Water-soluble Organic Carbon Fraction Research Articles

Water-soluble organic aerosols over South Asia – Seasonal changes and source characteristics

Water-soluble organic carbon (WSOC) has been identified as a key component in atmospheric aerosols due to its ability to act as cloud condensation nuclei (CCN) owing to their highly hygroscopic nature. This paper discusses about the spatio-temporal variability in WSOC mass concentration, sources (primary and secondary contributions), the role of long-range air-mass transport in modulating their abundance, at distinct sectors over South Asia. We found from our observations that, photochemical ageing of primary organic aerosols that are derived from biomass emissions, significantly contribute to the total WSOC budget over South Asia. The wide range of water-soluble compounds released by biomass burning can contribute directly to the WSOC fraction or undergo further atmospheric processing, such as oxidation or ageing, leading to the formation of additional WSOC. WSOC/OC (organic carbon) ratio and the correlation between the WSOC and secondary organic carbon (SOC) are used for assessing the contribution from secondary sources. The three different ratios are used to delineate different source processes; OC/EC (elemental carbon) for source identification, WSOC/OC for long-range atmospheric transport (ageing) and WSOC/SOC to understand the primary and secondary contribution of WSOC. The present investigation revealed that, the primary OC that have undergone significant chemical processing as a result of long-range transport have a substantial influence on WSOC formation over South Asia, especially in Indo Gangetic Plain outflow regions such as southern peninsular and adjacent marine regions. Overall, oxidation and ageing of primary organic aerosols emitted from biomass burning was found to serve as an important source of WSOC over South Asia.

Field evidence for enhanced generation of reactive oxygen species in atmospheric aerosol containing quinoline components

Organic constituents of atmospheric particular matter (PM) contribute significantly to prompt generation of reactive oxygen species (ROS) in particle phase, which is often quantified in terms of its oxidative potential (OP). In this study, we used complementary methods of the advanced molecular characterization and the OP quantitation to explore potential of different organic species to enhance ROS generation in ambient aerosol samples. We used seven PM2.5 samples collected in the Midwest US, and extracted them sequentially into a set of solvents with different polarity: first non-polar hexane (HEX), then moderately polar dichloromethane (DCM) and finally polar deionized (DI) water. The DI extracts were further separated using solid phase extraction to isolate water-soluble organic carbon (WSOC) from inorganic ions. The OP of obtained extracts was analyzed using dithiothreitol (DTT) assay and reported here in terms of the DTT consumption rate (called DTT activity). The molecular composition of the same extracts was analyzed using a tandem platform of high-performance liquid chromatography (HPLC) coupled with a photodiode array detector (PDA) and a high-resolution mass spectrometer (HRMS). Highest DTT activities were observed in WSOC fractions (>1.1 μM min−1) followed by DCM (0.75–1.1 μM min−1) and HEX (<0.75 μM min−1) fractions, respectively. These results were complemented by the HPLC-PDA-HRMS molecular characterization data indicating numerous redox-active polar organics detected in the WSOC fractions. In particular, chemical component with elemental formula of C11H11N - attributed to dimethyl quinoline (DMQ) - was found systematically across all DTT-active fractions. The unprotonated nitrogen atom in the pyridine ring of quinolines facilitates electron transfer in the redox reactions, catalyzing generation of ROS in the quinoline containing samples. This is the first study that unambiguously identifies quinoline as a promoter of ROS generation determined within complex mixtures of ambient organic aerosols.

1H NMR structural signatures of source and atmospheric organic aerosols in India.

Organic aerosols (OA) play significant roles in several atmospheric processes and adversely impact human health. This study examines the key structural units present in water- and methanol-soluble organic carbon (WSOC, MSOC) fraction of OA from emission sources (traffic and biomass cooking) and an urban background location in India. Proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to assess the distribution of non-exchangeable proton structural groups of the OAs. Organic carbon, elemental carbon, black carbon, and water-soluble organic carbon (WSOC) analyses were also conducted. The 1H NMR analysis corroborated that the WSOC and MSOC fractions hold similar 1H structural groups; however, they differ in their relative distribution and absolute concentrations across the ambient locations and source emissions. The relative contribution of the proton structural groups to OA was in the order C-H>H-C-C=> H-C-O>Ar-H. The aliphatic concentration was lower in the morning tunnel entry aerosols when compared to other tunnel aerosols, whereas the unsaturated structures (H-C-C=) were present in all the tunnel aerosols within a range of 47.2-62.3μmol/m3. The aromatic groups were the maximum in the firewood aerosols, about 1.4 and 3.7 times higher than the crop residue and the mixed fuel aerosols, respectively. The total functional groups, i.e., the sum of all the observed groups, significantly correlated with C-H (r=0.96) and WSOC (r=0.7), suggesting the higher contribution of aliphatic groups in the WSOC fraction. WSOC examined in this study fits well in the established 1H NMR source identification fingerprints of urban aerosols. However, biomass cooking aerosols do not fit the established biomass burning organic aerosols (BBOAs) boundaries, exhibiting a smaller relative contribution of carbon-oxygen double bonds and a less oxidised character than open-field burning. Our results provide essential insights into the nature of urban atmospheric, near-traffic and biomass cooking OAs in India.

Chemical Composition, Optical Properties and Sources of PM2.5 From a Highly Urbanized Region in Northeastern Mexico

Here, we report the chemical composition and optical properties of the fine particles (PM2.5) and water-soluble organic carbon (WSOC) of these particles. Additionally, the potential sources of WSOC emission were determined through the study on fluorescence excitation–emission matrix spectra and parallel factor analysis (EEM-PARAFAC). Samples were collected in an urban site of the Monterrey Metropolitan Area in Mexico during summer and winter and characterized using attenuated total reflectance-Fourier-transform infrared spectroscopy (ATR-FTIR), ultraviolet-visible-near infrared-diffuse reflectance spectroscopy (UV–Vis-NIR-DRS), fluorescence spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) techniques. The ATR-FTIR analyses allowed the identification of inorganic ions (e.g., CO32−, SO42−, and NO3−), organic functional groups [e.g., carbonyls (C=O), organic hydroxyl (C-OH), carboxylic acid (COOH)], and aromatic and unsaturated aliphatic hydrocarbons. The results obtained by XRD and XPS revealed the presence of organic and inorganic chemical species in PM2.5. The diffuse reflectance spectra of PM2.5 provided the absorption bands in the UV region for CaSO4, CaCO3, and aluminosilicates. The absorption coefficient at 365 nm (Abs365) and Ångström absorption exponent (AAE) values obtained for the aqueous extracts suggest that many of the water-soluble organic compounds corresponded to brown carbon (BrC) chromophores. The mass absorption efficiency values at 365 nm (MAE365) were higher in the winter than summer samples, suggesting the presence of more BrC compounds in the winter samples. The fluorescence indices combined with EEM-PARAFAC analysis showed that the WSOC fraction was mainly composed of humic-like substances (HULIS) which are both of terrestrial and microbial origin.

Organic Molecular Tracers in PM2.5 at Urban Sites during Spring and Summer in Japan: Impact of Secondary Organic Aerosols on Water-Soluble Organic Carbon

To understand the characteristics of secondary organic aerosols (SOAs) and estimate their impact on water-soluble organic carbon (WSOC) in urban areas in Japan, we measured 17 organic tracers using gas chromatography–mass spectrometry from particulate matter with an aerodynamic diameter smaller than 2.5 μm collected at five urban sites in Japan during spring and summer. Most anthropogenic, monoterpene-derived, and isoprene-derived SOA tracers showed meaningful correlations with potential ozone in both these seasons. These results indicate that oxidants play an important role in SOAs produced during both seasons in urban cities in Japan. WSOC was significantly affected by anthropogenic and monoterpene-derived SOAs during spring and three SOA groups during summer at most of the sites sampled. The total estimated secondary organic carbons (SOCs), including mono-aromatic, di-aromatic, monoterpene-derived, and isoprene-derived SOCs, could explain the WSOC fractions of 39–63% in spring and 46–54% in summer at each site. Notably, monoterpene-derived and mono-aromatic SOCs accounted for most of the total estimated SOCs in both spring (85–93%) and summer (75–82%) at each site. These results indicate that SOAs significantly impact WSOC concentrations during both these seasons at urban sites in Japan.

Characterization of Seasonal Difference of HULIS-C Sources from Water Soluble PM2.5 in Seoul, Korea: Probing Secondary Processes

HUmic-LIke Substances (HULIS) consists of a significant fraction of water-soluble organic carbon (WSOC) and optically active brown carbon. Understanding seasonality in their abundance and sources is an important step to quantifying their impacts on air quality and climate. In this study, we characterized the seasonal variation of HULIS-C (the carbon component of HULIS) and identified primary and secondary sources contributing to HULIS-C at an urban site in Seoul, Korea by analyzing 131 PM2.5 samples collected over a year from October 2012 to September 2013. The HULIS-C in Seoul had an annual average of 2.0 µg m–3, and displayed a seasonality of highest abundance in the winter (2.7 ± 1.3 µg m–3) and the lowest in the summer (1.7 ± 0.8 µg m–3). Its fraction in WSOC reached up to 0.96 in the summer while remained relatively constant in the range of 0.4–0.6 in other seasons. Sources of HULIS-C were resolved using Positive Matrix Factorization (PMF) and checked using inter-species relationships between HILIS-C and aerosol components. Specifically, secondary processes including aging and heterogeneous reaction (26%) contributes to the year-round background concentration of HULIS-C and fresh biomass burning (38%) and incomplete combustion (16%) were the major sources of underlying seasonal variation. We also found aging process in the secondary process had an important role in HULIS-C formation and was a dominant contributor in the summer while heterogenous reaction contributed considerably in other seasons. It implies that the different secondary processes in forming HULIS should be considered when the radiative forcing of brown carbon is estimated. Because these processes can lead the different physicochemical properties of HULIS in aerosols.

Time-resolved characterization of organic compounds in PM2.5 collected at Oki Island, Japan, affected by transboundary pollution of biomass and non-biomass burning from Northeast China

To evaluate the transboundary pollution of organic aerosols from Northeast Asia, a highly time-resolved measurement of organic compounds was performed in March 2019 at Oki Island located in Japan, which is a remote site and less affected by local anthropogenic sources. PM2.5, water-soluble organic carbon (WSOC) concentrations, and WSOC fraction in PM2.5 showed high values on March 22–23 (high-WSOC period (HWSOC)) when the air mass passed through the area where many fire spots were detected in Northeast China. Biomass burning tracers showed higher concentration, especially levoglucosan exceeded 1 μg/m3 during the HWSOC than the low-WSOC period (LWSOC). Notably, high time-resolved measurements of biomass burning tracers and back trajectory analysis during HWSOC revealed a difference in the variation of lignin pyrolyzed compounds and anhydrous sugars on 22 and 23 March. The air mass passed to different areas in Northeast China in which fire spots were detected, such as the eastern area on the 22nd and the western area on the 23rd. Almost-organic compounds also showed high concentration and strong correlations with levoglucosan and sulfate during HWSOC. Moreover, low-carbon dicarboxylic acids (e.g., adipic acid) and secondary products from anthropogenic volatile organic compounds (e.g., 2,3-dihydroxy-4-oxopentanoic, phthalic, 5-nitrosalicylic acids), also showed a strong correlation with sulfate ions during the HWSOC and LWSOC, respectively. These higher concentrations and strong correlations with levoglucosan and sulfate during the HWSOC propose that their generation could be enhanced by biomass burning. The ratios of organics (e.g., levoglucosan/mannnosan, pinic/3-methylbutane-1,2,3-tricarboxylic acids) suggest that the high concentrations of PM2.5 and WSOC observed during the HWSOC were caused by aged organic aerosols that originated from the combustion of herbaceous plants transported from Northeast China. Our findings indicate that biomass combustion in Northeast China could significantly affect the chemical compositions and the characterization of organic aerosols in downwind regions of Northeast China.

Inflammation Response of Water-Soluble Fractions in Atmospheric Fine Particulates: A Seasonal Observation in 10 Large Chinese Cities.

Spatiotemporal trends in pro-inflammatory (interleukin (IL)-6 and IL-8) release after exposure to the water-soluble fractions of PM2.5 sampled in 10 large Chinese cities over 1 year were investigated. Chemical components (water-soluble ions, metal(loid) elements, water-soluble organic carbon (WSOC), humic-like substances (HULIS), and endotoxins) in PM2.5 samples were measured, and the molecular structure of WSOC was also analyzed by nuclear magnetic resonance. Changes in DNA methylation and gene expression of candidate genes were also evaluated to explore the potential mechanisms. PM2.5 from southern cities induced lower pro-inflammatory responses compared to those from northern cities. Seasonal differences in toxicity were noted among the cities. IL-6 was significantly correlated with HULIS (as the main fraction of WSOC with oxygenated carbohydrate structures characteristic), Pb, and endotoxin. Furthermore, DNA methylation and gene expression changes in RASSF2 and CYP1B1 were related to pro-inflammatory secretion. Certain components of PM2.5, rather than PM2.5 mass itself, determine the pro-inflammatory release. In particular, HULIS, which originated from primary biomass burning and residual coal combustion, and secondary organic aerosols, appear to be the key component in PM2.5 to induce human health risk.

Abundance and Light Absorption Properties of Brown Carbon Emitted from Residential Coal Combustion in China.

Brown carbon (BrC) fractions, including water-soluble organic carbon (WSOC), water-soluble humic-like substances (HULISw), alkaline soluble organic carbon (ASOC), and methanol soluble organic carbon (MSOC) were extracted from particles emitted from the residential combustion of coal with different geological maturities. The abundances and light absorption properties of these BrC fractions were comprehensively studied. The results showed that the abundances of the different constituents of the BrC fraction varied greatly with the extraction solvent, accounting for 4.3%-46%, 2.3%-23%, 3.2%-14%, and 76%-98% of the total carbon content in particles. The specific UV-vis absorbance (SUVA254) of BrC fractions followed the order of MSOC > ASOC > HULISw > WSOC. The WSOC and MSOC fractions from the combustion of low maturity coal had relatively low SUVA254 and high SR values. The mass absorption efficiencies (MAE365) for ASOC and MSOC were higher than for WSOC, and WSOC and MSOC from low maturity coal combustion had relatively low levels of light absorption. These findings indicated that coal combustion is a potential source of atmospheric BrC and the abundance and light absorption of the coal combustion-derived BrC fractions were strongly dependent on the extraction methods used and the coal maturity rather than the coal shapes.

Water uptake by fresh Indonesian peat burning particles is limited by water-soluble organic matter

Abstract. The relationship between hygroscopic properties and chemical characteristics of Indonesian biomass burning (BB) particles, which are dominantly generated from peatland fires, was investigated using a humidified tandem differential mobility analyzer. In addition to peat, acacia (a popular species at plantation) and fern (a pioneering species after disturbance by fire) were used for experiments. Fresh Indonesian peat burning particles are almost non-hygroscopic (mean hygroscopicity parameter, κ &lt; 0.06) due to predominant contribution of water-insoluble organics. The range of κ spans from 0.02 to 0.04 (dry diameter = 100 nm, hereinafter) for Riau peat burning particles, while that for Central Kalimantan ranges from 0.05 to 0.06. Fern combustion particles are more hygroscopic (κ = 0. 08), whereas the acacia burning particles have a mediate κ value (0.04). These results suggest that κ is significantly dependent on biomass types. This variance in κ is partially determined by fractions of water-soluble organic carbon (WSOC), as demonstrated by a correlation analysis (R = 0.65). κ of water-soluble organic matter is also quantified, incorporating the 1-octanol–water partitioning method. κ values for the water extracts are high, especially for peat burning particles (A0 (a whole part of the water-soluble fraction): κ = 0.18, A1 (highly water-soluble fraction): κ = 0.30). This result stresses the importance of both the WSOC fraction and κ of the water-soluble fraction in determining the hygroscopicity of organic aerosol particles. Values of κ correlate positively (R = 0.89) with the fraction of m∕z 44 ion signal quantified using a mass spectrometric technique, demonstrating the importance of highly oxygenated organic compounds to the water uptake by Indonesian BB particles. These results provide an experimentally validated reference for hygroscopicity of organics-dominated particles, thus contributing to more accurate estimation of environmental and climatic impacts driven by Indonesian BB particles on both regional and global scales.

Summertime Day-Night Differences of PM2.5 Components (Inorganic Ions, OC, EC, WSOC, WSON, HULIS, and PAHs) in Changzhou, China

This work reports the day-night differences of a suite of chemical species including elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), water-soluble organic nitrogen (WSON), selected polycyclic aromatic hydrocarbons (PAHs), and secondary inorganic ions (NO3−, SO42−, NH4+) in ambient fine particles (PM2.5) collected from 23 July to 23 August 2016 in Changzhou, China. Mass concentrations of PM2.5 and SO42− show a 10–20% increase during daytime, while NO3− concentration decreases by a factor of three from nighttime to daytime due to its semi-volatile nature. PAHs, EC, and WSON show higher mass concentration in the night too. Mass ratios of WSOC to OC are high in both day and night, indicating that secondary organic aerosol (SOA) formation could occur throughout the day, while the slightly higher ratio during daytime suggests a more significant contribution from daytime photochemical oxidation. Strong positive correlations between HULIS-C and WSOC, and HULIS-C with O3 both in day and night, imply that HULIS-C, similar to WSOC, is mainly composed of secondary species. HULIS-C accounted for a large fraction of WSOC, with an average of ~60%. Moreover, the average WSON concentrations are 1.08 and 1.46 µg/m3, constituting ~16% and ~18% of water-soluble total nitrogen in day and night, respectively. Correlation analyses suggest that WSON is also predominantly produced from secondary processes. PAHs concentrations are found to be very low in summer aerosols. Overall, our findings highlight the dominant contribution of secondary processes to the major aerosol components in Changzhou, suggesting proper measures to effectively reduce gaseous precursors are also important to improve air quality.

Contribution of Biomass Burning to Carbonaceous Aerosols in Mexico City during May 2013

ABSTRACTDuring the springtime fire season, wildfires and agricultural burning represent a potentially large contribution to air quality degradation in the Mexico City Metropolitan Area (MCMA). PM10 filter samples were collected at six different stations in May 2013, the month with the maximum reported regional fire counts from 2002 to 2013. Two regimes were identified considering changes in predominant wind direction and precipitation patterns inside MCMA. The filter samples were analyzed for water-soluble organic carbon (WSOC) and the biomass burning tracers including levoglucosan (LEV) and water-soluble potassium (WSK+). LEV concentrations correlated positively with ambient concentrations of PM2.5 and PM10 (R2 = 0.61 and R2 = 0.46, respectively). Strong correlations were also found between WSOC and LEV (R2 = 0.94) and between WSK+ and LEV (R2 = 0.75). PM2.5 accounted for 60% of the PM10 mass concentrations. Our speciated measurements accounted for 37% of the total PM10 mass concentration and ~60% of the PM2.5 mass concentrations; the missing mass was attributed to crustal material (soil or dust) and carbonaceous aerosols that were not segregated into the WSOC fraction. Average LEV/WSOC ratios ranged from 0.015 in the first, smokier and drier part of the month, to 0.006 during the rainier end of the measurement period. Using previously reported LEV/WSOC emissions ratios, the estimated biomass burning contributions to WSOC ranged from 7–23% assuming LEV is stable in the atmosphere, and 8–57% when accounting for LEV photochemical degradation in the atmosphere. Thus, our findings indicate that primary emissions from biomass burning sources represent significant contributions to ambient WSOC and PM in MCMA during the springtime fire season.

Source identification of water-soluble organic aerosols at a roadway site using a positive matrix factorization analysis

Daily PM2.5 measurements were carried out at a local roadway every sixth day from May 2011 to August 2013 to obtain seasonal quantitative information on the primary and secondary sources of two water-soluble organic carbon (WSOC) fractions. Filter samples were analyzed for OC, elemental carbon (EC), WSOC, hydrophilic and hydrophobic WSOC fractions (WSOCHPI and WSOCHPO), and ionic species. An XAD solid phase extraction method and a total organic carbon analyzer were used to isolate the two WSOC fractions and determine their amounts, respectively.The WSOC/OC and WSOCHPI/WSOC ratios were 0.62±0.13 and 0.47±0.14, respectively. Similar seasonal profiles in EC, OC, and WSOC concentrations were observed, with higher concentrations occurring in the cold season and lower concentrations in the warm season. However, opposite results were obtained in WSOC/OC and WSOCHPI/WSOC ratios, with the higher in the warm season and the lower in the cold season. Correlation analyses indicated that two WSOC fractions in winter were likely attributed to secondary formation processes, biomass burning (BB), and traffic emissions, while WSOCHPI observed in other seasons were associated with secondary formation processes similar to those of oxalate and secondary inorganic species.A positive matrix factorization (PMF) model was employed to investigate the sources of two WSOC fractions. PMF indicated that concentrations of WSOC fractions were affected by five sources: secondary NO3− related, secondary SO42− and oxalate related, traffic emissions, BB emissions, and sea-salt. Throughout the study period, secondary organic aerosols were estimated to be the most dominant contributor of WSOC fractions, with higher contributions occurring in the warm seasons. The contribution of secondary aerosol formation processes (NO3− related+SO42− and oxalate related) to WSOCHPI and WSOCHPO was on an average 56.2% (45.0–73.8%) and 47.7% (39.6–52.1%), respectively. The seasonal average contribution of WSOCHPI and WSOCHPO attributed to BB was 19.0% (14.3–25.3%) and 14.8% (7.2–19.5%), respectively, with higher fractions occurring in the fall and winter. Traffic sources contributed to WSOCHPI and WSOCHPO from 4.2 to 21.0% (an average of 11.6%) and from 7.9 to 32.3% (an average of 19.9%), respectively, with higher fractions in the fall and winter compared with the other seasons. During the study period, for an episode associated with high local O3 level (~110ppbv) and high WSOCHPI/WSOC (0.80), secondary formation processes contributed 67.1% to WSOCHPI, and 72.6% to WSOCHPO, respectively. However, for an episode associated with local and severe regional haze pollutions, contributions of secondary formation processes to WSOC fractions were observed to be low (32.4–43.1%), while traffic and BB emissions contributed 16.8% and 24.3% to WSOCHPI, respectively, and 18.3% and 18.7% to WSOCHPO, respectively. The PMF results suggest that the contribution of traffic emissions to concentrations of two WSOC fractions cannot be neglected at the studied roadway site.

Sources of humic-like substances in the Pearl River Delta, China: positive matrix factorization analysis of PM&amp;lt;sup&amp;gt;2.5&amp;lt;/sup&amp;gt; major components and source markers

Abstract. Humic-like substances (HULIS), the hydrophobic part of water-soluble organic carbon (WSOC), account for a significant fraction of PM2.5 mass. Their source studies are so far largely qualitative. In this study, HULIS and WSOC were determined in 100 PM2.5 samples collected in 2009 at an urban site (Guangzhou) and a suburban site (Nansha) in the Pearl River Delta in South China. The annual average concentration of HULIS was 4.83 and 4.71 μg m−3, constituting 8.5 and 10.2% of the PM2.5 mass, while HULIS-C (the carbon component of HULIS) contributed 48 and 57% of WSOC at the two sites, respectively. HULIS were found to correlate with biomass burning (BB) tracers (i.e., levoglucosan and K) and secondary species (e.g., SO42− and NH4+), suggesting its association with BB emissions and secondary formation processes. Sources of HULIS were investigated using positive matrix factorization analysis of PM2.5 chemical composition data, including major components and source markers. In addition to secondary formation process and BB emissions, residual oil combustion related to shipping was identified for the first time as a significant source of HULIS. Secondary formation process contributed the most, accounting for 49–82% of ambient HULIS at the two sites in different seasons. BB emissions contributed a seasonal average of 8–28%, with more contributions observed in the winter months (November–February) due to crop residue burning during harvest season. Residual oil combustion was revealed to be an important source at the suburban site in summer (44% of HULIS-C) due to its proximity to one of the ports and the shipping lane in the region. Vehicle emissions were found to contribute little to HULIS, but had contributions to the hydrophilic WSOC fraction. The contrast in contributions from different combustion sources to HULIS and hydrophilic WSOC suggests that primary sources of HULIS are linked to inefficient combustion. This source analysis suggests further study of HULIS be focused on secondary formation process and source characteristics of HULIS from BB and residual oil combustion.

Characteristics of nanoparticles emitted from burning of biomass fuels

The characteristics of the particles of the smoke that is emitted from the burning of biomass fuels were experimentally investigated using a laboratory-scale tube furnace and different types of biomass fuels: rubber wood, whole wood pellets and rice husks. Emitted amounts of particles, particle-bound polycyclic aromatic hydrocarbons (PAHs) and water-soluble organic carbon (WSOC) are discussed relative to the size of the emitted particles, ranging to as small as nano-size (<70nm), and to the rate of heating rate during combustion. differential thermal analysis (DTA) and thermogravimetric analysis (TG) techniques were used to examine the effect of heating rate and biomass type on combustion behaviors relative to the characteristics of particle emissions. In the present study, more than 30% of the smoke particles from the burning of biomass fuel had a mass that fell within a range of <100nm. Particles smaller than 0.43μm contributed greatly to the total levels of toxic PAHs and WSOC. The properties of these particles were influenced by the fuel component, the combustion conditions, and the particle size. Although TG–DTA results indicated that the heating rate in a range of 10–20°C did not show a significant effect on the combustion properties, there was a slight increase in the decomposition temperature as heating rate was increased. The nano-size particles had the smallest fraction of particle mass and particle-bound PAHs, but nonetheless these particles registered the largest fraction of particle-bound WSOC.

Possible sources of two size-resolved water-soluble organic carbon fractions at a roadway site during fall season

To examine the formation pathways of two size-resolved water-soluble organic carbon (WSOC) fractions, a total of 16 sets of size-segregated aerosol samples were collected using a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI) at a roadway site in Korea from September 29 to October 29, 2010. A XAD7HP (non-ionic aliphatic acrylic polymer) resin column was used to separate the filtered extracts into hydrophilic (WSOCHPI) and hydrophobic (WSOCHPO) WSOC fractions. Also the size distributions of water-soluble inorganic species and oxalate were examined to determine the formation pathways of size-resolved WSOCHPI and WSOCHPO fractions.The size distribution of WSOCHPI showed a dominant mode at 0.55 μm, while the WSOCHPO had dominant modes at both 0.17–0.32 μm and 0.55 μm. On the basis of the size distribution characteristics, it was found that the formation pathways of both WSOCHPI and WSOCHPO were dependent on the particle size; in the condensation mode (0.17–0.32 μm), both the WSOCHPI and WSOCHPO could be produced through atmospheric processes similar to those of SO42− and oxalate, which were derived from the gas-phase oxidations of organic compounds. In the droplet mode (0.55–1.8 μm), the cloud processing of both the organic compounds and biomass burning emissions could be a major pathway for the WSOCHPI formation. However, the droplet mode WSOCHPO was likely produced through cloud processing and heterogeneous reactions or aerosol-phase reactions. In the coarse mode (>3.1 μm), the WSOCHPI formation was more likely associated with soil-related particles (Ca(NO3)2 and CaSO4) than with sea-salt particles (NaNO3 and Na2SO4).

Brown carbon in atmospheric outflow from the Indo-Gangetic Plain: Mass absorption efficiency and temporal variability

The simultaneous measurements of brown carbon (BrC) and elemental carbon (EC) are made in ambient aerosols (PM2.5), collected from a site in north-east India during November'09–March'10, representing the atmospheric outflow from the Indo-Gangetic Plain (IGP) to the Bay of Bengal (BoB). The absorption coefficient of BrC (babs), assessed from water-soluble organic carbon (WSOC) at 365 nm, varies from 2 to 21 M m−1 and exhibits significant linear relationship (P < 0.05) with WSOC concentration (3–29 μg m−3). The angstrom exponent (α: 8.3 ± 2.6, where babs ≈ λ−α.) is consistent with that reported for humic-like substances (HULIS) from biomass burning emissions (BBE). The impact of BBE is also discernible from mass ratios of nss-K+/EC (0.2–1.4) and OC/EC (3.4–11.5). The mass fraction of WSOC (10–23%) in PM2.5 and mass absorption efficiency of BrC (σabs-BrC: 0.5–1.2 m2 g−1) bring to focus the significance of brown carbon in atmospheric radiative forcing due to anthropogenic aerosols over the Indo-Gangetic Plain.

Aerosol hygroscopicity derived from size-segregated chemical composition and its parameterization in the North China Plain

Abstract. Hygroscopic growth of aerosol particles is of significant importance in quantifying the aerosol radiative effect in the atmosphere. In this study, hygroscopic properties of ambient particles are investigated based on particle chemical composition at a suburban site in the North China Plain during the HaChi campaign (Haze in China) in summer 2009. The size-segregated aerosol particulate mass concentration as well as the particle components such as inorganic ions, organic carbon and water-soluble organic carbon (WSOC) are identified from aerosol particle samples collected with a ten-stage impactor. An iterative algorithm is developed to evaluate the hygroscopicity parameter κ from the measured chemical composition of particles. During the HaChi summer campaign, almost half of the mass concentration of particles between 150 nm and 1 μm is contributed by inorganic species. Organic matter (OM) is abundant in ultrafine particles, and 77% of the particulate mass with diameter (Dp) of around 30 nm is composed of OM. A large fraction of coarse particle mass is undetermined and is assumed to be insoluble mineral dust and liquid water. The campaign's average size distribution of κ values shows three distinct modes: a less hygroscopic mode (Dp &lt; 150 nm) with κ slightly above 0.2, a highly hygroscopic mode (150 nm &lt; Dp &lt; 1 μm) with κ greater than 0.3 and a nearly hydrophobic mode (Dp &gt; 1 μm) with κ of about 0.1. The peak of the κ curve appears around 450 nm with a maximum value of 0.35. The derived κ values are consistent with results measured with a high humidity tandem differential mobility analyzer within the size range of 50–250 nm. Inorganics are the predominant species contributing to particle hygroscopicity, especially for particles between 150 nm and 1 μm. For example, NH4NO3, H2SO4, NH4HSO4 and (NH4)2SO4 account for nearly 90% of κ for particles of around 900 nm. For ultrafine particles, WSOC plays a critical role in particle hygroscopicity due to the predominant mass fraction of OM in ultrafine particles. WSOC for particles of around 30 nm contribute 52% of κ. Aerosol hygroscopicity is related to synoptic transport patterns. When southerly wind dominates, particles are more hygroscopic; when northerly wind dominates, particles are less hygroscopic. Aerosol hygroscopicity also has a diurnal variation, which can be explained by the diurnal evolution of planetary boundary layer, photochemical aging processes during daytime and enhanced black carbon emission at night. κ is highly correlated with mass fractions of SO42−, NO3− and NH4+ for all sampled particles as well as with the mass fraction of WSOC for particles of less than 100 nm. A parameterization scheme for κ is developed using mass fractions of SO42−, NO3−, NH4+ and WSOC due to their high correlations with κ, and κ calculated from the parameterization agrees well with κ derived from the particle's chemical composition. Further analysis shows that the parameterization scheme is applicable to other aerosol studies in China.

Influence of hydrophilic and hydrophobic water-soluble organic carbon fractions on light extinction at an urban site

Until now, quantitative contributions of hydrophilic and hydrophobic water-soluble organic carbon (WSOC) fractions to aerosol light extinction have not been studied. In this study, concentrations of chemical species in PM2.5 (particulate matter with diameters less than 2.5 µm), including elemental carbon (EC), organic carbon (OC), total WSOC, two fractionated WSOCs, water-soluble inorganic species, and metal species, were measured twice a day between December 27, 2010 and January 20, 2011, at an urban site in Seoul, Korea. A macro-porous XAD7HP resin column was used to separate the liquid extracts into hydrophilic and hydrophobic WSOC (WSOCHPI and WSOCHPO) fractions. Water-insoluble OC (WIOC), WSOCHPI and WSOCHPO were used to estimate the aerosol light extinction from the original IMPROVE algorithm. Organic mass to organic carbon (OM/OC) ratios of 1.6, 2.0, and 1.8 were applied to the WIOC, WSOCHPI, and WSOCHPO, respectively. Light extinctions for ammonium sulfate, ammonium nitrate, POM (particulate organic matter = WIOM + WSOMHPI + WSOMHPO), and EC (which is light absorbing) were determined as 38.9 ± 34.0, 64.7 ± 70.6, 69.5 ± 27.7, and 27.1 ± 11.0 Mm−1, respectively, and contributed 15.0% (range: 5.4–25.6), 22.2% (7.1–50.8), 30.8% (13.0–42.3) and 12.0% (5.1–21.3), respectively, to the total light extinction budgets. Light scattering due to the WIOM, WSOMHPI and WSOMHPO were 27.3 ± 13.1, 17.1 ± 8.7, and 24.1 ± 9.9 Mm−1, respectively, and accounted for 12.5, 7.5, and 10.7% of the total light extinction budget. The results indicate WSOCHPO has a greater impact on visibility reduction in wintertime than WSOCHPI at this site. Light scattering by total OC concentration (POM=1.6 × OC) was 62.2 ± 25.1 Mm−1, which was approximately 9.7% lower than the sum of light scattering due to each of the three OC components with different OM/OC ratios. As the relative humidity (RH) increased, light extinction was higher in the water-soluble inorganic components ((NH4)2SO4 and NH4NO3) than in the water-soluble organic fractions. In the IMPROVE algorithm, the hygroscopic growth factor for POM was assumed to be 1 (non-hygroscopic) due to a lack of evidence for water growth by ambient POM. However, the relationships between the RH and light scattering due to WSOMHPI (R2=0.49) and WSOMHPO (R2 = 0.31) suggest that different hygroscopic growth factors should be applied to the hydrophilic and the hydrophobic WSOC fractions. Consequently, additional experimental work is needed to explore hygroscopic growth curves for the two fractionated WSOC components.

Measuring and modeling the hygroscopic growth of two humic substances in mixed aerosol particles of atmospheric relevance

Abstract. The hygroscopic growth of atmospheric particles affects atmospheric chemistry and Earth's climate. Water-soluble organic carbon (WSOC) constitutes a significant fraction of the dry submicron mass of atmospheric aerosols, thus affecting their water uptake properties. Although the WSOC fraction is comprised of many compounds, a set of model substances can be used to describe its behavior. For this study, mixtures of Nordic aquatic fulvic acid reference (NAFA) and Fluka humic acid (HA), with various combinations of inorganic salts (sodium chloride and ammonium sulfate) and other representative organic compounds (levoglucosan and succinic acid), were studied. We measured the equilibrium water vapor pressure over bulk solutions of these mixtures as a function of temperature and solute concentration. New water activity (aw) parameterizations and hygroscopic growth curves at 25 °C were calculated from these data for particles of equivalent composition. We examined the effect of temperature on the water activity and found a maximum variation of 9% in the 0–30 °C range, and 2% in the 20–30 °C range. Five two-component mixtures were studied to understand the effect of adding a humic substance (HS), such as NAFA and HA, to an inorganic salt or a saccharide. The deliquescence point at 25 °C for HS-inorganic mixtures did not change significantly from that of the pure inorganic species. However, the hygroscopic growth of HA / inorganic mixtures was lower than that exhibited by the pure salt, in proportion to the added mass of HA. The addition of NAFA to a highly soluble solute (ammonium sulfate, sodium chloride or levoglucosan) in water had the same effect as the addition of HA to the inorganic species for most of the water activity range studied. Yet, the water uptake of these NAFA mixtures transitioned to match the growth of the pure salt or saccharide at high aw values. The remaining four mixtures were based on chemical composition data for different aerosol types. As expected, the two solutions representing organic aerosols (40% HS/40% succinic acid/20% levoglucosan) showed lower water uptake than the two solutions representing biomass burning aerosols (25% HS/27% succinic acid/18% levoglucosan/30% ammonium sulfate). However, interactions in multicomponent solutions may be responsible for the large variation of the relative water uptake of identical mixtures containing different HSs above a water activity of 0.95. The ZSR (Zdanovskii, Stokes, and Robinson) model was able to predict reasonably well the hygroscopic growth of all the mixtures below aw = 0.95, but produced large deviations for some multicomponent mixtures at higher values.