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1.
This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SOx (=SO2+SO42−) and NOy (=NO+NO2 + PAN + HNO3+NO3+ organicnitrates + HONO + 2N2O5 …) at Whiteface Mountain, New York. Continuous real-time measurements of SO2 and total gaseous NOy 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 NOy 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 NOy 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  相似文献   

2.
A collocated, dry deposition sampling program was begun in January 1987 by the US Environmental Protection Agency to provide ongoing estimates of the overall precision of dry deposition and supporting data entering the Clean Air Status and Trends Network (CASTNet) archive. Duplicate sets of dry deposition sampling instruments were installed adjacent to existing instruments and have been operated for various periods at 11 collocated field sites. All sampling and operations were performed using standard CASTNet procedures. The current study documents the bias-corrected precision of CASTNet data based on collocated measurements made at paired sampling sites representative of sites across the network. These precision estimates include the variability for all operations from sampling to data storage in the archive. Precision estimates are provided for hourly, instrumental ozone (O3) concentration and meteorological measurements, hourly model estimates of deposition velocity (Vd) from collocated measurements of model inputs, hourly O3 deposition estimates, weekly filter pack determinations of selected atmospheric chemical species, and weekly estimates of Vd and deposition for each monitored filter pack chemical species and O3.Estimates of variability of weekly pollutant concentrations, expressed as coefficients of variation, depend on chemical species: NO3∼8.1%; HNO3∼6.4%; SO2∼4.3%; NH4+∼3.7%; SO42−∼2.3%; and O3∼1.3%. Precision of estimates of weekly Vd from collocated measurements of model inputs also depends on the chemical species: aerosols ∼2.8%; HNO3∼2.6%; SO2∼3.0%; and O3∼2.0%. Corresponding precision of weekly deposition estimates are: NO3∼8.6%; HNO3∼5.2%; SO2∼5.6%; NH4+∼3.9%; SO42−∼3.5%; and O3∼3.3%. Precision of weekly concentration, Vd estimates, and deposition estimates are comparable in magnitude and slightly smaller than the corresponding hourly values. Annual precision estimates, although uncertain due to their small sample size in the current study, are consistent with the corresponding weekly values.  相似文献   

3.
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/NO3 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.  相似文献   

4.
Winter rains have lower NO3 levels but higher SO2−4 levels than snows in the NE United States. In this study, four years of winter precipitation data from SE Michigan were examined to help understand these differences. Although NO3 levels were indeed higher in snow than winter rain, the higher concentrations could be attributed to the generally lower precipitation depths associated with snow events than with rain events. The NO3 concentrations are inversely correlated with precipitation depth. There was no evidence that snow scavenged HNO3 in the air more efficiently than rain.Conversely, SO2−4 was far higher in winter rain than in snow. This could not be explained in terms of ground-level ambient S concentrations or the wind direction from which the storm originated. However, the cloud temperatures were high enough in the case of rain to suggest that the cloud hydrometeors could have been present as liquid droplets rather than ice crystals. The SO2−4 concentrations of the precipitation were highly correlated with the temperatures of the cloud layers. The data suggest that SO2 is incorporated and oxidized to SO2−4 in clouds most efficiently when the hydrometeors are present as liquid droplets. The fact that NO3does not show the same relationship suggests that incorporation of N species into cloud water followed by oxidation is not as important a process for N as for S.  相似文献   

5.
Vertical concentration profiles for NH3, HNO3 and HCl-gas and for NH4+, NO3, SO2−4, Cl and Na+ aerosol were obtained from a meteorological tower in the central part of the Netherlands. An upward NH3 flux of 0.12 μgm−2 s−1 was calculated from the NH3 profiles and meteorological data. From the HNO3 profiles a maximum HNO3 dry deposition velocity of 4 cm s−1 was calculated. Good agreement was found between the measured concentration products [NH3](g) × [HNO3](g) and the theoretical values at temperatures above 0°C and relative humidities below 80%. In other cases, higher NH3 and/or HNO concentrations in the gas phase were measured than theoretically predicted.  相似文献   

6.
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.  相似文献   

7.
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 (molc) 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.  相似文献   

8.
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 NHx (NHx=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.  相似文献   

9.
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.  相似文献   

10.
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.  相似文献   

11.
A 14-week filter pack (FP) sampler evaluation field study was conducted at a site near Bondville, IL to investigate the impact of weekly sampling duration. Simultaneous samples were collected using collocated filter packs (FP) from two independent air quality monitoring networks (CASTNet and Acid-MODES) and using duplicate annular denuder systems (ADS). Precision estimates for most of the measured species are similar for weekly ADS and composited FPs. There is generally good agreement between the weekly CASTNet FP results aggregated from weekly daytime and weekly nighttime samples and those aggregated from daily 24 h Acid-MODES samples; although SO2 is the exception, and CASTNet concentrations are higher than Acid-MODES. Comparison of weekly ADS results with composited weekly FP results from CASTNet shows good agreement for SO2-4. With the exception of the two weeks where the FP exceeded the ADS, both HNO3 and the sum of particulate and gaseous NO-3 show good agreement. The FP often provides good estimates of HNO3, but when used to sample atmospheres that have experienced substantial photochemical reactivity, FP HNO3 determinations using nylon filters may be biased high. It is suggested that HNO2 or some other oxidized nitrogen compound can accumulate on a regional scale and may interfere with the FP determination of HNO3. FP particulate NO-3 results are in fair agreement with the ADS. Since FP SO2 results are biased low by 12–20%, SO2 concentration in the CASTNet data archive should be adjusted upward. Nylon presents problems as a sampling medium in terms of SO2 recovery and specificity for HNO3. Additional comparative sampler evaluation studies are recommended at several sites over each season to permit comprehensive assessment of the concentrations of atmospheric trace constituents archived by CASTNet.  相似文献   

12.
Measurements of gas-phase nitric acid were made by four separate techniques during a 7-day summertime period at a near-coastal site on Long Island, NY. Results from methods intercomparison data for HNO3, and their relationship to particulate NO3 and other odd N and oxidant species show the following: (a) high-volume filter pack HNO3 concentrations are well correlated with diffusion denuder difference (DD) results, except for small absolute losses with the former; (b) daytime real-time two-channel chemiluminescence HNO3 levels correlated well with DD results, but were higher during night-time periods; (c) results by a new Al2(SO4)3 denuder/thermal evolution technique were not in agreement with other techniques. Based on HNO3 and paniculate NO3 results reported herein, it appears that negative errors in HNO3filter-sampling techniques resulting from HNO3 loss by sorption generally exceed positive errors NH4NO3 volatilization at this site.  相似文献   

13.
ABSTRACT

A thermodynamic equilibrium model was used to investigate the response of aerosol NO3 to changes in concentrations of HNO3, NH3, and H2SO4. Over a range of temperatures and relative humidities (RHs), two parameters provided sufficient information for indicating the qualitative response of aerosol NO3. The first was the excess of aerosol NH4 + plus gas-phase NH3 over the sum of HNO3, particulate NO3, and particulate SO4 2- concentrations. The second was the ratio of particulate to total NO3 concentrations. Computation of these quantities from ambient measurements provides a means to rapidly analyze large numbers of samples and identify cases in which inorganic aerosol NO3 formation is limited by the availability of NH3. Example calculations are presented using data from three field studies. The predictions of the indicator variables and the equilibrium model are compared.  相似文献   

14.
The concentrations of PM2.5−10, PM2.5 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 PM2.5−10 and PM2.5 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 PM2.5−10 and PM2.5 masses. Chloride, Na+ and Mg2+ were the predominant ions in PM2.5−10, indicating a significant influence of sea-salt aerosols. In PM2.5, 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 PM2.5 NO3 concentration was eight times smaller than those of SO42− and NH4+. The PM2.5 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 NOy 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 PM2.5.  相似文献   

15.
The effects of the burning of fireworks on air quality in Beijing was firstly assessed from the ambient concentrations of various air pollutants (SO2, NO2, PM2.5, PM10 and chemical components in the particles) during the lantern festival in 2006. Eighteen ions, 20 elements, and black carbon were measured in PM2.5 and PM10, and the levels of organic carbon could be well estimated from the concentrations of dicarboxylic acids. Primary components of Ba, K, Sr, Cl, Pb, Mg and secondary components of C5H6O42−, C3H2O42−, C2O42−, C4H4O42−, SO42−, NO3 were over five times higher in the lantern days than in the normal days. The firework particles were acidic and of inorganic matter mostly with less amounts of secondary components. Primary aerosols from the burning of fireworks were mainly in the fine mode, while secondary formation of acidic anions mainly took place on the coarse particles. Nitrate was mainly formed through homogeneous gas-phase reactions of NO2, while sulfate was largely from heterogeneous catalytic transformations of SO2. Fe could catalyze the formation of nitrate through the reaction of α-Fe2O3 with HNO3, while in the formation of sulfate, Fe is not only the catalyst, but also the oxidant. A simple method using the concentration of potassium and a modified method using the ratio of Mg/Al have been developed to quantify the source contribution of fireworks. It was found that over 90% of the total mineral aerosol and 98% of Pb, 43% of total carbon, 28% of Zn, 8% of NO3, and 3% of SO42− in PM2.5 were from the emissions of fireworks on the lantern night.  相似文献   

16.
17.
Dimethyl sulfide (DMS) and atmospheric aerosols were sampled simultaneously over the Atlantic Ocean in the vicinity of Bermuda using the NOAA King Air research aircraft. Total and fine (50% cutoff at 2 μm diameter) aerosol fractions were sampled using two independent systems. The average nonsea-salt (nss)SO42− concentrations were 1.9 and 1.0 μg m−3 (as SO42−) for the total and the fine fractions in the boundary layer (BL) and 0.53 and 0.27 μg m−3 in the free troposphere (FT). Non-sea-salt SO42− in the two aerosol fractions were highly correlated (r = 0.90), however a smaller percentage (55%) was found in the fine aerosol near Bermuda relative to that (90%) near the North American continent. The BL SO42− concentrations measured in this study were higher than those measured by others at remote marine locations despite the fact that the 7-day air mass back trajectories indicated little or no continental contact at altitudes of 700 mb and below; the trajectories were over subtropical oceanic areas that are expected to be rich in DMS. DMS concentrations were higher near the ocean surface and decreased with increasing altitude within the BL; the average DMS concentration was 0.13 μg m−3. Trace levels of DMS were also measured in the FT (0.01 μg m−3). Computer simultation of the oxidation and removal of DMS in the marine atmosphere suggests that <50% of the SO42− observed could be related to the natural S cycle.  相似文献   

18.
Concentrations of 23 elements plus NO3, SO42− and Cl were determined for samples collected continuously every 3 or 6 h during 22–27 July, 1985 at a suburban site in Karachi, Pakistan. Concentrations of lithophilic elements and several anthropogenic elements were ~ 80 % higher during daytime than at night. These elevated levels were attributed to daytime increases in wind velocity and anthropogenic activity. Factor analysis showed that ~ 50% of the variance was associated with soil, and ~ 14 % each with oceanic Na and Cl, anthropogenic Sb and Pb, and Zn, Se and SO42−. A cement (limestone/dolomite) factor was not separated even though Ca and Mg concentrations were unusually high and a cement factory was located nearby. This led to an investigation of a chemical approach to determine the sources. Concentrations of Na, Mg and Ca were determined in water-extracts of the samples. Assuming soluble Na (~ 92 % of total) to be sea derived, marine components of Mg, SO42−, Ca and Br were determined. Solubility considerations were then used to reveal the cement source and apportion the aerosol sources. On the average, approximately 48 % of the total aerosol mass could be accounted for by the ‘cement’ and ‘soil’ components; about 12 % by the ‘sea salt’, about 3% by the ‘fossil fuel’ SO42− (as (NH4)2SO4); about 1 % by the NO3 (as NH4NO3); the remaining 36 % of the aerosol mass was unassigned.  相似文献   

19.
Ambient suspended particulate (PM2.5, PM2.5–10, 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 (PM2.5) concentration is the dominant species of the total suspended particles in Taichung, central Taiwan. The dominant species for PM2.5 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.  相似文献   

20.
The influence of dissolved NO2 and iron on the oxidation rate of S(IV) species in the presence of dissolved oxygen is presented. To match the conditions in the real environment, the concentration of iron in the reaction solution and trace gases in the gas mixture was typical for a polluted atmosphere. The time dependence of HSO3, SO42−, NO2 and NO3 and the concentration ratio between Fe(II) and total dissolved iron were monitored. Sulphate formation was the most intensive in the presence of an SO2/NO2/air gas mixture and Fe(III) in solution. The highest contribution to the overall oxidation was from Fe-catalysed S(IV) autoxidation. The reaction rate in the presence of both components was equal to the sum of the reaction rates when NO2 and Fe(III) were present separately, indicating that under selected experimental conditions there exist two systems: SO2/NO2/air and SO2/NO2/air/Fe(III), which are unlikely to interact with each other. The radical chain mechanism can be initiated via reactions Fe(III)–HSO3 and NO2–SO32−/HSO3.  相似文献   

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