A new measurement method for nitrogen oxides in the air using an annular diffusion scrubber coated with titanium dioxide

A new convenient measurement method of nitrogen oxides (NO_x) in the ambient air was developed. The collection of NO_x is performed by an annular diffusion scrubber coated with a mixture of titanium dioxide (TiO₂) and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) and the analysis is carried out by ion chromatography with conductivity detection. Under ultraviolet light (UV) illumination, TiO₂ produces reactive oxygen species such as super oxide (O₂⁻), hydroxyl radical (OH·) and peroxyhydroxyl radical (HO₂·), by which nitric oxide (NO) is oxidized to nitrogen dioxide (NO₂), and is further oxidized to nitric acid (HNO₃). The yielded HNO₃ and NO₂ are effectively adsorbed on the surface of TiO₂ and hydroxyapatite. The collection efficiencies of NO and NO₂ by the annular diffusion scrubber coated with the catalysts under UV illumination are higher than 98%, respectively, at the air flow rate of 0.2–1.0 l min⁻¹. After the collection of NO_x, by feeding deionized water into the annular diffusion scrubber, HNO₃ and NO₂ which adsorbed on the catalysts are extracted as forms of nitrite ion (NO₂⁻) and nitrate ion (NO₃⁻). The extraction efficiencies of NO and NO₂ are almost 100%. The activity of the washed catalysts can be completely recovered by drying with the purified air. Further, a simultaneous separated measurement of NO and NO₂ can be performed by utilizing the UV illumination dependence. This method was applied to the measurement of NO_x in the ambient air. The NO_x concentration measured by this method was in good agreement with that obtained using the chemiluminescence NO_x analyzer.     

Simulation of Sulfate and Nitrate Chemistry in Power Plant Plumes

ABSTRACT

The rate of formation of secondary particulate matter (PM) in power plant plumes varies as the plume material mixes with the background air. Consequently, the rate of oxidation of sulfur dioxide (SO₂) and nitrogen dioxide (NO₂) to sulfate and nitric acid, respectively, can be very different in plumes and in the background air (i.e., air outside the plume). In addition, the formation of sulfate and nitric acid in a power plant plume is a strong function of the chemical composition of the background air and the prevailing meteorological conditions.

We describe the use of a reactive plume model, the Reactive and Optics Model of Emissions, to simulate sulfate and nitrate formation in a power plant plume for a variety of background conditions. We show that SO₂ and NO₂ oxidation rates are maximum in the background air for volatile organic compound (VOC)-limited airsheds but are maximum at some downwind distance in the plume when the background air is nitrogen oxide (NO_x)-limited. Our analysis also shows that it is essential to obtain measurements of background concentrations of ozone, aldehydes, peroxyacetyl nitrate, and other VOCs to properly describe plume chemistry.     

Source apportionment analysis of atmospheric particulates in an industrialised urban site in southwestern Spain

A detailed physical and chemical characterisation of total suspended particles (TSP) in the highly industrialised city of Huelva (southwestern Spain) was carried out. The results evidenced a coarse grain-size prevalence (PM₁₀ accounting for only 40% of TSP mass, 37 and 91 μg/m³, respectively). PM₁₀ levels are in the usual range for urban background sites in Spain. The crustal, anthropogenic and marine components accounted for a mean of a 40%, 24% and 5% of bulk TSP, respectively. As expected from the industrial activities, relatively high PO₄³⁻ and As levels for an urban site were detected. In addition to the crustal and marine components, source apportionment analysis revealed three additional emission sources influencing the levels and composition of TSP: (a) a petrochemical source, (b) a mixed metallurgical-phosphate source, (c) and an unknown source (Sb and NO₃⁻).Due to the high local emissions, the mean TSP anthropogenic contribution (mostly PM₁₀) obtained for all possible air mass transport scenarios reached 18–29 μg/m³. The 2010 annual EU PM₁₀ limit value (20 μg/m³) would be exceeded by the anthropogenic load recorded for all the air mass transport scenarios, with the exception of the North Atlantic transport (only 15% of the sampling days). Under African air mass transport scenarios (20% of sampling days), the TSP crustal contribution reached near three times the local crustal contribution. It must be pointed out that this crustal input should diminish when sampling PM₁₀ due to the dominant coarse size distribution of this type of particles.     

Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

Dry atmospheric inputs of trace metals at the Mediterranean coast of Israel (SE Mediterranean): sources and fluxes

This study presents the first detailed data on aerosol concentrations of trace metals (Cd, Pb, Cu, Zn, Cr, Mn, Fe and Al) at the SE Mediterranean coast of Israel, and assesses their sources and fluxes. Aerosol samples were collected at two sampling stations (Tel-Shikmona and Maagan Michael) along the coast between 1994 and 1997. Two broad categories of aerosol trace metal sources were defined; anthropogenic (Cd, Cu, Pb and Zn) and naturally derived elements (Al, Fe, Mn and Cr). The extent of the anthropogenic contribution was estimated by the degree of enrichment of these elements compared to the average crustal composition (EF_crust). High values (median >100) were calculated for Cd, Pb and Zn, minor values for Cu and relatively low values (<10) for Fe, Mn and Cr. The crustal-derived elements exhibited a statistically significant seasonal pattern of higher concentrations during spring and autumn (e.g. Al concentrations in some cases during these periods were observed to be in excess of 1500 ng m⁻³). In the eastern Mediterranean basin crustal-dominated elements are enriched by 2–3 times while others (Cd and Pb) are comparable to the northwestern Mediterranean. The Pb : Cd ratios of ∼150 are higher than in coastal European sites (60–116) or emission materials (∼50). It is speculated that these differences are attributed mainly to the mixing of crustal material with local and European emissions. At present, it is impossible to quantify the latter two fractions. Back trajectory analysis and the subsequent categorization of two main aerosol populations, ‘European’ and ‘North Africa–Arabian’, exhibited a significantly different geochemical imprint on the aerosol chemical composition. ‘European’-derived air masses indicated significantly higher EF_crust values for Cd and Pb due to the greater anthropogenic character of the aerosol population, with a dilution by crustal material of this population leading to comparatively lower EF_crust values associated with the North African–Arabian air masses.     

Atmospheric gas and particle measurements at a rural northeastern U.S. site

Ammonia, nitric acid, sulfur dioxide and particles in two size ranges were collected at a rural site in northeastern U.S. in January–March 1984. Ammonia was collected with an oxalic acid coated denuder, all other components were collected on filters. The concentrations of ammonia ranged between 0.0 and 0.5 ppbv, nitric acid: 0.1 and 2.3 ppbv and sulfur dioxide: 1 and 52 ppbv. Ammonium and sulfate in the fine particles were highly correlated, the regression line indicated that the most abundant compound was ammonium sulphate. The content of free hydronium ions in the fine particles was well below the ammonium content. No correlation between NH₃ and NH⁺₄, HNO₃ and NO₃ SO₃ and SO⁻²₄ could be observed.     

Formation of particulate sulfur species (sulfate and methanesulfonate) during summer over the Eastern Mediterranean: A modelling approach

To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO₄²⁻) and methanesulfonate (MS_x used here to represent the sum of gaseous methanesulfonic acid, MSA, and particulate methanesulfonate, MS⁻) in the eastern Mediterranean and to evaluate the relative contribution of biogenic and anthropogenic sources to the S budget, a chemical box model coupled offline with an aerosol–cloud model has been used.Based on the measurements of gaseous dimethyl sulfide (DMS) and methanesulfonic acid (MSA) and the MSA sticking coefficient determined during the Mediterranean Intensive Oxidant Study (MINOS) experiment, the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to be about 0.3%. Consequently, MSA production from gas-phase oxidation of DMS is too small to explain the observed levels of MS⁻. On the other hand, heterogeneous reactions of dimethyl sulfoxide (DMSO) and its gas-phase oxidation product methanesulfinic acid (MSIA) can account for most of the observed MS⁻ levels. The modelling results indicate that about 80% of the production of MS⁻ can be attributed to heterogeneous reactions.Observed submicron nss-SO₄²⁻ levels can be fully explained by homogeneous (photochemical) gas-phase oxidation of sulfur dioxide (SO₂) to sulfuric acid (H₂SO₄), which is subsequently scavenged by (mainly submicron) aerosol particles. The predominant oxidant during daytime is hydroxyl radical (OH) showing very high peak levels in the area during summer mostly under cloudless conditions. Therefore, during summer in the east Mediterranean, heterogeneous sulfate production appears to be negligible. This result is of particular interest for sulfur abatement strategy. On the other hand only about 10% of the supermicron nss-SO₄²⁻ can be explained by condensation of gas-phase H₂SO₄, the rest must be formed via heterogeneous pathways.Marine biogenic sulfur emissions contribute up to 20% to the total oxidized sulfur production (SO₂ and H₂SO₄) in good agreement with earlier estimates for the area.     

Fine particle measurements at two background sites in Korea between 1996 and 1997

Five intensive field measurements were carried out at two background sites in Korea; Kosan and Kangwha during spring, fall, and winters of 1996 and 1997 to investigate the characteristics of long-range transport of air pollutants in northeastern Asia. Fine particles (PM_2.5) were collected by low-volume samplers and the concentrations of major ions, organic and elemental carbons, and nitric acid were quantified. The concentrations of anthropogenic species in PM_2.5 measured at both sites were generally higher than those at other background areas, Nagano, Japan and San Nicolas Is., USA due to continental outflow of air pollutants, but lower than those at an urban background site, Qingdao, China. The major components of PM_2.5 were sulfate, organic carbon (OC), and ammonium for Kosan and sulfate, OC, ammonium, and nitrate for Kangwha. The major fractions of sulfate at both sites are non-sea-salts (nss) sulfate. Based on the relationship among major anthropogenic species, analysis of the nss sulfate to total nitrate molar ratios, and backward air parcel trajectories, it was found that fine particles measured at both sites during the measurement periods are mainly coming from China. At Kosan, the concentrations of anthropogenic species were higher when air parcels were coming from southern China than when air parcels were from northern China. At Kangwha, however, the differences of the concentrations were not statistically significant since most air parcels were from northern China and local effects are prominent.     

Chemical characteristics of atmospheric aerosols over southwest coast of India

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

Measurements of Sulfur Oxides,Nitrogen Oxides,Haze and Fine Particles at a Rural Site on the Atlantic Coast

During August, 1982 and January and February, 1983, General Motors Research Laboratories operated air monitoring sites on the Atlantic Coast near Lewes, Delaware and 1250 km to the east on the southwest coast of Bermuda. The overall purpose of this project was to study the transformations of the principal acid precipitation precursors, NO _x and SO _x species, as they transport under conditions not complicated by emissions from local sources. In this paper, the measurements of gas and particulate species from Lewes are described and the composition and sources of sulfate aerosol, which is the most important haze-producing species, are investigated.

On the average, the total suspended particulate (TSP) concentration was 27.9 μg/m³ while the PM₁₀ (mass of particles with a diameter less than or equal to 10 μm) concentration was 22.0 μg/m³ or 79 percent of the TSP. The PM₁₀ consisted of 6.1 μg/m³ of coarse particles (CPM, diameter = 2.5 ? 10μm) and 15.9 μg/m³ of fine particles (FPM, diameter < 2.5 μm).

On a mass basis the most important constituents of the fine particulate fraction were sulfate compounds, 50 percent, and organic compounds, 30 percent. The mean light extinction coefficient corresponds to a visual range of 18-20 km. Most of the extinction can be attributed to the sulfate (60 percent) and organic carbon (13 percent). Particle size measurements show that the mass median aerodynamic diameter for both species is 0.43 μm. This is a typical size for a hydrated sulfate aerosol. For carbon, however, this is a larger size than previously reported and results in a more efficient light scattering aerosol. Principal component analyses indicate that coal combustion emissions from the midwestern U.S. are the most significant source of sulfate in Lewes during the summer and winter.     

Background levels of air and precipitation quality for Europe

This paper is intended to be used by specialists engaged in air and precipitation quality management on regional and continental scales. Major goals are to establish definition, methodology and specific values of background air and precipitation quality for sulfur (S) and nitrogen (N) species to be used in practical applications of air resources management. Major findings are the following:

• 1.(a) 69% of SO₂ and 63 % of NO₂ concentration over Europe originate from continental scale anthropogenic sources,
• 2.(b) 15% of precipitation sulfate and 11% of precipitation nitrate over Europe are contributed by hemispheric background,
• 3.(c) hemispheric background pollution values for Europe were found as 1.25 μg (SO₂-S)m⁻³, 0.80 μg (SO₄²⁻-S)m⁻³, 0.157 mg (SO₄²⁻-S)l⁻¹ and 0.04 mg (NO₃⁻-N)ℓ⁻¹.

     

Characteristics of PM2.5 carbonaceous aerosol in the Sihwa industrial area,Korea

In order to investigate the characteristics of carbonaceous fine aerosols, PM_2.5 particulate samples were collected in the Sihwa industrial complex area between February 1998 and 1999 and in Seoul between 31 May and 9 June 1999, respectively. The carbonaceous species were analyzed by the selective thermal manganese dioxide oxidation (TMO) method. In Sihwa, average OC and EC concentrations for the entire data set were measured to be 9.8 and 1.8 μg m⁻³, respectively. The OC concentrations were higher than those measured in other urban environments. The EC concentrations were lower than those of other urban environments. The OC/EC ratio measured at the Sihwa area was higher than those at other urban and rural environments. Backward trajectories of sampled air masses were performed to find out the sources of those higher OC/EC levels. Enrichment in the organic compounds during winter periods can be explained by the combination of primary local emissions from the industrial complex area and long-range transport of organic species from outside the Sihwa area. High OC values in June resulted from primary anthropogenic emissions and secondary organic aerosol formation rather than the atmospheric transport of organic compounds from the outside. In urban area of Seoul, the OC and EC concentrations in PM_2.5 during the summer were higher than those measured at other urban atmospheres. OC/EC ratios obtained in Seoul were lower than Sihwa. It can be concluded that carbonaceous species in Seoul were mainly emitted from primary anthropogenic sources.     

Arctic air pollution: An overview of current knowledge

From December to April, the Arctic air mass is polluted by man-made mid-latitudinal emissions from fossil fuel combustion, smelting and industrial processes. In the rest of the year, pollution levels are much lower. This is the outcome of less efficient pollutant removal processes and better south (S) to north (N) transport during winter. In winter, the Arctic air mass covers much of Eurasia and N. America. Meteorological flow fields and the distribution of anthropogenic SO₂ emissions in the northern hemisphere favor northern Eurasia as the main source of visibility reducing haze. Observations of SO₄²⁻ concentrations in the atmosphere throughout the Arctic yield, depending on location and year, a January–April mean of 1.5–3.9 μg m⁻³ in the Norwegian Arctic to 1.2–2.2 μg m⁻³ in the N. American Arctic. An estimate of the mean vertical profile of fine particle aerosol mass during March and April shows that, on average, pollution is concentrated in the lower 5 km of the atmosphere. Not only are anthropogenic particles present in the Arctic atmosphere but also gases such as SO₂, perfluorocarbons and pesticides. The acidic nature and seasonal variation of Arctic pollution is reflected in precipitation, the snowpack and glacier snow in the Arctic. A pH of 4.9–5.2 in winter and ~ 5.6 in summer is expected in the absence of calcareous wind blown soil. Glacial records indicate that Arctic air pollution has undergone a marked increase since the mid 1950s paralleling a marked increase in SO₂ and NO_x emissions in Europe. Effects of Arctic pollution include a reduction in visibility and perturbation of the solar radiation budget in April–June. Potential effects are the acidification and toxification of sensitive ecosystems.     

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.     

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

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

Processes Influencing Secondary Aerosol Formation in the San Joaquin Valley during Winter

Abstract

Air quality data collected in the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM_2.5) mass concentrations in California (≤188 μg/m³ 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO_x)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO_x and volatile organic compound (VOC) emissions plus background O₃ levels are expected to determine NO_x oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Statistical summary and analyses of event precipitation chemistry from the MAP3S network, 1976–1983

The MAP3S precipitation chemistry network base of event chemistry data includes nine sites widely distributed over the northeastern quadrant of the United States. Eight or these sites now have a period of record of at least 5 years. Four species (total sulfur, NO⁻₃, H⁺ and NH⁺₄) account for the bulk of ionic equivalents at seven inland sites; Ca²⁺ is nearly as important as NH⁺₄ at several of the inland sites, and sea salt species are major components at the two coastal sites. Average pH values (from arithmetic mean H⁺) range from 4.03 to 4.24 over the network. Time trend analyses for the period for sulfur and H⁺ show a consistent decrease, but the decrease is quite small and has low statistical significance; NO⁻₃; and NH⁺₄ show similar though less consistent trends. Significant seasonal trends (summer maximum, winter minimum) are found at most sites for sulfur and NH⁺₄; NO⁻₃ has a much weaker seasonal trend except at the coastal sites. Species pair correlations are strong among the four major ions, with the exception of correlations involving H⁺ at sites where crustal species are more important (Illinois, Ohio). Correlations can qualitatively be explained by common sources (crustal, sea-salt, anthropogenic), polluted vs nonpolluted events, and strong seasonal trends.     

A dynamic dilution system for the production of sub-ppb concentrations of reactive and labile species

A three-stage dynamic dilution system has been developed capable of generating calibration standards below 100 pptv using gravimetrically calibrated permeation tubes as a trace species source. Multistage dilution permits the use of equivalent one-step diluent flows approaching 1000 std 1 min ⁻¹. An allfluorocarbon flow path facilitates the handling of reactive and labile species. Accuracies of about ± 3 % have been demonstrated for several sulfur compounds including H₂S and SO₂ at mixing ratios below 200 ppt.     

Study of aerosol transport through precipitation chemistry over Arabian Sea during winter and summer monsoons

Precipitation samples over the Arabian Sea collected during Arabian Sea Monsoon Experiment (ARMEX) in 2002–2003 were examined for major water soluble components and acidity of aerosols during the period of winter and summer monsoon seasons. The pH of rain water was alkaline during summer monsoon and acidic during winter monsoon. Summer monsoon precipitation showed dominance of sea-salt components (∼90%) and significant amounts of non-sea salt (nss) Ca²⁺ and SO₄²⁻. Winter monsoon precipitation samples showed higher concentration of NO₃⁻ and NH₄⁺ compared to that of summer monsoon, indicating more influence of anthropogenic sources. The rain water data is interpreted in terms of long-range transport and background pollution. In summer monsoon, air masses passing over the north African and Gulf continents which may be carrying nss components are advected towards the observational location. Also, prevailing strong southwesterly winds at surface level produced sea-salt aerosols which led to high sea-salt contribution in precipitation. While in winter monsoon, it was observed that, air masses coming from Asian region towards observational location carry more pollutants like NO₃⁻and nss SO₄²⁻ that acidify the precipitation.     

Application of positive matrix factorization in source apportionment of particulate pollutants in Hong Kong

An advanced algorithm called positive matrix factorization (PMF) in receptor modeling was used to identify the sources of respirable suspended particulates (RSP) in Hong Kong. The compositional data obtained from the Hong Kong Environmental Protection Department from 1992 to 1994 were analyzed. The species analyzed in this study are Al, Ca, Mg, Pb, Na⁺, V, Cl⁻, NH₄⁺, SO₄²⁻, Br⁻, Mn, Fe, Ni, Zn, Cd, K⁺, Ba, Cu, and As. Unlike the conventional receptor modeling algorithm, factor analysis PMF only generates non-negative source profiles. To eliminate sulfate from such factors where it is not physically plausible, special penalty terms were included in the model so that sulfate concentrations could be selectively decreased in specified factors. A 9-factor model containing non-zero sulfate concentrations in three factors gives the most satisfactory source profiles. Ammonium sulfate, chloride depleted marine aerosols and crustal aerosols are the three non-zero sulfate sources. Other factors are marine aerosols, non-ferrous smelters, particulate copper, fuel oil burning, vehicular emission and bromide/road dust. The last two sources can be combined as a single source of vehicle/road dust. The compositional profiles of these factors were also developed. The mass profiles obtained can be improved by further refinement of distribution of sulfate in the sources.