Atmospheric concentrations of ammonia and ammonium at an agricultural site in the southeast United States

In this study, we present ∼1 yr (October 1998–September 1999) of 12-hour mean ammonia (NH₃), ammonium (NH₄⁺), hydrochloric acid (HCl), chloride (Cl⁻), nitrate (NO₃⁻), nitric acid (HNO₃), nitrous acid (HONO), sulfate (SO₄²⁻), and sulfur dioxide (SO₂) concentrations measured at an agricultural site in North Carolina's Coastal Plain region. Mean gas concentrations were 0.46, 1.21, 0.54, 5.55, and 4.15 μg m⁻³ for HCl, HNO₃, HONO, NH₃, and SO₂, respectively. Mean aerosol concentrations were 1.44, 1.23, 0.08, and 3.37 μg m⁻³ for NH₄⁺, NO₃⁻, Cl⁻, and SO₄²⁻, respectively. Ammonia, NH₄⁺, HNO₃, and SO₄²⁻ exhibit higher concentrations during the summer, while higher SO₂ concentrations occur during winter. A meteorology-based multivariate regression model using temperature, wind speed, and wind direction explains 76% of the variation in 12-hour mean NH₃ concentrations (n=601). Ammonia concentration increases exponentially with temperature, which explains the majority of variation (54%) in 12-hour mean NH₃ concentrations. Dependence of NH₃ concentration on wind direction suggests a local source influence. Ammonia accounts for >70% of NH_x (NH_x=NH₃+NH₄⁺) during all seasons. Ammonium nitrate and sulfate aerosol formation does not appear to be NH₃ limited. Sulfate is primarily associated ammonium sulfate, rather than bisulfate, except during the winter when the ratio of NO₃⁻–NH₄⁺ is ∼0.66. The annual average NO₃⁻–NH₄⁺ ratio is ∼0.25.     

Annual and seasonal trends in chemical composition of precipitation in Japan during 1989–1998

Annual and seasonal trends were discussed for precipitation chemistry in Japan on the basis of a nationwide monitoring network by Japan Environment Agency. For this analysis, 17 sites, selected from the 23 network sites after evaluation of data completeness for the present purpose, were grouped into four areas in terms of the sea which could characterize each area: the Pacific Ocean, the Japan Sea, the Seto Inland Sea and the East China Sea areas. Major ion concentrations at each site were subjected to least-squares multiple regression analysis, and discussion was principally focused on the area-groups. Each area showed significant (p<0.05) decreasing trends in non-sea-salt sulfate (nss-SO₄²⁻) concentrations with the annual mean change rate of −3.0% yr⁻¹, whereas no significant trends were detected for NO₃⁻ at 59% of the sites. Ammonium (NH₄⁺) showed significant increasing trends for 35%, and decreasing trends for 18% of the sites; and, the maximum change rate of 3.8% yr⁻¹ was recorded in the Pacific Ocean area. Non-sea-salt calcium (nss-Ca²⁺) concentrations significantly decreased in northern and some industrialized areas. Both the annual cycle-amplitudes and effects of precipitation amounts were significant for the four ions at almost all sites. The maximum concentrations of nss-SO₄²⁻ and -Ca²⁺ occurred from winter to spring at most sites. The seasons when the maximum concentrations of NO₃⁻ and NH₄⁺ occurred, were found to differ from area to area. Furthermore, the trends in precipitation nss-SO₄²⁻, and NO₃⁻ were qualitatively consistent with those of anthropogenic emissions of SO₂, and NO_x in Japan, respectively.     

The water-soluble ionic composition of PM2.5 in Shanghai and Beijing,China

A year-long field study to characterize the ionic species in PM2.5 was carried out in Shanghai and Beijing, China, in 1999–2000. Weekly samples of PM2.5 were collected using a special low flow rate (0.4 l min⁻¹) sampler. In Shanghai, SO₄²⁻ NO₃⁻ and NH₄⁺ were the dominant ionic species, which accounted for 46%, 18% and 17% of the total mass of ions, respectively. Local SO₂ emissions were an important source of SO₄²⁻ in PM2.5 because the SO₄²⁻ concentration was correlated with the SO₂ concentration (r=0.66). The relatively stable SO₄²⁻/SO₂ mass ratio over a large range of temperatures suggests that gas-phase oxidation of SO₂ played a minor role in the formation of SO₄²⁻. The sum of SO₄²⁻ and NO₃⁻ was highly correlated with NH₄⁺ (r=0.96), but insufficient ammonium was present to totally neutralize the aerosol. In Beijing, SO₄²⁻, NO₃⁻ and NH₄⁺ were also the dominant ionic species, constituting 44%, 25% and 16% of the total mass of water-soluble ions, respectively. Local SO₂ emissions were an important source of SO₄²⁻ in the winter since SO₄²⁻ was correlated with SO₂ (r=0.83). The low-mass SO₄²⁻/SO₂ ratio (0.27) during winter, which had low humidity, suggests that gas-phase oxidation of SO₂ was a major route of sulfate formation. In the summer, however, much higher mass ratios of SO₄²⁻/SO₂ (5.6) were observed and were ascribed to in-cloud sulfate formation. The annual average ratio of NO₃⁻/SO₄²⁻ was 0.4 and 0.6 in Shanghai and in Beijing, respectively, suggesting that stationary emissions were still a dominant source in these two cities.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

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 distribution of wet deposition of nitrogen in South Korea

A method is developed to estimate wet deposition of nitrogen in a 11×14 km (0.125°Lon.×0.125°Lat.) grid scale using the precipitation chemistry monitored data at 10 sites scattered over South Korea supplemented by the routinely available precipitation rate data at 65 sites and the estimated emissions of NO₂ and NH₃ at each precipitation monitoring site. This approach takes into account the contributions of local NO₂ and NH₃ emissions and precipitation rates on wet deposition of nitrogen. Wet deposition of nitrogen estimated by optimum regression equations for NO₃⁻ and NH₄⁺ derived from annual total monitored wet deposition and that of emissions of NO₂ and NH₃ is incorporated to normalize wet deposition of nitrogen at each precipitation rate class, which is divided into 6 classes. The optimum regression equations for the estimation of wet deposition of nitrogen at precipitation monitoring sites are developed using the normalized wet deposition of nitrogen and the precipitation rate at 10 precipitation chemistry monitoring sites. The estimated average annual total wet depositions of NO₃⁻ and NH₄⁺ are found to be 260 and 500 eq ha⁻¹ yr⁻¹ with the maximum values of 400 and 930 eq ha⁻¹ yr⁻¹, respectively. The annual mean total wet deposition of nitrogen is found to be about 760 eq ha⁻¹ yr⁻¹, of which more than 65% is contributed by wet deposition of ammonium while, the emission of NH₃ is about half of that of NO₂, suggesting the importance of NH₃ emission for wet deposition of nitrogen in South Korea.     

Study of aerosol transport through precipitation chemistry over Arabian Sea during winter and summer monsoons

Precipitation samples over the Arabian Sea collected during Arabian Sea Monsoon Experiment (ARMEX) in 2002–2003 were examined for major water soluble components and acidity of aerosols during the period of winter and summer monsoon seasons. The pH of rain water was alkaline during summer monsoon and acidic during winter monsoon. Summer monsoon precipitation showed dominance of sea-salt components (∼90%) and significant amounts of non-sea salt (nss) Ca²⁺ and SO₄²⁻. Winter monsoon precipitation samples showed higher concentration of NO₃⁻ and NH₄⁺ compared to that of summer monsoon, indicating more influence of anthropogenic sources. The rain water data is interpreted in terms of long-range transport and background pollution. In summer monsoon, air masses passing over the north African and Gulf continents which may be carrying nss components are advected towards the observational location. Also, prevailing strong southwesterly winds at surface level produced sea-salt aerosols which led to high sea-salt contribution in precipitation. While in winter monsoon, it was observed that, air masses coming from Asian region towards observational location carry more pollutants like NO₃⁻and nss SO₄²⁻ that acidify the precipitation.     

Ambient suspended particulate matters and related chemical species study in central Taiwan,Taichung during 1998–2001

Ambient suspended particulate (PM_2.5, PM_2.5–10, TSP) was collected from June 1998 to February 2001 in Taichung, central Taiwan. In addition, the related water-soluble ionic species (Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺) and metallic species (Fe, Zn, Pb, Ni) were also analyzed in this study. The results showed that the concentrations of particulate mass are higher in the traffic site (CCRT) than the other sampling sites in this study. Also, the fine particle (PM_2.5) concentration is the dominant species of the total suspended particles in Taichung, central Taiwan. The dominant species for PM_2.5 are sulfate and ammonium at all sampling sites during the period of 1998–2001. The results of diurnal variation at THUC sampling site are also discussed in this study. Overall, acidic and secondary aerosol (Cl⁻, NO₃⁻, SO₄²⁻ and NH₄⁺) is a more serious air pollutant issue in southern and central Taiwan than at several sites around the world. Therefore, ambient suspended particulate monitoring in Taichung, central Taiwan will be continuing in our following study to provide more information for the government to formulate environmental strategy.     

Seasonal variations in atmospheric SOx and NOy species in the adirondacks

This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SO_x (=SO₂+SO₄²⁻) and NO_y (=NO+NO₂ + PAN + HNO₃+NO₃⁻+ organicnitrates + HONO + 2N₂O₅ …) at Whiteface Mountain, New York. Continuous real-time measurements of SO₂ and total gaseous NO_y provided data for about 50% and 65% of the period, respectively, and 122 filter pack samples were obtained for HNO₃, SO₂ and aerosol SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺. Concentrations of SO₂ and NO_y were greatest in winter, whereas concentrations of the reaction products SO₄²⁻ and HNO₃were greatest in summer. The seasonal variation in SO₄²⁻ was considerably more pronounced than that of HNO₃and the high concentrations of SO₄²⁻ aerosol present in summer were also relatively more acidic than SO₄²⁻ aerosol in other seasons. As a result, SO₄²⁻ aerosol was the predominant acidic species present in summer, HNO₃was predominant in other seasons. Aerosol NO₃⁻ concentrations were low in all seasons and appeared unrelated to simultaneous NO_y and HNO₃concentrations. These data are consistent with seasonal variations in photochemical oxidation rates and with existing data on seasonal variations in precipitation composition. The results of this study suggest that emission reductions targeted at the summer season might be a cost-effective way to reduce deposition of S species, but would not be similarly cost-effective in reducing deposition of N species. kwAcid deposition, seasonal variation, sulfate, nitrate, nitric acid, sulfur dioxide, oxides of nitrogen, hydrogen peroxide, ozone, air pollution, Adirondack Mountains     

Chemical composition of rainwater and anthropogenic influences in the Piracicaba River Basin,Southeast Brazil

The influences of different kinds of anthropogenic activities on rainwater chemistry in a tropical area were studied during one uninterrupted year at Piracicaba River Basin (Southeast Brazil). A total of 272 rainwater samples collected continuously from August 1997 to July 1998 at four different sites were analyzed for F⁻, CH₃COO⁻, HCOO⁻, MSA, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻, PO₄³⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, DOC (dissolved organic carbon), DIC (dissolved inorganic carbon), pH and conductivity. The most abundant ion was H⁺ and rain acidity was significant at all sampling sites (average pH of 4.4–4.5). The sources of this free acidity differ among sites and appear to be correlated to the different land-uses. The composition of rainwater appeared to be controlled mostly by three sources: soil dust, sugar cane burning and industrial emissions.     

Influence of meteorological factors and polluting environment on rain chemistry and wet deposition in a rural area near Chimay,Belgium

This paper focuses on a detailed analysis of the effects of meteorological factors explaining the variability of rain composition.Inorganic composition of 113 individual rain events was measured from May 2002 to October 2005 at a rural site near Chimay, in the western part of the Belgian Ardennes. Original models were fitted for each studied ion (H⁺, Mg²⁺, Ca²⁺, K⁺, NH₄⁺, Na⁺, Cl⁻, NO₃⁻ and SO₄²⁻) to relate rain event concentration or wet deposition to the rainfall volume (R), the length of the antecedent dry period (ADP), the volume of the previous event (R_prev) as well as to the mean wind speed and the prevailing wind direction during both the dry and the rainy periods. These variables explained from 32% (H⁺) to 69% (NO₃⁻) of rain concentration variability. Concentrations decreased logarithmically with increasing R values except in case of H⁺ for which a positive effect of rain volume on rain concentration was observed. ADP affected positively rain concentrations of all ions excluding K⁺ and H⁺ for which, respectively, a nonsignificant and a negative effect of this variable was observed. Increasing R_prev strengthened the effect of the variable R on H⁺, Mg²⁺, Ca²⁺, Na⁺, NH₄⁺ and SO₄²⁻ concentrations while it softened the effect of ADP on NO₃⁻ concentrations. Wind speed and direction during dry and rainy periods explained together from 8% (K⁺) to 38% (Na⁺) of rain concentration total variability. R² coefficients of the wet deposition models ranged from 0.51 (K⁺) to 0.79 (SO₄²⁻). For all ions, wet deposition increased significantly with increasing R values while the effects of the other variables were similar to those on concentrations. Wind conditions during dry and rainy periods explained from 4% (H⁺) to 24% (Na⁺) of wet deposition total variability. On an annual scale, the total dry period duration, the total rainfall volume as well as the shape of the distributions of the length of the antecedent dry periods and of the rain event volume are important parameters that influence annual wet deposition.     

Association between ionic composition of fine and coarse aerosol soluble fraction and peak expiratory flow of asthmatic patients in São Paulo city (Brazil)

Air pollutants are associated with adverse respiratory effects mainly in susceptible groups. This study was designed to assess the impact of the ionic composition of particulate matter on asthmatic respiratory functions in São Paulo city. From May to July 2002, fine and coarse particulate matter fractions were collected and their respective chemical composition with respect to major ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, NH₄⁺, Cl⁻, NO₃⁻ and SO₄²⁻) were determined in each aqueous-extract fraction. The results showed predominant concentrations of SO₄²⁻ (48.4%), NO₃⁻ (19.6%) and NH₄⁺ (12.5%) in the fine fraction, whereas NO₃⁻ (35.3%), SO₄²⁻ (29.1%), Ca²⁺ (13.1%) and Cl⁻ (12.5%) were the predominant species in the coarse fraction. The association between the chemical components of both fractions and the daily peak expiratory flow (PEF) measurements (morning and evening) of the 33 asthmatic individuals were assessed through a linear mixed-effects model. The results showed a significant negative correlation (decrease of PEF) between morning PEF and coarse chloride (3-day moving average) and between evening PEF and coarse Na⁺ (3-day moving average), coarse Mg²⁺ (3-day moving average) and coarse NH₄⁺ (2- and 3-day moving average). A significant negative correlation has also been observed between morning and evening PEF and Mg²⁺ in the fine fraction. These results suggest that some particle chemical constituents may increase the responsiveness of airways and that coarse particles that deposit in the upper airways may be more relevant for asthmatic response and irritation. However, the results do not prove a clear causal relationship.     

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 characterization of particles in winter-night smog in Tokyo

Continuous measurement of PM₁₀, PM_2.5 and carbon (organic, elemental composition) concentrations, and samples of PM₁₀ and PM_2.5 collected on a polycarbonate membrane filter (Nuclepore^®, pore size: 0.8 μm), were carried out during a period from December 1998 to January 1999 at Shinjuku in Tokyo in order to investigate the chemical characterization of particles in winter-night smog within a large area of the Japan Kanto Plain including the Tokyo Metropolitan area. These were measured using an ambient particulate monitor (tapered element oscillating microbalance—TEOM) and a carbon particulate monitor. Elemental compositions in the filter samples of PM₁₀ and PM_2.5 were determined by means of particle-induced X-ray emission (PIXE) analysis. Ionic species (anion: F⁻, Cl⁻, NO₃⁻, SO₄²⁻ and C₂O₄²⁻; cation: Na⁺, NH₄⁺, K⁺, Ca²⁺ and Mg²⁺) in the filter samples were analyzed by ion chromatography. The temporal variation patterns of PM_2.5 were similar to those of PM₁₀ and carbon. PM_2.5 made up 90% of the PM₁₀ at a high concentration, and 70% at a low concentration. Concentrations of 22 elements in both the PM₁₀ and PM_2.5 samples were consistently determined by PIXE, and Na, Mg, Al, Si, S, Cl, K, Ca, Fe, Zn and Pb were found to be the major components. Among these S and Cl were the most dominant elements of the PM_2.5 and PM₁₀ at high concentrations. Ionic species were mainly composed of Cl⁻, NO₃⁻, SO₄²⁻ and NH₄⁺. The component proportion of carbon, the other elements (total amount of measured elements other than S and Cl) and secondary-formed particles of PM_2.5 was similar to that of PM₁₀. The major component was carbon particles at a low concentration and secondary-formed particles at a high concentration. The proportion of NH₄NO₃ and NH₄Cl plus HCl in secondary-formed particles at a high concentration, in particular, was as high as 90%.     

Chemical composition of the fine and coarse fraction of aerosols in the northeastern Mediterranean

Two-stage aerosol samples (PM_10–2.5 and PM_2.5) were collected at a coastal rural site located in the northeastern Mediterranean, between April 2001 and 2002. A total of 562 aerosol samples were analyzed for trace elements (Fe, Ti, Mn, Ca, V, Ni, Zn, Cr) and water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻ and MS⁻:methane sulfonate). PM₁₀, crustal elements, sea salt aerosols and NO₃⁻ were mainly associated with the coarse mode whereas non-sea salt (nss)SO₄²⁻, C₂O₄²⁻; MS⁻, NH₄⁺, Cr and Ni were found predominantly in the fine fraction. Concentrations of aerosol species exhibited orders of magnitude change from day to day and the aerosol chemical composition is heavily affected by dust events under the influence of airflow from North Africa. During the sampling period, 11 specific mineral dust events of duration varying from 1 day to a week have been identified and their influence on the chemical composition of aerosols has been studied in detail. Ionic balance analysis performed in the coarse and fine aerosol fractions indicated anion and cation deficiency due to CO₃²⁻ and H⁺, respectively. A relationship between nssSO₄²⁻ and NH₄⁺ denoted that sulfate particles were partially neutralized (70%) by ammonium. Excess-K/BC presented two distinct ratios for winter and summer, indicating two different sources: fossil fuel burning in winter and biomass burning in summer.     

Characterization of the major chemical species in PM2.5 in the Kaohsiung City,Taiwan

The concentrations and characteristics of the major components in ambient fine particles in the urban city of Kaohsiung, Taiwan were measured and evaluated. PM_2.5 samples were collected using a dichotomous sampler from November 1998 to April 1999 and analyzed for water-soluble ion species using ion chromatography and for carbonaceous species using an elemental analyzer. It was found that SO₄²⁻, NO₃⁻, and NH₄⁺ dominated the identifiable components, and occupied 42.2% and 90.0% of PM_2.5 mass and total dissolved ionic concentrations. Carbonaceous species (organic and elemental carbon) accounted for 20.8% of PM_2.5. The secondary aerosol formed through the NO₂/SO₂ gas-to-particle conversion was estimated based on the sulfur/nitrogen oxidation ratio (SOR/NOR), i.e., sulfate sulfur/nitrate nitrogen to total sulfur/total nitrogen. The average SOR and NOR values were 0.25 and 0.07 for PM_2.5. The high SOR and NOR values obtained in this study suggested that there existed a secondary formation of SO₄²⁻ from SO₂ along with NO₃⁻ from NO₂ in the atmosphere. The secondary organic carbon formed through the volatile organic compound gas-to-particle conversion was estimated from the minimum ratio between organic and elemental carbon obtained in this study, and was found to constitute 40.0% of the total organic carbon for PM_2.5 (6.6% of the particle mass). The results obtained in this study suggest that the formation of secondary aerosols due to conversion from gaseous precursors is significant and important in urban locations.     

Measurements of nitric acid and ammonium salts in lower Bavaria

Nitric acid and ammonium-containing particulate species were measured by the annular denuder-filter pack technique at Manndorf, a rural site in South Germany, in July 1990. The analyses of filter packs indicated that nitrate was present as ammonium salt which mostly dissociated during sampling. Moreover, due to the NH⁺₄/NO⁻₃ ratios higher than unity found in back-up filters, NH₄Cl was assumed to represent an appreciable fraction of the total particulate ammonium. Finally, the molar ratios NH⁺₄/SO²⁻₄ found on front (Teflon) filters, suggested a large predominance of (NH₄)₂SO₄ among the different forms of sulphate. The concentration levels of gaseous HNO₃ observed in the daytime were characterised by a maximum after midday, whereas particulate nitrate showed five times out of eight days an opposite trend with early afternoon minima. The total nitrate (HNO₃+NH₄NO₃) showed in turn a diurnal pattern similar to that of sulphate. These findings led to the conclusion that a significant HNO₃ production pathway involved the thermal dissociation of NH₄NO₃ rather than the reaction of NO₂ with OH radical.     

Simulation of long-range transport of acidic pollutants in East Asia during the Yellow Sand event

The atmospheric chemical process was simulated using the Carbon Bond 4 (CB-4) model, the aqueous-phase chemistry in Regional Acid Deposition Model and the thermodynamic equilibrium relation of aerosols with the emission inventories of the Emission Database for Global Atmospheric Research, the database of China and South Korea and the Mesoscale Model version 2 (MM5) meteorological fields to examine the spatial distributions of the acidic pollutant concentrations in East Asia for the case of the long-lasting Yellow Sand event in April 1998. The present models simulate quite well the observed general trend and the diurnal variation of concentrations of gaseous pollutants, especially for O₃ concentration. However, the model underestimates SO₂ and NO_x concentration but overestimates O₃ concentration largely due to uncertainty in NO_x and VOC emissions. It is found that the simulated gaseous pollutants such as SO₂, NO_x, and NH₃ are not transported far away from the source regions but show significant diurnal variations of their concentrations. However, the daily variations of the concentrations are not significant due to invariant emission rates. On the other hand, concentrations of the transformed pollutants including SO₄²⁻, NH₄⁺, and NO₃⁻ are found to have significant daily variations but little diurnal variations. The model-estimated deposition indicates that dry deposition is largely contributed by gaseous pollutants while wet deposition of pollutants is mainly contributed by the transformed pollutants.     

Transport and evolution of a winter-time Yellow sand observed in Korea

Long-range transport of mineral dust such as Yellow sand (YS) is not restricted to the springtime periods in Northeast Asia. A YS phenomenon was observed during 25–27 January 1999, which was a remarkably distinctive episode in the occurrence time and intensity that had ever observed in the wintertime in Korea. This YS event was traced to be originated from the arid region of central and eastern Asia; the Gobi desert and Loess plateau. The traveling speed of the dust storm was found to be about 70 km h⁻¹ with it's horizontal size of larger than the whole Korean peninsula during this episode. Aerosol mass loadings changed by an order of magnitude within a few hours. The dominant ion components were SO₄²⁻, NO₃⁻, Ca²⁺ and Na⁺ during the passage of YS. The mode diameter of these compounds of YS was around 4 μm, compared to 0.4–0.9 μm after the passage of YS. SO₄²⁻ and NO₃⁻ concentrations were found to be well correlated with Ca²⁺ concentration in the coarse mode during the YS event, whereas they were well correlated with NH₄⁺ concentration during the non-YS period, indicating a significant amount of SO₄²⁻ and NO₃⁻ formations on the Ca²⁺-rich coarse aerosol during the long-range transport of YS.     

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.