A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

上海青浦地区大气降水的化学特征

利用上海青浦地区2003—2014年观测的大气降水监测资料,分析该区域12 a以来大气降水的酸化程度、化学组成特征,探讨降水中化学成分的不同来源及相对贡献。结果表明:降水pH年均值为4.43~6.33,酸雨频率为2.6%~86.8%,降水酸化程度大致经历了明显恶化和波动变化2个阶段。降水电导率年均值为1.77~4.01 m S/m,呈下降趋势。降水中各离子雨量加权平均当量浓度顺序为SO_4~(2-)NH_4~+Ca~(2+)NO_3~-Cl~-Na~+Mg~(2+)F-K~+,SO_4~(2-)、NH+4、Ca~(2+)和NO_3~-是降水中的主要离子,占离子总量的83.0%;降水类型由硫酸型向硫酸和硝酸混合型转变。降水离子中的二次组分SO_4~(2-)、NO_3~-和NH_4~+绝大部分来源于人为源,Ca~(2+)、Mg~(2+)和K+主要来自于土壤源和人为源的贡献,Cl~-主要来自海洋源,同时人为源的影响也不可忽视。     

On density of precipitation chemistry networks

Using Scandinavian precipitation chemistry data the dependence of the accuracy of the interpolation and areal averaging of SO _inf4 ^sup2- , NO _inf3 ^sup- , NH _inf4 ^sup+ , and Ca²⁺ contents of precipitation water on the density of the network and on the size of the area considered is studied. On the basis of the results obtained the density of networks operating with a given accuracy can be determined as a function of the area. As an example the density of the networks determining the annual and monthly areal SO_f4/^p2- deposition as well as the point values of the monthly SO_f4/^p2- concentration with an accuracy of 10%, 25%, and 30%, respectively, is calculated. The accuracy provided by such networks for other components in precipitation water is also studied.     

The predicted effect of SO2 emission controls on the water quality of eastern Canadian lakes

Changes in SO _inf4 ^sup2- deposition predicted to occur in response to implementation of announced SO₂ emission control programs in Canada and the U.S.A. have been used as input to water chemistry models thereby giving an estimate of the changes in lake acid neutralizing capacity (ANC) and pH that can be expected from these programs. Eastern Canada has been divided into 22 subregions for the purpose of this analysis. Relative to the current level (1982–86) of SO _inf4 ^sup2- deposition (Scenario 1), the effect of the Canadian SO₂ emission control program alone (Scenario 2) is compared to that obtained when controls are implemented throughout North America (Scenarios 3 and 4). SO₂ emission reduction will effect a shrinkage of the high wet SO _inf4 ^sup2- deposition field in NE North America such that under Scenario 4 conditions, almost no area will remain in Canada that receives >20 kg ha^-1 yr^-1. The greatest decrease in deposition and resulting change in lake chemistry occurs in southern Ontario and southwestern Quebec. ANC distributions shift to higher concentrations and the percentage of lakes having pH<6 decreases in these areas. The Atlantic Provinces will obtain only a minor benefit from the control programs, i.e. experiencing only a small decrease in deposition and improvement in water quality. High sensitivity of the terrain in many parts of Atlantic Canada means that large numbers of lakes will remain acidic (i.e. ANC<0) and/or have pH<6 (an important biological threshold) even after full implementation of the current plans for SO₂ control in Canada and the U.S.     

重庆市黔江区降水地球化学特征

为了解生态旅游城市重庆市黔江区大气污染状况,2015年采集了91个降水样品,分析了降水中离子组分分布特征,运用富集因子法、海盐示踪法、相关性分析、主成分分析、聚类分析和HYSPLIT模型分析了降水化学组分来源。研究结果表明:黔江区域降水p H为5.66~6.96,加权平均值为6.34,降水离子组分浓度大小次序为SO_4~(2-)Ca~(2+)NH_4~+Mg~(2+)NO_3~-Cl~-Na~+K~+F~-,SO_4~(2-)、Ca~(2+)之和占总离子的63.95%;除Mg~(2+)和K+外,其余组分离子浓度与总离子浓度随季节变化(冬季春季秋季夏季)呈同样的变化特征。Ca~(2+)、Mg~(2+)和K+大部分均来源于陆源贡献,Na~+可能受到了海洋源的影响,SO_4~(2-)和NO_3~-主要来源于人为输入源的贡献,Cl~-是受土壤物质和海洋的双重影响。轨迹水汽运输结果表明:黔江区域的降水主要受到西北气团、西南季风、西风环流和极地气候共同作用输入。降水中各个离子组分均表现出显著性或极显著性关系,主成分分析结果表明,第一主成分上研究的降水离子组分中都具有相对较大正载荷,第二组分pH、降水量和气温为一类。     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

1997—2010年北京市大气降水离子特征变化趋势研究

依据北京市环境保护监测中心1997—2010年降水监测资料,分析北京地区降水中离子特征及变化趋势,阐明北京市降水污染现状及变化特征。结合北京市特有的气象条件、地形地貌和工业分布情况,分析污染物来源及污染变化趋势。研究表明:年度降水电导率呈现波动变化,降水污染严重程度依次为南部郊区>市区>北部背景点。北京地区大气降水中的主要阳离子成分是Ca²⁺和NH₄⁺,主要阴离子成分是SO₄^2-和NO₃^-。近年来[SO₄^2-]/[NO₃^-]比值逐步下降,污染类型由典型硫酸型发展为硫酸+硝酸混合型。阳离子[Ca²⁺]/[NH₄⁺]比值下降,碱性离子缓冲能力降低。9种离子各季节浓度变化趋势基本一致,由高到低依次是春季>秋季>冬季>夏季,这种季节变化特征与气象因素密切相关。相关性及聚类分析表明:NO₃^-与SO₄^2-存在很强相关性,说明其前体物SO₂和NO_X在大气中经常一同排放且进入降水途径相同;H⁺浓度不是由某个离子决定,是所有致酸离子和中和离子相互作用的结果,而NH₄⁺来源不同于其它离子,北京地区的氨存在其单独排放源。     

A Comparison of the Precipitation Chemistry Measurements Obtained by the CAPMoN and NADP/NTN Networks

Precipitation chemistry measurementsobtained by the Canadian Air and PrecipitationMonitoring Network (CAPMoN) and the U.S. NationalAtmospheric Deposition Program/National Trends Network(NADP/NTN) have been examined using more than 7 yrof collocated data from two sites, namely, Sutton,Quebec, Canada and State College, Pennsylvania, U.S.A.In the case of the CAPMoN data, weeklyprecipitation-weighted mean concentrations, totalsample depths and total standard gauge depths werecomputed from daily data and compared to thecorresponding weekly sampling data of the NADP/NTNnetwork. Seasonal and annual precipitation-weightedmean concentrations and deposition values were alsocomputed for both networks and compared. Statisticallysignificant between-network biases were found to existin the weekly results for most of the measuredvariables, particularly standard gauge depth, sampledepth, pH, H⁺, NO₃ ^-,NH₄ ⁺,Na⁺; the NADP/NTN values were consistently lowerthan those of CAPMoN with the exception of pH andNa⁺. The magnitude of the biases was less than35% of the median CAPMoN weekly value for the 7 yr. For most of the measured parameters, thevariability of the between-network differencesrepresented less than 20% of the median CAPMoN weeklyvalue. Both the between-network biases andvariabilities were functions of several physicalparameters, the most dominant being the sample depthand the ionic concentration. For seasonal and annualdeposition values, statistically significantbetween-network biases were found for H⁺,SO₄ ^2-, NO₃ ^-,Ca²⁺,NH₄ ⁺ for both periods; for Mg²⁺ andK⁺ for seasonal data; and Cl^- for yearlydata, with the NADP/NTN deposition values being lowerthan those of CAPMoN. The relative biases ranged from7 to 37%. Part of the between-network bias in thedeposition estimates was directly attributable to astrong bias in the standard gauge depths of the two networks.     

Evaluation of the effects of acid precipitation in eastern Canada using the raison system

Evaluations have been made of the key chemical factors in the aquatic effects upon surface waters due to acidic precipitation in eastern Canada. The region of Canada east of the Manitoba/Ontario border was divided into 22 aggregates and assessments of inorganic and organic ion chemistry appraised relative to sulphate deposition rates and distributions. Aquatic sensitivity is largely dominated by the concentration, distribution and magnitude of SO _inf4 ^sup2- (sulphate) deposition and by the prevalent geology and derived soils found in each aggregate. The RAISON system provided an adaptable and highly flexible platform to evaluate interactively, multiple data sets of divergent characteristics. Attributes usually associated with geographical information systems are significantly augmented by quantitative numerical and stochastic capabilities that were used extensively in this study.     

2010—2019年台州市市区降水化学组成特征及变化趋势

为了解台州市市区大气降水化学成分组成特征及变化规律,对2010—2019年台州市市区降水监测数据进行了统计分析。结果表明:2010—2019年降水样品pH为4.20～4.84夏高冬低,强酸性降水频率下降显著,电导率平均值为3.16 mS/cm。SO₄^2-和NO₃^-是降水中最主要的阴离子,NH₄⁺和Ca²⁺是降水中最主要的阳离子。Ca²⁺浓度在2018年开始有所抬升,SO₄^2-和NO₃^-浓度整体呈波动下降趋势。SO₄^2-与NO₃^-浓度比均值为1.50,呈下降趋势,同大气中SO₂与NO₂的质量浓度比变化趋势基本一致。SO₄^2-和NO₃<...     

Interactions of Atmospheric Deposition with Coniferous Canopies in Estonia

Throughfall and open field bulk precipitation were measured at three coniferous sites during 1995–2002 in the framework of ICP Integrated Monitoring and at five coniferous sites during 1996–2002 in the framework of ICP Forests (Level II). The coniferous canopies acted as a sink for nitrate and ammonium and as a source for base cations: Ca²⁺, Mg²⁺ and K⁺. The estimated share of SO₄–S dry deposition from total deposition was 1.5–4 times higher for dormant period compared to growing period. During the study period average annual throughfall and bulk deposition of SO₄–S decreased significantly, 2.8 and 2.3 times, respectively. Throughfall enrichment with base cations increased in the order Mg < Na < Ca < K. Using Na as a tracer ion, average dry deposition and canopy leaching were calculated. Leaching was the dominant process for TF enrichment by potassium. Leaching of base cations occurred during growing as well as dormant period. The calculated internal flux of Ca²⁺ and Mg²⁺ varied in the range of 0.6–2.0 and 0.6–1.2 kg ha⁻¹ per year in spruce and pine stands, respectively. The internal circulation of K⁺ was significantly higher (8.9–10.9 kg ha⁻¹ per year) in spruce stands than in pine stands (2.7–4.4 kg ha⁻¹ per year).     

Quantitative Ethnobotany in an Atlantic Forest Fragment of Northeastern Brazil – Implications to Conservation

Two new methods for assessing temporal trends in stream-solute concentrations at specific streamflow ranges were applied to long (40 to 50-year) but sparse (bi-weekly to quarterly sampling) stream-water quality data collected at three forested mesoscale basins along an atmospheric deposition gradient in the northeastern United States (one in north-central Pennsylvania, one in southeastern New York, and one in eastern Maine). The three data sets span the period since the implementation of the Clean Air Act in 1970 and its subsequent amendments.Declining sulfate (O ₄ ^2-) trends since the mid 1960s were identified for all 3 rivers by one or more of the 4 methods of trend detection used. Flow-specific trends were assessed by segmenting the data sets into 3-year and 6-year blocks, then determining concentration-discharge relationships for each block. Declining sulfate (O ₄ ^2-) trends at median flow were similar to trends determined using a Seasonal Kendall Tau test and Sen slope estimator. The trend of declining O ₄ ^2- concentrations differed at high, median and low flow since the mid 1980s at YWC and NR, and at high and low flow at WR, but the trends leveled or reversed at high flow from 1999 through 2002. Trends for the period of record at high flows were similar to medium- and low-flow trends for Ca²⁺+ Mg²⁺ concentrations at WR, non-significant at YWC, and were more negative at low flow than at high flow at NR; trends in nitrate (NO₃ ^-), and alkalinity (ALK) concentrations were different at different flow conditions, and in ways that are consistent with the hydrology and deposition history at each watershed. Quarterly sampling is adequate for assessing average-flow trends in the chemical parameters assessed over long time periods (∼decades). However, with even a modest effort at sampling a range of flow conditions within each year, trends at specified flows for constituents with strong concentration-discharge relationships can be evaluated and may allow early detection of ecosystem response to climate change and pollution management strategies.     

大同市大气颗粒物浓度与水溶性离子季度分布特征

为研究大同市大气颗粒物质量浓度与水溶性离子组成特征,于2013年2、7、9、12月,分别对大同市及其对照点庞泉沟国家大气背景点进行了PM2.5及PM10的采样,通过超声萃取-IC法测定了样品中的9种水溶性离子,结果表明,大同市大气颗粒物污染1、4季度重于2、3季度,PM2.5季度均值全年均未超标,PM10仅第1季度超标1.4倍,污染状况总体良好,PM2.5与PM10相关系数R为0.75,说明大同市颗粒物污染有较为相近的来源,且不同季节均以粗颗粒物为主;大同市PM2.5中水溶性离子浓度分布为SO2-4、NO-3、NH+4Cl-、Ca2+K+、Na+F-、Mg2+,PM10中Ca2+浓度仅次于SO2-4、NO-3,控制扬尘将有效降低PM10的浓度;PM2.5及PM10中的9种水溶性离子在不同季度的浓度与颗粒物浓度分布规律类似,1、4季度较高,2、3季度较低;由阴阳离子平衡计算结果可知,相关性方程的斜率K为1.045,表明大同市大气颗粒物中阳离子相对亏损,大气细粒子组分偏酸性。NO-3与SO2-4浓度比值均小于1,大同市以硫酸型污染为主,大气中的SO2-4主要来源于人类活动排放。     

Nitrogen mineralization in O horizon soils during 27 years of nitrogen enrichment at the Bear Brook Watershed in Maine,USA

Chronic elevated nitrogen (N) deposition has altered the N status of temperate forests, with significant implications for ecosystem function. The Bear Brook Watershed in Maine (BBWM) is a whole paired watershed manipulation experiment established to study the effects of N and sulfur (S) deposition on ecosystem function. N was added bimonthly as (NH₄)₂SO₄ to one watershed from 1989 to 2016, and research at the site has studied the evolution of ecosystem response to the treatment through time. Here, we synthesize results from 27 years of research at the site and describe the temporal trend of N availability and N mineralization at BBWM in response to chronic N deposition. Our findings suggest that there was a delayed response in soil N dynamics, since labile soil N concentrations did not show increases in the treated watershed (West Bear, WB) compared to the reference watershed (East Bear, EB) until after the first 4 years of treatment. Labile N became increasingly available in WB through time, and after 25 years of manipulations, treated soils had 10× more extractable ammonium than EB soils. The WB soils had 200× more extractable nitrate than EB soils, driven by both, high nitrate concentrations in WB and low nitrate concentrations in EB. Nitrification rates increased in WB soils and accounted for ~?50% of net N mineralization, compared to ~?5% in EB soils. The study provides evidence of the decadal evolution in soil function at BBWM and illustrates the importance of long-term data to capture ecosystem response to chronic disturbance.     

三峡水库干流氮和磷含量的季节变化

三峡水库成库后对6个水平断面、4个垂直断面采样分析,对水体水质参数、不同化学形态N以及不同物理形态P的水平分布和垂直分布进行了研究。研究结果表明,成库后TP、NH3-N、NO2--N、NO3--N、IN含量范围分别在0.06～0.34、0.01～0.72、0.002～0.100、0.76～2.09、0.855～2.52 mg/L。TP分布为丰水期>平水期>枯水期,受悬浮物沉降的影响,TP在水库区域含量低于上游区。枯水期、平水期水体中TP以可溶解态为主,丰水期以颗粒态为主。NO2--N、NO3--N、IN含量均为平水期>枯水期>丰水期。水体中IN以NO3--N为主,占IN70%～90%。NO2--N比例最低,占IN3.5%以下。表明水体虽受成库影响流速减缓,但水体依然有较强的自净能力。垂直分布上,TP、IN在3个层次变化不显著,未出现分层现象。各采样站点TP、NO3--N、IN通量和流量有显著相关。     

2001—2018年浙江省酸雨变化特征及影响因素分析

利用2001-2018年浙江省32个城市酸雨观测资料,结合数理统计和GIS空间插值,分析了全省降水酸度变化、化学组分特征及其影响因素.研究结果表明,以2009年为拐点,浙江省酸雨污染呈先加重后减轻的趋势,降水酸度和酸雨率均得到显著改善.2009年后,轻酸雨城市的比例不断上升.至2018年,全省大部分城市均处于轻酸雨区,...     

Monitoring the impact of dissolved oxygen and nitrite on anoxic biofilm in continuous denitrification process

An anoxic biofilm involved in continuous denitrificationprocess was monitored to investigate the effect of differentconcentrations of influent dissolved oxygen (DO) or nitrite onthe biofilm. Microelectrode measurements evidenced nitrateremoval activity of biofilm. When different concentrations ofDO were applied to the reactor, generally decreasedconcentrations of DO were observed as bed depth increased fromthe bottom of the reactor. Greatest decrease of the DO wasobserved in the lower 20% of the bed depth. Nitrate removalefficiency was inversely proportional to influent DOconcentrations (8.3-11.9 DO mg L^-1) or nitrite loadingrates (0-5.5 N-NO₂ ^- kg m^-3 day^-1) employed in this study. Nitrite loading rates to achieve morethan 90% of nitrate removal efficiency were 1.46 N-NO₂ ^-kg m^-3 day^-1 or less at pH 7.5 and 0.34 N-NO₂ ^- kg m^-3 day^-1 or less at pH 6.8. Nitrate removal efficiency was 63% or more within the lower 20% of the bed depth at the nitrite loading rates that allowed more than 90% of nitrate removal efficiency of the reactor. The results of this study provide first quantitative data that nitrate removalperformance of an anoxic biofilm is inhibited by DO or nitrite,reported to be a limiting factor in the suspended biologicaldenitrification process.     

Effects of acid deposition on watershed ecosystems of national parks in the great lakes basin

Legally protected national parks provide an appropriate substrate for essential long-term study of ecosystem structure and function, and for detecting trends in natural and human-induced stress. The absence of unplanned site manipulation in such areas is especially valuable for such research. Our present research has two major components. The first is the long-term ecosystem-level study of the effects of atmospheric contaminants on ecosystem processes. The overall objective is to evaluate ecosystem aquatic/terrestrial linkages and their role in establishing aquatic ecosystem sensitivity to anthropic atmospheric inputs. Four watershed/lake ecosystems, representative of much of the region's diversity, are under study. Two mature boreal sites on Isle Royale are characterized by first-order perennial surface stream input and lake outflow. Two additional mainland northern hardwood sites, one with shallow soils and one with soils derived from glacial till, are characterized by sensitive aquatic systems. One site is in a private reserve and the other in Pictured Rocks National Lakeshore. Surface outflow is gaged by Parshall flume and stage height recorder. Meteorological stations record variables for estimating evapotranspiration. One-tenth ha plots have been established in all watersheds and three sites have had intensive study of precipitation modification by canopy and forest soil. Five-year mean maximum and minimum lake pH varies from 6.85 to 4.94, Ca²⁺ from 1070 to 54 eq l^-1, K⁺ from 5.42 to 8.35 eq l^-1, NH ₄ ⁺ from 10.12 to 3.23 eq l^-1, HCO ₃ ^sup- from 635 to 24 eq l^-1, NO ₃ ^sup- from 3.27 to 1.54 eq l^-1, and SO ₄ ^sup2- from 110 to 52.7 eq l^-1. The relatively high NO ₃ ^sup- values observed in one lake are the result of stream drainage from a watershed dominated by Alnus rugosa, and another has high seasonal NO ₃ ^sup- inputs during spring runoff. However, owing to periodic winter thaws, significant snowpack release of nutrients generally precedes maximum spring stream runoff. Water chemistry in both sensitive and non-sensitive lakes appears to be primarily reflecting how the conterminous terrestrial system is retaining atmospheric inputs more than the quality of direct lake atmospheric input. This is especially evident for H⁺, NO ₃ ^sup- and SO ₄ ^sup2- .The second component is the assessment of watershed acidification, SO ₄ ^sup2- output and soil retention across an input gradient. An anthropic deposition gradient provides the opportunity for intersite time-trend analyses as to the effects of inputs. Our study objective was to see if the decreasing west to east input/output values for SO ₄ ^sup2- , noted in small first-order watersheds in national parks from Minnesota to Ohio, might be related to present atmospheric inputs, potential and total soil SO ₄ ^sup2- adsorption, or soil SO ₄ ^sup2- desorption from earlier higher inputs. Precipitation pH ranged from 5.05 at Fernberg, Minnesota to 4.24 at Wooster, Ohio. Minimum and maximum concentrations of NH ₄ ⁺ , NO ₃ ^sup- , SO ₄ ^sup2- and Cl^- were also found at these stations. Stream water concentrations of NO ₃ ^sup- and SO ₄ ^sup2- increase in a similar but sharper gradient. Streams are well buffered. Cation, HCO ₃ ^sup- , NO ₃ ^sup- and especially SO ₄ ^sup2- output increase west to east, but H⁺ output decreases. At the eastern site stream SO ₄ ^sup2- concentration and output exceed HCO ₃ ^sup- . Potential soil SO ₄ ^sup2- adsorption capacity increases eastward, but this capacity is filled. Crystalline Fe hydrous oxides appear more effective than amorphous Fe hydrous oxides at adsorbing SO ₄ ^sup2- . High anthropic anion inputs, inability of forest soil to adsorb additional inputs and perhaps SO ₄ ^sup2- desorption appear responsible for the replacement of HCO ₃ ^sup- by SO ₄ ^sup2- in stream water. The major cation accompanying SO ₄ ^sup2- is Ca²⁺.Contribution from Fourth World Wilderness Congress—Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Nitrification,soil acidification and streamwater chemistry following deglaciation,glacier bay national park and preserve

A major tool used in the assessment of anthropic atmospheric effects on aquatic and terrestrial ecosystems is biogeochemical nutrient cycling and budgets. However, to be most effective such study should be done in an ecosystem context. Also some assessment of natural variation in factors affecting nutrient cycling must be in place before trends, often subtle and long-term, attributable to man can be statistically quantified. The input and output balance of chemical species in watershed ecosystems is considerably influenced by ecosystem succession. It is hypothesized that during primary ecosystem succession chemical element output is initially relatively high due to rapid acidification and lack of plant uptake. Outputs decline during the period of high ecosystem productivity and biomass accumulation, and they again rise during late successional stages to approximate inputs from precipitation weathering, and aerosol capture. Glacier Bay provides a unique opportunity to quantify many mechanisms responsible for variation in nutrient cycles without the need for site manipulation. This is especially true for quantifying the rate and magnitude of natural acidification in ecosystems. The park has a spectrum of watersheds differing in stage of primary and secondary succession following deglaciation. These sites are not now subjected to or altered by anthropic atmospheric inputs. The objectives of this research were (1) determine the rate of soil chemical change which occurs following deglaciation, (2) relate soil acidification to presence of organic matter, soil NO _inf3 ^sup- , and total N, (3) estimate the downward movement of ionic species within the soil profiles with increasing acidification from advancing plant succession, and (4) determine if such processes and ionic movements might be reflected in watershed stream ionic outputs. We studied five watersheds ranging from 40–350 years since deglaciation. Soil samples were collected and lysimeters installed in seven vegetation successional stages following deglaciation. An anion of ecological importance and a common air contaminant is NO _inf3 ^sup- , and its discharge in streamflow from early successional ecosystems was found to be high. The terrestrial biota in such systems was dominated by Alnus sinuata, a major nitrogen fixer. Stream discharge of NO _inf3 ^sup- suggested that early successional ecosystem N fixation exceeded biotic uptake. This was confirmed by examining NO _inf3 ^sup- in soil extractions and lysimeters. This process was particularly evident beneath >20-year old Alnus (forty years since deglaciation). concurrent with increased NO _inf3 ^sup- concentrations below the rooting zone was increased H⁺ which increased 100x during 25 years of primary succession. This natural acidification from a mobile NO _inf3 ^sup- ion resulted in an pronounced increase in soil base cation leaching and mobilization of aluminium in the soil profile. The magnitude and short time required for such acidification greatly exceeded anything projected or modeled for systems impacted by anthropic inputs. Stream SO _inf4 ^sup2- concentrations also were high relative to precipitation inputs suggesting mineralization of sulfur within the ecosystem and/or poor soil adsorption of SO _inf4 ^sup2- . This is an important finding in such ecosystems where cation nutrient ion levels are often very low. Should atmospheric inputs of SO _inf4 ^sup2- increase additional loss of cations appears imminent. These data suggest that most early successional ecosystems at Glacier Bay would be sensitive to anthropic inputs of both NO _inf3 ^sup- and SO _inf4 ^sup2- . This is unusual in other ecosystems where many conserve ionic NO _inf3 ^sup- inputs, and older systems have considerable SO _inf4 ^sup2- adsorption capacity. The effect of any increased atmospheric inputs of these ions would be accelerated cation leaching and ecosystem acidification.Contribution from Fourth World Wilderness Congress—Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Evaluation of Bulk Deposition in Protected Woodland Area in Western Poland

Research on precipitation carried out systematically at the University station at Jeziory in the Wielkopolski National Park (western Poland) allowed the determination of pollutants deposited with precipitation in this forest ecosystem. During 13 years of study, the pH of precipitation was found to persist at a low level (4.33 on average), which resulted a substantial deposition of H⁺. Values of acidifying and basic ions deposited in this area were determined and compared with the respective figures obtained at selected EMEP stations studying background pollution, the means for Poland, and areas subjected to considerable human impact. The use of the critical load function made it possible to establish that the S and N deposition for 2002–2005 were below its line.