Particulate Matter Precursors Research Articles

Improvement of the anthropogenic emission rate estimate in Ulaanbaatar, Mongolia, for 2020–21 winter

Ulaanbaatar (UB), the fast-growing capital of Mongolia, is known for its world's worst level of particulate matter (PM) concentrations in winter. However, current anthropogenic emission inventories over the UB are based on data from more than fifteen years ago, and satellite observations are scarce because UB is in high latitudes. During the winter of 2020–21, the first period of the Fine Particle Research Initiative in East Asia considering the National Differences (FRIEND), several times higher concentrations of PM in UB compared to other urban sites in East Asia were observed but not reproduced with a chemical transport model mainly due to the underestimated anthropogenic emissions. Therefore, we devised a method for sequentially adjusting emissions based on the reactivity of PM precursors using ground observations. We scaled emission rates for the inert species (CO, elemental carbon (EC), and organic carbon (OC)) to reproduce their observed ambient concentrations, followed by SO2 to reproduce the concentration of SO42−, which was examined to have the least uncertainty based on the abundance of observed NH3, and finally NO and NH3 for NO3−, and NH4+. This improved estimation is compared to regional inventories for Asia and suggests more than an order of magnitude increase in anthropogenic emissions in UB. Using the improved emission inventory, we were able to successfully reproduce independent observation data on PM2.5 concentrations in UB in December 2021 from the U.S. Embassy. During the campaign period, we found more than 50% of the SO42−, NO3−, and NH4+ increased in UB due to the improvement could travel to Beijing, China (BJ), and about 20% of the SO42− could travel to Noto, Japan (NT), more than 3000 km away. Also, the anthropogenic emissions in UB can effectively increase OC, NO3−, and NH4+ concentrations in BJ when Gobi dust storms occur.

Road Traffic and Its Influence on Urban Ammonia Concentrations (France)

Ammonia (NH3) is an unregulated atmospheric gaseous pollutant in ambient air, involved in the formation of fine particles. Ammonia is therefore a major precursor of particulate matter (PM), the health effects of which have been widely demonstrated. NH3 emissions are clearly dominated by the agricultural sector (livestock and fertilizers), but other sources may also be important and less studied, such as road traffic with the increased use of catalytic converters in vehicles. This study is based on a long-term real-time measurements campaign (December 2019–September 2021) on two urban sites: a background site and a roadside site in the same agglomeration in France. The study of historical measurements at the background site clearly demonstrated the dominance of agriculture on the ammonia concentrations. This influence was also observed at both sites during the measurement campaign. The annual and monthly averages obtained in the study were similar to previous ones, with concentrations between 1–10 µg/m3 at both sites, indicating lower levels than previous studies for the roadside site. The ammonia levels measured during the campaign at the traffic site were significantly higher than those measured at the background site, highlighting the road traffic influence on ammonia in urban area. The biomass burning influence also seemed to be observed during this long measurement campaign at the agglomeration scale. The influences of road traffic and biomass burning on ammonia concentration remain small compared to agriculture.

Emissions of Carbonaceous Particulate Matter and Ultrafine Particles from Vehicles-A Scientific Review in a Cross-Cutting Context of Air Pollution and Climate Change.

Airborne particulate matter (PM) is a pollutant of concern not only because of its adverse effects on human health but also on visibility and the radiative budget of the atmosphere. PM can be considered as a sum of solid/liquid species covering a wide range of particle sizes with diverse chemical composition. Organic aerosols may be emitted (primary organic aerosols, POA), or formed in the atmosphere following reaction of volatile organic compounds (secondary organic aerosols, SOA), but some of these compounds may partition between the gas and aerosol phases depending upon ambient conditions. This review focuses on carbonaceous PM and gaseous precursors emitted by road traffic, including ultrafine particles (UFP) and polycyclic aromatic hydrocarbons (PAHs) that are clearly linked to the evolution and formation of carbonaceous species. Clearly, the solid fraction of PM has been reduced during the last two decades, with the implementation of after-treatment systems abating approximately 99% of primary solid particle mass concentrations. However, the role of brown carbon and its radiative effect on climate and the generation of ultrafine particles by nucleation of organic vapour during the dilution of the exhaust remain unclear phenomena and will need further investigation. The increasing role of gasoline vehicles on carbonaceous particle emissions and formation is also highlighted, particularly through the chemical and thermodynamic evolution of organic gases and their propensity to produce particles. The remaining carbon-containing particles from brakes, tyres and road wear will still be a problem even in a future of full electrification of the vehicle fleet. Some key conclusions and recommendations are also proposed to support the decision makers in view of the next regulations on vehicle emissions worldwide.

PAHs and PM formed by low temperature pyrolysis and oxidation of hydrocarbon fuel

Nano meter size particulate matter (PM) formed by the combustion process of hydrocarbon fuel has harmful effects on human health. Fundamental research works for investigation of formation behavior of PM precursor such as polycyclic aromatic hydrocarbons (PAHs) in combustion process were required for the reduction of nano-PM emission. In this study, PM and PAH formed by low temperature (less than 1350K) pyrolysis and oxidation of hydrocarbon fuel using a flow reactor were investigated. The mass concentration of PM was obtained by the filter sampling method with a glass-fiber filter, while the mass concentration of PAH was analyzed by a Gas Chromatography. In addition, numerical simulation for PAH formation was performed using a CHEMKIN-Pro software. As a result, it was found that the mass concentration of PM increased with temperature raise under various equivalent ratio conditions (φ = ∞, 6.2 and 2.8). Therefore, it was also found that the mass concentration of PM without oxidation condition was higher than that with oxidation condition.

A review of the potentiality of biochar technology to abate emissions of particulate matter originating from agriculture

Agricultural operations and processes generate copious quantities of particulate matter (PM) both directly and indirectly through emissions of PM precursor gases with dire consequences for human health, environment and climate. PM emissions from agricultural activities are projected to continually rise in the light of soaring food demand driven by a ballooning global population, and thus, plausible measures are needed to combat them. Recently, interest in using biochar to attenuate PM emissions of agricultural origin, especially the secondary PM precursors, has gained traction and this review study is purposed to examine the capacity of the technology to curb the agricultural-related PM emissions basing on observations made in the previously concluded studies. The study gives a brief overview of the effects of PM and delineates its weighty agricultural sources plus detailing whether and how the pyrolysis technology and biochar as its product can help to alleviate the emissions. Additional discussions address the looming dilemma of biochar applications becoming a PM emission problem and the techniques that should be applied to ensure its sustainable usage. It is overwhelmingly clear from the studies reviewed that pyrolysis and resultant biochar have an enormous potential to attenuate PM from agriculture if adequately utilised.

Applicability of TiO2 Penetration Method to Reduce Particulate Matter Precursor for Hardened Concrete Road Structures

Recently, air pollution is increasing sharply in Korea, caused by fine particulate matter. Nitrogen oxides (NOx) are particulate matter precursors that significantly contribute to air pollution. They are transmitted into the atmosphere by a large amount, especially in high-volume traffic areas. This pollutant is particularly harmful. Therefore, there are increasing efforts focused on NOx removal from the air. As the photocatalytic reaction of titanium dioxide (TiO2) is the mechanism that eliminates NOx, the ultraviolet (UV) rays in sunlight and TiO2 in existing concrete structure need to be contacted for reaction process. Generally, TiO2 concrete is produced by mixing the concrete binder with TiO2. However, a significant amount of TiO2 in the concrete cannot be exposed to air pollutants or UV. Additionally, this technique may not be applicable to existing structures. Therefore, an alternative method that utilizes surface penetration agents is used to add TiO2 to the concrete surface of the structures. This proposed method may not only be economical but also applicable to various types of structures. The applicability of the TiO2 penetration application method to existing concrete road structures for reducing NOx is the purpose of this study. The penetration depth of TiO2 particles was measured using scanning electron microscopy (SEM) combined with energy dispersive analysis of X-rays (EDAX). Additionally, the NOx removal efficiency was evaluated using the NOx analyzing system. The results of this study showed that the TiO2 penetration method was advantageous in removing NOx effectively and securing economic feasibility.

Distinguishing atmospheric nitrogen compounds (nitrate and ammonium) in lichen biomonitoring studies.

Nitrogen speciation, i.e. distinguishing nitrate (NO3-) and ammonium (NH4+), is commonly undertaken in soil studies, but has not been conducted extensively for lichens. Lichen total nitrogen contents (N wt%) reflect airborne atmospheric nitrogen loadings, originating from anthropogenic sources (e.g. vehicular and agricultural/livestock emissions). Albeit nitrogen being an essential lichen nutrient, nitrogen compound (i.e. NO3- and NH4+) concentrations in the atmosphere can have deleterious effects on lichens. Moreover, N wt% do not provide information on individual nitrogen compounds, i.e. NO3- and NH4+ which are major constituents of atmospheric particulate matter (e.g. PM10 and PM2.5). This study presents a novel method to separate and quantify NO3- and NH4+ extracted from lichen material. An optimal approach was identified by testing different strengths and volumes of potassium chloride (KCl) solutions and variable extraction times, i.e. the use of 3% KCl for 6 hours can achieve a same-day extraction and subsequent ion chromatography (IC) analysis for reproducible lichen nitrate and ammonium concentration determinations. Application of the method was undertaken by comparing urban and rural Xanthoria parietina samples to investigate the relative importance of the two nitrogen compounds in contrasting environments. Findings presented showed that lichen nitrogen compound concentrations varied in rural and urban X. parietina samples, suggesting different atmospheric nitrogen loadings from potentially different sources (e.g. agricultural and traffic) and varied deposition patterns (e.g. urban layout impacts). Despite potential impacts of nitrogen compounds on lichen metabolism, the approach presented here can be used for quantification of two different nitrogen compounds in lichen biomonitoring studies that will provide specific information on spatial and temporal variability of airborne NO3- and NH4+ concentrations that act as precursors of particulate matter, affecting air quality and subsequently human health.

Evaluation of NOx Removal Efficiency of Concrete Members Through Particulate Matter Precursor Reduction

Evaluation of NOx Removal Efficiency of Concrete Members Through Particulate Matter Precursor Reduction

Aerosol pH and liquid water content determine when particulate matter is sensitive to ammonia and nitrate availability

Abstract. Nitrogen oxides (NOx) and ammonia (NH3) from anthropogenic and biogenic emissions are central contributors to particulate matter (PM) concentrations worldwide. The response of PM to changes in the emissions of both compounds is typically studied on a case-by-case basis, owing in part to the complex thermodynamic interactions of these aerosol precursors with other PM constituents. Here we present a simple but thermodynamically consistent approach that expresses the chemical domains of sensitivity of aerosol particulate matter to NH3 and HNO3 availability in terms of aerosol pH and liquid water content. From our analysis, four policy-relevant regimes emerge in terms of sensitivity: (i) NH3 sensitive, (ii) HNO3 sensitive, (iii) NH3 and HNO3 sensitive, and (iv) insensitive to NH3 or HNO3. For all regimes, the PM remains sensitive to nonvolatile precursors, such as nonvolatile cations and sulfate. When this framework is applied to ambient measurements or predictions of PM and gaseous precursors, the “chemical regime” of PM sensitivity to NH3 and HNO3 availability is directly determined. The use of these regimes allows for novel insights, and this framework is an important tool to evaluate chemical transport models. With this extended understanding, aerosol pH and associated liquid water content naturally emerge as previously ignored state parameters that drive PM formation.

Regulated and Non-Regulated Emissions from Euro 6 Diesel, Gasoline and CNG Vehicles under Real-World Driving Conditions

The transport sector is one of the main sources air pollutants. Different exhaust after-treatment systems have been implemented over the years to control the emissions of criteria pollutants. However, while reducing the emissions of the target compounds these systems can lead to the emissions of other pollutants and/or greenhouse gases such as NH3 or N2O. Following the implementation of the Real Driving Emissions (RDE) test procedure in the EU, vehicles have been equipped with more complex after-treatment configurations. The impact that these technologies may have on the emissions of non-regulated pollutants during real-world driving have not been evaluated until now. In the current study we present the on-road emissions of a series of non-regulated pollutants, including NH3, N2O, CH4 and HCHO, measured with a portable FTIR from a series of Euro 6d, Euro 6c and Euro 6d-TEMP, gasoline diesel and compressed natural gas (CNG) vehicles during real-world testing. The obtained results show that it is possible to measure N2O, NH3, CH4 and HCHO during on-road operation. The results also highlight the importance of the measurement of the emissions of these pollutants during real-world driving, as the emissions of NH3 (a particulate matter precursor) and those of N2O and CH4 (green-house gases) can be high from some vehicle technologies. NH3 emissions were up to 49 mg/km for gasoline passenger cars, up to 69 mg/km for the CNG light-commercial vehicle and up to 17 mg/km a diesel passenger car equipped with a selective catalytic reduction system (SCR). On the other hand, N2O and CH4 emissions accounted for up to 9.8 g CO2 eqv/km for a diesel passenger car equipped with a combination of diesel oxidation catalysts (DOC), lean NOx traps (LNT), SCR and possibly an ammonia slip catalyst ASC.

Climatology of Air Quality in Arctic Cities—Inventory and Assessment

Freely available data of sulfur dioxide (SO2), ammonia (NH3), nitrogen dioxide (NO2), ozone (O3), and particulate matter (PM) observed in Arctic cities (north of 59.99 N) between 1972 and 2016 were compiled into an air-quality inventory of samples taken for limited periods. For cities with multiple years of data, air-quality climatology was determined in terms of daily means in the annual course. Mean urban air-quality climatology was calculated for regions of similar insolation, emission standards, topography, K&#246ppen-Geiger classification, and city size. Urban concentrations of PM precursors (SO2, NH3, NO2), PM2.5 and PM10 (PM with diameter less than 2.5 and 10 μm) were assessed in the sense of climatology with evidence from current knowledge. Typically, annual SO2 and NO2 means were lower for small than large Arctic cities, but can vary more than an order of magnitude over short distance. Cities seeing seasonal sea-ice had W-shaped mean annual courses of daily O3, while other cities had a spring maximum. Typically, annual means of urban pollutants in North America exceeded those in Scandinavia except for O3, where the opposite was true. Annual mean urban PM2.5 and PM10 concentrations varied from 1.6 to 21.2 μg·m-3 and 2 to 18.2 μg·m-3, respectively. Since PM10 encompasses PM2.5, annual PM10 means must be at least 21.2 μg·m-3. According to rural-to-urban ratios of species, seasonal transport of pollutants from wildfires, shipping, and the Kola Peninsula mining area occurred at some sites in Interior Alaska, western and northern Norway, respectively. Concurrent SO2 and PM or NO2 and PM measurements revealed combustion or traffic as major contributors to urban concentrations. Recommendations for potential future measurements of Arctic urban air quality were given based on the assessments of climatology and inventory.

Short review on PM-bound water. Its presence in the atmosphere, forms of occurrence and determination by Karl Fischer coulometric titration

Literature data indicate, that the conversion of secondary PM (particulate matter) precursors are largely controlled by the amount of atmospheric water vapor, and that higher capacity of water accumulation is demonstrated mainly by fine particles of anthropogenic origin, rich in ionic compounds like sulfates, nitrates, ammonia and chlorides, arising for example from biomass incineration processes. Smaller retention capability is however typical for coarse PM particles of natural origin, containing lot of crustal material like aluminosilicates. It is therefore suspect that both – the size of PM particles and the source of its origin will determine its hygroscopicity. The quantitative and qualitative measurements of water contributions in PM for example by means of Karl Fischer titration method could be therefore a good marker of PM origin. Due to analytical limitations the identification of water contents in PM and the differences in water fingerprint between PM collected in different locations is still quite challenging.

Abstract 16: Amyloidogenic Modifications of Apolipoprotein A-I Promote a Strong Pro-inflammatory Response in Macrophages, but Formation of Amyloid Fibrils Abrogates the Pro-inflammatory Effect

Inflammation is central to atherosclerosis, as inactivation of inflammation pathways strongly reduces atherosclerosis progression. Particulate matter, such as cholesterol crystals and amyloid materials, promotes release of the potent pro-inflammatory cytokine IL-1β in macrophages. Recently, it has been demonstrated that soluble substances that are precursors of particulate matter, such as free cholesterol, oxidized LDL and amyloidogenic peptides (i.e. amyloid-β, IAPP), can also induce an inflammatory response. In this study, we investigated the interplay between oxidation of apolipoprotein A-I (apoA-I), amyloid formation, and the inflammatory response of macrophages. We previously reported that oxidation of apoA-I methionines (MetO-ApoA-I) promotes protein aggregation and formation of amyloid fibrils when MetO-ApoA-I is incubated at pH 6.0. In contrast, at physiological pH, MetO-ApoA-I remains soluble and perfectly functional, as it promotes cholesterol efflux from macrophages with the same efficiency of intact-ApoA-I. However, upon incubation of mouse bone marrow derived macrophages with soluble pre-fibrillar MetO-ApoA-I, levels of pro-IL-1β synthesis were more than 2-fold higher than those induced by intact-ApoA-I. In contrast, amyloid fibrils produced by MetO-ApoA-I did not increase the levels of pro-IL-1β synthesis compared to intact-ApoA-I. Furthermore, the pro-inflammatory effect was not observed in macrophages derived from MyD88/TRIF knock-out mice, indicating that the response is membrane TLR receptors-dependent. In contrast, the >2-fold increase (MetO-ApoA-I vs. intact-apoA-I) in pro-IL-1β synthesis was maintained in macrophages derived from CD36 knock-out mice. This observation suggests that the signaling pathway is not exclusively dependent on the TLR2/TLR6/CD36 membrane complex. Thus, in atherosclerotic lesions, oxidized apoA-I species that are amyloidogenic, but otherwise functional, may induce a pro-inflammatory response in macrophages. Amyloid fibril formation in contrast, could reduce, rather than exacerbate, the inflammatory burden produced by these pro-inflammatory apoA-I species by sequestering them in the form of inert amyloids.

Particulate matter, air quality and climate: lessons learned and future needs

Abstract. The literature on atmospheric particulate matter (PM), or atmospheric aerosol, has increased enormously over the last 2 decades and amounts now to some 1500–2000 papers per year in the refereed literature. This is in part due to the enormous advances in measurement technologies, which have allowed for an increasingly accurate understanding of the chemical composition and of the physical properties of atmospheric particles and of their processes in the atmosphere. The growing scientific interest in atmospheric aerosol particles is due to their high importance for environmental policy. In fact, particulate matter constitutes one of the most challenging problems both for air quality and for climate change policies. In this context, this paper reviews the most recent results within the atmospheric aerosol sciences and the policy needs, which have driven much of the increase in monitoring and mechanistic research over the last 2 decades. The synthesis reveals many new processes and developments in the science underpinning climate–aerosol interactions and effects of PM on human health and the environment. However, while airborne particulate matter is responsible for globally important influences on premature human mortality, we still do not know the relative importance of the different chemical components of PM for these effects. Likewise, the magnitude of the overall effects of PM on climate remains highly uncertain. Despite the uncertainty there are many things that could be done to mitigate local and global problems of atmospheric PM. Recent analyses have shown that reducing black carbon (BC) emissions, using known control measures, would reduce global warming and delay the time when anthropogenic effects on global temperature would exceed 2 °C. Likewise, cost-effective control measures on ammonia, an important agricultural precursor gas for secondary inorganic aerosols (SIA), would reduce regional eutrophication and PM concentrations in large areas of Europe, China and the USA. Thus, there is much that could be done to reduce the effects of atmospheric PM on the climate and the health of the environment and the human population. A prioritized list of actions to mitigate the full range of effects of PM is currently undeliverable due to shortcomings in the knowledge of aerosol science; among the shortcomings, the roles of PM in global climate and the relative roles of different PM precursor sources and their response to climate and land use change over the remaining decades of this century are prominent. In any case, the evidence from this paper strongly advocates for an integrated approach to air quality and climate policies.

DISTRIBUTION OF METALS AND METALLOIDS IN SMELTER-DERIVED PARTICULATE MATTER IN SOILS AND MINERALOGICAL INSIGHTS INTO THEIR RETENTION AND RELEASE IN A LOW-T ENVIRONMENT

Over 10,000 tons of particulate matter (PM) has been emitted over the last 100 years as a result of mining activities in Sudbury, Ontario, Canada. Much of the PM has been deposited in the local soils, causing elevated concentrations of Cu, Ni, Zn, Se, As, and Pb. The goal of this study is to determine the distribution of metals and metalloids in PM in order to draw conclusions about their formation, their weathering, and the mobility of these elements in the local soils. The PM and associated secondary phases have been studied using optical microscopy, SEM, micro-Raman spectroscopy, and laser ablation inductively coupled plasma mass spectrometry. Spherical PM forms during the rapid cooling of hot gasses and is predominantly composed of Cu- and Ni-bearing spinel, silicate, and sulfide mineral inclusions. The collision of precursors of spherical PM with aerosols of residual matte and slag results in the formation of metal- and metalloid-rich outer rims on each sphere. These rims, as well as Fe-silicate and spinel minerals in the silicate-oxide matrix, weather to hematite during a dissolution-precipitation process. Metals and metalloids are released during this process in non-stoichiometric proportions relative to their initial concentration in the spinel, as they have different affinities to sorb on surface sites during their diffusion through the hematite precipitate. Metal-bearing sulfide inclusions alter to sulfate and occasionally into oxide minerals, which are enriched in Ni, Co, and Cu. Particulate matter composed of angular sulfide minerals and NiO particulates is often coated with Fe-Al-hydroxide and aluminosilicate minerals. The coatings contain higher trace-metal and metalloid concentrations than the underlying PM and are thus sinks for metals and metalloids released by other types of PM. The mobility of metals and metalloids in the soils decreases in the sequence Zn > Cu > Ni > Pb and is the result of differences in element adsorption affinities and dissolution rates of phases in the PM.

Enhancement in secondary particulate matter production due to mountain trapping

As China's largest economic development zone, the Pearl River Delta (PRD) is subject to particulate matter (PM) and visibility deterioration problems. Due to high PM concentration, haze days impacting ambient visibility have occurred frequently in this region. Besides visibility impairment, PM pollution also causes a negative impact on public health. These negative impacts have heightened the need to improve our understanding of the PM pollution of the PRD region. One major cause of the PRD pollution problem is cold front passages in the winter; however, the mechanism of pollution formation stays unclear. In this study, the Comprehensive Air Quality Model (CAMx) is utilized to investigate the detailed PM production and transport mechanisms in the PRD.Simulated concentrations of PM2.5 species, which have a good correlation with observation, show that sulfate and nitrate are the dominant pollutants among different PM2.5 species. Before the cold front passage a large amount of gas-phase and particle-phase pollutants are transported to the mountainous regions in the north of the PRD, and become trapped by the terrain. Over the mountain regions, cloud driven by upwelling flow promotes aqueous-phase reactions including oxidations of PM precursors such as SO2 and NO2. By this process, production of secondary PM is enhanced. When the cold front continues to advance further south, PM is transported to the PRD cities, and suppressed into a thin layer near the ground by a low planetary boundary layer (PBL). Thus high PM concentration episodes take place in the PRD cities.After examining production and transportation pathways, this study presents that the complex terrain configuration would block pollutant dispersion, provide cloudy environment, and advance secondary PM production. Previous studies have pointed out that pollution emitted from outside this region largely influences the air quality in the PRD; however, this study shows that pollutants from the outside could be originated from the PRD and transported back resulting in significant increase of secondary PM concentration, and provides new insight into PM production and transport mechanism in the PRD.

Measurement of Volatile Particulate Matter Emissions From Aircraft Engines Using a Simulated Plume Aging System

Aircraft exhaust contains nonvolatile (soot) particulate matter (PM), trace gas pollutants, and volatile PM precursor material. Nonvolatile soot particles are predominantly present at the engine exit plane, but volatile PM precursors form new particles or add mass to the existing ones as the exhaust is diluted and cooled. Accurately characterizing the volatile PM mass, number, and size distribution is challenging due to this evolving nature and the impact of local ambient conditions on the gas-to-particle conversion processes. To accurately and consistently measure the aircraft PM emissions, a dilution and aging sampling system that can condense volatile precursors to particle phase to simulate the atmospheric evolution of aircraft engine exhaust has been developed. In this paper, a field demonstration of its operation is described. The dilution/aging probe system was tested using both a combustor rig and on-wing CFM56-7 engines. During the combustor rig testing at NASA Glenn Research Center, the dilution/aging probe supported formation of both nucleation/growth mode particles and soot coatings. The results showed that by increasing residence time, the nucleation particles become larger in size, increase in total mass, and decrease in number. During the on-wing CFM56-7 engine testing at Chicago Midway Airport, the dilution/aging probe was able to form soot coatings along with nucleation mode particles, unlike conventional 1-m probe engine measurements. The number concentration of nucleation particles depended on the sample fraction and relative humidity of the dilution air. The performance of the instrument is analyzed and explained using computational microphysics simulations.

Intercontinental influence of NOx and CO emissions on particulate matter air quality

Anthropogenic emissions of nitrogen oxides (NOx h NO þ NO2) and carbon monoxide (CO) affect particulate matter (PM) air quality on an intercontinental scale by changing background concentrations of oxidants (OH, ozone, H2O2) and thus increasing the oxidation rate of sulfur dioxide (SO2) to sulfate and NOx to nitrate. We conduct sensitivity simulations with the GEOSeChem chemical transport model and find that these intercontinental influences of NOx and CO emissions on PM can be greater than those from SO2 emissions (a direct PM precursor). The intercontinental impact of oxidant precursors is greatest in receptor regions with high domestic SO2 ,N Ox, and ammonia emissions and hence already high levels of PM. US NOx and CO emissions increase annual mean PM in northern Europe and eastern China by up to 0.25 m gm �3 . The increase in Europe is mostly as sulfate, whereas in China it is mostly as nitrate. East Asian NOx and CO emissions have a weaker intercontinental influence (w0.2 m gm �3 in northern Europe, w0.1 m gm �3 in the eastern US). These intercontinental effects of NOx and CO emissions on PM

Spatial and Temporal Characterization of PM2.5 Mass Concentrations in California, 1980–2007

ABSTRACT Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 μm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r 2 > 0.9; mean absolute error ∼2 μg m−3) from PM with an aerodynamic diameter ≤10 μm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980–2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 μg m−3 yr−1 (median -0.11 μg m−3 yr−1), whereas urban-site trends ranged from -0.13 to -1.29 μg m−3 yr−1 (median -0.59 μg m−3 yr−1). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 μg m−3 at IMPROVE sites and from 9.3 to 37.1 μg m−3 at urban sites. IMPLICATIONS Mean measured and reconstructed fine particulate matter mass concentrations declined by about a factor of 2 in California over the period 1980 to 2007 and varied by about a factor of 4 among air basins. The integrated data record is of interest for epidemiological studies and for assessments of emission control programs.

Thermochemical Evaluation of Hydroxyl and Peroxyl Radical Precursors in the Formation of Tropospheric Ozone Reactions

The thermochemical properties of varieties of species needed to assess the most prominent pathways of tropospheric ozone transformation have been established. In the troposphere, ozone which is a secondary pollution produced by photochemical induced transformation, acts as an oxidizing agent to numerous atmospheric reactions leading to the formation of particulate matter. Based on the climate related problems resulting from the precursor of particulate matter, it is adequate to establish the feasible routes of ozone formation. In this study, the electronic structure methods which approximate the Schrödinger equation to compute Gibbs free energies and enthalpies of formation of the various chemical species participating in the reactions were used. These thermodynamic properties were determined using four computational model chemistry methods integrated in the Gaussian 03 (G03) chemistry package. Five known reaction pathways for the formation of NO2 (the O3 precursor specie), as well as the dominant ozone formation route from NO2 were examined and their energies determined. Of all the computational methods, the complete basis set (CBS-4M) method produced energies for all species of the five reaction routes. Out of the five routes, only the reactions involving radical species were favoured to completion over a temperature range of -100 and +100oC. The most relevant reaction route for the formation of NO2 and subsequently O3 is that involving the peroxyl acetyl nitrate (PAN) and hydroxyl radicals. Chemical equilibrium analyses of the reaction routes also indicated that reduction in temperature encourages NO2 formation while increase in temperature favours O3 production.