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

다국어 초록 (Multilingual Abstract)

We measured 1H and 13C 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 13C 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.

참고문헌 (Reference)

1 Malcolm, R.L., "The uniqueness of humic substances in each of soil, stream and marine environments" 232 : 19-30, 1990

2 Hedges, J.I., "The molecularly-uncharacterized component of nonliving organic matter in natural environments" 31 : 945-958, 2000

3 Kogel-Knabner, I., "The macromolecular organic composition of plant and microbial residues as inputs to soil organic matter" 34 : 139-162, 2002

4 Willey, J.D., "Temporal variability of iron speciation in coastal rainwater" 37 : 185-205, 2000

5 Krivacsy, Z., "Study on the chemical character of water soluble organic compounds in fine atmospheric aerosol at the Jungfraujoch" 39 : 235-259, 2001

6 Krivacsy, Z., "Study of humic-like substances in fog and interstitial aerosol by size-exclusion chromatography and capillary electrophoresis" 34 : 4273-4281, 2000

7 Kawahigashi, M., "Structural information obtained from spectral analysis (UVVIS, IR, $^1H$ NMR) of particle size fractions in two humic acids" 42 : 355-360, 1996

8 Duarte, R.M.B.O., "Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions" 530 : 7-14, 2005

9 Havers, N., "Spectroscopic characterization of humic-like substances in airborne particulate matter" 29 : 45-54, 1998

10 Decesari, S., "Source attribution of water-soluble organic aerosol by nuclear magnetic resonance spectroscopy" 41 : 2479-2484, 2007

11 Hiraide, M., "Separation and determination of dissolved and particulate humic substances in river water" 113 : 269-276, 1994

12 Baduel, C., "Seasonal variations of concentrations and optical properties of water soluble HULIS collected in urban environments" 10 : 4085-4095, 2010

13 Environmental Bureau of the Tokyo Metropolitan Government, "Release Inventory of $PM_{2.5}$ etc"

14 Okochi, H., "Potential trace metalorganic complexation in the atmosphere" 2 : 767-786, 2002

15 Hoffer, A., "Optical properties of humic-like substances (HULIS) in biomassburning aerosols" 6 : 3563-3570, 2006

16 Gelencser, A., "On the possible origin of humic matter in fine continental aerosol" 107 : D12-, 2002

17 Chalbot, M.-C.G., "Nuclear magnetic resonance spectroscopy for determining the functional content of organic aerosols: A review" 191 : 232-249, 2014

18 Zheng, G., "Measurement of humic-like substances in aerosols: A review" 181 : 301-314, 2013

19 Varga, B., "Isolation of water-soluble organic matter from atmospheric aerosol" 55 : 561-572, 2001

20 Duarte, R.M.B.O., "Investigation the water-soluble organic functionality of urban aerosols using two-dimensional of solid-state $^{13}C$ NMR and FTIR spectral data" 116 : 245-252, 2015

21 Stone, E.A., "Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry" 43 : 4205-4213, 2009

22 Wang, B., "Heterogeneous ice nucleation on particles composed of humic-like substances impacted by $O_3$" 116 : 1-14, 2011

23 Samburova, V., "Functional group analysis of high-molecular weight compounds in the water-soluble fraction of organic aerosols" 41 : 4703-4710, 2007

24 Chalbot, M.-C.G., "Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley" 14 : 6075-6088, 2014

25 Kiss, G., "Estimation of the average molecular weight of humic-like substances isolated from fine atmospheric aerosol" 37 : 3783-3794, 2003

26 Lin, P., "Elemental composition of HULIS in the Pearl River delta region, China: results inferred from positive and negative electrospray high resolution mass spectrometric data" 46 : 7454-7462, 2012

27 Paris, R., "Effect of atmospheric organic complexation on iron-bearing dust solubility" 13 : 4895-4905, 2013

28 Okochi, H., "Effect of atmospheric humic-like substances on the enhanced dissolution of volatile organic compounds into dew water" 87 : 213-223, 2008

29 Feczko, T., "Determination of water and alkaline extractable atmospheric humic-like substances with the TU Vienna HULIS analyzer in samples from six background sites in Europe" 112 : D23-, 2007

30 Scheinhardt, S., "Complexation of trace metals in size-segregated aerosol particles at nine sites in Germany" 74 : 102-109, 2013

31 Duarte, R.M.B.O., "Comparison of structural features of watersoluble organic matter from atmospheric aerosols with those of aquatic humic substances" 41 : 8100-8113, 2007

32 Fan, X., "Comparison of isolation and quantification methods to measure humic-like substances (HULIS) in atmospheric particles" 60 : 366-374, 2012

33 Baduel, C., "Comparison of analytical methods for Humic Like Substances (HULIS) measurements in atmospheric particles" 9 : 5949-5962, 2009

34 Fan, X., "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)" 93 : 1710-1719, 2013

35 Fujitake, N., "Chemical properties of fulvic acids isolated from Lake Biwa, a clear water system in Japan" 5/6 : 45-53, 2009

36 Song, J., "Chemical and Isotopic Composition of Humic-Like Substances (HULIS) in Ambient Aerosols in Guangzhou" 46 : 533-546, 2012

37 Chalbot, M.-C.G., "Characterization of watersoluble organic matter in urban aerosol by $^{1}H$-NMR spectroscopy" 128 : 235-245, 2015

38 Decesari, S., "Characterization of water-soluble organic compounds in atmospheric aerosol: a new approach" 105 : 1481-1489, 2000

39 Sannigrahi, P., "Characterization of water soluble organic carbon in urban atmospheric aerosols using solid-state C-13 NMR spectroscopy" 40 : 666-672, 2006

40 Katsumi, N., "Characterization of soil organic matter with different degree of humification using evolved gas analysis-mass spectrometry" 155 : 28-37, 2016

41 Kiss, G., "Characterization of Water-Soluble Organic Matter Isolated from Atmospheric Fine Aerosol" 107 : 8339-, 2002

42 Yamanokoshi, E., "Behavior and origin of water-soluble humic-like substances in particulate matter in central Tokyo" 49 : 43-52, 2014

43 Sun, J., "Atmospheric organic and bioaerosols as cloud condensation nuclei (CCN): A review" 40 : 795-920, 2006

44 Graber, E.R., "Atmospheric HULIS: How humic-like are they? A comprehensive and critical review" 6 : 729-753, 2006

45 Duarte, R.M.B.O., "Application of non-ionic solid sorbents (XAD Resins) for the isolation and fractionation of water-soluble organic compounds from atmospheric aerosols" 51 : 79-93, 2005

46 Lin, P., "Abundance and size distribution of HULIS in ambient aerosols at a rural site in South China" 41 : 74-87, 2010

47 Fujitake, N., "$^{13}C$ NMR spectra and elemental composition of fractions with different particle sizes from an Andosol humic acid" 45 : 359-366, 1999