Characterization and source identification of respirable particulate matter in Athens,Greece

Twenty-seven samples of respirable particulate matter (RP) were collected in central Athens during the summer of 1987. The samples were analyzed for the concentration SO₄²⁻ and NO₃⁻ (collected with Teflon and nylon filters and analyzed by ion-chromatography); organic and elemental carbon (collected on quartz fiber filters and analyzed with a thermo-optical method); and 20 elements (collected on Teflon filters and analyzed by proton-induced X-ray emission spectroscopy). Simultaneously collected samples for SO₂ and HNO₃ were also evaluated (collected with annular denuders and analyzed by ion-chromatography). T The average RP concentration measured was 80.7 μg m⁻³, well above the USEPA annual standard for PM₁₀ aerosol. In addition, high levels of organic (16.9 μg m⁻³) and elemental carbon (4.2 μg m⁻³) were found. Correlations between aerosol carbon and Br, Pb, NO and NMHC (all > 0.8) confirm that gasoline and diesel powered vehicles are one of the major sources of pollution in the region. Correlations between RP and Al, Si, K, Ca and Fe also suggest that soil aerosols contribute to the high RP concentrations. Enrichment factors for the RP samples relative to the composition of soil in the Athens basin indentify major contributions from vehicles (Pb and Br) and industrial operations (S, Ti, Mn, Fe, Ni, Cu, Zn). Based on these results, a Chemical Mass Balance receptor model was applied to each of the 27 samples and the contributions to RP from soil (4.5 %), vehicles (20.3 %), steel industries (4.6. %) and cement plant emissions (3.2 %) estimated. Other major components of the RP were SO₄²⁻ (13.0 %) and organic carbon from non-vehicle and industrial sources (15.5 %).     

Heterogeneous sulfur conversion in sea-salt aerosol particles: the role of aerosol water content and size distribution

Meteorological and chemical conditions during the July 1988 Bermuda-area sampling appear to have been favorable for conversion of sulfur gases to particulate excess sulfate (XSO₄). Observed average XSO₄ and SO₄ concentrations of 11 and 2.1 nmol m⁻³, respectively, at 15 m a.s.l. in the marine boundary layer (MBL) upwind of Bermuda, indicate that conversion of SO₂ to XSO₄, over and above homogeneous conversion, may be necessary to explain the > 5.0 average molar ratio of XSO₄ to SO₂. Given an observed cloud cover of <15% over the region and the <3 nmol m⁻³ SO₃ concentrations observed by aircraft, heterogeneous conversion mechanisms, in addition to cloud conversion of SO₂, are necessary to explain the observed 11 nmol XSO₄ m⁻³.Aerosol water content, estimated as a function of particle size distribution plus consideration of SO₂ mass transfer for the observed particle size distribution, shows that SO₂ was rapidly transferred to the sea-salt aerosol particles. Assuming that aqueous-phase SO₂ reaction kinetics within the high pH sea-salt aerosol water are controlled by O₃ oxidation, and considering mass-transfer limitations, SO₂ conversion to XSO₄ in the sea-salt aerosol water occurred at rates of approximately 5% h⁻¹ under the low SO₂ concentration, Bermuda-area sampling conditions. All of the 2 nmol XSO₄ m⁻³ associated with sea-salt aerosol particles during low-wind-speed, Bermuda-area sampling can be explained by this conversion mechanism. Higher wind speed, greater aerosol water content and higher SO₂ concentration conditions over the North Atlantic are estimated to generate more than 4 nmol XSO₄ m⁻³ by heterogeneous conversion of SO₂ in sea-salt aerosol particles.     

Evaluation of absorption properties of atmospheric aerosols at solar wavelengths based on chemical characterization

The imaginary part of the complex index of refraction of atmospheric aerosols was determined by calculation based on chemical characterization. Atmospheric aerosols in Sapporo were chemically characterized, and were estimated to be mainly composed of elemental C, organics, (NH₄)₂SO₄, NH₄NO₃, sea salt and soil particles. Using the complex index of refraction of each chemical species, the volume extinction and scattering coefficients of the particles composed of the chemical species were calculated, using Mie scattering theory. The single scattering albedo of the aerosols was obtained as the ratio of the total volume scattering coefficient to the total volume extinction coefficient. The imaginary part of the complex index of refraction of the aerosols was determined by matching the calculated sigle scattering albedo for the aggregate aerosol to that calculated from the sum of the individual aerosol components. The monthly mean imaginary part of the complex index of refraction of aerosols in Sapporo ranged from 0.024 in August to 0.047 in February in 1982.The atmospheric solar heating rate was calculated by solving the equation of radiative transfer in turbid atmospheres. It was estimated that the atmospheric boundary layer in Sapporo was heated at the rate of 2.0–2.5°C day⁻¹ in February as a result of absorption of visible solar radiation by aerosols.     

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.     

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.     

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.     

Wintertime measurements of aerosol acidity and trace elements in Wuhan,a city in central China

A 2-week intensive ambient aerosol study was conducted in December 1988 in Wuhan (Hubei Province), a city of nearly 2 million located on the Yangtze River in central China (P.R.C.). This is an industrial region where soft coal burning is widespread, and emission controls for vehicles and industrial facilities are minimal. The sampling site was located in one of the civic centers where residential and commercial density is highest. An Andersen dichotomous sampler was operated with Teflon membrane filters to collect fine (d_p < 2.5 μmad) and coarse (2.5 ⩽ d_p < 10 μmad) particles for total mass and element determinations. An annular denuder system (ADS) was used to collect fine fraction aerosols for analyses of ionic species including strong acidity (H⁺).The study was conducted between 18 and 30 December, which was rainless, consistently cool (3–10°C) and overcast, but without fog or acute stagnation. Fine particulate mass (PM, as μ m⁻³) averaged 139 (range 54–207); coarse PM averaged 86 (range 29–179). Trace element concentrations were also high. Crustal elements (Si, Al, Ca and Fe) were found primarily in the coarse fraction, while elements associated with combustion (S, K, Cl, Zn and Se) were enriched in the fine fraction. The concentrations of arsenic and selenium were evidence of a large source of coal burning, while vanadium levels (associated with fuel oil use) were not especially enriched.Despite the seemingly high PM loadings, ionic concentrations were not especially high. The average composition of soluble fine aerosol species (in neq m⁻³) were SO₄²⁻: 520 (range 180–980), NO₃⁻: 225 (range 50–470), Cl⁻: 215 (range 20–640), and NH₄⁺: 760 (range 280–1660). A deficit in accountable FP components (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³. (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³Aerosol acidity was negligible during most monitoring periods, H⁺: 14 (range 0–50 neq m⁻³, equivalent to 0–2.5 μm m⁻³ as H₂SO₄). Sulfur dioxide, measured by the West-Gaeke method for part of the study, concentrations were low. Although not directly measured, the aerosol measurments suggested that gaseous HCl (from refuse incineration) and NH₃ (animal wastes) concentrations might have been high. Higher aerosol acidity might be expected if HCl sources were more prominent and not neutralized by local ammonia or other base components.     

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.     

Fogwater chemistry at Riverside,California

Fog, aerosol, and gas samples were collected during the winter of 1986 at Riverside, California. The dominant components of the aerosol were NH₄⁺, NO₃⁻, and SO₄₂₋. Gaseous NH₃ was frequently present at levels equal to or exceeding the aerosol NH₄⁺. Maximum level were 3800, 3100, 690 and 4540 neq m⁻³ for NH₄⁺, NO₃²⁻ and NH_3(g), respectively. The fogwater collected at Riverside had very high concentrations, particularly of the major aerosol components. Maximum concentrations were 26,000 29,000 and 6200 μM for NH₄⁺, NO₃⁻ and SO₄²⁻, respectively. pH values in fogwater ranged from 2.3 to 5.7. Formate and acetate concentrations as high as 1500 and 580 μM, respectively, were measured. The maximum CH₂O concentration was 380 μM. Glyoxal and methylglyoxal were found in all the samples; their maximum concentrations were 280 and 120 μM, respectively. Comparison of fogwater and aerosol concentrations indicates that scavenging of precursor aerosol by fog droplets under the conditions at Riverside is less than 100% efficient.The chemistry at Riverside is controlled by the balance between HNO₃ production from NO_x emitted throughout the Los Angeles basin and NH₃ emitted from dairy cattle feedlots just west of Riverside. The balance is controlled by local mixing. Acid fogs result at Riverside when drainage flows from the surrounding mountains isolate the site from the NH₃ source. Continued formation of HNO_3(g) in this air mass eventually depletes the residual NH_3(g). A simple box model that includes deposition, fog scavenging, and dilution is used to assess the effect of curtailing the dairy cattle feedlot operations. The calculations suggest that the resulting reduction of NH₃ levels would decrease the total NO₃⁻ in the atmosphere, but nearly all remaining NO₃⁻ would exist as HNO₃. Fogwater in the basin would be uniformly acidic.     

Transported acid aerosols measured in southern Ontario

During the period 29 June 1986–9 August 1986, a field health study assessing the acute health effects of air pollutants on children was conducted at a summer girls' camp on the northern shore of Lake Erie in SW Ontario. Continuous air pollution measurements of SO₂, O₃, NO_x, particulate sulfates, light scattering, and meteorological measurements including temperature, dew point, and wind speed and direction were made. Twelve-hour integrated samples of size fractioned particles were also obtained using dichotomous samplers and Harvard impactors equipped with an ammonia denuder for subsequent hydrogen ion determination. Particulate samples were analyzed for trace elements by X-ray fluorescence and Neutron Activation, and for organic and elemental carbon by a thermal/optical technique. The measured aerosol was periodically very acidic with observed 12-h averaged H⁺ concentrations in the range < 10–560 nmoles m⁻³. The aerosol H⁺ appeared to represent the net strong acidity after H₂SO₄ reaction with NH₃(g). Average daytime concentrations were higher than night-time for aerosol H⁺, sulfate, fine mass and ozone. Prolonged episodes of atmospheric acidity, sulfate, and ozone were associated with air masses arriving at the measurement site from the west and from the southwest over Lake Erie. Sulfate concentrations measured at the lakeshore camp were more than twice those measured at inland sites during extreme pollution episodes. The concentration gradient observed with onshore flow was potentially due to enhanced deposition near the lakeshore caused by discontinuities in the meteorological fields in this region.     

Aerosols in Santiago de Chile: A study using receptor modeling with X-ray fluorescence and single particle analysis

Between 15 January and 26 February 1987, 51 fine and coarse mode aerosol samples were collected at the Universidad de Santiago de Chile Planetarium using a dichotomous sampler. The samples were analyzed by X-ray fluorescence for up to 17 elements (Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb). Aerosol particles were individually studied by Electron Probe Microanalysis (EPMA) and Laser Microprobe Mass Analysis (LAMMA). The data set consisting of aerosol elemental concentrations and meteorological variables was subjected to Principal Factor Analysis (PFA), allowing the identification of six fine mode particle source classes (soil, industrial, sulfate particles, traffic, residual oil, wood-burnings), and five coarse mode particle source classes (soil, industrial, traffic, residual oil, sulfate particles). Both PFA solutions explained about 81 and 90% of the total variance in the data set, respectively. The regression of elemental mass concentrations on the Absolute Principal Factor Scores allowed the estimation of the contribution of the different source classes to the Santiago aerosol. Within the fine fraction, secondary SO₄²⁻ particles were responsible for about 49% of the fine mode aerosol mass concentration, while 26, 13, 6.4 and 5.6% were attributed to wood-burning/car exhausts, residual oil combustion, soil dust/metallurgical, and soil dust/wood-burning releases, respectively. The coarse fraction source apportionment was mainly dominated by soil dust, accounting for 74% of the coarse mode aerosol mass concentration. A composite of soil dust and industrial release accounted for 13%; a composite of secondary sulfates contributed with 9%; a composite of soil dust and automotive emissions, and secondary sulfates were responsible for 4 and 0.03% of the coarse aerosol mass concentration, respectively. EPMA results are in satisfactory agreement with those from the bulk analysis and allowed the identification of eight particle types in both fine and coarse mode aerosols, pertaining to different source classes, namely soil, seaspray, secondary SO₄²⁻, metallurgical emissions and biomass burning release. EPMA also evidenced that one of the most abundant particle types corresponded to marine aerosol, having an average diameter of 0.7 μm for the fine mode and 2.2 μm for the coarse mode aerosol. LAMMA results indicate that, in fact, seaspray has been transported into the city of Santiago de Chile airshed, suffering several transformations and a sulfur enrichment. This analytical technique also provided evidence of the abundance of carbon-rich particles, which were not detected by either the bulk X-ray analysis or EPMA; they are probably due to fossil-fuel combustion releases.     

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.     

The vertical distribution of aerosols and acid related compounds in air and cloudwater

Vertical profiles (surface to 5 km) of aerosol particle number concentration, NO_y′ mixing ratio, and cloudwater SO₄²⁻ and NO₃⁻ equivalent concentration were obtained in three field studies: North Bay, Ontario, during the summer of 1982 and the winter of 1983–1984, and Syracuse, New York, during the fall of 1984. The measurements from these locations and different seasons are compared. Generally, airborne concentrations are highest with air-mass back trajectories from the south and lowest with back trajectories from the north. For the southerly trajectories, median particle number concentrations (0.2–2 μm) near ground level (950 mb) vary from 1700 cm⁻³ during the summer project to 800 cm⁻³ during the winter project. At 700 mb, the south trajectory particle number concentration ranged between 60 and 170 cm⁻³. Median NO_y′ mixing ratios for southerly back trajectories were approximately 6 and 9 ppb at 950 mb and 0.4 and 0.8 ppb at 700 mb for the fall and winter projects, respectively. Comparison of particle number concentration profiles outside of cloud with cloud droplet plus interstitial aerosol particle number concentrations inside cloud indicate that cumulus clouds can transport aerosols vertically from below cloud base. In contrast, stratiform clouds have similar concentrations inside the clouds as outside at the same altitude. The vertical variations of cloudwater sulphate and nitrate concentrations and the NO₃⁻/SO₄²⁻ equivalent concentration ratio are discussed for each of the three field studies.     

Size distributions of aerosol and water-soluble ions in Nanjing during a crop residual burning event

To investigate the impact on urban air pollution by crop residual burning outside Nanjing, aerosol concentration, pollution gas concentration, mass concentration, and water-soluble ion size distribution were observed during one event of November 4-9, 2010. Results show that the size distribution of aerosol concentration is bimodal on pollution days and normal days, with peak values at 60-70 and 200-300 nm, respectively. Aerosol concentration is 10⁴ cm^-3. nm^-1 on pollution days. The peak value of spectrum distribution of aerosol concentration on pollution days is 1.5-3.3 times higher than that on a normal day. Crop residual burning has a great impact on the concentration of fine particles. Diurnal variation of aerosol concentration is trimodal on pollution days and normal days, with peak values at 03:00, 09:00 and 19:00 local standard time. The first peak is impacted by meteorological elements, while the second and third peaks are due to human activities, such as rush hour traffic. Crop residual burning has the greatest impact on SO₂ concentration, followed by NO₂, O₃ is hardly affected. The impact of crop residual burning on fine particles (< 2.1 μm) is larger than on coarse particles (> 2.1 μm), thus ion concentration in fine particles is higher than that in coarse particles. Crop residual burning leads to similar increase in all ion components, thus it has a small impact on the water-soluble ions order. Crop residual burning has a strong impact on the size distribution of K⁺, Cl^-, Na⁺, and F^- and has a weak impact on the size distributions of NH₄⁺, Ca²⁺, NO₃^- and SO₄^2-.     

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.     

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.     

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 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.     

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 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.