• Journal of Korean Society for Atmospheric Environment
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• v.31 no.3
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• pp.239-254
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• 2015

Little information on HUmic-Like Substances (HULIS) in ambient particulate matter has been reported yet in Korea. HULIS makes up a significant fraction of the water-soluble organic mass in the atmospheric aerosols and influence their water uptake properties. In this study 24-hr $PM_{2.5}$ samples were collected between December 2013 and October 2014 at an urban site in Gwangju and analyzed for organic carbon (OC), elemental carbon (EC), water-soluble OC (WSOC), HULIS, and ionic species, to investigate possible sources and formation processes of HULIS. HULIS was separated using solid phase extraction method and quantified by total organic carbon analyzer. During the study period, HULIS concentration ranged from 0.19 to $5.65{\mu}gC/m^3$ with an average of $1.83{\pm}1.22{\mu}gC/m^3$, accounting for on average 45% of the WSOC (12~ 73%), with higher in cold season than in warm season. Strong correlation of WSOC with HULIS ($R^2=0.91$) indicates their similar chemical characteristics. On the basis of the relationships between HULIS and a variety of chemical species (EC, $K^+$, $NO_3{^-}$, $SO_4{^{2-}}$, and oxalate), it was postulated that HULIS observed during summer and winter were likely attributed to secondary formation and primary emissions from biomass burning (BB) and traffics. Stronger correlation of HULIS with $K^+$, which is a BB tracer, in winter ($R^2=0.81$) than in summer ($R^2=0.66$), suggests more significant contribution of BB emissions in winter to the observed HULIS. It is interesting to note that BB emissions may also have an influence on the HULIS in summer, but further study using levoglucosan that is a unique organic marker of BB emissions is required during summer. Higher correlation between HULIS and oxalate, which is mainly formed through cloud processing and/or photochemical oxidation processes, was found in the summer ($R^2=0.76$) than in the winter ($R^2=0.63$), reflecting a high fraction of secondary organic aerosol in the summer.

• Asian Journal of Atmospheric Environment
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• v.12 no.2
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• pp.153-164
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• 2018

We measured $^1H$ and $^{13}C$ nuclear magnetic resonance (NMR) spectra of Humic-like substances (HULIS) in urban atmospheric aerosols isolated by diethylaminoethyl (DEAE) and hydrophilic-lipophilic balance (HLB) resin to characterize their chemical structure. HULIS isolated by DEAE resin were characterized by relatively high contents of aromatic protons and relatively low contents of aliphatic protons in comparison with HULIS isolated by HLB resin, while the contents of protons bound to oxygenated aliphatic carbon atoms were similar. These results were consistent with the results of the $^{13}C$ NMR analysis and indicate that hydrophobic components were more selectively adsorbed onto HLB, while DEAE resins selectively retained aromatic carboxylic acids. Furthermore, we demonstrated that the chemical structural features of HULIS were significantly different between spring and summer samples and that these disparities were reflective of their different sources. The estimated concentrations of HULIS in spring were found to be regulated by vehicle emissions and pollen dispersion, while the behavior of HULIS in summer was similar to photochemical oxidant and nitrogen dioxide concentrations. The proportion of aliphatic protons for summer samples was higher than that for spring samples, while the proportion of aromatic protons for summer samples was lower than that for spring samples. These seasonal changes of the chemical structure may also involve in their functional expression in the atmosphere.

• Asian Journal of Atmospheric Environment
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• v.11 no.2
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• pp.96-106
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• 2017

In this study, measurements of size-segregated particulate matter (PM) emitted from the combustion of rice straw, pine needles, and sesame stem were conducted in a laboratory chamber. The collected samples were used to analyze amounts of organic and elemental carbon (OC and EC), water-soluble organic carbon (WSOC), humic-like substances (HULIS), and ionic species. The light absorption properties of size-resolved water extracts were measured using ultraviolet-visible spectroscopy. A solid-phase extraction method was first used to separate the size-resolved HULIS fraction, which was then quantified by a total organic carbon analyzer. The results show that regardless of particle cut sizes, the contributions of size-resolved HULIS ($=1.94{\times}HULIS-C$) to PM size fractions ($PM_{0.32}$, $PM_{0.55}$, $PM_{1.0}$, and $PM_{1.8}$) were similar, accounting for 25.2-27.6, 15.2-22.4 and 28.2-28.7% for rice straw, pine needle, and sesame stem smoke samples, respectively. The $PM_{1.8}$ fraction revealed WSOC/OC and HULIS-C/WSOC ratios of 0.51 and 0.60, 0.44 and 0.40, and 0.50 and 0.60 for the rice straw, pine needle, and sesame stem burning emissions, respectively. Strong absorption with decreasing wavelength was found by the water extracts from size-resolved biomass burning aerosols. The absorption ${\AA}ngstr{\ddot{o}}m $ exponent values of the size-resolved water extracts fitted between 300 and 400 nm wavelengths for particle sizes of $0.32-1.0{\mu}m$ were 6.6-7.7 for the rice straw burning samples, and 7.5-8.0 for the sesame stem burning samples. The average mass absorption efficiencies of size-resolved WSOC and HULIS-C at 365 nm were 1.09 (range: 0.89-1.61) and 1.82 (range: 1.33-2.06) $m^2/g{\cdot}C$ for rice straw smoke aerosols, and 1.13 (range: 0.85-1.52) and 1.83 (range: 1.44-2.05) $m^2/g{\cdot}C$ for sesame stem smoke aerosols, respectively. The light absorption of size-resolved water extracts measured at 365 nm showed strong correlations with WSOC and HULIS-C concentrations ($R^2=0.89-0.93$), indicating significant contribution of HULIS component from biomass burning emissions to the light absorption of ambient aerosols.

• Atmosphere
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• v.31 no.3
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• pp.267-282
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• 2021

Characteristics of carbonaceous components and organic compounds in PM_2.5 over the atmosphere of the Yellow Sea were investigated. PM_2.5 samples were collected onboard the meteorological research vessel, GISANG 1, over the Yellow Sea during the YES-AQ campaign in 2018 and 2019, respectively. The average concentrations of carbonaceous components in this region were 2.59 ± 1.59 ㎍ m^-3 for the OC, 0.24 ± 0.10 ㎍ m^-3 for the EC, 2.14 ± 1.30 ㎍ m^-3 for the WSOC and 1.17 ± 0.94 ㎍ m^-3 for the HULIS-C, respectively. The total concentration of 56 organic compounds (ΣOCs) accounts for 10% of OC. The main group among organic compounds were dicarboxylic acids which account for 57% of ΣOCs, followed by n-alkanoic acids accounting for 34% of ΣOCs. In n-alkanoic acid distribution, hexanoic (C_6:0) and octanoic (C_8:0) acids which are low molecular weight n-alkanoic acids and known as emitted from marine biogenic activities were dominant in this region. Furthermore, non-HULIS-C fraction increased when the air mass originated from the marine region rather than the continental region. When the Asian dust episode was observed, the WISOC concentrations along with the levoglucosan were increased, while the haze episodes caused the increase of WSOC, HULIC-S and DCAs. In this study, we found that the components of carbonaceous and organic aerosols in PM_2.5 over the Yellow Sea were changed with the specific air pollution episodes. It indicates that the physicochemical properties of PM_2.5 can be changed by the air pollution episodes in this region.

• Journal of Korean Society for Atmospheric Environment
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• v.34 no.3
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• pp.418-429
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• 2018

Measurements of 24-hr size-segregated ambient particles were made at an urban site of Gwangju under high pressure conditions occurred in the Korean Peninsula late in March 2018. The aim of this study was to understand the effect of air stagnation on mass size distributions and formation pathways of water-soluble organic and inorganic components. During the study period, the $NO_3{^-}$, $SO_4{^{2-}}$, $NH_4{^+}$, water-soluble organic carbon (WSOC), and humic-like substances(HULIS) exhibited mostly bi-modal size distributions peaking at 1.0 and $6.2{\mu}m$, with predominant droplet modes. In particular, outstanding droplet mode size distributions were observed on March 25 when a severe haze occurred due to stable air conditions and long range transport of aerosol particles from northeastern regions of China. Air stagnation conditions and high relative humidity during the study period resulted in accumulation of primary aerosol particles from local emission sources and enhanced formation of secondary ionic and organic aerosols through aqueous-phase oxidations of $SO_2$, $NO_2$, $NH_3$, and volatile organic compounds, leading to their dominant droplet mode size distributions at particle size of $1.0{\mu}m$. From the size distribution of $K^+$ in accumulation mode, it can be inferred that in addition to the secondary organic aerosol formations, accumulation mode WSOC and HULIS could be partly attributed to biomass burning emissions.

• Particle and aerosol research
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• v.15 no.3
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• pp.91-104
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• 2019

In this study, hourly measurements of $PM_{2.5}$ and its major chemical constituents such as organic and elemental carbon (OC and EC), and ionic species were made between January 15 and February 10, 2018 at the air pollution intensive monitering station in Gwangju. In addition, 24-hr integrated $PM_{2.5}$ samples were collected at the same site and analyzed for OC, EC, water-soluble OC (WSOC), humic-like substance (HULIS), and ionic species. Over the whole study period, the organic aerosols (=$1.6{\times}OC$) and $NO_3{^-}$ concentrations contributed 26.6% and 21.0% to $PM_{2.5}$, respectively. OC and EC concentrations were mainly attributed to traffic emissions with some contribution from biomass burning emissions. Moreover, strong correlations of OC with WSOC, HULIS, and $NO_3{^-}$ suggest that some of the organic aerosols were likely formed through atmospheric oxidation processes of hydrocarbon compounds from traffic emissions. For the period between January 18 and 22 when $PM_{2.5}$ pollution episode occurred, concentrations of three secondary ionic species ($=SO{_4}^{2-}+NO_3{^-}+NH_4{^+}$) and organic matter contributed on average 50.8 and 20.1% of $PM_{2.5}$, respectively, with the highest contribution from $NO_3{^-}$. Synoptic charts, air mass backward trajectories, and local meteorological conditions supported that high $PM_{2.5}$ pollution was resulted from long-range transport of haze particles lingering over northeastern China, accumulation of local emissions, and local production of secondary aerosols. During the $PM_{2.5}$ pollution episode, enhanced $SO{_4}^{2-}$ was more due to the long-range transport of aerosol particles from China rather than local secondary production from $SO_2$. Increasing rate in $NO_3{^-}$ was substantially greater than $NO_2$ and $SO{_4}^{2-}$ increasing rates, suggesting that the increased concentration of $NO_3{^-}$ during the pollution episode was attributed to enhanced formation of local $NO_3{^-}$ through heterogenous reactions of $NO_2$, rather than impact by long-range transportation from China.