Browse > Article
http://dx.doi.org/10.5572/ajae.2018.12.2.153

Chemical Structural Features of Humic-like Substances (HULIS) in Urban Atmospheric Aerosols Collected from Central Tokyo with Special Reference to Nuclear Magnetic Resonance Spectra  

Katsumi, Naoya (Department of Environmental Science, Faculty of Bioresources and Environmental Sciences, Ishikawa Prefectural University)
Miyake, Shuhei (Department of Resources and Environmental Engineering, School of Creative Science and Engineering, Waseda University)
Okochi, Hiroshi (Department of Resources and Environmental Engineering, School of Creative Science and Engineering, Waseda University)
Publication Information
Asian Journal of Atmospheric Environment / v.12, no.2, 2018 , pp. 153-164 More about this Journal
Abstract
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.
Keywords
Humic-like substances; Aerosols; $^1H$ nuclear magnetic resonance; $^{13}C$ nuclear magnetic resonance;
Citations & Related Records
연도 인용수 순위
  • Reference
1 Duarte, R.M.B.O., Pio, C.A., Duarte, A.C. (2005) Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions. Analytica Chimica Acta 530, 7-14.   DOI
2 Duarte, R.M.B.O., Santos, B.H.E., Pio, C.A., Duarte, A.C. (2007) Comparison of structural features of watersoluble organic matter from atmospheric aerosols with those of aquatic humic substances. Atmospheric Environment 41, 8100-8113.   DOI
3 Duarte, R.M.B.O., Freire, S.M.S.C., Duarte, A.C. (2015) Investigation the water-soluble organic functionality of urban aerosols using two-dimensional of solid-state $^{13}C$ NMR and FTIR spectral data. Atmospheric Environment 116, 245-252.   DOI
4 Environmental Bureau of the Tokyo Metropolitan Government (2011) Release Inventory of $PM_{2.5}$ etc. https://www.kankyo.metro.tokyo.jp/air/attachement/013_inbentori.pdf (in Japanese, 9 February 2017)
5 Fan, X., Song, J., Peng, P. (2012) Comparison of isolation and quantification methods to measure humic-like substances (HULIS) in atmospheric particles. Atmospheric Environment 60, 366-374.   DOI
6 Fan, X., Song, J., Peng, P. (2013) Comparative study for separation of atmospheric humic-like substance (HULIS) by ENVI-18, HLB, XAD-8 and DEAE sorbents: elemental composition, FT-IR, $^1H NMR$ and off-line thermochemolysis with tetramethylammonium hydroxide (TMAH). Chemosphere 93, 1710-1719.   DOI
7 Feczko, T., Puxbaum, H., Kasper-Giebl, A., Handler, M., Limbeck, A., Gelencser, A., Pio, C., Preunkert, S., Legrand, M. (2007) Determination of water and alkaline extractable atmospheric humic-like substances with the TU Vienna HULIS analyzer in samples from six background sites in Europe. Journal of Geophysical Research: Atmospheres 112, D23.
8 Okochi, H., Sato, E., Matsubayashi, Y., Igawa, M. (2008) Effect of atmospheric humic-like substances on the enhanced dissolution of volatile organic compounds into dew water. Atmospheric Research 87, 213-223.   DOI
9 Hedges, J.I., Eglinton, G., Hatcher, P.G., Kirchman, D.L., Arnosti, C., Derenne, S., Evershed, R.P., Kogel-Knabner, I., de Leeuw, J.W., Littke, R., Michaelis, W., Rullkotter, J. (2000) The molecularly-uncharacterized component of nonliving organic matter in natural environments. Organic Geochemistry 31, 945-958.   DOI
10 Hiraide, M., Shima, T., Kawaguchi, H. (1994) Separation and determination of dissolved and particulate humic substances in river water. Microchimica Acta 113, 269-276.   DOI
11 Hoffer, A., Gelencer, A., Guyon, P., Schmid, O., Frank, G.P., Artaxo, P., Andreae, M.O. (2006) Optical properties of humic-like substances (HULIS) in biomassburning aerosols. Atmospheric Chemistry and Physics 6, 3563-3570.   DOI
12 Katsumi, N., Yonebayashi, K., Okazaki, M., Nishiyama, S., Nishi, T., Hosaka, A., Watanabe, C. (2016) Characterization of soil organic matter with different degree of humification using evolved gas analysis-mass spectrometry. Talanta 155, 28-37.   DOI
13 Kawahigashi, M., Fujitake, N., Takahashi, T. (1996) Structural information obtained from spectral analysis (UVVIS, IR, $^1H$ NMR) of particle size fractions in two humic acids. Soil Science and Plant Nutrition 42, 355-360.
14 Kiss, G., Varga, B., Galambos, I., Ganszky, I. (2002) Characterization of Water-Soluble Organic Matter Isolated from Atmospheric Fine Aerosol. Journal of Geophysical Research 107, 8339.
15 Chalbot, M.-C.G., Kavouras, I.G. (2014) Nuclear magnetic resonance spectroscopy for determining the functional content of organic aerosols: A review. Environmental Pollution 191, 232-249.   DOI
16 Baduel, C., Voison, D., Jaffrezo, J.L. (2009) Comparison of analytical methods for Humic Like Substances (HULIS) measurements in atmospheric particles. Atmospheric Chemistry and Physics 9, 5949-5962.   DOI
17 Baduel, C., Voison, D., Jaffrezo, J.L. (2010) Seasonal variations of concentrations and optical properties of water soluble HULIS collected in urban environments. Atmospheric Chemistry and Physics 10, 4085-4095.   DOI
18 Chalbot, M.-C.G., Brown, J., Chitranshi, P., Gamboa da Costa, G., Pollock, E.D., Kavouras, I.G. (2014) Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley. Atmospheric Chemistry and Physics 14, 6075-6088.   DOI
19 Chalbot, M.-C.G., Chitranshi, P., Costa, G.G., Pollock, E., Kavouras, I.G. (2015) Characterization of watersoluble organic matter in urban aerosol by $^{1}H$-NMR spectroscopy. Atmospheric Environment 128, 235-245.
20 Decesari, S., Facchini, M.C., Fuzzi, S., Tagliavini, E. (2000) Characterization of water-soluble organic compounds in atmospheric aerosol: a new approach. Journal of Geophysical Research: Atmospheres 105, 1481-1489.   DOI
21 Decesari, S., Mircea, M., Cavalli, F., Fuzzi, S., Moretti, F., Tagliavini, E., Facchini, M.C. (2007) Source attribution of water-soluble organic aerosol by nuclear magnetic resonance spectroscopy. Environmental Science & Technology 41, 2479-2484.   DOI
22 Gelencser, A., Hoffer, A., Krivacsy, Z., Kiss, G., Molnar, A., Meszaros, E. (2002) On the possible origin of humic matter in fine continental aerosol. Journal of Geophysical Research: Atmospheres 107, D12.
23 Kiss, G., Tombacz, E., Varga, B., Alsberg, T., Persson, L. (2003) Estimation of the average molecular weight of humic-like substances isolated from fine atmospheric aerosol. Atmospheric Environment 37, 3783-3794.   DOI
24 Fujitake, N., Kawahigashi, M. (1999) $^{13}C$ NMR spectra and elemental composition of fractions with different particle sizes from an Andosol humic acid. Soil Science and Plant Nutrition 45, 359-366.   DOI
25 Fujitake, N., Kodama, H., Nagao, S., Tsuda, K., Yonebayashi, K. (2009) Chemical properties of fulvic acids isolated from Lake Biwa, a clear water system in Japan, Humic substances research 5/6, 45-53.
26 Graber, E.R., Rudich, Y. (2006) Atmospheric HULIS: How humic-like are they? A comprehensive and critical review. Atmospheric Chemistry and Physics 6, 729-753.   DOI
27 Havers, N., Burba, P., Lambert, J., Klockow, D. (1998) Spectroscopic characterization of humic-like substances in airborne particulate matter. Journal of Atmospheric Chemistry 29, 45-54.   DOI
28 Wang, B., Knopf, D.A. (2011) Heterogeneous ice nucleation on particles composed of humic-like substances impacted by $O_3$. Journal of Geophysical Research: Atmospheres 116, 1-14.
29 Willey, J.D., Kieber, R.J., Williams, K.H., Crozier, J.S., Skrabal, S.A., Avery, G.B. (2000) Temporal variability of iron speciation in coastal rainwater. Journal of Atmospheric Chemistry 37, 185-205.   DOI
30 Duarte, R.M.B.O., Duarte, A.C. (2005) Application of non-ionic solid sorbents (XAD Resins) for the isolation and fractionation of water-soluble organic compounds from atmospheric aerosols. Journal of Atmospheric Chemistry 51, 79-93.   DOI
31 Yamanokoshi, E., Okochi, H., Ogata, H., Kobayashi, Y. (2014) Behavior and origin of water-soluble humic-like substances in particulate matter in central Tokyo. Journal of Japan Society for Atmospheric Environment 49, 43-52. (in Japanese with English summary)
32 Stone, E.A., Hedman, C.J., Sheesley, R.J., Shafer, M.M., Schauer, J.J. (2009) Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry. Atmospheric Environment 43, 4205-4213.   DOI
33 Zheng, G., He, K., Duan, F., Cheng, Y., Ma, Y. (2013) Measurement of humic-like substances in aerosols: A review. Environmental Pollution 181, 301-314.   DOI
34 Samburova, V., Didenko, T., Kunenkov, E., Emmenegger, C., Zenobi, R., Kalberer, M. (2007) Functional group analysis of high-molecular weight compounds in the water-soluble fraction of organic aerosols. Atmospheric Environment 41, 4703-4710.   DOI
35 Sannigrahi, P., Sullivan, A., Weber, R., Ingall, E. (2006) Characterization of water soluble organic carbon in urban atmospheric aerosols using solid-state C-13 NMR spectroscopy. Environmental Science & Technology 40, 666-672.   DOI
36 Scheinhardt, S., Muller, K., Spindler, G., Herrmann, H. (2013) Complexation of trace metals in size-segregated aerosol particles at nine sites in Germany. Atmospheric Environment 74, 102-109.   DOI
37 Song, J., He, L., Peng, P., Zhao, J., Ma, S., Song, J., Ma, S. (2012) Chemical and Isotopic Composition of Humic-Like Substances (HULIS) in Ambient Aerosols in Guangzhou. Aerosol Science and Technology 46, 533-546.   DOI
38 Sun, J., Ariya, P.A. (2006) Atmospheric organic and bioaerosols as cloud condensation nuclei (CCN): A review. Atmospheric Environment 40, 795-920.   DOI
39 Varga, B., Kiss, G., Ganszky, I., Glencser, A., Krivacsy, Z. (2001) Isolation of water-soluble organic matter from atmospheric aerosol. Talanta 55, 561-572.   DOI
40 Paris, R., Desboeufs, K.V. (2013) Effect of atmospheric organic complexation on iron-bearing dust solubility. Atmospheric Chemistry and Physics 13, 4895-4905.   DOI
41 Lin, P., Huang, X.F., He, L.Y., Yu, J.Z. (2010) Abundance and size distribution of HULIS in ambient aerosols at a rural site in South China. Journal of Aerosol Science 41, 74-87.   DOI
42 Kogel-Knabner, I. (2002) The macromolecular organic composition of plant and microbial residues as inputs to soil organic matter. Soil Biology & Biochemistry 34, 139-162.   DOI
43 Krivacsy, Z., Kiss, G., Varga, B., Galambos, I., Sarvari, Z., Gelencser, A., Molnar, A., Fuzzi, S., Facchini, M.C., Zappoli, S., Andracchio, A., Alsberg, T., Hansson, H.C., Persson, L. (2000) Study of humic-like substances in fog and interstitial aerosol by size-exclusion chromatography and capillary electrophoresis. Atmospheric Environment 34, 4273-4281.   DOI
44 Krivacsy, Z., Gelencser, A., Kiss, G., Meszaros, E., Molnar, A., Hoffer, A., Meszaros, T., Sarvari, Z., Temesi, D., Varga, B., Baltensperger, U., Nyeki, S., Weingartner, E. (2001) Study on the chemical character of water soluble organic compounds in fine atmospheric aerosol at the Jungfraujoch. Journal of Atmospheric Chemistry 39, 235-259.   DOI
45 Lin, P., Rincon, A.G., Kalberer, M., Yu, J.Z. (2012) Elemental composition of HULIS in the Pearl River delta region, China: results inferred from positive and negative electrospray high resolution mass spectrometric data. Environmental Science & Technology 46, 7454-7462.   DOI
46 Malcolm, R.L. (1990) The uniqueness of humic substances in each of soil, stream and marine environments. Analytica Chimica Acta 232, 19-30.   DOI
47 Okochi, H., Brimblecombe, P. (2002) Potential trace metalorganic complexation in the atmosphere. The scientific world 2, 767-786.   DOI