In situ assessment of microbial sulfate reduction in a petroleum-contaminated aquifer using push-pull tests and stable sulfur isotope analyses

Anaerobic microbial activities such as sulfate reduction are important for the degradation of petroleum hydrocarbons (PHC) in contaminated aquifers. The objective of this study was to evaluate the feasibility of single-well push-pull tests in combination with stable sulfur isotope analyses for the in situ quantification of microbial sulfate reduction. A series of push-pull tests was performed in an existing monitoring well of a PHC-contaminated aquifer in Studen (Switzerland). Sulfate transport behavior was evaluated in a first test. In three subsequent tests, we injected anoxic test solutions (up to 1000 l), which contained 0.5 mM bromide (Br-) as conservative tracer and 1 mM sulfate (SO4(2-)) as reactant. After an initial incubation period of 42.5 to 67.9 h, up to 1100 l of test solution/groundwater mixture was extracted in each test from the same location. During the extraction phases, we measured concentrations of relevant species including Br-, SO4(2-) and sulfide (S(-II)), as well as stable sulfur isotope ratios (delta 34S) of extracted, unconsumed SO4(2-) and extracted S(-II). Results indicated sulfate reduction activity in the vicinity of the test well. Computed first-order rate coefficients for sulfate reduction ranged from 0.043 +/- 0.013 to 0.130 +/- 0.015 day-1. Isotope enrichment factors (epsilon) computed from sulfur isotope fractionation of extracted, unconsumed SO4(2-) ranged from 20.2 +/- 5.5@1000 to 22.8 +/- 3.4@1000. Together with observed fractionation in extracted S(-II), isotope enrichment factors provided strong evidence for microbially mediated sulfate reduction. Thus, push-pull tests combined with stable sulfur isotope analyses proved useful for the in situ quantification of microbial sulfate reduction in a PHC-contaminated aquifer.     

Sulfur and carbon cycling in a flue gas desulfurization sludge disposal site

Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial delta13C 3.2-3.8 per thousand), gypsum (initial delta34S 7.6-8.6 per thousand), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-delta34S sulfide, consuming organic carbon and generating low-delta13C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has delta34S near 6 per thousand, and calcite has delta13C as low as -1.7 per thousand; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of bacterial reduction. After the pond is abandoned, these products may adversely affect attempts to revegetate the site. Future bacterial reduction may be best controlled by dewatering and limiting the supply of organic matter in percolating surface water.     

Trends in atmospheric sulfur and nitrogen species in the eastern United States for 1989–1995

Emission reductions were mandated in the Clean Air Act Amendments of 1990 with the expectation that they would result in major reductions in the concentrations of atmospherically transported pollutants. This paper investigates the form and magnitude of trends from 1989 to 1995 in atmospheric concentrations of sulfur dioxide, sulfate, and nitrogen at 34 rural sites in the eastern US. Across all sites, there is strong evidence of statistically significant declining trends in sulfur dioxide (median change of -35%) and sulfate concentrations (median change of -26%). In general, trends in nitrogen concentrations were not as pronounced (median change of -8%) as trends in the sulfur compounds. A regional estimate of trend for a cluster of sites in the Ohio River valley showed close correspondence between declining sulfur dioxide concentrations (-35%) and changes in sulfur dioxide emissions (-32%) in this region.     

Anthropogenic impacts on natural nitrogen isotope variations in Pinus sylvestris stands in an industrially polluted area

Natural variations of the nitrogen isotopes 15N/14N (delta15N values) and the N concentrations of one-year-old needles from 7-12-year-old pine trees (Pinus sylvestris L.) were determined on 27 sites in the heavily polluted Leipzig-Halle region (former GDR). At three selected sites measurements were repeated over a period of 2 years. N concentrations and delta15N values in different needle age classes were compared at the three sites. The delta15N values of the N in the humus layer and the potential plant available N in the A(h) horizon of the local soil were determined. The 15N/14N isotope ratios (delta15N values) of one-year-old pine needles in the region of Leipzig-Halle were found to vary depending on their specific location by a factor of up to one order of magnitude (-9.6 per thousand to + 0.4 per thousand ). N concentrations in one-year-old pine needles varied between 0.71 and 1.38 mmol eq N g dw(-1). Pine stands with positive or slightly negative delta15N values and high N concentrations in one-year-old needles were concentrated around the cities of Leipzig and Halle and in the industrial areas. More negative delta15N values and lower N concentrations in one-year-old pine needles were found on sites at greater distances from the industrial agglomerations, mainly in the NE forested part. Site specific differences in the delta15N values of the N in the humus layer from three selected sites were similar to those found for the needles. No site specific differences, however, were found for the delta15N values of the water soluble nitrogen fraction from the mineral soil horizons of the same sites.     

Use of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks

Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual δ³⁴S values at individual sites ranged from +4.0 to +8.2‰ and standard deviations ranged from 0.4 to 1.6‰. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 μeq l⁻¹ and pH ranged from 4.82 to 5.70. The range of δ³⁴S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between δ³⁴S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO₂ in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in δ³⁴S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps reflecting the paucity of major point sources of SO₂ in the northern part of the network.     

Recovery of Soil Water,Groundwater, and Streamwater From Acidification at the Swedish Integrated Monitoring Catchments

Recovery from anthropogenic acidification in streams and lakes is well documented across the northern hemisphere. In this study, we use 1996–2009 data from the four Swedish Integrated Monitoring catchments to evaluate how the declining sulfur deposition has affected sulfate, pH, acid neutralizing capacity, ionic strength, aluminum, and dissolved organic carbon in soil water, groundwater and runoff. Differences in recovery rates between catchments, between recharge and discharge areas and between soil water and groundwater are assessed. At the IM sites, atmospheric deposition is the main human impact. The chemical trends were weakly correlated to the sulfur deposition decline. Other factors, such as marine influence and catchment features, seem to be as important. Except for pH and DOC, soil water and groundwater showed similar trends. Discharge areas acted as buffers, dampening the trends in streamwater. Further monitoring and modeling of these hydraulically active sites should be encouraged.     

Source apportionment of wet sulfate deposition in eastern North America

An analytical model of long distance transport of air pollutants (Fay and Rosenzweig, 1980. Atmospheric Environment 14, 355–365) has been adapted for the estimation of long term (e.g. annual) wet sulfate deposition in eastern N America. The model parameters have been optimized for best agreement with 1980–1982 measurements at 109 monitoring sites in this region. The root mean square residual of the model and measurement comparison is 4 kg ha ⁻¹y ⁻¹ ( 17% of the mean measured value). Transfer coefficients were found to decrease exponentially with source-receptor distance, having length scales between 1100 and 400 km depending upon whether the source is upwind or downwind of the receptor. Source apportionment calculated for four sites from this model shows that about half of the deposition is due to 7–8 of the largest source contributors to each site (aggregated to the state and sub-province level). A 17-year record of precipitation sulfate measured at Hubbard Brook, New Hampshire, compares favourably with the model calculation. Calculated U.S.-Canada transboundary fluxes differ from previous estimates. Isopleths of 1980–1982 yearly depositions were determined. A proposed 45 % reduction in U.S. sulfur emissions was found to produce about a 35% reduction of deposition at environmentally sensitive areas in the U.S. and Canada.     

Natural attenuation of trichloroethylene in fractured shale bedrock

This paper describes one of the first well-documented field examples of natural attenuation of trichloroethylene (TCE) in groundwater in a fractured shale bedrock. The study was carried out adjacent to a former waste burial site in Waste Area Grouping 5 (WAG5) on the Oak Ridge Reservation, Oak Ridge, TN. A contaminant plume containing TCE and its daughter products were detected downgradient from the buried waste pits, with most of the contamination occurring in the upper 6 m of the bedrock. The monitoring well array consists of a 35-m-long transect of multilevel sampling wells, situated along a line between the waste pits and a seep which discharges into a small stream. Concentrations of volatile organic carbons (VOCs) were highest in the waste trenches and decreased with distance downgradient towards the seep. Sampling wells indicated the presence of overlapping plumes of TCE, cis-dichloroethylene (cDCE), vinyl chloride (VC), ethylene, ethane, and methane, with the daughter products extending further downgradient than the parent (TCE). This type of distribution suggests anaerobic biodegradation. Measurements of redox potential at the site indicated that iron-reduction, sulfate reduction, and potentially methanogensis were occurring and are conducive to dechlorination of TCE. Bacteria enrichment of groundwater samples revealed the presence of methanotrophs, methanogens, iron-reducing bacteria and sulfate-reducing bacteria, all of which have previously been implicated in anaerobic biodegradation of TCE. 16S rDNA sequence from DNA extracted from two wells were similar to sequences of organisms previously implicated in the anaerobic biodegradation of chlorinated solvents. The combined data strongly suggest that anaerobic biodegradation of the highly chlorinated compounds is occurring. Aerobic biodegradation may also be occurring in oxygenated zones, including near a seep where groundwater exits the site, or in the upper bedrock during seasonal fluctuations in water table elevation and oxygen levels.     

Experimental study and steady-state simulation of biogeochemical processes in laboratory columns with aquifer material

Packed bed laboratory column experiments were performed to simulate the biogeochemical processes resulting from microbially catalyzed oxidation of organic matter. These included aerobic respiration, denitrification, and Mn(IV), Fe(III) and SO(4) reduction processes. The effects of these reactions on the aqueous- and solid-phase geochemistry of the aquifer material were closely examined. The data were used to model the development of alkalinity and pH along the column. To study the independent development of Fe(III)- and SO(4)-reducing environments, two columns were used. One of the columns (column 1) contained small enough concentrations of SO(4) in the influent to render the reduction of this species unimportant to the geochemical processes in the column.The rate of microbially catalyzed reduction of Mn(IV) changed with time as evidenced by the variations in the initial rate of Mn(II) production at the head of the column. The concentration of Mn in both columns was controlled by the solubility of rhodochrosite (MnCO(3(S))).In the column where significant SO(4) reduction took place (column 2), the concentration of dissolved Fe(II) was controlled by the solubility of FeS. In column 1, where SO(4) reduction was not important, maximum dissolved Fe(II) concentrations were controlled by the solubility of siderite (FeCO(3(S))). Comparison of solid-phase and aqueous-phase data suggests that nearly 20% of the produced Fe(II) precipitates as siderite in column 1. The solid-phase analysis also indicates that during the course of experiment, approximately 20% of the total Fe(III) hydroxides and more than 70% of the amorphous Fe(III) hydroxides were reduced by dissimilatory iron reduction.The most important sink for dissolved S(-II) produced by the enzymatic reduction of SO(4) was its direct reaction with solid-phase Fe(III) hydroxides leading initially to the formation of FeS. Compared to this pathway, precipitation as FeS did not constitute an important sink for S(-II) in column 2. In this column, the total reacted S(-II) estimated from the concentration of dissolved sulfur species was in good agreement with the produced Cr(II)-reducible sulfur in the solid phase. Solid-phase analysis of the sulfur species indicated that up to half of the originally produced FeS may have possibly transformed to FeS(2).     

Atmospheric Sulfates from Biological Sources

Bacteriogenic production of H₂S occurs in fine-grained anoxic muds, is promoted by organic and nutrient pollution of water, peaks in the warm months of the year, and is the source of most of the estimated 100 to 200 million tons of biogenic sulfur annually contributed to the global atmosphere. We tested the hypothesis that biogenic sulfur contributes to the atmospheric load of sulfate in urban and nonurban sites by statistical analyses of the 24 hour sulfate levels measured in 4 coastal and 3 Inland nonurban sites where pollutant sulfur dioxide emissions are absent or negligible, and in 8 coastal and 10 inland urban sites, all located in New England or Middle Atlantic states.

Comparisons of annual and seasonal mean sulfate levels show that in nonurban groups summertime sulfate levels significantly exceed wintertime levels, and in summer, sulfate levels in urban sites are nearly the same as in nonurban sites. Comparisons of group sulfate means in 4 New York cities near extended bodies of polluted water with those in 10 inland upstate New York cities show significantly higher levels in the cities near polluted water in spring, summer, and fall and for the year as a whole, but not in winter, when the levels were similar. When the nonurban and urban sites are grouped for proximity to coasts (where bacterial sulfate reduction is active in sediments) paired groups of coastal and inland urban and nonurban sites show no significant differences in sulfate levels in summer and fall.

Studies of the summertime sulfate means in New York state show no evidence of an elevated anthropogenic background which could explain the high summertime sulfate level observed in one nonurban site in that state, while analyses of the day to day fluctuations in urban and nonurban sites support the conclusion that nonurban sites have large local (biogenic) sulfate sources in summer and fall, and that local sulfate sources also exist in spring and may exist in winter.

We conclude that biogenic sulfate sources contribute most of the sulfate observed in the cities studied during summer and fall, and in some cities also contribute in other seasons. These biogenic contributions vary with local conditions and are estimated to contribute up to 6 µg/m³ (50%) or more to the annual geometric mean sulfate levels observed in some cities located near extensive bodies of polluted water.     

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.     

Preliminary study of prairies forested with Eucalyptus sp. at the northwestern Uruguayan soils

The land cover change of Uruguayan Forestal Plan provoked biogeochemical changes on horizon Au(1) of Argiudols; in native prairies which were replaced by monoculture Eucalyptus sp. plantation with 20 year rotations as trees. Five fields forested and six natural prairies were compared. The results not only show a statistical significant soil acidification, diminution of soil organic carbon, increase of aliphaticity degree of humic substances, and increase of affinity and capacity of hydrolytic activity from soil microbial communities for forested sites with Eucalyptus sp. but also, a tendency of podzolization and/or mineralization by this kind of land cover changes, with a net soil organic lost of 16.6 tons ha(-1) in the horizon Au(1) of soil under Eucalyptus sp. plantation compared with prairie. Besides, these results point out the necessity of correction of the methodology used by assigned Uruguayan commission to assess the national net emission of greenhouse gases, since the mineralization and/or podzolization process detected in forested soil imply a overestimation of soil organic carbon. The biochemical parameters show a statistical significant correlation between the soil organic carbon status and these parameters which were presented as essential for the correct evaluation of Uruguayan soil carbon sink.     

Cumulative impact of 40 years of industrial sulfur emissions on a forest soil in west-central Alberta (Canada)

The impact of 40 years of sulfur (S) emissions from a sour gas processing plant in Alberta (Canada) on soil development, soil S pools, soil acidification, and stand nutrition at a pine (Pinus contorta x Pinus banksiana) ecosystem was assessed by comparing ecologically analogous areas subjected to different S deposition levels. Sulfur isotope ratios showed that most deposited S was derived from the sour gas processing plant. The soil subjected to the highest S deposition contained 25.9 kmol S ha(-1) (uppermost 60 cm) compared to 12.5 kmol S ha(-1) or less at the analogues receiving low S deposition. The increase in soil S pools was caused by accumulation of organic S in the forest floor and accumulation of inorganic sulfate in the mineral soil. High S inputs resulted in topsoil acidification, depletion of exchangeable soil Ca2+ and Mg2+ pools by 50%, podzolization, and deterioration of N nutrition of the pine trees.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.     

Organotin compounds in precipitation, fog and soils of a forested ecosystem in Germany

Organotin compounds (OTC) are highly toxic pollutants and have been mostly investigated so far in aquatic systems and sediments. The concentrations and fluxes of different organotin compounds, including methyl-, butyl-, and octyltin species in precipitation and fog were investigated in a forested catchment in NE Bavaria, Germany. Contents, along with the vertical distribution and storages in two upland and two wetland soils were determined. During the 1-year monitoring, the OTC concentrations in bulk deposition, throughfall and fog ranged from 1 ng Sn l(-1) to several ten ng Sn l(-1), but never over 200 ng Sn l(-1). The OTC concentrations in fog were generally higher than in throughfall and bulk deposition. Mono-substituted species were the dominant Sn species in precipitation (up to 190 ng Sn l(-1)) equaling a flux of up to 70 mg Sn ha(-1) a(-1). In upland soils, OTC contents peaked in the forest floor (up to 30 ng Sn g(-1)) and decreased sharply with the depth. In wetland soils, OTC had slightly higher contents in the upper horizons. The dominance of mono-substituted species in precipitation is well reflected in the contents and storages of OTC in both upland and wetland soils. The ratios of OTC soil storages to the annual throughfall flux ranged from 20 to 600 years. These high ratios are probably due to high stability and low mobility of OTC in soils. No evidence was found for methylation of tin in the wetland soils. In comparison with sediments, concentrations and contents of organotin in forest soils are considerably lower, and the dominant species are less toxic. It is concluded that forested soils may act as sinks for OTC deposited from the atmosphere.     

Characterization of the Atlanta area aerosol,elemental composition and possible sources

This paper presents a study or the elemental characterization of the Atlanta area aerosol at one rural and several urban sites. It includes a determination of the concentrations of major elemental components of the aerosol and a statistical analysis of the relationships between these components as a means of investigating possible sources. This research has emphasized the study of the graphitic carbon, C_e, and elemental sulfur, S, components of the aerosol (these two components are important in visibility reduction studies). The measurements show that C_e and S represent, respectively 3.1–9.9% and 1.9–4.4% of the total suspended paniculate, TSP, mass. The concentrations of C_e, S and TSP exhibit strong seasonal variations with C_e decreasing from winter to summer and S and TSP increasing over this period. All elemental components exhibit less concentration at the rural site than at the urban sites. Analysis results show that C_e appears to be statistically separate from S, which is assumed to be present as sulfate, indicating that the sources for C_e and particulate sulfate are distinct. S and TSP, however, appear to be linked through common regional scale meteorological processes.     

Stable sulphur and nitrogen isotopes of the moss Haplocladium microphyllum at urban,rural and forested sites

Elemental (S and N) and isotopic (δ³⁴S and δ¹⁵N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ³⁴S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ¹⁵N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NH_x in these sites. More negative δ¹⁵N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH₃ released from untreated city sewage and wastes, while relatively less negative δ¹⁵N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH₃.     

Sulfate,chloride and fluoride retention in Andosols exposed to volcanic acid emissions

The continuous emissions of SO(2), HCl and HF by Masaya volcano, Nicaragua, represent a substantial source of atmospheric S-, Cl- and F-containing acid inputs for local ecosystems. We report on the effects of such acid depositions on the sulfate, chloride and fluoride contents in soils (0-40 cm) from two distinct transects located downwind from the volcano. The first transect corresponds to relatively undifferentiated Vitric Andosols, and the second transect to more weathered Eutric Andosols. These soils are exposed to various rates of volcanogenic acid addition, with the Vitric sites being generally more affected. Prolonged acid inputs have led to a general pH decrease and reduced exchangeable base cation concentrations in the Andosols. The concentrations of 0.5 M NH(4)F- and 0.016 M KH(2)PO(4)-extractable sulfate (NH(4)F-S and KH(2)PO(4)-S, respectively) indicate that volcanic S addition has increased the inorganic sulfate content of the Vitric and Eutric soils at all depths. In this process, the rate of sulfate accumulation is also dependent on soil allophane contents. For all soils, NH(4)F extracted systematically more (up to 40 times) sulfate than KH(2)PO(4). This difference suggests sulfate incorporation into an aluminum hydroxy sulfate phase, whose contribution to total inorganic sulfate in the Vitric and Eutric Andosols is estimated from approximately 34 to 95% and approximately 65 to 98%, respectively. The distribution of KH(2)PO(4)-extractable chloride in the Vitric and Eutric Andosols exposed to volcanic Cl inputs reveals that added chloride readily migrates through the soil profiles. In contrast, reaction of fluoride with Al and Fe oxyhydroxides and allophanes is an important sink mechanism in the Masaya Andosols exposed to airborne volcanic F. Fluoride dominates the anion distribution in all soil horizons, although F is the least concentrated element in the volcanic emissions and depositions. The soil anion distribution reflects preferential retention of fluoride over sulfate and chloride, and of sulfate over chloride. The primary acidifying agent of the Andosols subject to the volcanic acid inputs is HCl.     

Distribution and speciation of mercury in the peat bog of Xiaoxing'an Mountain,northeastern China

Most reports on mercury (Hg) in boreal ecosystems are from the Nordic countries and North America. Comparatively little information is available on Hg in wetlands in China. We present here a study on Hg in the Tangwang River forested catchment of the Xiaoxing'an Mountain in the northeast of China. The average total Hg (THg) in peat profile ranged from 65.8 to 186.6 ng g(-1) dry wt with the highest at the depth of 5-10 cm. THg in the peat surface was higher than the background in Heilongjiang province, the Florida Everglades, and Birkeness in Sweden. MethylHg (MeHg) concentration ranged from 0.16 to 1.86 ng g(-1) dry wt, with the highest amount at 10-15 cm depth. MeHg content was 0.2-1.2% of THg. THg and MeHg all decreased with the depth. THg in upland layer of soil (0-20 cm) was comparable to the peat surface, but in deeper layers THg concentration in peat was much higher than that in the forested mineral soil. THg in the peat bog increased, but MeHg decreased after it was drained. THg content in plant was different; THg contents in moss (119 ng g(-1) dry wt, n=12) were much higher than in the herbage, the arbor, and the shrubs. The peat bog has mainly been contaminated by Hg deposition from the atmosphere.