Sampling and physico-chemical analysis of precipitation: a review

Wet deposition is one of two processes governing the transfer of beneficial and toxic chemicals from the atmosphere on to surfaces. Since the early 1970s, numerous investigators have sampled and analyzed precipitation for their chemical constituents, in the context of "acidic rain" and related atmospheric processes. Since then, significant advances have been made in our understanding of how to sample rain, cloud and fog water to preserve their physico-chemical integrity prior to analyses. Since the 1970s large-scale precipitation sampling networks have been in operation to broadly address regional and multi-regional issues. However, in examining the results from such efforts at a site-specific level, concerns have been raised about the accuracy and precision of the information gathered. There is mounting evidence to demonstrate the instability of precipitation samples (e.g. with N species) that have been subjected to prolonged ambient or field conditions. At the present time precipitation sampling procedures allow unrefrigerated or refrigerated collection of wet deposition from individual events, sequential fractions within events, in situ continuous chemical analyses in the field and even sampling of single or individual rain, cloud and fog droplets. Similarly analytical procedures of precipitation composition have advanced from time-consuming methods to rapid and simultaneous analyses of major anions and cations, from bulk samples to single droplets. For example, analytical techniques have evolved from colorimetry to ion chromatography to capillary electrophoresis. Overall, these advances allow a better understanding of heterogeneous reactions and atmospheric pollutant scavenging processes by precipitation. In addition, from an environmental perspective, these advances allow better quantification of semi-labile (e.g. NH4+, frequently its deposition values are underestimated) or labile species [e.g. S (IV)] in precipitation and measurements of toxic chemicals such as Hg and PCBs (polychlorinated biphenyls). Similarly, methods now exist for source-receptor studies, using for example, the characterization of reduced elemental states and/or the use of stable isotopes in precipitation as tracers. Future studies on the relationship between atmospheric deposition and environmental impacts must exploit these advances. This review provides a comprehensive and comparative treatment of the state of the art sampling methods of precipitation and its physico-chemical analysis.     

Rain and throughfall chemistry in a Norway spruce forest in the Western Prealps

From January 1987 to December 1989 precipitation was collected in an open field in a forested area of the Western Prealps. The site faces the intensely industrialized area of the Po Valley. In a Norway spruce plantation, next to the open field sampler, throughfall was collected from January 1987 to August 1989 for a period of 32 months. In the common sampling period median pH values of the open field precipitation and throughfall were 4.28 and 4.19 respectively. Open field precipitation has yearly deposition rates of acidity, Ca, S, and N of 0.81, 9.82, 24.83 and 32.81 kg/ha(-1) respectively. The throughfall showed significant increases in the deposition rates for Ca, Mg, K, N and S, due to abundant dry deposition and, probably, to nutrient leaching contributed by the canopies of the spruce. On the basis of available data, an initial approach to atmosphere-canopy interaction was made.     

Indications for changing deposition patterns in central Europe

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

Chemistry of fog waters in California's Central Valley—Part 3: concentrations and speciation of organic and inorganic nitrogen

Although organic nitrogen (ON) has been found to be a ubiquitous and significant component in wet and dry deposition, almost nothing is known about its concentration or composition in fog waters. To address this gap, we have investigated the concentration and composition of ON in fog waters collected in Davis, in California's Central Valley. Significant quantities of dissolved organic nitrogen (DON) were found in these samples, with a median concentration of 303 μM N (range=120–1630 μM N). DON typically represented approximately 16% of the total dissolved nitrogen (inorganic+organic) in Davis fog waters. The median concentration of nitrogen in free amino acids and alkyl amines was 16 μM N (range=3.8–120 μM N), which accounted for 3.4% of the DON in Davis fogs. Thus, although the absolute concentrations of free amino compounds were significant, they were only a minor component of the DON pool. Combined amino nitrogen (e.g., proteins and peptides) was present at higher concentrations and accounted for 6.1–29% (median=16%) of DON. Overall, free and combined amino compounds typically accounted for a median value of 22% of DON in the fog waters.The high concentrations of DON found, and the fact that amino and other N-containing organic compounds can serve as nitrogen sources for microorganisms and plants, indicate that atmospheric ON compounds likely play an important role in nitrogen cycling in the Central Valley. In addition, due to the basicity of some N functional groups, ON compounds likely contribute to the previously observed acid buffering capacity of Central Valley fog waters. Finally, a comparison of fog waters with fine particles (PM_2.5) collected from the same site during the same period of time indicated that the median concentrations (mol N m⁻³-air) of total water-soluble ON, free amino nitrogen and total amino nitrogen were very similar in the fog water and PM_2.5. Given the high water solubility of many organic N compounds, this result suggests that ON might contribute to the hygroscopic properties of atmospheric particles.     

Composition of wet and bulk deposition in Erzurum, Turkey

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

Chemical composition of fogwater in an urban area: Strasbourg (France)

To investigate the acidity and to identify the predominant compounds, this work presents the chemical analysis of 18 fogwater samples collected during the year 1991 in Strasbourg, in the east of France. For each fog event, two droplet size categories (2-6 microm and 5-8 microm) have been separately collected and 16 ionic components have been analysed. These two fraction sizes were chosen because they correspond approximately to the size range that can penetrate the human lung and they may have possible health effects. The dominant species were NH4+, NO3-, SO4(2-) and Cl-, with a maximum level of 12,640, 17,270, 21,620 and 13,540 microeq litre(-1), respectively. For most of the fog events the highest concentrations of all analysed species were observed in the 2-6 microm droplets. pH values ranged between 2.79 and 5.70 and the fogwater acidity was governed by three strong acids, H2SO4, HNO3 and HCl and was partially neutralised by NH3 and probably by the presence of CaCO3 in the 'loess', which is the major constituent of soils in the upper Rhine valley. In other respects the acetate/formate ratio (methanoate/ethanoate), generally lower than 1, indicates an important pollution due to automobile exhaust, although the Pb concentrations are moderate due to the general use of unleaded gasoline in France since 1989.     

Foliar and ground deposits of fenitrothion following aerial application over a plantation forest

Abstract

Spray deposits were measured on spruce foliage at tree canopy level and on glass plates at ground level, after aerial application of an emulsion formulation of fenitrothion at the rate of 0.21 kg AI in 1.46 L per ha over a 16 ha plot in a plantation forest. Fenitrothion deposits were quantified by gas‐liquid chromatography. A wide variation was observed in deposits on foliage and at the forest floor. Deposits were relatively higher on foliar samples collected from the upwind side of a tree canopy than those on the downwind side. Similarly, the glass plate placed under a tree on the upwind side received relatively higher deposit than the one on the downwind side. However, the glass plates placed in the adjacent forest openings collected markedly higher deposits. Results clearly indicate filtration of the spray droplets by canopy foliage. Assessment of the average deposit of fenitrothion at ground level (mean deposit from all sampling locations) indicated that ca. 19.4% of the applied material reached the forest floor. Within a sampling station, correlation was poor between foliar depsits and those on glass plates under the same trees or in nearby clearings. Analysis of fenitrothion deposits on foliage collected at 1 and 2 h after application indicated that the droplets took, more than 1 h for deposition on the tree canopy. On the other hand, deposition on the glass plates at ground level appeared to be practically complete within 1 h post‐treatment. This was attributed to the higher sedimentation velocities of the larger droplets which tend to travel faster to the floor level than the smaller droplets which float for a longer period near the tree canopy.     

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

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

Spatial and temporal variations in San Joaquin Valley fog chemistry

Fog was sampled at four locations in California’s San Joaquin Valley (SJV) during December 1995 and January 1996 as part of the 1995 Integrated Monitoring Study (IMS95). The fog sampling campaign was conducted in two phases. During the first phase, fog was sampled at three southern SJV surface locations, two urban (Fresno and Bakersfield) and one rural (near the Kern Wildlife Refuge). Both bulk samples (representative of the entire fog drop spectrum) and size-fractionated samples were collected. During the second phase, bulk fog samples were collected at three elevations on a 430 m television transmission tower in the northern SJV, representing some of the first observations of vertical variations in fog composition. SJV fog was observed to be consistently alkaline. The median pH measured in the southern SJV was 6.49, with a range from 4.97 to 7.43. Dominant species in the fog water were ammonium (median southern SJV concentration of 1008 microequivalents/l (μN)), nitrate (483 μN), sulfate (117 μN), acetate (117 μN), formate (63 μN), and formaldehyde (46 μM). Concentrations of the inorganic ions were similar in the urban and rural fogs, although occasionally much higher spikes of S(IV) and sulfate were observed in Bakersfield fog. Acetate, formaldehyde, and total organic carbon, by contrast, were observed to be present in greater concentration in the urban fogs. Bakersfield IMS95 fog concentrations of most species were similar to those measured there in the early 1980s, although concentrations of S(IV) and sulfate were much lower in IMS95 fogs. Significant differences were found between the composition of large and small fog drops, with pH differences at times exceeding one pH unit. The chemical heterogeneity present among SJV fog drop populations is likely to result in significant enhancement of aqueous sulfate production rates over those expected from average fog properties. Significant vertical variations were also observed in fog composition. Liquid water content was observed to increase strongly with elevation, while major ion aqueous concentrations in fog drops decreased with altitude. The total amount of solute contained within the fog (per unit volume of air) was observed to increase with altitude. These observations form a unique data set to be used for model evaluation and for further analysis of aerosol processing by fogs.     

Airborne pollutants along a roadside: assessment using snow analyses and moss bags

Vertical snow sampling and moss bag transplants were used to estimate the local inorganic and organic pollutant load deposited from traffic along a major highway in Finland. The pH and concentrations of Cl(-), NO(3)(-), SO(4)(2-), Ca(2+), Na(+) and polyaromatic hydrocarbons (PAHs) were determined from snow samples collected in winter at different sites along the highway. In summer, moss bags containing 20 g of fresh red-stemmed feather moss (Pleurozium schreberi) were transplanted at the same sites. The moss bag transplants remained exposed to roadside traffic for a period of one month following which the samples were collected and the PAH profiles and concentrations were analysed. The deposition of inorganic and organic pollutants from road traffic was observed up to 60 m from the road. The prevailing winds had a significant effect on the dispersion of pollutants. Snow appears to be a good collector of inorganic pollutants from the atmosphere and can be used to monitor local airborne pollution from road traffic. Snow packs can also be used as passive collectors of organic pollutant loads from road traffic on a local scale. To monitor organic PAH deposition from the road traffic, moss bags appeared to be better indicators compared to snow sampling. The efficiency of moss bags in accumulating PAH compounds indicate that vegetation may be an important sink for traffic pollution.     

Size-resolved aerosol chemical composition over the Italian Peninsula during typical summer and winter conditions

In the frame of the MIUR-AEROCLOUDS project (Study of Direct and Indirect Aerosol Effects on Climate), night-time and daytime size-segregated aerosol samples were collected concurrently at five different sites (near-city, urban, rural, marine and mountain background sites). The paper reports on the daily evolution of the main aerosol chemical characteristics as a function of particle size in different environments over the Italian Peninsula, spanning from the Po Valley to the south Tyrrhenian coast.Two 4-day intensive observation periods (IOPs) were undertaken in July 2007 and February 2008, under meteorological conditions typical of the summer and winter climate for Italy.In the summer IOP, under stable atmospheric conditions, at the low-altitude continental sites the diurnal evolution of the planetary boundary layer (PBL), induces an atmospheric dilution effect driving the particulate matter (PM) concentrations, while, at the mountain site, it determines the upward motion of polluted air masses from the Po Valley PBL in daytime.The fine fraction was dominated by ammonium salts and carbonaceous matter (water-soluble organic matter, WSOM, and water-insoluble carbonaceous matter, WINCM). High concentrations of ammonium sulphate and WSOM due to enhanced photochemical activity constituted the background aerosol composition over the whole country, whereas, ammonium nitrate and WINCM were more associated to local emissions (e.g. urban site with concentrations peaking in the finest size range due to strong local traffic-related sources of ultrafine particles).During the winter IOP in the Po Valley, the shallow PBL depths and low wind velocity, especially at night, favoured the condensation of semi-volatile species (i.e. organic matter and ammonium nitrate), causing the high fine PM concentration observed at ground level.     

Characterization of polycyclic aromatic hydrocarbons deposition in PM2.5 and cloud/fog water at Mount Taishan (China)

Polycyclic aromatic hydrocarbons (PAHs) in PM2.5 and cloud/fog water samples were collected at Mount Taishan in an autumn–winter period, and were analyzed by GS-MS. Higher molecular weight PAHs (4–6 rings) predominated in PM2.5 samples, whereas lighter PAH compounds contributed 61.71% of the total PAH concentration in cloud/fog samples. Particles tended to contain more PAHs and have a more intensive influence on the atmospheric environment on colder days. During cloud/fog events, the scavenging ratio based on PAHs associated with particles was estimated to be about 13.45%. PAHs in PM2.5 samples had a significant positive relationship with CO and SO₂, suggesting that PAHs, SO₂, and CO may originated from the same sources, such as residential coal combustion activities. Diagnostic ratio analysis and factor analysis indicated that the sources of PAHs were mainly from coal combustion during this period.     

Cooling Pond Steam Fog

This paper is responsive to needs to describe and predict the environmental effects from power plant cooling ponds. A study was made to determine atmospheric and pond surface conditions required for steam fog to occur from power plant cooling ponds, to define the dimensions of the fog, and to collect data on deposition of ice. Data, collected principally at the 4-Corners Plant over a three-year period, included water surface temperature, ambient meteorological conditions and occurrence and magnitude of steam fog and ice deposition. With strong winds, the fog extended onshore without lifting. With light winds, the fog extended some distance onshore but then lifted to form stratus. With almost calm winds, the steam fog lifted over the pond and drifted downwind as stratus. Steam fog was observed in winds to 28 mph, air-water temperature differences from 21.5° to 68°F and in atmospheric stability categories C, D, E, and F. A fog index number, Ar/(e_s — e_a)°F/mbs, was defined and used for data interpretation, where Ar is temperature of water less temperature of ambient air, e_s is the saturation vapor pressure of the ambient air and e_a is the actual vapor pressure of the ambient air. The probability of occurrence of steam fog as a function of the fog index number varied from 0.04 for an index number less than 10 to 1.00 for an index number greater than 90. From the data, if fog occurred, its extent along the ground was ≥100 feet 88% of the time, ≥500 feet 35% of the time, ≥1000 feet 18% of the time, and ≥5000 feet 12% of the time. If stratus occurred its extent above ground was ≥1 mile 91% of the time, ≥5 miles 55% of the time and ≥10 miles 36% of the time. Measurements showed that steam fog droplet sizes predominate in the 10 micron diameter size. Values of liquid water content up to 0.20 g/m³ were reported. Ice accretion data show build-up rates from 0.23 to 13 mm/hr of rime.     

Bioconcentration of metals in the moss Scleropodium purum in the area surrounding a power plant. A geotopographical predictive model for mercury

Samples of the moss Scleropodium purum collected in 1995 and 1997 were used to biomonitor the deposition of metals in the area surrounding a thermal power plant. Significantly higher levels of Cu (p<0.05), Fe (p<0.01), As and Hg (p<0.001) were found in the 1997 samples than in the 1995 samples, due to changes in atmospheric conditions. The influence on bioconcentration of the orientation of the sampling sites relative to the source of emission was studied. It was found that the increase recorded in 1997 generally occurred in the sampling sites in the south east of the study area. Analysis of the effect of distance from the source of emission revealed that the increase in metal levels in 1997 took place close to the power station (10–30 km). Finally, multiple regression analysis was used to construct a model that related different topographical variables to the concentrations of Hg in moss. The model, constructed using the data collected in both sampling periods, included the orientation of the sampling sites relative to the source of emission as well as the height of sampling sites in 1995 and the distance from the emission point in 1997. The model allowed us to determine the extent of the area affected by deposition and to establish the magnitude of deposition.     

Quality of roof runoff waters from an urban region (Gdańsk,Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gdańsk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na+, K+, NH4+, Mg2+, Ca2+, F-, Cl-, NO2-, NO3-, PO4(3-), SO4(2-) ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

Origin of polluted air masses in the Alps. An overview and first results for MONARPOP

The contribution of ZAMG to MONAROP consists of special weather forecasts to control the SOCs sampling procedure and of the analysis of the specific transport processes for SOCs, which is still in progress.In this paper, air pollutant transport into the Alps is demonstrated by examples of inorganic pollutants: Measurements of NO_x and ozone provide evidence for air pollutant transport by local wind systems (valley and slope winds), especially at low elevated sites of the Alps. In addition, trajectory analyses for the high elevation sites demonstrate the importance of large scale synoptic air pollutant transport. The effects of these transport processes with different spatial and temporal scales are governed by the physical and chemical properties of the particular pollutant.First results for the high alpine MONARPOP stations show that air masses from east Europe influence mostly Sonnblick (Austria), whereas the influence of the Po basin is strongest at Weissfluhjoch (Switzerland).     

Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream

Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.     

Internal acid buffering in San Joaquin Valley fog drops and its influence on aerosol processing

Although several chemical pathways exist for S(IV) oxidation in fogs and clouds, many are self-limiting: as sulfuric acid is produced and the drop pH declines, the rates of these pathways also decline. Some of the acid that is produced can be buffered by uptake of gaseous ammonia. Additional internal buffering can result from protonation of weak and strong bases present in solution. Acid titrations of high pH fog samples (median pH=6.49) collected in California's San Joaquin Valley reveal the presence of considerable internal acid buffering. In samples collected at a rural location, the observed internal buffering could be nearly accounted for based on concentrations of ammonia and bicarbonate present in solution. In samples collected in the cities of Fresno and Bakersfield, however, significant additional, unexplained buffering was present over a pH range extending from approximately four to seven. The additional buffering was found to be associated with dissolved compounds in the fogwater. It could not be accounted for by measured concentrations of low molecular weight (C₁–C₃) carboxylic acids, S(IV), phosphate, or nitrophenols. The amount of unexplained buffering in individual fog samples was found to correlate strongly with the sum of sample acetate and formate concentrations, suggesting that unmeasured organic species may be important contributors. Simulation of a Bakersfield fog episode with and without the additional, unexplained buffering revealed a significant impact on the fog chemistry. When the additional buffering was included, the simulated fog pH remained 0.3–0.7 pH units higher and the amount of sulfate present after the fog evaporated was increased by 50%. Including the additional buffering in the model simulation did not affect fogwater nitrate concentrations and was found to slightly decrease ammonium concentrations. The magnitude of the buffering effect on aqueous sulfate production is sensitive to the amount of ozone present to oxidize S(IV) in these high pH fogs.     

Atmospheric depositions around a heavily industrialized area in a seasonally dry tropical environment of India

Clear and through-fall bulk depositions were collected in the downwind of a highly industrialized region in Sonbhadra district of India to estimate the influence of anthropogenic activities on chemical composition of depositions. Significant spatial and temporal variations in depositions of cations and anions were observed. Depositions were higher near the thermal power stations and coal mines as compared to distantly situated site. Seasonally summer samples showed maximum cation and anion depositions followed by winter and minimum in rainy season. The mean pH of the depositions indicates that rainfall in the area is alkaline. Among the anions, maximum deposition was recorded for SO4(2-) followed by NO3- and minimum for Cl-. Among the cations, Ca2+ deposition was maximum followed by NH4+. Na+, K+ and Mg2+ deposition rates showed more or less similar values. The depositions of cations and anions as well as pH were higher in through-fall than clear-fall samples. Results of the present study suggest that atmospheric depositions are strongly modified due to thermal power stations and coal mines in the area.     

Composition of wet deposition in Kaynarca,Turkey

In this work, composition of wet deposition in Kaynarca, Turkey is studied by collecting precipitation samples during more than a 2-year period. August 1993-November 1995. Concentrations of the main cations Na+, Mg2+, Ca2+, K+, NH4+ and the main anions Cl-, NO3- and SO4(2-) together with pH were studied. The average pH value at Kaynarca was near neutral, 5.59. Results indicated that SO4(2-) concentration in precipitation was very high, as was Ca2+, neutralizing the acidity. Acidic wet deposition samples were generally obtained in winter. Enrichment factors for sea and soil indicate the strong effects of sea and soil, specifically limestone on the composition of precipitation. Non-sea salt fractions of SO4(2-) were found to range from 0.955 to 0.980, showing the effect of non-sea sources, especially emissions from fossil-fuel combustion, on the pH of samples. Trajectory analysis showed that cyclones originating from northwestern, central and eastern parts of Europe have generally high sulfate and nitrate concentrations and low pH.