The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.     

Trace gas and aerosol measurements at a remote site in the northeast U.S.

This paper presents the results of continuous measurements of trace atmospheric gases and aerosol composition made at the summit of Whiteface Mountain, New York, for 28 days in July 1982. The gas phase species NO, NO_x ( = NO + NO₂ + PAN), HNO₃, SO₂ and NH₃ were measured, as well as aerosol SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺. Mean and median NO_x concentrations were 1.1 and 1.0 ppb, respectively, with maximum and minimum values of 3.2 and 0.3 ppb. HNO₃ concentrations were variable, occasionally exceeding the simultaneously measured NO_x levels. Mean and median SO₂ were 0.8 and 0.3 ppb, with concentrations up to 12 ppb in pollution episodes. Mean and median NH₃ were both 2.2 ppb. Monthly mean SO₄²⁻ was 5.3 μg m⁻³, with values in clean air of about 1.5 μg m⁻³, and in polluted air up to 80 μg m⁻³. Trajectory calculations indicate that episodes of high pollutant concentrations occur in air masses arriving at Whiteface from the southwest. These episodes contributed most of the SO₄²⁻, HNO₃ and aerosol acidity, and about half the SO₂ and NO_x to which the site was exposed during the measurement period. Limited comparisons of air chemistry data with the composition of cloudwater collected during the program are also presented.     

Effects of dry deposition on the concentration-distributions of atmospheric pollutants within land- and sea-breeze circulations

In a land- and sea-breeze situation, effects of dry deposition on the dynamics of the concentrations of chemically reacting air pollutants are investigated using a transport/transformation/removal model with diurnally varying deposition velocities modeled in terms of the aerodynamic, surface, and residual resistances. The results show that the diurnally varying flows and eddy diffusivities, which are characteristic of the landand sea-breeze system, transfer the effects of dry deposition on the concentrations quickly to the upper layer over the land and sea surfaces. The dry deposition effect on one species can be transmitted to others through the network of chemical reactions, e.g. inclusion of dry deposition into the simulation resulted in the increase of hydrocarbon concentrations. It is also predicted that the dry deposition processes could remove a considerable part of emitted NO_x, and SO₂ from the local circulations, e.g. for 2 days about 40% of the emitted NO_x was removed by the dry deposition of NO, NO₂, HNO₃ and PAN and in the case of SO₂, 25 % by that of SO₂ and SO₄²⁻.     

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     

Concentration and dry deposition of atmospheric sulfur and nitrogen compounds in Hungary

The level of regional air pollution is regularly monitored at three stations in Hungary. The comparison of regional concentrations of SO₂ and NO₂ to those measured in Budapest shows that urban level concentration of SO₂ is ten times higher than the value for background conditions. The corresponding figure for NO₂ is five. An increase eastwards across the country can be observed for NO₂ and SO₂, while particulate sulphate, nitrate and ammonium have practically identical concentrations. The concentration of gaseous ammonia has a summer maximum, while the annual variation of particulate ammonium suggests a winter maximum. The ratio of the level of nitric acid to aerosol nitrate is higher than unity in summer, while in winter it is less than 1. The dry deposition of sulfur and oxidized nitrogen compounds is comparable to their wet deposition. However, in the case of NH_x (x = 3 or 4) the wet deposition exceeds the dry deposition by an order of magnitude.     

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.     

The Berlin smog project—Description and summary of results

The composition of ambient air pollution, emphasising the ambient particulate matter, has been investigated for 14 wintertime smog periods (SO₂ and/or suspended particulate concentrations exceeding 400 μg m⁻³) in Berlin (West). The total aerosol mass concentration, the SO₂, CO, NO and NO₂ and pertinent meteorological parameters were measured. For chemical characterization the aerosol was collected by hi-volume, low-volume samplers and cascade impactors. The samples were analysed for the metals Pb, Cd, Mn, Ni; the water soluble ions: NH₄⁺, SO₄²⁻, NO₃⁻; and the PAH's: Fl, Py, Per, BaP, BghiP and Cor. The aerosol size distribution (0,01 < d_p < 20 μm) was measured by a combination of electrical and optical analysers with a time resolution of 10 min.The smog periods lasted from 6 to 100 h and occured during anticyclonic conditions with restricted vertical mixing and low to moderate wind velocities. The smog producing pollutants originated either in the city of Berlin or in the industrial regions 100–200 km away.Ambient air quality standards were exceeded by SO₂ (highest 24-h concentration: 760 μg m⁻³), NO_x (320), TSP (930) and SO₄²⁻ (190). BaP levels of up to 92 μg m⁻³ were measured. The total sulfate level increases with the SO₂ concentration and exceeds 100 μg m⁻³ for SO₂ levels above 600 μg m⁻³. In 40% of all cases the aerosol sulfate seems to be more acidic than (NH₄)HSO₄. The secondary aerosol fraction, i.e. the sum of SO₄²⁻, NH₄⁺ and NO₂⁻ ranges from 23 up to 65% of TSP and is related to the age of the pollutants.The composition of the pollutants reflects the different emission patterns of the various source regions and chemical conversions during the trip from the sources to the measuring station. Therefore, the patterns of the composition of the pollutants provide a means to apportion the pollutants among contributing source regions. Thus, it seems possible to develop a scheme to determine during an ongoing smog condition the major contributing source region on the basis of real time measurements of selected physical and chemical parameters of ambient pollutants.     

Seasonal variation in atmospheric aerosol concentration and composition at urban and rural sites in northern England

Seasonal variations in atmospheric aerosol concentration and composition have been determined at two nearby sites, one urban and one rural, near Leeds, W. Yorkshire. Aerosols, sampled on a daily basis and collected in the size ranges < 2.5 μm and 2.5−15 μm, were analysed for total mass, SO²⁻₄, NO⁻₃, Cl⁻ and NH⁺₄. Dark smoke and SO₂ were also measured at both sites. Results are given covering the period October 1982–September 1983. The average concentration of particles was higher at the urban site. The urban-rural difference in coarse particle concentration, which was about a factor of 2, was more significant than the difference in the fine particle concentration, which was only 1.3. Smoke and SO₂ concentrations showed strong wintertime maxima and summertime minima. Fine NO⁻₃ and Cl⁻ concentrations also had pronounced wintertime maxima and summertime minima attributed to the variation in volatility of their ammonium salts. Total mass, SO²⁻₄ and NH⁺₄ did not show any clear seasonal variations. Anti-cyclonic conditions in summer resulted in elevated mass concentrations of secondary pollutants, e.g. SO²⁻₄. The fine fraction contained ca 50% water-soluble inorganic ions at Leeds and slightly more at the rural site. These proportions showed little seasonal variation.     

Sensitivity analyses of factors influencing CMAQ performance for fine particulate nitrate

Improvement of air quality models is required so that they can be utilized to design effective control strategies for fine particulate matter (PM_2.5). The Community Multiscale Air Quality modeling system was applied to the Greater Tokyo Area of Japan in winter 2010 and summer 2011. The model results were compared with observed concentrations of PM_2.5 sulfate (SO₄^2-), nitrate (NO₃^?) and ammonium, and gaseous nitric acid (HNO₃) and ammonia (NH₃). The model approximately reproduced PM_2.5 SO₄^2? concentration, but clearly overestimated PM_2.5 NO₃^? concentration, which was attributed to overestimation of production of ammonium nitrate (NH₄NO₃). This study conducted sensitivity analyses of factors associated with the model performance for PM_2.5 NO₃^? concentration, including temperature and relative humidity, emission of nitrogen oxides, seasonal variation of NH₃ emission, HNO₃ and NH₃ dry deposition velocities, and heterogeneous reaction probability of dinitrogen pentoxide. Change in NH₃ emission directly affected NH₃ concentration, and substantially affected NH₄NO₃ concentration. Higher dry deposition velocities of HNO₃ and NH₃ led to substantial reductions of concentrations of the gaseous species and NH₄NO₃. Because uncertainties in NH₃ emission and dry deposition processes are probably large, these processes may be key factors for improvement of the model performance for PM_2.5 NO₃^?.

Implications: The Community Multiscale Air Quality modeling system clearly overestimated the concentration of fine particulate nitrate in the Greater Tokyo Area of Japan, which was attributed to overestimation of production of ammonium nitrate. Sensitivity analyses were conducted for factors associated with the model performance for nitrate. Ammonia emission and dry deposition of nitric acid and ammonia may be key factors for improvement of the model performance.     

Measurements of the chemical composition of stratiform clouds

Measurements are reported of the chemical composition of the liquid water and interstitial air in warm (> 0°C), non-precipitating stratus and strato-cumulus clouds at various locations in the eastern United States. Inorganic ionic composition of the cloud water was generally dominated by H⁺, NH₄⁺, NO₃⁻ and SO₄²⁻, similar to the composition of precipitation in this region of the U.S. Concentrations of the corresponding interstitial aerosol species and gaseous HNO₃ were invariably low in comparison to concentrations of the respective ionic species in cloudwater. In contrast, the concentration of NO_x (i.e. NO + NO₂ + organic nitrates) was invariably comparable to or in excess of that of cloudwater nitrate. Sulfur dioxide was found at varying concentrations relative to cloudwater sulfate. In many cases, the SO₂ concentration was quite low (< 0.2 ppb) even in the presence of substantial quantities of cloudwater SO₄²⁻ (> 1 ppb equivalent gas-phase concentration), suggesting large fractional conversion and incorporation into cloudwater. In other cases, in which dilute SO₂ plumes (pso, > 5 ppb) were observed in the cloud interstitial air, the gaseous SO₂ concentration substantially exceeded the cloudwater sulfate concentration.Concentrations of H₂O₂ in cloudwater were found to exhibit strong inverse correlation with interstitial SO₂. Appreciable concentrations of SO₂ in cloud interstitial air and H₂O₂ in cloudwater were only rarely observed to coexist, for the most part only one or the other being present above the limit of detection. These observations are consistent with aqueous-phase oxidation of SO₂ by H₂O₂, as has been inferred previously on the basis of laboratory kinetic studies, and with the hypothesis that depending on relative concentrations, either of these species can be a limiting reagent for in-cloud SO₂ oxidation. The uptake of NO_x as cloudwater nitrate is less complete than the uptake of SO₂ as sulfate, and evidence for the occurrence of similar in-cloud processes causing the conversion of NO or NO₂ to cloudwater nitrate has not been found.     

Seasonal variations of acidic air pollutants in Seoul,South Korea

The annular denuder system (ADS) was used to characterize seasonal variations of acidic air pollutants in Seoul, South Korea. Fifty- four 24 h samples were collected over four seasons from October 1996 to September 1997. The annual mean concentrations of HNO₃, HNO₂, SO₂ and NH₃ in the gas phase were 1.09, 4.51, 17.3 and 4.34 μg m^-3, respectively. The annual mean concentrations of PM_2.5(d_p≤2.5 μm in aerodynamic diameter, 50% cutoff), SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were 56.9, 8.70, 5.97 and 4.19 μg m^-3, respectively. All chemical species monitored from this study showed statistical seasonal variations. Nitric acid (HNO₃) and ammonia (NH₃) exhibited substantially higher concentrations during the summer, while nitrous acid (HNO₂) and sulfur dioxide(SO₂) were higher during the winter. Concentrations of PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were higher during the winter months. SO^2-₄, NO^-₃ and NH⁺₄ accounted for 26–38% of PM_2.5. High correlations were found among PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄. The mean H⁺ concentration measured only in the fall was 5.19 nmole m^-3.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

Analysis of emission databases for regional models

General procedures for adapting emission inventories to regional models and for studying the impact of differences in inventories on model predictions are outlined. To illustrate the methods, analysis of two inventories which are still being validated is presented. The inventories together satisfy current requirements for the NCAR regional acid deposition model (RADM). These include anthropogenic emissions of SO₂, sulfate aerosol, NO, NO₂, NH₃ and volatile organic compounds (VOC) in 10 reactivity classes, from United States and Canadian point and area sources on 80-km grid resolutions, for weekend and weekday seasonally representative days on a diurnal basis during the 1980–1982 period. Application of checking procedures, designed by our group to screen for subtle anomalies not identified at previous stages of quality assurance employed by the inventory developers, resulted in adjustments primarily to VOC emissions. Comparisons of the modified inventories, which provide an indication of uncertainties in emissions due to variations in inventory development procedures, revealed differences in the eastern United States total daily emissions to be at most on the order of 5 % for SO_x, and NO_x, 20% for VOC and 85% for NH₃. Studies of the impact of inventory differences on predictions of RADM were conducted for the 22–24 April 1981 period, which was monitored as part of the Oxidation and Scavenging Characteristics of April Rains program. Event total wet sulfate deposition differed by 10% or less while midday O₃ concentrations differed by 1% or less for individual grids over the modeling domain.     

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NOx photooxidation system

High concentrations (>15 μm³ cm^?3) of CaSO₄, Ca(NO₃)₂ and (NH₄)₂SO₄ were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO_x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO₄ and aqueous Ca(NO₃)₂), even at elevated concentrations. The presence of high concentrations of (NH₄)₂SO₄ aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH₄)₂SO₄ on SOA yield is found to be positively correlated with the (NH₄)₂SO₄ surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH₄)₂SO₄ seed aerosols.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Analysis of Short-Term and Episodic Variations in PM2.5 Concentrations Using Hourly Air Monitoring Data

Abstract

One-hour average ambient concentrations of particulate matter (PM) with an aerodynamic diameter <2.5 μm (PM_2.5) were determined in Steubenville, OH, between June 2000 and May 2002 with a tapered element oscillating microbalance (TEOM). Hourly average gaseous copollutant [carbon monoxide (CO), sulfur dioxide (SO₂), nitrogen oxide (NO_x), and ozone (O₃)] concentrations and meteorological conditions also were measured. Although 75% of the 14,682 hourly PM_2.5 concentrations measured during this period were ≤17 μg/m³, concentrations >65 μg/m³ were observed 76 times. On average, PM_2.5 concentrations at Steubenville exhibited a diurnal pattern of higher early morning concentrations and lower afternoon concentrations, similar to the diurnal profiles of CO and NO_x. This pattern was highly variable; however, PM_2.5 concentrations >65 μg/m³ were never observed during the mid-afternoon between 1:00 p.m. and 5:00 p.m. EST. Twenty-two episodes centered on one or more of these elevated concentrations were identified. Five episodes occurred during the months June through August; the maximum PM_2.5 concentration during these episodes was 76.6 μg/m³. Episodes occurring during climatologically cooler months often featured higher peak concentrations (five had maximum concentrations between 95.0 and 139.6 μg/m³), and many exhibited strong covariation between PM_2.5 and CO, NO_x, or SO₂. Case studies suggested that nocturnal surface-based temperature inversions were influential in driving high nighttime concentrations of these species during several cool season episodes, which typically had dramatically lower afternoon concentrations. These findings provide insights that may be useful in the development of PM_2.5 reduction strategies for Steubenville, and suggest that studies assessing possible health effects of PM_2.5 should carefully consider exposure issues related to the intraday timing of PM_2.5 episodes, as well as the potential for toxicological interactions among PM_2.5 and primary gaseous pollutants.     

Seasonal variation of atmospheric ammonia and particulate ammonium concentrations in the urban atmosphere of yokohama over a 5-year period

Measurements of ammonia and particulate ammonium were made in the daytime (1200–1500) at a urban site in Yokohama during the 5-year period, 1982–1986. Diurnal NH₃ concentrations showed a distinct seasonal trend with a maximum in summer. The diurnal monthly average concentrations were above 10 ppb during the late spring and summer months, while the concentrations during the winter months were between 1 and 5 ppb. The seasonal variation was found to be very similar to that of the average air temperature and showed a periodic pattern over 1 year. A good correlation was observed between diurnal NH₃ concentrations and average air temperatures during the 5-year period. The annual mean concentrations were in the range of 6.6–7.6 ppb with only a minor deviation. The diurnal monthly average concentrations of particulate NH₄⁺ were between 1 and 4 μg m⁻³ and no significant seasonal variations were seen. As a short-term study, simultaneous measurements of NH₃, HNO₃ and particulate NO₃⁻ were made. The diurnal mean concentrations of NH₃ and HNO₃ were 7.6 and 0.8 ppb, respectively. The concentration of particulate NO₃⁻ ranged from 0.3 to 6μg⁻³. Both HNO₃ and particulate NO₃⁻ concentrations were relatively low and constant. Thus, NH₃ and HNO₃ levels did not agree with the concentrations predicted from the NH₄NO₃ equilibrium constant.     

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.     

Ground level ozone concentrations and its association with NOx and meteorological parameters in Kathmandu valley, Nepal

This paper summarizes the results of a yearlong continuous measurements of gaseous pollutants, NO, NO₂, NO_x and O₃ in the ambient air at Kathmandu valley. Measured concentration of the pollutants in study area is a function of time. NO, NO₂ and O₃ peak occurred in succession in presence of sunlight. At the time of maximum O₃ concentration most of the NO_x are utilized. The diurnal cycle of ground level ozone concentrations, revealed mid-day peak with lower nocturnal concentrations and inverse relationship exists between O₃ and NO_x, which are evidences of photochemical O₃ formation. The observed ground level ozone during monsoon is slight lower than the pre-monsoon value. Further, lack of rainfall and higher temperature, solar radiation in the pre-monsoon have given rise to the gradual build up of ozone and it is lowest during winter. Ground level ozone concentrations measured during bandha (general strike) and weekend are 19% and 13% higher than those measured during weekdays. The most effective ozone abatement strategy for Kathmandu Valley may be control of NO_x emissions.     

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.     

Modelling the atmospheric transport and deposition of sulphur and nitrogen over the United Kingdom and assessment of the influence of SO2 emissions from international shipping

A statistical Lagrangian atmospheric transport model was used to generate annual maps of deposition of sulphur and oxidised and reduced nitrogen for the UK at a 5×5 km² resolution. The model was run using emissions for the year 2002. The model was compared with measurements of gas concentrations (SO₂, NO_x, HNO₃ and NH₃) and of wet deposition and aerosol concentrations of SO₄²⁻, NO₃⁻ and NH₄⁺ from national monitoring networks. Good correlation was obtained, demonstrating that the model is capable of accurately estimating the mass balance and spatial distribution of sulphur and nitrogen compounds in the atmosphere. A future emissions scenario for the year 2020 was used to test the influence of shipping emissions on sulphur deposition in the UK. The results show that, if shipping emissions are assumed to increase at a rate of 2.5% per year, their relative contribution to sulphur deposition is expected to increase from 9% to 28% between 2002 and 2020. The model was compared to both a European scale and a global scale chemical transport model and found to give broad agreement with the magnitude and location of sulphur deposition associated with shipping emissions. Enforcement of the MARPOL convention to reduce the sulphur content in marine fuel to 1% was estimated to result in a 6% reduction in total sulphur deposition to the UK for the year 2020. The percentage area of sensitive habitats with exceedance of critical loads for acidity in the UK was predicted to decrease by 1% with the implementation of the MARPOL convention.