In-cloud scavenging and deposition of sulfates and nitrates: Case studies and parameterization

Scavenging of sulfates and nitrates—two most common ions leading the cloudwater acidity—was investigated during field studies atop a site in Mt. Mitchell (35°44′05″N, 82°17′15″W) State Park where the highest peak (2038 m MSL) of the eastern U.S. is located. Experiments were conducted during the growing seasons (15 May–30 September) of 1986 and 1987 using an instrumented meteorological tower (16.5 m tall) and a passive cloudwater collector. A cloud episode that occurred on 12 October 1987, was also comprehensively investigated. Clouds were frequently observed in which the Fraser fir and red spruce stands stayed immersed 28% and 41% of the time during the 1986 and 1987 seasons, respectively. Rate of cloudwater deposition on the forest canopy was determined using an inferential cloud deposition model. It was found by analysing nine short duration (lasting 8 h or less) and 16 long duration cloud events that the ionic concentration (SO₄²⁻ and NO₃⁻) is inversely proportional to the rate (I_c) of cloudwater deposition (in mm h⁻¹) and can be expressed by the following relationship: [SO₄²⁻] = aI_c^−b or [NO₃⁻] = aI_c^−b. Theoretical arguments leading to these relationships are presented. The b values for predicting NO₃²⁻ concentration are found in the range of 0.14–1.24 (mean = 0.48) for short duration and 0.062–0.63 (mean = 0.27) for long duration cloud events, respectively. The corresponding b values for predicting NO₃⁻ concentrations are 0.19–1.16 (mean = 0.49) and 0.072–0.59 (mean = 0.27), respectively. When the b parameter was between 0.2 and 0.6, the correlation coefficients between measured and predicted ionic concentrations were found to exceed 0.7. The parameter a is shown to represent the maximum ionic flux for a given cloud event. The ratio of the a parameter for SO₄²⁻ to NO₃⁻ varied between 1.75 and 6.95, indicating that the SO₄²⁻ contributes to the total ionic concentration substantially more than the NO₃⁻ leading to the conclusion that the cloudwater acidity is primarily due to the presence of sulfuric acid which has been demonstrated to cause foliar injury and growth retardation in red spruce trees. The above parameterization is similar to the one that is frequently used to relate ionic concentration in precipitation to the rainfall rate. In order to understand physico-chemical processes leading to the proposed parameterization schemes, meteorological and chemical variables are comprehensively analysed for one short duration and two long duration cloud events. The concentrations of principal ions (SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺) during the short duration cloud events were found to be much higher than those during the long duration ones, especially at colder temperatures. Such short cloud events have a potential of causing foliar narcosis in red spruce stands because of unusually acidic cloudwater to which these stands stay exposed intermittently during each growing season.     

The chemical composition of intercepted cloudwater in the Sierra Nevada

The chemical composition of cloudwater in the Sierra Nevada is dominated by NO₃⁻, SO₄²⁻, and NH₄⁺. Cloudwater pH is determined largely by the balance between the concentrations of these three species, although inputs of formic and acetic acid also are believed to be important, particularly when anthropogenic inputs are small. Cloudwater samples collected in Sequoia National Park (SNP) exhibited pH values ranging from 3.9 to 6.5; Yosemite National Park (YNP) cloudwater samples had pH values ranging from 3.8 to 5.2. Samples collected at YNP were more acidic than those collected at SNP. The difference in pH between the two regions appears to be due to relatively small differences in inputs of NO₃⁻, SO₄²⁻, and NH₄⁺. In the absence of inputs of NH₃, cloudwater pH values in the Sierra may fall below 3.Over 250 h of cloud interception were observed during a 12 month period at a cloud monitoring site at 1856 m elevaton in SNP. Estimates of cloudwater deposition of NO₃⁻, SO₄²⁻, and NH₄⁺ indicate that cloud interception contributes significantly to regional acid deposition for closed forest canopies. Cloud interception may be the dominant deposition mechanism for isolated conifers and ridgetop canopies, where wind speeds are higher and cloudy air parcels can impact directly on foliar surfaces.     

Seasonal contrasts in modelled and observed dry deposition velocities of O3, SO2 and NO2 over three surfaces

Results of modelled and observed deposition velocities (V_d) for O₃, SO₂ and NO₂ for time-averaged diurnal cycles and sometimes for a collection of hourly values taken from different days are discussed for different seasons. From the observations, it was found that the O₃V_d values over a deciduous forest had a daytime representative value of 1.0 cm s⁻¹ in the summer and 0.3 cm s⁻¹ in the winter. For SO₂ over the same forest and over a carrot field the daytime values ranged from 0.0 to 0.65 cm s⁻¹ in the autumn, and for SO₂ over a snow surface the V_d ranged from 0.0 to 0.15 cm s⁻¹. The NO₂V_d was mostly negative over the forest and the carrot field in the autumn and had a range of 0.0-0.15 cm s⁻¹ over snow. From the model, it was found that for the three seasons the V_d values over all the land-use types were much larger than the observations. The model could not simulate the observed negative values of the NO₂V_d. The impact of the V_d model and its modified version on the concentrations of O₃ and SO₂ were tested with a comprehensive Eulerian air quality model.     

Deposition and forest canopy interactions of airborne sulfur: Results from the integrated forest study

The Integrated Forest Study (IFS) was a long-term research project designed to determine the effects of atmospheric deposition on forest nutrient cycles. Concentrations and fluxes of airborne sulfur compounds were determined for several years at the 13 IFS research forests in North America and Europe using a standard set of protocols. Annual mean air concentrations of sulfur ranged from ∼1.5 to 8 μgSm⁻³ and were generally dominated by SO₂ (∼60% of total sulfur on the average). Atmospheric deposition of sulfate at these forests was highest at the high elevation (∼ 1000–2000 eq ha⁻¹yr⁻¹) and at the southeastern U.S. sites (∼800–1000 eq ha⁻¹yr⁻¹), and lowest in the Pacific northwest (∼300 eq ha⁻¹yr⁻¹). Cloud water contributed significantly to the sulfur flux at the mountain sites (45–50%), and dry deposition was comparable to wet at the drier southeastern sites (>40% of total). Deposited sulfur appeared to behave more or less conservatively in these canopies, showing little net uptake (ofSO₂) and minor foliar leaching (of soil-derived, internal SO₄²⁻) relative to the total atmospheric flux. The estimated fluxes in total deposition were generally within 15% of the measured fluxes in throughfall plus stemflow, indicating that useful estimates of total atmospheric deposition of sulfur can be derived from measurements of throughfall.     

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.     

Source-receptor relationships for wet SO42− and NO3− production

Precipitation chemistry data for the years 1982–1985 from 110 stations distributed across the continental U.S. and southern Ontario Province are used to describe the geographic distributions of SO₄²⁻ and NO₃⁻ in precipitation. Volume-weighted, wet SO₄²⁻ and NO₃⁻ concentrations, averaged over the 4 years of observation by season and annullly, show coherent patterns with maxima in the northeastern U.S. and southeastern Canada about ten times greater than the minima observed in the Intermountain and Pacific Northwest regions.Tests for empirical source-receptor relationships indicate that, in land areas with relatively low emissions of SO₂ and NO_x, the associations between wet SO₄²⁻ concentrations and SO₂ emissions and between wet NO₃⁻ concentrations and NO_x emissions within 560 km of each precipitation chemistry station are weak or nonexistent (r²⩽0.42). The remaining land areas show moderate to strong associations between SO₂ and SO₄²⁻ and NO_x and NO₃⁻ during the spring and summer, but only weak to nonexistent associations during the winter. The associations between emissions and concentrations, e.g. SO₂ and SO₄²⁻, are equally well represented by either a linear or a power law function. However, at the level of aggregation employed, the data do not substantiate a linear-proportional relationship between concentrations and anthropogenic emissions. Furthermore, emissions of SO₂ and NO_x are highly correlated, as are the emissions of RHC and NO_x.     

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.     

Two options to explain the ammonia gap in The Netherlands

This paper addresses two hypothesis that try to explain the difference observed between the estimated NH₃ emission levels in The Netherlands and those indicated by atmospheric measurements, the so called ‘ammonia gap’: the role of SO₂ emissions regulating ambient NH₃ concentrations through co-deposition, and long-term NH₃ emissions after slurry injection. It was found that throughfall measurements of NH₄⁺ could not be used as indicator for changes in NH₃ emissions. The throughfall deposition of NH₄⁺ is in close equilibrium to SO₄²⁻ and NO₃⁻ and is thus regulated by the equilibrium of ambient NH₃ and NH₄⁺ in wet deposition and canopy water layers. When SO₂ emissions decrease, the amount of available SO₄²⁻ decreases, which imposes a limit on the deposition of (NH₄)₂SO₄. Long-term emissions of NH₃ after application of manure were monitored using a new technique, which continuously measures the concentration of NH₃ in a cross-section of the emission plume downwind of the source. The emissions could be registered for 3 weeks after application of manure. The results indicate that the long-term emissions only contribute 1–2% to the total emission level. Both the effect of SO₂ on the NH₃ deposition levels and the long-term emission fluxes are not enough to explain the observed ammonia gap. It seems that several counteracting effects, some of them emerging from the new emission reduction regulations, contribute to the ammonia gap. An integrated approach to abate ammonia emissions is, therefore, needed. The implementation and regulation of production ceilings for reactive nitrogen might be a good option.     

Field study investigations of the impact of shape,size and orientation on dry deposition induced corrosion of galvanized steel

A controlled field study was conducted at Research Triangle Park, NC, to determine how shape, size and orientation of galvanized steel structures affect (1) dry deposition of SO_x and NO_x compounds and (2) dissolution of Zn corrosion products resulting from such deposition. Thirteen structures of various shapes, sizes and orientations were exposed to dry deposition only for 100 weeks, during which they were rinsed with deionized water every 2 weeks and the rinses were analysed for Zn, Ca, and their ionic contents. The rinse data are consistent with size, orientation and exposure history affecting dry deposition of SO²⁻₄ precursors such as SO₂. Dry deposition of precursors of surface NO⁻₃, including HNO₃, is affected by structure size. A model regression equation is presented that shows that Zn dissolution can be explained in terms of the SO⁻²₄ and NO⁻₃ rinse concentrations. The experimental results suggest that there is likely to be some error associated with extrapolating galvanized steel test panel results to actual structures.     

Atmospheric pollutant deposition to high-elevation ecosystems

Current knowledge regarding deposition of atmospheric pollutants to mountain ecosystem is reviewed focusing on the mountains of eastern North America. Despite a general paucity of published data on the subject, some generalization emerge. Wet deposition (i.e. precipitation input) of SO₄²⁻, NO₃⁻, H⁺ and Pb tends to increase with elevation, primarily because of the orographic increase in precipitation amount. Cloud water deposition of these substances can be very significant for mountain forests, but is highly variable spatially because of its strong dependence on wind speed, cloud characteristics, and vegetation canopy structure, which are all heterogeneously distributed. Dry deposition has not been quantified sufficiently to draw empirical generalizations, but the processes involved are discussed with regard to expected elevational trends. Based on the few studies in which total annual deposition (wet, dry, plus cloud water inputs for an entire year) has been measured, it appears that some high-elevation sites in the Appalachian Mountains receive substantially more SO₄²⁻, NO₃⁺ deposition than do typical low-elevation sites. The amount of elevational increase depends largely on the amount of cloud water deposition at the mountain site. Data from two clusters of sites in the northern Appalachians indicate that total deposition of SO₄²⁻, NO₃⁻, and H⁺ to mountaintop sites is typically 3–7 times greater than deposition to nearby lowland sites. Similarly, some studies of Pb accumulation in organic soil horizons suggest a two- to four-fold increase from lowlands to mountaintops. Deposition in mountain areas can be highly variable over short distances because of the patchiness of meteorological conditions and vegetation canopy characteristics, and also because exposed trees and forest edges can receive deposition loads much higher than the landscape average. Night-time and early-morning O₃ concentrations are greater at high-elevation than at low-elevation sites. Daytime O₃ levels are equal or slightly higher at high-elevation sites. Additional studies are suggested which would allow better characterization of pollutant exposure along elevational gradients.     

Measurements of ammonia flux to a spruce stand in Denmark

This work demonstrates the existence of a linear relation between the deposition velocity of ammonia and the friction velocity measured above a spruce stand in the western part of Denmark. In order to estimate the ammonia deposition velocity and flux to a Norway spruce forest, concentration gradients of ammonia and several meteorological parameters were measured in a meteorology tower during two periods, 1 week in spring and 1 week in late summer 1991. The estimated deposition velocities lie in the range −0.125 to 0.201 m s⁻¹, with a mean of 0.026 m s⁻¹. The deposition velocity and the flux were generally largest in the afternoon. On the basis of 24-h measurements of ammonia and routine meteorological measurements the relation between deposition velocity and friction velocity is extrapolated to an estimate of the average flux for the growing season May to September 1991. The estimate gave an average flux of 87 μg NH₃N m⁻² h⁻¹ (=0.02 μg NH₃N m⁻² s⁻¹). The average deposition velocity for the period was 0.045 m s⁻¹.     

Chemical characterization of acid precipitation in Albany,New York

Chemical composition of precipitation in Albany, NY from July 1986 to December 1988 has been studied. Mean volume-weighted concentrations (μeq^ℓ−1) were: acidity, 104.0; alkalinity, −63.7; SO₄²⁻, 52.8; NO₃⁻, 29.8; Cl⁻, 5.6; F⁻, 0.50; NH₄⁺, 19.3; Ca²⁺, 6.5; Mg²⁺, 2.8; Na⁺, 3.5; and K⁺, 1.4. Mean pH was 4.2 . Seasonal patterns were pronounced for most species. Concentrations of H⁺, SO₄²⁻, NO₃⁻, NH₄⁺ and Ca²⁺ peaked in the summer and spring. Deposition was related to rainfall amount by a power law relationship in which the exponent of the equation was ∮.6. Wet SO₄²⁻ deposition was 2.35 keq ha⁻¹ over a 30-month period. The SO₄²⁻ and NO₃⁻ deposition rates observed at Albany indicate that transport from midwestern sources have a major influence at this site. On the average, free H⁺ ion concentrations determined from pH measurements accounted for 51% of the measured total acidity. There were unknown species, most likely organic acids, that could contribute to the acidity. Correlation and regression analyses indicated that major anions, SO₄²⁻ and NO₃⁻, were closely associated with H⁺ and NH₄⁺ ions. Factor analysis revealed four common factors which are related to fossil-fuel combustion, sea spray, cement factory and biomass burning.     

中亚热带典型林分不同层次氮硫湿沉降动态变化

基于野外定点监测的方法,于2012年9月~2013年8月对四面山常绿阔叶林大气降水、穿透水、枯透水、土壤渗滤液进行了持续1 a的氮、硫湿沉降动态变化的研究.结果表明:四面山大气降水全年p H平均值为4.89,最大值为5.14,大气降水明显偏酸性;土壤层和林冠层能使降雨的p H值有所升高,其中土壤层对p H值的调升幅度最大,其次为森林冠层;森林冠层对NO-3、NO-2、SO2-4有一定的吸附净化作用,平均截留率分别为56.68%、45.84%、35.51%;研究结果也表明:枯枝落叶的降解是导致各离子质量浓度在枯透水中增加的原因;森林土壤能够吸附中和NO-3、SO2-4、NH+4,释放出NO-2.中亚热带常绿阔叶林生态系统对大气降水中NO-3、NO-2、NH+4、SO2-4的总截留率分别为92.86%、57.86%、87.24%、87.25%,对酸性降雨有一定的缓冲作用.     

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).     

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.     

Aspects of wet,acidifying deposition in Arnhem: Source regions,correlations and trends (1984–1991)

A time series of wet deposition in Arnhem, the Netherlands, was analysed for the period 1984–1991. Precipitation was collected with four samplers on a daily basis. A comparative study by the Dutch National Precipitation Network showed significant biases for the observations of the National Network station due to longer exposure to dry deposition. Simultaneous operation of wet-only and bulk collectors demonstrated a concentration bias of about 10% for daily bulk sampling.Using a cluster analysis of backward trajectories, clear distinctions could be made between precipitation from continental and maritime origin. Event-to-event variations in deposition seemed to be determined largely by meteorological influences. As major anthropogenic source regions, the U.K., France, Belgium and the Netherlands itself were identified. The contribution of Dutch sources to wet acid deposition in Arnhem was estimated at 30–40%.Trends and seasonal variations were analysed with an advanced time-series model based on Kalman filtering. Similar seasonal variations were found for SO₄²⁻ and NH₄⁺. Also, seasonal variations in the concentrations of H⁺ and NO₃⁻ corresponded. Significant long-term changes in deposition and concentration were found for SO₄²⁻ (about −3% yr⁻¹) and H⁺ (about −9% yr⁻¹) only. The analysed trends were decreasing, but decreases were larger in the years 1984–1986 than in the following years. The relative decrease in the wet deposition of SO₄²⁻ was substantially smaller than decrease in dry-deposited SO₂ and SO₄²⁻.     

Cloud chemistry measurements and estimates of acidic deposition on an above cloudbase coniferous forest

The wet, dry and cloud water deposition of acidic substances on the forest canopy are considered as major mechanisms for pollutant induced forest decline at high elevations. Direct cloud capture plays a predominant role of intercepting acidic substances in above cloud-base forests. We conducted a field study at Mt. Mitchell, North Carolina (35°44′05″N, 82°17′15″W; 2038 m MSL)—the highest peak in the eastern U.S.—during May–September 1986 and 1987 in order to analyze the chemistry of clouds in which the red spruce and Fraser fir stands stay immersed. It was found that Mt. Mitchell was exposed to cloud episodes 71% of summer days, the cloud immersion time being 28% for 1986 (a record drought summer in southeastern U.S.) and 41% for 1987. Sulfate, NO₃⁻, NH₄⁺ and H⁺ ions were found to be the major constituents of the cloud water, which was collected atop a 16.5 m tall meteorological tower situated among 6–7 m tall Fraser fir trees. The initiation of precipitation in clouds invariably diluted the cloud water acidity. The cloud water pH during short episodes (8 h duration or less), which resulted from the orographic lifting mechanisms, was substantially lower than that during long episodes, which were associated with meso-scale and synoptic-scale disturbances. Sulfate accounted for 65% acidity in cloud water, on the average, and contributed 2–3 times more than the NO₃⁻. Inferential micrometeorological models were used to determine deposition of SO₄²⁻ and NO₃⁻ on the forest canopy and the hydrological input due to direct cloud capture mechanism. The cloud water deposition ranged between 32 and 55 cm a⁻¹ in contrast to the bulk precipitation which was about 130 cm a⁻¹ as measured by an on-site NADP (National Atmospheric Deposition Program) collector. For S compounds, wet, dry and cloud water deposition accounted for 19%, 11% and 70%, respectively for 1986, and 16%, 8% and 76%, respectively for 1987. For N compounds, dry deposition contributed 35% and 23% for 1986 and 1987, respectively, whereas, cloud water deposition contributed 50% and 65% for 1986 and 1987, respectively. Our estimates are compared with the reported literature values for the other sites.     

Ambient concentrations,scavenging ratios,and source regions of acid related compounds and trace metals during winter in northern michigan

Daily measurements the atmospheric cocnentrations of HNO₃, NO₃^-, NO₂, SO₂, SO₄²⁻, NH₄⁺, and several trace metals were made at the University of Michigan Biological Station over a 124-day period during the 1984–1985 winter. The composition of the daily precipitation was also determined. The relative contributions of scavenged NO₃⁻ and HNO₃ to the precipitation was estimated by assuming that the NO₃⁻ scavenging ratio was the same as that of trace metals with a similar particle size. Similarly, the SO₄²⁻ and SO₂ contributions were based on the scavenging ratios of NH₄⁺ and trace metals. On this basis, it was determined that the event median NO₃⁻ and HNO₃ scavenging ratios were 500 and 3500, respectively. HNO₃ scavenging accounted for 83% of the total scavenged NO₃⁻. Scavenging of SO₄²⁻ accounted for all the snow SO₄²⁻ in 67% of the events. In the remaining events, some SO₂ was scavenged, with a median scavenging ratio of 219. Overall, 67% of the snowfall acidity appeared to be due to HNO₃ scavenging. Backward air-mass trajectories that were calculated for each event were used to determine the general source regions of the acidic species. Snow associated with air masses from the south and west accounted for 81 and 75% of the deposited NO₃⁻ and SO₄²⁻, respectively.     

Characterization of pollen deposition in a forest environment

Measurements of the dry deposition of pollen were made during the months of May and June 1987 in northern Wisconsin, using a smooth surrogate surface. Samples were taken on a raft located on Little Rock Lake and at a nearby field monitoring station. Rain samples were also collected at the field station. The wet SO₄²⁻ flux was 102.7 mg m⁻², compared with a dry SO₄²⁻ flux of 118 mg m⁻² at the field monitoring site and 45 mg m⁻² at the lake site.The SO₄²⁻ content of pollen ranged from 0.2 to 0.8% of the weight of the pollen, and NO₃⁻ concentrations were an order of magnitude lower. Between 9 and 22% of the pollen weight was available as total organic carbon (TOC) upon addition to water.The addition of pollen to distilled water produced an acid reaction, due to organic acids and not inorganic acidity.     

Chemistry of atmospheric precipitation at the Western Arabian Gulf Coast

Rainwater and atmospheric bulk deposition samples were collected at a station on the rooftop of the Research Institute of King Fahd University of Petroleum and Minerals in Dhahran. Continuous sampling was carried out manually throughout the rainy season between December 1987 and February 1988, and for one rainfall event in March 1987. A total number of 13 samples were collected and investigated for pH and dissolved ionic composition using inductivity coupled plasma emission spectrometry (ICP) and ion chromatography (IC). The range and volume-weighted average pH were 5.1–7.2 and 5.48, respectively. Significant negative linear correlations were observed between the precipitation pH and rain depth, and between pH and the summation of dissolved {(Ca²⁺ + Mg²⁺)−(SO₄²⁻ + NO₃⁻ + NO₂⁻)} (in μeqℓ⁻¹). The ionic summation also correlated negatively with rain depth. The ionic abundance in rainwater (in μeqℓ⁻¹) expressed in concentration order showed the general trend SO₄²⁻ > HCO₃⁻¹ = Cl⁻ = NO₃⁻ > NO₂⁻ for anions and Ca²⁺ > Na⁺ > Mg²⁺ > NH₄⁺ > K⁺ > H⁺ > Sr²⁺ for cations. Good mass balance between cations and anions was observed. Total NO₃⁻ contribute equally to precipitation acidity as SO₄²⁻ and Ca²⁺ plus Mg²⁺ in alkaline suspended particulates from natural sources are the major ions which buffer the acidity of precipitation. The NH₄⁺ ion which is also present plays an insignificant role in the acid/base equilibrium of rainwater.