Atmospheric conversion of sulfur dioxide to particulate sulfate and nitrogen dioxide to particulate nitrate and gaseous nitric acid in an urban area

Sulfur dioxide, nitrogen dioxide, particulate sulfate and nitrate, gaseous nitric acid, ozone and meteorological parameters (temperature and relative humidity) were measured during the winter season (1999-2000) and summer season (2000) in an urban area (Dokki, Giza, Egypt). The average particulate nitrate concentrations were 6.20 and 9.80 microg m(-3), while the average gaseous nitric acid concentrations were 1.14 and 6.70 microg m(-3) in the winter and summer seasons, respectively. The average sulfate concentrations were 15.32 microg m(-3) during the winter and 25.10 microg m(-3) during the summer season. The highest average concentration ratio of gaseous nitric acid to total nitrate was found during the summer season. Particulate sulfate and nitrate and gaseous nitric acid concentrations were relatively higher in the daytime than those in the nighttime. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) defined in the text were calculated from the field measurement data. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) in the summer were about 2.22 and 2.97 times higher than those in the winter season, respectively. Moreover, sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) were higher in the daytime than those in the nighttime during the both seasons. The sulfur conversion ratio (Fs) increases with increasing ozone concentration and relative humidity. This indicates that the droplet phase reactions and gas phase reactions are important for the oxidation of SO2 to sulfate. Moreover, the nitrogen conversion ratio (Fn) increases with increasing ozone concentration, and the gas phase reactions are important and predominant for the oxidation of NO2 to nitrate.     

Inorganic PM2.5 at a U.S. agricultural site

In this study, we present approximately two years (January 1999-December 2000) of atmospheric NH3, NH4+, HCl, Cl-, HNO3, NO3-, SO2, and SO4= concentrations measured by the annular denuder/filter pack method at an agricultural site in eastern North Carolina. This site is influenced by high NH3 emissions from animal production and fertilizer use in the surrounding area and neighboring counties. The two-year mean NH3 concentration is 5.6 (+/-5.13) microg m(-3). The mean concentration of total inorganic PM2.5, which includes SO4=, NO3-, NH4+, and Cl-, is 8.0 (+/-5.84) microg m(-3). SO4=, NO3-, NH4+, and Cl- represent, respectively, 53, 24, 22, and 1% of measured inorganic PM2.5. NH3 contributes 72% of total NH3 + NH4+, on an average. Equilibrium modeling of the gas+aerosol NH3/H2SO4/HNO3 system shows that inorganic PM2.5 is more sensitive to reductions in gas + aerosol concentrations of sulfate and nitrate relative to NH3.     

Source identification and trends in concentrations of gaseous and fine particulate principal species in Seoul, South Korea

Ambient measurements were made using two sets of annular denuder system during the four seasons (April 2001 to February 2002) and were then compared with the results during the period of 1996-1997 to estimate the trends and seasonal variations in concentrations of gaseous and fine particulate matter (PM2.5) principal species. Annual averages of gaseous HNO3 and NH3 increased by 11% and 6%, respectively, compared with those of the previous study, whereas HONO and SO2 decreased by 11% and 136%, respectively. The PM2.5 concentration decreased by -17%, 35% for SO4(2-), and 29% for NH4+, whereas NO3- increased by 21%. Organic carbon (OC) and elemental carbon (EC) were 12.8 and 5.98 microg/m(-3), accounting for -26 and 12% of PM2.5 concentration, respectively. The species studied accounted for 84% of PM2.5 concentration, ranging from 76% in winter to 97% in summer. Potential source contribution function (PSCF) analysis was used to identify possible source areas affecting air pollution levels at a receptor site in Seoul. High possible source areas in concentrations of PM2.5, NO3-, SO4(2-), NH4+, and K+ were coastal cities of Liaoning province (possibly emissions from oil-fired boilers on ocean liners and fishing vessels and industrial emissions), inland areas of Heibei/Shandong provinces (the highest density areas of agricultural production and population) in China, and typical port cities (Mokpo, Yeosu, and Busan) of South Korea. In the PSCF map for OC, high possible source areas were also coastal cities of Liaoning province and inland areas of Heibei/Shandong provinces in China. In contrast, high possible source areas of EC were highlighted in the south of the Yellow Sea, indicating possible emissions from oil-fired boilers on large ships between South Korea and Southeast Asia. In summary, the PSCF results may suggest that air pollution levels in Seoul are affected considerably by long-range transport from external areas, such as the coastal zone in China and other cities in South Korea, as well as Seoul itself.     

Nitrogen deposition in California forests: a review

Atmospheric concentrations and deposition of the major nitrogenous (N) compounds and their biological effects in California forests are reviewed. Climatic characteristics of California are summarized in light of their effects on pollutant accumulation and transport. Over large areas of the state dry deposition is of greater magnitude than wet deposition due to the arid climate. However, fog deposition can also be significant in areas where seasonal fogs and N pollution sources coincide. The dominance of dry deposition is magnified in airsheds with frequent temperature inversions such as occur in the Los Angeles Air Basin. Most of the deposition in such areas occurs in summer as a result of surface deposition of nitric acid vapor (HNO3) as well as particulate nitrate (NO3-) and ammonium (NH4+). Internal uptake of gaseous N pollutants such as nitrogen dioxide (NO2), nitric oxide (NO), HNO3, peroxyacetyl nitrate (PAN), ammonia (NH3), and others provides additional N to forests. However, summer drought and subsequent lower stomatal conductance of plants tend to limit plant utilization of gaseous N. Nitrogen deposition is much greater than S deposition in California. In locations close to photochemical smog source areas, concentrations of oxidized forms of N (NO2, HNO3, PAN) dominate, while in areas near agricultural activities the importance of reduced N forms (NH3, NH4+) significantly increases. Little data from California forests are available for most of the gaseous N pollutants. Total inorganic N deposition in the most highly-exposed forests in the Los Angeles Air Basin may be as high as 25-45 kg ha(-1) year(-1). Nitrogen deposition in these highly-exposed areas has led to N saturation of chaparral and mixed conifer stands. In N saturated forests high concentrations of NO3- are found in streamwater, soil solution, and in foliage. Nitric oxide emissions from soil and foliar N:P ratios are also high in N saturated sites. Further research is needed to determine the ecological effects of chronic N deposition, and to develop appropriate management options for protecting water quality and managing plant nutrient resources in ecosystems which no longer retain excess N.     

Effects of changes in sulfate,ammonia, and nitric acid on particulate nitrate concentrations in the southeastern United States

A thermodynamic equilibrium model, Simulating Composition of Atmospheric Particles at Equilibrium (SCAPE2), was used to investigate the response of fine particulate NO3(-) to changes in concentrations of HNO3, NH3, and SO4(2-) in the southeastern United States. The data consisted of daily, 24-hr time resolution measurements from the Aerosol Research Inhalation Epidemiology Study (ARIES) Jefferson Street (Atlanta) site and five other sites of the Southeastern Aerosol Research and Characterization Project (SEARCH). Reductions of total NH3 (gas-phase NH3 plus particulate NH4(+)), total NO3(-) (HNO3 plus particulate NO3(-)), SO4(2-), or combined total NO3(-) (HNO3 plus particulate NO3(-)) with SO4(2-) were used to estimate the effects of changing emission levels. The conversion of SO2 to SO4(2-) and NO2 to HNO3 involves additional nonlinear reactions not incorporated into the model. For all sites, fine particulate NO3(-) concentrations decreased in response to reductions of either NH3 or total NO3(-), but the particulate NO3(-) decreases were greater for the NH3 reductions than for the total NO3(-) reductions. Particulate NO3(-) concentrations increased in response to reductions of SO4(2-). For the combined reduction (total NO3(-) plus SO4(2-)), the resulting particulate NO3(-) concentrations were on average no different than the base-case NO3(-) levels. Measurements of fine particulate NO3(-) and HNO3 support the modeling conclusions and indicate that particulate NO3(-) formation is limited by the availability of NH3 at most times at all SEARCH sites.     

Summer-time distribution of air pollutants in Sequoia National Park, California

Concentrations of air pollutants were monitored during the May November 1999 period on a network of forested sites in Sequoia National Park, California. Measurements were conducted with: (1) active monitors for nitric oxide (NO), nitrogen dioxide (NO2) and ozone (O3); (2) honeycomb denuder/filter pack systems for nitric acid vapor (HNO3), nitrous acid vapor (HNO2), ammonia (NH3), sulfur dioxide (SO2), particulate nitrate (NO3-), ammonium (NH4+), and sulfate (SO4(2-)); and (3) passive samplers for O3, HNO3 and NO2. Elevated concentrations of O3 (seasonal means 41-71 ppb), HNO3 (seasonal means 0.4-2.9 microg/m3), NH3 (seasonal means 1.6-4.5 microg/m3), NO3 (1.1-2.0 microg/m3) and NH4+ (1.0-1.9 microg/m3) were determined. Concentrations of other pollutants were low. With increasing elevation and distance from the pollution source area of O3, NH3 and HNO3 concentrations decreased. Ammonia and NH4+ were dominant N pollutants indicating strong influence of agricultural emissions on forests and other ecosystems of the Sequoia National Park.     

Determination of atmospheric nitrogen input to Lake Greenwood, South Carolina: part 2--Gaseous measurements and modeling

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. A series of experiments were carried out to investigate atmospheric nitrogen (N) input into the lake. N was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. Episodic atmospheric measurements during January and March 2001 have shown that the dry N flux onto the lake ranged from 0.9 to 17.4 kg N/ha-yr, and on average is caused by nitric acid (HNO3; 31%), followed by nitrogen dioxide (NO2; 23%), fine ammonium (NH4+; 20%), coarse nitrate (NO3-; 16%), fine NO3 (5%), and coarse NH4+ (5%). Similar measurements in Greenville, SC (the upper watershed of the Reedy River), showed that the dry N deposition flux there ranged from 1.4 to 9.7 kg N/ha-yr and was mostly caused by gaseous deposition (40% NO2 and 40% HNO3). The magnitude of this dry N deposition flux is comparable to wet N flux as well as other point sources in the area. Thermodynamic modeling showed low concentrations of ammonia, relative to the particulate NH4+ concentrations.     

The use of ambient measurements to identify which precursor species limit aerosol nitrate formation

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.     

Acid neutralization of precipitation in Northern China

There is an increasing concern over the impact of human-related emissions on the acid precipitation in China. However, few measurements have been conducted so far to clarify the acid-neutralization of precipitation on a regional scale. Under a network of 10 sites across Northern China operated during a 3-year period from December 2007 to November 2010, a total of 1118 rain and snow samples were collected. Of this total, 28% was acid precipitation with pH < 5.6. Out of these acid samples, 53% were found heavily acidic with pH value below 5.0, indicating significantly high levels of acidification of precipitation. Most of the acidity of precipitation was caused by H2SO4 and HNO3, their relative contribution being 72% and 28%, respectively. However; the contribution of HNO3 to precipitation acidity will be enhanced due to the increasing NO(x) and stable SO2 emissions in future. Neutralization factors for K+, NH4+, Ca2+, Na+, and Mg2+ were estimated as 0.06, 0.71, 0.72, 0.15, and 0.13, respectively. The application of multiple regression analysis further quantified higher NH4+ and Ca2+ contribution to the neutralization process, but the dominant neutralizing agent varied from site to site. The neutralization was less pronounced in the rural than urban areas, probably due to different levels of alkaline species, which strongly buffered the acidity. Presence of high concentrations of basic ions was mainly responsible for high pH of precipitation with annual volume-weighted mean (VWM) values larger than 5.6 at several sites. It was estimated that in the absence of buffering ions, for the given concentration of SO4(2-) and NO3-, the annual VWM pH of precipitation would have been recorded around 3.5 across Northern China. This feature suggested that emissions of particles and gaseous NH3 played very important role in controlling the spatial variations of pH of precipitation in the target areas.     

Aerosol ion characteristics during the Big Bend Regional Aerosol and Visibility Observational study

The ionic compositions of particulate matter with aerodynamic diameter < or = 2.5 microm (PM2.5) and size-resolved aerosol particles were measured in Big Bend National Park, Texas, during the 1999 Big Bend Regional Aerosol and Visibility Observational study. The ionic composition of PM2.5 aerosol was dominated by sulfate (SO4(2-)) and ammonium (NH4+). Daily average SO4(2-) and NH4+ concentrations were strongly correlated (R2 = 0.94). The molar ratio of NH4+ to SO4(2-) averaged 1.54, consistent with concurrent measurements of aerosol acidity. The aerosol was observed to be comprised of a submicron fine mode consisting primarily of ammoniated SO4(2-) and a coarse particle mode containing nitrate (NO3-). The NO3- appears to be primarily associated with sea salt particles where chloride has been replaced by NO3-, although formation of calcium nitrate (Ca(NO3)2) is important, too, on several days. Size-resolved aerosol composition results reveal that a size cut in particulate matter with aerodynamic diameter < or = 1 microm would have provided a much better separation of fine and coarse aerosol modes than the standard PM2.5 size cut utilized for the study. Although considerable nitric acid exists in the gas phase at Big Bend, the aerosol is sufficiently acidic and temperatures sufficiently high that even significant future reductions in PM2.5 SO4(2-) are unlikely to be offset by formation of particulate ammonium nitrate in summer or fall.     

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

Evaluation of ozone-nitrogen oxides-volatile organic compound sensitivity of Cincinnati, Ohio

Ambient concentrations of ozone (O3), nitrogen oxides (NOx), total reactive nitrogen (NOy), nitric acid (HNO3), and hydrogen peroxide (H2O2) were measured during September 2003 at an urban site of Cincinnati, OH. The aim of this study was two-fold: to investigate whether O3 formation in this population exposure-type site is NOx, sensitive or volatile organic compound (VOC) sensitive and to test the practicality of using two combined observational-based methods to identify the sensitivity of O3 formation in midlevel polluted locations. The evaluation of the indicator species: NOy, O3/NOy, O3/HNO3, H2O2/ HNO3, and O3/(estimated NOx reaction products), as well as the combined hypothesis testing analysis of the weekend/weekday (WE/WD) differences of 1-hr and 8-hr average maximum O3 and of the 6:00 a.m.-9:00 a.m. average nitric oxide and NOx concentrations, show evidence that Cincinnati is likely VOC sensitive. Average WE 1-hr and 8-hr maximum O3, as well as duration of WE O3 accumulation, were not lower than the corresponding WD levels in spite of the observed significant reduction in NO, emissions on WE, a typical situation in VOC-sensitive locations. The possibility that the seasonal transition from summer to autumn could have influenced the results was also investigated through an exploratory analysis of the afternoon O3 maximum/NOx measured and of the WE/WD differences of peak O3 and morning average NO and NO, concentrations observed at this site from June through September 2003. The results suggest that a VOC-sensitive chemistry regime dominated along the summer season. The findings of this study suggest that additional reductions in regional NO, emissions in Cincinnati, a potential nonattainment area under the 8-hr O3 standard, may cause an increase in local O3. Future strategies to reduce O3 in Southwest Ohio should be further evaluated carefully. The combination of observational-based methods might provide a consistent complementary approach in the identification of the NO,-VOC sensitive characteristics of mid-to-moderate polluted urban areas.     

Differences between weekday and weekend air pollutant levels in southern California

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) emissions on weekday and weekend levels of ozone (O3; 1991-1998) and particulate NO3- (1980-1999) in southern California. Despite significantly lower O3 precursor levels on weekends, 20 of 28 South Coast Air Basin (SoCAB) sites (28 of all 78 southern California sites) showed statistically significant higher mean O3 levels on Sundays than on weekdays (p < 0.01); 49 of the remaining 50 sites showed no significant differences between mean weekday and Sunday peak O3 levels. We also observed no statistically significant differences between mean weekday and weekend concentrations of particulate NO3- or nitric acid (HNO3, the precursor of particulate NO3-). Averaged over sites, the mean Sunday NOx and nonmethane hydrocarbon concentrations were 25-41% and 16-30% lower, respectively, than on weekdays. Site-to-site differences between weekend and weekday mean peak hourly O3 levels were related to whether O3 formation was limited by the availability of NOx. A thermodynamic equilibrium model predicts that particulate NO3- levels would decrease in response to a reduction of HNO3, and that particulate ammonium NO3- formation was not limited by the availability of ammonia. The similarity of mean weekday and weekend levels of NO3- therefore did not result from limitations on the formation of particulate NO3- from its precursor, HNO3.     

Preliminary data from the USEPA dry deposition network: 1989

The objective of the National Dry Deposition Network is to determine patterns and trends of dry deposition for various sulfur and nitrogen species at roughly 50 locations throughout the continental USA. Each site is equipped for collection of continuous meteorological and ozone data and weekly average concentrations of SO4(2-), NO3-, SO2 and HNO3, using a three-stage filter pack. Results from 40 eastern US sites operational throughout 1989 show species-dependent variability from site to site, season to season, and day to night. Annual average concentrations of atmospheric SO4(2-), NO3-, SO2 and HNO3 ranged from 2.7 to 7.9, 0.2 to 3.9, 2.4 to 23.2 and 0.7 to 3.6 microg/m(-3), respectively. Seasonal variability was considerable for all constituents. Day/night data indicate that SO2 and HNO3, but not SO4(2-) and NO3-, are typically found at moderately to substantially lower concentrations at night, especially during spring and summer. Estimated dry deposition for SO2 and HNO3 appear to be much greater than for SO4(2-) and NO3-, respectively. Comparison of measured wet deposition and estimated dry deposition at numerous sites suggests that the two are similar in magnitude over much of the eastern USA.     

Characterization of major chemical components of fine particulate matter in North Carolina

This paper presents measurements of daily sampling of fine particulate matter (PM2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM2.5 is organic matter, and the major soluble components are sulfate (SO4(2-)), ammonium (NH4(+)), and nitrate (NO3(-)). NH4(+) is neutralized mainly by SO4(2-) rather than by NO3(-), except in winter when SO4(2-) concentration is relatively low, whereas NO3(-) concentration is high. The equivalent ratio of NH4(+) to the sum of SO4(2-) and NO3(-) is < 1, suggesting that SO4(2-) and NO3(-) are not completely neutralized by NH4(+). At both rural and urban sites, SO4(2-) concentration displays a maximum in summer and a minimum in winter, whereas NO3(-) displays an opposite seasonal trend. Mass ratio of NO3(-) to SO4(2-) is consistently < 1 at all sites, suggesting that stationary source emissions may play an important role in PM2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM2.5 mass concentrations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Evidence of enhanced atmospheric ammoniacal nitrogen in Hells Canyon national recreation area: implications for natural and cultural resources

Agriculture releases copious fertilizing pollutants to air sheds and waterways of the northwestern United States. To evaluate threats to natural resources and historic rock paintings in remote Hells Canyon, Oregon and Idaho, deposition of ammonia (NH3), nitrogen oxides (NOx), sulfur dioxide (SO2), and hydrogen sulfide (H2S) at five stations along 60 km of the Snake River valley floor were passively sampled from July 2002 through June 2003, and ozone data and particulate chemistry were obtained from the Interagency Monitoring of Protected Visual Environments (IMPROVE) station at Hells Canyon. NH3 concentrations were high; biweekly averages peaked at 5-19 ppb in spring and summer and the nutrient-laden Snake River is a likely source. Fine particulate ammonium nitrate (NH4NO3) averaged 2.6 microg/m3 during the 20% of worst visibility days with winter drainage of air masses from the Snake River Basin and possibly long distance transport from southern California. Other pollutants were within background ranges. NH3 is corrosive to clay-based pictographs; nitrogen deposition can alter natural biotic communities and terrestrial ecosystem processes at levels reported here.     

Response of inorganic fine particulate matter to emission changes of sulfur dioxide and ammonia: the eastern United States as a case study

A three-dimensional chemical transport model (PMCAMx) was used to investigate changes in fine particle (PM2.5) concentrations in response to changes in sulfur dioxide (SO2) and ammonia (NH3) emissions during July 2001 and January 2002 in the eastern United States. A uniform 50% reduction in SO2 emissions was predicted to produce an average decrease of PM2.5 concentrations by 26% during July but only 6% during January. A 50% reduction of NH3 emissions leads to an average 4 and 9% decrease in PM2.5 in July and January, respectively. During the summer, the highest concentration of sulfate is in South Indiana (12.8 microg x m(-3)), and the 50% reduction of SO2 emissions results in a 5.7 microg x m(-3) (44%) sulfate decrease over this area. During winter, the SO2 emissions reduction results in a 1.5 microg x m(-3) (29%) decrease of the peak sulfate levels (5.2 microg x m(-3)) over Southeast Georgia. The maximum nitrate and ammonium concentrations are predicted to be over the Midwest (1.9 (-3)g x m(-3) in Ohio and 5.3 microg x m(-3) in South Indiana, respectively) in the summer whereas in the winter these concentrations are higher over the Northeast (3 microg x m(-3) of nitrate in Connecticut and 2.7 microg x m(-3) of ammonium in New York). The 50% NH3 emissions reduction is more effective for controlling nitrate, compared with SO2 reductions, producing a 1.1 microg x m(-3) nitrate decrease over Ohio in July and a 1.2 microg x m(-3) decrease over Connecticut in January. Ammonium decreases significantly when either SO2 or NH3 emissions are decreased. However, the SO2 control strategy has better results in July when ammonium decreases, up to 2 microg x m(-3) (37%), are predicted in South Indiana. The NH3 control strategy has better results in January (ammonium decreases up to 0.4 microg x m(-3) in New York). The spatial and temporal characteristics of the effectiveness of these emission control strategies during the summer and winter seasons are discussed.     

Deposition of nitrogen-containing compounds to an extensively managed grassland in central Switzerland

During four intensive observation periods in 1992 and 1993, dry deposition of nitrogen dioxide (NO(2)) and ammonia (NH(3)), and wet deposition of nitrogen (N) were determined. The measurements were carried out in a small, extensively managed litter meadow surrounded by intensively managed agricultural land. Dry deposition of NH(3) was estimated by the gradient method, whereas eddy correlation was used for NO(2). Rates of dry deposition of total nitrate (= nitric acid (HNO(3)) + nitrate (NO(3)(-))), total nitrite (= nitrous acid (HONO) + nitrite (NO(2)(-))) and aerosol-bound ammonium (NH(4)(+)) were estimated using deposition velocities from the literature and measured concentrations. Both wet N deposition and the vertical NH(3) gradient were measured on a weekly basis during one year. Dry deposition was between 15 and 25 kg N ha(-1) y(-1), and net wet deposition was about 9.0 kg N ha(-1) y(-1). Daily average NO(2) deposition velocity varied from 0.11 to 0.24 cm s(-1). Deposition velocity of NH(3), was between 0.13 and 1.4 cm s(-1), and a compensation point between 3 and 6 ppbV NH(3) (ppb = 10(-9)) was found. Between 60 and 70% of dry deposition originated from NH(3) emitted by farms in the neighbourhood. It is concluded that total N deposition is exceeding the critical load for litter meadows, is highly correlated to local NH(3) emissions, and that NH(3) is of utmost importance with respect to possible strategies to reduce N deposition in rural regions.     

Dry deposition, ionic species measured and source interpretation during seasonal cycle at offshore areas near Taiwan Strait

The characterization for water-soluble species of total suspended particulate (TSP), dry deposition flux, and dry deposition velocity (V(d)) were studied at Taichung Harbor (TH) and Wuchi traffic sampling sites at offshore sampling site near Taiwan Strait of central Taiwan during March 2004-January 2005. The average concentrations of TSP and dry deposition flux at the TH sampling site were higher than at the WT sampling site during the sampling period. The samples collected were analyzed by a ion chromatography (DIONEX-100) for the ionic species (Cl(-), SO(4)(2-), NO(3)(-), NH(4)(+), Na(+), Ca(2+), and Mg(2+)) analysis. The dominant ionic species for TSP are SO(4)(2-), NO(3)(-), and NH(4)(+) of the total mass of the inorganic ions at both sampling sites. In addition, the results indicated that the NH(4)(+), NO(3)(-) and SO(4)(2-) showed higher concentrations in winter and lower in summer for both TH and Wuchi sampling sites. Statistical methods such as correlation coefficient and principal component analysis were also used to identify the possible pollutant source.     

Atmospheric nitrogen inputs to the Delaware Inland Bays: the role of ammonia

A previous assessment of nitrogen loading to the Delaware Inland Bays indicates that atmospheric deposition provides 15-25% of the total, annual N input to these estuaries. A large and increasing fraction of the atmospheric wet flux is NH(4)(+), which for most aquatic organisms represents the most readily assimilated form of this nutrient. Particularly noteworthy is a 60% increase in the precipitation NH(4)(+) concentration at Lewes, DE over the past 20 years, which parallels the increase in poultry production on the Delmarva Peninsula over this period (currently standing at nearly 585 million birds annually). To further examine the relationship between local NH(3) emissions and deposition, biweekly-integrated gaseous NH(3) concentrations were determined using Ogawa passive samplers deployed at 13 sampling sites throughout the Inland Bays watershed over a one-year period. Annual mean concentrations at the 13 sites ranged from <0.5 microg NH(3)m(-3) to >6 microg NH(3)m(-3), with a mean of 1.6+/-1.0 microg NH(3)m(-3). At most sites, highest NH(3) concentrations were evident during spring and summer, when fertilizer application and poultry house ventilation rates are greatest, and seasonally elevated temperatures induce increased rates of microbial activity and volatilization from soils and animal wastes. The observed north-to-south concentration gradient across the watershed is consistent with the spatial distribution of poultry houses, as revealed by a GIS analysis of aerial photographs. Based on the average measured NH(3) concentration and published NH(3) deposition rates to water surfaces (5-8 mm s(-1)), the direct atmospheric deposition of gaseous NH(3) to the Inland Bays is 3.0-4.8 kg ha(-1)yr(-1). This input, not accounted for in previous assessments of atmospheric loading to the Inland Bays, would effectively double the estimated direct dry deposition rate, and is on par with the NO(3)(-) and NH(4)(+) wet fluxes. A second component of this study examined spatial differences in NO(3)(-) and NH(4)(+) wet deposition within the Inland Bays watershed. In a pilot study, precipitation composition at the Lewes NADP-AIRMoN site (DE 02) was compared with that at a satellite site established at Riverdale on the Indian River Estuary, approximately 21 km southwest. While the volume-weighted mean precipitation NO(3)(-) concentrations did not differ significantly between sites, the NH(4)(+) concentration observed at Riverdale (26.3 micromoles L(-1)) was 73% greater than at Lewes (15.2 micromoles L(-1)). More recently, a NADP site was established at Trap Pond, DE (DE 99), which was intentionally located within the region of intense poultry production. A comparison of the initial two years (6/2001-5/2003) of precipitation chemistry data from Trap Pond with other nearby NADP-AIRMoN sites (Lewes and Smith Island) reveals fairly homogeneous NO(3)(-) wet deposition, but significant spatial differences ( approximately 60%) in the NH(4)(+) wet flux. Overall, these results suggest that local emissions and below-cloud scavenging provide a significant contribution to regional atmospheric N deposition.