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 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.     

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.     

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.     

Deposition of sulphur,nitrogen and acidity in precipitation over Ireland: chemistry,spatial distribution and long-term trends

The chemical composition of pollutant species in precipitation sampled daily or weekly at 10 sites in Ireland for the five-year period, 1994–1998, is presented. Sea salts accounted for 81% of the total ionic concentration. Approximately 50% of the SO₄²⁻ in precipitation was from sea-salt sources. The proportion of sea salts in precipitation decreased sharply eastwards. In contrast, the concentration of NO₃⁻ and the proportion of non-sea-salt SO₄²⁻ increased eastwards reflecting the closer proximity to major emission sources. The mean (mol_c) ratio of SO₄²⁻:NO₃⁻ was 1.6 for all sites, indicating that SO₄²⁻ was the major acid anion.The spatial correlation between SO₄²⁻, NO₃⁻ and NH₄⁺ concentrations in precipitation was statistically significant. The regional trend in NO₃⁻ concentration was best described by linear regression against easting. SO₄²⁻ concentration followed a similar pattern. However, the regression was improved by inclusion of elevation. Inclusion of northing in the regression did not significantly improve any of the relationships except for NH₄⁺, indicating a significant increase in concentrations from northwest to southeast.The spatial distribution of deposition fluxes showed similar gradients increasing from west and southwest to east and northeast. However, the pattern of deposition shows the influence of precipitation volume in determining the overall input. Mean depositions of sulphur and nitrogen in precipitation were ≈30 ktonnes S yr⁻¹ and 48 ktonnes N yr⁻¹ over the five-year period, 1994–1998, for Ireland.Least-squares linear regression analysis indicated a slight decreasing trend in precipitation concentrations for SO₄²⁻ (20%), NO₃⁻ (13%) and H⁺ (24%) and a slight increasing trend for NH₄⁺ (15%), over the period 1991–1998.     

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.     

Multivariate Space Analysis of the Major Precipitation Ions over Europe, 1986–1997

ABSTRACT

The annual average concentrations (1986–1997) of the major ions SO₄ ^2-, NO₃ ^-, Cl^-, NH₄+, Na+, Mg²+, Ca²+, and K+ in precipitation are analyzed for selected EMEP stations. The objective is to determine the ion patterns or typologies in precipitation by principal component analysis (PCA) combined with a cluster analysis. SO₄ ^2- and NO₃ ^- ions are predominant in central and eastern Europe. This area corresponds to high emissions of SO₂ and NO₂. Sea spray ions are predominant in coastal sites. The soil components show an important contribution in southern Europe, possibly due to the soil dust transported from northern Africa.     

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.     

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.     

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.     

Water soluble ions of atmospheric aerosols in three New Zealand cities: seasonal changes and sources

The results of one year's measurements (typically a two week sampling campaign in each season) of the concentrations of eight major water soluble ions, namely Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₃⁻ and SO₄²⁻, in atmospheric aerosols collected in three New Zealand cities (Auckland, Christchurch and Hamilton) are presented. The data has provided important information on particulate soluble ion profiles in New Zealand urban areas and revealed some useful trends.A significant correlation has been found between the average meteorological conditions in a sampling campaign and the average particulate concentrations of some of these soluble ions in the campaign. For example, average particulate NO₃⁻ concentration in a campaign was found to correlate well with the average calm or weak wind duration percentage in the campaign, and the average concentrations of Na⁺, Mg²⁺ and Cl⁻ related closely to the average wind pattern and rainfall in the campaign.Significant site and seasonal variations have been observed with Hamilton having the lowest overall concentrations of all the soluble ions in the particles sampled. On average all sites had the highest particulate concentrations of Na⁺, Mg²⁺ and Cl⁻ in the summer but the highest particulate concentrations of NH₄⁺ and non-sea-salt Ca²⁺ (nss-Ca²⁺) in the winter. The possible sources of PM₁₀ mass have been deduced and in particular the relative contribution of sea salts to PM₁₀ mass in the cities are reported.     

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.     

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.     

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.     

Cereal waste burning pollution observed in the town of Vitoria (northern Spain)

Agricultural waste burning is a widespread practice throughout the world but there is little information about its pollutant impact. This paper deals with a preliminary study of the pollution observed in Vitoria (Northern Spain) caused by cereal waste burning. The mean hourly flux of pollutants produced by cereal waste burning fires can reach values of 1.4 kt of CO₂, 13 t of TPM and 3 t of NO_x in the area around Vitoria. Measurements obtained in the area of emission and inside fire plumes show high ratios (NO₂/NO_x) indicating that nitrogen oxides emitted by the source undergo a rapid transformation in the same area of emission. Results relating to aerosol composition collected in Vitoria during burning periods show an increase in the concentration of K⁺, NO₃⁻ and Cl⁻ ions, that are inter-correlated. The modification of the ionic composition of aerosols also affects the chemistry of the rain collected in Vitoria. During the burning period, it is particularly noticeable that anthropogenic pollution (usually identifiable by the correlation between SO₄²⁻ and NO₃⁻ concentrations) disappears, indicating the existence of an independent source of NO₃⁻ not linked to the SO₄²⁻ source. Similar results were deduced studying BAPMON data collected in Spain during cereal waste burning. Finally, we note that ozone concentration measured at Vitoria is not affected by the pollution generated by the burning fires.     

Chemical characteristics of atmospheric aerosols over southwest coast of India

Ambient aerosol samples, collected from Mangalore region in the southwest coast of India during the period of late winter (February and March) to early summer (April and May), have been analysed for water-soluble ionic species. Their abundance pattern is dominated by HCO₃⁻, SO₄²⁻, Na⁺, Cl⁻, with minor contribution from NO₃⁻, Ca²⁺, NH₄⁺, K⁺ and Mg²⁺ indicating the contribution from not only sea salt, but also from anthropogenic and dust sources; with pronounced seasonal variability. The suspended particulate matter concentration varied from 35 to 160 μg m⁻³, with consistently higher values during the late winter. Back trajectory analysis suggests the origin of the air masses shifting from Indo-Gangetic Plains (during late winter) to those from the Arabian Sea and the area around Persian Gulf during April–May. Air masses passing over Northern India (Indo-Gangetic Plains) impart characteristic contribution of ionic species from fossil fuel combustion, biomass burning and eolian dust as asserted by the factor analysis. A detailed study on characterisation of aerosols from south Asian region is rather sparse but essential for modelling the effect of tropospheric aerosols on climate.     

Chemical characteristics of cloud water over the Japan Sea and the Northwestern Pacific Ocean near the central part of Japan: airborne measurements

Cloud water was collected by aircraft over the Japan Sea and the Northwestern Pacific Ocean during the winter and early spring seasons. The concentrations of major ions in the cloud water were higher at cloud bases than at cloud tops. The equivalents based ratio of Na⁺/nssSO₄²⁻ and NO₃⁻/nssSO₄²⁻ at cloud bases was higher than that at cloud tops, whereas the nssCa²⁺/nssSO₄²⁻ ratio was higher at cloud tops. The concentrations of nssSO₄²⁻ were higher than those of NO₃⁻ over the Japan Sea. The ratio of NO₃⁻/nssSO₄²⁻ in the cloud water over the Pacific Ocean was higher than that over the Japan Sea. Especially, when the winter monsoon wind pressure pattern collapsed, the concentrations of NO₃⁻ were much higher than those of nssSO₄²⁻. The concentrations of peroxides in the cloud water ranged from below the detection limit to 6.2 μM, and were much lower than those in the fog water near the summit of Mt. Norikura during the summer season. Most of the samples showed the condition (NH₄⁺+nssCa²⁺)<(NO₃⁻+nssSO₄²⁻), which implies insufficient amounts of bases to neutralize the acids. Chloride loss in the cloud water was observed, and this may be caused by the deposition of HCl gas to the sea surface.     

Time study of trace elements and major ions during two cloud events at the Mt. Brocken

Cloud water investigations have been performed at the highest elevation of Central Germany in 1997. Results of extensive trace element measurements are presented. Besides conductivity, pH, liquid water content and major ions the data set includes 49 minor and trace elements. Estimation of crustal enrichment factors (EFs) provides an indication of the anthropogenic contributions to the cloud water concentrations. The variation of cloud composition with time has been illustrated for two selected events with different air mass origins. The chemical composition of the cloud condensation nuclei on which the droplets grow mainly determines the cloud water chemistry. For a cloud event in June 1997 the concentrations of the crustally derived elements Si, Al, Fe, Ti, Ce, La and Nd follow each other closely. The fact that SO₄²⁻, NO₃⁻ and NH₄⁺ are only moderately correlated with the particular pollutants with high enrichment factors such as Cd, Sb, Pb, Zn, Cu, As, Bi, Sn, Mo, Ni, Tl and V indicates that their source regions are more widespread. During an event in October 1997 the time trends for most minor and trace elements follow rather closely those for the major ions NH₄⁺, SO₄²⁻ and NO₃⁻. Back trajectories show that the transport from continental and marine European sources was the likely cause of the sample concentrations. EFs of trace elements in cloud water samples during the June and October event show a strong correlation with those obtained for urban particulate matter. Although both events are influenced by air masses of different origin, there is a good agreement between the EF signatures.     

Biases in Clean Air Status and Trends Network filter pack results associated with sampling protocol

Network filter pack sampling protocol changed in 1989 from requiring a week-long daytime sample and a week-long nighttime sample to requiring a single week-long sample per week at each monitoring site. In the current study, single-filter pack weekly results are compared with weekly results aggregated from separate daytime and nighttime weekly filter pack samples collected at the monitoring site located at Egbert, Ontario, Canada. Comparisons of the concentrations resulting from the two sampling protocols for all major chemical species (SO₄²⁻, NO₃⁻, NH₄⁺, HNO₃, and SO₂) show median biases of <5 nmol m⁻³ (0.1 ppb) and median relative biases of <10%. Median relative biases have the same sign for each species, suggesting biases in the same direction. Based on median differences, composite day–night weekly sampler results generally exceed the single-sampler weekly results (in all cases except for the summer nylon filter HNO₃), and the magnitude depends on the constituent and on the season. Examination of seasonal results reveals large discrepancies in some cases, especially during summer. To use Clean Air Status and Trends Network results for trends analyses over time periods encompassing the 1989 protocol change, it may be useful to put all of the data on the same basis of sampler protocol. Algorithms derived from linear regression analyses using paired bootstrap sampling are offered to convert the recent results to the pre-1989 basis; however, they may only be appropriate for sites in the eastern US. Chemical and statistical reasoning suggests that the results of day–night weekly sampling are usually consistent with higher accuracy than single-sampler weekly results. Adjustments are indicated for summer Teflon NO₃ and nylon HNO₃, for summer and fall Teflon NH₄, and for Total SO₂ in each season. Nylon filters are also shown to have variable collection characteristics for SO₂ that are consistent with a humidity effect. A network-wide change in the SO₂ collection and/or retention characteristics of the nylon filters is found in April 1997.