⁰. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ³⁴S-values of pyrite down to −38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The ¹⁸O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations.     

Potential application of oxygen-18 and deuterium in mining effluent and acid rock drainage studies

 Oxygen-18 (¹⁸O) and deuterium (D, or ²H) are routinely used in hydrologic, climatologic and geothermal studies. In hydrology, stable isotopes provide information on the type and topology (altitude and latitude) of the recharge waters and the historical effects on water, related to such physical processes as evaporation (in ponds), melting (of snow or ice), condensation, evapotranspiration and mixing. In geothermal studies, stable isotopes provide key information related to recharge and the various temperature-dependent water/rock isotope exchange reactions. The latter is assessed through the oxygen shift in the ¹⁸O/D correlation. At acid rock drainage (ARD) sites, water/rock interactions are primarily controlled by pH and oxidation potential. Using the isotopic characteristics of the rocks and the recharge waters as a basis, the relative oxygen shift of the ARD effluent can provide information on: (1) the residence time, (2) the rate of water/rock reactions, and (3) the actual pH at the rock/water interface. This paper offers a methodology for conducting oxygen and hydrogen isotope studies related to ARD and other mineral effluent problems. The methodology is based on: (1) comprehensive sampling of regional waters, ARD effluent and major contributing minerals and rocks, (2) isotopic and elemental analysis, and (3) data interpretation on the basis of a zero-dimensional (mass balance), multi-component mixing model. Received: 15 January 1999 · Accepted: 3 May 1999     

Stable isotope fractionation between mollusc shells and marine waters from Martinique Island

Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ¹⁸O=0.5‰) are characterized by mean δ¹³C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ¹⁸O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ¹⁸O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude.     

Sulfur cycling in a stratified euxinic lake with moderately high sulfate: Constraints from quadruple S isotopes

We present a 3-year study of concentrations and sulfur isotope values (δ³⁴S, Δ³³S, and Δ³⁶S) of sulfur compounds in the water column of Fayetteville Green Lake (NY, USA), a stratified (meromictic) euxinic lake with moderately high sulfate concentrations (12-16 mM). We utilize our results along with numerical models (including transport within the lake) to identify and quantify the major biological and abiotic processes contributing to sulfur cycling in the system. The isotope values of sulfide and zero-valent sulfur across the redox-interface (chemocline) change seasonally in response to changes in sulfide oxidation processes. In the fall, sulfide oxidation occurs primarily via abiotic reaction with oxygen, as reflected by an increase in sulfide δ³⁴S at the redox interface. Interestingly, S isotope values for zero-valent sulfur sampled at this time still reflect production and recycling by phototrophic S-oxidation. In the spring, sulfide S isotope values suggest an increased input from phototrophic oxidation, consistent with a more pronounced phototroph population at the chemocline. This trend is associated with smaller fractionations between sulfide and zero-valent sulfur, suggesting a metabolic rate control on fractionation similar to that for sulfate reduction. Comparison of our data with previous studies indicates that the S isotope values of sulfate and sulfide in the deep waters are remarkably stable over long periods of time, with consistently large fractionations of up to 58‰ in δ³⁴S. Models of the δ³⁴S and Δ³³S trends in the deep waters (considering mass transport via diffusion and advection along with biological processes) require that these fractionations are a consequence of sulfur compound disproportionation at and below the redox interface in addition to large fractionations during sulfate reduction. The large fractionations during sulfate reduction appear to be a consequence of the high sulfate concentrations and the distribution of organic matter in the water column. The occurrence of disproportionation in the lake is supported by profiles of intermediate sulfur compounds and by lake microbiology, but is not evident from the δ³⁴S trends alone. These results illustrate the utility of including minor S isotopes in sulfur isotope studies to unravel complex sulfur cycling in natural systems.     

Stable isotope composition of Hellenic bottled waters

Bottled waters are an increasingly significant product in the human diet. In this work, we present a dataset of stable isotope ratios for bottled waters sampled in Greece. A total of 25 domestic brands of bottled still waters, collected on the Greek market in 2009, were analysed for δ¹⁸O and δ²H. The measured stable isotope ratios range from − 9.9‰ to − 6.9‰ for δ¹⁸O and from − 67.50‰ to − 46.5‰ for δ²H. Comparison of bottled water isotope ratios with natural spring water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, showing that bottled water isotope ratios preserve information about the water sources from which they were derived and suggesting that in many cases bottled water should not be considered as an isotopically distinct component of the human diet. This investigation also helped to determine the natural origin of bottled water, and to indicate differences between the natural and production processes. The production process may influence the isotopic composition of waters. No such modification was observed for sampled waters in this study. The isotopic methods applied can be used for the authentication of bottled waters and for use in the regulatory monitoring of water products.     

Modelling fractionation of stable isotopes in stalagmites

High resolution δ¹³C and δ¹⁸O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ¹³C and δ¹⁸O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water p_CO2 and a mixing coefficient describing mixing processes between the solution layer and the impinging drop.The evolution of δ¹³C values is modelled as a Rayleigh distillation process and shows a pronounced dependence on the residence time of the solution on the stalagmite surface and the drip interval, respectively. The evolution of δ¹⁸O values, in contrast, is also influenced by buffering reactions between the bicarbonate in the solution and the drip water driving the δ¹⁸O value of the bicarbonate towards the value expected for equilibrium isotope fractionation between drip water and calcite. This attenuates the dependence of the δ¹⁸O values on drip interval. The temperature dependence of δ¹⁸O, however, is more pronounced than for δ¹³C and in a similar range as expected for fractionation under equilibrium conditions.We also investigate the isotopic enrichment of the δ¹³C and δ¹⁸O values along individual growth layers and, thus, the slopes expected for Hendy tests. The results show that a positive Hendy test is only possible if isotope fractionation occurred under disequilibrium conditions. However, a negative Hendy test does not exclude that isotope fractionation occurred under disequilibrium conditions. A more reliable indicator for disequilibrium fractionation is the enrichment of the δ¹³C values along an individual growth layer.     

Tracing stable isotope values from meteoric water to groundwater in the southwestern part of the Chad basin

The southwestern Chad basin is a semi-arid region with annual rainfall that is generally less than 500 mm and over 2,000 mm of evapotranspiration. Surface water in rivers is seasonal, and therefore groundwater is the perennial source of water supply for domestic and other purposes. Stable isotope has been measured for rainwater, surface water and groundwater samples in this region. The stable isotope data have been used to understand the inter-relationships between the rainwater, surface water, shallow and deep groundwater of this region. This is being used in a qualitative sense to demonstrate present day recharge to the groundwater. Stable isotope in rainwater for the region has an average value of –4‰ δ¹⁸O and –20‰ δ²H. Surface water samples from rivers and Lake Chad fall on the evaporation line of this average value. The Upper Zone aquifer water samples show stable isotope signal with a wide range of values indicating the complex character of the aquifer Zone with three distinguishable units. The wide range of values is attributable to waters from individual unit and/or mixture of waters of different units. The Middle and Lower aquifers Zones’ waters show similar stable isotopes values, probably indicating similarity in timing and/or mechanism of recharge. These are palaeowaters probably recharged under a climate that is different from today. The Upper Zone aquifer is presently being recharged as some of its waters show stable isotope compositions similar to those of average rainfall waters of the region.     

Stable isotope geochemistry of acid mine drainage: Experimental oxidation of pyrite

Sulfate and water from experiments in which pyrite was oxidized at a pH of 2.0 were analyzed for sulfur and oxygen stable isotopes. Experiments were conducted under both aerobic and anaerobic sterile conditions, as well as under aerobic conditions in the presence of Thiobacillus ferrooxidans, to elucidate the pathways of oxidation. Oxygen isotope fractionation between SO^2?₄ and H₂O varied from +4.0 %. (anaerobic, sterile) to + 18.0 %. (aerobic, with T. ferrooxidans.). The oxygen isotope composition of dissolved oxygen utilized in both chemical and microbially-mediated oxidation was also determined (+11.4 %., by T. ferrooxidans; +18.4 %., chemical). Contributions of water-derived oxygen and dissolved oxygen to the sulfate produced in the oxidation of pyrite could thus be estimated. Water-derived oxygen constituted from 23 to ~ 100 percent of the oxygen in the sulfate produced in the experiments, and this closely approximates the range of contribution in natural acid mine drainage. Oxidation of sulfides in anaerobic, water-saturated environments occurs primarily by chemical oxidation pathways, whereas oxidation of sulfides in well-aerated, unsaturated zone environments occurs dominantly by microbially mediated pathways.     

Assessment of interconnection between surface water and groundwater in Sawa Lake area,southern Iraq,using stable isotope technique

Interaction between surface water represented by the Euphrates River, natural springs, and Sawa Lake with groundwater (11 wells) in southern Iraq was investigated in this study. Water samples were collected for hydrochemistry and stable isotope (²H and ¹⁸O) analysis. Sampling of water from determined stations (10 stations along the Euphrates, 3 springs, and Sawa Lake) were carried out during two stages; the first was in October 2013(dry season) and the second one was in March 2014 (wet season). The aim of the research is to assess the interaction of groundwater–surface water, which includes Al-Atshan River (branch of the Euphrates River), Sawa Lake, and the groundwater in the study area by using hydrochemistry and stable isotope techniques. The results indicate that surface waters have a different type of water from that of groundwater. In δ ²H and δ ¹⁸O diagrams, all groundwater, springs, and Sawa Lake waters are plotted below the Global Meteoric Water Line (GMWL) and the local meteoric water line (LMWL) indicating the influence of evaporation processes and seasonal variation. The LMWL deviates by a d-excess about +13.71 toward the East Mediterranean meteoric water line (EMWL) indicating that the origin of the vapor source is the Mediterranean Sea. The river water has different isotopic compositions from that of groundwater, springs, and Sawa Lake. The final conclusion is that there is no clear influence of the groundwater on the river water while there is an intermixing between the groundwater in the different locations in the study area.     

Geochemistry and stable isotope investigation of acid mine drainage associated with abandoned coal mines in central Montana,USA

The Great Falls-Lewistown Coal Field (GFLCF) in central Montana contains over 400 abandoned underground coal mines, many of which are discharging acidic water with serious environmental consequences. Areas of the mines that are completely submerged by groundwater have circum-neutral pH and relatively low concentrations of metals, whereas areas that are only partially flooded or freely draining have acidic pH (< 3) and high concentrations of metals. The pH of the mine drains either decreases or increases after discharging to the surface, depending on the initial ratio of acidity (mainly Al and Fe²⁺) to alkalinity (mainly HCO₃^?). In acidic, Fe-rich waters, oxidation of Fe²⁺ after exposure to air is microbially catalyzed and follows zero-order kinetics, with computed rate constants falling in the range of 0.97 to 1.25 mmol L^? 1 h^? 1. In contrast, Fe²⁺ oxidation in near-neutral pH waters appears to be first-order with respect to Fe²⁺ concentration, although insufficient data were collected to constrain the rate law expression. Rates of Fe²⁺ oxidation in the field are dependent on temperature such that lower Fe²⁺ concentrations were measured in down-gradient waters during the day, and higher concentrations at night. Diel cycles in dissolved concentrations of Zn and other trace metals (Mn, Ni) were also noted for down-gradient waters that were net alkaline, but not in the acidic drains.The coal seams of the GFLCF and overlying Cretaceous sandstones form a perched aquifer that lies ~ 50 m above the regional water table situated in the underlying Madison Limestone. The δD and δ¹⁸O values of flooded mine waters suggest local derivation from meteoric water that has been partially evaporated in agricultural soils overlying the coal mines. The S and O isotopic composition of dissolved sulfate in the low pH mine drains is consistent with oxidation of biogenic pyrite in coal under aerated conditions. A clear distinction exists between the isotopic composition of sulfate in the acid mine waters and sulfate in the adjacent sedimentary aquifers, making it theoretically possible to determine if acid drainage from the coal mines has leaked into the underlying Madison aquifer.     

Oxygen-isotope variations in sulfate ions in the water of some Italian lakes

The results obtained by measuring the sulfate content and its $\text{O}{}^{18}\text{O}{}^{16}$ ratios through time in some volcanic, tectonic and dam Italian lakes are reported here. The variations with time of the oxygen isotopic composition of the lake waters are also reported. The measurements refer mainly to surface water; however, a few deep samples were also studied.In the case of all the lakes examined, the variations with time of the oxygen isotopic composition and of the concentration of the dissolved sulfate cannot be explained in terms of the addition and of seasonal variations of the O¹⁸ content of rainwater sulfate. Biological redox processes involving bacterial reduction of sulfate and sulfide oxidation can reasonably account for the results obtained.According to Lloyd (1967), when sulfate is formed by bacterial sulfide oxidation, 68 per cent of the sulfate oxygen is water oxygen, while 32 per cent is dissolved molecular oxygen. The isotopic enrichment of the dissolved molecular oxygen in the lake waters relative to the isotope content of the atmospheric oxygen is mainly related to the biological activity in the waters.Assuming that a stagnation period takes place during summer and fall while a period of strong bio-respiratory activity takes place during winter and spring, it follows that a small isotope fractionation effect on molecular dissolved oxygen can be expected during stagnation while a high isotope fractionation can be expected during winter and spring. The O¹⁸ content of the sulfate dissolved in volcanic and tectonic lakes varies according to this hypothesis. The fact that similar O¹⁸ contents of the dissolved sulfate are or are not found in the same period of different years is probably related to similarities or differences in the climatic conditions.The bio-physical behaviour of the Corbara dam lake is different from that of other lakes. However, because of the continuous feeding by the Tiber River, variations of the sulfate concentration and its oxygen isotopic composition can be caused by the contribution of polluted water.     

Influence of the enzyme dissimilatory sulfite reductase on stable isotope fractionation during sulfate reduction

The stable isotopes of sulfate are often used as a tool to assess bacterial sulfate reduction on the macro scale. However, the mechanisms of stable isotope fractionation of sulfur and oxygen at the enzymatic level are not yet fully understood. In batch experiments with water enriched in ¹⁸O we investigated the effect of different nitrite concentrations on sulfur isotope fractionation by Desulfovibrio desulfuricans.With increasing nitrite concentrations, we found sulfur isotope enrichment factors ranging from −11.2 ± 1.8‰ to −22.5 ± 3.2‰. Furthermore, the δ¹⁸O values in the remaining sulfate increased from approximately 50-120‰ when ¹⁸O-enriched water was supplied. Since ¹⁸O-exchange with ambient water does not take place in sulfate, but rather in intermediates of the sulfate reduction pathway (e.g. ), we suggest that nitrite affects the steady-state concentration and the extent of reoxidation of the metabolic intermediate sulfite to sulfate during sulfate reduction. Given that nitrite is known to inhibit the production of the enzyme dissimilatory sulfite reductase, our results suggest that the activity of the dissimilatory sulfite reductase regulates the kinetic isotope fractionation of sulfur and oxygen during bacterial sulfate reduction. Our novel results also imply that isotope fractionation during bacterial sulfate reduction strongly depends on the cell internal enzymatic regulation rather than on the physico-chemical features of the individual enzymes.     

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H₂S of Cu and Cd, relative to Zn; (2) stable isotope ratios of ³⁴S/³²S and ¹⁸O/¹⁶O in dissolved SO₄ that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures.     

Hydrochemical and stable isotopic investigation of groundwater quality and its sustainability for irrigation in the Hammamet-Nabeul basin,northeastern Tunisia

The major ion hydrochemistry, sodium absorption ratio (SAR), sodium percentage, and isotopic signatures of Hammamet-Nabeul groundwaters were used to identify the processes that control the mineralization, irrigation suitability, and origin of different water bodies. This investigation highlights that groundwater mineralization is mainly influenced by water-rock interaction and pollution by the return flow of irrigation water. The comparison of groundwater quality with irrigation suitability standards proves that most parts of groundwater are unacceptable for irrigation and this long-term practice may result in a significant increase of the salinity and alkalinity in the soils. Based on isotopic signatures, the shallow aquifer groundwater samples were classified into (i) waters with depleted δ¹⁸O and δ²H contents, highlighting recharge by modern precipitation, and (ii) waters with enriched stable isotope contents, reflecting the significance of recharge by contaminated water derived from the return flow of evaporated irrigation waters. The deep-aquifer groundwater samples were also classified into (i) waters with relatively enriched isotope contents derived from modern recharge and mixed with shallow-aquifer groundwater and (ii) waters with depleted stable isotope contents reflecting a paleoclimatic origin. Tritium data permit to identify three origins of recharge, i.e., contemporaneous, post-nuclear, and pre-nuclear. Carbon-14 activities demonstrate the existence of old paleoclimatic recharge related to the Holocene and Late Pleistocene humid periods.     

A geochemical study of the impact of irrigation and aquifer lithology on groundwater in the Upper Yakima River Basin,Washington, USA

The Yakima River, a major tributary of the Columbia River, is currently overallocated in its surface water usage in part because of large agricultural water use. As a result, groundwater availability and surface water/groundwater interactions have become an important issue in this area. In several sub-basins, the Yakima River water is diverted and applied liberally to fields in the summer creating artificial recharge of shallow groundwater. Major ion, trace element, and stable isotope geochemistry of samples from 26 groundwater wells from a transect across the Yakima River and 24 surface waters in the Kittitas sub-basin were used to delineate waters with similar geochemical signatures and to identify surface water influence on groundwater. Major ion chemistry and stable isotope signatures combined with principal component analysis revealed four major hydrochemical groups. One of these groups, collected from shallow wells within the sedimentary basin fill, displays temporal variations in NO₃ and SO₄ along with high δ¹⁸O and δD values, indicating significant contribution from Yakima River and/or irrigation water. Two other major hydrochemical groups reflect interaction with the main aquifer lithologies in the basin: the Columbia River basalts (high-Na groundwaters), and the volcaniclastic rocks of the Ellensburg Formation (Ca–Mg–HCO₃ type waters). The fourth major group has interacted with the volcaniclastic rocks and is influenced to a lesser degree by surface waters. The geochemical groupings constrain a conceptual model for groundwater flow that includes movement of water between underlying Columbia River basalt and deeper sedimentary basin fill and seasonal input of irrigation water.     

Diel behavior of stable isotopes of dissolved oxygen and dissolved inorganic carbon in rivers over a range of trophic conditions,and in a mesocosm experiment

Rates of diel (24-h) biogeochemical processes in rivers and their effect on daily changes in the concentration of metals and metalloids have been well documented in the literature over the last 20 years. Investigations into the effects of these processes on aquatic systems and the underlying mechanisms that control the processes can significantly improve our understanding of how natural aquatic environments function and will respond to changing environmental conditions and anthropogenic impacts. Daily changes in the rates of biogeochemical processes have, more recently, been shown to influence the stable isotope composition of dissolved oxygen and dissolved inorganic carbon in natural waters. Here we present a comprehensive picture of the persistence and reproducibility of diel cycles of the ¹⁸O composition of dissolved molecular oxygen (δ¹⁸O-DO) and the ¹³C composition of dissolved inorganic carbon (δ¹³C-DIC) across five Montana, USA rivers investigated over a 4-year period. A mesocosm experiment showed the same behavior in δ¹⁸O-DO and δ¹³C-DIC as seen in riverine settings across light and dark periods.A cross plot of δ¹⁸O-DO and δ¹³C-DIC from each stream exhibits a clockwise elliptical pattern which is attributed to the daily changes in the balance of metabolic rates as well as air–water gas exchange. The amplitude of the change in the isotope composition is shown to be directly related to the trophic state of the river and a relationship between net productivity and diel changes in δ¹⁸O-DO and δ¹³C-DIC is presented. This relationship between trophic status with δ¹⁸O-DO, δ¹³C-DIC and production emphasizes the significance of how rates of biogeochemical processes in natural systems can influence the daily changes in the composition of surface waters.     

Recharge of the plio-quaternary water table aquifer in Tunisian chotts region estimated from stable isotopes

The hydrodynamic groundwater data and stable isotopes of water have been used jointly for better understanding of upward leakage and mixing processes in the Djerid aquifer system (southwestern Tunisia). The aquifer system is composed of the upper unconfined Plio-Quaternary (PQ) aquifer, the intermediate (semi-)confined Complex Terminal (CT) aquifer and the deeper confined Continental Intercalaire (CI) aquifer. A total of 41 groundwater samples from the CT and PQ aquifers were collected during June 2001. The stable isotope composition of waters establishes that the CT deep groundwater (depleted as compared to present Nefta local rainfall) is ancient water recharged during late Quaternary time. The relatively recent water in the shallow PQ aquifer is composed of mixed water resulting from upward leakage and sporadic meteoric recharge. In order to characterize the meteoric input signal for PQ in the study area, rainfall water samples were collected during 4 years (2000–2003) at the Nefta meteorological station. Weighted mean values of isotopic contents with respect to rainfall amounts have been computed. Despite the short collection period in the study area, results agree with those found in Beni Abbes (southwestern Algerian Sahara) by Fontes on 9 years of rainfall surveillance. Stable isotopic relationships provide clear evidence of shallow PQ aquifer replenishment by deep CT groundwater. The ¹⁸O/upward leakage rate allowed the identification of distinctive PQ waters related to CT aquifer configuration (confined in the western part of the study area, semi-permeable in the eastern part). These trends were confirmed by the relation ¹⁸O/TDS. The isotope balance model indicated a contribution of up to 75% of the deep CT groundwater to the upper PQ aquifer in the western study area, between Nefta and Hazoua.     

Recharge sources and hydrogeochemical evolution of groundwater in semiarid and karstic environments: A field study in the Granada Basin (Southern Spain)

The objective of this study is to refine the understanding of recharge processes in watersheds representative for karstic semiarid areas by means of stable isotope analysis and hydrogeochemistry. The study focuses on the Granada aquifer system which is located in an intramontane basin bounded by high mountain ranges providing elevation differences of almost 2900 m. These altitude gradients lead to important temperature and precipitation gradients and provide excellent conditions for the application of stable isotopes of water whose composition depends mainly on temperature. Samples of rain, snow, surface water and groundwater were collected at 154 locations for stable isotope studies (δ¹⁸O, D) and, in the case of ground- and surface waters, also for major and minor ion analysis. Thirty-seven springs were sampled between 2 and 5 times from October 2004 to March 2005 along an altitudinal gradient from 552 masl in the Granada basin to 2156 masl in Sierra Nevada. Nine groundwater samples were taken from the discharge of operating wells in the Granada basin which are all located between 540 and 728 masl. The two main rivers were monitored every 2–3 weeks at three different altitudes. Rainfall being scarce during the sampling period, precipitation could only be sampled during four rainfall events. Calculated recharge altitudes of springs showed that source areas of mainly snowmelt recharge are generally located between 1600 and 2000 masl. The isotope compositions of spring water indicate water sources from the western Mediterranean as well as from the Atlantic without indicating a seasonal trend. The isotope pattern of the Quaternary aquifer reflects the spatial separation of different sources of recharge which occur mainly by bankfiltration of the main rivers. Isotopic signatures in the southeastern part of the aquifer indicate a considerable recharge contribution by subsurface flow discharged from the adjacent carbonate aquifer. No evaporation effects due to agricultural irrigation were detected.     

Sulfur and oxygen isotope study of sulfate reduction in experiments with natural populations from Fællestrand, Denmark

This study investigates the sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and works to reconcile the relationships between the oxygen and sulfur isotopic and elemental systems. We report results of experiments with natural populations of sulfate-reducing bacteria using sediment and seawater from a marine lagoon at Fællestrand on the northern shore of the island of Fyn, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45‰ for ³⁴S/³²S) with higher δ¹⁸O accompanying higher δ³⁴S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of ¹⁷O-labeled water and the ¹⁷O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The ¹⁷O data provides evidence for recycling of sulfur from metabolic intermediates and for an ¹⁸O/¹⁶O fractionation of ∼25-30‰ for dissimilatory sulfate reduction. The close correlation between the ¹⁷O data and the sulfur isotope data suggests that isotopic exchange between cell water and external water (reactor water) was rapid under experimental conditions. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. This value is slightly lower than observed in studies of natural ecosystems [e.g., Wortmann U. G., Chernyavsky B., Bernasconi S. M., Brunner B., Böttcher M. E. and Swart P. K. (2007) Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130). Geochim. Cosmochim. Acta71, 4221-4232]. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96%), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate and released back to the external sulfate pool (∼70%), and also that a fraction of the sulfur intermediates between sulfite and sulfide were recycled to sulfate. These parameters can be constrained because of the independent information provided by δ¹⁸O, δ³⁴S, δ¹⁷O labels, and Δ³³S.