Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy

Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO₄.Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO₄ and 663 for HCO⁻₃. Very good positive correlations are observed for the Ca²⁺–Mg²⁺–HCO⁻₃–SO²⁻₄–NO⁻₃ system, indicating that dissolution of Ca (±Mg)-carbonate particles by H₂SO₄ and HNO₃ from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na⁺ and Cl⁻ in monthly precipitation derive essentially from sea spray, but the contribution of Na⁺ from continental sources is appreciable in a number of individual rains. NH⁺₄ appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K⁺ is probably of continental origin from soil dust.The S isotopic composition of SO₄ is systematically positive, with mean δ³⁴S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO₄ is estimated to have a δ³⁴S value in the range +2.5 to +4.5‰, whereas a distinctive δ³⁴S of −4.5‰ or lower indicates SO₄ from oxidation of biogenic gases.The isotopic and chemical compositions of SO₄ do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.     

Sulfide Inhibition of Nitrate Removal in Coastal Sediments

Microbial nitrate (NO₃⁻) removal via denitrification (DNF) at high sulfide (H₂S) concentrations was compared in sediment from a coastal freshwater pond in a developed area that receives salt-water influx during storm events, and a saline pond proximal to an undeveloped estuary. Sediments were incubated with added SO₄²⁻ (1,000 μg per gram dry weight basis (gdw)) to determine whether acid volatile sulfides (AVS) were formed. DNF in the sediments was measured with NO₃–N (300 μg gdw⁻¹) alone, and with NO₃–N and H₂S (1,000 μg S²⁻ gdw⁻¹). SO₄²⁻ addition to the freshwater sediments resulted in AVS formation (970 ± 307 μg S gdw⁻¹) similar to the wetland with no added SO₄²⁻ (986 ± 156 μg S gdw⁻¹). DNF rates measured with no added H₂S were greater in the freshwater than the wetland site (10.6 ± 0.6 vs. 6.4 ± 0.1 μg N₂O–N gdw⁻¹ h⁻¹, respectively). High H₂S concentrations retained NH₄–N in the undeveloped wetland and retained NO₃–N in the developed freshwater site, suggesting that potential salt-water influx may reduce the ability of the freshwater sediments to remove NO₃–N.     

Oxidation of As-bearing gold ore—a comparison of batch and column experiments

This study deals with the experimental determination of the rate of weathering and As release from Au-bearing sulfide ores of the Mokrsko-West deposit (Czech Republic). The elevated As contents in the ore and the possible As mobilisation must be taken into account due to the close proximity of the deposit to the Vltava River, a source of drinking water for Prague. Crushed and homogenized ore material was divided into four grain-size fractions showing uniform chemical and mineralogical composition and subjected to batch and column leaching experiments. The most important reactions controlling metal leaching include (i) oxidation of sulfides, (ii) carbonate equilibrium and (iii) precipitation of hydrated ferric oxides (HFO). Hydrated ferric oxides were found to be important sorbents of mobilized As. The highest concentration of As in the leachates was obtained from the 64–1000 μm fraction. The oxidation rate in the agitated batch experiment calculated on the basis of sulfate concentrations is an order of magnitude higher (3.8×10⁻⁹ to 4.4×10⁻⁸ mol SO₄²⁻ h⁻¹ g⁻¹) than in the static column experiment (9.6×10⁻¹⁰ to 7.4×10⁻⁹ mol SO₄²⁻ h⁻¹ g⁻¹). The higher oxidation rate of batch experiments is explained by abrasion of oxidation products (mainly HFO) and by further exposition of reaction surfaces of the sulfide grains.     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

Simultaneous determination of sulfide, polysulfides and thiosulfate as an aid to ore exploration

The interaction of water and sulfide minerals yields dissolved species which can be utilized to trace back the presence of sulfide minerals and associated minerals. Computer modeling and laboratory and field results show that the most characteristic dissolved species are hydrogen sulfide (H₂S, HS⁻), polysulfide ions (S_n²⁻) and thiosulfate (S₂O₃²⁻), derived from the hydrolysis of sulfide minerals. Typical concentration ranges are: 10⁻⁵ – 10⁻⁷ mole/l for hydrogen sulfide, 10⁻⁶ – 10⁻⁹ mole/l for polysulfides and 10⁻⁵ – 10⁻⁸ mole/l for thiosulfate. The chemical reactivity of these species at contact with air makes them difficult to assess unless determined immediately after sampling.These sulfur species can be determined rapidly and accurately in field conditions by simultaneous titration with mercuric chloride employing an Ag/Ag₂S electrode for the determination of the end points.The application to ore exploration is exemplified by the results of the research on roll-type uranium deposits in the southwest of France.     

Geochemical characteristics of shallow groundwater in Datong basin, northwestern China

Located in semi-arid regions of northwestern China, Datong basin is a Quaternary sedimentary basin, where groundwater is the most important source for water supply. It is very important to study groundwater characteristics and hydrogeochemical processes for better management of the groundwater resource. We have identified five geochemical zones of shallow groundwater (between 5 and 80 m) at Datong: A. Leaching Zone (Zone I); B. Converging Zone (Zone II); C. Enriching Zone (Zone III); D. Reducing Zone (Zone IV); E. Oxidizing Zone (Zone V). In Zones I, II, and V and some parts of Zones III and IV, hydrolysis of albite/K-feldspar/chalcedony system and/or albite/K-feldspar/quartz system enhanced concentrations of Na⁺, K⁺, HCO₃⁻ and silicate. In Zone I, dissolution of carbonate and hydrolysis of feldspar generally controlled the groundwater chemistry. Infiltration of meteoric water promoted the formation of HCO₃⁻ in the water. In Zone II, the main geochemical processes influencing the groundwater chemistry were dissolutions of calcite and dolomite, ion exchange and evaporation. In Zones III and IV, in addition to ion exchange, evaporation and precipitation of calcite and dolomite, leaching of NaHCO₃ in saline–alkaline soils dominated the water quality. Zone IV was under anoxic condition, and reduction reactions led to the decrease of SO₄²⁻, NO₃⁻ and occurrence of H₂S, with the highest arsenic content (mean value of 366 μg/L), far exceeding Maximum Contaminant Level (MCL). Abnormal arsenic in the groundwater resulted in endemic disease of waterborne arsenic poisoning among local people. Zone V overlapped Zone I was intensively affected by coal mining activities. Sulfide minerals, such as pyrite, would have been oxidized when exposed to air due to coal mining, which directly added sulfate to groundwater and thus increased SO₄²⁻ concentration. Oxidization of sulfide minerals also decreased pH and promoted dissolutions of calcite and dolomite.     

Geochemical evidence for Se mobilization by the weathering of pyritic shale, San Joaquin Valley, California, U.S.A.

Acidic (pH 4) seeps issue from the weathered Upper Cretaceous-Paleocene marine sedimentary shales of the Moreno Formation in the semi-arid Coast Ranges of California. The chemistry of the acidic solutions is believed to be evidence of current reactions ultimately yielding hydrous sodium and magnesium sulfate salts, e.g. mirabilite and bloedite, from the oxidation of primary pyrite. The selenate form of Se is concentrated in these soluble salts, which act as temporary geological sinks. Theoretically, the open lattice structures of these hydrous minerals could incorporate the selenate (SeO₄⁻²) anion in the sulfate (SO₄⁻²) space. When coupled with a semi-arid to arid climate, fractional crystallization and evaporative concentration can occur creating a sodium-sulfate fluid that exceeds the U.S. Environmental Protection Agency limit of 1000 μg l⁻¹ for a toxic Se waste. The oxidative alkaline conditions necessary to ensure the concentration of soluble selenate are provided in the accompanying marine sandstones of the Panoche and Lodo Formations and the eugeosynclinal Franciscan assemblage. Runoff and extensive mass wasting in the area reflect these processes and provide the mechanisms which transport Se to the farmlands of the west-central San Joaquin Valley. Subsurface drainage from these soils consequently transports Se to refuge areas in amounts elevated to cause a threat to wildlife.     

Chemistry and sulfur isotope investigation of industrial wastewater contamination into groundwater aquifers, Piteå County, N. Sweden

The possible contamination of a groundwater system with industrial wastewater originating from a paper mill factory has been investigated in Piteå, N. Sweden. Six samples were collected from the wastewater in the waste dump and twelve samples from the adjacent groundwater were analyzed for chemistry and sulfur isotopes. The industrial wastewater is a saline water consisting mainly of Na–HCO₃–SO₄, having a high pH and showing δ³⁴S values between 7‰ and 9‰ affected by bacterial sulfate reduction. The groundwaters are relatively dilute, dominated by Na⁺, Ca²⁺ and HCO₃⁻, but with varying concentrations as exemplified by sulfate with concentrations varying between 3 and 69 mg L^− 1 while the δ³⁴S values range from − 0.5‰ to 14.3‰. The data suggest that the main S sources in the waters are the bedrock sulfides and/or atmospheric deposition, which, sometimes, are overlapped by bacterial sulfate reduction. Contamination from the waste dump does not occur.     

Reduced sulfur and iron species in anoxic water column of meromictic crater Lake Pavin (Massif Central, France)

The vertical distribution of reduced sulfur species (RSS including H₂S/HS⁻, S⁰, electroactive FeS) and dissolved Fe(II) was studied in the anoxic water column of meromictic Lake Pavin. Sulfide concentrations were determined by two different analytical techniques, i.e. spectophotometry (methylene blue technique) and voltammetry (HMDE electrode). Total sulfide concentrations determined with methylene blue method (∑H₂S_MBRS) were in the range from 0.6 µM to 16.7 µM and were substantially higher than total reduced sulfur species (RSS_V) concentrations determined by voltammetry, which ranged from 0.1 to 5.6 μM. The observed difference in the sulfide concentrations between the two methods can be assigned to the presence of FeS colloidal species.Dissolved Fe was high (> 1000 µM), whereas dissolved Mn was only 25 µM, in the anoxic water column. This indicates that Fe is the dominant metal involved in sulfur redox cycling and precipitation. Consequently, in the anoxic deep layer of Lake Pavin, “free” sulfide, H₂S/HS⁻, was low; and about 80% of total sulfide detected was in the electroactive FeS colloidal form. IAP calculations showed that the Lake Pavin water column is saturated with respect to FeS_am phase. The upper part of monimolimnion layer is characterized by higher concentrations of S(0) (up to 3.4 µM) in comparison to the bottom of the lake. This behavior is probably influenced by sulfide oxidation with Fe(III) oxyhydroxide species.     

Hydrology of a spring complex, studied by geochemical time-series data, Acquarossa, Switzerland

A case study of three springs in Switzerland is used to demonstrate the value of geochemical time-series data as a powerful tool to study the dynamics of groundwater systems. Values of repeatedly measured parameters revealed intermixings of two water types: (a) a 29°C water, circulating to a depth of 1100 m and containing approximately 700 mg/l Ca, 2000 mg/l SO₄, 700 mg/l HCO₃, 20 mg/l of Na and Cl, 6 mg/l Fe, at least 47 mg/l SiO₂, and with an isotopic composition of δD = − 73.0‰ and δ¹⁸ O = −10.9‰, and (b) a 12°C or colder water, shallow, and of a post-1953 age, containing 420 mg/l TDI or less, very low in Na and Cl (4 mg/l or less), isotopic values of δD = −71.0‰ and δ¹⁸ O = −10.5‰ and tritium as in recent (post-bomb) precipitation.     

The sources and budget for dissolved sulfate in a fractured carbonate aquifer,southern Sacramento Mountains,New Mexico,USA

Climate change in the SW USA is likely to involve drier conditions and higher surface temperatures. In order to better understand the evolution of water chemistry and the sources of aqueous SO₄ in these semi-arid settings, chemical and S isotope compositions were determined of springs, groundwater, and bedrock associated with a Permian fractured carbonate aquifer located in the southern Sacramento Mountains, New Mexico, USA. The results suggest that the evolution of water chemistry in the semi-arid carbonate aquifer is mainly controlled by dedolomitization of bedrock, which was magnified by increasing temperature and increasing dissolution of gypsum/anhydrite along the groundwater flow path. The δ³⁴S of dissolved SO₄ in spring and groundwater samples varied from +9.0‰ to +12.8‰, reflecting the mixing of SO₄ from the dissolution of Permian gypsum/anhydrite (+12.3‰ to +13.4‰) and oxidation of sulfide minerals (−24.5‰ to −4.2‰). According to S isotope mass balance constraints, the contribution of sulfide-derived SO₄ was considerable in the High Mountain recharge areas, accounting for up to ∼10% of the total SO₄ load. However, sulfide weathering decreased in importance in the lower reaches of the watershed. A smaller SO₄ input of ∼2–4% was contributed by atmospheric wet deposition. This study implies that the δ³⁴S variation of SO₄ in semi-arid environments can be complex, but that S isotopes can be used to distinguish among the different sources of weathering. Here it was found that H₂SO₄ dissolution due to sulfide oxidation contributes up to 5% of the total carbonate weathering budget, while most of the SO₄ is released from bedrock sources during dedolomitization.     

Zero-valent iron and organic carbon mixtures for remediation of acid mine drainage: Batch experiments

A series of laboratory batch experiments was conducted to evaluate the potential for treatment of acid mine drainage (AMD) using organic C (OC) mixtures amended by zero-valent Fe (Fe⁰). Modest increases in SO₄ reduction rates (SRRs) of up to 15% were achieved by augmenting OC materials with 5 and 10 dry wt% Fe⁰. However, OC was essential for supporting SO₄ reducing bacteria (SRB) and therefore SO₄ reduction. This observation suggests a general absence of autotrophic SRB which can utilize H₂ as an electron donor. Sulfate reduction rates (SRRs), calculated using a mass-based approach, ranged from −12.9 to −14.9 nmol L⁻¹ d⁻¹  g⁻¹ OC. Elevated populations of SRB, iron reducing bacteria (IRB), and acid producing (fermentative) bacteria (APB) were present in all mixtures containing OC. Effective removal of Fe (91.6–97.6%), Zn (>99.9%), Cd (>99.9%), Ni (>99.9%), Co (>99.9%), and Pb (>95%) was observed in all reactive mixtures containing OC. Abiotic metal removal was achieved with Fe⁰ only, however Fe, Co and Mn removal was less effective in the absence of OC. Secondary disordered mackinawite [Fe_1+xS] was observed in field-emission scanning electron microscopy (FE-SEM) backscatter electron micrographs of mixtures that generated SO₄ reduction. Energy dispersive X-ray (EDX) spectroscopy revealed that Fe–S precipitates were Fe-rich for mixtures containing OC and Fe⁰, and S-rich in the absence of Fe⁰ amendment. Sulfur K-edges determined by synchrotron-radiation based bulk X-ray absorption near-edge structure (XANES) spectroscopy indicate solid-phase S was in a reduced form in all mixtures containing OC. Pre-edge peaks on XANES spectra suggest tetragonal S coordination, which is consistent with the presence of an Fe–S phase such as mackinawite. The addition of Fe⁰ enhanced AMD remediation over the duration of these experiments, however long-term evaluation is required to identify optimal Fe⁰ and OC mixtures.     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Distribution of reduced inorganic sulfur compounds in lake sediments receiving acid mine drainage

The sediments of Lake Anna, Virginia, act as a major sink for incoming acid mine drainage (AMD) pollutants (Fe, SO₄²⁻, H⁺) due to bacterial sulfate reduction (SR). Acid-volatile sulfide (AVS), elemental S, and pyrite concentrations in the sediments of the polluted arm of the lake are significantly greater than those in unpolluted sections of the lake. Measurements of SR using ³⁵SSO₄²⁻ showed that AVS and S⁰ are the major short-term (48 h) products of SR in these sediments. Inorganic forms of S(AVS, S⁰, and FeS₂) made up from 60 to 100% of the total sediment S concentration. Pyrite concentrations in the sediment were high but decreased exponentially with distance from the AMD source, suggesting that the pyrite was deposited as stream detritus from the abandoned mines. Iron monosulfide and elemental S concentrations were highest at a station 1 km away from the AMD inflow, indicating formation in situ. There was no evidence for the formation of organic S species. The results suggest that in Fe- and S-rich locations such as those contaminated with acid mine drainage, the distribution of end products of SR may vary substantially from those reported for more moderate environments.     

The aqueous geochemistry of Zr and the solubility of some Zr-bearing minerals

Literature data on the thermodynamics of complexation of Zr with inorganic species, at 25°C, have been critically reviewed. The preponderance of published complexation constants deal with F⁻ and OH⁻ ions. Stability constants for the complexation reactions are relatively independent of ionic strength and thus recomended values for each ligand type are averages of the most reliable data. Complexation constants under elevated conditions (T 250°C andP_v = P_H2O) have been predicted for various Zr complexes (F⁻, Cl⁻, SO₄²⁻ and OH⁻) using Helgeson's electrostatic approach. Predominance diagrams (calculated for simple systems with these constants) suggest that, over a wide range of pH conditions, Zr(OH)_4(aq) will dominate the aqueous geochemistry of Zr except under very high activities of competing ligands (e.g., F⁻, SO₄²⁻).The solubilities of vlasovite [Na₂ZrSi₄O₁₁] and weloganite [Sr₃Na₂Zr(CO₃)₆·3H₂O have been measured in KCI solutions (0.5–1.0 M) at 50°C. Weloganite dissolution is complicated by the predictable precipitation of strontianite (SrCO₃) whereas vlasovite dissolves incongruently. Solubility products for the dissolution of welonganite and vlasovite are determined to be −28.96±0.14 and −20.40±1.18, respectively. Concentrations of Zr up to 10⁻³ m were present in the experimental solutions; the presence of large amounts of Zr in aqueous solutions support the possibility of extensive remobilization of Zr during hydrothermal mineralization.     

H2S fluxes from Mt. Etna, Stromboli, and Vulcano (Italy) and implications for the sulfur budget at volcanoes

We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO₂/H₂S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H₂S flux of 6 to 9 t · d⁻¹ for the summit crater. For Mt. Etna and Stromboli, we found SO₂/H₂S molar ratios of ≈20 and ≈15, respectively, which combined with SO₂ flux measurements, suggest H₂S emission rates of 50 to 113 t · d⁻¹ and 4 to 8 t · d⁻¹, respectively. We observe that “source” and plume SO₂/H₂S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H₂S emission.     

Landscape variations in stream water SO4 and δSSO4 in a boreal stream network

Despite reduced anthropogenic deposition during the last decades, deposition sulphate may still play an important role in the biogeochemical cycles of S and many catchments may act as net sources of S that may remain for several decades. The aim of this study is to elucidate the temporal and spatial dynamics of both SO₄²⁻ and δ³⁴S_SO4 in stream water from catchments with varying percentage of wetland and forest coverage and to determine their relative importance for catchment losses of S. Stream water samples were collected from 15 subcatchments ranging in size from 3 to 6780 ha, in a boreal stream network, northern Sweden. In forested catchments (<2% wetland cover) S-SO₄²⁻ concentrations in stream water averaged 1.7 mg L⁻¹ whereas in wetland dominated catchments (>30% wetland cover) the concentrations averaged 0.3 mg L⁻¹. A significant negative relationship was observed between S-SO₄²⁻ and percentage wetland coverage (r² = 0.77, p < 0.001) and the annual export of stream water SO₄²⁻ and wetland coverage (r² = 0.76, p < 0.001). The percentage forest coverage was on the other hand positively related to stream water SO₄²⁻ concentrations and the annual export of stream water SO₄²⁻ (r² = 0.77 and r² = 0.79, respectively). The annual average δ³⁴S_SO4 value in wetland dominated streams was +7.6‰ and in streams of forested catchments +6.7‰. At spring flood the δ³⁴S_SO4 values decreased in all streams by 1‰ to 5‰. The δ³⁴S_SO4 values in all streams were higher than the δ³⁴S_SO4 value of +4.7‰ in precipitation (snow). The export of S ranged from 0.5 kg S ha⁻¹ yr⁻¹ (wetland headwater stream) to 3.8 kg S ha⁻¹ yr⁻¹ (forested headwater stream). With an average S deposition in open field of 1.3 kg S ha⁻¹ yr⁻¹ (2002-2006) the mass balance results in a net export of S from all catchments, except in catchments with >30% wetland. The high temporal and spatial resolution of this study demonstrates that the reducing environments of wetlands play a key role for the biogeochemistry of S in boreal landscapes and are net sinks of S. Forested areas, on the other hand were net sources of S.     

Chemistry of rainwaters in the south Pacific area of Russia

On the south-eastern edge of Russia, the chemical composition of rainwater is controlled by sea salts, terrestrial material, as well as volcanic (Kuril islands volcanic area) and anthropogenic emissions, mostly in the southern part of the area. The predominant major ions of the Primorye, Sakhalin and the Kuril Islands rainwaters were respectively HCO₃⁻–SO₄²⁻, Ca–Na, and of Cl–Na. Concentration of trace elements changes within 1–2 orders of magnitude but some difference in the distribution of the elements between continental and island rainwater is found. The concentration of the chemical elements in the particulate fraction varies from < 10% to 90% of the total concentration (dissolved + particulate) with the following distribution: Tl, Na, Ca, Sr, Zn, Cd (< 10%)–Be, Th, Bi, Rb, U, K, Sc (10–20%)–Cu, Mn, Mg, Mo, Se, Ba, Ni, As, Ag, Cs, Co, Y, Ga, V (20–50%)–Sb, Pb, Ge, Cr, Fe, Al (50–90%).The concentration of elements of the particulate fraction of the rainwater usually is significantly different from concentrations in the crust, including both higher and lower concentrations. The terrestrial contribution to dissolved elements was evaluated and follows the decreasing order: Fe > K, Mg, Ca > Ba, Sr > Na (65–1%). Close order was found for total (dissolved and solid) concentrations. Sea salt contribution to dissolved element concentration in the rainwater decrease in the following order: Cl, Mg > K, SO₄ > Ca > HCO₃⁻, Ba, Fe (78–0.1%). Calculation of anthropogenic and volcanic inputs for two ions (Cl⁻ and SO₄²⁻) shows that anthropogenic inputs for the Vladivostok and Yuzno-Sakhalinsk cities can be evaluated as 15–20% of Cl⁻ and up to 80–90% of SO₄²⁻. Volcanic components in the Kuril Islands, where anthropogenic inputs are absent, can reach up to 76% of SO₄²⁻ and 36% of Cl⁻.     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.     

A pilot-scale field experiment for the microbial neutralization of a holomictic acidic pit lake

A strategy to neutralize acidic pit lakes was tested in an upscaling process using field mesocosms of 26 to ca. 4500 m³ volume in the acidic pit Mining Lake 111 in Germany. After addition of the substrates Carbokalk and straw a neutral sediment layer formed, in which microbial sulfate and iron reduction as well as sulfide precipitation occurred. The net rate of neutralization was limited by the precipitation of iron sulfides rather than by microbial reactions. Oxidation of H₂S by ferric iron in the anoxic sediment lowered the net sulfate reduction rate. Seasonal fluctuations of iron sulfides in the sediment showed that the reaction products were not necessarily stable. The long-term success of the approach depends on the net partition of the precipitated iron-(mono-/di-) sulfide that is permanently buried in the anoxic sediment. It could be shown by field experiments that the long-term success of the neutralization depends on the spatial scale and duration of the experiments. Volumes from 26 to 4500 m³, exposition times from 4 months to 5 years, and increasingly thick coverings of the sediments with straw, from zero to 40 cm, were used. Net neutralization rates decreased from 41 meq m^− 2 d^− 1 in laboratory microcosms to a mean rate of 2.3 meq m^− 2 d^− 1 in the 4500 m³ field experiment. The results show that the success of the microbial treatment of acid pit lakes lastly depends on the limnological conditions in the lake that cannot be simulated by upscaling of simple laboratory experiments.