Chemical composition of rain in Thessaloniki,Greece, in relation to meteorological conditions

Wet precipitation was collected in Thessaloniki, Greece, during the period March 1989–December 1990 by using an automatic wet-only precipitation sampler.Rainwater samples were analysed for major cations (H⁺, NH₄⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (Cl⁻, NO₃⁻, SO₄²⁻), in addition to acidity and conductivity measurements. The majority of rain had a neutral or alkaline character as a result of neutralization, primarily caused by calcareous soil dust and secondarily by atmospheric ammonia. In all rain, SO₄²⁻ concentration exceeded NO₃⁻ concentration. The contribution of maritime sources to the total SO₄²⁻ concentration was very low (<2%).The chemical composition of precipitation was analysed in conjunction with meteorological variables (season of the year, precipitation type, airflow patterns) to evaluate temporal variations and chemical source influence. Rain caused by weak, localized flows showed the highest acidity and the minimum influence of neutralization processes.     

Elements in the precipitation of S. Paulo City (Brazil)

Rainwater samples in S. Paulo city were collected on an event basis from October 1983 to October 1985 covering two dry and two rainy periods. Bulk samples only were obtained. At the same site and period, fine, coarse and inhalable particles were also collected. Na⁺, Ca²⁺, K⁺, Mg²⁺, NO₃⁻, SO₄²⁻ and NH₄⁺ contents were determined in rainwater samples, while Na, Ca, K, Cl and S concentrations were measured in aerosol samples. Rainwater is slightly acid (mean pH = 5.0), and contains high concentrations of Ca²⁺, NO₃⁻, SO₄²⁻ and NH₄⁺. Dry and wet fluxes and washout ratios were determined for some elements. Results obtained suggest that the atmospheric composition in this city is strongly influenced by anthropogenic sources.     

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.     

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⁻.     

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.     

Cloud chemistry at Mt Rigi,Switzerland: Dependence on drop size and relationship to precipitation chemistry

The chemical composition of winter and spring cloud water sampled at 1620 masl elevation on Mt Rigi in central Switzerland was dominated by NO₃⁻, SO₄²⁻, NH₄⁺ and H⁺. A wide range of concentration levels was observed, with maxima of 3700, 1800 and 4600 micronormal for NO₃⁻, SO₄²⁻ and NH₄⁺, respectively. Concentrations at a lower elevation (1030 masl) site on the mountain were higher due to lower cloud liquid water contents and higher pollutant levels at that site. The lowest pH observed was 2.95; large concentrations of NH₃ in the region prevented pH values from falling even lower. A comparison of simultaneously sampled cloud water and precipitation revealed much higher concentrations for most species in the cloud water, except in one case of extreme precipitation riming when the concentrations in the two phases converged. An exception to the pattern was H⁺; at times the precipitation was more acidic than the cloud water. The chemical composition of the cloud drops varied with drop size. Drops smaller than 10 μm diameter were enriched in NO₃⁻, SO₄²⁻ and NH₄⁺ relative to larger drops. Since the larger drops are the ones most effeciently captured by snow crystals, knowledge of their composition is essential to understanding the chemical implications of accretional growth of precipitation.     

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.     

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.     

Estimates of ion sources in deciduous and coniferous throughfall

Estimates of external and internal sources of ions in net througfall deposition were derived for a deciduous and coniferous canopy by use of multiple regression. The external source component appears to be dominated by dry deposition of Ca²⁺, SO₂ and NO₃⁻ during dormant and growing seasons for the two canopy types. Increases in the leaching rates of K⁺ and Mg²⁺ during the growing season reflect the presence of leaves in the deciduous canopy and increased physiological activity in both canopies. Internal leaching rates for SO₄²⁻ doubled during the growing season presumably caused by increased physiological activity and uptake of SO₂ through stomates. Net deposition of SO₄²⁻ in throughfall during the growing season appears highly dependent on stomatal uptake of SO₂. Estimates of SO₂ deposition velocities were 0.06 cm s⁻¹ and 0.13 cm s⁻¹ for the deciduous and coniferous canopies, respectively, during the dormant seasons, and 0.30 cm s⁻¹ and 0.43 cm s⁻¹ for the deciduous and coniferous canopies, respectively, during the growing season. For the ions of major interest with respect to ecosystem effects, namely H⁺, NO₃⁻ and SO₄²⁻, precipitation inputs generally outweighed estimates of dry deposition input. However, net throughfall deposition of NO₃⁻ and SO₄²⁻ accounted for 20–47 and 34–50 per cent, respectively, of total deposition of those ions. Error estimates of ion sources were at least 50–100 per cent and the method is subject to several assumptions and limitations.     

Aerosol characteristics of Arctic haze sampled during AGASP-II

As part of the second Arctic Gas and Aerosol Sampling Program (AGASP-II), Arctic aerosol samples were collected by the NOAA WP-3D aircraft in spring 1986. The samples were analyzed in bulk and individual-particle form, using ion chromatography (IC) and electron microscopy (EM), respectively. Information on the chemical composition of the aerosol as determined by various techniques is presented, as well as morphology, concentration, and size distribution data obtained from individual particle analyses. For most flights, a stratospheric sample and a haze profile samople were collected. Haze samples exhibited greater particle concentrations than stratospheric samples, the highest concentrations in haze reaching ∼10³ cm⁻³ (non-volatile particles > 0.05 μm diam). Sulfur was consistently observed to be a major element in both large and small particles in haze samples. Crustal elements such as Si, Al, K, Ca and Fe were often present in significant concentrations together with S. Particles that did not emit X-rays, possibly organic or sooty C, were observed in significant concentrations in both tropospheric and stratospheric samples. Chemical spot tests confirmed that SO₄²⁻ was the major S-containing species and that NO₃⁻ was not nearly as prevalent as SO₄²⁻ in the Arctic aerosol particles. The mass concentrations of major anions (Cl⁻, SO₄²⁻ and NO₃⁻) and cations (Na⁺, K⁺, NH₄⁺, Ca²⁺ and Mg²⁺) in the bulk aerosols were determined using IC. The ratios between ion concentrations, e.g. Ca²⁺/Na⁺, SO₄²⁻/Na⁺ and Cl⁻/Na⁺, may serve as indicators of aerosol origins and mixing status of various air masses. Aerosols collected on six flights demonstrated variability of particle characteristics in relation to sources and transport of Arctic haze.     

Measurement and evaluation of acid air pollutants in Chicago using an annular denuder system

The cyclone/annular denuder/filter pack sampling system (ADS) was used to collect and evaluate ambient air pollutants in Chicago. Eighty-one 12-h samples, equally divided into day/night intervals, were collected from April 1990 to March 1991. The chemical species measured were HNO₃, HNO₂, SO₂ and NH₃ in the gas phase, and SO₄²⁻, NO₃⁻, NH₄⁺, and H⁺ in the particulate phase.The ADS data were collected simultaneously with PM10 samples. The particulate matter was analysed for elemental composition. These compositions were combined with the ADS observations and subjected to evaluation using a chemical mass balance receptor model (CMB). From the CMB analysis, the sum of the contributions from soil (15%), mobile (14%), incinerator (2%), coal (0.6%), steel (0.3%) and refinery (0.2%) was 32% of the PM10. NO₃⁻, which was not included in the fingerprints, represented an additional 9% of the PM10. Residual SO₄²⁻ and residual organic carbon, possibly formed in the atmosphere, represented an additional 22 and 20% of the PM10, respectively, leaving only 17% from other unidentified sources. From the standpoint of source contributions of sulfur and nitrogen compounds, coal combustion (23%) and refinery emissions (23%) are the major contributors of ambient sulfur (with 49% from unidentified sources). Mobile sources (87%) contributed most of the ambient nitrogen (with only 2% from unidentified sources).     

A chemical characterization of atmospheric aerosol in Sapporo

Monthly mean chemical composition of aerosol with diameter less than 8 μm was identified in Sapporo in 1982. The mass of aerosol was made up of nine components: elemental C, organics, SO₄²⁻, NO₃⁻, NH₄⁺, Cl⁻, Na⁺, soil particles and water. The concentrations of carbonaceous particles (elemental C and organics) was relatively high (12.7–16.0μ m⁻³) in autumn and winter (October–February) due to emission from domestic heating and comprised 36–41% of total aerosol mass. Higher concentration of soil particles was observed in spring (March–May) (9.7–13.1 μg m⁻³) and comprised 22–29% of total aerosol mass due to suspension by strong wind. On the other hand, the concentration of excess SO₄²⁻ (non-sea salt SO₄²⁻), which ranged from 2.6–5.2 μg m⁻³, did not change remarkably with season, and the fraction of excess sulfate increased to 21% in summer (July–August) probably due to photochemical transformation from SO₂. Nitrate concentration was far less than that of SO₄²⁻ throughout the year in Sapporo.     

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).     

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.     

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.     

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.     

Mid-latitude northern hemisphere background sulfate concentration in rainwater

The pH is not sufficient to characterize the acidity of precipitation, but rather its acid-base components must be described. The chemistry of natural emission sources as well as the mechanism of precipitation formation determine the chemistry of precipitation at mid-latitude, Northern Hemisphere locations. With the ocean biota as a source of atmospheric aerosol SO₄²⁻, it is expected that this “background” chemistry will be dominated by SO₄²⁻. For the purpose of this study, background was defined as a remote site generally upwind of urban areas, with the additional requirement that samples with evidence of contamination by anthropogenic sources be excluded. Canadian and U.S. data from long term precipitation monitoring sites along the coasts of British Columbia, Oregon, and Washington were evaluated to estimate a background SO₄²⁻ concentration in rainwater. In addition to screening the data for charge balance, collection efficiency, and anthropogenic influence, the data were corrected for SO₄²⁻ associated with sea salt. The results of this analysis suggest that the mid-latitude, Northern Hemisphere background excess SO₄²⁻ concentration in rainfall occurs most frequently in the range of 2–16 μeqℓ⁻¹ with a mean of 5.5 μeqℓ⁻¹ and an average measured pH of 5.3.     

Factor analysis of trends in Texas acidic deposition

Precipitation chemistry data collected between 1980 and 1987 for 11 NADP/NTN sites in Texas have been analyzed using factor analysis and a trend analysis of monthly averages. Factor analysis identified four major factors which differed significantly from site to site: (1) a Gulf factor of Na⁺, Cl^-, and Mg²⁺; (a) a soil factor of Ca²⁺, K⁺, Na⁺, and Mg²⁺; (3) an acid factor of H⁺, NO₋³, and SO₄⁴⁻; and (4) an aged aerosol factor of NO₃⁻, SO₄²⁻, and NH₄⁺. At Longview, the acid and Gulf factors accounted for 18 and 46%, respectively, of the variation of the data. A trend analysis was performed on the logarithm of the monthly averages at the Longview and Victoria sites, the two sites with the largest and most complete data. Results suggest that hydrogen ions have been increasing at both sites, while calcium ions have been decreasing.     

Origin of soluble chemical species in bulk precipitation collected in Tokyo,Japan: Statistical evaluation of source materials

An iterative least-squares method with a receptor model was applied to the analytical data of the precipitation samples collected at 23 points in the suburban area of Tokyo, and the number and composition of the source materials were determined. Thirty-nine monthly bulk precipitation samples were collected in the spring and summer of 1987 from the hilly and mountainous area of Tokyo and analyzed for Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, Br⁻, NO₃⁻ and SO₄²⁻ by atomic absorption spectrometry and ion chromatography. The pH of the samples was also measured. A multivariate ion balance approach (Tsurumi, 1982, Anal. Chim. Acta138, 177–182) showed that the solutes in the precipitation were derived from just three major sources; sea salt, acid substance (a mixture of 53% HNO₃, 39% H₂SO₄ and 8% HCl in equivalent) and CaSO₄. The contributions of each source to the precipitation were calculated for every sampling site. Variations of the contributions with the distance from the coast were also discussed.     

Spatial and temporal patterns in summertime sulfate aerosol acidity and neutralization within a metropolitan area

A study of sulfate aerosol acidity in Metropolitan Toronto was conducted during the summer of 1986. Fine-fraction aerosol (<2.5-μm) were collected using Teflon membrane filters and analyzed for major ionic species (H⁺, NH⁺₄, NO⁻₃, SO²⁻₄). Samples were collected for 6 weeks at three study sites: one in the Center City and the others 13 km (WNW) and 20 km (NE) away. There were very strong correlations among the three sites with respect to measured aerosol species (r² > 0.9 for 24-h data). However, spatial variations in the magnitude of aerosol acidity were observed during sulfate episodes. For example, the peak concentrations for all sites occurred on 25–26 July 1986. While the 24-h data for sulfate were quite uniform at the three sites (34, 34 and 35 μg m⁻³), H⁺ concentrations were 9.4, 8.3 and 6.0 μg m⁻³ (as H₂SO₄) for the NE, WNW and Center City sites, respectively. For most of the summertime episodes, the downtown area also had lower aerosol acidity compared to the two sites in suburban areas.