典型生物质燃烧排放酚类有机物的大气液相氧化动力学

雷若媛; 刘雨; 虞婉宁; 缪静秋; 盖鑫磊

doi:10.13205/j.hjgc.202209007

典型生物质燃烧排放酚类有机物的大气液相氧化动力学

doi: 10.13205/j.hjgc.202209007

南京信息工程大学环境科学与工程学院江苏省大气环境监测与污染控制高技术研究重点实验室, 南京 210044

基金项目:

国家自然科学基金项目(21976093,42021004)

详细信息

作者简介:
雷若媛(1999-),女,博士,主要研究方向为大气二次有机气溶胶的液相氧化动力学、生成机制及其毒理效应。ruoyuan_lei@163.com

通讯作者:
盖鑫磊(1982-),男,教授,主要研究方向为大气环境化学与大气污染防治。caxinra@163.com

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出版历程
- 收稿日期: 2022-01-17
- 网络出版日期: 2022-11-09

KINETICS OF ATMOSPHERIC AQUEOUS-PHASE OXIDATION OF REPRESENTATIVE PHENOLIC COMPOUNDS EMITTED FROM BIOMASS BURNING

Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, China

摘要

摘要: 生物质燃烧排放有机物是大气二次有机气溶胶(SOA)的重要前体物,但相关反应参数仍较为匮乏。选择其中4种代表性物质,间苯二酚(RES)、4-乙基苯酚(4-EP)、丁香酚(Eug)和2,4,6-三甲基苯酚(Trmp),利用相对速率法测定了其与·OH在液相(云雾条件)中的二级反应动力学参数,并估算了其在实际大气条件下的液相反应寿命。在pH=5.4,T=298 K条件下,测定以上4种前体物液相氧化的二级动力学常数(K)分别为(7.68±0.04)×10⁹,(18.12±0.56)×10⁹,(23.11±0.60)×10⁹,(16.90±0.58)×10⁹ L/(mol·s),所得到的K值不确定性为3.5%~12%。此外,还测定了体系在T=293,288 K时的K值,发现288 K时的K值比298 K时的低了22%~38%,说明温度对于酚类液相反应的双分子速率常数有一定影响。研究还发现,反应过程中前体物浓度为初始值1/2时,pH降低,说明反应过程中可能生成一定量的有机酸;这些化合物在不同情境下使用CAPRAM 3.0多相机制计算得到的大气寿命在数十秒到数十小时之间,进一步说明生物质燃烧排放酚类化合物对SOA的生成贡献值得重视。
- 二次有机气溶胶 /
- VOCs/IVOCs /
- 酚类化合物 /
- 液相光氧化 /
- 二级动力学常数
Abstract: The organic compounds emitted from biomass burning are important precursors of atmospheric secondary organic aerosols, but relevant reaction parameters are still relatively lacking. This study selected four representative species, including resorcinol(RES), 4-ethylphenol(4-EP), eugenol(Eug) and 2,4,6-trimethylphenol(Trmp), and used the relative rate method to determine the second-order reaction rate constants of those species against oxidation by the hydroxyl radical in the atmospheric aqueous-phases(such as conditions of fog/cloud droplets), also estimated the liquid phase reaction life under actual atmospheric conditions. The kinetic constants(K) of the four precursors at 298 K, pH=5.4 were(7.68±0.04)×10⁹ L/(mol·s),(18.12±0.56)×10⁹ L/(mol·s),(23.11±0.60)×10⁹ L/(mol·s) and(16.90±0.58)×10⁹ L/(mol·s), respectively. The uncertainties of K values were 3.5%~12%. In addition, the K value at T=293 K and 288 K were also determined, and the values at 288 K were 22%~38% lower than those at 298 K, indicating that temperature had a significant influence on the bimolecular rate constants of those compounds. It was also found that when the precursor was consumed nearly half, the solution pH decreased, suggesting that a certain number of organic acids might be generated during oxidation. The atmospheric lifetimes calculated according to the CAPRAM 3.0 under different scenarios ranged from tens of seconds to tens of hours, indicating that the aqueous-phase oxidation of biomass burning emitted phenolic species had a considerable impact on the secondary organic aerosol formation.
- secondary organic aerosol /
- VOCs/IVOCs /
- phenolic compounds /
- aqueous phase photooxidation /
- kinetic constant

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参考文献(52)

[1]	ZHAO Y,HENNIGAN C J,MAY A A,et al.Intermediate-volatility organic compounds:a large source of secondary organic aerosol[J].Environmental Science & Technology,2014,48(23):13743-13750.
[2]	ERVENS B,TURPIN B J,WEBER R J.Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA):a review of laboratory,field and model studies[J].Atmospheric Chemistry and Physics,2011,11(21):11069-11102.
[3]	YU L,SMITH J,LASKIN A,et al.Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical[J].Atmospheric Chemistry and Physics,2014,14(24):13801-13816.
[4]	YE Z L,QU Z X,MA S S,et al.A comprehensive investigation of aqueous-phase photochemical oxidation of 4-ethylphenol[J].Science of the Total Environment,2019,685(OCT.1):976-985.
[5]	SMITH J D,KINNEY H,ANASTASIO C.Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol[J].Physical Chemistry Chemical Physics,2015,17(15):10227-10237.
[6]	YE Z L,ZHUANG Y,CHEN Y,et al.Aqueous-phase oxidation of three phenolic compounds by hydroxyl radical:insight into secondary organic aerosol formation yields,mechanisms,products and optical properties[J].Atmospheric Environment,2020,223:117240.
[7]	LIU Y,LU J C,CHEN Y F,et al.Aqueous-phase production of secondary organic aerosols from oxidation of dibenzothiophene (DBT)[J].Atmosphere,2020,11(2):151.
[8]	ALVES C A,VICENTE A,MONTEIRO C,et al.Emission of trace gases and organic components in smoke particles from a wildfire in a mixed-evergreen forest in Portugal[J].Science of the Total Environment,2011,409(8):1466-1475.
[9]	HATCH L E,LUO W,PANKOW J F,et al.Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography-time-of-flight mass spectrometry[J].Atmospheric Chemistry and Physics,2015,15(4):1865-1899.
[10]	ROMONOSKY D E,LASKIN A,LASKIN J,et al.High-resolution mass spectrometry and molecular characterization of aqueous photochemistry products of common types of secondary organic aerosols[J].The Journal of Physical Chemistry A,2015,119(11):2594-2606.
[11]	LI G H,ZHANG Q Q,ZHUANG W H,et al.Divergent synthesis of oxacyclophenylpropanoids from biomass-derived eugenol[J].Tetrahedron Letters,2019,60(22):1501-1504.
[12]	SCHAUER J J,KLEEMAN M J,CASS G R,et al.Measurement of emissions from air pollution sources.3.C1-C29 organic compounds from fireplace combustion of wood[J].Environmental Science & Technology,2001,35(9):1716-1728.
[13]	ZHANG H X,YANG B,WANG Y F,et al.Gas-phase reactions of methoxyphenols with NO₃ radicals:kinetics,products,and mechanisms[J].The Journal of Physical Chemistry A,2016,120(8):1213-1221.
[14]	BEJAN I,SCHÜRMANN A,BARNES I,et al.Kinetics of the gas-phase reactions of OH radicals with a series of trimethylphenols[J].International Journal of Chemical Kinetics,2012,44(2):117-124.
[15]	HENNIGAN C J,BERGIN M H,DIBB J E,et al.Enhanced secondary organic aerosol formation due to water uptake by fine particles[J].Geophysical Research Letters,2008,35(18):L18801.
[16]	CHEN H,GE X L,YE Z L.Aqueous-phase secondary organic aerosol formation via reactions with organic triplet excited states:a short review[J].Current Pollution Reports,2018,4(1):8-12.
[17]	CHEN Y T,LI N W,LI X D,et al.Secondary organic aerosol formation from ³C*-initiated oxidation of 4-ethylguaiacol in atmospheric aqueous-phase[J].Science of the Total Environment,2020,723:137953.
[18]	HENNIGAN C J,BERGIN M H,RUSSELL A G,et al.Gas/particle partitioning of water-soluble organic aerosol in Atlanta[J].Atmospheric Chemistry and Physics,2009,9(11):3613-3628.
[19]	ANASTASIO C,FAUST B C,ALLEN J M.Aqueous phase photochemical formation of hydrogen peroxide in authentic cloud waters[J].Journal of Geophysical Research,1994,99:8231-8248.
[20]	HERRMANN H,TILGNER A,BARZAGHI P,et al.Towards a more detailed description of tropospheric aqueous phase organic chemistry:CAPRAM 3.0[J].Atmospheric Environment,2005,39(23/24):4351-4363.
[21]	LERICHE M,VOISIN D,CHAUMERLIAC N,et al.A model for tropospheric multiphase chemistry:application to one cloudy event during the CIME experiment[J].Atmospheric Environment,2000,34(29/30):5015-5036.
[22]	TILGNER A,HERRMANN H.Radical-driven carbonyl-to-acid conversion and acid degradation in tropospheric aqueous systems studied by CAPRAM[J].Atmospheric Environment,2010,44(40):5415-5422.
[23]	DEGUILLAUME L,LERICHE M,MONOD A,et al.The role of transition metal ions on HO_x radicals in clouds:a numerical evaluation of its impact on multiphase chemistry[J].Atmospheric Chemistry & Physics,2004,4(1):95-110.
[24]	RICHARDS-HENDERSON N K,HANSEL A K,VALSARAJ K T,et al.Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA:kinetics and SOA yields[J].Atmospheric Environment,2014,95:105-112.
[25]	WITKOWSKI B,GIERCZAK T.cis-Pinonic acid oxidation by hydroxyl radicals in the aqueous phase under acidic and basic conditions:kinetics and mechanism[J].Environmental Science & Technology,2017,51(17):9765-9773.
[26]	CHU L,ANASTASIO C.Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide[J].Journal of Physical Chemistry A,2005,109(28):6264-6271.
[27]	ANASTASIO C,MCGREGOR K G.Chemistry of fog waters in California’s Central Valley:1.In situ photoformation of hydroxyl radical and singlet molecular oxygen[J].Atmospheric Environment,2001,35(6):1079-1089.
[28]	YU L,SMITH J,LASKIN A,et al.Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical[J].Atmospheric Chemistry and Physics,2014,14(24):13801-13816.
[29]	ANASTASIO C,FAUST B C,ALLEN J M.Aqueous phase photochemical formation of hydrogen peroxide in authentic cloud waters[J].Journal of Geophysical Research Atmospheres,1994,99(D4):8231-8248.
[30]	SCHONE L,SCHINDELKA J,SZEREMETA E,et al.Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein,methyl vinyl ketone,methacrylic acid and acrylic acid--kinetics and product studies[J].Physical Chemistry Chemical Physics:PCCP,2014,16(13):6257-6272.
[31]	OTTO T,STIEGER B,METTKE P,et al.Tropospheric aqueous-phase oxidation of isoprene-derived dihydroxycarbonyl compounds[J].The Journal of Physical Chemistry A,2017,121(34):6460-6470.
[32]	WITKOWSKI B,AL-SHARAFI M,GIERCZAK T.Kinetics and products of the aqueous-phase oxidation of β-caryophyllonic acid by hydroxyl radicals[J].Atmospheric Environment,2019,213:231-238.
[33]	BUXTON G V,GREENSTOCK C L,HELMAN W P,et al.Critical Review of rate constants for reactions of hydrated electrons,hydrogen atoms and hydroxyl radicals (·OH/·O- in aqueous solution[J].Journal of Physical and Chemical Reference Data,1988,17(2):513-886.
[34]	HERRMANN H,HOFFMANN D,SCHAEFER T,et al.Tropospheric aqueous-phase free-radical chemistry:radical sources,spectra,reaction kinetics and prediction tools[J].ChemPhysChem,2010,11(18):3796-3822.
[35]	FANG T,LAKEY P S J,RIVERA-RIOS J C,et al.Aqueous-phase decomposition of isoprene hydroxy hydroperoxide and hydroxyl radical formation by fenton-like reactions with iron ions[J].The Journal of Physical Chemistry A,2020,124(25):5230-5236.
[36]	WANG Y,ZHAO J,LIU H H,et al.Photooxidation of methacrolein in Fe(Ⅲ)-oxalate aqueous system and its atmospheric implication[J].Advances in Atmospheric Sciences 2021,38(7):1252-1263.
[37]	LIU Y,HADDAD I E,SCARFOGLIERO M,et al.In-cloud processes of methacrolein under simulated conditions-Part 1:aqueous phase photooxidation[J].Atmospheric Chemistry and Physics,2009,9:5093-5105.
[38]	SARANG K,OTTO T,RUDZINSKI K,et al.Reaction kinetics of green leaf volatiles with sulfate,hydroxyl,and nitrate radicals in tropospheric aqueous phase[J].Environmental Science & Technology,2021,55(20):13666-13676.
[39]	ABICHANDANI B C T,JATKAR S K K.Dissociation constants of ortho-,meta and para-hydroxy benzoic acids,gallic acid,catechol,resorcinol,hydroquinone,pyrogallol and phloroglucinol[J].Journal of the Indian Institute of Science,1938,21:417.
[40]	HANAI T,KOIZUMI K,KINOSHITA T,et al.Prediction of pKa values of phenolic and nitrogen-containing compounds by computational chemical analysis compared to those measured by liquid chromatography[J].Journal of Chromatography A,1997,762(1/2):55-61.
[41]	HANAI T.Simulation of chromatography of phenolic compounds with a computational chemical method[J].Journal of Chromatography A,2004,1027(1/2):279-287.
[42]	LIU H X,YANG G L,WANG D X,et al.Determination of dissociation constants of complicated compounds by capillary zone electrophoresis[J].Chinese Journal of Chemistry,2001,19(7):675-680.
[43]	SHI G L,XU J,PENG X,et al.pH of aerosols in a polluted atmosphere:source contributions to highly acidic aerosol[J].Environmental Science & Technology,2017,51(8):4289-4296.
[44]	SONG S J,GAO M,XU W Q,et al.Fine-particle pH for Beijing winter haze as inferred from different thermodynamic equilibrium models[J].Atmospheric Chemistry and Physics,2018,18(10):7423-7438.
[45]	SMITH J D,KINNEY H,ANASTASIO C.Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol[J].Physical Chemistry Chemical Physics,2015,17(15):10227-10237.
[46]	HEATH A A,EHRENHAUSER F S,VALSARAJ K T.Effects of temperature,oxygen level,ionic strength,and pH on the reaction of benzene with hydroxyl radicals in aqueous atmospheric systems[J].Journal of Environmental Chemical Engineering,2013,1(4):822-830.
[47]	LAND E,EBERT M.Pulse radiolysis studies of aqueous phenol.Water elimination from dihydroxycyclohexadienyl radicals to form phenoxyl[J].Transactions of the Faraday Society,1967,63:1181-1190.
[48]	ABELLAR K A,COPE J D,NGUYEN T B.Second-order kinetic rate coefficients for the aqueous-phase hydroxyl radical (OH) oxidation of isoprene-derived secondary organic aerosol compounds at 298 K[J].Environmental Science & Technology,2021,55(20):13728-13736.
[49]	OTTO T,SCHAEFER T,HERRMANN H.Aqueous-phase oxidation of terpene-derived acids by atmospherically relevant radicals[J].The Journal of Physical Chemistry A,2018,122(47):9233-9241.
[50]	HERRMANN H,SCHAEFER T,TILGNER A,et al.Tropospheric aqueous-phase chemistry:kinetics,mechanisms,and its coupling to a changing gas phase[J].Chemical Reviews,2015,115(10):4259-4334.
[51]	PERCIVAL C,MCGILLEN M.Overview of Structure-Activity Relationship Methods for Predicting Gas-Phase Rate Coefficients[M].Springer Netherlands,2008:47-59.
[52]	FINEWAX Z,de GOUW J A,ZIEMANN P J.Products and secondary organic aerosol yields from the OH and NO₃ radical-initiated oxidation of resorcinol[J].ACS Earth and Space Chemistry,2019,3(7):1248-1259.