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.     

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。     

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.     

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。     

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。SO_4~(2-)和NO_3~-是降水中最主要的阴离子,NH_4~+和Ca~(2+)是降水中最主要的阳离子。Ca~(2+)浓度在2018年开始有所抬升,SO_4~(2-)和NO_3~-浓度整体呈波动下降趋势。SO_4~(2-)与NO_3~-浓度比均值为1.50,呈下降趋势,同大气中SO_2与NO_2的质量浓度比变化趋势基本一致。SO_4~(2-)和NO_3~-相关性显著,Cl~-、Na~+及Mg~(2+)三者之间具有较好相关性。降水与气态污染物相关性不大,对颗粒物有明显冲刷去除作用。SO_2和NO_x的排放量显著下降,酸雨污染呈现改善过程。     

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).