Sulfur biogeochemistry and isotopic fractionation in shallow groundwater and sediments of Owens Dry Lake, California

Groundwater and sediment samples (∼ 1 m depth) at sites representative of different groundwater pathways were collected to determine the aqueous speciation of sulfur and the fractionation of sulfur isotopes in aqueous and solid phases. In addition, selected sediment samples at 5 depths (from oxic to anoxic layers) were collected to investigate the processes controlling sulfur biogeochemistry in sedimentary layers. Pyrite was the dominant sulfur-bearing phase in the capillary fringe and groundwater zones where anoxic conditions are found. Low concentrations of pyrite (< 5.9 g kg^− 1) coupled with high concentrations of dissolved sulfide (4.81 to 134.7 mg L^− 1) and low concentrations of dissolved Fe (generally < 1 mg L^− 1) and reducible solid-phase Fe indicate that availability of reactive Fe limits pyrite formation. The relative uniformity of down-core isotopic trends for sulfur-bearing mineral phases in the sedimentary layers suggests that sulfate reduction does not result in significant sulfate depletion in the sediment. Sulfate availability in the deeper sediments may be enhanced by convective vertical mixing between upper and lower sedimentary layers due to evaporative concentration. The large isotope fractionation between dissolved sulfate and sedimentary sulfides at Owens Lake provides evidence for initial fractionation from bacterial sulfate reduction and additional fractionation generated by sulfide oxidation followed by disproportionation of intermediate oxidation state sulfur compounds. The high salinity in the Owens Lake brines may be a factor controlling sulfate reduction and disproportionation in hypersaline conditions and results in relatively constant values for isotope fractionation between dissolved sulfate and total reduced sulfur.     

Nitrate distribution and potential attenuation mechanisms of a municipal water supply bedrock aquifer

The Silurian bedrock aquifer constitutes a major aquifer system for groundwater supply across the Ontario province in Canada. The application of natural and industrial fertilizers near urban centers has led to groundwater NO₃⁻-N concentrations that sometimes have exceeded the drinking water limit, posing a threat to the usage of groundwater for the human consumption. Therefore, there is a growing interest and concern about how nitrate is being leached, transported and potentially attenuated in bedrock aquifers. This study assesses the local distribution of groundwater NO₃⁻ in the up-gradient area of two historically impacted municipal wells, called Carter Wells, in the City of Guelph, Canada, in order to evaluate the potential nitrate attenuation mechanisms, using both groundwater geochemical and isotopic analysis (³H, δ¹⁵N-NO₃, δ¹⁸O-NO₃, δ¹⁸O-SO₄, δ³⁴S-SO₄) and a detailed vertical hydrogeological and geochemical bedrock characterization. The results indicate that probably the main source of nitrate to the Carter Wells is the up-gradient Arkell Research Station (ARS), an agricultural research facility where manure has been historically applied. The overburden and bedrock groundwater with high NO₃ concentrations at the ARS exhibits a manure-related δ¹⁵N and δ¹⁸O signature, isotopically similar to the high nitrate in the down-gradient groundwater from domestic wells and from the Carter Wells. The nitrate spatial distribution appears to be influenced and controlled by the geology, in which more permeable rock is found in the Guelph Formation which in turn is related to most of the high NO₃⁻ groundwater. The presence of an underlying low permeability Eramosa Formation favors the development of oxygen-depleted conditions, a key factor for the occurrence of denitrification. Groundwater with low NO₃⁻-N concentrations associated with more oxygen-limited conditions and coincident with high SO₄²⁻ concentrations are related to more enriched δ¹⁵N and δ¹⁸O values in NO₃⁻ and to more depleted δ³⁴S and δ¹⁸O values in SO₄²⁻, suggesting that denitrification coupled with pyrite oxidation is taking place. The presence of macro crystalized and disseminated pyrite especially in the Eramosa Formation, can support the occurrence of this attenuation process. Moreover, based on tritium analysis, some denitrification can occur in shallow bedrock and within relatively short residence times, associated with less permeable conditions in depth which facilitates oxygen consumption through sulfide oxidation. The role of denitrification mediated by organic carbon cannot be discarded at the study site. This study suggests that the geological configuration and particularly the presence of low permeability Eramosa Formation can play an important role on nitrate natural attenuation, which may serve as a decision factor on defining the bedrock water supply system for both domestic and municipal purposes.     

Impact of isostatic land uplift and artificial drainage on oxidation of brackish-water sediments rich in metastable iron sulfide

This study examines the dynamics of sulfur and trace elements (As, Co, Mo, Ni, Ti and Zn) when brackish-water sediments, unusually rich in metastable iron sulfide (probably a mixture of mackinawite and greigite), are brought into the oxidation zone by postglacial isostatic land uplift and farmland drainage. When subaqueous sediments approach the sea level, metastable iron sulfide is oxidized in the upmost layers and pyrite preserved and even accumulated concomitantly trapping Co, Ni and Zn but not As and Mo. When the land uplift has brought the sediments above sea level and natural drainage thus is initiated, the pyrite is oxidized and Co, Ni and Zn are released and transported down the profile. If this setting remained undisturbed, the slightly oxidized sediment (unripe soil) would become covered by peat and thus protected from further oxidation and metal translocation. Often these sediments are, however, artificially drained resulting in extensive oxidation and fast soil-profile development. The soil is an acid sulfate (AS) soil, characterized by low pH (<4), extensive leaching of metals and an abundance of disseminated brownish Fe(III) precipitates. We suggest that the fast soil development is due to initial oxidation of metastable iron sulfide, followed by pyrite oxidation. Drain bottom sediment, which in terms of chemistry and S-isotopes resembled that of the surfacing sea bottom strata, acted during the sampling period as a sink for metals. The abundant preservation of metastable iron sulfide below the groundwater table, even long periods after uplift above the sea level, is a puzzling feature. We suggest that it is the net result of sulfur starvation, an abundance of Fe(II) and strongly reducing conditions.     

Function of a deltaic silt deposit as a repository and long-term source of sulfate and related weathering products in a glaciofluvial aquifer derived from organic-rich shale (North Dakota,USA)

A shallow unconfined glaciofluvial aquifer in North Dakota (USA) has largest groundwater sulfate concentrations near the bottom boundary. A deltaic silt layer underlying the aquifer, at >16 m, is the modern proximate sulfate source for the aquifer. The original sulfate source was pyrite in the organic-rich shale component of the aquifer and silt grain matrix. An oxidizing event occurred during which grain-matrix pyrite sulfur was oxidized to sulfate. Thereafter the silt served as a “conserving” layer, slowly feeding sulfate into the lower part of the aquifer and the underlying till. A method was developed for estimating the approximate initial sulfate concentration in the source layer and the redistribution time since the oxidizing event, using a semi-generic convection–dispersion model. The convection–dispersion model and a model for the evolution of modern sulfate δ ³⁴S in silt-layer pore water from the initial grain-matrix pyrite δ ³⁴S, both estimated that the oxidizing event occurred several thousand years ago, and was likely related to the dry conditions of the Hypsithermal Interval. The silt layer also serves as an arsenic source. Results indicate that deltaic silts derived from organic-rich shale parent materials in a glacial environment can provide long-term sources for sulfate and arsenic and possibly other related oxidative weathering products.     

The role of sediment denitrification in reducing groundwater-derived nitrate inputs to Nauset Marsh estuary, Cape Cod, Massachusetts

The Nauset Marsh estuary is the most extensive (9.45 km²) and least disturbed salt marsh/estuarine system within the Cape Cod National Seashore, even though much of the 19 km² watershed area of the estuary is developed for residential or commercial purposes. Because all of the Nauset watershed is serviced by on-site individual sewage disposal systems, there is concern over the potential impact of groundwater-derived nutrients passing from these systems to the shallow receiving waters of the estuary. The purpose of this study was to determine whether denitrification (the bacterial conversion of nitrate to gaseous nitrogen) in estuarine sediments could effectively remove the nitrate from contaminated groundwater before it passed from the watershed to the estuary. Rates of denitrification were measured both in situ and in sediment cores, in areas of active groundwater discharge, in relatively pristine locations, and in areas situated down-gradient of moderate to heavily developed regions of the watershed. Denitrification rates for 47 sediment cores taken over an annual cycle at 5 stations ranged from non-detectable to 47 μmol N₂ m⁻² h⁻. Mean denitrification rates were positively correlated with sediment organic content, and varied seasonally due to changes in sediment organic content and to the effect of water temperatures on sediment oxygen penetration depths. There was no correlation between observed denitrification rates and corresponding nitrate concentrations in groundwater. A comparison of in situ denitrification rates (supported by groundwater nitrate) with denitrification rates observed in sediment cores (supported by remineralized nitrate) showed that groundwater-driven denitrification rates were small, and not in excess of denitrification rates supported by remineralized nitrate. Most of the denitrification in Nauset sediments was apparently fueled by remineralized nitrate through coupled nitrification/denitrification. Denitrification did not contribute significantly to the direct loss of nitrate from incoming groundwater at Nauset Marsh estuary. Groundwater flow was rapid, and much of it occurred in freshwater springs and seeps through very coarse, sandy, well-oxygenated sediments of limited organic content. There was little opportunity for denitrification to occur during groundwater passage through these sediments. These results have important management implications because they suggest that the majority of nitrogen from contaminated groundwater crosses the sediment/water interface and arrives at Nauset Estuary, where it is available to primary producers. Preliminary budget calculations suggest that while denitrification was not an effective mechanism for the direct removal of nitrate in contaminated groundwater flowing to Nauset Marsh estuary, it may contribute to significant nitrogen losses from the estuary itself.     

Tracking sources of groundwater nitrate contamination using nitrogen and oxygen stable isotopes at Beijing area,China

The identification of sources and behavior of contaminants is important to control and manage groundwater quality of aquifer systems in urban areas. In this study, hydrogeochemistry of major constituents and stable isotope ratios of nitrate in groundwater were determined to identify contamination sources and transformation processes occurring in soils and deeper groundwater of Beijing with intense human activities. The nitrogen and oxygen isotopic compositions of nitrate in pore water extracts from groundwater samples indicate at least three potential sources of nitrate in groundwaters at Beijing. Stable isotope analyses from this study site, which has atmospheric, chemical fertilizer and human waste nitrate sources, provide a tool to distinguish nitrate sources in a confined aquifer where concentrations alone do not. These data indicate that the most common sources of high nitrate concentrations in groundwater at Beijing are wastewater and denitrification process occurred specially in the Central area. NO₃–N and cation and anion concentrations (Ca²⁺, Mg²⁺ Cl^? and SO ₄ ² ) showed strong correlations indicating that they originated from the same sources. This study demonstrates that a thorough evaluation of hydrodynamic and hydrochemical parameters with dual isotopes of NO₃ ^? constitutes an effective approach for identifying sources and transformation processes of NO₃ ^? in deeper groundwater systems.     

Coupled Reactive Transport Modeling of Redox Processes in a Nitrate-Polluted Sandy Aquifer

The reactive transport modeling of a complicated suite of reactions apparent in the aquifer during the application of N-containing fertilizers is reported. The unconfined sandy aquifer can be subdivided into an oxic zone which contains groundwater with oxygen and nitrate and an anoxic zone characterized by elevated iron and sulfate concentrations in groundwater. Oxygen and nitrate are being reduced by pyrite and organic matter that commonly apparent in the aquifer. The oxidation of pyrite is modeled using the local equilibrium approach, whereas decomposition of organic matter, with the adoption of kinetic approach. The system is buffered by dissolution of aluminum and iron oxides. The modeling process is a two-step procedure. First, the processes are modeled in the one-dimensional (1D) column using PHREEQC code. Subsequently, the calibrated and verified data were copied and used in two-dimensional (2D) PHAST model. Prior to the performance of reactive transport modeling operations with PHAST, a reliable flow model was executed. Finally, predictions are made for the distribution of water chemistry for the year 2008. Model predicts that sulfate derived from the ongoing pyrite oxidation is reduced by the dissolved organic carbon at the higher depth and forms pyrite by the reaction with iron. The results of this study highlight the importance of understanding the interplay between the transport and chemical reactions that occur during the input of nitrate to the aquifer. Reactive transport modeling incorporating the use of a newly developed code PHAST have proved to be a powerful tool for analyzing and quantifying such interactions.     

Field tracer test for denitrification in a pyrite-bearing schist aquifer

A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO₃ was injected as a pulse simultaneously with a conservative tracer -Br⁻. During the test, which lasted 210 h, 73% of the injected Br⁻ was recovered, as against only 47% of the NO₃. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS₂+14NO₃⁻+4H⁺→7N₂+10SO₄²⁻+5Fe²⁺+2H₂O, and in part due to subsequent iron oxidation according to the reaction: NO₃⁻+5Fe²⁺+6H⁺→1/2N₂+5Fe³⁺+3H₂O. Despite the potential increase in SO₄ and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO₃-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO₃-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.     

Microbial nitrogen removal in a developing suburban estuary along the South Carolina coast

The conversion of undisturbed coastal regions to commercial and suburban developments may pose a threat to surface and groundwater quality by introducing nitrate-nitrogen (NO₃ ^?-N) from runoff of land-applied wastewater and fertilizers. Microbial denitrification is an important NO₃ ^?-N removal mechanism in coastal sediments. The objective of this study was to compare denitrification and nitrate conversion rates in coastal sediments from a golf course, suburban site, undeveloped marsh, and nonmarsh area near rapidly developing Hilton Head Island, South Carolina. Nitrous oxide was measured using gas chromatography and nitrate and ammonium concentrations were measured using a flow injection autoanalyzer in microcosms spiked, with 50 μg NO₃ ^?-N gdw^?1. The two marsh sites had the greatest ammonium production, which was correlated with fine sediment particle size and higher background sediment nitrate and surface water sulfate concentrations. The golf course swale had greatest denitrification rates, which were correlated with higher total carbon and organic nitrogen in sediments. Nitrate was consumed in golf course sediments to a greater extent than in the undeveloped marsh and upland freshwater sites, suggesting that the undeveloped sites and receiving estuaries may be more susceptible to nitrate contamination than the golf course swale and marsh under nonstorm conditions. Construction of swales and vegetated buffers using sediments with high organic carbon content as best management practices may aid in removing nitrate and other contaminants from runoff prior to its transport to the receiving marsh and estuary.     

Correlation between nitrate concentration in groundwater and parameters affecting aquifer intrinsic vulnerability

This paper is the result of a study which was carried out in order to verify if the traditional methods to evaluate the intrinsic vulnerability or vulnerability related parameters, are able to clarify the problem of nitrate pollution in groundwater. In particular, the aim was to evaluate limitations and problems connected to aquifer vulnerability methods applied to nitrate contamination prevision in groundwater. The investigation was carried out by comparing NO₃ ⁻ concentrations, measured in March and November 2004 in the shallow aquifer, and the vulnerability classes, obtained by using GOD and TOT methods. Moreover, it deals with a comparison between NO₃ ⁻ concentrations and single parameters (depth to water table, land use and nitrogen input). The study area is the plain sector of Piemonte (Northern Italy), where an unconfined aquifer nitrate contamination exists. In this area the anthropogenic presence is remarkable and the input of N-fertilizers and zootechnical effluents to the soil cause a growing amount of nitrates in groundwater. This approach, used in a large area (about 10,000 km²) and in several monitoring wells (about 500), allowed to compare the efficiency of different vulnerability methods and to verify the importance of every parameter on the nitrate concentrations in the aquifer. Furthermore it allowed to obtain interesting correlations in different hydrogeological situations. Correlations between depth to water table, land use and nitrogen input to the soil with nitrate concentrations in groundwater show unclear situations: in fact these comparisons describe the phenomenon trend and highlight the maximum nitrate concentrations for each circumstance but often show wide ranges of possible nitrate concentrations. The same situation could be observed by comparing vulnerability indexes and nitrate concentrations in groundwater. These results suggest that neither single parameters nor vulnerability methods (GOD and TOT) are able to describe individually the complex phenomena affecting nitrate concentrations in soil, subsoil and groundwater. In particular, the traditional methods for vulnerability analysis do not analyze physical processes in aquifers, such as denitrification and nitrate dilution. According to a recent study in the shallow unconfined aquifer of the Piemonte plain, dilution can be considered as the main cause for nitrate attenuation in groundwater.     

Geochemistry of Peruvian near-surface sediments

Sixteen short sediment cores were recovered from the upper edge (UEO), within (WO) and below (BO) the oxygen minimum zone (OMZ) off Peru during cruise 147 of R/V Sonne. Solids were analyzed for major/trace elements, total organic carbon, total inorganic carbon, total sulfur, the stable sulfur isotope composition (δ³⁴S) of pyrite, and sulfate reduction rates (SRR). Pore waters were analyzed for dissolved sulfate/sulfide and δ³⁴S of sulfate. In all cores highest SRR were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and/or diffusion of sulfate from bottom water. δ³⁴S of dissolved sulfate showed only minor downcore increases. Strong ³²S enrichments in sedimentary pyrite (to −48‰ vs. V-CDT) are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. Manganese and Co are significantly depleted in Peruvian upwelling sediments most likely due to mobilization from particles settling through the OMZ, whereas release of both elements from reducing sediments only seems to occur in near-coastal sites. Cadmium, Mo and Re are exceptionally enriched in WO sediments (<600 m water depth). High Re and moderate Cd and Mo enrichments are seen in BO sediments (>600 m water depth). Re/Mo ratios indicate anoxic and suboxic conditions for WO and BO sediments, respectively. Cadmium and Mo downcore profiles suggest considerable contribution to UEO/WO sediments by a biodetrital phase, whereas Re presumably accumulates via diffusion across the sediment-water interface to precipitation depth. Uranium is distinctly enriched in WO sediments (due to sulfidic conditions) and in some BO sediments (due to phosphorites). Silver transfer to suboxic BO sediments is likely governed by diatomaceous matter input, whereas in anoxic WO sediments Ag is presumably trapped due to sulfide precipitation. Cadmium, Cu, Zn, Ni, Cr, Ag, and T1 predominantly accumulate via biogenic pre-concentration in plankton remains. Rhenium, Sb, As, V, U and Mo are enriched in accordance with seawater TE availability. Lead and Bi enrichment in UEO surface sediments is likely contributed by anthropogenic activity (mining). Accumulation rates of TOC, Cd, Mo, U, and V from Peruvian and Namibian sediments exceed those from the Oman Margin and Gulf of California due to enhanced preservation off Peru and Namibia.     

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ~(34)S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ~(34)S values(0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the ~(34)S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ~(34)S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H_2~(32)S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.     

Distribution of nitrate in groundwater affected by the presence of an aquitard at an agricultural area in Chiba, Japan

Geological and geographical parameters including land use, stratigraphic structure, groundwater quality, and N- and O-isotopic compositions of nitrate in groundwater were investigated to elucidate the mechanism of groundwater pollution by NO₃ ^? in the agricultural area of Katori, Chiba, Japan. An aquitard distributed in the western part of the study area has produced two unconfined aquifers. The average concentrations of NO₃ ^? and dissolved oxygen (DO) were high in the aquifer above the aquitard (7.5 and 7.6 mg/L, respectively) and in the aquifer of the eastern part of the study area that was not influenced by the aquitard (11.9 and 7.8 mg/L, respectively); however, the levels in the aquifer under the aquitard were relatively low (2.2 and 3.7 mg/L, respectively). The δ¹⁵N and δ¹⁸O values of NO₃ ^? generally increased exponentially in the groundwater that flowed into the aquifer under the aquitard as the concentration of NO₃ ^? decreased, although this decrease in NO₃ ^? also occasionally occurred without isotopic changes. These results indicated that the aquitard prevented the penetration of NO₃ ^?, DO, and gaseous O₂. Under the aquitard, denitrification and dilution with unpolluted water that entered from natural forested areas reduced the NO₃ ^? concentrations in the groundwater. The major sources of NO₃ ^? in groundwater in the study area were estimated to be NH₄-chemical fertilizer, livestock waste, and manure.     

豫北山前平原深层地下水硫酸盐来源与污染途径的同位素示踪

豫北山前冲洪积平原深层地下水硫酸盐(SO42?)呈现持续增高趋势,但其机制仍不清楚.为探讨深层地下水SO42?来源与污染机制,选择山前冲洪积平原不同赋存条件深层地下水作对比分析,借助水体水化学、氢氧同位素(δDH2O和δ18OH2O)、硫酸盐硫和氧同位素(δ34SSO4和δ18OSO4),示踪人类活动影响下深层地下水S...     

Assessing nitrate origin in a volcanic aquifer using a dual isotope approach

Identifying the origin of nitrate is important for the control and management of groundwater quality in aquifer systems. In the southern Apennines (Italy), the Mount Vulture volcanic aquifer is a large and valuable resource of potable and mineral water supply. Unfortunately, signs of anthropogenic impact, especially nitrogen contamination, have recently become evident. In this study, and for the first time, stable isotope ratios (δ¹⁵N and δ¹⁸O) of NO₃ ^? were determined in groundwater to identify their origins and evaluate the presence of transformation processes. The Mount Vulture groundwaters are meteoric in origin, as demonstrated by measurements of δD and δ¹⁸O, and can be divided into two distinct areas based on their NO₃ ^? content. In the southeastern area, characterized by active agricultural land use, the high NO₃ ^? content and the δ¹⁵N–NO₃ isotopic values are due to anthropogenic contamination (inorganic fertilizer). In groundwaters from the western area, the NO₃ ^? contents below 4 mg/L and the δ¹⁵N–NO₃ values can be associated at organic soil N. Evidence for local denitrification may be assumed in a few groundwater samples of the western area showing relatively heavy δ¹⁵N values and low concentrations of nitrate. Finally, the low measured δ¹⁸O values indicate that nitrification occurred in both investigated areas.     

Modeling groundwater quality in an agriculturally used water catchment

The sulfate pollution in an agriculturally used watershed has been investigated with respect to the transport in the saturated zone and the development of sulfate in the unsaturated zone. Besides of other sources such as acid wet and dry deposition or sulfate input by agricultural activities, most of the sulfate originates from oxidation of pyrite by either NO₃ or O₂. High sulfate concentrations coincided with high nitrate leaching caused by plowing of former grassland or by vegetable crop residues and with former wet lands that have become dry. By using soil water concentration data and maps showing the extension of former wetlands and grassland as well as agricultural land use, it was possible to delineate regions of high sulfate input. The transport of sulfate in the aquifer was analyzed with a modified version of the USGS MOC model, which takes into account the nonlinearity of the underlying equation describing unconfined groundwater flow. The calibration of the transport model showed good agreement between the estimated and modeled sulfate input rates. A prediction of future sulfate concentrations in the aquifer was feasible by using worst-case parameters.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Iron monosulfide formation and oxidation in drain-bottom sediments of an acid sulfate soil environment

Iron monosulfide formation and oxidation processes were studied in the extensively drained acid sulfate soil environment of the Tweed River floodplain in eastern Australia. Porewater profiles of pH, Eh, SO₄²⁻, Fe²⁺, Fe³⁺, Cl⁻, HCO₃⁻, and metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) were obtained using in situ dialysis membrane samplers (`peepers'). Concentrations of acid volatile S (AVS), pyrite, total S, reactive Fe, total and organic C, simultaneously extracted metals (SEMs) and total elemental composition by X-ray fluorescence, were determined on sediment samples. The oxidation of pyrite in the surrounding landscape provides a source of acidity, Fe, Al, SO₄ and metals, which are exported into the drainage system where they accumulate in the sediments and porewaters. Negative porewater concentration gradients of SO₄²⁻ and Fe²⁺, and large AVS concentrations in the sediments, indicate Fe monosulfides form rapidly under reducing conditions and consume acidity and metals. Oxidation of the sediments during previous drought episodes has resulted in the conversion of monosulfides and pyrite to oxidised Fe minerals and the release of acidity, SO₄²⁻, Fe³⁺, and metals to the surface waters. These formation and oxidation cycles show that Fe monosulfides play an important role in controlling water quality in the drainage system.     

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.