生物质燃烧源类腐殖质的臭氧老化特征

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摘要针对生物质燃烧排放类腐殖质（BC-HULIS）的臭氧（O₃）氧化开展模拟研究，利用总有机碳分析仪（TOC）、紫外-可见吸收光谱（UV-vis）、荧光激发发射矩阵光谱结合平行因子分析（EEM-PARAFAC）以及傅里叶变换红外光谱（FTIR）表征老化前后HULIS的光学性质和化学结构变化.研究表明，经臭氧氧化后BC-HULIS占相应的水溶性有机碳（WSOC）的比例降低，表明部分HULIS发生降解生成水溶性小分子化合物.此外经O₃老化后，HULIS的质量吸收指数（MAE₃₆₅）和芳香性指数（SUVA₂₅₄）分别从1.8~2.7和4.2~5.0m²/gC下降到1.1~1.3和3.7~4.1m²/gC，表明老化后HULIS的吸光能力和芳香度均呈现降低.EEM-PARAFAC解析结果显示，BB-HULIS中荧光发色团主要由类蛋白荧光组分（C2）和类腐殖质荧光组分（C1、C3、C4）组成.O₃老化后，BB-HULIS的总荧光强度显著降低，两种性质的荧光组分相对含量和荧光参数发生显著变化，如老化后HULIS中类腐殖质荧光组分的相对含量和腐质化指数（HIX）均显著高于老化前样品，表明老化过程发生类蛋白的降解和类腐殖质的聚合.另外，FTIR分析结果显示O₃老化后含氧官能团含量显著增强，表明了O₃老化对HULIS官能团的影响.

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关键词 ：生物质燃烧, 类腐殖质, 臭氧氧化, 光学性质, 化学结构

Abstract：Biomass combustion (BC) is an important source of humic-like substances (HULIS) in atmospheric aerosol, and the oxidation process has a significant impact on the optical properties and chemical structures of BC-HULIS. This study focused on the changes in primary BB-HULIS due to ozone (O₃) oxidation and the optical properties and chemical structure of HULIS before and after oxidation were characterized with the total organic carbon (TOC) analyzer, UV-Vis spectroscopy, Excitation-Emission Matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform infrared spectroscopy (FTIR). The results showed that the relative contents of HULIS in the corresponding water-soluble organic carbon (WSOC) decreased with O₃ oxidation, suggesting the transformation of HULIS into water-soluble low molecular weight compounds. Furthermore, mass absorption efficiency (MAE₃₆₅) and aromatic index (SUVA₂₅₄) of HULIS decreased from 1.8~2.7m²/gC and 4.2~5.0m²/gC to 1.1~1.3m²/gC and 3.7~4.1m²/gC, respectively, indicating that both the absorption capacity and aromaticity of HULIS declined with O₃ oxidation. The fluorescent components in BC-HULIS were mainly composed of protein-like compounds (C2) and humic-like substances (C1, C3, C4). After O₃ oxidation, the total fluorescence intensities of BC-HULIS weakened greatly, and the relative contribution of two types of fluorophores and fluorescence index were all significantly changed. For instances, the relative contents of humic-like components and the humidification index (HIX) of BC-HULIS after O₃ oxidation were obviously higher than those before O₃ oxidation, suggesting the degradation of protein-like compounds and the aggregation of humic-like substances during the O₃ oxidation process. In addition, FTIR results showed that the oxygen-containing functional groups were markedly enhanced after O₃ oxidation, indicating effects of O₃ oxidation on the chemical functional groups of BC-HULIS.

Key words： biomass burning HULIS ozone oxidation optical properties chemical structure

收稿日期: 2022-01-17

PACS:

X513

基金资助:国家自然科学基金资助项目（41977188）；有机地球化学国家重点实验室开放基金资助项目（SKLOG202101）；安徽省自然科学基金资助项目（2108085MD140）

通讯作者: 范行军,副教授,fanxj@ahstu.edu.cn E-mail: fanxj@ahstu.edu.cn

作者简介: 操涛(1995-)男,安徽安庆人,中国科学院广州地球化学研究所博士研究生,主要从事生物质和煤燃烧排放棕色碳等吸光性物质的研究.发表论文1篇.

引用本文:

操涛, 宋建中, 范行军. 生物质燃烧源类腐殖质的臭氧老化特征[J]. 中国环境科学, 2022, 42(8): 3483-3491. CAO Tao, SONG Jian-zhong, FAN Xing-jun. Changes in optical properties and chemical functional groups of humic substances emitted from biomass combustion with O₃ oxidation. CHINA ENVIRONMENTAL SCIENCECE, 2022, 42(8): 3483-3491.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2022/V42/I8/3483

[1]	Fan X J, Wei S Y, Zhu M B, 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.
[2]	Graber E R, Rudich Y. Atmospheric HULIS:How humic-like are they? A comprehensive and critical review[J]. Atmospheric Chemistry and Physics, 2006,6:729-753.
[3]	Zheng G, He K, Duan F, et al. Measurement of humic-like substances in aerosols:a review[J]. Environmental Pollution, 2013,181:301-14.
[4]	Katsumi N, Miyake S, Okochi H, et al. Humic-like substances global levels and extraction methods in aerosols[J]. Environmental Chemistry Letters, 2018,17(2):1023-1029.
[5]	Laskin A, Laskin J, Nizkorodov S A. Chemistry of Atmospheric Brown Carbon[J]. Chemical Reviews, 2015,115:4335-4382.
[6]	Xu X Y, Lu X H, 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.
[7]	Lin P, Yu J Z. Generation of reactive oxygen species mediated by humic-like substances in atmospheric aerosols[J]. Environmental Science & Technology, 2011,45(24):10362-10368.
[8]	Park S S, Yu J. Chemical and light absorption properties of humic-like substances from biomass burning emissions under controlled combustion experiments[J]. Atmospheric Environment, 2016,136:114-122.
[9]	Fan X J, Li M J, Cao T, et al. Optical properties and oxidative potential of water-and alkaline-soluble brown carbon in smoke particles emitted from laboratory simulated biomass burning[J]. Atmospheric Environment, 2018,194:48-57.
[10]	Li M J, Fan X J, Zhu M B, et al. Abundances and light absorption properties of brown carbon emitted from residential coal combustion in China[J]. Environmental Science & Technology, 2019,53:595-603.
[11]	Tang S S, Li F H, 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.
[12]	Tsui W G, McNeill V F. Modeling secondary organic aerosol production from photosensitized Humic-like substances (HULIS)[J]. Environmental Science & Technology Letters, 2018,5(5):255-259.
[13]	郭子雍,阳宇翔,彭龙,等.广州地区不同粒径段大气颗粒物中水溶性有机碳的吸光贡献[J]. 中国环境科学, 2021,41(2):497-504 Guo Z Y, Yang Y X, Peng L, et al. The size-resolved light absorption contribution of water soluble organic carbon in the atmosphere of Guangzhou[J]. China Environmental Science, 2021,41(2):497-504.
[14]	Huo Y Q, Li M, Jiang M H, et al. Light absorption properties of HULIS in primary particulate matter produced by crop straw combustion under different moisture contents and stacking modes[J]. Atmospheric Environment, 2018,191:490-499.
[15]	Pillar E A, Camm R C, Guzman M I. Catechol oxidation by ozone and hydroxyl radicals at the air-water interface[J]. Environmental Science & Technology, 2014,48:14352-14360.
[16]	Pillar E A, Zhou R X, Guzman M I, Heterogeneous oxidation of catechol[J]. The Journal of Physical Chemistry A, 2015,119(41):10349-59.
[17]	Vione D, Albinet A, Barsotti F, et al. Formation of substances with humic-like fluorescence properties, upon photoinduced oligomerization of typical phenolic compounds emitted by biomass burning[J]. Atmospheric Environment, 2019,206:197-207.
[18]	Fan X J, Cao T, Yu X F, et al. The evolutionary behavior of chromophoric brown carbon during ozone aging of fine particles from biomass burning[J]. Atmospheric Chemistry and Physics, 2020,20(8):4593-4605.
[19]	Song J Z, Li M J, Jiang B, et al. Molecular characterization of water-soluble Humic-like substances in smoke particles emitted from combustion of biomass materials and coal using ultrahigh-resolution electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Environmental Science & Technology, 2018,52(5):2575-2585.
[20]	范行军,操涛,余旭芳,等.薪柴燃烧溶解性棕色碳排放特征及光学性质[J]. 中国环境科学, 2019,39(8):3215-3224. Fan X J, Cao T, Yu X F, et al. Emission characteristics and optical properties of extractable brown carbon from residential wood combustion[J]. China Environmental Science, 2019,39(8):3215-3224.
[21]	Murphy K R, Stedmon C A, Graeber D, et al. Fluorescence spectroscopy and multi-way techniques. PARAFAC[J]. Analytical Methods, 2013,5(23):6557.
[22]	Stedmon C A, Bro R. Characterizing dissolved organic matter fluorescence with parallel factor analysis:a tutorial[J]. Limnology and Oceanography-Methods, 2008,6:572-579.
[23]	Matos J T V, Freire S M S C, Duarte R M B O, et al. Natural organic matter in urban aerosols:Comparison between water and alkaline soluble components using excitation-emission matrix fluorescence spectroscopy and multiway data analysis[J]. Atmospheric Environment, 2015,102:1-10.
[24]	Qin J J, Zhang L M, Zhou X M, et al. Fluorescence fingerprinting properties for exploring water-soluble organic compounds in PM2.5 in an industrial city of northwest China[J]. Atmospheric Environment, 2018,184:203-211.
[25]	Zhu J L, Chen Y Y, Shang J, et al. Effects of air/fuel ratio and ozone aging on physicochemical properties and oxidative potential of soot particles[J]. Chemosphere, 2019,220:883-891.
[26]	D'Anna B, Jammoul A, George C, et al. Light-induced ozone depletion by humic acid films and submicron aerosol particles[J]. Journal of Geophysical Research-Atmospheres, 2009,114:D12301.
[27]	Salma I, Ocskay R, Lang G G. Properties of atmospheric humic-like substances-water system[J]. Atmospheric Chemistry and Physics, 2008,8(8):2243-2254.
[28]	Wong J P S, Nenes A, Weber R J. Changes in light absorptivity of molecular weight separated brown carbon due to photolytic aging[J]. Environmental Science & Technology, 2017,51(15):8414-8421.
[29]	Liu D, Li S, Hu D, et al. Evolution of aerosol optical properties from wood smoke in real atmosphere influenced by burning phase and solar radiation[J]. Environmental Science & Technology, 2021,55:5677-5688.
[30]	Saleh R, Hennigan C J, McMeeking G R, et al. Absorptivity of brown carbon in fresh and photo-chemically aged biomass-burning emissions[J]. Atmospheric Chemistry and Physics, 2013,13(15):7683-7693.
[31]	Wu H, Taylor J W, Langridge J M, et al. Rapid transformation of ambient absorbing aerosols from West African biomass burning[J]. Atmospheric Chemistry and Physics, 2021,21:9417-9440.
[32]	Forrister H, Liu J, Scheuer E, et al. Evolution of brown carbon in wildfire plumes[J]. Geophysical Research Letter, 2015,42:4623-4630.
[33]	Dinar E, Taraniuk I, Graber E R, et al. Cloud condensation nuclei properties of model and atmospheric HULIS[J]. Atmospheric Chemistry and Physics, 2006,6:2465-2481.
[34]	Chin Y P, Aiken G, O'Loughlin E. Molecular-weight, polydispersity, and spectroscopic properties of aquatic Humic-like substances[J]. Environmental Science & Technology, 1994,28(11):1853-1858.
[35]	Mostofa K M G, Wu F C, Liu C Q, et al. Photochemical, microbial and metal complexation behavior of fluorescent dissolved organic matter in the aquatic environments[J]. Geochemical Journal, 2011,45(3):235-254.
[36]	Chen Q C, Ikemori F, Mochida M. Light absorption and excitation-emission fluorescence of urban organic aerosol components and their relationship to chemical structure[J]. Environmental Science & Technology, 2016,50(20):10859-10868.
[37]	Chen Q C, Hua X Y, Dyussenova A. Evolution of the chromophore aerosols and its driving factors in summertime Xi'an, Northwest China[J]. Chemosphere, 2021,281:130838.
[38]	Mu Z, Chen Q C, Zhang L X, et al. Photodegradation of atmospheric chromophores:changes in oxidation state and photochemical reactivity[J]. Atmospheric Chemistry and Physics, 2021,21:11581-11591.
[39]	Tang J, Wang J Q, Zhong G C, et al. Long-emission-wavelength chromophores dominate the light absorption of brown carbon in aerosols over Bangkok:impact from biomass burning[J]. Atmospheric Chemistry and Physics, 2021,21:11337-11352.
[40]	Cottrell B A, Cheng W R, Lam B, et al. An enhanced capillary electrophoresis method for characterizing natural organic matter[J]. Analyst, 2013,138(4):1174-1179.
[41]	Kumar V, Goel A, Rajput P. Compositional and surface characterization of HULIS by UV-Vis, FTIR, NMR and XPS:Wintertime study in Northern India[J]. Atmospheric Environment, 2017,164:468-475.
[42]	叶招莲,瞿珍秀,马帅帅,等.气溶胶水相反应生成二次有机气溶胶研究进展[J]. 环境科学, 2018,39(8):3954-3964. Ye Z L, Qu Z X, Ma S S, et al. Secondary organic aerosols from aqueous reaction of aerosol water[J]. Environmental Science, 2018,39(8):3954-3964.
[43]	肖瑶,吴志军,郭松,等.大气气溶胶液态水中二次有机气溶胶生成机制研究进展[J]. 科学通报, 2020,32(5):627-641. Xiao Y, Wu Z J, Guo S, et al. Formation mechanism of secondary organic aerosol in aerosol liquid water:A review[J]. Chinese Science Bulletin, 2020,32(5):627-641.
[44]	王玉钰,胡敏,李晓,等.大气颗粒物中棕色碳的化学组成、来源和生成机制[J]. 化学进展, 2020,32(5):627-641. Wang Y J, Hu M, Li X, et al. Chemical composition, sources and formation mechanisms of particulate brown carbon in the atmosphere[J]. Progress in Chemistry, 2020,32(5):627~641.