Chemical composition of snowfall in the high Arctic: 1990–1994

From 1990 to 1994 at Alert, Nunavut, Canada, weekly snow samples were collected under low wind conditions to avoid contamination by blowing snow. They were analysed for major ions, Br⁻, and the organic ions methylsulphonate, formate, acetate and propionate. In the Arctic, where annual precipitation is low and blowing snow is common, these observations are unique. On an equivalent weight basis, acids and sea salt in snowfall are mixed approximately equally from December to January but from March to May acids dominate. The acidity of snowfall increases progressively throughout the winter to a May peak of ∼16 μeq l⁻¹. SO₄²⁻, Br⁻, and the organic acids acetate, and propionate peak in snowfall after polar sunrise indicate the influence of enhanced photochemical reactions. The greater enrichment of halides relative to sea salt Na⁺ in snow compared to aerosols indicates that gaseous uptake by snowflakes is important in the removal of these substances from the atmosphere and their deposition on to the Earth's surface. There is a marked difference between the seasonal variation of enrichment of Cl⁻ and Br⁻ in snow. The latter show a marked increase after polar sunrise while the former does not. These results provide valuable baseline information on the ionic content of fresh snowfall to be used in understanding the results of snowpack chemistry and post-depositional process studies conducted in the high Arctic.     

Bacterial utilization of formic and acetic acid in rainwater

Rain samples were collected aseptically, during 1983 and 1984, in Charlottesville, Virginia to determine the ability of bacteria in precipitation to utilize formate and acetate. The total number of bacteria, as counted by Acridine Orange Direct Counts, was one to two orders of magnitude greater from April to September (10⁵ cells ml⁻¹) than during the rest of the year (10³−10⁴ cells ml⁻¹). Formate and acetate concentrations ranged between 6–23 and 3–9 μM, respectively and were higher from June to September. Heterotrophic uptake on the day of collection was not different from the controls, but after incubation at room temperature for a minimum of three days, the turnover rate constants were 0.14 and 0.17 h⁻¹ for formate and acetate, respectively. Total bacterial counts increased an order of magnitude during that interval. These turnover rate constants were used to calculate losses of 44 and 24 μmoll⁻¹day⁻¹ of formic and acetic acid, respectively. Turnover times were 1.5 and 34 days for formate and acetate, respectively. This study demonstrated that there are viable microorganisms in the atmosphere capable of utilizing formate and acetate for growth.     

Formate,acetate and methanesulfonate measurements in antarctic ice: Some geochemical implications

Serious contamination problems are encountered when measuring organic acids in polar ice. Using an involved experimental protocol, methanesulfonate, formate and acetate have been investigated in ice core sections from Antarctica. With CH₃SO₃⁻ concentrations of a few ppb, HCOO⁻at a few tenths of ppb and CH₃COO⁻ around our detection limit, the organic acids represent only a small percentage of the total acidity in Antarctic ice.Analysis of the various possible sources indicates that methane is probably the major atmospheric precursor (via formaldehyde) of formate present in the ice.The significant presence of CH₃SO₃⁻ in Antarctic ice confirms the preponderant role played by marine biogenic emissions in the Antarctic sulfate budget. The CH₃SO₃⁻ ratio with respect to non-sea-salt sulfate is higher in Antarctic precipitation than in marine aerosol. Finally, CH₃SO₃⁻ in polar ice is suggested to be a more suitable parameter than excess sulfate for the study of marine biogenic emissions in the past.     

Chemical composition of precipitation at Marion Island (sub-Antarctic)

Over a 1-year period 16.40g Cl⁻m⁻², 10.35 g Na m⁻², 2.11 g SO₄-S m⁻², 1.24g Mg m⁻², 0.39 g K m⁻², 0.37 g Ca m⁻² and 0.21 g inorganic N m⁻² were deposited in precipitation 450 m inland on the eastern coastal plain of sub-Antarctic Marion Island (46°54′S, 37°45′E). Dissolved PO₄-P and organic forms of N were not detected in the precipitation samples. Concentrations of Cl⁻, Na, Mg, Ca and K, as well as the total ionic concentration in the precipitation samples were significantly negatively correlated with the amount of precipitation. The ionic concentration order (Cl > Na > SO₄-S > Mg > K ≈ Ca) in the precipitation was very similar to that in the surrounding ocean. It is likely that most of the inorganic N found in the precipitation originated in penguin rookeries on the nearby shore zone. A comparison is made between precipitation inputs of nutrients at the island and those at other subpolar sites in the S and N Hemispheres.     

Gran's titrations: Inherent errors in measuring the acidity of precipitation

Gran's titrations are commonly used to differentiate strong and weak acidity in precipitation. However, in the course of such titrations, dissociation of the weak organic acids found in precipitation causes overestimates of both strong and free acidity. In addition, the reaction of NH₄⁺ with OH⁻ in the alkaline range of titrations causes overestimates of total acidity. Because of these effects, Gran's technique and related modifications have limited usefulness in characterizing the acidity of precipitation.     

Chemometric analysis of rainwater and throughfall at several sites in Poland

Precipitation and throughfall samples were collected over a period of 4 years (1 January 1996–31 December 1999) at three different sites in Poland: one on moraine hills, one in the lowlands and one in a mountainous region. The aim of this project was to study the chemical composition of the samples, ionic correlations and fluctuations of selected variables with time in relation to geographical location, type of tree cover and climatic conditions. The samples were characterized by determining the values of pH, electrolytic conductivity and concentrations levels of SO₄²⁻, NO₃⁻, Cl⁻, Ca²⁺, K⁺, Na⁺ and Mg²⁺. Statistical analysis revealed significant differences between the results obtained for different sampling site locations and characteristics (region of Poland, open area vs. throughfall) in four cases. The results obtained for precipitation samples were similar to those for throughfall samples only for acidic anions (SO₄²⁻ and Cl⁻). For open areas, pH fluctuations were observed in 12-month cycles. Differences between the concentration levels of ions in the samples from the three sites could be explained by different amounts of precipitation at these sites. Concentrations of ions in precipitation and throughfall samples followed similar trends, the concentration levels being dependent on the kind of trees in the area, their age, and acidity of the precipitation. Significant differences were found for the concentration factors of the individual ions in throughfall between the sampling sites. Ionic correlations were examined to determine which salts contributed to the observed ion levels.     

Chemical differences between event and weekly precipitation samples in northeastern Illinois

We examine the chemical differences between event and weekly samples of precipitation collected in northeastern Illinois from April 1980 to March 1982. Analyses were conducted for H⁺, Ca²⁺, Mg²⁺, NH₄⁺, SO₄²⁻ and NO₃⁻ concentrations as well as for pH and conductivity. In addition, the 1980–1981 samples, were titrated to determine the total, strong and weak acid concentrations. Although seasonal and annual precipitation amounts were different for the two years, the general pattern of event and weekly sample ion concentrations were similar. Weekly samples had significantly less [NH₄⁺] and higher laboratory pH in all seasons and more [SO₄²⁻] in every season but summer. Weekly samples had significantly more [Ca²⁻] and [Mg²⁺] during seasons with little precipitation. Event and weekly [NO₃⁻] were never significantly different. The weekly samples had more total acidity in the spring but less in the summer. The observed differences may be attributed to chemical degradation of the weekly samples while waiting collection and during shipment between the field and the laboratory.     

Monsoon rain chemistry and source apportionment using receptor modeling in and around National Capital Region (NCR) of Delhi,India

Studies on monsoon precipitation chemistry were carried out to understand the nature of rainwater and sources of pollution at eight different locations in and around the National Capital Region (NCR) of Delhi during southwest monsoon in the years 2003–2005. These sites were Bulandshahr (BUL), Garhmuktesar (GAR), Muradnagar (MUR), Sardhana (SAR), Panipat (PAN), Charkhi Dadri (CHA), Hodal (HOD) and Bahror (BAH). The rainwater samples, collected at these locations, were analyzed for major anions, cations and pH. The data were assessed for its quality. In general, the order of concentrations of major ions was observed to be: Ca²⁺>SO₄²⁻>HCO₃⁻>NH₄⁺>Cl⁻>NO₃⁻>Na⁺>Mg²⁺>K⁺>F⁻. The average pH of rainwater at these stations was observed to be 6.39, ranging from 5.77 to 6.62, indicating alkaline nature. However, a few rain events, 31% at Panipat, 12% at Muradnagar and 29% at Sardhana, were observed to be acidic (pH<5.6). Acidity observed at Panipat and Muradnagar is attributed to industrial influence but at Sardhana to weak organic acids contributed by surrounding vegetation. No definite trends are found for most of the components at all the sites. However, concentrations of Cl⁻ at Bulandshahr; NO₃⁻ at Muradnagar and Hodal; F⁻ at Panipat and Bahror; Na⁺ at Bulandshahr; K⁺ at Bahror and Bulandshahr; Ca²⁺ at Bulandshahr, Muradnagar, Charkhi Dadri and Sardhana; Mg²⁺ at Panipat, Bahror, Bulandshahr, Hodal and Sardhana have increased from 2003 to 2005. For source identification, principal component analysis (PCA) was made, which showed that in general, at all the sites; suspended soil–dust and sea salts which are natural sources, were identified as the most dominating. Sources like agriculture including cattle, brick kilns and industries were reflected in third or fourth PC indicating moderate influence of anthropogenic activities in this region.     

Ionic composition of precipitation at the Central Anatolia (Turkey)

Concentrations of major ions, SO₄²⁻, NO₃⁻, Cl⁻, H⁺, Ca²⁺, K⁺, Mg²⁺, Ca²⁺ and conductivity were measured in approximately 300 daily, wet-only rain samples collected at a permanent rural station between 1993 and 1998. Concentrations of anthropogenic ions NH₄⁺, SO₄²⁻ and NO₃⁻ were among the highest values reported in whole EMEP network, suggesting that the Anatolian plateau is under strong influence of distant emission sources. Although transport of pollutants have significant influence on the chemical composition of precipitation, average pH of the rainwater is 6.2 due to extensive neutralization of acidity. Approximately 95% of the acidity in collected samples is neutralized, particularly in summer season. The neutralizing agents are primarily CaCO₃ and NH₃. Concentrations of crustal ions are higher in summer season due to enhanced resuspension of soil particles from dry surface soil. Concentrations of anthropogenic ions SO₄²⁻ and NO₃⁻ do not change significantly between summer and winter due to higher intensity of rains in summer season. Although concentrations of ions measured in this study is among the highest reported in EMEP network, wet deposition fluxes are low compared to flux values reported for similar sites in Europe, due to low annual precipitation in the Anatolia. Wet deposition fluxes of all measured parameters are highly episodic. Source regions affecting chemical composition precipitation in the Central Anatolia is investigated using trajectory statistics.     

Spatial and historical trends in acidic deposition: A graphical intersite comparison

Precipitation chemistry from different regions of the Continental United States is characterized in terms of a graph of annual mean μ (+) vs μ(−), where μ (+) = Ca²⁺ +Mg⁺² + NH⁺₄ + K⁺ and Na⁺,and σ (−) = SO²⁻₄ + NO ⁻₃ + Cl⁻; concentrations are given in μeq. ℓ⁻¹. Sites receiving acid precipitation (pH < 4.5) tend to lie below a slope of 0.5 on such a graph, whereas sites that receive a (H⁺) < 31.6 μeq. ℓ⁻¹ (i.e pH > 4.5) tend to cluster near a line of slope one. Four regions. North Central (Minnesota, Wisconsin), Midwest (Illinois, Ohio), East Central (North Carolina, Virginia), and North East (Pennsylvania, New York, Vermont, New Hampshire, Maine) are presented as areas in terms of minimum and maximum μ (+) and μ (−) values. Seasonal variations of μ (+) and σ (−) tend to occur along lines of constant slope within these regions. The results from the last decade have been compared with the few measurements from the 1950s. Although one possible interpretation from this comparison is that σ(−) has increased in one or more of the regions considered, this view is tempered by the inherent difficulty in comparing single sites with regions.     

Influence of air mass trajectories on the chemical composition of precipitation in India

Chemical composition of precipitation was measured with wet-only samplers at a rural site at Bhubaneswar in eastern India during 1997–1998. All rain events were compared with trajectories and precipitation fields from the ECMWF. The pH and ionic concentrations were found to vary systematically with the origin of air and the amount of rainfall along the trajectory. A seasonal cycle for pH was found with a monthly median pH below 5.0 during October–December. The highest monthly median concentration of Ca²⁺ was found in May with 20 μmol l⁻¹ and for SO₄²⁻ in January with 52 μmol l⁻¹. Samples with trajectories within 400 km from Bhubaneswar during the last 5 days were found to have a median pH slightly below 5.0 as an average. These samples also had the highest concentration for all measured ions, indicating large pollution sources within the region. Samples with continental origin showed a decrease of ∼70% in concentration if there had been rain during >50% of the last 5 days compared to rain during <50% of the last 5 days. High concentrations of Na⁺ and Cl⁻ were also found in continental samples. Resuspension of previously deposited sea salt is believed to be the reason. The data were compared with data from three other sites in western India and higher concentrations of almost all ions (NH₄⁺ being the exception) compared to Bhubaneswar were found at the west coast in monsoon samples.     

Oxidation of SO2 in rainwater and its role in acid rain chemistry

A limited survey of rainwater composition covering 80 precipitation events was carried out to establish the levels of soluble metal ions which may influence the oxidation rate of SO₂ in the aqueous phase. For 40 of the samples sodium sulphite was added at low concentrations and the rate of oxidation of S(IV) to S(VI) established. The first order rate constant k_s(IV) was found to vary over three orders of magnitude, from 10⁻⁵ to 10⁻² s⁻¹. pH and iron concentrations were found to be the most important factors affecting the rate. There was poor correlation between the rate of oxidation and the manganese, copper and zinc concentrations. The absolute values of the rate constants are lower than those used in recent modelling studies of atmospheric droplets and the importance of iron relative to manganese also differs from earlier studies.     

Distribution of ions of marine origin in Galicia (NW Spain) as a function of distance from the sea

In order to know how far marine salts can be transported inland, bulk deposition was collected periodically at 9 sites located at increasing distances from the Atlantic coast in Galicia (NW Spain) and water samples taken from 16 streams, along a similar transect, were also analysed.In bulk deposition samples Cl⁻ and Na⁺ were the ions that presented maximum concentrations especially until 57 km from the sea. Chloride appeared as the best marker of marine influence in the studied area, whereas Na⁺ showed variations attributable to other sources. On the other hand, Ca²⁺ and SO₄²⁻ were more related to non-marine sources. From a factorial analysis of ion concentrations and deposition volumes, the ions with dominant marine origin appeared to be associated to precipitation.Ions analysed in stream waters after heavy rain events showed similar trends than those in bulk deposition, especially in the case of Cl⁻. Therefore, this methodological approach can be very useful to determine marine influence as it implies a great simplification in sampling.     

Sampling and chemical analysis of ice crystals as a function of size

Size-classified ice crystal samples were collected during the Spring of 1998, at the Jungfraujoch High-Alpine Research Station (3454 m), located in Switzerland. A procedure modified from the Guttalgor method, originally developed for size-selective sampling of raindrops by Bächmann et al. (Atmos. Environ. 26A (1992) 1795) was used to sample ice crystals during precipitation events. The size-classified ice crystal samples were analyzed using ion chromatography to determine the concentrations of Na⁺, NH₄⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃⁻, and SO₄²⁻ in each size class. For ions associated with coarse mode aerosol, Na⁺, K⁺, Ca²⁺, Mg²⁺, and Cl⁻, concentration increased with decreasing ice crystal size, suggesting scavenging by nucleation. For the remaining ions, mixed behavior was observed suggesting a combination of gas phase scavenging and scavenging via riming.     

Chemical characteristics of precipitation at metropolitan Newark in the US East Coast

To investigate the chemical characteristics of precipitation in the polluted coastal atmosphere, a total of 46 event-based precipitation samples were collected using a wet-only automatic precipitation collector from September 2006 to October 2007 at metropolitan Newark, New Jersey in the US East Coast. Samples were analyzed by ion chromatography for the concentrations of major inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺) and organic acid species (CH₃COO⁻, HCOO⁻, CH₂(COO)₂²⁻, C₂O₄²⁻). Selected trace metals (Sb, Pb, Al, V, Fe, Cr, Co, Ni, Cu, Zn, Cd) in samples were determined by ICPMS. Mass concentration results show that SO₄²⁻ was the most dominant anion accounting for 51% of the total anions, controlling the acidity of the precipitation. NH₄⁺ accounted for 48.6% of the total cations, dominating the precipitation neutralization. CH₃COO⁻ and HCOO⁻ were the two dominant water-soluble organic acid species, accounting for 42% and 40% of the total organic acids analyzed, respectively. Al, Zn and Fe were the three major trace metals in precipitation, accounting for 34%, 27%, and 25% of the total mass of metals analyzed. The pH values in precipitation ranged from 4.4 to 4.9, indicating an acidic nature. Enrichment Factor (EF) Analysis showed that Na⁺, Cl⁻, Mg²⁺ and K⁺ in the precipitation were primarily of marine origin, while most of the Fe, Co and Al were from crust sources. Pb, V, Cr, Ni were moderately enriched with EFs ranging 43–410, while Zn, Sb, Cu, Cd and F⁻ were highly enriched with EFs > 700, indicating significant anthropogenic influences. Factor analysis suggests 6 major sources contributing to the observed composition of precipitation at this location: (1) nitrogen-enriched soil, (2) secondary pollution processes, (3) marine sources, (4) incinerations, (5) oil combustions, and (6) malonate–vanadium enriched sources. To further explore the source–precipitation event relationships and seasonality, cluster analysis was performed for all precipitation events. Results show that about half of the precipitation events were characterized by mixed sources. Significant influences of nitrogen-enriched soil and marine sources were associated with precipitation events in spring and autumn, while secondary pollution processes, incineration and oil combustion contributed greatly in summer.     

Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley,RSA)

In this study aerosol samples from the South African savanna were analyzed for their polar organic constituents. Samples were collected with a front/back-up filter tandem system of quartz fiber filters (dual filter strategy). In all samples (n=15) dicarboxylic acids and a variety of phthalates, aldehydes and monocarboxylic acids were observed. Oxalic acid was the dominating compound with an average amount of 79.2 ng m⁻³ on the front filter and 11.3 ng m⁻³ on the back-up filter. The presence of significant concentrations of dicarboxylic acids on the back-up filter was rather unexpected. There are two possible sources to explain the presence of individual compounds on the back-up filter – particle penetration through the front filter or adsorption of compound parts from the gas phase. Interpretation of the data indicates that the dicarboxylic acid concentrations on the back-up filters appear to be caused by the adsorption of gaseous organic species. Dicarboxylic acids semivolatilic behavior is evident with this results. This conclusion refutes the commonly held view that dicarboxylic acids in the atmosphere were associated with the aerosol phase only. Additionally, it was found that the distribution of dicarboxylic acids between the gas and particle phase in the atmosphere is not only dependent on their vapor pressures. The actual gas phase concentration appears to be more determined by the chemical properties of the particles than by pure physical influences. Surprisingly, malonic acid exhibits an anomaly, as it does not show a semivolatile tendency.     

Determination of total organic chlorine and bromine in water samples by adsorption onto activated carbon and neutron activation analysis

A method was developed for the analysis of total organic chlorine and bromine compounds (TOCl, TOBr) in water samples. The method is based on the adsorption of organic compounds on specially prepared activated carbon. Neutron activation analysis (neutron flux 4·10¹² n cm⁻² s⁻¹) was used for the quantitative determination of chlorine and bromine.The factors investigated were the adsorption of organic chlorine and bromine compounds on activated carbon, the effect of pH on the adsorption, the removal of chlorine ions from activated carbon by nitrate washing, the amount of activated carbon required, the adsorption time, the potential number of successive adsorptions and the preservation of samples.The detection limits for TOC1 and TOBr were 5 and 0.5 μg 1⁻¹, respectively, when the sample size was 100 ml.     

Altitude-dependent wet,dry and occult nitrogen deposition in an Alpine Region

From November 1995 to October 1996 and from October 1997 to September 1998, samples of wet precipitation, cloud water, as well as of reactive gases and particulate matter, were collected at three elevational levels (920 m, 1280 m and 1758 m a.s.l.) in Achenkirch, Austria. The samples were analysed for ammonium and nitrate in wet precipitation and in cloud water, for ammonia, nitric acid and nitrogen dioxide in the gas phase and for particulate ammonium and particulate nitrate in aerosol. Total nitrogen deposition was calculated combining measured concentrations in wet, dry and occult depositions with the corresponding deposition fluxes. Two multilayer deposition models were used for the calculation of dry and occult deposition. The total nitrogen input in 1995/96 was estimated to be 29 kg N ha⁻¹a⁻¹ at the Christlumkopf station (1758 m), 20 kg N ha⁻¹a⁻¹ at the Christlumalm station (1280 m) and 28 kg N ha⁻¹a⁻¹ at the Talboden station (930 m). Respective data for the 1997/98 observation period were 31 kg N ha⁻¹a⁻¹ at the Christlumkopf station (1758 m) and 18 kg N ha⁻¹a⁻¹ at the Mühleggerköpfl station (920 m). Critical Loads of nitrogen for coniferous forests were exceeded significantly near-source regions represented by areas of intense agricultural use and at high elevation sites.

     

Anthropogenic inputs of boron into urban atmosphere: Evidence from boron isotopes of precipitations in Guiyang City,China

Boron (B) concentrations and isotopic compositions were measured in the precipitations of Guiyang, China for one year. Most precipitation samples have boron concentrations of from 2.1 to 4.8 ng ml^?1, and δ¹¹B values of from +2.0‰ to +30.0‰. Boron concentrations and δ¹¹B values of heavy rain samples are generally higher than those of light rain and snow samples. Anthropogenic inputs provided most of the SO₄^2? and NO₃^?, which were predominant ions in the precipitation. The major cation Ca²⁺ in the precipitation was mainly originated from local dust.The total boron in precipitation from Guiyang is explained by the mixing model of three boron sources. Assuming a δ¹¹B value of +45‰ for the seawater component, contributions of marine source, organic matter and biomass combustion, and coal combustion were estimated to be 32%, 49%, and 19%, respectively to the total boron in Guiyang precipitations. The coal combustion and biomass (and/or organic matter) combustion showed different contributions of boron to the rainwaters in different seasons, the former in cold season while the latter in summer season had a more marked influence on the chemical and isotopic composition of the rainwater. The largest contribution of seawater-originated boron was observed for the heavy rain samples, which was up to 68%. This study indicates that the atmospheric environment of Guiyang city was strongly influenced by human activities, and boron isotopic composition is of great sensitivity to anthropogenic sources and can be a powerful technique to trace various sources of atmospheric emissions and even their origins.     

Wet and dry deposition monitoring in Southeastern Michigan

Wet and dry deposition as collected by a bucket were measured at two sites in southeastern Michigan for two years. The precipitation had an average pH of 4.27 and a SO²⁻₄ to NO⁻₃ ratio of 2.0. Particulate dry deposition velocities of 0.6 cm s⁻¹ for SO²⁻₄ and NO⁻₃ and > 2 cm s⁻¹ for Cl⁻, Ca²⁺, Mg²⁺,Na⁺ and K⁺ were calculated. The ambient particle composition, dry bucket collection and wet deposition were compared at two sites, one urban and the other rural. Higher ambient particle concentrations and dry deposition rates were measured at the urban site than the rural site, indicating the influence of local emissions. However, local emissions had no effect on the wet deposition concentrations. The influence of more distant source regions was examined by separating the precipitation events by wind direction. The events from the south and east had the highest SO²⁻₄ to NO⁻₃ ratios, which corresponded to the areas with the highest sulfur emissions. NO⁻₃ showed no directional dependence.Wet deposition was examined for the effect of storm type and seasonal trends. Contrary to a recent study on Long Island, we found higher concentrations of H⁺, SO²⁻₄ and NH⁺₄ in winter rain compared to snow. The wet deposition concentrations of H⁺, SO²⁻₄, and NH⁺₄ were highest in the summer, while only Na⁺ and Cl⁻ concentrations were highest in the winter, presumably due to winter road salting. The total deposition of acidic ions was highest in the summer and lowest in the winter, due both to lower concentrations and lower precipitation volumes in the winter. The dry deposition as collected by a bucket accounted for 1 % of total H⁺ deposition, 21 % of SO²⁻₄ deposition, 27% of NO⁻₃ deposition, 50% of Cl⁻ deposition and 61 % of Ca²⁺ deposition.