Particulate composition characteristics under different ambient air quality conditions

Particulate compositions including elemental carbon (EC), organic carbon (OC), water-soluble ionic species, and elemental compositions were investigated during the period from 2004 to 2006 in southern Taiwan. The correlation between the pollutant standard index (PSI) of ambient air quality and the various particle compositions was also addressed in this study. PSI revealed a correlation with fine (r = 0.74) and coarse (r = 0.80) particulate matter (PM). PSI manifested a significant correlation with the amount of analyzed ionic species (r approximately 0.80) in coarse and fine particles and a moderate correlation with carbon content (r = 0.63) in fine particles; however, it showed no correlation with elemental content. Although the ambient air quality ranged from good to moderate, the ionic species including chloride (Cl-), nitrate (NO3-), sulfate (SO4(2-)), sodium (Na+), ammonium (NH4+), magnesium (Mg2+), and calcium (Ca2+) increased significantly (1.5-3.7 times for Daliao and 1.8-6.9 times for Tzouying) in coarse PM. For fine particles, NO3-, SO4(2-), NH4+, and potassium (K+) also increased significantly (1.3-2.4 times for Daliao and 2.8-9.6 times for Tzouying) when the air quality went from good to moderate. For meteorological parameters, temperature evidenced a slightly negative correlation with PM concentration and PSI value, which implied a high PM concentration in the low-temperature condition. This reflects the high frequency of PM episodes in winter and spring in southern Taiwan. In addition, the mixing height increase from 980 to 1450 m corresponds to the air quality condition changing from unhealthy to good.     

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.     

Multivariate space analysis of the major precipitation ions over Europe, 1986-1997

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

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.     

Assessment of the potential for soil acidification in North India using the critical load approach and locally derived data for acidic and basic inputs

Major ions (Cl-, NO3(-), SO4(2-), Ca2+, Mg2+, Na+, K+ and NH4(+)) were analysed in wet and dry deposition samples collected for 2 years using a polyethylene bottle and funnel collector at Agra in India. The deposition of ionic components (Ca2+ and Mg2+) derived from natural sources i.e. soil were higher than those of anthropogenic origin. In rainwater samples, non-sea-salt fraction was found to be 60-90%. In both wet and dry deposition Ca2+ was found to be the dominant ion which may be due to its large particle diameter. Results suggest that most of the acidity, which occurs due to NO3(-), SO4(2-) and Cl- is neutralized by alkaline constituents, which originate from airborne local soil and dust transported from the Thar desert. Acid neutralizing capacity of soil has also been quantified and found to be 33 x 10(3) neqg(-1). Using deposition data, the critical load for acidity of soil with respect to Ashoka and Eucalyptus was evaluated. The present level of deposition of S and N was found to be much lower than critical loads calculated for S and N. Critical load of exceedance in terms of deposition acidity was also calculated and found to be negative. This indicates that with respect to these species, the ecosystem is protected at the current level of deposition.     

Application and evaluation of two air quality models for particulate matter for a southeastern U.S. episode

The Models-3 Community Multiscale Air Quality (CMAQ) Modeling System and the Particulate Matter Comprehensive Air Quality Model with extensions (PMCAMx) were applied to simulate the period June 29-July 10, 1999, of the Southern Oxidants Study episode with two nested horizontal grid sizes: a coarse resolution of 32 km and a fine resolution of 8 km. The predicted spatial variations of ozone (O3), particulate matter with an aerodynamic diameter less than or equal to 2.5 microm (PM2.5), and particulate matter with an aerodynamic diameter less than or equal to 10 microm (PM10) by both models are similar in rural areas but differ from one another significantly over some urban/suburban areas in the eastern and southern United States, where PMCAMx tends to predict higher values of O3 and PM than CMAQ. Both models tend to predict O3 values that are higher than those observed. For observed O3 values above 60 ppb, O3 performance meets the U.S. Environmental Protection Agency's criteria for CMAQ with both grids and for PMCAMx with the fine grid only. It becomes unsatisfactory for PMCAMx and marginally satisfactory for CMAQ for observed O3 values above 40 ppb. Both models predict similar amounts of sulfate (SO4(2-)) and organic matter, and both predict SO4(2-) to be the largest contributor to PM2.5. PMCAMx generally predicts higher amounts of ammonium (NH4+), nitrate (NO3-), and black carbon (BC) than does CMAQ. PM performance for CMAQ is generally consistent with that of other PM models, whereas PMCAMx predicts higher concentrations of NO3-, NH4+, and BC than observed, which degrades its performance. For PM10 and PM2.5 predictions over the southeastern U.S. domain, the ranges of mean normalized gross errors (MNGEs) and mean normalized bias are 37-43% and -33-4% for CMAQ and 50-59% and 7-30% for PMCAMx. Both models predict the largest MNGEs for NO3- (98-104% for CMAQ 138-338% for PMCAMx). The inaccurate NO3- predictions by both models may be caused by the inaccuracies in the ammonia emission inventory and the uncertainties in the gas/particle partitioning under some conditions. In addition to these uncertainties, the significant PM overpredictions by PMCAMx may be attributed to the lack of wet removal for PM and a likely underprediction in the vertical mixing during the daytime.     

Precipitation chemistry in the coast of the Metropolitan Region of Rio de Janeiro, Brazil

Precipitation chemistry was studied in the Metropolitan Region of Rio de Janeiro (MRRJ). This study reveals that rainwater in the MRRJ is affected by emissions of air pollutants and provides essential data for future estimates of regional biogeochemical cycles and the impacts of acid deposition on tropical ecosystems. The volume-weighted mean (VWM) pH was 4.77, varying from 3.50 to 6.85. Sea-salt aerosols were the dominant sources of the Na+, Cl- and Mg2+. Excess SO4(2-), Ca2+ and K+ comprised 82, 91, and 87% of their total VWM concentrations, respectively. There were very strong correlations (r > 0.75, P > 0.01) for NO3- and H+, NO3- and excess(exc-)SO4(2-), NH4+ and exc-K+, and exc-SO4(2-) and exc-Ca2+, suggesting causal relationships between these ion pairs. The VWM concentrations of all major ions, except H+, were higher in the dry season, with dry to wet VWM concentration ratios varying from 1.1 (NH4+) to 4.7 (for total K+).     

Determination of source contributions to ambient PM2.5 in Kaohsiung, Taiwan, using a receptor model

Ambient particulates of PM2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM2.5. The mean concentration of ambient PM2.5 was 42.69-53.68 micrograms/m3 for the sampling period. The abundant species in ambient PM2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO4(2-) (12.8-15.1%), NO3- (8.1-10.3%), NH4+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO4(2-) and NO3-), and outdoor burning of agriculture wastes (13-17%).     

Mass-size distributions of particulate sulfate, nitrate, and ammonium in a particulate matter nonattainment region in southern Taiwan

Concentrations and distributions of three major water-soluble ion species (sulfate, nitrate, and ammonium) contained in ambient particles were measured at three sampling sites in the Kao-ping ambient air quality basin, Taiwan. Ambient particulate matter (PM) samples were collected in a Micro-orifice Uniform Deposit Impactor from February to July 2003 and were analyzed for water-soluble ion species with an ion chromatograph. The PM1/ PM2.5 and PM1/PM10 concentration ratios at the emission source site were 0.73 and 0.53 and were higher than those (0.68 and 0.48) at the background site because there are more combustion sources (i.e., industrial boilers and traffic) around the emission source site. Mass-size distributions of PM NO3- were found in both the fine and coarse modes. SO4(2-)and NH4+ were found in the fine particle mode (PM2.5), with significant fractions of submicron particles (PM1). The source site had higher PM1/PM10(79, 42, and 90%) and PM1/PM2.5 concentration ratios (90, 58, and 93%) for the three major inorganic secondary aerosol components (SO4(2-), NO3-, and NH4+) than the receptor site (65, 27, and 65% for PM1/PM10, 69, 51, and 70% for PM1/PM2.5. Results obtained in this study indicate that the PM1 (submicron aerosol particles) fraction plays an important role in the ambient atmosphere at both emission source and receptor sites. Further studies regarding the origin and formation of ambient secondary aerosols are planned.     

Temporal variation in daily concentrations of ozone and acid-related substances at Saturna Island, British Columbia

A multiple linear regression model was used to investigate seasonal and long-term trends in concentrations of ozone (O3) and acid-related substances at the Saturna Island monitoring station in southwestern British Columbia from 1991 to 2000. Statistically significant primary (dominant) cycles with a period of 1 yr were found for O3, sulfur dioxide (SO2), nitric acid (HNO3), and aerosol concentrations of sulfate (SO4(2-)), calcium (Ca2+) and chloride (Cl-). Of these, peak median concentrations occurred during the spring for O3 and Ca2+, during the warmer, drier months (April-September) for SO4(2-) and HNO3, and during the cooler, wetter months (October-March) for SO2 and Cl-. Statistically significant secondary cycles of 6 months duration were seen for concentrations of O3, SO4(2-), HNO3, Ca2+, and Cl-. Daily maximum O3 concentrations exhibited a statistically significant increase over the period of record of 0.33 +/- 0.26 ppb/yr. Statistically significant declines were found for concentrations of SO2, SO4(2-), HNO3, Ca2+, and potassium, ranging from 20 to 36% from levels at the start of the sampling period. Declines in ambient concentrations of SO2, SO4(2-), and HNO3 reflect local declines in anthropogenic emissions of the primary precursors SO2 and NOx over the past decade. Trends in Ca2+ and potassium ion concentrations are in line with a broader North American declining trend in acid-neutralizing cations.     

Chemical fingerprint and source apportionment of PM 2.5 in highly polluted events of southern Taiwan

To investigate the spatial distribution and diurnal variation of the chemical composition of PM2.5 pollution in an industrial city of southern Taiwan, 12-h PM2.5 was diurnally continuously collected simultaneously at the Kaoping Air Quality Zone (KAQZ) during one highly PM2.5-polluted episode. Water-soluble ions, metallic elements, carbonaceous contents, dicarboxylic acids, and anhydrosugars were analyzed to characterize the chemical fingerprint of PM2.5. Backward trajectory simulation and chemical mass balance (CMB) receptor modeling were applied to identify the potential sources of PM2.5 and their contributions. It showed that Chaozhou (rural area) accompanying the highest SORs and NORs suffered from the most severe PM2.5 pollution during the episode. Sulfate (SO42−) was probably formed by the atmospheric chemical reaction in the daytime, while NO3− processed at nighttime at the KAQZ. A homogeneous formation of NO3− occurred at Chaozhou. The concentrations of Zn, Pb, Fe, Cu, V, and Al, mainly emitted from anthropogenic sources, increased significantly at the KAQZ. The highest OC, SOC/OC, and DA/OCs at Daliao (industrial area) were attributed to the transformation of primary VOCs to secondary OC via photo-oxidation during the episode. Oxalic acid was mainly produced through photochemical reactions since a high correlation between oxalic acid and Ca2+ was observed at Nanzi (urban area) and Daliao during the episode. During the episode, PM2.5 mostly originated from local primary or secondary aerosol than long-range overseas transport. The dominant source was anthropogenic emissions, accounting for 67.1% and 70.4% of PM2.5 at Nanzi and Daliao, respectively. At Chaozhou, the contribution of anthropogenic emissions was the lowest (42.4%), but secondary aerosols had the highest contribution of 38.3% of PM2.5 among the three areas during the episode.     

Particle size distribution and anion content at a traffic site in Sha-Lu, Taiwan.

Ambient air particle concentrations were sampled by two total suspended particle (TSP) samplers, PM10/PM2.5 specific sampler and micro-orifice uniform deposit impactor (MOUDI) during July-October 2000 at a traffic sampling site in central Taiwan. The average TSP concentration (194 microg/m3) was about a factor of two higher than that of the fraction <2.5 microm (93.2 microg/m3). The mean level of the fraction <10 microm collected by MOUDI (93.2 microg/m3) was about 1 1/2 times higher than that of the size class <2.5 microm (43.8 microg/m3). Furthermore, this fraction showed a certain correlation with the TSP concentration. The particle size distribution was bimodal in the ambient air at the traffic site. The major peaks appear at particle diameters between 0.56-1.0 and 3.2-5.6 microm. The percentages of anions contained in TSP were 0.24% F-, 13.7% Cl, 0.52% Br, 12.0% NO-, 18.9% NO2-, and 54.6% SO2-. The Cl-, NO2-, and NO3- size distributions were all unimodal and the major peaks appeared at 3.2-5.6 microm. The SO2 size distribution was bimodal, with major peaks at 0.32-0.56 and 3.2-5.6.     

Composition of wet deposition in Kaynarca,Turkey

In this work, composition of wet deposition in Kaynarca, Turkey is studied by collecting precipitation samples during more than a 2-year period. August 1993-November 1995. Concentrations of the main cations Na+, Mg2+, Ca2+, K+, NH4+ and the main anions Cl-, NO3- and SO4(2-) together with pH were studied. The average pH value at Kaynarca was near neutral, 5.59. Results indicated that SO4(2-) concentration in precipitation was very high, as was Ca2+, neutralizing the acidity. Acidic wet deposition samples were generally obtained in winter. Enrichment factors for sea and soil indicate the strong effects of sea and soil, specifically limestone on the composition of precipitation. Non-sea salt fractions of SO4(2-) were found to range from 0.955 to 0.980, showing the effect of non-sea sources, especially emissions from fossil-fuel combustion, on the pH of samples. Trajectory analysis showed that cyclones originating from northwestern, central and eastern parts of Europe have generally high sulfate and nitrate concentrations and low pH.     

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.     

Atmospheric deposition and ionic interactions within a beech canopy in the Karkonosze Mountains

A method, of artificial foliage placed above rain collectors, which enables to estimate total atmospheric inputs of elements, was employed to study processes related to ionic flow through a tree canopy. The investigations were conducted within a beech forest in the Karkonosze Mountains, in 1996-1997. An analysis of net canopy exchange (throughfall flux-atmospheric input) revealed that NH4+, NO3-, H+ had been retained in the canopy, Ca2+, Na+, Cl-, SO(2-)4, PO(3-)4 flowed passively, whereas K+ and Mg2- had been removed from the tree foliage. Ammonium absorption was more efficient than that of NO3- ions, because NH4+ was taken up from rain-waters and aerosol-gaseous fraction of the atmospheric input, whereas NO3- ions were captured primarily from the latter source. Retention of H+ was also related exclusively to the aerosol-gaseous input. Leaching losses of K+ and Mg2+ did not result from exchange reactions of these ions with retained H+, but from ionic exchange between NH4+ and K+ + Mg2+. At the same time, neutralisation of H+ in the canopy has been attributed to NO3- absorption, resulting most likely from HNO3 vapour penetration into the plants.     

Quality of roof runoff waters from an urban region (Gdańsk,Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gdańsk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na+, K+, NH4+, Mg2+, Ca2+, F-, Cl-, NO2-, NO3-, PO4(3-), SO4(2-) ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

Atmospheric dry deposition to leaf surfaces at a rural site of India

Dry deposition flux of major ions (Na+, K+, Ca2+, Mg2+, NH4+, F-, Cl-, NO3- and SO4(2-) to natural surfaces [guava (Psidium guyava) and peepal (Ficus religiosa) leaves] are determined at Rampur, a rural site of semi-arid region of India. Dry deposition flux is the highest for Ca2+ on guava leaves and for NH4+ on peepal leaves. Overall dry deposition flux is higher on guava leaves than of peepal leaves. The variation in deposition flux may be due to surface characteristics (surface roughness) and arrangement of leaves. Peepal leaves are arranged along the axis of the stem, whereas guava leaves are at right angles to the stem. The deposition flux of cations contributes 66% and 76% of dry deposition of all major ions on guava and peepal leaves, respectively as soil is major contributor towards dry deposition flux in tropical regions. ANOVA revealed no significant seasonal difference in deposition, although there is a trend for higher in winter. Deposition velocities of NH4+, NO3- and SO4(2-) are greater on guava leaves than peepal leaves, which can be attributed to the rougher surface of the guava leaf.     

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.     

Size mass distribution of water-soluble ionic species and gas conversion to sulfate and nitrate in particulate matter in southern Taiwan

A Micro-Orifice Uniform Deposition Impactor (MOUDI) and a Nano-MOUDI were employed to determine the size-segregated mass distributions of ambient particulate matter (PM) and water-soluble ionic species for particulate constituents. In addition, gas precursors, including HCl, HONO, HNO₃, SO₂, and NH₃ gases, were analyzed by an annular denuder system. PM size mass distribution, mass concentration, and ionic species concentration were measured during the day and at night during episode and non-episode periods in winter and summer. Average total suspended particle (TSP) concentrations during episode days in winter were as high as 153?±?33 μg/m³, and PM mass concentrations in summer were as low as one-third of that in winter. Generally, PM concentration at night was higher than that in the daytime in southern Taiwan during the sampling periods. In winter during the episode periods, the size-segregated mass distribution of PM mass concentration was mostly in the 0.32–3.2-μm range, and the PM concentration increased significantly in the range of 0.32–3.2 μm at night. Ammonium, nitrate, and sulfate were the dominant water-soluble ionic species in PM, contributing 34–48 % of TSP mass. High concentrations of ammonia (12.9–49 μg/m³) and SO₂ (2.6–27 μg/m³) were observed in the gas precursors. The conversion ratio was high in the PM size range of 0.18–3.2 μm both during the day and at night in winter, and the conversion ratio of episode days was 20 % higher than that of non-episode days. The conversion factor was high for both nitrogen and sulfur species at nighttime, especially on episode days.     

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.