Contributions of biogenic volatile organic compounds to the formation of secondary organic aerosols over Mt. Tai,Central East China

To better understand the contribution of biogenic volatile organic compounds to the formation of secondary organic aerosol (SOA) in high mountain regions, ambient aerosols were collected at the summit of Mt. Tai (1534 m, a.s.l.), Central East China (CEC) during the Mount Tai Experiment 2006 campaign (MTX2006) in early summer. Biogenic SOA tracers for the oxidation of isoprene, α/β-pinene, and β-caryophyllene were measured using gas chromatography/mass spectrometry. Most of the biogenic SOA tracers did not show clear diurnal variations, suggesting that they are formed during long-range atmospheric transport or over relatively long time scales. Although isoprene- and α/β-pinene-derived SOA tracers did not correlate with levoglucosan (a biomass burning tracer), β-caryophyllinic acid showed a good correlation with levoglucosan, indicating that crop residue burning may be a source for this acid. Total concentrations of isoprene oxidation products are much higher than those of α/β-pinene and β-caryophyllene oxidation products. The averaged ratio of isoprene to α/β-pinene oxidation products (R_iso/pine) was 4.9 and 6.7 for the daytime and nighttime samples, respectively. These values are among the highest in the aerosols reported in different geographical regions, which may be due to the large isoprene fluxes and relatively high levels of oxidants such as OH in CEC. Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) derived from isoprene, α/β-pinene, and β-caryophyllene to be 0.42–3.1 μgC m^?3 (average 1.6 μgC m^?3) during the daytime and 0.11–4.2 μgC m^?3 (1.7 μgC m^?3) during the nighttime. These values correspond to 2.9–23% (10%) and 3.2–28% (9.8%) of the total OC concentrations, in which isoprene-derived SOC accounts for 58% and 63% of total SOC during the daytime and nighttime, respectively. This study suggests that isoprene is a more significant precursor for biogenic SOA than α/β-pinene and β-caryophyllene at high altitudes in CEC.     

Carbonaceous aerosol over a Pinus taeda forest in Central North Carolina,USA

Organic aerosol is the least understood component of ambient fine particulate matter (PM_2.5). In this study, organic and elemental carbon (OC and EC) within ambient PM_2.5 over a three-year period at a forested site in the North Carolina Piedmont are presented. EC exhibited significant weekday/weekend effects and less significant seasonal effects, in contrast to OC, which showed strong seasonal differences and smaller weekend/weekday effects. Summer OC concentrations are about twice as high as winter concentrations, while EC was somewhat higher in the winter. OC was highly correlated with EC during cool periods when both were controlled by primary combustion sources. This correlation decreased with increasing temperature, reflecting higher contributions from secondary organic aerosol, likely of biogenic origin. PM_2.5 radiocarbon data from the site confirms that a large fraction of the carbon in PM_2.5 is indeed of biogenic origin, since modern (non-fossil fuel derived) carbon accounted for 80% of the PM_2.5 carbon over the course of a year. OC and EC exhibited distinct diurnal profiles, with summertime OC peaking in late evening and declining until midday. During winter, OC peaked during the early morning hours and again declined until midday. Summertime EC peaked during late morning hours except on weekends. Wintertime EC often peaked in late PM or early AM hours due to local residential wood combustion emissions. The highest short term peaks in OC and EC were associated with wildfire events. These data corroborate recent source apportionment studies conducted within 20 km of our site, where oxidation products of isoprene, α-pinene, and β-caryophyllene were identified as important precursors to organic aerosols. A large fraction of the carbon in rural southeastern ambient PM_2.5 appears to be of biogenic origin, which is probably difficult to reduce by anthropogenic controls.     

Contribution of Primary and Secondary Sources to Organic Aerosol and PM2.5 at SEARCH Network Sites

Abstract

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 µm or less in aerodynamic diameter (PM_2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO₄ ^2?], nitrate [NO₃ ^?], ammonium [NH₄ ⁺]), metals, and metal oxides and compared with the measured PM_2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and β-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12–42 µg m^?3. Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM_2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM_2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

Source apportionment of primary and secondary organic aerosols using positive matrix factorization (PMF) of molecular markers

Monthly average ambient concentrations of more than eighty particle-phase organic compounds, as well as total organic carbon (OC) and elemental carbon (EC), were measured from March 2004 through February 2005 in five cities in the Midwestern United States. A multi-variant source apportionment receptor model, positive matrix factorization (PMF), was applied to explore the average source contributions to the five sampling sites using molecular markers for primary and secondary organic aerosols (POA, SOA). Using the molecular makers in the model, POA and SOA were estimated for each month at each site. Three POA factors were derived, which were dominated by primary molecular markers such as EC, hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs), and which represented the following POA sources: urban primary sources, mobile sources, and other combustion sources. The three POA sources accounted for 57% of total average ambient OC. Three factors, characterized by the presence of reaction products of isoprene, α-pinene and β-caryophyllene, and displaying distinct seasonal trends, were consistent with the characteristics of SOA. The SOA factors made up 43% of the total average measured OC. The PMF-derived results are in good agreement with estimated SOA concentrations obtained from SOA to tracer yield estimates obtained from smog chamber experiments. A linear regression comparing the smog chamber yield estimates and the PMF SOA contributions had a regression slope of 1.01 ± 0.07 and an intercept of 0.19 ± 0.10 μg OC m^?3 (adjusted R² of 0.763, n = 58).     

Primary source attribution and analysis of α-pinene photooxidation products in Duke Forest,North Carolina

Samples of fine particulate organic matter were collected outside Durham, NC in the Duke Research Forest as part of the CELTIC study in July 2003. Particulate samples were collected on quartz filters using high volume air sampling equipment, and samples were analyzed for polar and non-polar organic species. Among compounds analyzed, oxidation products of α-pinene, namely pinic acid and pinonic acid, were identified in all samples. Pinic acid, being a dicarboxylic acid, has a low vapor pressure of the order of 10⁻⁸ Torr and is expected to contribute significantly to secondary organic aerosol (SOA) formation from the oxidation of α-pinene. Source contribution estimates from primary organic aerosol emissions were computed using the organic species as molecular markers with the chemical mass balance (CMB) model. The unapportioned organic carbon (OC) was determined as the difference between measured OC and OC apportioned to primary sources. This unapportioned OC was then correlated with pinic and pinonic acid to get a better understanding of the role of monoterpene oxidation products to form SOA. A reasonably good fit between pinic acid concentrations and unapportioned OC levels is indicative of the contribution of α-pinene oxidation products to SOA formation in ambient atmosphere. The results are significant considering the role of monoterpene emissions to global atmospheric chemistry.     

Estimations of primary and secondary organic carbon formation in PM2.5 aerosols of Santiago City,Chile

High concentration of fine airborne particulates is considered one of the major environmental pollutants in Santiago, the Chilean Capital city, which in 1997 was declared a PM₁₀ saturated zone. To date there is no control of the amounts of fine and coarse aerosols concentrations and the source and chemical characterizations of the PM_2.5 particulates in the carbonaceous fractions are not well known even though this fraction could be represented almost the 50% in mass of the PM_2.5.In this work, we present for the first time determinations of primary organic aerosol (POA) and secondary organic aerosol composition (SOA) fractions of the total mass of PM_2.5 particulates collected in the urban atmosphere of Santiago City. Our purpose is to know the anthropogenic contributions to the formation of SOA. To accomplish this we used the elemental carbon (EC) and organic carbon (OC) determinations developed by automatic monitoring stations installed in the city during the period 2002–2005, with a particular analysis of the summer time occurred in February 2004. Based on the EC tracer method, we have estimated the POA and SOA fraction and our data permit us to estimate the SOA reaching up to 20% of total organic aerosol matter, in good agreement to other measurements observed in large cities of Europe and U.S.A.     

Sources and characteristics of carbonaceous aerosol in two largest cities in Pearl River Delta Region,China

PM_2.5 samples were collected at five sites in Guangzhou and Hong Kong, Pearl River Delta Region (PRDR), China in both summer and winter during 2004–2005. Elemental carbon (EC) and organic carbon (OC) in these samples were measured. The OC and EC concentrations ranked in the order of urban Guangzhou > urban Hong Kong > background Hong Kong. Total carbonaceous aerosol (TCA) contributed less to PM_2.5 in urban Guangzhou (32–35%) than that in urban Hong Kong (43–57%). The reason may be that, as an major industrial city in South China, Guangzhou would receive large amount of inorganic aerosol from all kinds of industries, however, as a trade center and seaport, urban Hong Kong would mainly receive organic aerosol and EC from container vessels and heavy-duty diesel trucks. At Hong Kong background site Hok Tsui, relatively lower contribution of TCA to PM_2.5 may result from contributions of marine inorganic aerosol and inland China pollutant. Strong correlation (R²=0.76–0.83) between OC and EC indicates minor fluctuation of emission and the secondary organic aerosol (SOA) formation in urban Guangzhou. Weak correlation between OC and EC in Hong Kong can be related to the impact of the long-range transported aerosol from inland China. Averagely, secondary OC (SOC) concentrations were 3.8–5.9 and 10.2–12.8 μg m⁻³, respectively, accounting for 21–32% and 36–42% of OC in summer and winter in Guangzhou. The average values of 4.2–6.8% for SOA/ PM_2.5 indicate that SOA was minor component in PM_2.5 in Guangzhou.     

Insights into the primary–secondary and regional–local contributions to organic aerosol and PM2.5 mass in Pittsburgh,Pennsylvania

This paper presents chemical mass balance (CMB) analysis of organic molecular marker data to investigate the sources of organic aerosol and PM_2.5 mass in Pittsburgh, Pennsylvania. The model accounts for emissions from eight primary source classes, including major anthropogenic sources such as motor vehicles, cooking, and biomass combustion as well as some primary biogenic emissions (leaf abrasion products). We consider uncertainty associated with selection of source profiles, selection of fitting species, sampling artifacts, photochemical aging, and unknown sources. In the context of the overall organic carbon (OC) mass balance, the contributions of diesel, wood-smoke, vegetative detritus, road dust, and coke-oven emissions are all small and well constrained; however, estimates for the contributions of gasoline-vehicle and cooking emissions can vary by an order of magnitude. A best-estimate solution is presented that represents the vast majority of our CMB results; it indicates that primary OC only contributes 27±8% and 50±14% (average±standard deviation of daily estimates) of the ambient OC in the summer and winter, respectively. Approximately two-thirds of the primary OC is transported into Pittsburgh as part of the regional air mass. The ambient OC that is not apportioned by the CMB model is well correlated with secondary organic aerosol (SOA) estimates based on the EC-tracer method and ambient concentrations of organic species associated with SOA. Therefore, SOA appears to be the major component of OC, not only in summer, but potentially in all seasons. Primary OC dominates the OC mass balance on a small number of nonsummer days with high OC concentrations; these events are associated with specific meteorological conditions such as local inversions. Primary particulate emissions only contribute a small fraction of the ambient fine-particle mass, especially in the summer.     

The influence of the North-Föhn on tracer organic compounds in ambient air PM10 at a pre-alpine site in Northern Italy

The ambient air in Northern Italy is characterised by relatively high PAH and PM₁₀ concentrations in relation to calm wind and intensive temperature inversions, especially during cold periods. These stagnant conditions are occasionally interrupted by North-Föhn events, which cause a drop in relative humidity and an increase in O₃ levels, indicating the mixing of local and free troposphere air flows. In this study the influence of the North-Föhn on concentrations of tracer organic compounds, including polycyclic aromatic hydrocarbons (PAHs), PM₁₀, O₃ and black carbon (BC) was studied during a North-Föhn event in November 2007. Large fluctuations in the concentration of these compounds, as well as changes in PM₁₀ composition due to daytime and night-time variations of local source emissions were observed. Although these events occur at low frequencies (6-10%) they can for short periods, strongly affect the regional air quality by quickly decreasing the concentrations of these tracer organic compounds.     

Assessment of Secondary Organic Carbon in the Southeastern United States: A Review

Abstract

Organic carbon (OC) is one of the major components of ambient PM_2.5 (particulate matter [PM] ≤ 2.5 µm in aerodynamic diameter) and a significant portion of OC is from secondary organic aerosol (SOA) formation in the southeastern United States. Various approaches (based on measurement and modeling results) are applied to estimate secondary organic carbon (SOC) and its origins in the region. SOC estimates by various methods are consistent as to clear seasonal variation (i.e., relatively higher SOC in summer) and little spatial variability (i.e., a regional characteristic of SOC). However, there are differences as to the origins of SOC. SOA organic tracer and emission-based modeling studies indicate that the biogenic origin of SOC is dominant in the Southeast, showing that biogenic-origin SOC accounts for 90% of SOC in summer and more than 70% even in other seasons. However, results from other studies suggest that the anthropogenic origin of SOC is dominant, significant amounts of anthropogenic-origin SOC, or important roles of anthropogenic pollutants for SOA formation, especially at urban areas, as strong correlations between water-soluble OC (an indicator of SOC) and anthropogenic pollutants, considerable amounts of fossil water-soluble OC, and significant contributions of fossil SOC (37–52% in summer months, 70–73% in winter months) are observed. Therefore, more studies are needed to reconcile the differences in the source attribution of SOC measurements.     

Formation of organic tracers for isoprene SOA under acidic conditions

The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC–MS methods. In addition to the known isoprene photooxidation products 2-methylglyceric acid, 2-methylthreitol, and 2-methylerythritol, three other peaks of note were detected: one of these was consistent with a silylated-derivative of sulfuric acid, while the remaining two were other oxidized organic compounds detected only when acidic aerosol was present. These two oxidation products were also detected in field samples, and their presence was found to be dependent on both the apparent degree of aerosol acidity as well as the availability of isoprene aerosol. The average concentrations of the sum of these two compounds in the ambient PM_2.5 samples ranged from below the GC–MS detection limit during periods when the isoprene emission rate or apparent acidity were low to approximately 200 ng m^?3 (calibrations being based on a surrogate compound) during periods of high isoprene emissions. These compounds presently unidentified have the potential to serve as organic tracers of isoprene SOA formed exclusively in the presence of acidic aerosol and may also be useful in assessments in determining the importance and impact of aerosol acidity on ambient SOA formation.     

Wood smoke as a source of particle-phase organic compounds in residential areas

The objective of this study was to investigate the organic composition of wood smoke emissions and ambient air samples in order to determine the wood smoke contribution to the ambient air pollution in the residential areas. From November 2005 to March 2006 particle-phase PM₁₀ samples were collected in the residential town Dettenhausen surrounded by forests near Stuttgart in southern Germany. Samples collected on pre-baked glass fibre filters were extracted using toluene with ultrasonic bath and analysed by gas chromatography mass spectrometry (GC-MS). 21 polycyclic aromatic hydrocarbons (PAH) including 16 USEPA priority pollutants, different organic wood smoke tracers, primarily 21 species of syringol and guaiacol derivatives, levoglucosan and its isomers mannosan, galactosan and dehydroabietic acid were detected and quantified in this study. The concentrations of these compounds were compared with the fingerprints of emissions from hardwood and softwood combustion carried out in test facilities at Universitaet Stuttgart and field investigations at a wood stove during real operation in Dettenhausen. It was observed that the combustion derived PAH was detected in higher concentrations than other PAH in the ambient air PM₁₀ samples. Syringol and its derivatives were found in large amounts in hardwood burning but were not detected in softwood burning emissions. On the other hand, guaiacol and its derivatives were found in both softwood and hardwood burning emissions, but the concentrations were higher in the softwood smoke compared to hardwood smoke. So, these compounds can be used as typical tracer compounds for the different types of wood burning emissions. In ambient air samples both syringol and guaiacol derivatives were found which indicates the wood combustion contribution to the PM load in such residential areas. Levoglucosan was detected in high concentrations in all ambient PM₁₀ samples. A source apportionment modelling, Positive Matrix Factorization (PMF) was implemented to quantify the wood smoke contribution to the ambient PM₁₀ bound organic compounds in the residential area.     

An examination of oxidant amounts on secondary organic aerosol formation and aging

The effect of HO_x radicals (OH and HO₂) and ozone (O₃) on aerosol formation and aging has been studied. Experiments were performed in presence as well as in absence of oxygen in a flow-through chamber at 299 K for three organic precursor gases, isoprene, α-pinene and m-xylene. The HO_x source was the UV photolysis of humidified air or nitrogen and was measured with a GTHOS (Ground-based Tropospheric Hydrogen Oxides Sensor). The precursor gases concentration was monitored with an online GC-FID. The aerosol mass was then quantified by a Tapered Element Oscillating Microbalance (TEOM). Typical oxidant mixing ratios were (0–4.5) ppm for O₃, 200 pptv for OH and 3 ppbv for HO₂. A simple kinetics model is used to infer the aerosol production mechanism. In the present of O₃ (or O₂), the SOA yields were 0.46, 0.036 and 0.12 for α-pinene with an initial concentration of 100 ppbv (RH = 37%), isoprene with an initial concentration of 177 ppbv (RH = 50%) and m-xylene with an initial concentration of 100 ppbv (RH = 37%), respectively. When the chosen precursor gases reacted with HO_x in the absence of O₃, the maximum SOA yields were significantly increased by factors of 1.6 for isoprene 1.1 for α-pinene, and 3 for m-xylene respectively. The comparison of the calculated and measured potential aerosol mass concentrations as function of time shows that presence of ozone or oxygen can influence the aerosol yield and the absence of ozone or oxygen in the system resulted in high concentrations of its organic aerosol products.     

Insights into the nature of secondary organic aerosol in Mexico City during the MILAGRO experiment 2006

This study targets understanding the secondary sources of organic aerosol in Mexico City during the Megacities Impact on Regional and Global Environment (MIRAGE) 2006 field campaign. Ambient PM_2.5 was collected daily at urban and peripheral locations. Particle-phase secondary organic aerosol (SOA) products of anthropogenic and biogenic precursor gases were measured by gas chromatography mass spectrometry. Ambient concentrations of SOA tracers were used to estimate organic carbon (OC) from secondary origins (SOC). Anthropogenic SOC was estimated as 20–25% of ambient OC at both sites, while biogenic SOC was less abundant, but was relatively twice as important at the peripheral site. The OC that was not attributed secondary sources or to primary sources in a previous study showed temporal consistency with biomass-burning events, suggesting the importance of secondary processing of biomass-burning emissions in the region. The best estimate of biomass-burning-related SOC was in the range of 20–30% of ambient OC during peak biomass burning events. Low-molecular weight (MW) alkanoic and alkenoic dicarboxylic acids (C₂–C₅) were also measured, of which oxalic acid was the most abundant. The spatial and temporal trends of oxalic acid differed from tracers for primary and secondary sources, suggesting that it had different and/or multiple sources in the atmosphere.     

Chemical characterization and source apportionment of fine and coarse particulate matter in Lahore,Pakistan

Lahore, Pakistan is an emerging megacity that is heavily polluted with high levels of particle air pollution. In this study, respirable particulate matter (PM_2.5 and PM₁₀) were collected every sixth day in Lahore from 12 January 2007 to 19 January 2008. Ambient aerosol was characterized using well-established chemical methods for mass, organic carbon (OC), elemental carbon (EC), ionic species (sulfate, nitrate, chloride, ammonium, sodium, calcium, and potassium), and organic species. The annual average concentration (±one standard deviation) of PM_2.5 was 194 ± 94 μg m^?3 and PM₁₀ was 336 ± 135 μg m^?3. Coarse aerosol (PM_10?2.5) was dominated by crustal sources like dust (74 ± 16%, annual average ± one standard deviation), whereas fine particles were dominated by carbonaceous aerosol (organic matter and elemental carbon, 61 ± 17%). Organic tracer species were used to identify sources of PM_2.5 OC and chemical mass balance (CMB) modeling was used to estimate relative source contributions. On an annual basis, non-catalyzed motor vehicles accounted for more than half of primary OC (53 ± 19%). Lesser sources included biomass burning (10 ± 5%) and the combined source of diesel engines and residual fuel oil combustion (6 ± 2%). Secondary organic aerosol (SOA) was an important contributor to ambient OC, particularly during the winter when secondary processing of aerosol species during fog episodes was expected. Coal combustion alone contributed a small percentage of organic aerosol (1.9 ± 0.3%), but showed strong linear correlation with unidentified sources of OC that contributed more significantly (27 ± 16%). Brick kilns, where coal and other low quality fuels are burned together, are suggested as the most probable origins of unapportioned OC. The chemical profiling of emissions from brick kilns and other sources unique to Lahore would contribute to a better understanding of OC sources in this megacity.     

Carbon content of common airborne fungal species and fungal contribution to aerosol organic carbon in a subtropical city

Interest in the role and contribution of fungi to atmospheric aerosols and processes grows in the past decade. Substantial data or information such as fungal mass or carbon loading to ambient aerosols is however still lacking. This study aimed to quantify the specific organic carbon content (OC per spore) of eleven fungal species commonly found airborne in the subtropics, and estimated their contribution to organic carbon in aerosols. The specific OC contents showed a size-dependent relationship (r = 0.64, p < 0.05) and ranged from 3.6 to 201.0 pg carbon per spore or yeast cell, giving an average of 6.0 pg carbon per spore (RSD 51%) for spore or cell size less than 10 μm. In accounting for natural variations in the composition and abundance of fungal population, weighted-average carbon content for field samples was adopted using the laboratory determined specific OC values. An average of 5.97 pg carbon per spore (RSD 3.8%) was enumerated from 28 field samples collected at the university campus. The mean fungal OC concentration was 3.7, 6.0 and 9.7 ng m^?3 in PM_2.5, PM_2.5–10 and PM₁₀, respectively. These corresponded to 0.1%, 1.2% and 0.2% of the total OC in PM_2.5, PM_2.5–10 and PM₁₀, respectively. In the study period, rain provided periods with low total OC but high fungal prevalence and fungi contributed 7–32% OC in PM_2.5–10 or 2.4–7.1% OC in PM₁₀. More extensive studies are deserved to better understand the spatial-, temporal- and episodic dependency on the fungal OC contribution to the atmospheric aerosols.     

Wood Smoke Contribution to Winter Aerosol in Fresno,CA

Abstract

In an effort to better quantify wintertime particulate matter (PM) and the contribution of wood smoke to air pollution events in Fresno, CA, a field campaign was conducted in winter 2003–2004. Coarse and fine daily PM samples were collected at five locations in Fresno, including residential, urban, and industrial areas. Measurements of collected samples included gravimetric mass determination, organic and elemental carbon analysis, and trace organic compound analysis by gas chromatograph mass spectrometry (GC/MS). The wood smoke tracer levoglucosan was also measured in aqueous aerosol extracts using high-performance anion exchange chromatography coupled with pulsed amperometric detection. Sample preparation and analysis by this technique is much simpler and less expensive than derivatized levoglucosan analysis by GC/MS, permitting analysis of daily PM samples from all five of the measurement locations. Analyses revealed low spatial variability and similar temporal patterns of PM_2.5 mass, organic carbon (OC), and levoglucosan. Daily mass concentrations appear to have been strongly influenced by meteorological conditions, including precipitation, wind, and fog events. Fine PM (PM_2.5) concentrations are uncommonly low during the study period, reflecting frequent precipitation events. During the first portion of the study, levoglucosan had a strong relationship to the concentrations of PM_2.5 and OC. In the later portion of the study, there was a significant reduction in levoglucosan relative to PM_2.5 and OC. This may indicate a change in particle removal processes, perhaps because of fog events, which were more common in the latter period. Combined, the emissions from wood smoke, meat cooking, and motor vehicles appear to contribute ~65–80% to measured OC, with wood smoke, on average, accounting for ~41% of OC and ~18% of PM_2.5 mass. Two residential sites exhibit somewhat higher contributions of wood smoke to OC than other locations.     

Concentrations of aliphatic and polycyclic aromatic hydrocarbons in ambient PM2.5 and PM10 particulates in Doha,Qatar

Organic carbon (OC), elemental carbon (EC), and 90 organic compounds (36 polycyclic aromatic hydrocarbons [PAHs], 25 n-alkane homologues, 17 hopanes, and 12 steranes) were concurrently quantified in atmospheric particulate matter of PM_2.5 and PM₁₀. The 24-hr PM samples were collected using Harvard Impactors at a suburban site in Doha, Qatar, from May to December 2015. The mass concentrations (mean ± standard deviation) of PM_2.5 and PM₁₀ were 40 ± 15 and 145 ± 70 µg m^?3, respectively, exceeding the World Health Organization (WHO) air quality guidelines. Coarse particles comprised 70% of PM₁₀. Total carbonaceous contents accounted for 14% of PM_2.5 and 10% of PM₁₀ particulate mass. The major fraction (90%) of EC was associated with the PM_2.5. In contrast, 70% of OC content was found in the PM_2.5–10 fraction. The secondary OC accounted for 60–68% of the total OC in both PM fractions, indicating photochemical conversions of organics are much active in the area due to higher air temperatures and solar radiations. Among the studied compounds, n-alkanes were the most abundant group, followed by PAHs, hopanes, and steranes. n-Alkanes from C₂₅ to C₃₅ prevailed with a predominance of odd carbon numbered congeners (C₂₇–C₃₁). High-molecular-weight PAHs (5–6 rings) also prevailed, within their class, with benzo[b + j]fluoranthene (Bb + jF) being the dominant member. PAHs were mainly (80%) associated with the PM_2.5 fraction. Local vehicular and fugitive emissions were predominant during low-speed southeasterly winds from urban areas, while remote petrogenic/biogenic emissions were particularly significant under prevailing northwesterly wind conditions.

Implications: An unprecedented study in Qatar established concentration profiles of EC, OC, and 90 organic compounds in PM_2.5 and PM₁₀. Multiple tracer organic compounds for each source can be used for convincing source apportionment. Particle concentrations exceeded WHO air quality guidelines for 82–96% of the time, revealing a severe problem of atmospheric PM in Doha. Dominance of EC and PAHs in fine particles signifies contributions from combustion sources. Dependence of pollutants concentrations on wind speed and direction suggests their significant temporal and spatial variability, indicating opportunities for improving the air quality by identifying sources of airborne contaminants.     

Mass spectrometric study of secondary organic aerosol formed from the photo-oxidation of aromatic hydrocarbons

From measurements by an Aerodyne Aerosol Mass Spectrometer (AMS), secondary organic aerosol (SOA) formed in laboratory chambers is believed to be less oxidized than well-oxidized ambient organic aerosol (OA). However, the mass spectrum of SOA formed from the photo-oxidation of aromatic hydrocarbons has not been sufficiently studied by using AMS though these reactions are potential sources of urban SOA. In this study, we studied SOA formed from the photo-oxidation of seven aromatic hydrocarbons by using Time-of-Flight AMS. Strong mass signals from SOA were found at m/z 43 (m43) and 44 (m44) in all the experiments. The m44 to total organic aerosol mass ratio (m44/OA) increased with irradiation time. For example, the m44/OA ratio increased from 10.6% to 13.3% during irradiation for 11 h in an experiment with toluene. The average m44/OA ratios were determined to be 5.8–17.1% for all the experiments. The m44/OA decreased and the m43/OA increased with increasing number of alkyl substituents of precursor aromatic hydrocarbons. This is because low-reactive ketones are preferentially produced rather than aldehydes with increasing number of alkyl substituents. The m44/OA ratios of the benzene and monoalkylbenzene oxidation were 12.2–17.1% and were close to those of well-oxidized ambient OA. These findings are consistent with the hypothesis that the photo-oxidation of aromatic hydrocarbons is a potential source of urban SOA. In addition to oxygenated organic compounds, organic nitrogen oxides were also shown to be present in SOA by high-resolution mass spectra.     

Characterization of organic aerosol in Big Bend National Park,Texas

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was conducted in Big Bend National Park, Texas, July through October 1999. Daily PM_2.5 organic aerosol samples were collected on pre-fired quartz fiber filters. Daily concentrations were too low for detailed organic analysis by gas chromatography-mass spectrometry (GC-MS) and were grouped based on their air mass trajectories. A total of 12 composites, each containing 3–10 daily samples, were analyzed. Alkane carbon preference indices suggest primary biogenic emissions were small contributors to primary PM_2.5 organic matter (OM) during the first 3 months, while in October air masses advecting from the north and south were more strongly influenced by biogenic sources. A series of trace organic compounds previously shown to serve as particle phase tracers for various carbonaceous aerosol source types were examined. Molecular tracer species were generally at or below detection limits, except for the wood smoke tracer levoglucosan in one composite, so maximum possible source influences were calculated using the detection limit as an upper bound to the tracer concentration. Wood smoke was found not to contribute significantly to PM_2.5 OM, with contributions for most samples at <1% of the total organic particulate matter. Vehicular exhaust also appeared to make only minor contributions, with maximum possible influences calculated to be 1–4% of PM_2.5 OM. Several factors indicate that secondary organic aerosol formation was important throughout the study, and may have significantly altered the molecular composition of the aerosol during transport.