Hydrogen peroxide photoproduction by humic substances and their model compounds
LI Jian-hua1, ZHANG Ya2, WU Xin-an3, WANG Meng-jie3, SHI Qin-ren3, PENG Jian-biao4, GAO Shi-xiang3
1. Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China; 2. Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environmental of the People's Republic of China, Nanjing 210042, China; 3. State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China; 4. School of Environment, Henan Normal University, Key Laboratory for Yellow River and Huai River Water Environmental and Pollution Control, Ministry of Education, Henan Key Laboratory for Environmental Pollution Control, Xinxiang 453007, China
Abstract：The present study systematically investigated H2O2 generation kinetics and potential mechanism from irradiated humic substances (HS) and their model compounds under simulated sunlight. Our results indicated that all the selected HS with different sources or forms can produce H2O2 under irradiation, and no significant difference was observed between them, with the generation rate ranging from 6.379 to 15.784nmol/(L·min). The H2O2 generation rate from humic acid (HA) was slightly faster than that from fulvic acid (FA). In the case of humus model compounds, 7compounds including veratryl alcohol, p-aminobenzoic acid, 3,5-dihydroxybenzoic acid (DHBA), 2,5-dihydroxy-1,4-benzoquinone, phenol, benzoic acid and aniline could produce detectable H2O2, while other compounds including catechol, resorcinol, hydroquinone, quinone, o-anisidine, p-anisidine, salicylic acid and 2,6-dimethoxy-1,4-benzoquinone can't. Nevertheless, the H2O2 generation rate from the model compounds varies from each other, with one or two orders of magnitude. Among them, 2,5-dihydroxyl-1,4-benquione and DHBA exhibited the highest H2O2 yields, while phenol, benzoic and p-aminobenzoic acid showed a relative low H2O2 generation potential. Based on the generation mechanism of H2O2 from HS, a possible H2O2 formation mechanism from a typical model compound, i.e. DHBA, was proposed. DHBA was believed to excite to a singlet state, after an intramolecular electron transfer process, giving a reducing intermediate. The intermediate could further react with O2 to form O2·- and subsequently generate H2O2.
李建华, 张亚, 吴欣安, 王梦杰, 施沁人, 彭建彪, 高士祥. 腐殖质及其模型化合物的H2O2光化学生成研究[J]. 中国环境科学, 2020, 40(12): 5337-5342.
LI Jian-hua, ZHANG Ya, WU Xin-an, WANG Meng-jie, SHI Qin-ren, PENG Jian-biao, GAO Shi-xiang. Hydrogen peroxide photoproduction by humic substances and their model compounds. CHINA ENVIRONMENTAL SCIENCECE, 2020, 40(12): 5337-5342.
Garg S, Rose A L, Waite T D. Production of reactive oxygen species on photolysis of dilute aqueous quinone solutions[J]. Photochemistry and Photobiology, 2007,83:904-913.
[2]
Moffett J W, Zika R G. Reaction kinetics of hydrogen peroxide with copper and iron in seawater[J]. Environmental Science & Technology, 1987,21:804-810.
[3]
Rose A L, Waite T D. Role of superoxide in the photochemical reduction of iron in seawater[J]. Geochimica et Cosmochimica Acta, 2006,70:3869-3882.
[4]
Clark C D, de Bruyn W J, Jakubowski S D, et al. Hydrogen peroxide production in marine bathing waters:implications for fecal indicator bacteria mortality[J]. Marine Pollution Bulletin, 2008,56:397-401.
[5]
Clark C D, De Bruyn W J, Jones J G. Photochemical production of hydrogen peroxide in size-fractionated southern California coastal waters[J]. Chemosphere, 2009,76:141-146.
[6]
Scully N M, Lean D, McQueen D, et al. Photochemical formation of hydrogen peroxide in lakes:effects of dissolved organic carbon and ultraviolet radiation[J]. Canadian Journal of Fisheries and Aquatic Sciences, 1995,52:2675-2681.
[7]
Helz G R, Zepp R G, Crosby D G. Aquatic and surface photochemistry[M]. Lewis Publishers, 1994:111-127.
[8]
Cooper W, Zika R, Pestasne R, et al. Photochemical formation of H2O2in natural waters exposed to sunlight[J]. Environmental Science & Technology, 1988,22:1156-1160.
[9]
Garg S, Rose A, Waite T. Photochemical production of superoxide and hydrogen peroxide from natural organic matter[J]. Geochimica et Cosmochimica Acta, 2011,75:4310-4320.
[10]
Kavins M, Purmalis O. Humic substances as surfactants[J]. Environmental Chemistry Letters, 2010,8:349-354.
[11]
Rehm H J, Reed G. "Humification" Process or Formation of Refractory Soil Organic Matter[J]. Wiley-VCH Verlag GmbH, 2000:90-125.
[12]
Park J, Dec J, Kim J, et al. Effect of humic constituents on the transformation of chlorinated phenols and anilines in the presence of oxidoreductive enzymes of birnessite[J]. Environmental Science & Technology, 1999,33:2028-2034.
[13]
Montero L, Conradi S, Weiss H, et al. Determination of phenols in lake and ground water samples by stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry[J]. Journal of Chromatography A, 2005,1071:163-169.
[14]
Davi M, Gnudi F. Phenolic compounds in surface water[J]. Water Research, 1999,33:3213-3219.
[15]
Rosarioortiz F L, Canonica S. Probe compounds to assess the photochemical activity of dissolved organic matter[J]. Environmental Science & Technology, 2016,50:12532-12547.
[16]
Clark C, De Bruyn W, Jones J. Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)[J]. Marine Pollution Bulletin, 2014,79:54-60.
[17]
Klassen N, Marchington D, McGowan H. H2O2Determination by the I3- method and by KMnO4titration[J]. Analytical Chemistry, 1994, 66:2921-5.
[18]
Wang M J, Li J H, Shi H H, et al. Photolysis of atorvastatin in aquatic environment:Influencing factors, products, and pathways[J]. Chemosphere, 2018,212:467-475.
[19]
Zhou L, Zhang Y, Wang Q, et al. Photochemical behavior of carbon nanotubes in natural waters:reactive oxygen species production and effects on·OH generation by Suwannee river fulvic acid, nitrate, and Fe (Ⅲ)[J]. Environmental Science and Pollution Research, 2016,23:19520-19528.
[20]
Nosaka Y, Nosaka, A Y. Generation and detection of reactive oxygen species in photocatalysis[J]. Chemical Review, 2017,117:11302-11336.
[21]
Zhang Y, Vecchio R, Blough N. Investigating the mechanism of hydrogen peroxide photoproduction by humic substances[J]. Environmental Science & Technology, 2012,46:11836-11843.
[22]
Clark C, Bruyn W, Hirsch D, et al. Hydrogen peroxide measurements in recreational marine bathing waters in Southern California, USA[J]. Water Research, 2010,44:2203-2210.
[23]
Plane J M C, Blough N V, Ehrhardt M G, et al. Photochemistry in the sea-surface microlayer[M]. 1997:383-424.
[24]
Valentine J. Active oxygen in chemistry[M]. Springer Netherlands, 2013:280-333.
[25]
Petasne R, Zika R. Fate of superoxide in coastal sea water[J]. Nature. 1987,325(6104):516-518.
[26]
Ren D, Wang T, Chen F, et al. Effect of sodium hypochlorite on the structural and optical characteristics of humic acid in waters[J]. China Environmental Science, 2018,38(6):2264-2272.
[27]
Ren D, Yang X X, Ma X D, et al. Structural characteristics of DOM and its effects on the photodegradation of 17β-estradiol. China Environmental Science, 2015,35(5):1375-1383.
[28]
Suominen K, Kitunen V, Smolander A. Characteristics of dissolved organic matter and phenolic compounds in forest soils under silver birch (Betula pendula), Norway spruce (Picea abies) and Scots pine (Pinus sylvestris)[J]. European Journal of Soil Science, 2003,54(2):287-293.
[29]
Sierra M, Fernandes A N, Szpoganicz B. Influence of amide linkages on acidity determinations of humic substances:Testing with model-mixtures[J]. Talanta, 2004,62(4):687-693.
