Decreasing Sulfate Concentrations Research Articles

Performance analysis of three pilot-scale multi-compartment anaerobic baffled reactors treating domestic wastewater at psychrophilic temperatures in Colorado.

A transition from inefficient aerobic wastewater treatment methods to sustainable approaches is needed. Anaerobic bioreactors are a viable solution as they consume less energy, reduce biosolid production, and provide a source of renewable methane-rich biogas. A barrier to widespread implementation of anaerobic technologies is the lack of design guidance, especially in colder climates. This study bridges this knowledge gap by deriving design principles from three long-running pilot-scale anaerobic baffled reactors (ABRs) operating under psychrophilic conditions. The ABRs removed an average of 56% and 80% chemical oxygen demand (COD) and suspended solids, respectively, with a methane yield of 0.21L CH4 /g CODrem . Methane production may be improved with increased influent sCOD concentrations and decreased sulfate concentrations. Results suggest that ABRs can treat a range of wastewater strengths accompanied by useable methane production. Despite sharing location, temperature, and HRT, the ABRs displayed distinct performances, highlighting the significance of influent wastewater characteristics. PRACTITIONER POINTS: ABRs achieved 56% and 80% removal efficiencies for COD and suspended solids. Average biogas was 63% methane, and methane yield was 0.21 L CH4 /g CODrem . Volumetric methane production was positively correlated with the influent sCOD/sulfate ratio and negatively correlated with influent sulfate loading.

Interlinked marine cycles of methane, manganese, and sulfate in the post-Marinoan Doushantuo cap dolostone

The strongly 13C-depleted calcite in the Doushantuo cap dolostones (∼635 Ma) of South China is considered to form via thermochemical or biological oxidation of methane by sulfate in an environment with sulfate concentrations close to that of modern seawater (∼28 mM). Here we demonstrate that the coeval seawater sulfate levels were indeed low (∼1 to 3 mM) because all bulk δ34S values of pyrites are close to and higher than the coeval seawater, with only a few showing a wide in situ δ34S range from 5 to 62‰. Such low sulfate concentrations were initially consumed by sulfate reducing microorganisms to extremely low levels (<∼0.2 mM), and thus Mn-driven anaerobic oxidation of methane (AOM) by sulfate occurred in pore water to produce H2S, which was in turn oxidized by Mn oxides back to sulfate. Consequently, with increasing Mn reduction and decreasing sulfate concentrations in pore waters, the produced pyrite shows an increase of in situ δ34S values, and is in association with calcite with more negative δ13C values, and an inherited positive Ce anomaly from Mn oxides. Finally, the pyrite with the highest δ34S value may have co-precipitated with the 13C-depelted calcite (with a nadir of −58‰), and thus show similarly high Mn concentrations (∼20000 μg/g). This is the first report of sulfate-dependent AOM driven by Mn- or Fe- oxides from the entire Precambrian record. Such a previously unrecognized biogeochemical cycling during Marinoan global deglaciation may serve as the mechanism for major methane sink during the Proterozoic and Archean with low sulfate concentrations in the oceans.

Records of carbon and sulfur cycling during the Silurian Ireviken Event in Gotland, Sweden

Abstract Early Silurian (∼431 Ma) carbonate rocks record a ca. 4.5‰ positive excursion in the stable isotopic composition of carbonate carbon (δ13Ccarb). Associated with this isotopic shift is a macroevolutionary turnover pulse known as the ‘Ireviken Event’. The onset of this carbon isotope excursion is commonly associated with a shallowing-upward facies transition that may have been accompanied by climatic change, as indicated by a parallel positive shift (∼0.6‰) in the stable isotopic composition of carbonate oxygen (δ18Ocarb). However, the relationships among carbon cycle perturbations, faunal turnover, and environmental changes remain enigmatic. Here we present a suite of new isotopic data across the Ireviken Event from multiple sections in Gotland, Sweden. These samples preserve no systematic change in δ18Ocarb but show positive excursions of equal magnitude in both carbonate (δ13Ccarb) and organic (δ13Corg) carbon. In addition, the data reveal a synchronous perturbation in sulfur isotope ratios, manifest as a ca. 7‰ positive excursion in carbonate-associated sulfate (δ34SCAS) and a ca. 30‰ positive excursion in pyrite (δ34Spyr). The increase in δ34Spyr values is accompanied by a substantial, concomitant increase in stratigraphic variability of δ34Spyr. The relatively constant offset between the δ13Ccarb and δ13Corg excursions throughout the Ireviken Event could be attributed to increased organic carbon burial, or possibly a change in the isotopic composition of CO2 sources from weathering. However, a positive correlation between carbonate abundance and δ13Ccarb suggests that local to regional changes in dissolved inorganic carbon (DIC) during the shallowing-upward sequence may have been at least partly responsible for the observed excursion. The positive excursion recorded in δ34SCAS suggests a perturbation of sufficient magnitude and duration to have impacted the marine sulfate reservoir. An inverse correlation between CAS abundance and δ34SCAS supports the notion of decreased sulfate concentrations, at least locally, consistent with a concomitant increase in pyrite burial. A decrease in the offset between δ34SCAS and δ34Spyr values during the Ireviken Event suggests a substantial reduction in the isotopic fractionations (epyr) expressed during microbial sulfur cycling and pyrite precipitation through this interval. Decreased epyr and the concomitant increase in stratigraphic variation in δ34Spyr are typical of isotope systematics observed in modern shallow-water environments, associated with increased closed-system behavior and/or oxidative sedimentary reworking during early sediment diagenesis. While the isotopic trends associated with the Ireviken Event have been observed in multiple locations around the globe, many sections display different magnitudes of isotopic change, and moreover, are typically associated with local facies changes. Due to the stratigraphic coherence of the carbon and sulfur isotopic and abundance records across the Ireviken Event, and their relationship to changes in local depositional environment, we surmise that these patterns more closely reflect biogeochemical processes related to deposition and lithification of sediment than global changes in carbon and sulfur burial fluxes.

Increasing algal biomass in Lake Vänern despite decreasing phosphorus concentrations: A lake-specific phenomenon?

Algal blooms in lake waters are frequently associated with elevated nutrient levels, in particular phosphorus. Here we show, with long-term data from Sweden’s largest lake, Lake Vänern, that total phytoplankton biomass has significantly increased since the 1980s at the same time as total phosphorus and inorganic nitrogen concentrations have significantly decreased (non-parametric Mann-Kendall test: P &amp;lt; 0.01). Lake Vänern was not the only lake showing such a pattern: evaluating long-term data from 13 small oligotrophic reference lakes revealed the same pattern. Other synchronous changes observed in Sweden’s oligotrophic lakes included strongly decreasing sulfate concentrations and increasing water temperatures. We found that alkalinity, water temperatures, silica and sulfate concentrations were the strongest predictors for total phytoplankton biomass at all three sites in Lake Vänern when we used partial least squares regression models with 11 input variables. From our results, we suggest that decreasing acidity in combination with increasing water temperatures has been more important for phytoplankton growth than total phosphorous and nitrogen concentrations. Thus, we conclude that phytoplankton biomass in oligotrophic small and large lakes is strongly associated with climate and atmospheric depositional changes, and consequently needs to be managed beyond catchment scales.

Patterns of temporal community turnover are spatially synchronous across boreal lakes

Summary1. Ecosystems are often exposed to broad‐scale environmental change, which can potentially synchronise community dynamics and biodiversity trends. Detection of temporal coherence may, however, depend on the metrics used and their sensitivity to detect change, requiring several lines of evidence to elucidate the full range of temporal responses to environmental change.2. Here, we tested whether the patterns of synchrony among littoral invertebrate communities of Swedish lakes over 20 years (1988–2007) differed when analysed using univariate (taxon richness, evenness, Shannon diversity and total abundance) or multivariate (temporal turnover in community composition) metrics. We included both culturally acidified and circumneutral lakes to examine whether anthropogenic stress influenced the patterns of synchrony.3. Average total abundance, taxon richness and temporal turnover in community composition changed monotonically with time, while evenness and Shannon diversity fluctuated around a long‐term mean. However, among‐lake variability was high, resulting in a weak temporal coherence. Only trends of temporal turnover changed synchronously across lakes, irrespective of their acidification history.4. Spatially synchronous trends in turnover across lakes were correlated with increasing water colour and decreasing sulphate concentrations, showing the importance of regional drivers of spatiotemporal coherence.5. Our results underpin an increasing body of evidence that the detection of diversity patterns varies among metrics that ignore (taxon richness, evenness, Shannon diversity) or consider (turnover) species identities. More generally, our results suggest that community‐level studies of synchrony are suitable for elucidating the role of intrinsic versus extrinsic factors in mediating complex community assembly processes in the long term. This, in turn, contributes to our understanding of temporal patterns of biodiversity.

Characterization of the relationship between microbial degradation processes at a hydrocarbon contaminated site using isotopic methods

Decisions to employ monitored natural attenuation (MNA) as a remediation strategy at contaminated field sites require a comprehensive characterization of the site-specific biodegradation processes. In the present study, compound-specific carbon and hydrogen isotope analysis (CSIA) was used to investigate intrinsic biodegradation of benzene and ethylbenzene in an aquifer with high levels of aromatic and aliphatic hydrocarbon contamination. Hydrochemical data and isotope fractionation analysis of sulfate and methane was used complementarily to elucidate microbial degradation processes over the course of a three year period, consisting of six sampling campaigns, in the industrial area of Weißandt-Gölzau (Saxony-Anhalt, Germany).Enrichment of 13C and 2H isotopes in the residual benzene and ethylbenzene pool downgradient from the pollution sources provided evidence of biodegradation of BTEX compounds at this site, targeting both compounds as the key contaminants of concern. The enrichment of heavy sulfur isotopes accompanied by decreasing sulfate concentrations and the accumulation of isotopically light methane suggested that sulfate-reducing and methanogenic processes are the major contributors to overall biodegradation in this aquifer. Along the contaminant plume, the oxidation of methane with δ13CCH4 values of up to +17.5‰ was detected. This demonstrates that methane formed in the contaminant source can be transported along groundwater flow paths and be oxidized in areas with higher redox potentials, thereby competing directly with the pollutants for electron acceptors. Hydrochemical and isotope data was summarized in a conceptual model to assess whether MNA can be used as viable remediation strategy in Weißandt-Gölzau. The presented results demonstrate the benefits of combining different isotopic methods and hydrochemical approaches to evaluate the fate of organic pollutants in contaminated aquifers.

Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, Southern Gulf of Mexico

At the Chapopote Knoll in the Southern Gulf of Mexico, deposits of asphalt provide the substrate for a prolific cold seep ecosystem extensively colonized by chemosynthetic communities. This study investigates microbial life and associated biological processes within the asphalts and surrounding oil-impregnated sediments by analysis of intact polar membrane lipids (IPLs), petroleum hydrocarbons and stable carbon isotopic compositions (δ 13C) of hydrocarbon gases. Asphalt samples are lightly to heavily biodegraded suggesting that petroleum-derived hydrocarbons serve as substrates for the chemosynthetic communities. Accordingly, detection of bacterial diester and diether phospholipids in asphalt samples containing finely dispersed gas hydrate suggests the presence of hydrocarbon-degrading bacteria. Biological methanogenesis contributes a substantial fraction to the methane captured as hydrate in the shallow asphalt deposits evidenced by significant depletion in 13C relative to background thermogenic methane. In sediments, petroleum migrating from the subsurface stimulates both methanogenesis and methanotrophy at a sulfate–methane transition zone 6–7 m below the seafloor. In this zone, microbial IPLs are dominated by archaeal phosphohydroxyarchaeols and archaeal diglycosidic diethers and tetraethers. Bacterial IPLs dominate surface sediments that are impregnated by severely biodegraded oil. In the sulfate-reduction zone, diagnostic IPLs indicate that sulfate-reducing bacteria (SRB) play an important role in petroleum degradation. A diverse mixture of phosphohydroxyarchaeols and mixed phospho- and diglycosidic archaeal tetraethers in shallow oil-impregnated sediments point to the presence of anaerobic methane-oxidizing ANME-2 and ANME-1 archaea, respectively, or methanogens. Archaeal IPLs increase in relative abundance with increasing sediment depth and decreasing sulfate concentrations, accompanied by a shift of archaeol-based to tetraether-based archaeal IPLs. The latter shift is suggested to be indicative of a community shift from ANME-2 and/or methanogenic archaea in shallower sediments to ANME-1/methanogenic archaea and possibly benthic archaea in deeper sediments.

Site-to-site variability and temporal trends of DOC concentrations and fluxes in temperate forest soils

Here, we report site-to-site variability and 12–14 year trends of dissolved organic carbon (DOC) from organic layers and mineral soils of 22 forests in Bavaria, Germany. DOC concentrations in the organic layer were negatively correlated with mean annual precipitation and elevation whereas air temperature had a positive effect on DOC concentrations. DOC fluxes in subsoils increased by 3 kg ha−1 yr−1 per 100 mm precipitation or per 100 m elevation. The highest DOC concentrations were found under pine stands with mor humus. Average DOC concentrations in organic layer leachates followed the order: pine>oak>spruce>beech. However, the order was different for mean DOC fluxes (spruce>pine>oak>beech) because of varying precipitation regimes among the forest types. In 12 of 22 sites, DOC concentrations of organic layer leachates significantly increased by 0.5 to 3.1 mg C L−1 yr−1 during the sampling period. The increase in DOC concentration coincided with decreasing sulfate concentration, indicating that sulfate concentration is an important driver of DOC solubility in the organic layer of these forest sites. In contrast to the organic layer, DOC concentrations below 60 cm mineral soil depth decreased by <0.1–0.4 mg C L−1 yr−1 at eight sites. The negative DOC trends were attributed to (i) increasing adsorption of DOC by mineral surfaces resulting from desorption of sulfate and (ii) increasing decay of DOC resulting from decreasing stabilization of DOC by organo-Al complexes. Trends of DOC fluxes from organic layers were consistent with those of DOC concentrations although trends were only significant at seven sites. DOC fluxes in the subsoil were with few exceptions small and trends were generally not significant. Our results suggest that enhanced mobilization of DOC in forest floors contributed to the increase of DOC in surface waters while mineral horizons did not contribute to increasing DOC export of forest soils.

The effect of sulfate concentration on (sub)millimeter-scale sulfide δ 34S in hypersaline cyanobacterial mats over the diurnal cycle

Substantial isotopic fractionations are associated with many microbial sulfur metabolisms and measurements of the bulk δ 34S isotopic composition of sulfur species (predominantly sulfates and/or sulfides) have been a key component in developing our understanding of both modern and ancient biogeochemical cycling. However, the interpretations of bulk δ 34S measurements are often non-unique, making reconstructions of paleoenvironmental conditions or microbial ecology challenging. In particular, the link between the μm-scale microbial activity that generates isotopic signatures and their eventual preservation as a bulk rock value in the geologic record has remained elusive, in large part because of the difficulty of extracting sufficient material at small scales. Here we investigate the potential for small-scale (∼100 μm–1 cm) δ 34S variability to provide additional constraints for environmental and/or ecological reconstructions. We have investigated the impact of sulfate concentrations (0.2, 1, and 80 mM SO 4) on the δ 34S composition of hydrogen sulfide produced over the diurnal (day/night) cycle in cyanobacterial mats from Guerrero Negro, Baja California Sur, Mexico. Sulfide was captured as silver sulfide on the surface of a 2.5 cm metallic silver disk partially submerged beneath the mat surface. Subsequent analyses were conducted on a Cameca 7f-GEO secondary ion mass spectrometer (SIMS) to record spatial δ 34S variability within the mats under different environmental conditions. Isotope measurements were made in a 2-dimensional grid for each incubation, documenting both lateral and vertical isotopic variation within the mats. Typical grids consisted of ∼400–800 individual measurements covering a lateral distance of ∼1 mm and a vertical depth of ∼5–15 mm. There is a large isotopic enrichment (∼10–20‰) in the uppermost mm of sulfide in those mats where [SO 4] was non-limiting (field and lab incubations at 80 mM). This is attributed to rapid recycling of sulfur (elevated sulfate reduction rates and extensive sulfide oxidation) at and above the chemocline. This isotopic gradient is observed in both day and night enrichments and suggests that, despite the close physical association between cyanobacteria and select sulfate-reducing bacteria, photosynthetic forcing has no substantive impact on δ 34S in these cyanobacterial mats. Perhaps equally surprising, large, spatially-coherent δ 34S oscillations (∼20–30‰ over 1 mm) occurred at depths up to ∼1.5 cm below the mat surface. These gradients must arise in situ from differential microbial metabolic activity and fractionation during sulfide production at depth. Sulfate concentrations were the dominant control on the spatial variability of sulfide δ 34S. Decreased sulfate concentrations diminished both vertical and lateral δ 34S variability, suggesting that small-scale variations of δ 34S can be diagnostic for reconstructing past sulfate concentrations, even when original sulfate δ 34S is unknown.

Biogeochemistry of two types of permeable reactive barriers, organic carbon and iron-bearing organic carbon for mine drainage treatment: Column experiments

Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe 0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe 0-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d − 1 , which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d − 1 for both columns. The OC column showed an initial sulfate reduction rate of 0.4 µmol g (OC) − 1 d − 1 and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 µmol g (OC) − 1 d − 1 for at least 65 PVs (17 months). In the FeOC column, the δ 34S values increase with the decreasing sulfate concentration. The δ 34S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6‰. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H 2 by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the δ 13C value of the dissolved inorganic carbon and a decrease in the concentration of HCO 3 − indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column.

In situ determination of sulfate turnover in peatlands: A down‐scaled push–pull tracer technique

AbstractBacterial sulfate reduction (BSR) is a key process in anaerobic respiration in wetlands and may have considerable impacts on methane emissions. A method to determine sulfate production and consumption in situ is lacking to date. We applied a single‐well, injection‐withdrawal tracer test for the in situ determination of potential sulfate turnover in a northern temperate peatland. Piezometers were installed in three peat depth levels (20, 30, and 50 cm) during summer 2004, and three series of injection‐withdrawal cycles were carried out over a period of several days. Turnover rates of sulfate, calculated from first‐order‐reaction constant k (–0.097 to 0.053 h–1) and pore‐water sulfate concentrations (approx. 10 µmol L–1), ranged from –1.3 to –9.0 nmol cm–3 d–1 for reduction and from +0.7 to +25.4 nmol cm–2 d–1 for production, which occurred after infiltration of water following a heavy rainstorm. Analysis of stable isotopes in peat‐water sulfate revealed slightly increasing δ34S values and decreasing sulfate concentrations indicating the presence of BSR. The calculated low sulfur‐fractionation factors of &lt;2‰ are in line with high sulfate‐reduction rates during BSR. Routine application will require technical optimization, but the method seems a promising addition to common ex situ techniques, as the investigated soil is not structurally altered. The method can furthermore be applied at low expense even in remote locations.

Immobilization of uranium and arsenic by injectible iron and hydrogen stimulated autotrophic sulphate reduction

The main object of the study was the development of a long-term efficient and inexpensive in-situ immobilization technology for uranium (U) and arsenic (As) in smaller and decentralized groundwater discharges from abandoned mining processing sites. Therefore, corrosion of grey cast iron (gcFe) and nano-scale iron particles (naFe) as well as hydrogen stimulated autotrophic sulphate reduction (aSR) were investigated. Two column experiments with sulphate reducing bacterias (SRB) (biotic gcFe , biotic naFe) and one abiotic gcFe-column experiment were performed. In the biotic naFe column, no particle translocation was observed and a temporary but intensive naFe corrosion indicated by a decrease in E h , a pH increase and H 2 evolution. Decreasing sulphate concentrations and 34S enrichment in the column effluent indicated aSR. Fe(II) retention could be explained by siderite and consequently FeS precipitation by geochemical modeling (PhreeqC). U and As were completely immobilised within the biotic naFe column. In the biotic gcFe column, particle entrapment in open pore spaces resulted in a heterogeneous distribution of Fe-enriched zones and an increase in permeability due to preferential flow. However, Fe(II) concentrations in the effluent indicated a constant and lasting gcFe corrosion. An efficient immobilization was found for As, but not for U.

Sulphate and Nitrate in Precipitation and Soil Water in Pine Forests in Latvia

The SO4–S and NO3–N concentrations and pH in bulk precipitation, throughfall, stemflow and soil water for the 1994–2004 period were studied in pine forests in Latvia (Rucava and Taurene Integrated Monitoring stations). The SO4–S and NO3–N concentrations decreased over the study period, simultaneously with a decrease of acidity in precipitation. The changes were more evident in the western part of Latvia, probably due to declining long-range air pollution from West Europe. The trend of decreasing sulphate concentrations and increasing pH in precipitation were not followed by respective changes in soil water. In the upper soil horizon sulphate ion concentrations and acidity increased in soil water. Over the observation period, nitrate concentrations also showed an increasing trend in soil water at Rucava and Taurene, but these changes were not statistically significant.

Geological and anthropogenic influences on the inorganic water chemistry of the Jukskei River, Gauteng, South Africa

This study evaluates the inorganic water quality of the Jukskei River from 1979 until 2002 in order to assess the geological and anthropogenic factors that have influenced the inorganic water quality of the Jukskei River. The non-polluted Little Jukskei River has been used as a baseline reference. The Jukskei River is characterised in the early 1980s by low pH values (3 to 4), high sulphate concentrations (up to 500 mg/L) and high concentrations of sodium, chloride, fluoride, orthophosphate, and nitrate. Potential pollution sources include the Central Rand area and industry situated along the Modderfontein Spruit. The water quality has subsequently improved over time as is demonstrated, in particular, by steadily increasing pH values up to 8+ and decreasing sulphate concentrations down to <200 mg/L. Orthophosphate, nitrate, sodium, potassium and chloride concentrations in 2002 were significantly lower than in 1979 but still higher compared to the Little Jukskei River. This may be explained by communal effluent input as a result of increased urbanisation in the Jukskei Catchment area.

Sources and Processes Affecting Sulfate in a Karstic Groundwater System of the Franconian Alb, Southern Germany

Chemical and isotope analyses on groundwater sulfate and 3H measurements on groundwaterwere used to determine the sulfate sources and sulfur transformation processes in a heterogeneous karst aquifer of the Franconian Alb, southern Germany. Sulfate was found to be derived from atmospheric deposition. Young groundwater was characterized by high sulfate concentrations and delta34S values similar to those of recent atmospheric sulfate deposition. However, the delta18O values of groundwater SO4(2-) were depleted by several per mil with respect to those of atmospheric deposition. This isotopic shift is indicative of mineralization of carbon-bonded S in the vadose zone of the karst system. In groundwater with mean residence times of more than 60 years, a trend of increasing delta34S values and delta18O values with decreasing sulfate concentrations was observed. This trend could not be solely explained by preindustrial atmospheric sulfate deposition with higher delta34S values, and hence, we conclude that bacterial (dissimilatory) sulfate reduction in the porous matrix of the karst aquifer must have occurred. This process has the potential to contribute to long-term biodegradation of contaminants in the porous rock matrix representing the dominantwater reservoir of the fissured porous karst aquifer.

Long-term trends in the chemistry of atmospheric deposition in Northwestern Italy: the role of increasing Saharan dust deposition

The Lake Maggiore watershed is one of the areas most affected by acid deposition in Italy. Decreasing sulfate concentration and increasing pH values of precipitation have been observed in this area in the last 15–20 yr. Besides atmospheric deposition, an important factor controlling water acidification and recovery is the episodic deposition of Saharan calcareous dust, which contributes significantly to alkalinity and base cation deposition. At the sampling site at Pallanza, rain chemistry has been investigated since 1975. The frequency and chemical characteristics of alkaline events (pH > 5.6) and Saharan events in particular (distinguished by an exceptionally high calcium and alkalinity content and by the visible presence of red dust) were evaluated at this site. Saharan events, despite their small contribution to total annual precipitation (3–17%), carry a considerable fraction of the annual total calcium and bicarbonate deposition (up to 70 and 100% respectively). The frequency and intensity of alkaline events affect the acidity/alkalinity budget on an annual basis. Apart from the major effect of sulfate decline, the increasing pH of precipitation recorded at the study site since the 1980s might also be influenced by an increased occurrence and intensity of alkaline events. An increase in the export of Saharan dust from arid regions together with changes in the circulation pattern over the Mediterranean area has been hypothesized as the main causes of this trend.

MERCER COMPLETES MILL FINANCING

Decisions to employ monitored natural attenuation (MNA) as a remediation strategy at contaminated field sites require a comprehensive characterization of the site-specific biodegradation processes. In the present study, compound-specific carbon and hydrogen isotope analysis (CSIA) was used to investigate intrinsic biodegradation of benzene and ethylbenzene in an aquifer with high levels of aromatic and aliphatic hydrocarbon contamination. Hydrochemical data and isotope fractionation analysis of sulfate and methane was used complementarily to elucidate microbial degradation processes over the course of a three year period, consisting of six sampling campaigns, in the industrial area of Weißandt-Gölzau (Saxony-Anhalt, Germany).Enrichment of 13C and 2H isotopes in the residual benzene and ethylbenzene pool downgradient from the pollution sources provided evidence of biodegradation of BTEX compounds at this site, targeting both compounds as the key contaminants of concern. The enrichment of heavy sulfur isotopes accompanied by decreasing sulfate concentrations and the accumulation of isotopically light methane suggested that sulfate-reducing and methanogenic processes are the major contributors to overall biodegradation in this aquifer. Along the contaminant plume, the oxidation of methane with δ13CCH4 values of up to + 17.5‰ was detected. This demonstrates that methane formed in the contaminant source can be transported along groundwater flow paths and be oxidized in areas with higher redox potentials, thereby competing directly with the pollutants for electron acceptors. Hydrochemical and isotope data was summarized in a conceptual model to assess whether MNA can be used as viable remediation strategy in Weißandt-Gölzau. The presented results demonstrate the benefits of combining different isotopic methods and hydrochemical approaches to evaluate the fate of organic pollutants in contaminated aquifers.

Bacterial sulfate reduction and salinity: two controls on dolomite precipitation in Lagoa Vermelha and Brejo do Espinho (Brazil)

The hydrological system of Lagoa Vermelha, a dolomite-precipitating lagoon in Brazil, was investigated using hydrogen and oxygen stable isotopic composition of the water collected during an annual cycle (1996–1997). These data demonstrated that dolomite formed in May–June during high saline conditions. High salinity apparently provides the ions and saturation state necessary for dolomite precipitation. Ion concentrations in the lagoon water indicated an identical timing of dolomite precipitation and demonstrated that dolomite formed at decreased sulfate concentrations. In Brejo do Espinho, a neighbouring lagoon, the ion concentrations in the water column revealed that dolomite precipitates throughout the year, most likely due to its higher salinity than Lagoa Vermelha during the measured period. In Lagoa Vermelha, high δ 34 S of pore water sulfate and high sulfide concentrations correlated with dolomitic horizons, demonstrating the association of bacterial sulfate reduction with dolomite formation. In Brejo do Espinho high δ 34 S of pore water sulfate and high sulfide concentrations occurred throughout the dolomitic sedimentary column. We conclude that elevated salinity and sulfate reduction are the main factors inducing dolomite precipitation in these lagoons, confirming the microbial dolomite formation theory. These results suggest that there may be other settings where sulfate-reducing bacteria induce dolomite precipitation under saline conditions, such as deep-sea sediments or sabkhas, and imply that microbial dolomite may significantly contribute to the sedimentary carbonate budget, particularly in the earliest Earth’s history when anoxic conditions were more prevalent.

Are there signs of acidification reversal in freshwaters of the low mountain ranges in Germany?

Abstract. The reversal of freshwater acidification in the low mountain ranges of Germany is of public, political and scientific concern, because these regions are near natural ecosystems and function as an important drinking water supply. The aim of this study was to evaluate the status and trends of acidification reversal after two decades of reduced anthropogenic deposition in selected freshwaters of the low mountain ranges in the Harz, the Fichtelgebirge, the Bavarian Forest, the Spessart and the Black Forest. In response to decreased sulphate deposition, seven out of nine streams investigated had significantly decreasing sulphate concentrations (all trends were calculated with the Seasonal Kendall Test). The decrease in sulphate concentration was only minor, however, due to the release of previously stored soil sulphur. No increase was found in pH and acid neutralising capacity (defined by Reuss and Johnson, 1986). Aluminum concentrations in the streams did not decrease. Thus, no major acidification reversal can currently be noted in spite of two decades of decreased acid deposition. Nevertheless, the first signs of improvement in water quality were detected as there was a decrease in the level and frequency of extreme values of pH, acid neutralising capacity and aluminium concentrations in streams. With respect to nitrogen, no change was determined for either nitrate or ammonium concentrations in precipitation or stream water. Base cation fluxes indicate increasing net loss of base cations from all ecosystems investigated, which could be interpreted as an increase in soil acidification. The latter was due to a combination of continued high anion leaching and significant reduction of base cation deposition. No major improvement was noted in biological recovery, however, initial signs of recovery were detectable as there was re-occurrence of some single macroinvertebrate species which were formerly extinct. The results of this study have important implications for water authorities, forest managers and policy makers: the delay in acidification reversal suggests a need for ongoing intensive amelioration of waters, a careful selection of management tools to guarantee sustainable management of forests and the reduction of nitrogen deposition to prevent further acidification of soils and waters. Keywords: freshwater, acidification reversal, drinking water supply, forested catchments, Germany

Asymmetric ion exchange mosaic membranes with unique selectivity

In this paper, we describe the investigation of membranes to concentrate aqueous low molecular weight (<500 Da) organics streams, while removing electrolytes including divalent salts such as sodium sulfate. Such membranes would be useful in many industrial applications as currently used pressure driven process such as nanofiltration (NF) or electrical processes such as electric dialysis (ED) cannot achieve such separations and concentrations. An analysis of ion/water transport in different membranes and, selectivity and flux requirements indicated that ion exchange mosaics in the form of integrally skinned asymmetric structures could achieve the required performance. The relationship between the internal structure of the mosaic membrane elements and the required separation properties was further analyzed as a development guide. It was found that such membranes could be made by casting a homogenous solution of two mutually incompatible polymers in a common solvent, containing non-solvents and additives, followed by a chemical modification. The process of forming such membranes involves phase separation between the two polymers and the phase inversion of each polymer. In this study the membrane consists of a cation exchange asymmetric membrane with a uniform distribution of anion exchange particles in the dense integrally skin layer. The choice of polymeric materials, their molecular weights, solvent combinations and surfactants determined the membranes’ surface morphology, mosaic dimensions and particle density. In this way membranes were formed with ∼1 μm sized anion exchange particles uniformly dispersed in a thin (∼1.0 μm) cation exchange selective layer of an asymmetric membrane. The best performance to date: Fluxes of 500+LMD, 10% rejection to sodium sulfate, 90% to sucrose and >98% rejection to 400 molecular weight organic ions. The membranes also show a mosaic effect of decreasing sulfate rejection with decreasing sulfate concentration. The membranes also show a musaic effect of decreasing sulfate rejection with decreasing sulfate concentration, which is desired to perform effectively the removal of mono and bivalent ions during diafiltration.