Soot particles and their impacts on the mass cycle in the Tibetan atmosphere

Atmospheric aerosol particles in urban and mountain areas around Lhasa city (29.65°N, 91.13°E) in the Tibetan Plateau were collected in the summers of 1998 and 1999. The particles were analyzed with electron microscopes and an energy dispersive X-ray spectrometer. Individual particle morphology, elemental composition and mixture of sulfate and nitrate were investigated. In the urban area, soot particles emitted from vegetation burning were dominant. These particles were characterized by chain or aggregate morphologies, and an elemental composition of potassium and sulfur. Such particles were frequently detected in mountain areas out of the city, where they formed droplets acting as condensation nuclei. Quantitative estimation indicated that sulfur was accumulated onto the soot particles during their dispersion from the urban area to mountain areas. Sulfate and nitrate detections indicated that soot particles collected in the urban area did not contain nitrate and BaCl₂-reactive sulfate, which revealed that the combination of sulfur and potassium in the particles was not K₂SO₄. In contrast, the particles dispersed to mountain areas contained BaCl₂-reactive sulfate and some contained nitrate, suggesting that soot particles emitted from the urban area could increase the buffering capacity of aerosol particles and enhance the formation of particulate sulfate through heterogeneous conversion in the Tibetan atmosphere.     

Indoor-outdoor Carbon Monoxide Concentrations at Four Sites in Riyadh,Saudi Arabia

Abstract

Nylon filters are a popular medium to collect atmospheric fine particles in different aerosol monitoring networks, including those operated by the U.S. Environmental Protection Agency and the Interagency Monitoring of Protected Visual Environments (IMPROVE) program. Extraction of the filters by deionized water or by a basic aqueous solution (typically a mixture of sodium carbonate and sodium bicarbonate) is often performed to permit measurement of the inorganic ion content of the collected particles. Whereas previous studies have demonstrated the importance of using a basic solution to efficiently extract gaseous nitric acid collected using nylon filters, there has been a recent movement to the use of deionized water for extraction of particles collected on nylon filters to eliminate interference from sodium ion (Na⁺) during ion chromatographic analysis of inorganic aerosol cations. Results are reported here from a study designed to investigate the efficiency of deionized water extraction of aerosol nitrate (NO₃ ^?) and sulfate from nylon filters. Data were obtained through the conduct of five field experiments at selected IMPROVE sites. Results indicate that the nylon filters provide superior retention of collected fine particle NO₃ ^?, relative to Teflon filters, and that deionized water extraction (with ultrasonication) of collected NO₃ ^? and sulfate is as efficient, for the situations studied, as extraction using a basic solution of 1.7 mM sodium bicarbonate and 1.8 mM sodium carbonate.     

Interpretation of Meteorological Pollutant Roses in Areas Subject to Nocturnal Drainage Winds

The composition of aerosol particle products formed from the photochemical reaction of terpenes with NO_x and the chemical reaction of terpenes with ozone was determined using direct insertion probe/high resolution mass spectrometry. Samples of the aerosol particles generated from these gas phase reactions were collected on stainless steel disks using a specially-designed impactor. The samples were analyzed using computer-controlled high resolution mass spectrometry. The photochemical reaction of limonene with NO_x produced more than 30 reaction products in the aerosol phase. The major products identified included aldehydes, alcohols, acids, peroxides, and nitrate esters of alcohols, acids, and peroxides. In addition, there was evidence of dimeric and possibly trimeric reaction products. The composition of aerosol particle products formed from the dark reaction of ozone with limonene was determined and found similar to those products generated in the photochemical reaction, excluding the nitrated species. Aerosol concentrations were monitored using nephelometry which indicated a conversion of terpene to aerosol of 50% or greater for both the limonene and terpinolene reaction systems. The results show that direct insertion probe high resolution mass spectrometric technique has the capability for determining the composition of very polar and high molecular weight materials in aerosol particles. The composition of terpene aerosol particle products and the mass spectral data obtained from their analysis can be used in further studies to determine the importance of terpene aerosol particle formation in ambient air.     

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.     

Composition and mixing state of the urban background aerosol in the Rhein-Main area (Germany)

Size-resolved aerosol particle samples in the size range 0.1–10 μm aerodynamic diameter were collected in the years 2003 and 2004 at an urban background station in Mainz, Germany. Size, morphology, chemical composition and mixing state of more than 5400 individual particles of 7 selected sampling days were analyzed in detail by scanning electron microscopy and energy-dispersive X-ray microanalysis. In addition, transmission electron microscopy, aerosol mass spectrometry and atomic force microscopy were applied to obtain detailed information about the mixing state of the particles. The fine particle fraction (diameter<1 μm) is always dominated by complex secondary aerosol particles (⩾90% by number) independent from air mass origin. These particles are complex internal mixtures of ammonium and sodium sulfates, nitrates, and organic material. Between 20% and 40% of the complex secondary aerosol particles contain soot inclusions. The composition of the coarse particle fraction (>1 μm diameter) is strongly dependant on air mass history with variable abundances of complex secondary aerosol particles, aged sea salt, silicates, silicate mixtures, calcium sulfates, calcium sulfate/carbonate mixtures, calcium nitrate/carbonate mixtures, biological particles, and external soot.The dominance of complex secondary aerosol particles shows that reduction of the precursor gases is a major goal for successful reduction strategies for PM₁₀.     

Influence of dust composition on cloud droplet formation

Previous studies suggest that interactions between dust particles and clouds are significant; yet the conditions where dust particles can serve as cloud condensation nuclei (CCN) are uncertain. Since major dust components are insoluble, the CCN activity of dust strongly depends on the presence of minor components. However, many minor components measured in dust particles are overlooked in cloud modeling studies. Some of these compounds are believed to be products of heterogeneous reactions involving carbonates. In this study, we calculate Kohler curves (modified for slightly soluble substances) for dust particles containing small amounts of K⁺, Mg²⁺, or Ca²⁺ compounds to estimate the conditions where reacted and unreacted dust can activate. We also use an adiabatic parcel model to evaluate the influence of dust particles on cloud properties via water competition. Based on their bulk solubilities, K⁺ compounds, MgSO₄·7H₂O, Mg(NO₃)₂·6H₂O, and Ca(NO₃)₂·4H₂O are classified as highly soluble substances, which enable activation of fine dust. Slightly soluble gypsum and MgSO₃·6H₂O, which may form via heterogeneous reactions involving carbonates, enable activation of particles with diameters between about 0.6 and 2 μm under some conditions. Dust particles>2 μm often activate regardless of their composition. Only under very specialized conditions does the addition of a dust distribution into a rising parcel containing fine (NH₄)₂SO₄ particles significantly reduce the total number of activated particles via water competition. Effects of dust on cloud saturation and droplet number via water competition are generally smaller than those reported previously for sea salt. Large numbers of fine dust CCN can significantly enhance the number of activated particles under certain conditions. Improved representations of dust mineralogy and reactions in global aerosol models could improve predictions of the effects of aerosol on climate.     

Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere

Nitrous acid (HONO), nitric acid (HNO₃), and organic aerosol were measured simultaneously atop an 18-story tower in Houston, TX during August and September of 2006. HONO and HNO₃ were measured using a mist chamber/ion chromatographic technique, and aerosol size and chemical composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Observations indicate the potential for a new HONO formation pathway: heterogeneous conversion of HNO₃ on the surface of primary organic aerosol (POA). Significant HONO production was observed, with an average of 0.97 ppbv event^?1 and a maximum increase of 2.2 ppb in 4 h. Nine identified events showed clear HNO₃ depletion and well-correlated increases in both HONO concentration and POA-dominated aerosol surface area (SA). Linear regression analysis results in correlation coefficients (r²) of 0.82 for HONO/SA and 0.92 for HONO/HNO₃. After correction for established HONO formation pathways, molar increases in excess HONO (HONO_excess) and decreases in HNO₃ were nearly balanced, with an average HONO_excess/HNO₃ value of 0.97. Deviations from this mole balance indicate that the residual HNO₃ formed aerosol-phase nitrate. Aerosol mass spectral analysis suggests that the composition of POA could influence HONO production. Several previously identified aerosol-phase PAH compounds were enriched during events, suggesting their potential importance for heterogeneous HONO formation.     

The aging process of naturally emitted aerosol (sea-salt and mineral aerosol) during long range transport

The aging processes of two representative natural aerosol, sea-salt and mineral aerosol, are investigated by using a box model equipped with a thermodynamic module (SCAPE). The model is shown to successfully describe the aging processes between the gas-phase anthropogenic pollutants (SO₂, NO_x, and NH₃) and primary aerosol particles, including self-neutralization process/chlorine depletion in the sea-salt aerosol; formation/dissipation of carbonate and bicarbonate ions in the mineral aerosol; irreversible dynamic deposition of SO₂ and H₂SO₄; and reversible thermodynamic distribution of inorganic volatile species. It is found that SO₂ and H₂SO₄ tend to deposit onto the mode with the largest surface area, and that ammonia deposition is controlled by preceding SO₂/H₂SO₄ deposition. During the SO₂/H₂SO₄ deposition, chloride and carbonate are continuously released from the sea-salt and mineral dust particles, respectively. The findings by the model predictions are consistent with field and observational studies.     

Study of size distribution of atmospheric aerosol at Agra

Measurements on size distribution of atmospheric aerosol were made at Dayalbagh, Agra during July to September 1998. A 4-stage cascade particle sampler (CPS - 105) which fractionates particles in sizes ranging between 0.7 and >10.9 μm, was used. Samples were collected on Whatman 41 filters. The filters were analyzed for the major water-soluble ions. The anions (F, Cl, NO₃ and SO₄) were analyzed by Dionex DX-500 ion chromatograph while atomic absorption and colorimetric techniques were used for the analysis of cations (Na, K, Ca and Mg) and NH₄, respectively. The average mass of aerosol was found to be 131.6 μg m⁻³ and aerosol composition was found to be influenced by terrigeneous sources. The mass size distribution of total aerosol and the ions NH₄, Cl, NO₃, K, Ca, Mg, SO₄ and Na was bimodal while that of F was unimodal. SO₄, F, K and NH₄ dominated in the fine mode while Ca, Mg, Cl and NO₃ were in abundance in coarse fraction. Na was found in both coarse as well as fine mode. Coarse mode SO₄ and NO₃ have been ascribed to contribution from re-suspension of soil and formation by heterogeneous oxidation on soil derived particles. Preponderance of K in fine mode is attributed to emissions from vegetation and from burning of plant materials. Ca, Mg, Cl and NO₃ are largely soil derived and hence dominate in coarse fraction. Equivalent ratios of NH₄/(SO₄+NO₃) were calculated for both fine and coarse aerosols. The coarse mode ratio varied between 0.7 and 1.4 while in fine mode it ranged between 1.4 and 1.9. It shows that aerosol is basic, the basicity of coarse mode is due to higher concentration of soil-derived alkaline components while the basicity in fine mode is due to neutralization of acidity by NH₃.     

The air pollution caused by the burning of fireworks during the lantern festival in Beijing

The effects of the burning of fireworks on air quality in Beijing was firstly assessed from the ambient concentrations of various air pollutants (SO₂, NO₂, PM_2.5, PM₁₀ and chemical components in the particles) during the lantern festival in 2006. Eighteen ions, 20 elements, and black carbon were measured in PM_2.5 and PM₁₀, and the levels of organic carbon could be well estimated from the concentrations of dicarboxylic acids. Primary components of Ba, K, Sr, Cl⁻, Pb, Mg and secondary components of C₅H₆O₄²⁻, C₃H₂O₄²⁻, C₂O₄²⁻, C₄H₄O₄²⁻, SO₄²⁻, NO₃⁻ were over five times higher in the lantern days than in the normal days. The firework particles were acidic and of inorganic matter mostly with less amounts of secondary components. Primary aerosols from the burning of fireworks were mainly in the fine mode, while secondary formation of acidic anions mainly took place on the coarse particles. Nitrate was mainly formed through homogeneous gas-phase reactions of NO₂, while sulfate was largely from heterogeneous catalytic transformations of SO₂. Fe could catalyze the formation of nitrate through the reaction of α-Fe₂O₃ with HNO₃, while in the formation of sulfate, Fe is not only the catalyst, but also the oxidant. A simple method using the concentration of potassium and a modified method using the ratio of Mg/Al have been developed to quantify the source contribution of fireworks. It was found that over 90% of the total mineral aerosol and 98% of Pb, 43% of total carbon, 28% of Zn, 8% of NO₃⁻, and 3% of SO₄²⁻ in PM_2.5 were from the emissions of fireworks on the lantern night.     

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

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

Seasonal variation of ionic species in fine particles at Qingdao,China

Totally nine measurement campaigns for ambient particles and SO₂ have been conducted during the period of 1997–2000 in Qingdao in order to understand the characteristics of the particulate matter in coastal areas of China. The mass fractions of PM_2.5, PM_2.5−10 and PM_>10 in TSP are 49%, 25% and 26%, respectively. The size distribution of particles mass concentrations in Qingdao shows bi-modal distribution. Mass fraction percentages of water-soluble ions in PM_2.5, PM_2.5−10 and PM_>10 decreased from 62% to 35% and 21%. In fine particles, sulfate, nitrate and ammonium, secondary formed compounds, are major components, totally accounting for 50% of PM_2.5 mass concentration.The ratios of sulfate, chloride, ammonium and potassium in PM_2.5 for heating versus non-heating periods are 1.34, 1.80, 1.56 and 1.44, respectively. The ratio of nitrate is 3.02 and this high ratio could be caused by reduced volatilization at lower temperature. Sulfate concentrations are higher than nitrate in PM_2.5. The chemical forms of sulfate and nitrate are probably (NH₄)₂SO₄ and NH₄NO₃ and chloride depletion was observed.Backward trajectory analysis reflected possible influence of air pollutant transport to Qingdao local aerosol pollution.     

Size partitioning of particulate inorganic nitrogen species between the fine and coarse mode ranges and its implication to their deposition on the surface ocean

In order to discuss the dry deposition fluxes of atmospheric fixed nitrogen species, observations of aerosol chemistry including nitrate (NO₃^?) and ammonium (NH₄⁺) were conducted at two islands, Rishiri Island and Sado Island, over the Sea of Japan. Although the atmospheric concentrations of particulate NH₄⁺–N showed higher values than those of particulate NO₃^?–N at both sites, the dry deposition fluxes of the particulate NO₃^?–N were estimated to be higher than those of the particulate NH₄⁺–N. This was caused by the difference of particle sizes between the particulate NO₃^? and NH₄⁺; NH₄⁺ was almost totally contained in fine particles (d < 2.5 μm) with smaller deposition velocity, whereas NO₃^? was mainly contained in coarse particles (d > 2.5 μm) with greater deposition velocity. Fine mode NO₃^? was strongly associated with fine mode sea-salt and mineral particles, of which higher concentrations shifted the size of particulate NO₃^? toward the fine mode range. This size shift would decrease the dry deposition flux of the fixed nitrogen species on coastal waters and accelerate atmospheric transport of them to the remote oceanic areas.     

The Influences of Ambient Particle Composition and Size on Particle Infiltration in Los Angeles,CA, Residences

Abstract

Particle infiltration is a key determinant of the indoor concentrations of ambient particles. Few studies have examined the influence of particle composition on infiltration, particularly in areas with high concentrations of volatile particles, such as ammonium nitrate (NH₄NO₃). A comprehensive indoor monitoring study was conducted in 17 Los Angeles–area homes. As part of this study, indoor/outdoor concentration ratios during overnight (nonindoor source) periods were used to estimate the fraction of ambient particles remaining airborne indoors, or the particle infiltration factor (F_INF), for fine particles (PM_2.5), its nonvolatile (i.e., black carbon [BC]) and volatile (i.e., nitrate [NO₃ ^?]) components, and particle sizes ranging between 0.02 and 10 μm. F_INF was highest for BC (median = 0.84) and lowest for NO₃ ^? (median = 0.18). The low F_INF for NO₃ ^? was likely because of volatilization of NO₃ ^? particles once indoors, in addition to depositional losses upon building entry. The F_INF for PM_2.5 (median = 0.48) fell between those for BC and NO₃ ^?, reflecting the contributions of both particle components to PM_2.5. F_INF varied with particle size, air-exchange rate, and outdoor NO₃ ^? concentrations. The F_INF for particles between 0.7 and 2 μm in size was considerably lower during periods of high as compared with low outdoor NO₃ ^? concentrations, suggesting that outdoor NO₃ ^? particles were of this size. This study demonstrates that infiltration of PM_2.5 varies by particle component and is lowest for volatile species, such as NH₄NO₃. Our results suggest that volatile particle components may influence the ability for outdoor PM concentrations to represent indoor and, thus, personal exposures to particles of ambient origin, because volatilization of these particles causes the composition of PM_2.5 to differ indoors and outdoors. Consequently, particle composition likely influences observed epidemiologic relationships based on outdoor PM concentrations, especially in areas with high concentrations of NH₄NO₃ and other volatile particles.     

NH4+, NO3−, and SO42− in roadside and rural size-resolved particles and transformation of NO2/SO2 to nanoparticle-bound NO3−/SO42−

This study investigates ammonium, nitrate, and sulfate (NH₄⁺, NO₃^?, and SO₄^2?) in size-resolved particles (particularly nano (PM_0.01–0.056)/ultrafine (PM_0.01–0.1)) and NO_x/SO₂ collected near a busy road and at a rural site. The average (mass) cumulative fraction of secondary inorganic aerosols (SO₄^2?+NO₃^?+NH₄⁺) in nano or ultrafine particles at the roadside was found to be three to four times that at the rural site. The above three secondary inorganic aerosol species were present in similar cumulative fractions in particles of size 1–18 μm at both sites; however, dissimilar fractions were observed for Cl^?, Na⁺, and K⁺. The nitrogen ratios (NRs: NR = NO₃^??N/(NO₃^??N + NO₂–N)), sulfur ratios (SRs: SR = SO₄^2??S/(SO₄^2??S + SO₂–S)), dNR/D_P (derivative of NR with respect to D_P (particle diameter)), and dSR/D_P (derivative of SR with respect to D_P) at the roadside were higher than those at the rural site for nano/ultrafine particles. At both sites (particularly the roadside), the nanoparticles had significantly higher dNR/D_P and dSR/D_P values than differently sized particles, implying that NO₃^?/SO₄^2? (from NO₂/SO₂ transformation or NO₃^?/SO₄^2? deposition) were present on these particles.     

Morphological and chemical composition characteristics of summertime atmospheric particles collected at Tokchok Island,Korea

Determination of the chemical compositions of atmospheric single particles in the Yellow Sea region is critical for evaluating the environmental impact caused by air pollutants emitted from mainland China and the Korean peninsula. After ambient aerosol particles were collected by the Dekati PM10 cascade impactor on July 17–23, 2007 at Tokchok Island (approximately 50 km west of the Korean coast nearby Seoul), Korea, overall 2000 particles (on stage 2 and 3 with cut-off diameters of 2.5–10 μm and 1.0–2.5 μm, respectively) in 10 samples were determined by using low-Z particle electron probe X-ray microanalysis. X-ray spectral and secondary electron image (SEI) data showed that soil-derived and sea-salt particles which had reacted or were mixed with SO₂ and NO_x (or their acidic products) outnumbered the primary and “genuine” ones (59.2% vs. 19.2% in the stage 2 fraction and 41.3% vs. 9.9% in the stage 3 fraction). Moreover, particles containing nitrate in the secondary soil-derived species greatly outnumbered those containing sulfate. Organic particles, mainly consisting of marine biogenic species, were more abundant in the stage 2 fraction than in the stage 3 fraction (11.6% vs. 5.1%). Their relative abundance was greater than the sum of carbon-rich, K-containing, Fe-containing, and fly ash particles, which exhibited low frequencies in all the samples. In addition, many droplets rich in C, N, O, and S were observed. They tended to be small, exhibiting a dark round shape on SEI, and generally included 8–20 at.% C, 0–12 at.% N, 60–80 at.% O, and 4–10 at.% S (sometimes with <3 at.% Mg and Na). They were attributed to be a mixture of carbonaceous matter, H₂SO₄, and NH₄HSO₄/(NH₄)₂SO₄, mostly from the reaction of atmospheric SO₂ with NH₃ under high relative humidity. The analysis of the relationship between the aerosol particle compositions and 72-h backward air-mass trajectories suggests that ambient aerosols at Tokchok Island are strongly affected not only by seawater from the Yellow Sea but also by anthropogenic pollutants emitted from China and the Seoul–Incheon metropolis, resulting in the dominance of complex secondary aerosol particles.     

Sensitivity analyses of factors influencing CMAQ performance for fine particulate nitrate

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

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

Simulation of aerosols and gas-phase species over Europe with the Polyphemus system. Part II: Model sensitivity analysis for 2001

This paper presents a multi-pollutant sensitivity study of an air quality model over Europe with a focus on aerosols. Following the evaluation presented in the companion paper, the aim here is to study the sensitivity of the model to input data, mathematical parameterizations and numerical approximations. To that end, 30 configurations are derived from a reference configuration of the model by changing one input data set, one parameterization or one numerical approximation at a time. Each of these configurations is compared to the same reference simulation over two time periods of the year 2001, one in summer and one in winter. The sensitivity of the model to the different configurations is evaluated through a statistical comparison between the simulation results and through comparisons to available measurements. The species studied are ozone (O₃), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), ammonia (NH₃), coarse and fine aerosol particles (PM_c and PM_2.5), sulfate, nitrate, ammonium, chloride and sodium.For all species, the modeled concentrations are very sensitive to the parameterization used for vertical turbulent diffusion and to the number of vertical levels. For the other configurations considered in this work, the sensitivity of the modeled concentration to configuration choice varies with the species and the period of the year. O₃ is impacted by options related to boundary conditions. PM_c is sensitive to sea-salt related options, to options influencing deposition and to options related to mass transfer between gas and particulate phases. PM_2.5 is sensitive to a larger number of options than PM_c: sea-salt, boundary conditions, heterogeneous reactions, aqueous chemistry and gas/particle mass transfer. NO₂ is strongly influenced by heterogeneous reactions. Nitrate shows the highest variability of all species studied. As with NO₂, nitrate is strongly sensitive to heterogeneous reactions but also to mass transfer, thermodynamic related options, aqueous chemistry and computation of the wet particle diameter. While SO₂ is mostly sensitive to aqueous chemistry, sulfate is also sensitive to boundary conditions and, to a lesser extent, to heterogeneous reactions. As with nitrate, ammonium is largely impacted by the different configuration choices, although the sensitivity is slightly lower than for nitrate. NH₃ is sensitive to aqueous chemistry, mass transfer and heterogeneous reactions. Chloride and sodium are impacted by sea-salt related options, by options influencing deposition and by options concerning the aqueous-phase module.     

Light Scattering from Sea-Salt Aerosols at Interagency Monitoring of Protected Visual Environments (IMPROVE) Sites

Abstract

A method is described to estimate light scattering (Bsp) by sea-salt aerosols at coastal locations in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network. Dry mass scattering efficiencies for fine and coarse sea-salt particles were based on previously measured dry sea-salt size distributions. Enhancement of sea-salt particle scattering by hygroscopic growth was based on NaCl water activity data. Sea-salt aerosol mass at the IMPROVE site in the Virgin Islands (VIIS) was estimated from strontium (Sr) concentrations in IMPROVE aerosol samples. Estimated Bsp, including contributions from sea-salt mass based on Sr, agreed well with measured Bsp at the VIIS IMPROVE site. On average, sea salt accounted for 52% of estimated Bsp at this site. Sea-salt aerosol mass cannot be reliably estimated from Sr unless its crustal enrichment factor exceeds 10. Sodium (Na) concentrations are not accurately determined by X-ray fluorescence analysis in IMPROVE samples. It is recommended that Na be measured in the fine and coarse modes by a more appropriate method, such as atomic absorption spectroscopy or ion chromatography, to account for scattering by sea-salt particles at IMPROVE sites where such contributions may be significant.