The contribution of ammonia emissions from agriculture to the deposition of acidifying and eutrophying compounds onto forests

In the vicinity of a large ammonia emission area, dry and wet deposition of acidifying and eutrophying compounds onto Douglas Fir forests was studied by sampling throughfall, stemflow and bulk precipitation. Deposition amounts of NH(4)(+) and SO(4)(2-) were recognised to be among the highest of Central Europe, resulting in extremely high inputs of (potential) acid to the forest soils (13.1 kEq ha(-1) year(-1)). The contribution of NH(3) emissions from agriculture to the total acid deposition to the forests was 52%. The total nitrogen deposition amounted to 115.0 kg ha(-1) year(-1), 83% originating from NH(3) emissions and 17% from NO(x) emissions. Calculated mean dry deposition velocities of NH(3) and SO(2) were much larger than reported in the literature. A synergistic effect between NH(3) and SO(2) in the process of dry deposition is suggested and evidence for this effect is discussed. When deposition models do not take this interaction into account, they will underestimate NH(3) and SO(2) deposition amounts in areas with intensive animal husbandry.     

A European survey of atmospheric heavy metal deposition in 2000-2001

The background, administration and current status of the monitoring programme "European Survey of Atmospheric Heavy Metal Deposition" is described. All European states are invited to join the survey 2000-2001. The co-ordination and responsibility for the survey will gradually be transferred from the Nordic Council of Ministers to the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation).     

Changes of emissions and atmospheric deposition of mercury,lead, and cadmium

This paper reviews the information on trends of past emissions of mercury, lead, and cadmium in Europe, as well as examines current levels and future scenarios of these emissions. The impact of various factors on emission changes is discussed including the implementation of various strategies of emission controls in Europe. Future emissions are forecasted on the basis of various scenarios of economy growth in Europe, implementation of European and global legislation (e.g. the Kyoto agreement), population changes, etc.Changes of emissions of mercury, lead, and cadmium are then related to the changes of concentrations of these contaminants in air and precipitation samples at selected stations in Europe. It can be concluded that the reduction trends of anthropogenic emissions of cadmium and lead in Europe are similar to the reduction trends of air concentrations of these metals during the last 2 decades. Somewhat different relationship has been noted for changes in emissions and precipitation. In general for Europe, 60% reduction of Cd emissions was met by about 45% reductions of Cd concentrations in precipitation at the studied stations during the last 2 decades.There is a potential for further reduction of these emissions until the year 2010 up to about 37% for Cd, 51% for Pb, and 49% for Hg as estimated within various emission scenarios presented in the paper.     

Changes in the atmospheric deposition of minor and rare elements between 1975 and 2000 in south Sweden, as measured by moss analysis

Elements emitted to the atmosphere are partly exported to more remote areas and contribute to the regional and territorial deposition rates. This study is based on the principle that carpet-forming bryophytes (pleurocarpic mosses) absorb elements and particles from rain, melting snow and dry deposition. We compare the concentrations of 60 elements in carpets of the forest moss Pleurozium schreberi sampled in 1975 and 2000 within a sparsely inhabited area dominated by forest and bogland in south Sweden. As an average for all the 60 elements, the median concentration was 2.7 times higher in 1975 than in 2000. The greatest difference was measured for Pb, although In, Bi, Ge, V, Sn, As and Ag had more than 5 times higher concentrations in 1975 than in 2000. Somewhat lower 1975/2000 concentration ratios (3.0-3.8) were measured for U, Sb, Cd, W, Ga, Fe, Li, and Be. The rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), except Eu as well as Th, Ni, Al, Ti, Hf, Nb, and Zr, had concentration ratios around the average (2.5-2.8). Possible causes of these changes are discussed. We conclude that reductions in anthropogenic dust emissions during recent decades have decreased the atmospheric deposition over northern Europe of most elements in the periodical system, as previously reported for a limited number of transition and heavy metals. Changes in the deposition of soil dust would be of minor importance to the decreased deposition rates.     

Long-term changes of acidifying deposition in Finland (1973-2000)

The long-term changes of acidifying deposition in Finland during the period 1973-2000 were studied using bulk deposition data from 19 stations belonging to the national monitoring network. The regional-scale approach (southern, central and northern Finland) was used for trend assessment with respect to implementation of European sulphur (S) emission reduction amendments involving deposition changes prior to (1973-1985) and after (1986-2000) the agreements (S protocols in 1985 and 1994). There were no marked changes in sulphate deposition between the 1970s and 1980s and consistent trends in 1973-1985 were not observed. Deposition of nitrogen (N) compounds, particularly NO3-N, were increasing between the 1970s and 1980s. Deposition of base cations exhibited a slight decline throughout the 1970s and 1980s. Decrease of calcium and magnesium deposition without corresponding decrease in sulphate resulted in increased acidifying potential (AP) of deposition. Due to successful implementation of S (and N) emission reduction measures, sulphate deposition has decreased substantially (30% in northern and up to 60% in southern Finland) since the late 1980s. N deposition also decreased, but less than S deposition. Base cation deposition has also declined substantially, but this decline appeared to be leveling off during the 1990s, accounting for the decrease of AP in deposition. The observed deposition pattern is in agreement with the on-going biochemical recovery of acidified small Finnish lakes taking place since the early 1990s.     

Physiological indicators and susceptibility of plants to acidifying atmospheric pollution: a multivariate approach

Plant susceptibility to acidifying atmospheric pollution was investigated for a wide range of plant species under normal environmental conditions. Physiological and biochemical parameters were recorded for each plant species. Multivariate analysis using hierarchical clustering, principal component analysis ordination, as well as regression analysis were used to interpret the data. Analysis of the data separated plants into pioneer tree species, ruderal herbaceous species and climax, slow growing species. Pioneer and ruderal species showed higher potential for foliar nitrate assimilation coupled with higher base cation content and a tendency to a more neutral leaf pH than climax species. Acidic buffering capacities for leaf tissue from pioneer and ruderal species were higher than those of climax species. Nitrate assimilation produces hydroxyl ions, which in conjunction with high base cation content and more neutral leaf pH, provides better metabolic buffering and therefore make pioneer and ruderal species less susceptible to acidifying inputs. Climax species are less able to buffer against acidifying inputs and are subsequently more prone to acidifying air pollution damage.     

Multi-elements atmospheric deposition study in Albania

For the first time, the moss biomonitoring technique and inductively coupled plasma–atomic emission spectrometric (ICP-AES) analytical technique were applied to study multi-element atmospheric deposition in Albania. Moss samples (Hypnum cupressiforme) were collected during the summer of 2011 and September–October 2010 from 62 sites, evenly distributed over the country. Sampling was performed in accordance with the LRTAP Convention–ICP Vegetation protocol and sampling strategy of the European Programme on Biomonitoring of Heavy Metal Atmospheric Deposition. ICP-AES analysis made it possible to determine concentrations of 19 elements including key toxic metals such as Pb, Cd, As, and Cu. Cluster and factor analysis with varimax rotation was applied to distinguish elements mainly of anthropogenic origin from those predominantly originating from natural sources. Geographical distribution maps of the elements over the sampled territory were constructed using GIS technology. The median values of the elements in moss samples of Albania were high for Al, Cr, Ni, Fe, and V and low for Cd, Cu, and Zn compared to other European countries, but generally were of a similar level as some of the neighboring countries such as Bulgaria, Croatia, Kosovo, Macedonia, and Romania. This study was conducted in the framework of ICP Vegetation in order to provide a reliable assessment of air quality throughout Albania and to produce information needed for better identification of contamination sources and improving the potential for assessing environmental and health risks in Albania, associated with toxic metals.     

Eutrophication trends in forest soils in Galicia (NW Spain) caused by the atmospheric deposition of nitrogen compounds

We calculated the sensitivity of Galician forest soils to eutrophication caused by atmospheric deposition of nitrogen compounds, using the Simple Mass Balance (SMB) method as described by [Posch, M., de Vries, W., Hettelingh, J.-P., 1995. Critical loads of sulphur and nitrogen. In: Posch, M., de Smet, P.A.M., Hettelingh, J.-P., Downing, R.J. Calculation and Mapping of Critical Thresholds in Europe. Status Report 1995, Coordination Center for Effects, National Institute for Public Health and the Environment, Bilthoven, The Netherlands, pp. 31-42]. Deposition values were used to calculate critical loads exceedance. Galician natural forest ecosystems can support nitrogen deposition loads of more than 10 kg Nha (-1) yr (-1). The lowest critical loads (approximately 10 kg Nha (-1) yr (-1)) mainly occurred in forest stands in the interior zone, while highest critical load values (approximately 68 kg Nha (-1) yr (-1)) were observed in eucalyptus stands at low altitudes in the littoral area. Exceedances based on N deposition levels, calculated from data recorded in 2001, occurred in 40% of the forest soils, showing the need to control N emissions in these areas to prevent possible eutrophication of soils and waters. Analysis of rainfall bulk composition revealed that ammonium, probably derived from agricultural and cattle activities, was the main compound responsible for N deposition in Galicia.     

Modeling atmospheric mercury deposition in the vicinity of power plants

Two mathematical models of the atmospheric fate and transport of mercury (Hg), an Eulerian grid-based model and a Gaussian plume model, are used to calculate the atmospheric deposition of Hg in the vicinity (i.e., within 50 km) of five coal-fired power plants. The former is applied using two different horizontal resolutions: coarse (84 km) and fine (16.7 km). More than 96% of the power plant Hg emissions are calculated with the plume model to be transported beyond 50 km from the plants. The grid-based model predicts a lower fraction to be transported beyond 50 km: >91% with a coarse resolution and >95% with a fine resolution. The contribution of the power plant emissions to total Hg deposition within a radius of 50 km from the plants is calculated to be <8% with the plume model, <14% with the Eulerian model with a coarse resolution, and <10% with the Eulerian model with a fine resolution. The Eulerian grid-based model predicts greater local impacts than the plume model because of artificially enhanced vertical dispersion; the former predicts about twice as much Hg deposition as the latter when the area considered is commensurate with the resolution of the grid-based model. If one compares the local impacts for an area that is significantly less than the grid-based model resolution, then the grid-based model may predict lower local deposition than the plume model, because two compensating errors affect the results obtained with the grid-based model: initial dilution of the power plant emissions within one or more grid cells and enhanced vertical mixing to the ground.     

Modelling the atmospheric fate and seasonality of polycyclic aromatic hydrocarbons in the UK

This paper presents the results from an exercise in atmospheric contaminant fate modelling, which had three main objectives: (1) to investigate the balance between estimated national atmospheric emissions of six selected PAHs and observed ambient measurements for the UK, as a means of testing the current emission estimates; (2) to investigate the potential influence of seasonally dependent environmental fate processes on the observed seasonality of air concentrations; and (3) after undertaking the first two objectives, to make inferences about the likely magnitude of seasonal differences in sources. When addressing objective 1 with annually averaged emissions data, it appeared that the UK PAH atmospheric emissions inventory was reasonably reliable for fluorene, fluoranthene, pyrene, benzo[a]pyrene and benzo[ghi]perylene--but not so for phenanthrene. However, more detailed analysis of the seasonality in environmental processes which may influence ambient levels, showed that the directions and/or magnitudes of the predicted seasonality did not coincide with field observations. This indicates either that our understanding of the environmental fate and behaviour of PAHs is still limited, and/or that there are uncertainties in the emissions inventories. It is suggested that better quantification of PAH sources is needed. For 3- and 4-ringed compounds, this should focus on those sources which increase with temperature, such as volatilisation from soil, water, vegetation and urban surfaces, and possible microbially-mediated formation mechanisms. The study also suggests that the contributions of inefficient, diffusive combustion processes (e.g. domestic coal/wood burning) may be underestimated as a source of the toxicologically significant higher molecular weight species in the winter. It is concluded that many signatory countries to the UNECE POPs protocol (which requires them to reduce national PAH emissions to 1990 levels) will experience difficulties in demonstrating compliance, because source inventories for 1990 and contemporary situations are clearly subject to major uncertainties.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.     

Seasonal variability and source apportionment of metals in the atmospheric deposition in Belgrade

The primary objective of this study is to assess anthropogenic impacts on the environment by determination of element atmospheric depositions. Bulk depositions were collected monthly, from June 2002 to December 2006, at three urban locations in Belgrade. Concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb were analyzed by atomic absorption spectrometry and the current deposition fluxes of atmospheric metals were established. Fourier analysis was applied in order to investigate seasonal variation of the monthly data set. Nickel, V, Fe and Al showed pronounced seasonal dependence, while seasonal variation of the other elements was not evident. The enrichment factors of Pb, Zn, Cd and Cu were obviously above those who could have been caused by natural processes, indicating a mainly anthropogenic origin. Nickel was intermediately enriched suggesting participation of both natural and anthropogenic sources. The multivariate receptor model, Unmix, was used to analyze a 5-yr element atmospheric depositions data set. Three main source profiles (mixed road dust, oil combustion and metal processing) were identified and the overall average percentage source contributions determined.     

南宁市郊空气和大气干湿沉降物中多环芳烃的污染特征

采用空气被动采样器和大气干湿采样器分夏、冬季采集大气及其干湿沉降物样品,利用气相色谱-质谱联用仪测定16种多环芳烃(PAHs)优先控制污染物。结果表明:冬、夏季大气干湿沉降物中PAHs的平均值分别为581.06、174.59ng/(m2·d),冬季PAHs的组成以2～3环PAHs为主,夏季以4～6环PAHs为主;冬、夏季空气中PAHs的平均值分别为149.16、168.70ng/d,均以2～3环PAHs为主。大气干湿沉降物PAHs的沉降通量时空变化为:冬季,商住文教混合区农业区工业区;夏季,工业区农业区商住文教混合区;冬季大于夏季3.3倍。空气PAHs沉降通量的时空变化为:冬季,工业区商住文教混合区农业区;夏季,农业区工业区商住文教混合区;冬季略低于夏季。     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

Biomonitoring trace element atmospheric deposition using lichens in China

Concentrations of 32 elements, Ag, As, Au, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, W, Yb, and Zn were determined by instrumental neutron activation analysis (INAA) in the early preserved epiphytic lichens (Parmotrema recticulatum) from the remote southwestern China area in the 1960s, 1980s and 1990s. The concentrations of Ag, As, Ce, Cr, Cs, Eu, Fe, Hf, La, Nd, Ni, Sc, Se, Sm, Tb, U, Yb and Zn were dropped down by the temporal prolongation. The elemental concentration levels obtained from the organisms indicate that the extent of heavy metal atmospheric deposition among the sampling sites has been declining during the past decades.     

Ecosystem effects of atmospheric deposition of nitrogen in The Netherlands

Atmospheric deposition of inorganic N, mainly ammonium volatilized from manure produced in intensive stockbreeding, on sensitive terrestrial and aquatic ecosystems in The Netherlands is in the order of 40 to 80 kg ha(-1) year(-1). Proven effects of this deposition are (i) eutrophication with N, leading to floristic changes (ii) acidification of base-poor sandy soils and of moorland pools, leading to higher concentrations of dissolved, potentially toxic metals such as Al3+, and (iii) increased levels of nitrate in groundwater below woodlands. In acid forest soils, but not in soils under heathland, nitrification and leaching of nitrate is common. However, in very poor sandy forest soils and at very high ammonium inputs, nitrification may be too slow to prevent the development of high concentrations of ammonium. Both excessive acidification and excessive levels of ammonium probably play an important role in the general forest decline, which is most severe in the southern and central parts of the country, where ammonium inputs are highest.     

Characterization of atmospheric dry deposition particulates in Kobe, Japan

The sources and character of individual metal and metalloid particles from atmospheric dry depositions in Kobe, Japan were investigated. Japan faces long-range pollutant transportation from northeastern Asia during winter and spring. Information regarding their properties and sources is useful for evaluating their affects on the environment and human health. Individual metal and metalloid particles that were collected for every 24 h on the plate, which was designed to reduce a local turbulence, were characterized for their composition, diameter, and deposition fluxes using a field emission scanning electron microscope with an energy dispersive X-ray spectrometer. Approximately 3,000 metal and metalloid particles were classified into 14 types based on their composition and further classified into four groups based on their distribution patterns. They are (A) Fe-O, Fe-Ba-Sb-Cu-S-Ti-O, Fe-Zn-O, Zn-O, Ni-O, and Mn-Fe-O; (B) Cu-Zn-O and Cu-Sn-O; (C) Pb-O, Sn-Sb-O, and Ag-O; (D) Pb-Zn-Cl-Si-S-O and Bi-Cl-O. From these data, this study suggests their sources as the Asian continent (Group A), local source (Group B), multiple sources (Group C), and incineration process (Group D). This study shows (1) the sources and character of individual metal and metalloid particles from short-term atmospheric depositions in Kobe, Japan and (2) application of individual particle analysis for atmospheric depositions.     

Reconciling models and measurements to assess trends in atmospheric mercury deposition

Changes in atmospheric mercury deposition are used to evaluate the effectiveness of regulations controlling emissions. This analysis can be complicated by seemingly incongruent data from different model runs, model types, and field measurements. Here we present a case study example that describes how to identify trends in regional scale mercury deposition using best-available information from multiple data sources. To do this, we use data from three atmospheric chemistry models (CMAQ, GEOS-Chem, HYSPLIT) and multiple sediment archives (ombrotrophic bog, headwater lake, coastal salt marsh) from the Bay of Fundy region in Canada. Combined sediment and modeling data indicate that deposition attributable to US and Canadian emissions has declined in recent years, thereby increasing the relative significance of global sources. We estimate that anthropogenic emissions in the US and Canada account for 28-33% of contemporary atmospheric deposition in this region, with the rest from natural (14-32%) and global sources (41-53%).