Atmospheric concentrations and deposition of nitrogen and major ions in conifer forests in the United States and Federal Republic of Germany

Emission densities of air pollutants are higher in Europe than in the U.S. as a whole, suggesting similar differences in atmospheric deposition. We determined air concentrations and deposition during the warm season at conifer forests in Tennessee and northern Germany. Our results confirmed major differences in both chemistry and fluxes. Atmospheric and precipitation concentrations of all ions except H⁺ were higher at the German site, most significantly for the nitrogen species. The much higher levels of NH₄⁺ at this site reflect higher emissions of NH₃, which was the species largely responsible for the lower levels of H⁺. Total airborne nitrate was dominated by HNO₃ in Tennessee. In Germany we found comparable amounts of HNO₃ and aerosol NO₃⁻, the concentration of which varied seasonally, apparently in response to agricultural emissions of NH₃ that reacted to form NH₄NO₃. Total deposition of all major ions was much higher at the German site, particularly for the nitrogen species, which exhibited a marked edge effect in throughfall. Dry deposition was determined from air concentrations by using a canopy resistance model and from a statistical model of throughfall fluxes, each of which yielded comparable fluxes for several ions. Dry deposition contributed 10–70% of the ion input and was most important at the German site. Both forest canopies absorbed 40–50% of total deposited nitrogen, primarily from dry deposition.     

Atmospheric dry deposition on pines in the Eastern Brook Lake Watershed,Sierra Nevada,California

Atmospheric dry deposition to branches of Pinus contorta and P. albicaulis was measured during summer 1987 in a sub-alpine zone at Eastern Brook Lake Watershed (EBLW), eastern Sierra Nevada, California. Results are presented as deposition fluxes of NO₃⁻, SO₄²⁻, PO₄³⁻, Cl⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺, Zn²⁺, Fe³⁺, Mn²⁺, Pb²⁺ and H⁺, and compared with other locations in California and elsewhere. Deposition fluxes of anions and cations to the pine branches were low, several times lower than the values determined near the Emerald Lake Watershed (ELW), another sub-alpine location in the western Sierra Nevada. The sums of deposition fluxes of the measured cations and anions to pine surfaces were similar, in contrast to the ELW location where the sums of cation fluxes were much higher than the sums of anion fluxes. A strong positive correlation between depositions of NO₃⁻ and NH₄⁺, as well as SO₄²⁻ and Ca²⁺, suggested that large portions of these ions might have originated from particulate NH₄NO₃ and CaSO₄ deposited on pine surfaces. An estimated total N dry deposition (surface deposition of NO₃⁻ and NH₄⁺ and internal uptake of NO₂ and HNO₃) to the forested area of the EBLW was 29.54 eq ha⁻¹ yr⁻ (about 414 g H ha⁻¹ yr⁻¹).     

Deposition of atmospheric ions to pine branches and surrogate surfaces in the vicinity of emerald lake watershed,Sequoia National Park

Atmospheric dry deposition of ions to branches of native Pinus contorta and Pinus monticola (natural surfaces), and nylon filters and Whatman paper filters (surrogate surfaces) were measured in the summer of 1987 in the vicinity of Emerald Lake Watershed (ELW) of the Sequoia National Park located on the western slope of the Sierra Nevada in California. Deposition fluxes of airborne NO⁻₃, NH⁺₄ and SO²⁻₄ to native pines at the ELW were much higher than in the eastern Sierra Nevada, but several times lower than deposition fluxes to natural and surrogate surfaces at the highly polluted site in the San Gabriel Mountains of southern California. Deposition fluxes of NO₃⁻ and NH₄⁺ to the natural and surrogate surfaces at the ELW were much higher than deposition of SO₄²⁻, providing the importance of N compounds in atmospheric dry deposition in this part of the western U.S. A deficit of inorganic anions in materials deposited to various surfaces indicated a possibility of substantial participation of organic acids in atmospheric dry deposition processes. Nylon and paper filters proved to be poor surrogate surfaces for the estimation of ionic dry deposition to conifer branches.     

Fluxes of NH3 and HNO3 over heathland in the Netherlands:implications for chemical interactions

The surface exchange of NH₃ and HNO₃ gases over heathland was measured with the aerodynamic gradient method in Leende,the Netherlands during April 25 and May 9,1991.Due to reactions in the system NH₃,HNO₃ and NH₄NO₃,the NH₃ deposition flux is overestimated,while HNO₃ shows apparent emission fluxes mostly during the field experiment.Results reveal that NH₃ gradients are influenced slightly by HNO₃ and the HNO₃ gradients are strongly controlled by the NH₃.A clear relationship between NH₃ and HNO₃ gradient is suggested by the Leende experiment. Before the late afternoon,NH₃ deposition gradients will cause HNO₃ upward gradients,meanwhile the NH₃ gradients themselves will become smaller.After the HNO₃ upward gradient reaches maximum,the NH₃ deposition gradients will be enlarged or the emission gradients depressed,while the HNO₃ upward gradients become smaller.     

Assessment of the nitrogen and carbon budget of two managed temperate grassland fields

Greenhouse gas budgets as well as the productivity of grassland systems are closely related to the carbon (C) and nitrogen (N) cycles. Within the framework of the CarboEurope and NitroEurope projects we have measured C and N exchange on the field scale at the grassland site Oensingen previously converted from arable rotation. The site is located on the Swiss Central Plateau and consists of two parallel fields of equal size. One field was subjected to intensive management with average nitrogen input of 230 kg-N ha⁻¹ year⁻¹ and 4–5 cuts per year, and the other to an extensive management with no fertilisation and less frequent cutting. The total C budget of the fields was assessed by measuring the CO₂ exchange by eddy covariance and analysing the carbon import by manure application and export by harvest. The N budget of the managed grassland is more complex. Besides the management related import and export, it includes gaseous exchange in many different forms (NO, NO₂, HNO₃, N₂O, NH₃, N₂) needing different analytical techniques, as well as input by rain and leaching of N-compounds with the soil water. The main (“level-3”) field sites in the NitroEurope project are supposed to measure 95% of the N fluxes at the field scale. For several of the N fluxes specific measurements have been performed for 1 year or longer at the site. Some of the remaining N budget components (dry and wet deposition) could be estimated from results of a national deposition network, while other components (NH₃ and N₂ emission) were estimated based on literature parameterisations. However, we found indications that the (systematic) uncertainties of these estimated N-fluxes are large and that it is important to make site-specific measurement for all relevant budget components. The suitability of corresponding experimental methods is discussed.Analysis of the C budget over a 6-year period (2002–2007) showed a significant mean difference between the two newly established grassland fields with a likely net carbon loss for the extensive management and a net sequestration for the intensive management. Since the C/N ratio of the soil organic matter of the grassland is constrained in a rather narrow range around 9.3, the change in the soil carbon pool is supposed to be accompanied by a corresponding change in the N storage. This approach provided an alternative method to check the N budget of the two grassland fields derived from the individual N fluxes.     

Scavenging ratios and deposition of sulphur,nitrogen and chlorine species in eastern England

Measurements of wet deposited NH₄⁺, SO₄²⁻, NO₃⁻ and Cl⁻, as well as airborne concentrations of these species and gaseous HNO₃, HCl and NH₃, have been made at a site in eastern England. Scavenging ratios based solely upon aerosol-associated species and upon aerosol plus gaseous airborne species are presented and compared with literature values. It appears that HCl and HNO₃ have only a rather minor influence upon wet deposition at our site. Gaseous NH₃ influences ground-level air chemistry appreciably, but scavenging ratios for NH₄⁺ are low, even when based upon aerosol NH₄⁺ concentrations alone, presumably due to altitudinal gradients in this species. The problems inherent in interpretation of scavenging ratios are discussed. Deposition of nitrogen in various chemical forms is estimated from rainwater and air composition. If a transport-limited deposition velocity is assumed for ammonia gas, dry deposition of this species accounts for around 40% of total nitrogen deposition to the ground.     

The spatial distribution and particle size of some inorganic nitrogen,sulphur and chlorine species over the North Sea

The use of filter packs and a cascade impactor during a series of research cruises in the southern area of the North Sea has yielded detailed spatial distribution patterns of aerosol concentrations, Cl⁻, NO₃⁻, SO₄²⁻¹ and NH₄⁺ and gaseous concentrations, HCl, HNO₃ and NH₃. The overall distribution of the atmospheric concentrations closely parallels published modelled results for metallic species. The chemical transformations of these aerosols and gases are investigated together with their interactions with the seasalt aerosol. Aerosol chloride loss is greatest in the more polluted areas, whilst concentrations products of NH₃ with HNO₃ and HCl appear insufficient to sustain the existence of NH₄NO₃ and NH₄Cl. Nitrate is associated predominantly with larger particles and appears to be present substantially as a surface coating on marine aerosol. The total dry deposition input for nitrogen species is calculated for the southern sector with extrapolation to the whole of the North Sea, using particle size weighted deposition velocities of 0.63 and 0.21 cm s⁻¹ for NO₃⁻¹ and NH₄⁺, respectively, and literature-derived values for the gaseous constituents. Finally the use of air-mass back trajectories illustrates the role of source regions in influencing the chemical composition of the North Sea atmosphere.     

大气氮沉降向典型红壤区农田生态系统定量输入研究

在2005年,通过对中国科学院红壤生态实验站(江西鹰潭)内农田小气候要素和湍流的观测及大气和雨水中氮化物的分析,借助大叶阻力相似模型,研究了大气氮素(N)通过干、湿沉降输入研究地农田生态系统的N通量.结果表明,全年通过大气沉降向该农田生态系统输入N 132.6 kg.hm-2,其中干沉降输入N 82.63 kg.hm-2,占大气总输入N的67.94%.干沉降过程中,气体中以NH3-N沉降为主,占气态N沉降的43.02%~89.89%(均值为71.05%);颗粒中以NO3--N为主,占颗粒态N的33.67%~94.54%(均值为61.01%).每月通过湿沉降(雨水)输入N 0.50~8.45 kg.hm-2,以7月和11月较高.     

Ammonia stomatal compensation point of young oilseed rape leaves during dark/light cycles under various nitrogen nutritions

The plant can be a source or a sink of ammonia (NH₃) depending on its nitrogen (N) supply, metabolism and on the background atmospheric concentrations. Thus plants play a major role in regulating atmospheric NH₃ concentrations. For a better understanding of the factors influencing the NH₃ stomatal compensation point, it is important to analyse the dynamics of leaf NH₃ fluxes. The relationship between the leaf NH₃ fluxes and the leaf apoplast ammonium and nitrate concentrations, N nutrition and the light and dark periods was studied here.We designed an experiment to quantitatively assess leaf-atmosphere NH₃ exchange and the stomatal compensation point and to identify the main factors affecting the variation of NH₃ fluxes in oilseed rape. We tested day and night dynamics as well as the effect of five different N treatments. Two experimental methods were used: a dynamic open flux chamber and extraction of the apoplastic solution.Chamber measurements showed that there was a good correlation between plant NH₃ fluxes and water fluxes. Compensation points were calculated by two different methods and ranged between 0.8 and 12.2 μg m⁻³ NH₃ (at 20 °C) for the different N treatments. Apoplastic solution measurements showed that there was no significant differences in the apoplastic NH₄⁺ concentrations ([NH₄⁺]_apo) extracted in dark and light periods for the same N treatment. Statistical analysis also showed that [NH₄⁺]_apo was correlated with [NH₄⁺] in the nutrient solution and weakly correlated with [NO₃⁻]. Apoplast NH₄⁺ concentrations ranged between 0.1 and 2.1 mM, bulk tissue NH₄⁺ concentrations between 3.9 and 6.6 mM and xylem concentrations between 2.4 and 6.1 mM depending on the N supply.Calculated NH₃ emission potential from the extraction measurements were over-estimated when compared with the value calculated from chamber measurements. Errors related to chamber measurements included separation of the cuticular and stomatal fluxes and the calculation of total resistance to NH₃ exchange. Errors related to the extraction measurements included assessing the amount of cytoplasmic contamination. We do not have another method to assess the NH₃ stomatal compensation point and the choice between these two measurement techniques should depend on the scales to which the measurements apply and the processes to be studied.     

Potential nitrogen enrichment of soil and surface water by atmospheric ammonia sorption in intensive livestock production areas

Elevated atmospheric NH₃ levels near intensive livestock operations can add significant N to local agroecosystems. In this study, the potential atmospheric NH₃ sorbed by soil and water was assessed over a 2-year period starting October 2000 in an intensive livestock production area in southern Alberta, Canada. Fifty-two uneven grid sampling sites were selected in the 53,905 ha study area. The sorption rate of atmospheric NH₃ was estimated weekly by exposing distilled water and air-dried soil samples to the atmosphere at the sampling sites. The increases in NH₄–N content in the samples after 1-week exposure was regarded as an index of the atmospheric NH₃ sorbed for that week. The NH₃ sorption rates were highly variable across the 52 sites, with water ranging from 4 to 125 kg ha⁻¹ year⁻¹ with a mean of 22 kg N ha⁻¹ year⁻¹ and soil from 5 to 84 kg N ha⁻¹ year⁻¹ with a mean of 20 kg N ha⁻¹ year⁻¹. Considerable variation in NH₃–N sorption across the study area reflects the effects of size, direction (upwind or downwind) and proximity of nearby livestock operations or other NH₃ sources and operators’ activities around the sampling sites. The NH₃ sorption rate at each site also varied considerably in response to weather conditions. The high rate of NH₃ input poses a direct risk of surface water eutrophication in intensive livestock operation areas. If fertilizer recommendations are not reduced to account for NH₃ sorption by soil, excess N may also contribute to eutrophication through runoff and leaching.     

南海东部大气湿沉降中无机氮的研究

通过分析2000至2014年菲律宾马尼拉(Manila)和洛斯巴诺斯(Los Banos)大气湿沉降资料,初步探讨近15年湿沉降中无机氮含量特征以及对南海东部海域水生生态系统的影响。结果显示,湿沉降中NO-3-N和NH+4-N的浓度均为旱季高雨季低;NO-3-N浓度在近15年虽有波动,但并无明显变化趋势;而洛斯巴诺斯区域的NH+4-N浓度自2009后稍有波动上升。NO-3-N和NH+4-N的沉降通量与浓度相反,表现为雨季高而旱季低,年际上总体表现为NH+4-N的沉降通量大于NO-3-N,马尼拉无机氮的沉降通量大于洛斯巴诺斯,并且在2003年之后,马尼拉和洛斯巴诺斯NH+4-N的沉降通量均呈明显上升趋势,菲律宾经济的快速增长及人类活动是主导其上升的主要因素。马尼拉和洛斯巴诺斯湿沉降中NO-3-N/NH+4-N值分别为0.33和0.41,该比值和无机氮浓度与南海东部各海区表层海水的值有明显的差别,因此降水可能改变该海域表层水体无机氮的组成结构,进而影响水体中浮游植物的生长及其群落结构。     

应用扩散管测量霾污染期间大气氮硫化合物浓度的方法

活性氮和硫化合物在大气颗粒物形成过程中扮演重要角色,但对它们气相/颗粒相的同步观测结果比较缺乏.本研究尝试基于扩散管的DELTA系统测量氮和硫化合物短时累积浓度,以期捕捉它们在霾污染期间的演变规律.结果表明,DELTA系统收集气态污染物的扩散管中以及颗粒物滤膜上NH_4~+和NO-3空白干扰较小,适用于研究NH_3、HNO_3、NH_4~+和NO-3的日均浓度,可以作为城市环境空气质量监测参数的有效补充;但采样系统中SO_2-4背景含量较高,仅适合监测48 h以上时间尺度的SO_2浓度和周~月尺度SO_2-4浓度,用于大气硫沉降观测.北京2016年5月9日~6月7日观测期间,大气NH_3、HNO_3、NH_4~+和NO-3浓度具有明显的逐日演变规律,呈现出随着风向转变而发生周期性波动的典型特征;这些含氮污染物与PM_(2.5)、CO、SO_2和NO_2浓度的变化规律一致,其来源可能与化石燃料燃烧源有关.污染天NH_3、HNO_3、NH_4~+和NO-3浓度约为清洁天的2倍,但还原性氮和氧化性氮的相态分布在清洁天和污染天无明显差异;整个观测期间,HNO_3/NO-3约为1.2,NH_3/NH_4~+为4.5,春夏之交较高的温度有利于活性氮在气粒平衡过程中偏向于气态形式存在.     

Nitrogen budget for eastern Canada

A Lagrangian model incorporating S and N chemistry has been developed by the Atmospheric Environment Service. It was used to produce an annual nitrogen budget including annual nitrogen transboundary flux estimates for 1980 for eastern Canada.The model used trajectories computed from the analyzed winds produced at the Canadian Meteorological Centre (CMC) in addition to the temperature and precipitation analyses. The model parameterized the dry and wet deposition and chemical transformation of NO₂, nitrate (including HNO₃) and PAN using monthly, time-dependent dry deposition velocities, scavenging ratios and transformation rates. The model was integrated throughout eastern Canada on a 6-h basis for 1980. The boundary point concentrations were used to compute input and output fluxes which were summed over several boundary segments to give annual transboundary flux estimates.The total annual N deposition was about 0.6 TgN with high deposition in August and December and the lowest in February. Wet NO₃⁻ deposition (0.2 TgN) was higher than the dry deposition of any single N species (NO₂, nitrate or PAN) but lower than all dry N deposition combined. The annual N input (output) flux was about 1.0 (0.5) TgN. The highest input and output fluxes occurred in December and the lowest input and output fluxes occurred in May.     

A variable-resolution transport model applied for NHχ in Europe

The statistical atmospheric transport model TREND has been applied for the calculation of concentrations and depositions of ammonia (NH₃) and ammonium (NH₄⁺). The model is capable of describing dispersion, conversion and deposition from both local sources (necessary to obtain good results for NH₃) and from more distant sources (necessary to obtain good results for NH₄⁺). Model results show that in western Europe 44% of the emitted NH₃ from a 1 m high score is dry deposited as NH₃, 6% is wet deposited as the contribution of NH₃ to the wet deposition of NH_x, 14% is dry deposited as NH₄⁺ and 36% is wet deposited as the contribution of NH₄⁺ to the wet deposition of NH_x. The model results agree well with measured NH₃ and NH₄⁺ concentrations—the latter in both aerosol form and precipitation—in The Netherlands, Belgium, Denmark, the U.K., the F.R.G., Sweden and other parts of Europe. Vertical concentration profiles of NH₃ and NH₄⁺ at Cabauw, The Netherlands are also reproduced well, as well as the diurnal variation of the NH₃ concentration at Elspeetsche Veld, The Netherlands.     

内蒙古温带草原氮沉降的观测研究

在内蒙古太仆寺旗对温带草原地区的氮沉降进行了为期1 a(2011年11月～2012年10月)的观测.在线分析大气NH3和NO2浓度,用CMAQ模型计算的干沉降速率计算了气体干沉降量;采集降水、降尘和穿透雨样品并测定NH4+和NO3-浓度,分别得到湿沉降、颗粒物干沉降和穿透雨沉降量.观测结果表明该地区的氮沉降量已经高达3.43 g.(m2.a)-1,有可能对草原生态系统产生危害.其中,湿沉降占44%,气体干沉降占38%,颗粒物干沉降占18%.干沉降对氮沉降的贡献大于湿沉降,必需重视干沉降的测定,而穿透雨沉降明显小于总沉降,说明穿透雨法不适合于草原地区.从组分上看,还原态氮(包括NH4+和NH3)对氮沉降的贡献为71%,而氧化态氮(NO3-和NO2)的贡献仅29%,因此在控制氮沉降时,不应只针对NOx排放进行削减,NH3减排同样重要.     

Kinetics of evaporation of ammonium chloride and ammonium nitrate aerosols

The evaporation rates of ammonium chloride and ammonium nitrate were measured by continuously and rapidly removing gaseous NH₃ and HNO₃ or HCl from aerosols in an annular denuder. The experiments gave the evaporation rates in terms of mass loss of chloride or nitrate which can be expressed conveniently as the rates of reduction of aerosol radius with time. Both dry aerosols (humidity 30–60% r.h.) and aqueous aerosols (humidity ca 97% r.h.) were studied. Dry aerosols evaporate at rates of −1.05 Å s⁻¹ for NH₄Cl and −0.45Å s⁻¹ for NH₄NO₃, while the evaporation rates of aqueous aerosols expressed as for equivalent dry particles are −4.52 Å s⁻¹ for NH₄Cl and −0.49 Å s⁻¹ for NH₄NO₃. The experimentally measured rates are independent of particle radius and remarkably low compared with those predicted from existing theories of aerosol evaporation, thus implying that there is an unknown kinetic constraint to the achievement of equilibrium at atmospheric temperature and pressures.     

太原市五年降尘及降水中主要离子特征

随着我国工业化和城镇化的深入推进,人们对城市大气环境质量关注日益增加。连续五年对山西省太原市5个点位进行监测,考察降水中主要离子时间变异及大气干湿沉降规律。结果表明:太原市五个监测点年均干沉降量排序为太钢工业区坞城(东)桃园(市中)晋祠(景区)上兰(市郊),其中太钢年均沉降量是上兰的三倍。降尘量除了在不同点位差异较大外,相同点上不同季节也有较大波动,表现为各监测点春季和冬季降尘量为全年最高。而夏季由于降雨较多,干沉降最少。总体上,近五年各点干沉降量呈现逐年下降的趋势。湿沉降方面以桃园为市区代表分析,SO_4~(2-)、NO_3~-、Ca~(2+)和NH_4~+是太原市桃园降水中主要的无机离子,其加权平均浓度范围为3.1～19 mg/L,各离子浓度在干燥的冬春季较高,且近五年其浓度及沉降量快速增加。桃园降雨中SO_4~(2-)和NO_3~-仍然是最主要的致酸离子,SO_4~(2-)年均沉降量分别是NO_3~-、Ca~(2+)和NH_4~+的1.7、3.9、5.9倍。Ca~(2+)、NH_4~+和Mg~(2+)的中和因子分别是0.42、0.30、0.14,说明Ca~(2+)、NH_4~+对酸雨缓冲作用大于Mg~(2+)。2013～2017年太原市桃园降雨SO_4~(2-)/NO_3~-和NH_4~+/NO_3~-比值分别为1.7和0.3,表明酸雨类型由硫酸型向混合型发展,主要是近年来NO_3~-浓度增幅大于SO_4~(2-)和NH_4~+。总的来看,近些年太原市政府大力提倡节能减排带来明显效果,但工业厂矿区周边降尘污染依然严重,属于今后城市环境治理的重点。     

Measurements of atmospheric HNO3, HCl and associated species on a small network in eastern England

Measurements of gaseous HNO₃, HCl and NH₃ and particulate NO₃⁻, SO₄²⁻, Cl⁻ and NH₄⁺ have been made at a small network of sites in eastern England using sampling intervals from 3 h to 7 days. Both HCl and HNO₃ are spatially rather uniform, with some variation apparently due to spatial variations in NH₃, which stoichiometrically exeeded the sum of both gaseous acids. Mean concentrations of NH₃, HCl and HNO₃ between February 1987 and January 1988 were 1.90, 0.67 and 1.01 μg m⁻³, respectively. Pollution roses revealed low NH₃ concentrations, and high associated HCl and HNO₃ with winds from the North Sea. HCl, but not HNO₃ showed an appreciable elevation in concentration on the sector NW from our site, which we speculate may be due to the large capacity of coal-fired power stations in this upwind sector. Three-hourly data have been examined for diurnal effects and its is concluded that nocturnal formation of NO₃⁻ is occurring.     

Atmospheric sulphur deposition to forest stands: Throughfall estimates compared to estimates from inference

Wet and dry deposition of sulphur was estimated for 30 forest stands in the Netherlands using a throughfall method and an inferential method. Dry deposition estimates of the throughfall method were significantly higher compared to estimates from inference. The major sources of uncertainty of the throughfall dry deposition estimates were associated with non-representative throughfall sampling, wet deposition estimates, canopy exchange processes, deposition of neutral salts, dry deposition directly onto the throughfall collectors, and with the omission of stemflow fluxes and dry deposition directly to the undergrowth vegetation and forest floor. These uncertainties were found to act both ways to approximately the same extent and were not able to explain the observed gap between the two dry deposition estimates. For the inferential method, major sources of uncertainty in the dry deposition estimates arose in calculation of the dry deposition velocity of SO₂ and the omission of occult deposition of SO₄²⁻. In this study, uncertainties associated with the spatial averaging of air concentrations of SO₂ and SO₄ aerosol and the calculation of the deposition velocity of SO₄ aerosol were found to be relatively small. Modifying the R_c parametrization of SO₂, based on recent dry deposition measurements made over heather in the Netherlands, resulted in fairly good agreement between both dry deposition estimates. Occult deposition of SO₄²⁻ was found to contribute significantly to the total sulphur deposition to the forest stands. Both the modified R_c parametrization and the incorporation of occult deposition led to systematically higher sulphur deposition estimates by the inferential method compared to originally inferred deposition. This implies that in the Netherlands, sulphur deposition to forest ecosystems might have been underestimated heretofore.     

Spatial variability of urban precipitation chemistry and deposition: Statistical associations between constituents and potential removal processes of precursor species

The precipitation chemistry of Greater Manchester, a Metropolitan County in the northwest of England, has been examined for small scale spatial variability using a network of 18 bulk precipitation collectors. Significant spatial variability was found for concentrations of non-marine SO₄²⁻, NO₃⁻, NH₄⁺, Ca²⁺ and H⁺ ions. The statistical associations between the data were investigated using correlation, partial correlation and principal components analyses. It was found that zero-order correlation coefficients were inadequate for the interpretation of the data and that the computation of first, and higher order partial correlation coefficients was necessary in order to explain the interrelationships between the data and their spatial variability. The statistical associations between the data suggest relationships between Ca²⁺ and non-marine SO₄²⁻, and NO₃⁺ in precipitation which are discussed in terms of their possible precursor species. Potential source effects were examined in conjunction with atmospheric removal processes. The dry deposition of SO₄ particles, rather than the dry deposition of SO₂, may explain the spatial variability of non-marine SO₄²⁻. The erosion of CaSO₄ formed from the reaction of SO₂ with CaCO₃ on urban surfaces with subsequent resuspension is thought to be the basis of the relationship between Ca²⁺ and non-marine SO₄²⁻ concentrations in precipitation. The wet and dry deposition of CaCO₃ particles from local sources may be partially responsible for the spatial variability of H⁺, and dry deposition and scavenging of NH₃, in conjunction with the predominant wind direction may explain the spatial variability of NO₃⁻ and NH₄⁺ ions. Ammonia is thought to originate from sources both outside the study area and within it.