Recovery of streams from episodic acidification in northern Sweden

Between 1990 and 1999, SO4(2-) deposition in northern Sweden decreased by over 50%. To determine if a corresponding amelioration of stream acidity has occurred, we analyzed trends in anthropogenically driven episodic acidification in five streams during the same time period, using the Boreal Dilution Model (BDM) (Bishop, K. H.; Laudon, H.; Kohler, S. Water Resour. Res. 2000, 36, 1873-1884). Although there was no significant change in the annual average streamwater chemistry, the anthropogenically driven episodic acidification associated with spring flood runoff decreased by between 40% and 80%. A strong correlation between winter SO4(2-) deposition and the anthropogenic component of episodic acidification in these five streams suggests that future reductions of acid deposition will further improve the spring flood acidification situation in northern Sweden. These results argue that reduced emissions of acid precursors have generated significant improvements in the surface water chemistry during episodes associated with spring runoff in northern Sweden.     

Suppression of dissolved organic carbon by sulfate induced acidification during simulated droughts

The relationship between dissolved organic carbon (DOC) and the acidification of soils and freshwaters by sulfate (SO4(2-)) has been a topic of great debate over the last few decades. Most interest has focused on long-term acidification. Few have considered the influence of episodic drought-induced acidification in peatlands on DOC mobility, even through the increased acidity and ionic strength associated with the oxidation of reduced sulfur to SO4(2-) are known to reduce DOC solubility. Reduced DOC concentrations during droughts have often been attributed to: (i) reduced hydrological export; (ii) physicochemical changes in the peat structure; or (iii) changes in the biological production and/or consumption of DOC. Our experimental drought simulations on peat cores showed that SO4(2-) induced acidification reduced DOC concentrations during droughts. However, the relationships between SO4(2-)/pH/ ionic strength and DOC were only apparent when the reductions in observed DOC were expressed as a fraction of the estimated DOC concentration in the absence of SO4(2-), which were derived from soil depth, temperature, and watertable data. This analysis showed that a pH fall from 4.3 to 3.5, due to a SO4(2-) rise from < 2.5 to 35 mg L(-1), caused a 60% reduction in DOC concentrations. In contrast, poor correlations were recorded between S042-/pH/ionic strength and the observed DOC data. As DOC both influences acidity and is influenced by acidity, the relative change in DOC needed to be considered to disentangle the effect of inputs of mineral acids into a system naturally dominated by variable concentrations of organic acids.     

Effect of declining lake base cation concentration on freshwater critical load calculations

Steady-state critical load models have been extensively used as the scientific underpinning for air pollution control policies in Europe and are currently being applied to other parts of the world. An important assumption of steady-state models is that critical load estimates do not change through time (or time scale of interest). The most commonly used model for estimating freshwater critical loads is the steady-state water chemistry (SSWC) model. In this study we examined changes in SSWC critical load estimates for 29 lakes in south-central Ontario using data collected 13 years apart (1985-1998), during which time bulk sulfate (SO4(2-)) deposition decreased by 35%. In lakes with the lowest base cation concentrations (<120 microequiv L(-1) Ca2+), the decrease in SO4(2-) concentration was accompanied by an approximately equivalent decrease in base cation concentration, resulting in only a minimal increase in Acid Neutralizing Capacity (ANC) during the 13-year period (median increase 1.6 microequiv L(-1)), and the median critical load for acidity (CL(A)) estimated by the SSWC model decreased by 14.6%. These changes may have been brought about by declining base cation concentrations owing to continued soil acidification in the region. In contrast, in lakes with higher base cation concentrations (>150 microequiv L(-1) Ca2+), the relative decline in base cation concentration was not as great, resulting in a larger increase in ANC (median increase 13.1 microequiv L(-1)) and an increase in the estimated CL(A) (median 5.1%). Lakes with moderate base cation concentrations (120-150 microequiv L(-1) Ca2+) exhibited an intermediate response; the median ANC increased by 8.8 microequiv L(-1) and the estimated CL-(A) decreased by 2.2%. In central Ontario, SSWC critical load estimates based on data taken only 13 years apart change quite dramatically due to changing lake base cation concentrations, and the response appears to depend on the base status of the lakes. The changing values obtained from the SSWC model have important consequences for policy decisions regarding acceptable levels of acid deposition. The application of dynamic models that take into account changes in lake/soil chemistry appears more appropriate for estimating acceptable levels of acid deposition in the region.     

Are brook trout streams in western Virginia and Shenandoah National Park recovering from acidification?

Streamwater composition data obtained through periodic sampling of streams that support brook trout (Salvelinus fontinalis) in the mountains of western Virginia were examined for evidence of recovery from acidification during the 1988-2001 period. Measurements of sulfate deposition in precipitation indicate that sulfate deposition in the region declined approximately 40% between 1985 and 2000. While no significant regional trends in acid-base constituents were observed for the set (n = 65) of western Virginia study streams, significant regional trends were observed for a subset (n = 14) of streams in Shenandoah National Park (SNP). For the subset of SNP streams, the median increase in acid-neutralizing capacity (ANC) was 0.168 microequiv L(-1) year(-1) and the median decrease in sulfate concentration was -0.229 microequiv L(-1) year(-1). Although these trends are consistent with recovery from acidification, the degree of apparent recovery is small compared to estimates of historic acidification in SNP streams and much less than observed in other, more northern regions in the United States. Correlation between sulfate concentration trends and current sulfate concentrations in streamwater suggests that recovery from stream acidification in the western Virginia region is determined by sulfur retention processes in watershed soils. A transient increase in nitrate concentrations that occurred among some western Virginia streams following forest defoliation by the gypsy moth (Lymantria dispar) complicates interpretation of the observed patterns of change in acid-base status.     

Factors affecting acid neutralizing capacity in the Adirondack region of New York: a solute mass balance approach

High rates of acidic deposition in the Adirondack region of New York have accelerated acidification of soils and surface waters. Annual input-output budgets for major solutes and acid-neutralizing capacity (ANC) were estimated for 43 drainage lake-watersheds in the Adirondacks from 1998 to 2000. Sulfate was the predominant anion on an equivalent basis in both precipitation and drainage export. Calcium ion had the largest cation drainage export, followed by Mg2+. While these watersheds showed net nitrogen (N) retention, the drainage losses of SO4(2-), Cl-, base cations, and ANC exceeded their respective inputs from precipitation. Land cover (forest type and wetlands) affected the export of SO4(2-), N solutes, and dissolved organic carbon (DOC). The relationships of solute export with elevation (negative for base cations and Cl-, positive for NO3- and H+) suggest the importance of the concomitant changes of biotic and abiotic watershed characteristics associated with elevational gradients. The surface water ANC increased with the sum of base cations and was greatest in the lakes with watersheds characterized by thick deposits of glacial till. The surface water ANC was also higher in the lake-watersheds with lower DOC export. Some variation in lake ANC was associated with variability in acidic deposition. Using a classification system previously developed for Adirondack lakes on the basis primarily of surficial geology, lake-watersheds were grouped into five classes. The calculated ANC fluxes based on the major sinks and sources of ANC were comparable with measured ANC for the thick-till (I) and the medium-till lake-watersheds with low DOC (II). The calculated ANC was overestimated for the medium-till with high DOC (III) and the thin-till with high DOC (V) lake-watersheds, suggesting the importance of naturally occurring organic acids as an ANC sink, which was not included in the calculations. The lower calculated estimates than the measured ANC for the thin-till lake-watersheds with low DOC (IV) were probably due to the mobilization of Al as an ANC source in these watersheds that were highly sensitive to strong acid inputs. Our analysis of various drainage lakes across the Adirondacks on the basis of solute mass balances, coupled with the use of a lake classification system and GIS data, demonstrates that the lake-watersheds characterized by shallow deposits of glacial till are highly sensitive to acidic deposition not only in the southwestern Adirondack region where previous field-based studies were intensively conducted but also across the entire Adirondack region. Moreover, the supply of organic acids and Al mobilization substantially modify the acid-base status of surface waters.     

Acid rain effects on aluminum mobilization clarified by inclusion of strong organic acids

Assessments of acidic deposition effects on aquatic ecosystems have often been hindered by complications from naturally occurring organic acidity. Measurements of pH and ANCG, the most commonly used indicators of chemical effects, can be substantially influenced by the presence of organic acids. Relationships between pH and inorganic Al, which is toxic to many forms of aquatic biota, are also altered by organic acids. However, when inorganic Al concentrations are plotted against ANC (the sum of Ca2+, Mg2+, Na+, and K+, minus S042-, N03-, and Cl-), a distinct threshold for Al mobilization becomes apparent. If the concentration of strong organic anions is included as a negative component of ANC, the threshold occurs at an ANC value of approximately zero, the value expected from theoretical charge balance constraints. This adjusted ANC is termed the base-cation surplus. The threshold relationship between the base-cation surplus and Al was shown with data from approximately 200 streams in the Adirondack region of New York, during periods with low and high dissolved organic carbon concentrations, and for an additional stream from the Catskill region of New York. These results indicate that (1) strong organic anions can contribute to the mobilization of inorganic Al in combination with SO42- and N03-, and (2) the presence of inorganic Al in surface waters is an unambiguous indication of acidic deposition effects.     

Response of surface water acidification in upper Yangtze River to SO2 emissions abatement in China

Surface waters in Europe and North America are slowly recovering from acidification following major reductions in emissions of sulfur dioxide (SO(2)) since the 1980s. In contrast, regions affected by acid rain have been reported to be growing in China. Here we show that the rapid change in surface water chemistry in the 1990s in large areas in Southwestern China, specifically the tributary rivers of the Upper Yangtze River, caused by increasing SO(2) emissions, has leveled off. During the 1990s the sulfate (SO(4)(2-)) concentrations in river water increased rapidly and, on average, doubled in only eight years. Simultaneously, calcium (Ca(2+)) concentrations increased, while pH values decreased. In the following decade (2000s), SO(2) emissions stabilized, causing a subsequent stop to the increasing SO(4)(2-) concentrations and pH decline in river water. Although a rapid response to future reduction in SO(2) emissions can be expected, a rapid increase of nitrogen (N) emissions could lead to increases in N leaching and delay recovery.     

Chemical response of lakes in the Adirondack Region of New York to declines in acidic deposition

Long-term changes in the chemistry of wet deposition and lake water were investigated in the Adirondack Region of New York. Marked decreases in concentrations of SO4(2-) and H+ in wet deposition have occurred at two sites since the late 1970s. These decreases are consistent with long-term declines in emissions of sulfur dioxide (SO2) in the eastern United States. Changes in wet NO3- deposition and nitrogen oxides (NOx) emissions have been minor over the same interval. Virtually all Adirondack Lakes have shown marked decreases in concentrations of SO4(2-), which coincide with decreases in atmospheric S deposition. Concentrations of NO3- have also decreased in several Adirondack lakes. As atmospheric N deposition has not changed over this period, the mechanism contributing to this apparent increase in lake/watershed N retention is not evident. Decreases in concentrations of SO4(2-) + NO3- have resulted in increases in acid-neutralizing capacity (ANC) and pH and resulted in a shift in the speciation of monomeric Al from toxic inorganic species toward less toxic organic forms in some lakes. Nevertheless, many lakes continue to exhibit pH values and concentrations of inorganic monomeric Al that are critical to aquatic biota. Extrapolation of rates of ANC increase suggests that the time frame of chemical recovery of Adirondack Lakes will be several decades if current decreases in acidic deposition are maintained.     

New insights into the source of decadal increases of dissolved organic matter in acid-sensitive lakes of the northeastern United States

The last several decades have seen decreases in SO(4)(2-) deposition across the northeastern United States. As a result, SO(4)(2-) concentrations in lakes and streams have also decreased and many surface water bodies have become less acidic. During the same time period, there has been a concurrent increase in dissolved organic carbon (DOC) concentrations in many lakes and streams. We used fluorescence spectroscopy to characterize the dissolved organic matter (DOM) quality of archived samples from nine acid-sensitive lakes in Maine collected between 1993 and 2009, and determined that increased DOM contributions to lakes were primarily derived from litter and soil. All five lakes with increasing DOC trends demonstrated significant decreasing (i.e., more terrestrial) trends in fluorescence index (FI) and significant positive correlations between SO(4)(2-) and FI. This study used the chemical signature of terrestrial DOM to support the hypothesis that increased DOC concentrations in lakes and streams are driven by declining acid deposition and increased solubility of soil organic matter across a large area of the landscape.     

High-calorific biogas production by selective CO₂ retention at autogenerated biogas pressures up to 20 bar

Autogenerative high pressure digestion (AHPD) is a novel configuration of anaerobic digestion, in which micro-organisms produce autogenerated biogas pressures up to 90 bar with >90% CH(4)-content in a single step reactor. (1) The less than 10% CO(2)-content was postulated to be resulting from proportionally more CO(2) dissolution relative to CH(4) at increasing pressure. However, at 90 bar of total pressure Henry's law also predicts dissolution of 81% of produced CH(4). Therefore, in the present research we studied whether CO(2) can be selectively retained in solution at moderately high pressures up to 20 bar, aiming to produce high-calorific biogas with >90% methane. Experiments were performed in an 8 L closed fed-batch pressure digester fed with acetate as the substrate. Experimental results confirmed CH(4) distribution over gas and liquid phase according to Henry's law, but the CO(2)-content of the biogas was only 1-2%, at pH 7, that is, much lower than expected. By varying the ratio between acid neutralizing capacity (ANC) and total inorganic carbon (TIC(produced)) of the substrate between 0 and 1, the biogas CO(2)-content could be controlled independently of pressure. However, by decreasing the ANC relative to the TIC(produced) CO(2) accumulation in the aqueous medium caused acidification to pH 5, but remarkably, acetic acid was still converted into CH(4) at a rate comparable to neutral conditions.     

Chemical recovery of surface waters across the northeastern united states from reduced inputs of acidic deposition: 1984-2001

Changes in lake water chemistry between 1984 and 2001 at 130 stratified random sites across the northeastern United States were studied to evaluate the population-level effects of decreases in acidic deposition. Surface-water S04(2-) concentrations decreased across the region at a median rate of -1.53 microequiv L(-1) year(-1). Calcium concentrations also decreased, with a median rate of -1.73 microequiv L(-1) year(-1). This decrease in Ca2+ retarded the recovery of surface water acid neutralizing capacity (Gran ANC), which increased at a median rate of 0.66 microequiv L(-1) year(-1). There were small increases in pH in all subregions except central New England and Maine, where the changes were not statistically significant. Median NO3- trends were not significant except in the Adirondacks, where NO3- concentrations increased at a rate of 0.53 microequiv L(-1) year(-1). A regionwide decrease in the concentration of total Al, especially in ponds with low ANC values (ANC < 25 microequiv L(-1)), was observed in the Adirondack subregion. These changes in Al were consistent with the general pattern of increasing pH and ANC. Despite the general pattern of chemical recovery, many ponds remain chronically acidic or are susceptible to episodic acidification. The continued chemical and biological recovery at sites in the northeastern United States will depend on further controls on S and N emissions.     

Model prognoses for future acidification recovery of surface waters in norway using long-term monitoring data

During the past 20 years, acid deposition in Europe has decreased by more than 60%, yet still a large number of lakes and streams in southern Norway have not recovered to a water quality sufficient to support sustainable populations of trout or salmon. Long-term (30 years) monitoring data were used hereto constrain the calibration of the acidification model MAGIC to three Norwegian calibrated catchments. The model accounted for 60-80% of the variance in the year-to-year variations in concentrations of most of the major ions in streamwater. The results support the use of the lumped parameter acid neutralizing capacity (ANC) to link chemical parameters to biological response, as the calibration efficiency for ANC is considerably higher than for other biologically important parameters such as inorganic aluminum (Al(n+)) and pH. Three different scenarios for future deposition of sulfur were run: current legislation, maximum feasible reductions, and an illustrative scenario removing all anthropogenic deposition. These analyses show that much of the potential improvement in water quality has already occurred and that only limited further improvement can be expected from the current legislation. The current legislation is unlikely to produce ANC values sufficiently high to allow self-reproducing populations of trout at two of the three sites. Most of the response in water chemistry to reduced acid deposition has been rapid; the water chemical responses largely occur the same year or a few years after reduction in the input. The soil pool of exchangeable base cations depleted during 150 years of acid deposition, however, requires several centuries for replenishment. The uncertainties in future predictions come from several factors, such as future nitrogen dynamics and impacts from changes in seasalt and precipitation events. The differences in future water chemistry predicted from changed seasalt deposition or nitrogen dynamics are larger that the differences between different deposition scenarios. Hence, these factors must be included in future assessments of recovery from acidification.     

Analysis of trends in episodic acidification of streams in western Maryland

In this study we report on changes in the magnitude and mechanisms of episodic acidification of a small acid-sensitive stream in western Maryland (U.S.) during the 1990s, a period in which wet sulfate deposition declined by 10-25% due to implementation of the Clean Air Act Amendments (CAAA) of 1990. We observed a relatively minor trend in the magnitude of episodic acidification over this period, as measured bytransient changes in acid neutralizing capacity (deltaANC) and minimum values of ANC (ANC(min)) during 22 events sampled prior to and following CAAA implementation. Any relationship to changes in atmospheric deposition appears to be confounded by large hydroclimatological variability between the two sampling periods. Nonetheless, results obtained prior to implementation of the CAAA indicated that the mechanism of episodic acidification was mostly attributable to flushing of accumulated sulfate from the watershed, whereas results obtained post-CAAA indicated domination by base cation dilution. This shift in the mechanism of episodic acidification is qualitatively consistent with hydrochemical theory, as well as with empirical results from surface waters in other regions where dramatic declines in sulfate deposition have taken place.     

Climate effects on stream nitrate concentrations at 16 forested catchments in south central Ontario

Increased nitrate (NO3) concentrations in streamwaters draining forested catchments are reportedly an early indicator of nitrogen (N) saturation. Nitrate concentrations in streams draining 16 forested catchments in south central Ontario were monitored over a 16-year period, during which time N bulk deposition was relatively constant (approximately 9 kg ha(-1) yr(-1)). Mean annual NO3 concentrations in streams were both highly variable among catchments and among years, although patterns of annual concentration were similar among many catchments. Coherence analysis identified two stream groupings. Shallow soils, moderate slopes, low NO3 concentration, and a large wetland component characterized the first group. The second group had primarily upland characteristics including deeper soils, steeper slopes, higher NO3 concentrations, and a much smaller wetland component. Patterns in NO3 concentration in wetland-influenced streams appeared to be related to summer drought and cumulative frost depth, whereas NO3 concentrations in upland-draining streams appeared to be related to both mean annual air temperature and summer drought. Because a number of different climate parameters as well as the physical character of the catchments apparently influence NO3 export, NO3 concentrations in streams are not a good indicator of N saturation in this region.     

Ion budgets and sediment-water interactions during the experimental acidification and recovery of Little Rock Lake, Wisconsin

Ion budgets for the two basins of experimentally acidified Little Rock Lake (Vilas County, WI, U.S.A.) indicate that Ca2+, Mg2+, and K+ were released from the bottom sediments to the water column during 1984-1994, and NH4+, NO3-, and SO4(2-) were removed for a net internal alkalinity generation (IAG). Sulfate removal contributed approximately 50% of the IAG in the reference basin, and cation production generated approximately 40%. In-lake processes in the reference basin removed approximately 38% of the sulfate input; 58% was lost to outflow, and 4% remained in the water column. As a result of acid additions that stimulated sulfate reduction and lower pH that enhanced ion exchange, sulfate removal and Ca2+ production were more important for IAG in the treatment basin. During 1984-1994, sulfate removal contributed about 61% of the IAG, and Ca2+ production contributed about half of the IAG from cation production. In the treatment basin, in-lake processes removed about 46% of the total input of sulfate (including acid additions); 36% was lost to outflow and 18% remained in the water column (representing approximately 25% of the added acid). In both basins of LRL, NH4+ consumption roughly balanced NO3- consumption, and net N transformations provided only 3-12% of the IAG. Overall, Na+ and Cl- were conservative in both basins during 1984-1994. Most ion budget components, including calculated internal reaction terms, showed fairly large interannual variations; e.g., ion inputs (dominated by atmospheric deposition) varied by a factor of about two. Over the 10-year period, ANC terms calculated from the budgets as the difference between base cation and acid anion terms agreed well with measured ANC terms for the budget components, indicating that the budgets accounted for all important IAG constituents.     

Regional assessment of the response of the acid-base status of lake watersheds in the Adirondack region of New York to changes in atmospheric deposition using PnET-BGC

Understanding the response of soil and surface waters to changes in atmospheric deposition is critical for guiding future legislation on air pollution. The Adirondack region of New York experiences among the most severe ecological impacts from acidic deposition. The region is characterized by considerable variability in atmospheric deposition, surficial and bedrock geology, hydrologic flow paths, and vegetation resulting in variability in effects of acidic deposition. In this study, an integrated biogeochemical model (PnET-BGC) was applied to 37 forest lake watersheds to assess the response of soil and surface waters of the Adirondacks to changes in atmospheric deposition at a regional scale. Model-simulated surface water chemistry was validated against data from two synoptic surveys conducted in 1984 and 2001. Results indicate that the model is able to capture the observed changes in surface water chemistry during this period. The model was further used to forecast the response of soil and surface waters to three future emission control scenarios. Results indicate that under the Clean Air Act, surface water SO4(2-) concentrations will continue to decrease at a median rate of -0.38 microeq/L-yr, and surface water ANC is predicted to increase at a median rate of 0.11 microeq/L-yr. More aggressive emission reductions will accelerate the rate of recovery. Under an aggressive control scenario, which represents an additional 75% reduction in SO2 emissions beyond the implementation of the Clean Air Act, surface water SO4(2-) concentrations are predicted to decrease at a median rate of -0.88 microeq/L-yr, and surface water ANC is predicted to increase at a median rate of 0.43 microeq/L-yr. Model predictions of several biologically relevant chemical indicators are also reported.     

Interaction between urbanization and climate variability amplifies watershed nitrate export in Maryland

We investigated regional effects of urbanization and land use change on nitrate concentrations in approximately 1,000 small streams in Maryland during record drought and wet years in 2001-2003. We also investigated changes in nitrate-N export during the same time period in 8 intensively monitored small watersheds across an urbanization gradient in Baltimore, Maryland. Nitrate-N concentrations in Maryland were greatest in agricultural streams, urban streams, and forest streams respectively. During the period of record drought and wet years, nitrate-N exports in Baltimore showed substantial variation in 6 suburban/urban streams (2.9-15.3 kg/ha/y), 1 agricultural stream (3.4-38.9 kg/ha/y), and 1 forest stream (0.03-0.2 kg/ha/y). Interannual variability was similar for small Baltimore streams and nearby well-monitored tributaries and coincided with record hypoxia in Chesapeake Bay. Discharge-weighted mean annual nitrate concentrations showed a variable tendency to decrease/increase with changes in annual runoff, although total N export generally increased with annual runoff. N retention in small Baltimore watersheds during the 2002 drought was 85%, 99%, and 94% for suburban, forest, and agricultural watersheds, respectively, and declined to 35%, 91%, and 41% during the wet year of 2003. Our results suggest that urban land use change can increase the vulnerability of ecosystem nitrogen retention functions to climatic variability. Further work is necessary to characterize patterns of nitrate-N export and retention in small urbanizing watersheds under varying climatic conditions to improve future forecasting and watershed scale restoration efforts aimed at improving nitrate-N retention.     

Contemporary trends in the acid-base status of two acid-sensitive streams in western Maryland

Recovery of streamwater acid neutralizing capacity (ANC) resulting from declines in regional acid deposition was examined using contemporary (1990-2005) data from two long-term monitoring stations located on the Appalachian Plateau in western Maryland, U.S. Two computational methods were used to estimate daily, monthly, and annual fluxes and discharge-weighted concentrations of ANC, sulfate, nitrate, and base cations over the period of record, and two statistical methods were used to evaluate long-term trends in fluxes and concentrations. The methods used to estimate concentrations, as well as the statistical techniques, produced very similar results, underlining the robustness of the identified trends. We found clear evidence that streamwater sulfate concentrations have declined at an average rate of about 3 microeq L(-1) yr(-1) at the two sites due to a 34% reduction in wet atmospheric sulfur deposition. Trends in nitrate concentrations appear to be related to other watershed factors, especially forest disturbance. The best evidence of recovery is based on a doubling of ANC (from 21 to 42 microeq L(-1)) at the more acid-sensitive site over the 16-year period. A slowing, or possible reversal, in the sulfate, nitrate, and SBC trends is evident in our data and may portend a decline in the rate of--or end to--further recovery.     

Photocatalysis for continuous air purification in wastewater treatment plants: from lab to reality

The photocatalytic efficiency of TiO(2)-SiMgO(x) plates to oxidize H(2)S was first evaluated in a flat laboratory reactor with 50 mL min(-1) synthetic air containing 100 ppm H(2)S in the presence of humidity. The use of the photocatalyst-adsorbent hybrid material enhanced the photocatalytic activity in terms of pollutant conversion, selectivity, and catalyst lifetime compared to previous H(2)S tests with pure TiO(2) because total H(2)S elimination was maintained for more than 30 operating hours with SO(2) appearing in the outlet as reaction product only after 18 h. Subsequently, the hybrid material was successfully tested in a photoreactor prototype to treat real polluted air in a wastewater treatment plant. For this purpose, a new tubular photocatalytic reactor that may use solar radiation in combination with artificial radiation was designed; the lamp was turned on when solar UV-A irradiance was below 20 W m(-2), which was observed to be the minimum value to ensure 100% conversion. The efficient distribution of the opaque photocatalyst inside the tubular reactor was achieved by using especially designed star-shaped structures. These structures were employed for the arrangement of groups of eight TiO(2)-SiMgO(x) plates in easy-to-handle channelled units obtaining an adequate flow regime without shading. The prototype continuously removed during one month and under real conditions the H(2)S contained in a 1 L min(-1) air current with a variable inlet concentration in the range of tens of ppmv without release of SO(2).     

Assessment of sulfate sources in high-elevation Asian precipitation using stable sulfur isotopes

Stable sulfur isotope measurements (delta34S) made on samples collected from a 2 m snowpit on the Inilchek Glacier, Tien Shan Mountains (42.16 degrees N, 80.25 degrees E, 5100 m) are used to estimate sources of sulfate (SO4(2-)) in high-elevation Central Asian precipitation. Comparison of snowpit oxygen isotope (delta18O) data with previous work constrains the age of the snowpit samples to the summer season during which they were retrieved (1999). Delta34S measurements were made at 10 cm resolution (20 samples total), with delta34S values ranging from 0.4/1000 during background ([SO4(2-)] < 1 microequiv L(-1)) periods to 19.4/1000 during a single high [SO4(2-)] event. On the basis of the significant correlation (r = 0.87) between [SO4(2-)] and delta34S values, coupled with major ion concentration time series and concentration ratios, we suggest a two-component mixing system consisting of evaporite dust and anthropogenic SO4(2-) to explain the observed delta34S values. Using a regression model, we estimate that during the 1999 summer season 60% of the deposited SO4(2-) was from an evaporite dust source, while 40% of the SO4(2-) was from anthropogenic sources. Due to the potentially large and unconstrained range of delta34S values for both evaporite and anthropogenic SO4(2-) sources in Asia, the error in our estimates is difficult to assess. However, the delta34S data from the 1999 Tien Shan snowpit provide the first unambiguous identification of evaporite and anthropogenic SO4(2-) in high-elevation Asian precipitation, and future ice core studies using improved analysis techniques and source delta34S values can provide detailed information on sulfur biogeochemistry and anthropogenic impacts in Asian alpine regions.