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.     

Nitrogen deposition in Mediterranean forests

Atmospheric deposition of inorganic nitrogen was studied at two forested sites in the Montseny mountains (northeast Spain), peripheral to the Barcelona conurbation, and at a nearby lowland town, using bulk deposition, wet-only deposition, throughfall, and dry deposition inferred from branch-washes and surrogate surfaces (metacrylate plates). Bulk deposition inputs of ammonium and nitrate did not show significant temporal trends over a 16-year period. Bulk inputs of inorganic N were moderate, ranging from 6 to 10 kg N ha(-1) year(-1) depending on the time period considered and the degree of site exposure to polluted air masses from the Barcelona conurbation. Large dry-sedimented particles played a minor role, since wet-only inputs were virtually identical to bulk inputs. On the contrary, branch- and plate-washes indicated substantial dry inputs of N gases and small particles. Total atmospheric deposition was estimated at 15-22 kg N ha(-1) year(-1), most of it being retained within the studied broadleaved evergreen forests. Ecosystem N availability is thus likely to be increasing in these forests.     

Bulk deposition in a rural area located around a large coal-fired power station, northeast Spain

This work focuses on bulk deposition in a rural area located around a large coal-fired power station in northeast Spain. Deposition chemistry was characterised by high concentrations of SO(4)(2-), Ca(2+) and NH(4)(+), which were relatively high when compared with other rural areas. Monthly bulk deposition evolution of major ions was the result of two superimposed patterns: one pattern related to the volume of precipitation and the other showed the seasonal influence of the major ionic sources. A major local origin was attributed to bulk deposition of SO(4)(2-), NH(4)(+), and Ca(2+), whereas a relatively higher contribution of an external source was deduced for NO(3)(-), Na(+) and Cl(-). The SO(4)(2-) concentrations showed a significant correlation with the local SO(2) emissions. High levels of Ca(2+) were due to the high alkalinity of soils in the study area, although an external origin was attributed to the frequent air mass intrusions from the Sahara. Sources of NH(4)(+) were related to intensive livestock farming in the area. Total suspended particles exert a marked influence over bulk deposition and neutralisation. Thus, despite the high emissions of SO(2) in the area, neutral pH values have always been attained given that the concentrations of Ca(2+) and NH(4)(+) account for the total neutralisation of NO(3)(-) and SO(4)(2-).     

Composition of wet and bulk deposition in Erzurum, Turkey

Seasonal variations in the chemical characteristics of wet and bulk deposition samples collected in Erzurum were investigated for the period March 2002-January 2003. Major cations (Ca2+, K+, Mg2+) and major anions (SO4(2-),NO3-) were determined in bulk and wet deposition samples; pH was also measured in wet deposition. The average pH of the wet deposition at Erzurum was 6.6 due to extensive neutralization of the acidity. A strong relationship between pH and SO4(2-) concentrations was observed in all seasons; however, only a weak relationship was found between pH and NO3-. On a seasonal basis, the correlation between Ca2+ and SO4(2-) concentrations was stronger in winter than in summer. Seasonal variations of ions were examined in both wet and bulk deposition samples. Although maximum concentrations of anions generally occurred during winter and spring, cation concentrations peaked in summer for both wet and bulk deposition. Results indicated that Ca2+ was the dominant cation and SO4(2-) the dominant anion in all deposition samples at Erzurum. Even though correlations among the crustal ions (calcium, magnesium and potassium) were high, the relationship between anthropogenic ions (sulfate and nitrate) was less clear in bulk deposition.     

Preliminary data from the USEPA dry deposition network: 1989

The objective of the National Dry Deposition Network is to determine patterns and trends of dry deposition for various sulfur and nitrogen species at roughly 50 locations throughout the continental USA. Each site is equipped for collection of continuous meteorological and ozone data and weekly average concentrations of SO4(2-), NO3-, SO2 and HNO3, using a three-stage filter pack. Results from 40 eastern US sites operational throughout 1989 show species-dependent variability from site to site, season to season, and day to night. Annual average concentrations of atmospheric SO4(2-), NO3-, SO2 and HNO3 ranged from 2.7 to 7.9, 0.2 to 3.9, 2.4 to 23.2 and 0.7 to 3.6 microg/m(-3), respectively. Seasonal variability was considerable for all constituents. Day/night data indicate that SO2 and HNO3, but not SO4(2-) and NO3-, are typically found at moderately to substantially lower concentrations at night, especially during spring and summer. Estimated dry deposition for SO2 and HNO3 appear to be much greater than for SO4(2-) and NO3-, respectively. Comparison of measured wet deposition and estimated dry deposition at numerous sites suggests that the two are similar in magnitude over much of the eastern USA.     

Foliage responses of spruce trees to long-term low-grade sulfur dioxide deposition

Foliage on spruce trees (Picea rubens Sarg.) growing on dry SO(2) deposition zones (dry SO(2) deposition ranging from 0.5 and 8.5 S kg ha(-1) year(-1)) downwind from a SO(2) emission source was analyzed to assess chronic effects of long-term low-grade SO(2) deposition on net photosynthesis, stomatal conductance, dark respiration, stomatal antechamber wax structures, elemental concentrations in and on foliage (bulk and surficial concentrations), and types of epiphytic fungi that reside in the phylloplane. Elemental distributions on stomatal antechambers, on fungal colonies, and on smooth surfaces between stomates and fungus colonies were determined with a scanning electronic microscope (SEM) by way of X-ray scanning. It was found that net photosynthesis of newly developed spruce foliage (current-year, and 1-year-old) was not significantly affected by the local SO(2) deposition rates. Sulfur dioxide deposition, however, may have contributed to the gradual decrease in net photosynthesis with increasing needle age. Dark respiration rates were significantly higher on foliage taken from high SO(2) deposition zones. Stomatal rod-web structures deteriorated to flakes with increasing needle age and increasing SO(2) deposition. Further inspection of the needle surfaces revealed an increasing abundance of fungal colonies with increasing needle age. Many fungal taxa were isolated and identified. It was found that black yeasts responded positively, and Xylohypha pinicola responded negatively to high rates of SO(2) deposition. Surficial concentrations of elements such as P, S, K, Cl, Ca were about 10 times higher on fungal colonies than on smooth needle surfaces. Surficial Ca contents on 4 or 5-year-old needles decreased with increasing SO(2) deposition, but surficial S concentrations remained the same. In contrast, bulk foliar Ca and S concentrations increased with increasing SO(2) deposition.     

Dry deposition of sulfur dioxide or nitric acid to oak, elm and pine leaves

To improve our knowledge of atmospheric inputs to forests, experiments were performed in the field to measure the dry deposition of SO2 and HNO3 to oak, elm, and pine leaves. A tree branch was enclosed in a Teflon chamber, through which SO2 or HNO3 flowed. The dry deposition characteristics of SO2 and HNO3 were very different. The SO2 deposition occurred primarily through stomatal openings for the oak and pine leaves, and equal stomatal and cuticular deposition was observed for the elm leaves. The deposited SO2 could not be removed from the branch by extracting in water or by revolatilization. In contrast, over 90% of HNO3 dry deposition occurred to the cuticle. Most of the deposited HNO3 could be extracted from the leaves. Revolatilization of HNO3 was negligible from an active branch, but increased from a dormant or detached branch. A deposition velocity was derived from the ratio of the flux of the gas to the leaves and the gas concentration in the chamber. Deposition velocities ranged from 0.02 to 0.11 cm s(-1) for SO2 and from 0.2 to 1.2 cm s(-1) for HNO3 to individual leaf surfaces.     

Diagnostic indicators of elevated nitrogen deposition

Tissue N content of mosses, which has been shown to be an indicator of enhanced N, was studied at a range of locations dominated either by wet or dry deposited and oxidised and reduced forms of N. Tissue N responded differently to wet and dry deposited N. For a 1 kg ha(-1) y(-1) increase in N deposition, tissue N increased by 0.01% at wet deposition sites but by 0.03% at sites dominated by dry deposited NH3. Tissue N at wet deposition sites responded more to concentrations of NO3- and NH4+ in precipitation (r(2) 0.63) than to total N deposition (r(2) 0.27), concentration explaining 66% of the variation in tissue N, wet deposition 33%. The study clearly concludes that tissue N concentration in mosses provides a good indication of N deposition at sites where deposition is dominated by NH3, and is also valuable in identifying vegetation exposed to large concentrations of NH4+ or NO3-, in wet deposition dominated areas, such as hilltops and wind exposed woodland edges.     

Atmospheric dry deposition to leaf surfaces at a rural site of India

Dry deposition flux of major ions (Na+, K+, Ca2+, Mg2+, NH4+, F-, Cl-, NO3- and SO4(2-) to natural surfaces [guava (Psidium guyava) and peepal (Ficus religiosa) leaves] are determined at Rampur, a rural site of semi-arid region of India. Dry deposition flux is the highest for Ca2+ on guava leaves and for NH4+ on peepal leaves. Overall dry deposition flux is higher on guava leaves than of peepal leaves. The variation in deposition flux may be due to surface characteristics (surface roughness) and arrangement of leaves. Peepal leaves are arranged along the axis of the stem, whereas guava leaves are at right angles to the stem. The deposition flux of cations contributes 66% and 76% of dry deposition of all major ions on guava and peepal leaves, respectively as soil is major contributor towards dry deposition flux in tropical regions. ANOVA revealed no significant seasonal difference in deposition, although there is a trend for higher in winter. Deposition velocities of NH4+, NO3- and SO4(2-) are greater on guava leaves than peepal leaves, which can be attributed to the rougher surface of the guava leaf.     

Dry deposition, ionic species measured and source interpretation during seasonal cycle at offshore areas near Taiwan Strait

The characterization for water-soluble species of total suspended particulate (TSP), dry deposition flux, and dry deposition velocity (V(d)) were studied at Taichung Harbor (TH) and Wuchi traffic sampling sites at offshore sampling site near Taiwan Strait of central Taiwan during March 2004-January 2005. The average concentrations of TSP and dry deposition flux at the TH sampling site were higher than at the WT sampling site during the sampling period. The samples collected were analyzed by a ion chromatography (DIONEX-100) for the ionic species (Cl(-), SO(4)(2-), NO(3)(-), NH(4)(+), Na(+), Ca(2+), and Mg(2+)) analysis. The dominant ionic species for TSP are SO(4)(2-), NO(3)(-), and NH(4)(+) of the total mass of the inorganic ions at both sampling sites. In addition, the results indicated that the NH(4)(+), NO(3)(-) and SO(4)(2-) showed higher concentrations in winter and lower in summer for both TH and Wuchi sampling sites. Statistical methods such as correlation coefficient and principal component analysis were also used to identify the possible pollutant source.     

Indications for changing deposition patterns in central Europe

The German Federal Environmental Agency (Umweltbundesamt) currently runs a network of 17 air pollution monitoring stations in rural areas within the Federal Republic of Germany. Since 1982, daily bulk precipitation samples have been collected and analysed at five of these stations. As no changes in sampling and chemical analysis techniques have been introduced in this time period, an interpretation with respect to trends is possible. An increase in pH is most obvious at Deuselbach in the western part of Germany. It is related to a decrease in sulphate ions. Reduced SO2 emissions in the western part of Europe have resulted in decreasing ambient air concentrations mainly in the western part of Germany, whereas changes in concentrations close to the eastern border of West Germany were not as pronounced. Part of the decrease, however, was a consequence of three mild winters in sequence at the end of the period, with little easterly air flow. Estimated dry deposition fluxes of sulphur at 3 rural stations in West Germany were lower in 1988/1989 compared to 1980-1987 by 44-69%. Wet deposition showed between 8% increase and 25% decrease. The resulting reduction in total sulphur deposition ranged from 17-54%. Deposition via interception of fog droplets was not measured.     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

Estimates of cloud water deposition at Mountain Acid Deposition Program sites in the Appalachian Mountains

Cloud water deposition was estimated at three high-elevation sites in the Appalachian Mountains of the eastern United States (Whiteface Mountain, NY; Whitetop Mountain, VA; and Clingman's Dome, TN) from 1994 through 1999 as part of the Mountain Acid Deposition Program (MADPro). This paper provides a summary of cloud water chemistry, cloud liquid water content, cloud frequency, estimates of cloud water deposition of sulfur and nitrogen species, and estimates of total deposition of sulfur and nitrogen at these sites. Other cloud studies in the Appalachians and their comparison to MADPro are also summarized. Whiteface Mountain exhibited the lowest mean and median concentrations of sulfur and nitrogen ions in cloud water, while Clingman's Dome exhibited the highest mean and median concentrations. This geographic gradient is partly an effect of the different meteorological conditions experienced at northern versus southern sites in addition to the difference in pollution content of air masses reaching the sites. All sites measured seasonal cloud water deposition rates of SO4(2-) greater than 50 kg/ha and NO3(-) rates of greater than 25 kg/ha. These high-elevation sites experienced additional deposition loading of SO4(2-) and NO3(-) on the order of 6-20 times greater compared with lower elevation Clean Air Status and Trends Network (CASTNet) sites. Approximately 80-90% of this extra loading is from cloud deposition.     

Dry deposition of airborne sulfate and nitrate to soybeans

Dry deposition contributes a substantial part of the total deposition of acidic pollutants and acid precursors to agricultural systems. However, because of the relative intractability of measurement of dry deposition fluxes, little work has been done to directly quantify dry inputs of pollutants to crops. In this research, foliar surface sampling ('leaf-washing') methods were developed and shown to be a practical and fairly precise means of monitoring the accumulation of dry-deposited SO4(2-) and NO3- on plant surfaces. Leaching of these ions from plant tissues was shown to be negligible; however, uptake by plants (e.g. stomatal gas exchange of SO2 or HNO3 and/or assimilation of surface accumulations of materials) is not accounted for by the sampling method. The significance of dry deposition to modification of the chemical microenvironment of leaf surfaces appears to be a factor of 3 to 20 or more greater than that of wet deposition alone. This is due to the cyclic reactivation of accumulated materials by dew and light rains, which may dissolve and mobilize, but not remove, the pollutant surface deposit. Therefore, while dry deposition of SO2 and SO4(2-) containing particles may contribute only part of the total mass of sulfur inputs to crop systems, the exposure of plant surface tissue to pollutants can be dominated by the dry-deposited material. The alteration of leaf surface chemistry may contribute to possible stress-producing mechanisms such as reduction of cuticular integrity, cellular injury and death, enhanced leaching of primary and secondary metabolites, and changes in pathogen infection efficiency.     

Simulated seasonal variations in wet acid depositions over East Asia

The air quality modeling system Regional Atmospheric Modeling System-Community Multi-scale Air Quality (RAMS-CMAQ) was applied to analyze temporospatial variations in wet acid deposition over East Asia in 2005, and model results obtained on a monthly basis were evaluated against extensive observations, including precipitation amounts at 704 stations and SO4(2-), NO3-, and NH4+ concentrations in the atmosphere and rainwater at 18 EANET (the Acid Deposition Monitoring Network in East Asia) stations. The comparison shows that the modeling system can reasonably reproduce seasonal precipitation patterns, especially the extensive area of dry conditions in northeast China and north China and the major precipitation zones. For ambient concentrations and wet depositions, the simulated results are in reasonable agreement (within a factor of 2) with observations in most cases, and the major observed features are mostly well reproduced. The analysis of modeled wet deposition distributions indicates that East Asia experiences noticeable variations in its wet deposition patterns throughout the year. In winter, southern China and the coastal areas of the Japan Sea report higher S04(2-) and NO3- wet depositions. In spring, elevated SO4(2-) and NO3-wet depositions are found in northeastern China, southern China, and around the Yangtze River. In summer, a remarkable rise in precipitation in northeastern China, the valleys of the Huaihe and Yangtze rivers, Korea, and Japan leads to a noticeable increase in SO4(2-) and NO3- wet depositions, whereas in autumn, higher SO4(2-) and NO3-wet depositions are found around Sichuan Province. Meanwhile, due to the high emission of SO2, high wet depositions of SO4(2-) are found throughout the entire year in the area surrounding Sichuan Province. There is a tendency toward decreasing NO3- concentrations in rainwater from China through Korea to Japan in both observed and simulated results, which is a consequence of the influence of the continental outflow from Eurasia. The same tendency is not found for SO4(2-).     

Measurement of dry deposition to surfaces in deciduous and pine canopies

The importance of dry deposition was assessed at perimeter and interior locations in two vegetative canopies. Dry deposition was measured directly by washing particles from leaves. Ambient particles and gases were also collected at both locations within the canopies. Ambient concentrations on the canopy interior were decreased relative to perimeter concentrations due to dry deposition scavenging by the canopy. The least scavenging was found for SO(4)(2-) and NH(4)(+) and the highest scavenging was found for HNO(3). Dry deposition of all species was higher to perimeter vegetative and surrogate surfaces than to interior surfaces, due both to the lower concentrations and the lower wind speeds in the sheltered interior. Deposition velocities compared well with other experimental and theoretical values.     

Relation between estimated dry deposition and throughfall in a coniferous forest exposed to controlled levels of SO2 and NO2

Throughfall was collected in a Scots pine forest exposed to about 14 microg m(-3) of both SO2 and NO2, and in a control forest with 1 microg m(-3) SO2 and < 1 microg m(-3) NO2. Precipitation was collected in a nearby open field. Collection was performed on an event basis during the whole vegetation period. Exposure was made by an open-air release system during the vegetation period, except during rain and at night. Additional sulfate deposition in the exposed forest (compared to control forest) was nearly equal to dry deposition of sulfur dioxide, as estimated with a stomatal conductance model adapted for the particular forest. It is thus concluded that essentially all of the dry deposited sulfur dioxide is eventually extracted and appears in throughfall-including the fraction that has been deposited through stomata. Attempts to relate net throughfall deposition to dry deposition of sulfate in the control forest were inconclusive, since a minor (10%) uncertainty in the water balance had a major influence on calculated deposition velocity for particulate sulfate. Nitrate throughfall deposition is about half of the open field wet deposition, both for the exposed and control forest. Thus, a long-term exposure with about 14 microg m(-3) NO2 decreased nitrate throughfall deposition.     

Deposition of nitrogen-containing compounds to an extensively managed grassland in central Switzerland

During four intensive observation periods in 1992 and 1993, dry deposition of nitrogen dioxide (NO(2)) and ammonia (NH(3)), and wet deposition of nitrogen (N) were determined. The measurements were carried out in a small, extensively managed litter meadow surrounded by intensively managed agricultural land. Dry deposition of NH(3) was estimated by the gradient method, whereas eddy correlation was used for NO(2). Rates of dry deposition of total nitrate (= nitric acid (HNO(3)) + nitrate (NO(3)(-))), total nitrite (= nitrous acid (HONO) + nitrite (NO(2)(-))) and aerosol-bound ammonium (NH(4)(+)) were estimated using deposition velocities from the literature and measured concentrations. Both wet N deposition and the vertical NH(3) gradient were measured on a weekly basis during one year. Dry deposition was between 15 and 25 kg N ha(-1) y(-1), and net wet deposition was about 9.0 kg N ha(-1) y(-1). Daily average NO(2) deposition velocity varied from 0.11 to 0.24 cm s(-1). Deposition velocity of NH(3), was between 0.13 and 1.4 cm s(-1), and a compensation point between 3 and 6 ppbV NH(3) (ppb = 10(-9)) was found. Between 60 and 70% of dry deposition originated from NH(3) emitted by farms in the neighbourhood. It is concluded that total N deposition is exceeding the critical load for litter meadows, is highly correlated to local NH(3) emissions, and that NH(3) is of utmost importance with respect to possible strategies to reduce N deposition in rural regions.     

Atmospheric deposition inputs and effects on lichen chemistry and indicator species in the Columbia River Gorge, USA

Topographic and meteorological conditions make the Columbia River Gorge (CRG) an 'exhaust pipe' for air pollutants generated by the Portland-Vancouver metropolis and Columbia Basin. We sampled fog, bulk precipitation, throughfall, airborne particulates, lichen thalli, and nitrophytic lichen distribution. Throughfall N and S deposition were high, 11.5-25.4 and 3.4-6.7 kg ha(-1) over 4.5 months at all 9 and 4/9 sites, respectively. Deposition and lichen thallus N were highest at eastern- and western-most sites, implicating both agricultural and urban sources. Fog and precipitation pH were frequently as low as 3.7-5.0. Peak NO(x), NH(3), and SO(2) concentrations in the eastern CRG were low, suggesting enhanced N and S inputs were largely from particulate deposition. Lichens indicating nitrogen-enriched environments were abundant and lichen N and S concentrations were 2x higher in the CRG than surrounding national forests. The atmospheric deposition levels detected likely threaten Gorge ecosystems and cultural resources.     

Assessment of the potential for soil acidification in North India using the critical load approach and locally derived data for acidic and basic inputs

Major ions (Cl-, NO3(-), SO4(2-), Ca2+, Mg2+, Na+, K+ and NH4(+)) were analysed in wet and dry deposition samples collected for 2 years using a polyethylene bottle and funnel collector at Agra in India. The deposition of ionic components (Ca2+ and Mg2+) derived from natural sources i.e. soil were higher than those of anthropogenic origin. In rainwater samples, non-sea-salt fraction was found to be 60-90%. In both wet and dry deposition Ca2+ was found to be the dominant ion which may be due to its large particle diameter. Results suggest that most of the acidity, which occurs due to NO3(-), SO4(2-) and Cl- is neutralized by alkaline constituents, which originate from airborne local soil and dust transported from the Thar desert. Acid neutralizing capacity of soil has also been quantified and found to be 33 x 10(3) neqg(-1). Using deposition data, the critical load for acidity of soil with respect to Ashoka and Eucalyptus was evaluated. The present level of deposition of S and N was found to be much lower than critical loads calculated for S and N. Critical load of exceedance in terms of deposition acidity was also calculated and found to be negative. This indicates that with respect to these species, the ecosystem is protected at the current level of deposition.