Deposition Of SO2 Research Articles

Quality Assurance Decisions with Air Models: A Case Study of Imputation of Missing Input Data Using EPA’s Multi-layer Model

Environmental models are frequently used within regulatory and policy frameworks to estimate environmental metrics that are difficult or impossible to physically measure. As important decision tools, the uncertainty associated with the model outputs should impact their use in informing regulatory decisions and scientific inferences. In this paper, we present a case study illustrating a process for dealing with a key issue in the use and application of air quality models, the additional error in annual mean aggregations resulting from imputation of missing data from model data sets. The case study is based on the US Environmental Protection Agency’s Multi-layer Model, which estimates the hourly dry deposition velocity of air pollutants based on hourly measurements of meteorology and site characteristics. A simulation was implemented to evaluate the effect of substituting historical hour-specific average values for missing model deposition velocity predictions on annual mean aggregations. Sensitivity studies were performed to test the effects of different missing data patterns and evaluate the relative impact of the substitution procedure on annual mean SO2 deposition velocity estimates. The substitution procedure was shown to result generally in long-term unbiased estimates of the annual mean and contributed less than 20% additional error to the estimate even when all data were missing. Consequently, it may be possible to use the historical record of deposition velocities to provide reasonably accurate and unbiased annual estimates of deposition velocities for years without meteorological measurements.

Siloxane-based polymers as protective coatings against SO2 dry deposition

The present research was focused on investigating the ability of different siloxane-based polymeric coatings to provide environmental protection to monumental limestone (Repedea from Romania) used in the north-eastern part of Romania for the construction of many stone monuments. Three siloxane-based polymers used throughout the world in protecting stone monuments, namely Lotexan-N, Silres® BS 290 and Tegosivin HL 100 and a newly designed hybrid nanocomposite containing silsesquioxane units (TMSPMA) were selected as polymeric coatings. The ability of the coatings to protect the stone from dry SO2 deposition in the presence of humidity in a standardized accelerated ageing test was determined. A comparative study of the obtained results indicates that the stone samples treated with the new hybrid siloxane-based nanocomposite exhibited improved resistance to degradation after being exposed to a SO2 saturated atmosphere.

Effects of canopy–deposition interaction on H + supply to soils in Pinus banksiana and Populus tremuloides ecosystems in the Athabasca oil sands region in Alberta, Canada

Soil acidification has been of concern in the oil sands region in Alberta due to increased acid deposition. Using the canopy budget model, and accounting for H + canopy leaching by organic acids, we determined sources and sinks of H + in throughfall in jack pine ( Pinus banksiana) and trembling aspen ( Populus tremuloides) stands in two watersheds from 2006 to 2009. In pine stands, H + deposition was greater in throughfall than in bulk precipitation while the opposite was true in aspen stands. The annual H + interception deposition was 148.8–193.8 and 49.7–70.0 mol c ha −1 in pine and aspen stands, respectively; while the annual H + canopy leaching was 127.1–128.7 and 0.0–6.0 mol c ha −1, respectively. The greater H + supply in pine stands was caused by greater interception deposition of SO 4 2− and organic acids released from the pine canopy. Such findings have significant implications for establishing critical loads for various ecosystems in the oil sands region.

Evaluation of ambient SO2 measurement methods at roadside sites

Abstract Accurate measurements of SO2 at low ambient concentrations are needed in order to investigate the role of SO2 in particle nucleation events and the long-term impact of reductions in sulfur emissions in recent decades. In this study, artifacts in SO2 concentration measurements were investigated using two identical ion chromatography-based instruments (the Gas Particle Ion Chromatograph, GP-IC, Dionex Corporation) and two identical UV fluorescence-based SO2 analyzers (the TECO 43CTL, an industry standard). The SO2 concentration values measured with the GP-IC at roadside sites were compared with simultaneous side-by-side measurements made with the fluorescence analyzers. The SO2 concentration measured with the GP-IC had an ∼30% negative calibration artifact. When the GP-ICs were calibrated using an improved procedure developed in the course of this study, only a ±5% difference from the TECO analyzers remained, except under high NO concentration conditions. The fluorescence analyzers exhibited a positive artifact under elevated NO concentration conditions. Sulfur oxidation ratios were calculated based on the GP-IC-measured SO2 and SO42- concentrations and used to help identify potential emission sources. The SO2 concentrations measured with the GP-IC were also compared to data obtained from a National Air Pollution Surveillance (NAPS) speciation sampler equipped with a Na2CO3-coated denuder. Good correlation between SO2 data from the two methods was seen during five months of measurement, but the GP-IC SO2 data were ∼30% lower than the NAPS data. Deposition of SO2 within an urban street canyon is discussed as a possible explanation for this difference.

Relative role of decreasing precipitation sulfate and climate on recent lake recovery

In the last 2 decades, acidic sulfur (S) depositions and SO4 concentration in surface water significantly decreased in many regions of the world, while at the same time temperatures have been increasing, particularly in the decade 1995–2005, which was one of the warmest ever recorded in the Northern Hemisphere. Understanding the potentially antagonistic or additive effects of decreasing S depositions and increasing temperatures on lake chemistry is essential to adequately evaluate the effectiveness of reduction programs for S emissions. By assessing the rate of change in climate variables, precipitation SO4 and lake chemistry for 47 temperate and boreal catchments, we found that changes in climate, particularly higher annual temperatures, were more often correlated to lake's pH and alkalinity than was the rate of decreasing S depositions between 1989 and 2005. It suggests that the recent improvement in the acid‐base status of the studied lakes that cover a large area of northeastern North America as well as a large array of acid‐base conditions cannot be attributed solely to a decrease in SO4 precipitation, but also to climatic variations. Not taking this information into account could lead to an overestimation of the benefit of lower SO4 deposition on aquatic ecosystems recovery.

Sources, transport, and sinks of SO2 over the equatorial Pacific during the Pacific Atmospheric Sulfur Experiment

The Pacific Atmospheric Sulfur Experiment (PASE) is the first sulfur-budget field experiment to feature simultaneous flux measurements of DMS marine emissions and SO2 deposition to the ocean surface. We make use of these data to constrain a 1-D chemical transport model to study the production and loss pathways for DMS and SO2 over the equatorial Pacific. Model results suggest that OH is the main sink for DMS in the boundary layer (BL), and the average DMS-to-SO2 conversion efficiency is ~73%. In an exploratory run involving the addition of 1 pptv of BrO as a second oxidant, a 14% increase in the DMS flux is needed beyond that based on OH oxidation alone. This BrO addition also reduces the DMS-to-SO2 conversion efficiency from 73% to 60%. The possibility of non-DMS sources of marine sulfur influencing the estimated conversion efficiency was explored and found to be unconvincing. For BL conditions, SO2 losses consist of 48% dry deposition, while transport loss to the BuL and aerosol scavenging each account for another 19%. The conversion of SO2 to H2SO4 consumes the final 14%. In the BuL, cloud scavenging removes 85% of the SO2, thus resulting in a decreasing vertical profile for SO2. The average SO2 dry deposition velocity from direct measurements (i.e., 0.36 cm sec−1) is approximately 50% of what is calculated from the 1-D model and the global GEOS-Chem model. This suggests that the current generation of global models may be significantly overestimating SO2 deposition rates over some tropical marine areas. Although the specific mechanism cannot be determined, speculation here is that the dry deposition anomalous results may point to the presence of a micro-surface chemical phenomenon involving partial saturation with either S(IV) and/or S(VI) DMS oxidation products. This could also appear as a pH drop in the ocean’s surface microfilm layer in this region. Finally, we propose that the enhanced SO2 level observed in the lower free troposphere versus that in the upper BuL during PASE is most likely the result of transported DMS/SO2-rich free-tropospheric air parcels from the east of the PASE sampling area, rather than an inadequate representation in the model of local convection.

Soil chemical and physical properties at the Bear Brook Watershed in Maine, USA

Acidic deposition leads to the acidification of waters and accelerated leaching and depletion of soil base cations. The Bear Brook Watershed in Maine has used whole-watershed chemical manipulations to study the effects of elevated N and S on forest ecosystem function on a decadal time scale. The objectives of this study were to define the chemical and physical characteristics of soils in both the reference and treated watersheds after 17 years of treatment and assess evidence of change in soil chemistry by comparing soil studies in 1998 and 2006. Results from 1998 confirmed depletion of soil base cation pools and decreased pH due to elevated N and S within the treated watershed. However, between 1998 and 2006, during a period of declining SO4(2-) deposition and continued whole-watershed experimental acidification on the treated watershed, there was little evidence of continued soil exchangeable base cation concentration depletion or recovery. The addition of a pulse of litterfall and accelerating mineralization from a severe ice storm in 1998 may have had significant effects on forest floor nutrient pools and cycling between 1998 and 2006. Our findings suggest that mineralization of additional litter inputs from the ice storm may have obscured temporal trends in soil chemistry. The physical data presented also demonstrate the importance of coarse fragments in the architecture of these soils. This study underscores the importance of long-term, quantitative soil monitoring in determining the trajectories of change in forest soils and ecosystem processes over time.

The evolution of the science of Bear Brook Watershed in Maine, USA

The Bear Brook Watershed in Maine (BBWM), USA is a paired watershed study with chemical manipulation of one watershed (West Bear = WB) while the other watershed (East Bear = EB) serves as a reference. Characterization of hydrology and chemical fluxes occurred in 1987-1989 and demonstrated the similarity of the ca. 10 ha adjacent forested watersheds. From 1989-2010, we have added 1,800 eq (NH(4))(2)SO(4) ha(-1) y(-1) to WB. EB runoff has slowly acidified even as atmospheric deposition of SO4(-2) has declined. EB acidification included decreasing pH, base cation concentrations, and alkalinity, and increasing inorganic Al concentration, as SO4(-2) declined. Organic Al increased. WB has acidified more rapidly, including a 6-year period of increasing leaching of base cations, followed by a long-term decline of base cations, although still elevated over pretreatment values, as base saturation declined in the soils. Sulfate in WB has not increased to a new steady state because of increased anion adsorption accompanying soil acidification. Dissolved Al has increased dramatically in WB; increased export of particulate Al and P has accompanied the acidification in both watersheds, WB more than EB. Nitrogen retention in EB increased after 3 years of study, as did many watersheds in the northeastern USA. Nitrogen retention in WB still remains at over 80%, in spite of 20+ years of N addition. The 20-year chemical treatment with continuous measurements of critical variables in both watersheds has enabled the identification of decadal-scale processes, including ecosystem response to declining SO4(-2) in ambient precipitation in EB and evolving mechanisms of treatment response in WB. The study has demonstrated soil mechanisms buffering pH, declines in soil base saturation, altered P biogeochemistry, unexpected mechanisms of storage of S, and continuous high retention of treatment N.

Trends in hydrometeorological conditions and stream water organic carbon in boreal forested catchments

Temporal trends in stream water total organic carbon (TOC) concentration and export were studied in 8 forested headwater catchments situated in eastern Finland. The Seasonal Kendall test was conducted to identify the trends and a mixed model regression analysis was used to describe how catchment characteristics and hydrometeorological variables (e.g. precipitation, air and stream water temperatures, and atmospheric deposition) related to the variation in the concentration and export of stream water TOC. The 8 catchments varied in size from 29 to 494 ha and in the proportion of peatland they contained, from 8 to 70%. Runoff and TOC concentration were monitored for 15–29 years (1979–2006). Trends and variation in TOC levels were analysed from annual and seasonal time series. Mean annual TOC concentration increased significantly in seven of the eight catchments. The trends were the strongest in spring and most apparent during the last decade of the study period. The slopes of the trends were generally smaller than the variation in TOC concentration between years and seasons and between catchments. The annual TOC export showed no clear trends and values were largely determined by the temporal variability in runoff. Annual runoff showed a decreasing trend in two of the eight catchments. Mean annual air and stream water temperatures showed increasing trends, most clearly seen in the summer and autumn series. According to our modeling results, stream water temperature, precipitation and peatland percentage were the most important variables explaining annual and most seasonal TOC concentrations. The atmospheric deposition of SO 4, NH 4, and NO 3 decreased significantly over the study period, but no significant link with TOC concentration was found. Precipitation was the main hydrometeorological driver of the TOC export. We concluded that stream water TOC concentrations and exports are mainly driven by catchment characteristics and hydrometeorological factors rather than trends in atmospheric acid deposition.

The influence of long term trends in pollutant emissions on deposition of sulphur and nitrogen and exceedance of critical loads in the United Kingdom

Abstract In the United Kingdom, as with other European countries, land-based emissions of NO x and SO 2 have fallen significantly over the last few decades. SO 2 emissions fell from a peak of 3185 Gg S in 1970 to 344 Gg S in 2005 and are forecast by business-as-usual emissions scenarios to fall to 172 Gg by 2020. NO x emissions were at a maximum of 951 Gg N in 1970 and fell to 378 by 2005 with a further decrease to 243 Gg N forecast by 2020. These large changes in emissions have not been matched by emissions changes for NH 3 which decreased from 315 Gg N in 1990 to 259 in 2005 and are forecast to fall to 222 by 2020. The Fine Resolution Atmospheric Multi-pollutant Exchange model (FRAME) has been applied to model the spatial distribution of sulphur and nitrogen deposition over the United Kingdom during a 15-year time period (1990–2005) and compared with measured deposition of sulphate, nitrate and ammonium from the national monitoring network. Wet deposition of nitrogen and sulphur was found to decrease more slowly than the emissions reductions rate. This is attributed to a number of factors including increases in emissions from international shipping and changing rates of atmospheric oxidation. The modelled time series was extended to a 50-year period from 1970 to 2020. The modelled deposition of SO x , NO y and NH x to the UK was found to fall by 87%, 52% and 25% during this period. The percentage area of sensitive habitats in the United Kingdom for which critical loads are exceeded is estimated to fall from 85% in 1970 to 37% in 2020 for acidic deposition and from 73% to 49% for nutrient nitrogen deposition. The significant reduction in land emissions of SO 2 and NO x focuses further attention in controlling emissions from international shipping. Future policies to control emissions of ammonia from agriculture will be required to effect further significant reductions in nitrogen deposition.

Dissolved Organic Carbon Concentrations in Throughfall and Soil Waters at Level II Monitoring Plots in Norway: Short- and Long-Term Variations

We investigated concentrations of dissolved organic carbon (DOC) in throughfall and soil solutions at 5, 15 and 40-cm depth in 16 Norway spruce and two Scots pine plots throughout Norway between 1996 and 2006. Average DOC concentrations ranged from 2.3 to 23.1 mg/l and from 1.1 to 53.5 mg/l in throughfall water and soil solutions, respectively. Concentrations of DOC in throughfall and soil waters varied seasonally at most plots with peaks in the growing season. By contrast to recently reported positive long-term trends in DOC concentrations in surface waters between 1986 and 2003, soil water data from 1996 to 2006 showed largely negative trends in DOC concentrations and no significant trends in throughfall. However, regression analysis for individual sites, particularly at 5- and 15-cm soil depths, showed that DOC concentrations in soil water were significantly and negatively related to non-marine sulphate (SO4) and chloride (Cl−). The lack of a long-term increase in DOC in soil water in the period May 1996–December 2006 may be due to the relatively small changes in the deposition of SO4 and Cl− in this period.

Deposition of sulfur dioxide to building stones: the influence of the ambient concentration on the deposition velocity

We report on extensive deposition measurements of sulfur dioxide (SO2) on three types of commonly used building stones (Obernkirchen sandstone, Sand sandstone, Ihrlerstein sandstone). The deposition velocities on the three materials were determined in a number of measuring campaigns at different sites with different levels of air pollution. The measurements clearly imply that there is a strong influence of SO2 concentration on the deposition velocity. With increasing concentration there is a strong decrease in the deposition velocity. To understand this deposition behavior a simple model with a single rate constant as the only adjustable parameter was established. Rate constants for the three stone materials were determined by least squares analysis and good agreement between experimental and calculated deposition velocities was obtained. According to the model treatment the surface resistance of stone materials increases with increasing SO2 concentration due to a decrease of the pH in surface films. It follows from the concentration dependence of the deposition velocity that emission control measures for the reduction of ambient SO2 concentrations do not lead to a proportional reduction of the SO2 deposition. At low SO2 concentrations the differences in the deposition behavior of different stone materials diminish and stone surfaces behave like ideal absorbers under such conditions, i.e., the deposition velocity is controlled by the aerodynamic resistance.

Climate control on sulphate and nitrate concentrations in alpine streams of Northern Italy along a nitrogen saturation gradient

Abstract. The role of meteorology, hydrology and atmospheric deposition on the temporal pattern of SO4 and NO3 concentrations was investigated for three streams draining alpine catchments in Northern Italy. The study sites lie on a gradient of atmospheric fluxes of SO4 and NO3 (from about 50 to 80 meq m−2 y−1, and from 40 to 90 meq m−2 y−1, respectively). As a consequence of the increasing N input, the three catchments are also representative of aggrading levels of N saturation. Different methods of statistical analysis were applied to monthly data for the period 1997–2005 to identify which variables (temperature, precipitation, hydrology, SO4 and NO3 deposition) were the main predictors of water chemistry and its change in time. Hydrological changes and snow cover proved to be the main confounding factors in the response to atmospheric deposition in the River Masino catchment. Its particular characteristics (small catchment area, rapid flushing during runoff and thin soil cover) meant that this site responded without a significant delay to SO4 deposition decrease. It also showed a clear seasonal pattern of NO3 concentration, in response to hydrology and biological uptake in the growing season. The selected driving variables failed to model the water chemistry at the other study sites. Nevertheless, temperature, especially extreme values, turned out to be important in both SO4 and NO3 export from the catchments. This result might be largely explained by the effect of warm periods on temperature-dependent processes such as mineralization, nitrification and S desorption. Our findings suggest that surface waters in the alpine area will be extremely sensitive to a climate warming scenario: higher temperatures and increasing frequency of drought could exacerbate the effects of high chronic N deposition.

The mineralogical composition of sandstone and its effect on sulphur dioxide deposition

Air pollutants often accelerate stone deterioration in historical buildings and monuments in urban areas. The pollutants are themselves the products of fossil fuel combustion and intensive farming. While this trend seems to have been curbed by strict emission laws in the European Union, in most developing and emerging countries air pollution is an ongoing process due to increasing energy needs and vehicle traffic. Many factors condition natural stone behaviour with respect to gaseous pollutants. Two of the more prominent of such factors are the composition of the atmosphere and the type of stone. Due to their porosity, sandstones are particularly vulnerable to air pollutant attack. Many of the reactions between non-carbonaceous sandstones and these gases are not well understood, however. The present study aimed to acquire an understanding of the processes and factors governing sandstone behaviour when exposed to sulphur dioxide. Seven different sandstones from southern and eastern Germany were analyzed for the study. The binder composition of the stones varied significantly. They also exhibited completely different behaviour in connection with SO2 sorption. Interestingly, while the amount of SO2 deposited was unrelated to the specific surface area of the sandstones, this parameter was closely correlated to the iron oxide content. Iron oxide phases are believed to act as a catalyst in the oxidation of SO2 to SO3. The type and amount of clay mineral, in turn, was found to have no significant impact on initial SO2 deposition in sandstones.

MICS-Asia II: Model inter-comparison and evaluation of acid deposition

This paper focuses on the comparison of chemical deposition of eight regional chemical models used in Model Inter-Comparison Study for Asia (MICS-Asia) II. Monthly-mean depositions of chemical species simulated by these models, including dry deposition of SO 2, HNO 3, NH 3, sulfate, nitrate and ammonium and wet deposition of SO 4 2−, NO 3 − and NH 4 +, have been provided for four periods (March, July, December 2001 and March 2002) in this work. Observations at 37 sites of the Acid Deposition Monitoring Network in East Asia (EANET) are compared with SO 4 2−, NO 3 − and NH 4 + wet deposition model results. Significant correlations appeared between the observation and computed ensemble mean of participant models. Also, differences among modeled sulfur and nitrogen dry depositions have been studied at the EANET sites. Based on the analysis of acid deposition for various species from different models, total depositions of sulfur (SO 2 and sulfate) and nitrogen (nitrate and ammonium) have been evaluated as the ensemble mean of the eight models. In general, all models capture the observed spatial distribution of sulfur and nitrogen deposition, although the absolute values may differ from measurements. High deposition often occurs in eastern China, Japan, the Republic of Korea, Thailand, Vietnam, Philippines and other parts of Southeast Asia. The magnitude of model bias is quite large for many of the models. In examining the reasons for model–measurement disagreement, we find that differences in chemical processes, deposition parameterization, and modeled precipitation are the main reasons for large model disparities.

The response of two remote, temperate lakes to changes in atmospheric mercury deposition, sulfate, and the water cycle

Atmospheric deposition is the ultimate source of Hg to many remote lakes, but the response to depositional change remains uncertain because of potential buffering by historical pools of Hg in sediments and soils. We investigated the responsiveness of two lakes over time scales ranging from weeks to decades. For waterborne Hg, results indicated that a precipitation-dominated seepage lake and a wetland-dominated drainage lake responded similarly to depositional change, despite high loadings of terrigeneous matter to the drainage lake. For methylmercury (meHg), the response was more complicated, reflecting the influence of multiple factors on in-lake methylation. In the seepage lake, waterborne meHg was correlated with the atmospheric deposition of Hg(II) and SO4, and there was an indirect dependence on the water cycle. In the drainage lake, although wetland export was always the dominant external source of meHg, mass balance indicated that net in-lake methylation was four- to seven-fold greater than loading from the wetland. However, in-lake meHg production was related to the export of Hg(II), SO4, dissolved organic carbon, and P from the wetland to the lake. The results suggest that atmospheric Hg deposition, weather, and microbial activity interactively effect the aquatic mercury cycle in ways that can be independent of historical pools of Hg in catchments.

Long-Term Increase in Dissolved Organic Carbon in Streamwaters in Norway Is Response to Reduced Acid Deposition

Concentrations of dissolved organic carbon (DOC) in freshwaters have increased significantly in Europe and North America, but the driving mechanisms are poorly understood. Here, we test if the significant increase in TOC (total organic carbon, 90-95% DOC) in three acid-sensitive catchments in Norway of 14 to 36% between 1985 and 2003 is related to climate, hydrology, and/or acid deposition. Catchment TOC export increased between 10 and 53%, which was significant at one site only. The seasonal variation in TOC was primarily climatically controlled, while the deposition of SO4 and NO3--negatively related to TOC--explained the long-term increase in TOC. We propose increased humic charge and reduced ionic strength--both of which increase organic matter solubility--as mechanistic explanations for the statistical relation between reduced acid deposition and increased TOC. Between 1985 and 2003, ionic strength decreased significantly at all sites, while the charge density of TOC increased at two of the sites from 1-2 meq g(-1) C to about 5 meq g(-1) C and remained constant at the third site at 5 meq g(-1) C. The solubility of organic matter is discussed in terms of the pH-dependent deprotonation of carboxylic groups and the ionic strength-dependent repulsion of organic molecules.

Precipitation composition and wet deposition temporal pattern in Central Serbia for the period from 1998 to 2004

Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate (NO(3)(-)), sulfate (SO(4)(2-)), sodium (Na(+)), ammonium (NH(4)(+)), potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was SO(2-)(4) with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of SO(4)(2-)/NO(3)(-) was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).

Characterization of atmospheric corrosion products of zinc exposed to SO2 and NO2 using XPS and GIXD

A complete characterization of corrosion products formed on zinc plates after exposure in a climatic chamber was conducted in this study. The dry deposition of NO2, SO2, and SO2 + NO2, at 25 °C and 35 °C, and relative humidity (RH) of 90% was simulated. Pollutant concentrations evaluated were selected to represent highly polluted industrial atmospheric levels. Analysis techniques included X-ray Photoelectron Spectroscopy (XPS) and Grazing Incidence X-ray Diffraction (GIXD). For tests conducted at 25 °C, the relative amount of sulfate was determined to be higher in the SO2 + NO2 atmosphere than in the SO2 atmosphere, and was associated with greater corrosivity in the former atmosphere. NO2 had an indirect role as a catalyst for SO2 reduction to sulfate, as evidenced by the greater proportion of sulfate ions detected and the lack of nitrogen compounds in corrosion products. At 35 °C, effect of NO2 was reduced, and was complicated by a greater tendency for drying so that it was more difficult to maintain the humidity layer. Therefore, no accelerating effect of exposure temperature was observed.

Sulfate exports from multiple catchments in a glaciated forested watershed in western New York, USA

Sulfate (SO4(2-)) concentrations and fluxes were studied for multiple storm events in the Point Peter Brook watershed, a glaciated, forested watershed located in Western New York, USA. Investigations were performed across one large (696 ha) and three small (1.6-3.4 ha) catchments with varying extent of riparian and wetland areas. Concentrations of SO4(2-) in groundwater sources (mean values: 238-910 micromol(c) L(-1)) were considerably greater than concentrations recorded for rainfall (60 micromol(c) L(-1)) and throughfall (72-129 micromol(c) L(-1)). Seasonality in SO4(2-) concentrations was most pronounced for valley-bottom riparian waters with maximum concentrations in late winter-spring (February-March) and a minimum in late summer (August). Concentrations of SO4(2-) in wetland water were considerably less than riparian water indicating the likelihood of SO4(2-) reduction in anoxic wetland conditions. Storm events displayed a dilution pattern in SO4(2-) concentrations with a minimum coinciding with the maximum in throughfall contributions. End member mixing analysis (EMMA) was able to predict the storm event concentrations of SO4(2-) for four of the six comparisons. Concentrations of SO4(2-) at the outlet of the large (696 ha) catchment were much greater than values recorded for the smaller catchments. Exports of SO4(2-) in streamflow exceeded the inputs from atmospheric deposition suggesting that watersheds like Point Peter Brook may not show any immediate response to decreases in atmospheric SO4(2-) deposition.