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.     

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.     

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⁻.     

Rainwater composition in Athens,Greece

Wet precipitation-only samplers were used to collect wet deposition at two sites in the Athens basin, Greece for the period March 1986–February 1987.Concentrations of major cations (H⁺, NH⁺₄, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and major anions (Cl⁻, NO⁻₃ and SO²⁻₄) were determined for the first time in rainwater samples in Greece. Bicarbonate concentrations were calculated. The relative importance of natural and anthropogenic sources were estimated by a chemical balance. The majority of rain collected has a neutral or alkaline character. Acidity was due to the presence of H₂SO₄ and HNO₃. The statistical analysis of the correlation between the concentration of chemical species confirm the influence of natural and anthropogenic sources. In all samples, SO²⁻₄ concentrations exceed NO⁻₃ concentrations despite the dominance of low S oil burning in the region. The wet flux of S was calculatd to be 0.34 gm⁻²a⁻¹.     

Transfer of atmospheric constituents into an alpine snow field

Simultaneous aerosol and snow sampling was performed during a field campaign at the Alpine site Weissfluhjoch Davos, Switzerland (2540 m a.s.1.) from 1 January through 30 March 1988. In addition, a snow pit was sampled on 30 March 1988. Very good agreement between the new snow and pit snow samples was found for the measured major ions as well as for the stable isotopes δ¹⁸O and δD. Thus, snow pit samples obtained at this site during the winter months yield representative deposition patterns with a conserved stratigraphy. Generally, concentrations in snow were very low, with 3.5, 8.5, 5.2 and 2.4 μeq ℓ⁻¹ for Cl⁻, NO₃⁻, SO₄²⁻, respectively. The ³⁶Cl and ¹⁰Be concentrations as well as the ¹⁰Be/³⁶Cl ratios were comparable to the ones measured at Arctic sites. With the exception of NO₃⁻, no linear relation was obtained between atmospheric and snow concentrations, showing that the concept of scavenging ratios must be used with caution when looking at single snowfall events. The following precipitation-weighted mean scavenging ratios were found: 300 for NH₄⁺, 350 for SO₄²⁻, 940 for total NO₃⁻(NO₃⁻+HNO₃), 175 for ²¹⁰Pb, and 750 for ¹⁰Be.     

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.     

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.     

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.     

Monsoon cloudwater chemistry on the Arabian Peninsula

The potentially catastrophic environmental consequences of the conflict in Iraq, Kuwait and Saudi Arabia, from mid 1990 to early 1991, have highlighted the need for background atmospheric chemistry measurements for the region. The only known cloudwater chemistry data obtained in the Arabian Peninsula are presented here. The samples were collected near the coast, in the Dhofar region of southern Oman, from 22 to 30 July 1990, immediately prior to the start of the conflict on 2 August. Analysis of the samples for pH, 10 major ion concentrations and 23 trace elements, demonstrates that the cloud water was very clean. Enrichment factor calculations showed the ions have oceanic and crusal origins, whereas trace elements such as B, V, Mn, Ni, Zn, Se, Sr, Mo and Ba have anthropogenic sources. In comparison with three mountain cloudwater sampling sites in eastern North America, the Omani site has higher pH values, higher Na⁺ and Cl⁻ concentrations, and lower SO₄²⁻ and NH₄⁺ concentrations.     

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.     

An analysis of precipitation chemistry measurements in Shimane,Japan

In order to understand the concentration and deposition levels of the major ions in Shimane, on the Japan Sea coast where precipitation chemistry data are scarce, the precipitation was collected at three sites (Matsue, Gotsu and Masuda) from April 1985 to March 1988.The mean precipitation chemistry was very close to each other except for the seasalt concentration. Masuda showed a halved seasalt contribution compared with the other sites. The volume-weighted annual pH mean at each site ranged from 4.6 to 4.9. Nitrate to SO₄⁻² equivalent ratios were in the range of 0.2 and 0.4 throughout the year. Ammonia and calcium species are interpreted to have neutralized approximately 70% of the original sulfuric and nitric acids.The annual depositions of the major ions in g m⁻²y⁻¹ were as follows: H⁺; 0.023–0.037, NH₄⁺; 0.57–0.68, Ca²⁺; 0.51–0.92, SO₄²⁻; 3.29–5.04, NO₃⁻; 1.20–1.70. These levels are of the same intensity as corresponding values of JEA network results.     

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.     

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.     

Sulphate in atmospheric particulate at five sites in Norwich (U.K.): Use of national survey archive filters

Air sample filters from a Local Authority archive have been analyzed for sulphate using XRF. This has allowed an assessment to be made of the spatial distribution of 24-h sulphate concentrations in the city of Norwich in eastern England, over a 9-month period. The overall mean sulphate concentration was 10.4 μg m⁻³, with a range of overall mean values between the sites of 7.7–12.2 μg m⁻³. This spatial variability within the city is similar to the spatial variability between cities found in another previous study. The mean SO²⁻₄/SO₂ and smoke/SO²⁻₄ ratios at the different sites are similar, but there are distinct variations in the overall mean ratios over the measurement period. There appear to be relationships between the SO²⁻₄/SO₂ ratio and temperature and humidity. The ratios are also related to wind direction, with some evidence that a proportion of the SO²⁻₄ in the urban atmosphere of Norwich originates via long-distance transport from the east.     

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.     

Influence of sea salt aerosols and long range transport on precipitation chemistry at El Verde,Puerto Rico

The chemistry of bulk precipitation was measured from November 1983 to September 1987 at El Verde in the Luquillo Experimental Forest, Puerto Rico. Wet-only precipitation was also analyzed as part of the National Atmospheric Deposition Program from 1984 to 1987. Volume-weighted mean pH was 5.14 in bulk precipitation and 5.12 in wet precipitation. Concentrations of most species were correlated negatively with weekly rainfall. Sea salt aerosols contributed most of the Na⁺, Cl⁻, Mg²⁺ and K⁺ found in wet and bulk precipitation; sulfate and calcium, however, were derived primarily from non-sea salt sources. Due to the high rainfall (3.4 m annually during the study period) and close proximity of the study site to the ocean, deposition rates of the major cations and anions were high relative to many other tropical sites. Precipitation chemistry at El Verde appears to be affected by several factors. During summer, Saharan dusts contribute a significant portion of the excess Ca²⁺, K⁺ and Mg²⁺. During winter months, cold fronts may transport SO₄²⁻ and NO₃⁻ from North America and the western part of Puerto Rico to the sampling site.     

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.     

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.     

Modeling of SO2, Pb and Cd atmospheric deposition over a one-year period

Atmospheric deposition of SO₂, and fine particles of Pb and Cd are calculated over a one-year period in a 66 km² airshed with a segment-puff model. Emission variations, hourly mixing heights and meteorological values are considered to compute monthly averages of concentrations and deposition. Dry deposition is calculated by means of deposition velocities which are season- and land use-dependent. Wet deposition is determined using a washout coefficient. To assess the simulation performance, calculated SO₂ results from the combination between the deposition velocity, the windspeed and direction and the location and type of sources. As annual averages, results for dry plus wet deposition are computed to be 0.84 mg m⁻²d⁻¹ for sulfur, 4.15 μgm⁻²d⁻¹ for lead and 0.0013 μgm⁻²d⁻¹ for cadmium. A variation factor is derived from a sensitivity analysis. This factor amounts to 2.3−2.8 for the concentrations and 2.6−3.1 for the deposition, depending on the pollutant.     

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.