Contribution Of Secondary Organic Carbon Research Articles

Bayesian inference-based estimation of hourly primary and secondary organic carbon in suburban Hong Kong: multi-temporal-scale variations and evolution characteristics during PM2.5 episodes

Abstract. Observation-based data of primary and secondary organic carbon in ambient particulate matter (PM) are essential for model evaluation, climate and air quality research, health effect assessments, and mitigation policy development. Since there are no direct measurement tools available to quantify primary organic (POC) and secondary organic carbon (SOC) as separate quantities, their estimation relies on inference approaches using relevant measurable PM constituents. In this study, we measured hourly carbonaceous components and major ions in PM2.5 for a year and a half in suburban Hong Kong from July 2020 to December 2021. We differentiated POC and SOC using a novel Bayesian inference approach. The hourly POC and SOC data allowed us to examine temporal characteristics varying from diurnal and weekly patterns to seasonal variations, as well as their evolution characteristics during individual PM2.5 episodes. A total of 65 city-wide PM2.5 episodes were identified throughout the entire study period, with SOC contributions during individual episodes varying from 10 % to 66 %. In summertime typhoon episodes, elevated SOC levels were observed during daytime hours, and high temperature and NOx levels were identified as significant factors contributing to episodic SOC formation. Winter haze episodes exhibited high SOC levels, likely due to persistent influences from regional transport originating from the northern region to the sampling site. Enhanced SOC formation was observed with increase in the nocturnal NO3 radical (indicated by the surrogate quantity of [NO2][O3]) and under conditions characterized by high water content and strong acidity. These results suggest that both NO3 chemistry and acid-catalyzed aqueous-phase reactions likely make notable contributions to SOC formation during winter haze episodes. The methodology employed in this study for estimating POC and SOC provides practical guidance for other locations with similar monitoring capabilities in place. The availability of hourly POC and SOC data is invaluable for evaluating and improving atmospheric models, as well as understanding the evolution processes of PM pollution episodes. This, in turn, leads to more accurate model predictions and a better understanding of the contributing sources and processes.

Contrasting compositions of PM2.5 in Northern Thailand during La Niña (2017) and El Niño (2019) years

There have been a very limited number of systematic studies on PM2.5 compositions and their source contribution in Southeast Asia. This study aims to explore the characteristics of PM2.5 composition collected in Chiang Mai (Thailand) during La Niña and El Niño years and to apportion their sources during smoke haze and non-haze periods. The average PM2.5 concentration of smoke haze episode in 2019 (El Niño) was much higher than in 2017 (La Niña). The ratios of organic carbon (OC) to elemental carbon (EC), as well as K (biomass burning (BB) tracer) to PM2.5, were higher during smoke haze episodes in 2019 than in 2017 indicating a significant influence from BB. The ratios of secondary organic carbon (SOC) levels to primary organic carbon (POC) levels during smoke haze episodes were higher than those in non-haze period, which indicated greater SOC contributions or more photo-oxidation of precursors in haze episodes with high ambient temperatures. However, the ratios of soil markers (Ca and Mg) during non-haze period were high implying that soil source contributed more to PM2.5 concentrations when there less BB occurred. The positive Matrix Factorization (PMF) model revealed that the source of BB, characterized by high K fractions, was the largest contributor during smoke haze episodes accounting for 50% (2017) and 79% (2019). Climate conditions influence meteorological patterns, particularly during incidences of extreme weather such as droughts, which affect the scale and frequency of open burning and thus air pollution levels.

Enhanced PM2.5 episodes in a small residential city of South Korea: Effects of biomass burning and secondary formations

In this study, the characteristics and possible causes of high-concentration PM2.5 episodes occurring in a small residential city with low anthropogenic emissions were investigated. The largest contributor to PM2.5 mass over the entire study period was organic carbon (OC). The OC apportioned by biomass burning (OCbb) was estimated using levoglucosan, and it was found to be highest in winter when the forest fire frequently occurred. In spring and fall, the burning of Asian crop residue was likely to be an important contributor. The contribution of secondary organic carbon (OCsec) was found to be consistently high throughout the year, and the high correlation between OCbb and OCsec suggests that aging of biomass burning emissions may promote the formation of OCsec in this study area. Regarding the high PM2.5 concentration episodes, the increments in secondary inorganic constituents and OCsec surpassed those of primary components and the decreased O3 and increased RH were observed, indicating that secondary aqueous-phase formations have a significant effect on enhancing PM2.5 in this region.

Secondary organic carbon in different atmospheric environments of a continental region and seasons

Secondary organic carbon (SOC) was derived using elemental carbon (EC) tracer method for primary organic carbon (OC) in daily aerosol samples collected in the regional background environment, suburban area, and central part of Budapest in each season. The estimation approaches of the OC/EC ratio for the major emission sources required for the tracer method were discussed, and the high EC edge approach was adopted separately for each location and season. The annual mean SOC concentrations in the environments listed were 1.16, 1.51 and 1.42 μg m−3, respectively. They were interpreted together with the PM2.5 mass, OC, EC, water-soluble OC (WSOC), levoglucosan (LVG) and meteorological variables. The annual mean contributions of SOC to OC were 45% at all sampling sites. However, they showed substantial seasonal variation at each location. The shares were the smallest (<≈30%) in winter, whereas they prevailed in summer (in the regional background, this even reached 66%). The secondary organic aerosol (obtained by multiplying the SOC concentrations by the organic mass-to-OC correction factor) made up roughly 25% of the PM2.5 mass except for winter, when it was 10%. Obvious associations of the SOC on the one side and PM2.5 mass, OC and WSOC on the other side were identified as joint relationships for all seasons. The SOC correlated with LVG only in winter when the relative intensity of biomass burning is the highest, and with O3 only in spring and summer, when the role of photochemistry is considerable. Elevations in PM2.5 mass, OC and WSOC concentrations on a daily scale were related to the enhancement of SOC concentration by factors of 0.14, 0.4 and 0.6, respectively, while higher LVG levels in winter enlarged the SOC 3-times. There was a relationship between the SOC and OC from fossil fuel combustion over all seasons, whereas the dependency between the SOC and OC from biomass burning could be established only in winter, and between the SOC and OC from biogenic sources apart from winter. The results and conclusions have importance for the health consequences of SOC in cities and rural areas over the whole Carpathian Basin.

Insights into sources and atmospheric processing at two polluted urban locations in the Indo-Gangetic plains from stable carbon and nitrogen isotope ratios and polycyclic aromatic hydrocarbons in ambient PM2.5

Ambient PM2.5 samples collected from two heavily polluted locations (Kanpur and Prayagraj) in Indo-Gangetic plains during wintertime were analyzed for stable isotopes (ẟ13C and ẟ15N), polycyclic aromatic hydrocarbons (PAHs), carbonaceous components, and ionic species. These data helped in understanding the aerosol composition, emission sources, and the associated atmospheric chemistry. Major contribution of high molecular weight (HMW) PAHs (4-ring, 5-ring, and 6-ring) to the total PAHs was observed at both the sampling sites. Organic carbon (OC) was a significant component of carbonaceous aerosols at both locations. In addition, OC/EC ratio (>2) revealed a dominant contribution from secondary organic carbon (SOC) during the sampling campaign. The contribution of SOC to total OC was much higher in Kanpur than in Prayagraj. A strong correlation between K+BB and OC observed for the two sites indicates a major influence of biomass burning. ẟ13C values of bulk PM2.5 samples at Prayagraj were slightly lower compared to Kanpur. ẟ13C and PAH isomeric ratios indicate significant contributions from biomass burning and petroleum combustion at both locations. Enhanced SOC formation appeared to control the ẟ13C at the Kanpur location, which may be due to the formation of secondary organic aerosol (SOA; 13C-depleted) from volatile organic compounds (VOCs) derived from combustion-generated aerosols (biomass/fossil fuel). This study also reports the ambient ẟ15N of aerosols at the Prayagraj site. The correlation of ẟ15N with nitrogenous components WSON, NH4+_N, and NO3−_N suggest 15N-depleted sources at the Prayagraj site. Like Kanpur, WSON and NH4+_N also influenced the bulk ẟ15N values of Prayagraj aerosols.

Elemental Carbon Observed at a Peri-Urban Forest Site near the Seoul Metropolitan Area as a Tracer of Seasonal Haze Occurrence

In order to identify the seasonal variability and source of carbonaceous aerosols in relation to haze occurrence, organic carbon (OC) and elemental carbon (EC) were continuously measured at the Taehwa Research Forest (TRF) near the Seoul metropolitan area from May 2013 to April 2014. For the entire experiment, the mean OC (5.1 µgC/m3) and EC (1.7 µgC/m3) concentrations of TRF were comparable to those of Seoul, with noticeably higher concentrations in winter and spring than in other seasons, and during haze days (6.6 ± 3.2 and 2.1 ± 1.0 μgC/m3) than during non-haze days (3.5 ± 2.2 and 1.3 ± 0.8 μgC/m3). The seasonal characteristics of OC and EC reveal the various sources of haze, including biomass combustion haze either transported for long distances or, in spring, from domestic regions, the greatest contribution of secondary organic carbon (SOC) in summer, and fossil fuel combustion in winter and fall. In addition, the seasonal OC/EC ratios between haze and non-haze days highlights that the increase in EC was more distinct than that of OC during haze episodes, thus suggesting that EC observed at a peri-urban forest site serves as a useful indicator for seasonally varying source types of haze aerosols in the study region.

Dramatic changes in Harbin aerosol during 2018–2020: the roles of open burning policy and secondary aerosol formation

Abstract. Despite the growing interest in understanding haze formation in Chinese megacities, air pollution has been largely overlooked for the Harbin–Changchun (HC) metropolitan area, located in the severe cold climate region in northeast China. In this study, we unfolded significant variations of fine particulate matter (PM2.5) in HC's central city (Harbin) during two sequential heating seasons of 2018–2019 and 2019–2020, and we explored major drivers for the observed variations. The two campaigns showed comparable organic carbon (OC) levels but quite different OC sources. The biomass burning (BB) to OC contribution decreased substantially for 2019–2020, which was attributed primarily to the transition of local policies on agricultural fires, i.e., from the “legitimate burning” policy released in 2018 to the “strict prohibition” policy in 2019. Meanwhile, the contribution of secondary OC (OCsec) increased significantly, associated with the much more frequent occurrences of high relative humidity (RH) conditions during the 2019–2020 measurement period. Similar to OCsec, the major secondary inorganic ions, i.e., sulfate, nitrate and ammonium (SNA), also exhibited RH-dependent increases. Given the considerable aerosol water contents predicted for the high-RH conditions, heterogeneous reactions were likely at play in secondary aerosol formation even in the frigid atmosphere in Harbin (e.g., with daily average temperatures down to below −20 ∘C). In brief, compared to 2018–2019, the 2019–2020 measurement period was characterized by a policy-driven decrease of biomass burning OC, a RH-related increase of OCsec and a RH-related increase of SNA, with the first two factors generally offsetting each other. In addition, we found that open burning activities were actually not eliminated by the strict prohibition policy released in 2019, based on a synthesis of air quality data and fire count results. Although not occurring during the 2019–2020 measurement period, agricultural fires broke out within a short period before crop planting in spring of 2020, and this resulted in off-the-charts air pollution for Harbin, with 1 h and 24 h PM2.5 concentrations peaking at ∼ 2350 and 900 µg/m3, respectively. This study indicates that sustainable use of crop residues remains a difficult challenge for the massive agricultural sector in northeast China.

Chemical Composition and Source Apportionment of Total Suspended Particulate in the Central Himalayan Region

The present study analyzes data from total suspended particulate (TSP) samples collected during 3 years (2005–2008) at Nainital, central Himalayas, India and analyzed for carbonaceous aerosols (organic carbon (OC) and elemental carbon (EC)) and inorganic species, focusing on the assessment of primary and secondary organic carbon contributions (POC, SOC, respectively) and on source apportionment by positive matrix factorization (PMF). An average TSP concentration of 69.6 ± 51.8 µg m−3 was found, exhibiting a pre-monsoon (March–May) maximum (92.9 ± 48.5 µg m−3) due to dust transport and forest fires and a monsoon (June–August) minimum due to atmospheric washout, while carbonaceous aerosols and inorganic species expressed a similar seasonality. The mean OC/EC ratio (8.0 ± 3.3) and the good correlations between OC, EC, and nss-K+ suggested that biomass burning (BB) was one of the major contributing factors to aerosols in Nainital. Using the EC tracer method, along with several approaches for the determination of the (OC/EC)pri ratio, the estimated SOC component accounted for ~25% (19.3–29.7%). Furthermore, TSP source apportionment via PMF allowed for a better understanding of the aerosol sources in the Central Himalayan region. The key aerosol sources over Nainital were BB (27%), secondary sulfate (20%), secondary nitrate (9%), mineral dust (34%), and long-range transported mixed marine aerosol (10%). The potential source contribution function (PSCF) and concentration weighted trajectory (CWT) analyses were also used to identify the probable regional source areas of resolved aerosol sources. The main source regions for aerosols in Nainital were the plains in northwest India and Pakistan, polluted cities like Delhi, the Thar Desert, and the Arabian Sea area. The outcomes of the present study are expected to elucidate the atmospheric chemistry, emission source origins, and transport pathways of aerosols over the central Himalayan region.

Variation Characteristics and Source Analysis of Carbonaceous Aerosols in Winter in Jiashan

Organic carbon (OC), elemental carbon (EC), and PM2.5 concentration data obtained from Shanxi Super Station in Jiashan County of Jiaxing City, in the winter of 2018 and 2019, were analyzed to determine the variation and potential source areas of carbonaceous aerosols. The results show that OC concentrations in the winter of 2018 and 2019 were 6.90 μg·m-3 and 5.63 μg·m-3, respectively, while EC concentrations were 2.47 μg·m-3 and 1.57 μg·m-3, respectively. The concentrations of OC and EC in the winter of 2019 were lower than those in the winter of 2018, by approximately 18.4% and 36.4%, respectively. In 2018 and 2019, the concentrations of secondary organic carbon (SOC), calculated using the minimum R-squared (MRS) method, were 1.49 μg·m-3 and 1.97 μg·m-3, respectively, and the concentrations of primary organic carbon (POC) were 5.41 μg·m-3 and 3.66 μg·m-3, respectively. The proportion of POC in OC showed a downward trend, from 96.0% in December 2018 to 64.9% in February 2020, indicating a decrease of 31.1 percentage points. SOC showed an upward trend, increasing by 31.1 percentage points from 4.0% in December 2018 to 35.1% in February 2020. It is worth noting that with the increase in PM2.5 concentration, the concentration of OC and EC increased by 474.7% and 408.2%, respectively, although the proportion of OC in PM2.5 decreased from 18.8% to 12.3%. and the percentage of OC decreased from 5.8% to 3.3%. The contribution of POC to PM2.5 did not fluctuate, and only decreased significantly above 150 μg·m-3, while the contribution of SOC to PM2.5 first decreased and then increased. In Jiaxing, the potential sources of OC and EC were mainly southern Jiangsu, southeastern Anhui, local Jiaxing, and northern Zhejiang. In the winter of the contribution concentrations of OC and EC in the main potential source regions were approximately 2 μg·m-3 and 6 μg·m-3 lower, respectively, than in winter 2018. The range of high values in the potential source regions also decreased in 2019. Before the COVID-19 epidemic, it was affected by both motor vehicle exhaust emissions and coal burning. During the Spring Festival and home isolation, due to traffic control and other reasons, motor vehicle emissions were reduced, which leaving coal burning as the main contributor.

Temporal trends of the concentration and sources of secondary organic aerosols in PM2.5 in Shanghai during 2012 and 2018

Based on the concentrations of the carbonaceous components and the typical organic tracers in 682 p.m.2.5 samples collected in Shanghai from 2012 to 2018, the temporal trends of the concentrations and potential sources of the secondary organic aerosols in PM2.5 in Shanghai were investigated. The annual average concentrations of organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) all showed a decreasing trend along with the PM2.5 concentration. The annual concentration of total carbon (TC) in 2018 (4.3 μg m−3) was about 34% of that in 2012. Compared with that in 2013, the concentrations of isoprene and sesquiterpene SOA tracers in 2018 decreased by 48% and 43%. Meanwhile, the concentration of monoterpene SOA tracers kept stable in 2 ng m−3 to 3 ng m−3, and the concentration of toluene SOA tracer decreased slightly from 1.3 ng m−3 in 2013 to 1.0 ng m−3 in 2018. Correlation analysis with levoglucosan suggested that biomass burning should be an important source of sesquitertene in Shanghai. It was found that the 2-MGA/2-MTLs ratio of the isoprene tracers was more strongly affected by the ambient temperature but not NOx in Shanghai. The concentration of secondary organic carbon (SOC) estimated with OC/EC-based, WSOC-based and tracer-based methods showed a decreasing trend during the study period, but the contribution of SOC to OC was increasing. Anthropogenic aromatic volatile organic compounds was the increasingly important contributor to the SOC in PM2.5, and should be the key pollutants to be controlled to further improve the air quality in Shanghai.

Regional sources and the economic cost assessment of PM2.5 in Ji'nan, eastern China

The problem of environmental pollution was troubling people in many cities in China, especially PM2.5 pollution. Aiming to a better understanding the influence of long-range transport sources and health effect of PM2.5 in Ji'nan, a field observation was carried out in from 23 December 2016 to 25 April 2017. The results showed that primary organic carbon (POC), secondary organic carbon (SOC) and element carbon (EC) during observation in Ji'nan were 5.45, 2.59 and 2.76 μg m−3, respectively. In heavy pollution days, OC and EC likely had similar primary emission and transmission sources. While the contribution of SOC increased in PM2.5 in clear days. Based on the potential source contribution function (PSCF) analysis, the emission sources leading to aggravation of PM2.5 pollution in Ji'nan were mainly distributed in the surrounding area of Ji'nan, especially in the eastern and southeastern Shandong. The risk assessment results show that the premature death caused by PM2.5 pollution could reach 666 people, and about 1.47% of total annual deaths in Ji'nan in 2016. The medical consumption related to PM2.5 pollution was about 202 millions USD, accounting for 2.05‰ of the GDP in Ji'nan in 2016. Lung-cancer mortality caused the highest economic cost of 47.97 millions USD, followed by respiratory mortality, chronic bronchitis, cardiovascular mortality, and acute bronchitis.

Understanding the origin of carbonaceous aerosols during periods of extensive biomass burning in northern India.

Post-harvest crop residue burning is extensively practiced in North India, which results in enhanced particulate matter (PM) concentrations. This study explores the PM2.5 (particulate matter with aerodynamic diameter≤2.5μm) emissions during various time periods (pre-monsoon, monsoon, and post-monsoon) over the biomass burning source region in Beas, Punjab. The PM2.5 concentrations during the pre-monsoon period (106-458μgm-3) and the post-monsoon period (184-342μgm-3) were similar but much higher than concentrations during the monsoon season (23-95μgm-3) due to enhanced wet deposition. However, the carbonaceous aerosol fraction in PM2.5 was nearly double in the post-monsoon season (∼27%) than the pre-monsoon period (∼15%). A higher contribution of secondary organic carbon (SOC) observed during the pre-monsoon season can be attributed to enhanced photochemical activity in dry conditions. Stable carbon isotope ratio (δ13C value) of ambient PM allowed elucidation of contributing sources. δ13CTC correlation with SOC during post-monsoon and pre-monsoon periods suggests significant influence of secondary formation processes during both time periods. The concentrations of carbon fractions in sampled sources and aerosols suggests contribution of biofuels, resulting in enhanced PM concentration at this location. δ13CTC values of pre- and post-monsoon samples show dominance of freshly emitted aerosols from local sources. Impact of biomass and biofuel combustion was also confirmed by biomass burning K+BB tracer, indicating that major agriculture residue burning occurred primarily during nighttime. C3 plant derived aerosols dominated at the sampling location during the entire sampling duration and contributed significantly during the pre-monsoon season. Whereas, both fossil fuel and C3 plant combustion contributed to the total mass of carbonaceous aerosols during the post-monsoon and monsoon seasons.

Characteristics of Carbonaceous Species in PM2.5 in Southern Beijing

To investigate the characteristics of carbonaceous species in PM2.5 in Beijing after the implementation of the Action Plan for the Prevention and Control of Air Pollution, PM2.5 was continuously sampled in the heavily polluted southern urban area of Beijing from December 2017 to December 2018. The characteristics of organic carbon (OC) and element carbon (EC) were then determined. The results showed that the annual concentrations of PM2.5, OC, and EC in Beijing varied in wide ranges of 4.2-366.3, 0.9-74.5, and 0.0-5.5 μg ·m-3, respectively, and the average mass concentration were (77.1±52.1), (11.2±7.8), and (1.2±0.8) μg ·m-3. Overall, the carbonaceous species (OC and EC) accounted for 16.1% of the PM2.5 mass. The seasonal characteristics of the OC mass concentrations were: winter [(13.8±8.7) μg ·m-3] > spring [(12.7±9.6) μg ·m-3] > autumn [(11.8±6.2) μg ·m-3] > summer [(6.5±2.1) μg ·m-3]. The concentration of the EC during the four seasons was low, ranging from 0.8 to 1.5 μg ·m-3. The annual average mass concentration and contribution of secondary organic carbon (SOC) were (5.4±5.8) μg ·m-3 and 48.2%, respectively, highlighting the significant contribution of the secondary process. With the aggravation of pollution, although the contribution proportion of OC and EC decreased, their mass concentrations during "heavily polluted" days were 6.3 and 3.2 times that of "excellent" days, respectively. Compare to non-heating period, the mass concentrations of PM2.5, OC, and SOC increased by 14.4%, 47.9%, and 72.1% in heating period, respectively, which emphasized the importance of carbonaceous species during heating periods. Potential source contribution function (PSCF) analysis showed that the southwest areas of Beijing (such as Shanxi and Henan province) were the main potential source areas of PM2.5 and OC. The high value area of the PSCF of EC was less and the main potential source area was in the south of Beijing (such as Shandong and Henan province).

Chemical characterization of wintertime aerosols over the Arabian Sea: Impact of marine sources and long-range transport

Abstract We examined here the compositional characteristics of total suspended particulate (TSP) samples collected along the east coast of the Arabian Sea during a winter cruise (SS379: 6–24 December 2018) to understand the extent of influence of air pollutants from terrestrial sources. The TSP samples (N = 17) were analyzed for water-soluble inorganic species (WSIS), elemental carbon (EC), organic carbon (OC) and water-soluble organic carbon (WSOC). Backward air mass trajectories and satellite-based fire counts revealed an influence of long-range transport of biomass burning emissions in the Indo-Gangetic Plain and southern India. Anthropogenic (82–97%) SO42− is the most abundant WSIS followed by Na+ and/or NH4+. Ambient EC loadings (0.5–2.4 μg m−3) and OC/EC ratios (2.5–10.5) are higher than usually expected for fossil-fuel combustion sources. Low mass ratios of NO3−/non-sea-salt SO42− (0.08–0.49), as well as high ratios of nss-K+/EC (0.14–1.18) and WSOC/OC (0.30–0.74), highlight the significance of coal combustion and biomass burning emissions in the regional influx of air pollutants to the Arabian Sea. The multiple linear regression analysis has indicated strong correlations among sea salt components (Na+, Cl− and Mg2+), carbonaceous components (OC, EC and WSOC), and anthropogenic WSIS (NH4+ and SO42−). Furthermore, we used minimum R-squared technique based primary OC/EC ratio in the EC-tracer method to estimate the contribution of secondary organic carbon (SOC) to OC (7–61%) and TSP mass (0.7–11%). Overall, the composition of TSP is characterized by 21 ± 10% of particulate organic matter, 2.3 ± 1.1% of EC, 21 ± 9% of anthropogenic WSIS and 43 ± 15% of unidentified fraction including dust. This study has implications for understanding the evolving nature of secondary inorganic and organic aerosols in the continental outflows.

Ambient air quality in the Kathmandu Valley, Nepal, during the pre-monsoon: concentrations and sources of particulate matter and trace gases

Abstract. The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM2.5 and PM10, respectively), online PM1, inorganic trace gases (NH3, HNO3, SO2, and HCl), and carbon-containing gases (CO2, CO, CH4, and 93 non-methane volatile organic compounds; NMVOCs) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated origins primarily from poorly maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those 2 weeks, daily average PM2.5 concentrations ranged from 30 to 207 µg m−3, which exceeded the World Health Organization 24 h guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas–aerosol phase partitioning of NH3, HNO3, and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (averaging 1230±1154 ng m−3), 1,3,5-triphenylbenzene (0.8±0.6 ng m−3), cholesterol (2.9±6.6 ng m−3), stigmastanol (1.0 ±0.8 ng m−3), and cis-pinonic acid (4.5±1.9 ng m−3) indicate contributions from biomass burning, garbage burning, food cooking, cow dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18±5 %), biomass burning (17±10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18±9 %). Model sensitivity tests with newly developed source profiles indicated contributions from biomass burning within a factor of 2 of previous estimates but greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM2.5 OC included those originating from anthropogenic precursors such as naphthalene (10±4 %) and methylnaphthalene (0.3±0.1 %) and biogenic precursors for monoterpenes (0.13±0.07 %) and sesquiterpenes (5±2 %). An average of 25 % of the PM2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) and/or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil fuel combustion) were the greatest contributors to PM2.5 and, as such, should be considered primary targets for controlling ambient PM pollution.

Comparison of fine particulate matter level, chemical content and oxidative potential derived from two dissimilar urban environments

Urban airborne particles contain a wide spectrum of components, known to have harmful effects on human health. This study reports a detailed investigation of fine particulate matter (PM2.5), chemical content and oxidative potential derived from two different urban environments. During summer and winter, 20-day campaigns were conducted at Belgrade city center (urban-background site – UB) and Bor (urban-industrial site – UI). Using various analytical techniques, carbonaceous compounds, water-soluble inorganic ions, major and trace elements were determined, while the oxidative potential of PM2.5 was estimated by dichloro-dihydro-fluorescein diacetate (DCFH-DA) assay (OPDCFH values).The mean PM2.5 concentrations in both urban environments were above the recommended daily value, and the dominant PM2.5 mass contributor was organic matter (29–55%). The OC/EC ratio was significantly higher at UB site during winter, which was an indication of a considerable contribution of secondary organic carbon to the overall organic carbon (OC). Water-soluble organic carbon (WSOC) was also higher at UB than at UI site, and it probably came from the same sources as OC. In general, the different partition of secondary organic aerosol (SOA) in warm and cold periods affected the number of organic components. Sulfates and nitrates were the most abundant ions at both sites and they counted approximately 40% (summer) and 50% (winter) of total ions. Further, the concentrations of the most elements, particularly some potentially carcinogenic elements such as As, Cd and Pb were significantly higher at UI, due to the emissions from the copper smelter complex in the vicinity. The mean OPDCFH values were similar during the summer at both sampling sites, whereas a statistically significant difference between sites was noticed in favor of UB environment in winter.

Molecular characteristics and diurnal variations of organic aerosols at a rural site in the North China Plain with implications for the influence of regional biomass burning

Abstract. Field burning of crop residue in early summer releases a large amount of pollutants into the atmosphere with significant impacts on the air quality and aerosol properties in the North China Plain (NCP). In order to investigate the influence of this regional anthropogenic activity on molecular characteristics of organic aerosols, PM2.5 filter samples were collected with a 3 h interval at a rural site of NCP from 10 to 25 June 2013 and analyzed for more than 100 organic tracer compounds, including both primary (n-alkanes, fatty acids/alcohols, sugar compounds, polycyclic aromatic hydrocarbons, hopanes, and phthalate esters) and secondary organic aerosol (SOA) tracers (phthalic acids, isoprene-, α-/β-pinene, β-caryophyllene, and toluene-derived products), as well as organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC). Total concentrations of the measured organics ranged from 177 to 6248 ng m−3 (mean 1806±1308 ng m−3) during the study period, most of which were contributed by sugar compounds, followed by fatty acids and fatty alcohols. Levoglucosan (240±288 ng m−3) was the most abundant single compound and strongly correlated with OC and WSOC, suggesting that biomass burning (BB) is an important source of summertime organic aerosols in this rural region. Based on the analysis of fire spots and backward trajectories of air masses, two representative periods were classified, which are (1) Period 1 (P1), 13 June 21:00–16 June at 15:00 CST (China Standard Time), when air masses were uniformly distributed from the southeast part of NCP, where intensive open-field biomass burning occurred; and (2) Period 2 (P2), 22 June at 12:00 to 24 June at 06:00 CST, which is representative of local emission. Nearly all the measured PM components showed much higher concentrations in P1 than in P2. Although n-alkanes, fatty acids, and fatty alcohols presented similar temporal–diurnal variations as those of levoglucosan throughout the entire period, their molecular distributions were more dominated by high molecular weight (HMW) compounds in P1, demonstrating an enhanced contribution from BB emissions. In contrast, intensive BB emission in P1 seems to have limited influence on the concentrations of polycyclic aromatic hydrocarbons (PAHs), hopanes, and phthalate esters. Both 3-hydroxyglutaric acid and β-caryophyllinic acid showed strong linearly correlations with levoglucosan (R2=0.72 and 0.80, respectively), indicating that BB is also an important source for terpene-derived SOA formation. A tracer-based method was used to estimate the distributions of biomass-burning OC, fungal-spore OC, and secondary organic carbon (SOC) derived from isoprene, α-/β-pinene, β-caryophyllene, and toluene in the different periods. The results showed that the contribution of biomass-burning OC to total OC in P1 (27.6 %) was 1.7 times that in P2 (17.1 %). However, the contribution of SOC from oxidation of the four kinds of volatile organic compounds (VOCs) increased slightly from 16.3 % in P1 to 21.1 % in P2.

Characteristics and sources of organic carbon in coastal and marine atmospheric particulates over East China

To understand the influences of emission sources, transport and environmental factors on the characteristics of organic carbonaceous aerosols in the marine area, organic carbon (OC) and water-soluble organic carbon (WSOC) were measured in atmospheric samples collected from the coastal region and over the Bohai and Yellow Seas from 2015 to 2016. Compared with the averages of 19.28 and 10.61 μg·m−3 in the coastal samples, the average concentrations of OC and WSOC decreased to 2.17 and 1.54 μg·m−3 in the marine aerosol samples, respectively. WSOC contributed 60% to OC in Qingdao, while 68.4% to OC over the ocean, suggesting that WSOC is likely influenced by the dissolved organic carbon (DOC) in surface seawater. The highest OC/EC ratios (6.56) were observed in the samples collected from the air masses originating from the north land source, indicating that OC mainly comes from anthropogenic sources. The OC concentrations in the air mass samples from marine sources were only 50% of those in the samples from terrestrial sources. A negative correlation between the WSOC and transport distance over the sea and decreased OC/EC ratios were observed, which indicated that the contribution of secondary organic carbon (SOC) to OC decreased during the transport from land to sea. OC increased by 88.5% under the influence of Asian dust, while WSOC did not exhibit substantial changes. The positive matrix factorization (PMF) model showed that anthropogenic sources were the major source of carbonaceous aerosols, contributing 70% of the OC in Qingdao. The positive correlation between OC and particulate matter (PM) suggested that the OC affected the air quality.

Seasonal variation of chemical characteristics of fine particulate matter at a high-elevation subtropical forest in East Asia

The aim of this study was to chemically characterize the fine particulate matter (PM2.5) at a subtropical forest in East Asia under the influences of anthropogenic and biogenic sources and a complex topographic setting. Four seasonal campaigns were conducted at the Xitou Experimental Forest in central Taiwan from the winter of 2013 to the autumn of 2014. The results indicated that the ambient levels and chemical features of PM2.5 exhibited pronounced seasonal variations. Non-sea-salt sulfate (nss-SO42-) constituted the major component of PM2.5, followed by ammonium (NH4+) and nitrate (NO3−) during winter, summer and autumn. However, it was revealed that the mass fraction of NO3− increased to be comparable with that of nss-SO42- in springtime. The mass contribution of secondary organic carbon (SOC) to PM2.5 peaked in summer (13.2%), inferring the importance of enhanced photo-oxidation reactions in SOC formation. Diurnal variations of O3 and SO2 coincided with each other, suggesting the transport of aged pollutants from distant sources, whereas CO and NOx were shown to be under the influences of both local and regional sources. Notably high sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) were observed, which were 0.93 ± 0.05 and 0.39 ± 0.20, respectively. Precursor gases (i.e. SO2 and NOx) could be converted to sulfate and nitrate during the transport by the uphill winds. Furthermore, due to the high relative humidity at Xitou, enhanced aqueous-phase and/or heterogeneous reactions could further contribute to the formation of sulfate and nitrate at the site. This study demonstrated the significant transport of urban pollutants to a subtropical forest by the mountain-valley circulations as well as the long-range transport from regional sources, whereas the implications of which for regional climate change necessitated further investigation.

Comparison of Measurement-Based Methodologies to Apportion Secondary Organic Carbon (SOC) in PM2.5: A Review of Recent Studies

Secondary organic aerosol (SOA) is known to account for a major fraction of airborne particulate matter, with significant impacts on air quality and climate at the global scale. Despite the substantial amount of research studies achieved during these last decades, the source apportionment of the SOA fraction remains difficult due to the complexity of the physicochemical processes involved. The selection and use of appropriate approaches are a major challenge for the atmospheric science community. Several methodologies are nowadays available to perform quantitative and/or predictive assessments of the SOA amount and composition. This review summarizes the current knowledge on the most commonly used approaches to evaluate secondary organic carbon (SOC) contents: elemental carbon (EC) tracer method, chemical mass balance (CMB), SOA tracer method, radiocarbon (14C) measurement and positive matrix factorization (PMF). The principles, limitations, challenges and good practices of each of these methodologies are discussed in the present article. Based on a comprehensive—although not exhaustive—review of research papers published during the last decade (2006–2016), SOC estimates obtained using these methodologies are also summarized for different regions across the world. Conclusions of some studies which are directly comparing the performances of different methodologies are then specifically discussed. An overall picture of SOC contributions and concentrations obtained worldwide for urban sites under similar conditions (i.e., geographical and seasonal ones) is also proposed here. Finally, further needs to improve SOC apportionment methodologies are also identified and discussed.