Biogenic Secondary Organic Carbon Research Articles

Seasonal characteristics of biogenic secondary organic aerosol tracers in a deciduous broadleaf forest in northern Japan

We collected total suspended particulate (TSP) samples from January 2010 to December 2010 at Sapporo deciduous forest to understand the oxidation processes of biogenic volatile organic compounds (BVOCs). The gas chromatography-mass spectrometric technique was applied to determine biogenic secondary organic aerosols (BSOAs) in the TSP samples. We found the predominance of the isoprene SOA (iSOA) tracers (20.6 ng m−3) followed by α/β-pinene SOA (pSOA) tracers (8.25 ng m−3) and β-caryophyllene SOA (cSOA) tracer (1.53 ng m−3) in the forest aerosols. The results showed large isoprene fluxes and relatively high levels of oxidants in the forest atmosphere. The iSOA and pSOA tracers showed a clear seasonal trend with summer and autumn maxima and winter and spring minima. Their seasonal trends were mainly controlled by BVOCs emission from the local broadleaf deciduous forest. Additionally, the regional level of isoprene emissions from the oceanic sources may also be contributed during summertime aerosols. cSOA tracer showed high concentrations in the winter and spring, possibly due to an additional contribution of biomass burning (BB) aerosols from the local or regional BB activities. The biogenic secondary organic carbon (BSOC) was contributed mainly by the oxidation products of isoprene (136 ngC m−3) followed by β-caryophyllene (63.0 ngC m−3) and α/β-pinene (35.9 ngC m−3). The mass concentration ratio (0.92) of pinonic acid + pinic acid and 3-methyl-1,2,3-butanetricarboxylic acid ((PNA + PA)/3-MBTCA) indicates the photochemical transformation of first-generation oxidation products to the higher generation oxidation products. The average ratios of isoprene to α/β-pinene (1.64) and β-caryophyllene (18.6) oxidation products suggested a large difference in the emissions of isoprene and α/β-pinene compared to β-caryophyllene. The cSOA tracers in the forest aerosols are also contributed by BB during the winter and spring. Positive matrix factorization analyses of the BSOA tracers confirmed that organic aerosols of deciduous forests are mostly related to isoprene emissions. This study suggests that isoprene is a more significant precursor for the BSOA than α/β-pinene and β-caryophyllene in a broadleaf deciduous forest.

Molecular characteristics, sources and influencing factors of isoprene and monoterpenes secondary organic aerosol tracers in the marine atmosphere over the Arctic Ocean

Biogenic secondary organic aerosols (BSOA) are important components of the remote marine atmosphere. However, the response of BSOA changes to sea ice reduction over the Arctic Ocean remains unclear. Here we investigated isoprene and monoterpenes secondary organic aerosol (SOAI and SOAM) tracers in three years of summer aerosol samples collected from the Arctic Ocean atmosphere. The results indicated that methyltetrols were the most abundant SOAI tracers, while the main oxidation products of monoterpenes varied over the years owing to different aerosol aging. The results of the principal component analysis (PCA)-generalized additive model (GAM) combined with correlation analysis suggested that SOAI tracers were mainly generated by the oxidation of isoprene from marine emissions, while SOAM tracers were probably more influenced by terrestrial transport. Estimation of secondary organic carbon (SOC) indicated that monoterpenes oxidation contributed more than isoprene and that sea ice changes had a relatively small effect on biogenic SOC concentration levels. Our study quantified the contribution of influencing factors to the atmospheric concentration of BSOA tracers in the Arctic Ocean, and showed that there were differences in the sources of precursors for different BSOA. Hence, our findings have contributed to a better understanding of the characteristics, sources and formation of SOA in the atmosphere of the Arctic Ocean.

Tracer-based characterization of fine carbonaceous aerosol in Beijing during a strict emission control period

Strict emission controls were implemented in Beijing and the surrounding regions in the North China Plain to guarantee good air quality during the 2014 Asia-Pacific Economic Cooperation (APEC) summit. Thus, the APEC period provides a good opportunity to study the sources and formation processes of atmospheric organic aerosol. Here, fine particles (PM2.5, particulate matter with a diameter of 2.5 μm or less) collected in urban Beijing before and during the APEC period were analyzed for molecular tracers of primary and secondary organic aerosol (SOA). The primary organic carbon (POC) and secondary organic carbon (SOC) were also reconstructed using a tracer-based method. The concentrations of biogenic SOA tracers ranged from 1.09 to 34.5 ng m−3 (mean 10.3 ± 8.51 ng m−3). Monoterpene oxidation products were the largest contributor to biogenic SOA, followed by isoprene- and sesquiterpene-derived SOA. The concentrations of biogenic SOA tracers decreased by 50 % during the APEC, which was largely attributed to the implementation of emission controls by the Chinese government. The increasing mass fractions of biogenic SOA tracers from isoprene and sesquiterpene during the pollution episodes implied that their photooxidation processes contributed to the poor air quality in urban Beijing. The reconstructed biogenic and anthropogenic SOC and POC concentrations were 89.6 ± 96.8 ng m−3, 570 ± 611 ng m−3, and 2.49 ± 2.08 μg m−3, respectively, accounting for 21.9 ± 11.4 % of OC in total. Biomass-burning derived OC was the largest contributor to carbonaceous aerosol over the North China Plain. By comparing the results before and during the APEC, the emission controls effectively mitigated about 34 % of the estimated OC and were more effective at reducing SOC than POC. This suggests that the reduction of the primary organic aerosol loading is harder than SOA over the North China Plain.

Oxidative potential associated with water-soluble components of PM2.5 in Beijing: The important role of anthropogenic organic aerosols

Oxidative stress is the mainstream toxicological mechanism for the adverse health outcomes of ambient aerosols. However, our understanding of the crucial redox-active species affecting the oxidative potential of water-soluble aerosols (OPWS) remains limited. In this study, the OPWS of PM2.5 in Beijing was measured using dithiothreitol (DTT) assay, including DTT consumption rate and ·OH formation rate. OPWS was more closely related to water-soluble organic compounds (WSOC) rather than transition metals. Laboratory simulations were conducted to investigate the effects of individual target species in the context of complex metal-organic interactions. The results showed that reducing WSOC can effectively decrease OPWS, while reducing Cu2+ increased OPWS. Parallel factor analysis demonstrated that OPWS was the most significantly correlated with the highly oxidized humic-like or quinone-like substances. Multiple linear regression showed that aromatic secondary organic carbon (SOC) (34.4%), other primary combustion sources of WSOC (20.0%), primary biomass burning WSOC (19.8%), transition metal ions (12.9%) and biomass burning SOC (12.8%) made significant contributions to DTTV. In addition to the anthropogenic sources of WSOC, the aged biogenic SOC also contributed to OHV, particularly in summer. Reducing anthropogenic WSOC was the key to the effective control of OPWS of PM2.5 in Beijing.

Seasonal Characteristics of Biogenic Secondary Organic Aerosols Over Chichijima Island in the Western North Pacific: Impact of Biomass Burning Activity in East Asia

AbstractTo better understand the formation processes of biogenic secondary organic aerosols (SOAs) over remote oceanic regions, aerosol samples were collected from 2010 to 2012 at Chichijima Island in the western North Pacific (WNP). The samples were analyzed by gas chromatography‐mass spectrometry for SOA tracers, which are produced by the photochemical oxidation of biogenic volatile organic compounds (BVOCs), including isoprene, monoterpenes, and sesquitepenes. Although no seasonal trend was identified for the isoprene‐derived SOA tracers, we observed higher levels of the monoterpene‐derived and sesquiterpene‐derived SOA tracers in winter/spring and lower levels in summer/autumn. We found a significant correlation (r = 0.87) of β‐caryophyllinic acid with levoglucosan, the latter being a specific tracer of biomass burning (BB). This suggests that the β‐caryophyllene accumulated in higher plants is evaporated by BB followed by atmospheric oxidation during long‐range transport from the Asian continent over the WNP. The biogenic secondary organic carbon concentration estimated using a tracer‐based approach ranged from 0.11 to 174 ngC m−3 (avg. 34.8 ± 38.2 ngC m−3), accounting for 0.02%–32.0% (avg. 6.11% ± 6.42%) of the measured organic carbon. Our results indicate that SOAs are formed by the photooxidation of BVOCs. The backward trajectories of air masses further support their transport from the central Pacific during mid‐spring to mid‐autumn, whereas BB aerosols are transported from the Asian continent during mid‐autumn to mid‐spring over the WNP. Positive matrix factorization analyses of the SOA tracers suggest that organic aerosols of Chichijima are mostly related to BVOC emissions, with BB’s additional contributions especially in winter and spring.

Apportioned primary and secondary organic aerosol during pollution events of DISCOVER-AQ Houston

Understanding the drivers for high ozone (O3) and atmospheric particulate matter (PM) concentrations is a pressing issue in urban air quality, as this understanding informs decisions for control and mitigation of these key pollutants. The Houston, TX metropolitan area is an ideal location for studying the intersection between O3 and atmospheric secondary organic carbon (SOC) production due to the diversity of source types (urban, industrial, and biogenic) and the on- and off-shore cycling of air masses over Galveston Bay, TX. Detailed characterization of filter-based samples collected during Deriving Information on Surface Conditions from Column and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) Houston field experiment in September 2013 were used to investigate sources and composition of organic carbon (OC) and potential relationships between daily maximum 8 h average O3 and PM. The current study employed a novel combination of chemical mass balance modeling defining primary (i.e. POC) versus secondary (i.e. SOC) organic carbon and radiocarbon (14C) for apportionment of contemporary and fossil carbon. The apportioned sources include contemporary POC (biomass burning [BB], vegetative detritus), fossil POC (motor vehicle exhaust), biogenic SOC and fossil SOC. The filter-based results were then compared with real-time measurements by aerosol mass spectrometry. With these methods, a consistent urban background of contemporary carbon and motor vehicle exhaust was observed in the Houston metropolitan area. Real-time and filter-based characterization both showed that carbonaceous aerosols in Houston was highly impacted by SOC or oxidized OC, with much higher contributions from biogenic than fossil sources. However, fossil SOC concentration and fractional contribution had a stronger correlation with daily maximum 8 h average O3, peaking during high PM and O3 events. The results indicate that point source emissions processed by on- and off-shore wind cycles likely contribute to peak events for both PM and O3 in the greater Houston metropolitan area.

Molecular composition and source apportionment of fine organic aerosols in Northeast China

Abstract We examined the characteristics and source apportionment of organic aerosols in ambient PM2.5 samples collected during the late autumn in Changchun, Northeast China. 8 compound classes (>90 individual species) were detected in the aerosol samples, including biomass burning tracers, aliphatic lipids (fatty acids and fatty alcohols), secondary oxidation products, polycyclic aromatic hydrocarbons (PAHs), sugar compounds, hopanes and biogenic secondary organic aerosol (SOA) tracers. The concentrations of total quantified organic species ranged from 138.2 to 6.8 × 103 ng m−3, among which levoglucosan was the most abundant compound. Biomass burning tracers (anhydrosugars, lignin and resin acids) were the most abundant compounds, followed by fatty acids, secondary oxidation products, PAHs, sugar compounds and fatty alcohols. Biogenic SOA tracers and hopanes were less abundant. The homohopane index [defined as 31abS/(31abS + 31abR)] was 0.5, indicating a potential contribution of traffic emission. PAHs showed a dominance of benzo(b)fluoranthene (BbF), and the diagnostic ratios implicated a substantial contribution of petroleum combustion as well as coal combustion. 2-methylglyceric acid to 2-methyltetrols ratio (2.2) indicated that NOx influence isoprene oxidation products formation. Furthermore, the average ratio of cis-pinonic acid plus pinic acid to 3-hydroxyglutaric acid (31.4) revealed the much fresher α/β-pinene oxidation products to some extent. A good correlation was found between β-caryophyllinic acid and levoglucosan (r = 0.61), suggesting that β-caryophyllene can mainly be generated by biomass burning. The biogenic secondary organic carbon (SOC) was underestimated by the tracer-based method, which only occupied 0.4% of the organic carbon (OC). In contrast, PMF model indicated that emissions from fossil fuel combustion and biomass burning were most important, accounting for 42.4% and 33.6%, respectively, followed by biogenic SOA emission (17.0%) and fungal spore derived source (7.0%), suggesting biogenic aerosol is a nonnegative contributor. Capsule Fossil fuel combustion (42.4%) as well as biomass burning (33.6%) were most important contributors of organic aerosols in a typical city in Northeast China.

Secondary organic aerosols from aromatic hydrocarbons and their contribution to fine particulate matter in Atlanta, Georgia

Tracers of secondary organic aerosols (SOA) from thirteen aromatic hydrocarbons were quantified in laboratory smog chamber experiments. Class-specific SOA tracers emerged, including 2,3-dihydroxy-4-oxo-pentatonic acid (DHOPA) from monoaromatic volatile organic compounds (VOCs), phthalic acid from naphthalene and 1-methylnaphthalene, and methyl-nitrocatechol isomers from o,m,p-cresol oxidation. Organic carbon mass fractions (fSOC) for these and other tracers were determined and extend the SOA tracer method widely used to apportion biogenic secondary organic carbon (SOC). The extended SOA tracer model was applied to evaluate the sources of SOC in Atlanta, GA during summer 2015 and winter 2016 after modifying the chamber-derived fSOC values to reflect SOA yields and local VOC levels (fSOC’). Monoaromatic, diaromatic, and cresol SOC contributed an average of 24%, 8%, and 0.12% of organic carbon (OC) mass during summer and 17%, 5%, and 0.27% during winter, respectively. Cresol SOC peaked during winter and was highly correlated with levoglucosan (r = 0.83, p < 0.001), consistent with its' precursors originating from biomass burning. Together, aromatic, biogenic, and biomass burning derived SOC accounted for an average of 77% and 28% of OC in summer and winter, respectively. The new understanding of SOA composition from aromatic VOCs advances the tracer-based method by including important precursors of SOC and enables a better understanding of the sources of atmospheric aerosol.

Source apportionment of fine particulate matter organic carbon in Shenzhen, China by chemical mass balance and radiocarbon methods

Chemical mass balance (CMB) modeling and radiocarbon measurements were combined to evaluate the sources of carbonaceous fine particulate matter (PM2.5) in Shenzhen, China during and after the 2011 summer Universiade games when air pollution control measurements were implemented to achieve air quality targets. Ambient PM2.5 filter samples were collected daily at two sampling sites (Peking University Shenzhen campus and Longgang) over 24 consecutive days, covering the controlled and uncontrolled periods. During the controlled period, the average PM2.5 concentration was less than half of what it was after the controls were lifted. Organic carbon (OC), organic molecular markers (e.g., levoglucosan, hopanes, polycyclic aromatic hydrocarbons), and secondary organic carbon (SOC) tracers were all significantly lower during the controlled period. After pollution controls ended, at Peking University, OC source contributions included gasoline and diesel engines (24%), coal combustion (6%), biomass burning (12.2%), vegetative detritus (2%), biogenic SOC (from isoprene, α-pinene, and β-caryophyllene; 7.1%), aromatic SOC (23%), and other sources not included in the model (25%). At Longgang after the controls ended, similar source contributions were observed: gasoline and diesel engines (23%), coal combustion (7%), biomass burning (17.7%), vegetative detritus (1%), biogenic SOC (from isoprene, α-pinene, and β-caryophyllene; 5.3%), aromatic SOC (13%), and other sources (33%). The contributions of the following sources were smaller during the pollution controls: biogenic SOC (by a factor of 10–16), aromatic SOC (4–12), coal combustion (1.5–6.8), and biomass burning (2.3–4.9). CMB model results and radiocarbon measurements both indicated that fossil carbon dominated over modern carbon, regardless of pollution controls. However, the CMB model needs further improvement to apportion contemporary carbon (i.e. biomass burning, biogenic SOC) in this region. This work defines the major contributors to carbonaceous PM2.5 in Shenzhen and demonstrates that control measures for primary emissions could significantly reduce secondary organic aerosol (SOA) formation.

Observation of SOA tracers at a mountainous site in Hong Kong: Chemical characteristics, origins and implication on particle growth

Secondary organic aerosol (SOA) is an important constituent of airborne fine particles. PM2.5 (particles with aerodynamic diameters≤2.5μm) samples were collected at a mountainous site in Hong Kong in autumn of 2010, and analyzed for SOA tracers. Results indicated that the concentrations of isoprene SOA tracers (54.7±22.7ng/m3) and aromatics SOA tracers (2.1±1.6ng/m3) were on relatively high levels in Hong Kong. Secondary organic carbon (SOC) derived from isoprene, monoterpenes, sesquiterpenes and aromatics was estimated with the SOA tracer based approach, which constituted 0.35±0.15μg/m3 (40.6±5.7%), 0.20±0.03μg/m3 (30.4±5.5%), 0.05±0.02μg/m3 (5.6±1.7%) and 0.26±0.20μg/m3 (21.3±8.2%) of the total estimated SOC. Biogenic SOC (0.60±0.18μg/m3) dominated over anthropogenic SOC (0.26±0.20μg/m3) at this site. In addition to the total estimated SOC (17.8±4.6% of organic carbon (OC) in PM2.5), primary organic carbon (POC) emitted from biomass burning also accounted for a considerable proportion of OC (11.6±3.2%). Insight into the OC origins found that regional transport significantly (p<0.05) elevated SOC from 0.37±0.17 to 1.04±0.39μg/m3. Besides, SOC load could also increase significantly if there was influence from local ship emission. Biomass burning related POC in regional air masses (0.81±0.24μg/m3) was also higher (p<0.05) than that in samples affected by local air (0.29±0.35μg/m3). Evidences indicated that SOA formation was closely related to new particle formation and the growth of nucleation mode particles, while biomass burning was responsible for some particle burst events in Hong Kong. This is the first SOA study in afforested areas of Hong Kong.

Spatial and seasonal variations of secondary organic aerosol from terpenoids over China

AbstractA majority of global secondary organic aerosol (SOA) comes from terpenoids. In this study, we carried out a 1 year nationwide observation of pinenes (α‐ and β‐pinene) and SOA tracers from monoterpenes (SOAM) and β‐caryophyllene (SOAC) over China for the first time. SOAM and SOAC tracers ranged from 9.80 to 49.0 ng m−3 and 1.72 to 7.72 ng m−3, respectively, with high levels in southern China. Pinenes ranged from 34 to 102 parts per trillion by volume, with α‐pinene dominant over β‐pinene. SOAM tracers were correlated between paired sites, suggesting a regional impact of SOAM, while pinenes were uncorrelated between sites due to their rapid oxidation. High levels of SOAM tracers were observed in spring and summer. However, at the Hailun site in Northeast China, SOAM tracers increased during winter. The positive correlation between SOAM tracers and the biomass burning (BB) tracer levoglucosan during winter at Hailun indicated that the unexpected increase of SOAM was associated with BB. The SOAC tracer, β‐caryophyllenic acid, increased during winter and was positively correlated with levoglucosan, suggesting substantial contributions from BB to SOAC production in wintertime. Together with SOA tracers from isoprene, these tracers were applied to estimate biogenic secondary organic carbon (BSOC) from isoprene, monoterpenes, and β‐caryophyllene. The annual average BSOC was 0.91 ± 0.41 μgC m−3,with the majority from monoterpenes and the highest level in Southwest China. BSOC was elevated from April to September and was lowest in January and February. BSOC composition dramatically changed from a monoterpene majority in fall‐spring to an isoprene majority in summer.

Fine and ultrafine particulate organic carbon in the Los Angeles basin: Trends in sources and composition

In this study, PM2.5 and PM0.18 (particles with dp<2.5μm and dp<0.18μm, respectively) were collected during 2012–2013 in Central Los Angeles (LA) and 2013–2014 in Anaheim. Samples were chemically analyzed for carbonaceous species (elemental and organic carbons) and individual organic compounds. Concentrations of organic compounds were reported and compared with many previous studies in Central LA to quantify the impact of emissions control measurements that have been implemented for vehicular emissions over the past decades in this area. Moreover, a novel hybrid approach of molecular marker-based chemical mass balance (MM-CMB) analysis was conducted, in which a combination of source profiles that were previously obtained from a Positive Matrix Factorization (PMF) model in Central LA, were combined with some traditional source profiles. The model estimated the relative contributions from mobile sources (including gasoline, diesel, and smoking vehicles), wood smoke, primary biogenic sources (including emissions from vegetative detritus, food cooking, and re-suspended soil dust), and anthropogenic secondary organic carbon (SOC). Mobile sources contributed to 0.65±0.25μg/m3 and 0.32±0.25μg/m3 of PM2.5 OC in Central LA and Anaheim, respectively. Primary biogenic and anthropogenic SOC sources were major contributors to OC concentrations in both size fractions and sites. Un-apportioned OC (“other OC”) accounted for an average 8.0 and 26% of PM2.5 OC concentration in Central LA and Anaheim, respectively. A comparison with previous studies in Central LA revealed considerable reduction of EC and OC, along with tracers of mobile sources (e.g. PAHs, hopanes and steranes) as a result of implemented regulations on vehicular emissions. Given the significant reduction of the impacts of mobile sources in the past decade in the LA Basin, the impact of SOC and primary biogenic emissions have a larger relative impact and the new hybrid model allows the impact of these sources to be better quantified.

Anthropogenic and biogenic organic compounds in summertime fine aerosols (PM2.5) in Beijing, China

Abstract Ambient fine aerosol samples (PM2.5) were collected at an urban site (PKU) in Beijing and its upwind suburban site (Yufa) during the CAREBEIJING-2007 field campaign. Organic molecular compositions of the PM2.5 samples were studied for seven organic compound classes (sugars, lignin/resin acids, hydroxy-/polyacids, aromatic acids, biogenic SOA tracers, fatty acids and phthalates) using capillary GC/MS to better understand the characteristics and sources of organic aerosol pollution in Beijing. More than 60 individual organic species were detected in PM2.5 and were grouped into different compound classes based on their functional groups. Concentrations of total quantified organics at Yufa (469–1410 ng m−3, average 1050 ng m−3) were slightly higher than those at PKU (523–1390 ng m−3, 900 ng m−3). At both sites, phthalates were found as the most abundant compound class. Using a tracer-based method, the contributions of the biogenic secondary organic carbon (SOC) to organic carbon (OC) were 3.1% at PKU and 5.5% at Yufa, among which isoprene-SOC was the dominant contributor. In addition, most of the measured organic compounds were higher at Yufa than those at PKU, indicating a more serious pollution in its upwind region than in urban Beijing.

Seasonal variation of secondary organic aerosol tracers in Central Tibetan Plateau

Abstract. Secondary organic aerosol (SOA) affects the earth's radiation balance and global climate. High-elevation areas are sensitive to global climate change. However, at present, SOA origins and seasonal variations are understudied in remote high-elevation areas. In this study, particulate samples were collected from July 2012 to July 2013 at the remote Nam Co (NC) site, Central Tibetan Plateau and analyzed for SOA tracers from biogenic (isoprene, monoterpenes and β-caryophyllene) and anthropogenic (aromatics) precursors. Among these compounds, isoprene SOA (SOAI) tracers represented the majority (26.6 ± 44.2 ng m−3), followed by monoterpene SOA (SOAM) tracers (0.97 ± 0.57 ng m−3), aromatic SOA (SOAA) tracer (2,3-dihydroxy-4-oxopentanoic acid, DHOPA, 0.25 ± 0.18 ng m−3) and β-caryophyllene SOA tracer (β-caryophyllenic acid, 0.09 ± 0.10 ng m−3). SOAI tracers exhibited high concentrations in the summer and low levels in the winter. The similar temperature dependence of SOAI tracers and isoprene emission suggested that the seasonal variation of SOAI tracers at the NC site was mainly influenced by the isoprene emission. The ratio of high-NOx to low-NOx products of SOAI (2-methylglyceric acid to 2-methyltetrols) was highest in the winter and lowest in the summer, due to the influence of temperature and relative humidity. The seasonal variation of SOAM tracers was impacted by monoterpenes emission and gas-particle partitioning. During the summer to the fall, temperature effect on partitioning was the dominant process influencing SOAM tracers' variation; while the temperature effect on emission was the dominant process influencing SOAM tracers' variation during the winter to the spring. SOAM tracer levels did not elevate with increased temperature in the summer, probably resulting from the counteraction of temperature effects on emission and partitioning. The concentrations of DHOPA were 1–2 orders of magnitude lower than those reported in the urban regions of the world. Due to the transport of air pollutants from the adjacent Bangladesh and northeastern India, DHOPA presented relatively higher levels in the summer. In the winter when air masses mainly came from northwestern India, mass fractions of DHOPA in total tracers increased, although its concentrations declined. The SOA-tracer method was applied to estimate secondary organic carbon (SOC) from these four precursors. The annual average of SOC was 0.22 ± 0.29 μgC m−3, with the biogenic SOC (sum of isoprene, monoterpenes and β-caryophyllene) accounting for 75 %. In the summer, isoprene was the major precursor with its SOC contributions of 81 %. In the winter when the emission of biogenic precursors largely dropped, the contributions of aromatic SOC increased. Our study implies that anthropogenic pollutants emitted in the Indian subcontinent could be transported to the TP and have an impact on SOC over the remote NC.

Evaluation of the ability of the EC tracer method to estimate secondary organic carbon

The elemental carbon (EC) tracer method has often been used to estimate the primary and secondary organic aerosol (OA) fractions using field measurements of organic carbon (OC) and EC. In this observation-based approach, EC is used as a tracer for primary OC (POC), which allows for the estimation of secondary OC (SOC). The accuracy of this approach is evaluated using concentrations generated by PMCAMx, a three-dimensional chemical transport model that simulates the complex processes leading to SOC formation (including evaporation and chemical processing of POC and chemical aging of semivolatile and intermediate volatility organics). The ratio of primary organic to elemental carbon [OC/EC]p is estimated in various locations in the Eastern United States, and is then used to calculate the primary and secondary OC concentrations. To estimate the [OC/EC]p from simulated concentrations, we use both a traditional approach and the high EC edge method, in which only values with the highest EC/OC ratio are used. Both methods perform best on a daily-averaged basis, because of the variability of the [OC/EC]p ratio during the day. The SOC estimated by the EC tracer methods corresponds to the biogenic and anthropogenic SOC formed during the oxidation of volatile organic compounds. On the other hand, the estimated POC corresponds to the sum of the fresh POC, the SOC from oxidation of the evaporated POC and the intermediate volatility organic compounds, and the OC from long-distance transport. With this correspondence, the traditional EC tracer method tends to overpredict primary OC and underpredict secondary OC for the selected urban areas in the eastern United States. The high EC edge method performs better, especially in areas where the primary contribution to OC is smaller. Despite the weaknesses of models like the one used here, the conclusions about the accuracy of observation-based methods like the EC-tracer approach should be relatively robust due to the internal consistency of the data and the approach.

Impact of regional transport on the anthropogenic and biogenic secondary organic aerosols in the Los Angeles Basin

This manuscript explores the role of regional transport on anthropogenic and biogenic secondary organic carbon (SOC) concentrations in ambient fine particulate (PM2.5) organic carbon (OC) in the Los Angeles (LA) Basin. Daily organic molecular markers, water soluble organic carbon (WSOC), OC, and elemental carbon (EC) measurements from May 2009 through April 2010 at a central site in downtown LA, and results from a positive matrix factorization (PMF) analysis of these data, were used to understand the role of regional transport on SOC concentrations. A backward-trajectory analysis, coupled with the measurements and estimated source contributions, were used to evaluate the origins of SOC aerosols. Anthropogenic and biogenic SOC were identified in central LA over the study period, together contributing 40% of the annual average PM2.5 OC mass. There were distinct seasonal variations, with high contributions of anthropogenic SOC in summer, and high contributions of biogenic SOC in spring. The back-trajectory analysis, coupled with daily source contributions of SOC and organic compounds as indicators, allowed us to identify potential source locations and dominant meteorological conditions contributing to elevated SOC at the measurement site. The results show that air mass movements from the Pacific Ocean are associated with higher contributions of anthropogenic SOC to the PM2.5 OC in downtown LA, suggesting that the combination of local meteorological conditions and local anthropogenic emissions led to an increase in the anthropogenic SOC. In contrast, air masses passing over the Central Valley and forested areas where there are biogenic hydrocarbon emissions are closely associated with higher contributions of biogenic SOC in the region. The study emphasizes that higher anthropogenic SOC contributions are due to the combination of local emissions with humidity air from the ocean, and that higher biogenic SOC contributions are impacted by transport of pollutants from regions outside the LA Basin.

Assessment of source contributions to air pollution in Beirut, Lebanon: a comparison of source-based and tracer-based modeling approaches

A chemical-transport model (CTM), Polyphemus/Polair3D, is used to investigate the contributions of various anthropogenic and biogenic sources to total organic carbon (OC) in PM2.5 in Beirut, Lebanon, during the summer of 2011. Those results are compared to a tracer-based source apportionment of OC at an ambient site in Beirut where a measurement campaign was conducted in July 2011. The results obtained from the CTM in the base simulation S1 suggest contributions to total simulated OC mass (3.24 μg/m3) of 66 % (2.14 ± 1.07 μg/m3) from fossil fuel burning (FFB) and 8 % (0.27 ± 0.135 μg/m3) from biogenic secondary organic carbon (BSOC). The tracer-based approach leads to contribution estimates to total measured OC mass (5.6 μg/m3) of 16 % (0.9 μg/m3 ± 0.22) from FFB, 53 % (2.9 ± 1.7 μg/m3) from BSOC, and 32 % (1.8 ± 0.88 μg/m3) from cooking activities. In a second CTM simulation S2, emissions related to cooking activities were added to the emission inventory, monoterpene and sesquiterpene secondary organic aerosol (SOA) surrogate species were added to the boundary conditions, and a lower ratio of semi-volatile organic compounds to primary organic aerosols (SVOC/POA) was used. The S2 results obtained showed contributions to total simulated OC mass (3.01 μg/m3) of 33 % (0.98 ± 0.49 μg/m3) from FFB, 18 % (0.53 ± 0.27 μg/m3) from BSOC, and 39 % (1.2 ± 0.6 μg/m3) from cooking activities. The differences between these two methods are discussed in terms of their uncertainties and biases. The comparison of both approaches showed that the model underestimates the secondary fraction of OC, which may be due to underestimations of some biogenic volatile organic compound (VOC) emissions and/or boundary concentrations as well as the use of SOA yields that may not be representative of the eastern Mediterranean region. Concerning the tracer-based approach, the use of tracer/OC ratios that are not specific to Lebanon because of a lack of data could represent a limitation of this methodology. Nevertheless, this comparative analysis suggests that on-road transportation and diesel generators used for electricity production are major sources of atmospheric PM and should be targeted for emission reduction. Finally, cooking activities, which were identified as a significant source of PM with the tracer-based approach, should be studied further.

Secondary production of organic aerosols from biogenic VOCs over Mt. Fuji, Japan.

We investigated organic molecular compositions of summertime aerosols collected at the summit of Mt. Fuji (3776 m a.s.l.) in July-August 2009. More than 120 organic species were identified using GC/MS. Concentrations of both primary and secondary organic aerosol (SOA) tracers in whole-day samples were 4-20 times higher than those in nighttime samples, suggesting that valley breeze is an efficient mechanism to uplift the aerosols and precursors from the ground surface to mountaintop in daytime. 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 2.2-51.2 ngC m(-3) in nighttime and 227-1120 ngC m(-3) during whole-day. These biogenic SOCs correspond to 0.80-31.9% and 26.8-57.4% of aerosol organic carbon in nighttime and whole-day samples, respectively. This study demonstrates that biogenic SOA, which is controlled by the valley breeze, is a significant fraction of free tropospheric aerosols over Mt. Fuji in summer.

Preliminary assessment of the anthropogenic and biogenic contributions to secondary organic aerosols at two industrial cities in the upper Midwest

The contributions of anthropogenic and biogenic secondary organic carbon (SOC) to total PM2.5 mass are of interest to air quality management agencies required to demonstrate maintenance of the PM2.5 NAAQS. Reductions of SOC can be used in conjunction with the mitigation of other PM2.5 constituents to maintain PM2.5 concentrations below the regulatory limit. Currently, quantitative tools to understand the SOC source contributions to PM2.5 mass are not well developed, and the spatial variation of different types of SOC is not known.In this study concentrations of anthropogenic and biogenic SOC mass were determined using PM2.5 measurements made in Cleveland, OH and Mingo Junction, OH. Twenty-four hour averaged samples were collected on the EPA 1-in-6 day schedule over the course of one year between June 2007 and May of 2008. Organic molecular markers for anthropogenic and biogenic SOC were extracted from the PM2.5, silylated, and then analyzed by GC–MS. Source apportionment calculations were conducted using the EPA CMB (v.8.2) software and organic molecular markers as source tracers.SOC concentrations calculated from SOC tracers measurements followed the expected seasonal patterns with maximum contributions during the summer and minimum contributions during the winter. Anthropogenic SOC constituted approximately 37% to the apportioned SOC and 6% to the measured OC, on average across both sites. Biogenic SOC contributed the 42% to the apportioned SOC, and 4% to the measured OC. Anthropogenic SOC contributed strongly to organic PM2.5 meaning that SOC may by partially controllable by reductions in VOC emissions from anthropogenic sources.Similarities in the month-to-month patterns in α-pinene markers were observed between Cleveland and Mingo Junction, suggesting a regional character to this type of SOC. However, such patterns were not readily apparent in the isoprene markers.Limitations were found in the current version of the model. Approximately half of the water soluble organic carbon unrelated to biomass burning (NB-WSOC) during spring, summer and early fall could not be apportioned by the CMB model with the SOC markers available during this study. This suggested that additional sources not included in the CMB model used in this study contributed to SOC, or that models using markers measured in chamber oxidations are not entirely representative of the study sites. The unapportioned OC did not correlate particularly well with any of the known OC sources. While performance of the model is limited due to uncertainties in the source profiles, the apportionments calculated still give a preliminary insight into the relative contributions to SOC from anthropogenic and biogenic emissions.

Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

Abstract. Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m−3 (mean 47.6 ng m−3), accounting for 1.8–11.0% (4.8%) of organic carbon in the marine aerosols. Primary saccharides were found to be dominant organic compound class, followed by secondary organic aerosol (SOA) tracers formed from the oxidation of biogenic volatile organic compounds (VOCs) such as isoprene, α-pinene and β-caryophyllene. Mannitol, the specific tracer for airborne fungal spores, was detected as the most abundant organic species in the samples with a concentration range of 0.052–53.3 ng m−3 (9.2 ng m−3), followed by glucose, arabitol, and the isoprene oxidation products of 2-methyltetrols. Biomass burning tracers such as levoglucosan are evident in all samples with trace levels. On the basis of the tracer-based method for the estimation of fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 10.7% (up to 26.2%) of the OC in the marine aerosols was due to the contribution of fungal spores, followed by the contribution of isoprene SOC (mean 3.8%) and α-pinene SOC (2.9%). In contrast, only 0.19% of the OC was due to the photooxidation of β-caryophyllene. This study indicates that primary organic aerosols from biogenic emissions, both from long-range transport of mid-latitude aerosols and from sea-to-air emission of marine organics, as well as secondary organic aerosols formed from the photooxidation of biogenic VOCs are important factors controlling the organic chemical composition of marine aerosols in the Arctic Ocean.