Research on the sources and optical properties of atmospheric humic-like substances during heavy pollution periods
LIU Jia-wen1,2, WANG Qi-yuan2, ZHANG Qian1, WANG Jin2, LI Chang-yan2, SUN Li3,4
1. School of Environmental and Municipal Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China; 2. Institute of Earth Environment, Chinese Academy of Sciences, Xi'an 710061, China; 3. Jiangsu Province Key Laboratory of Environmental Engineering, Jiangsu Province Environmental Science Research Institute, Nanjing 210036, China; 4. Jiangsu Province High-Tech Key Laboratory for Atmospheric Environmental Monitoring and Pollution Control, Jiangsu Province Collaborative Center for Atmospheric Environment and Equipment Technology, School of Environmental Science and Engineering, Nanjing University of Information Science and Technology, Nanjing 210044, China
Abstract：The solid-phase extraction method and the thermal-optical method were combined to obtain different polar HULIS and the carbon content of HULIS (HULIS-C) in PM2.5 with high temporal resolution during the heavy pollution event in Xi'an. The light absorption characteristics of HULIS were analyzed using a UV-Vis spectrophotometer equipped with a liquid waveguide capillary cell (LWCC), and the positive matrix factorization model (PMF) was used to analyze the sources of HULIS. At the same time, the source of HULIS is combined with the positive matrix factorization model (PMF). The results showed that the average mass concentration of neutral HULIS (HULIS-n) (6.6±2.6)μg/m3 was higher than that of acidic HULIS (HULIS-a) (3.7±3.5)μg/m3, accounting for approximately 30% and 18% of OC, respectively, indicating severe HULIS pollution during heavy pollution periods. The absorption coefficients (AAE, E2/E3, and MAE365) of HULIS-n were all greater than those of HULIS-a, suggesting that HULIS-n contains more conjugated and aromatic structures and has stronger light-absorbing properties, with a more significant impact on atmospheric visibility. The source analysis revealed clear differences in the contributions of HULIS-n and HULIS-a. The primary sources of HULIS-n included secondary sources, coal combustion, motor vehicle emissions., while the contributions of secondary sources and coal combustion were higher for HULIS-a.
刘佳文, 王启元, 张倩, 王锦, 李常艳, 孙力. 重污染期间大气类腐殖质来源与光学特性研究[J]. 中国环境科学, 2025, 45(4): 1789-1798.
LIU Jia-wen, WANG Qi-yuan, ZHANG Qian, WANG Jin, LI Chang-yan, SUN Li. Research on the sources and optical properties of atmospheric humic-like substances during heavy pollution periods. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(4): 1789-1798.
[1] Chakrabarty R K, Gyawali M, Yatavelli R L N, et al. Brown carbon aerosols from burning of boreal peatlands:microphysical properties, emission factors, and implications for direct radiative forcing[J]. Atmospheric Chemistry and Physics, 2016,16(5):3033-3040. [2] Hammer M S, Martin R V, Van Donkelaar A, et al. Interpreting the ultraviolet aerosol index observed with the OMI satellite instrument to understand absorption by organic aerosols:implications for atmospheric oxidation and direct radiative effects[J]. Atmospheric Chemistry and Physics, 2016,16(4):2507-2523. [3] Wu C, Zhu B, Liang W, et al. Molecular characterization of nitrogen-containing organic compounds in fractionated atmospheric humic-like substances (HULIS) and its relationship with optical properties[J]. Science of the Total Environment, 2022,832:155043. [4] Zhang T, Huang S, Wang D, et al. Seasonal and diurnal variation of PM2.5HULIS over Xi'an in Northwest China:Optical properties, chemical functional group, and relationship with reactive oxygen species (ROS)[J]. Atmospheric Environment, 2022,268:118782. [5] Zheng G, He K, Duan F, et al. Measurement of humic-like substances in aerosols:a review[J]. Environmental Pollution 2013,181:301-314. [6] Fan X, Wei S, Zhu M, et al. Comprehensive characterization of humic-like substances in smoke PM2.5 emitted from the combustion of biomass materials and fossil fuels[J]. Atmospheric Chemistry and Physics, 2016,16(20):13321-13340. [7] Graber E R, Rudich Y. Atmospheric HULIS:How humic-like are they?A comprehensive and critical review[J]. Atmospheric Chemistry and Physics, 2006,6(3):729-753. [8] Kida M, Kojima T, Tanabe Y, et al. Origin, distributions, and environmental significance of ubiquitous humic-like fluorophores in Antarctic lakes and streams[J]. Water Research, 2019,163. [9] Srivastava D, Tomaz S, Favez O, et al. Speciation of organic fraction does matter for source apportionment. Part 1:A one-year campaign in Grenoble (France)[J]. Science of the Total Environment, 2018,624:1598-1611. [10] Tang S, Li F, Tsona N T, et al. Aqueous-phase photooxidation of vanillic acid:A potential source of humic-like substances (HULIS)[J]. ACS Earth and Space Chemistry, 2020,4(6):862-872. [11] Hoffer A, Gelencsér A, Guyon P, et al. Optical properties of humic-like substances (HULIS) in biomass-burning aerosols[J]. Atmospheric Chemistry and Physics, 2006,6(11):3563-3570. [12] Xiao K, Wang Q, Lin Y, et al. Approval research for carcinogen humic-like substances (HULIS) emitted from residential coal combustion in high lung cancer incidence areas of China[J]. Processes, 2021,9(7):1254. [13] Xu X, Lu X, Li X,, et al. ROS-generation potential of Humic-like substances (HULIS) in ambient PM2.5 in urban Shanghai:Association with HULIS concentration and light absorbance[J]. Chemosphere, 2020,256:127050. [14] Yu G H, Zhang Y, Cho S Y, et al. Influence of haze pollution on water-soluble chemical species in PM2.5 and size-resolved particles at an urban site during fall[J]. Journal of Environmental Sciences, 2017, 57:370-382. [15] Zou C, Cao T, Li M, et al. Measurement report:Changes in light absorption and molecular composition of water-soluble humic-like substances during a winter haze bloom-decay process in Guangzhou, China[J]. Atmospheric Chemistry and Physics, 2022,23:963-979. [16] Li X, Han J, Hopke P K, et al. Quantifying primary and secondary humic-like substances in urban aerosol based on emission source characterization and a source-oriented air quality model[J]. Atmospheric Chemistry and Physics, 2019,19(4):2327-2341. [17] 顾远,李清,黄雯倩,等.常州市冬季PM2.5中类腐殖质昼夜特征分析[J].环境科学, 2019,40(3):1091-1100. Gu Y, Li Q, Huang W, et al. Day-night characteristics of humic-like substances in PM2.5 during winter in Changzhou[J]. Environmental Science, 2019,40(3):1091-1100. [18] Yu L, Shasha H, Tian Z, et al. Pollution characterizations and oxidative potentials of water-soluble organic matters at different polarity levels in winter PM2.5 over Xi¢an[J]. Environmental Science, 2023,44(4):1882-1889. [19] Havers N, Burba P, Lambert J, et al. Spectroscopic characterization of humic-like substances in airborne particulate matter[J]. Journal of Atmospheric Chemistry, 1998,29(1):45-54. [20] Yan G, Kim G. Speciation and sources of brown carbon in precipitation at Seoul, Korea:Insights from excitation-emission matrix spectroscopy and carbon isotopic analysis[J]. Environmental Science& Technology, 2017,51(20):11580-11587. [21] Kuang B Y, Lin P, Huang X H H, et al. Sources of humic-like substances in the Pearl River Delta, China:positive matrix factorization analysis of PM2.5 major components and source markers[J]. Atmospheric Chemistry and Physics, 2015,15(4):1995-2008. [22] M B, YL Z, F C, et al. Light absorption and source apportionment of water soluble humic-like substances (HULIS) in PM2.5 at Nanjing, China[J]. Environmental Research, 2021,206:112554. [23] Mukherjee A, Dey S, Rana A, et al. Sources and atmospheric processing of brown carbon and HULIS in the Indo-Gangetic Plain:Insights from compositional analysis[J]. Environmental Pollution, 2020,267:115440. [24] Fan X, Song J, Peng P A. Temporal variations of the abundance and optical properties of water soluble Humic-Like Substances (HULIS) in PM2.5 at Guangzhou, China[J]. Atmospheric Research, 2016,172-173:8-15. [25] Cao T, Li M, Xu C, et al. Technical note:Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation-emission matrix spectroscopy with parallel factor analysis-potential limitations and applications[J]. Atmospheric Chemistry and Physics, 2023,23(4):2613-2625. [26] Gierlus M K. Laboratory studies of the physicochemical properties of mixed organic/mineral dust atmospheric aerosols:hygroscopicity and cloud condensation nuclei activity[D]. Lowa State:The University of Iowa, 2011. [27] Stone E A, Hedman C J, Sheesley R J, et al. Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry[J]. Atmospheric Environment, 2009,43(27):4205-4213. [28] Feczko T, Puxbaum H, Kasper-Giebl A, et al. Determination of water and alkaline extractable atmospheric humic‐like substances with the TU Vienna HULIS analyzer in samples from six background sites in Europe[J]. Journal of Geophysical Research:Atmospheres, 2007,112(D23). [29] Hoffer A, Kiss G, Blazsó M, et al. Chemical characterization of humic-like substances (HULIS) formed from a lignin-type precursor in model cloud water[J]. Geophysical Research Letters, 2004,31(6):4. [30] haynes J, Miller K E, Majestic B J. Investigation into Photoinduced Auto-Oxidation of Polycyclic Aromatic Hydrocarbons Resulting in Brown Carbon Production[J]. Environmental Science& Technology, 2019,53(2):682-691. [31] Hong Y, Cao F, Fan M, et al. Using machine learning to quantify sources of light-absorbing water-soluble humic-like substances (HULISws) in Northeast China[J]. Atmospheric Environment, 2022, 291:119371. [32] Srivastava D, Xu J, Vu T V, et al. Insight into PM2.5 sources by applying positive matrix factorization (PMF) at urban and rural sites of Beijing[J]. Atmospheric Chemistry and Physics, 2021,21(19):14703-14724. [33] Xu X, Zhang H, Chen J, et al. Six sources mainly contributing to the haze episodes and health risk assessment of PM2.5 at Beijing suburb in winter 2016[J]. Ecotoxicology and Environmental Safety, 2018, 166:146-156. [34] Xu Q, Wang S, Jiang J, et al. Nitrate dominates the chemical composition of PM2.5 during haze event in Beijing, China[J]. Science of the Total Environment, 2019,689:1293-1303. [35] Xie Y, Liu Z, WEN T, et al. Characteristics of chemical composition and seasonal variations of PM2.5 in Shijiazhuang, China:Impact of primary emissions and secondary formation[J]. Science of the Total Environment, 2019,677:215-229. [36] Wu C, Yu J Z. Determination of primary combustion source organic carbon-to-elemental carbon (OC/EC) ratio using ambient OC and EC measurements:secondary OC-EC correlation minimization method[J]. Atmospheric Chemistry and Physics, 2016,16(8):5453-5465. [37] Wu C, Wu D, Yu J Z. Quantifying black carbon light absorption enhancement with a novel statistical approach[J]. Atmospheric Chemistry and Physics, 2018,18(1):289-309. [38] Sun H, Li X, Zhu C, et al. Molecular composition and optical property of humic-like substances (HULIS) in winter-time PM2.5 in the rural area of North China Plain[J]. Atmospheric Environment, 2021,252. [39] Wang H, Wang H, LU X, et al. Increased night-time oxidation over China despite widespread decrease across the globe[J]. Nature Geoscience, 2023,16(3):217-223. [40] 陶冶,陈彦彤,李楠旺,等.气溶胶中溶解性有机质(DOM)液相氧化[J].环境科学, 2021,42(6):2659-2667. Tao Y, Chen Y, Li N, et al. Aqueous-phase oxidation of dissolved organic matter (DOM) from extracts of ambient aerosols[J]. Environmental Science, 2021,42(6):2659-2667. [41] 胡俊.夜间大气边界层结构变化对大气污染物累积和传输影响研究[D].南京:南京信息工程大学, 2021. Hu J. Study on effects of nocturnal atmospheric boundary layer on atmospheric pollutants'accumulation and transport[D]. Nanjing:Nanjing University of Information Science and Technology, 2021. [42] Zhao S, Tian H, Luo L, et al. Temporal variation characteristics and source apportionment of metal elements in PM2.5 in urban Beijing during 2018~2019[J]. Environmental Pollution, 2021,268:115856. [43] Liu Y, Li C, Zhang C, et al. Chemical characteristics, source apportionment, and regional contribution of PM2.5 in Zhangjiakou, Northern China:A multiple sampling sites observation and modeling perspective[J]. Environmental Advances, 2021,3:100034. [44] Shen J, Zhao Q, Cheng Z, et al. Evolution of source contributions during heavy fine particulate matter (PM2.5) pollution episodes in eastern China through online measurements[J]. Atmospheric Environment, 2020,232:117569. [45] Rai P, Furger M, Slowik J G, et al. Characteristics and sources of hourly elements in PM10 and PM2.5 during wintertime in Beijing[J]. Environmental Pollution, 2021,278:116865. [46] Zhou S, Davy P K, Huang M, et al. High-resolution sampling and analysis of ambient particulate matter in the Pearl River Delta region of southern China:source apportionment and health risk implications[J]. Atmospheric Chemistry and Physics, 2018,18(3):2049-2064. [47] Chen Y, Xie S, Luo B, et al. Particulate pollution in urban Chongqing of southwest China:Historical trends of variation, chemical characteristics and source apportionment[J]. Science of the Total Environment, 2017,584-585:523-534. [48] Dallosto M, Booth M J, Smith W, et al. A study of the size distributions and the chemical characterization of airborne particles in the vicinity of a large integrated steelworks[J]. Aerosol Science and Technology, 2008,42(12):981-991. [49] Li M, Liu Z, Chen J, et al. Characteristics and source apportionment of metallic elements in PM2.5 at urban and suburban sites in Beijing:implication of emission reduction[J]. Atmosphere, 2019,10(3):105. [50] Dey S, Sarkar S. Compositional and optical characteristics of aqueous brown carbon and HULIS in the eastern Indo-Gangetic Plain using a coupled EEM PARAFAC, FT-IR and 1H NMR approach[J]. Science of The Total Environment, 2024,921:171084. [51] Ghauch A, Deveau P, Jacob V, et al. Use of FTIR spectroscopy coupled with ATR for the determination of atmospheric compounds[J]. Talanta, 2006,68(4):1294-1302. [52] Zhang T, Shen Z, Huang S, et al. Optical properties, molecular characterizations, and oxidative potentials of different polarity levels of water-soluble organic matters in winter PM2.5 in six China's megacities[J]. Science of the Total Environment, 2022,853:158600. [53] Cao J J, Wu F, Chow J C, et al. Characterization and source apportionment of atmospheric organic and elemental carbon during fall and winter of 2003 in Xi'an, China[J]. Atmospheric Chemistry and Physics, 2005,5(11):3127-3137. [54] Demir T, Karakaş D, Yenisoy Karakaş S. Source identification of exhaust and non-exhaust traffic emissions through the elemental carbon fractions and Positive Matrix Factorization method[J]. Environmental Research, 2022,204:112399. [55] 李小飞,余锋,赵纾樱,等.大气棕色碳来源与光学特征研究进展[J].陕西科技大学学报, 2022,40(5):38-53. Li X, Yu F, Zhao S, et al. An overview of studies on sources and optical properties of atmospheric brown carbon[J]. Journal of Shaanxi University of Science& Technology, 2022,40(5):38-53. [56] Huo Y, Guo Z, Li Q, et al. Chemical fingerprinting of HULIS in particulate matters emitted from residential coal and biomass combustion[J]. Environmental Science& Technology, 2021,55(6):3593-3603. [57] Tang J, Li J, Su T, et al. Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation-emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis[J]. Atmos Chem Phys, 2020,20(4):2513-2532. [58] Tang J, Li J, Mo Y, et al. Light absorption and emissions inventory of humic-like substances from simulated rainforest biomass burning in Southeast Asia[J]. Environmental Pollution, 2020,262:114266. [59] Voliotis A, Prokeš R, Lammel G, et al. New insights on humic-like substances associated with wintertime urban aerosols from central and southern Europe:Size-resolved chemical characterization and optical properties[J]. Atmospheric Environment, 2017,166:286-299.
