Formation of environmental persistent free radicals and its influence on organic pollutant behavior:a review

doi:10.16085/j.issn.1000-6613.2017-0541

Abstract

Abstract: Environmentally persistent free radicals (EPFRs) as new type of contaminants are detected in soil/sediment,suspended particles,natural organic matter and water and thus are ubiquitous. They may have higher reactivity and risks to organisms than the parent organic chemicals and thus it is urgent to understand the mechanisms for EPFRs generation and environmental behavior. Previous studies mainly focused on the generation mechanism of EPFRs from degradation process of organic pollutants in extreme condition(combustion or high temperature). However,the concern of EPFRs with more general under natural conditions is not enough. The extended study on natural conditions will definitely deepen our understanding on organic chemical risks. This paper reviewed the existence and generation mechanism of EPFRs in environmental medium,synthetic carbonaceous materials and degradation of organic pollutants. The influence of EPFRs to precursor organic pollutants and the promotion degradation of other organic pollutants in system were firstly summarized. The importance of understanding the environmental behaviors and risk of organic pollutants with EPFRs participating were mentioned,and the future research directions were suggested.

Key words: environmental persistent free radicals, generation mechanism, organic pollutant, degradation

摘要： 环境持久性自由基（EPFRs）作为一类新型的环境风险物质在环境中普遍存在，具有较高的反应活性和环境风险。以往研究主要关注污染物在燃烧或者高温等极端条件下EPFRs的产生机制，对更具普遍性的自然条件下产生的EPFRs的环境行为和风险关注不够。本文综述了环境介质、人工合成碳基材料以及有机污染物降解过程中EPFRs的存在和产生机制，着重论述了EPFRs对前体有机污染物环境行为的影响，以及EPFRs的存在能促进环境中共存有机污染物的降解。最后提出了EPFRs参与有机污染物的降解过程可能是理解有机污染物环境行为、风险研究中所缺失的重要环节，并对以后应注重开展的研究进行了展望。

关键词: 环境持久性自由基, 产生机制, 有机污染物, 降解

CLC Number:

WANG Peng, WU Min, LI Hao, LANG Di, PAN Bo. Formation of environmental persistent free radicals and its influence on organic pollutant behavior:a review[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4243-4249.

王朋, 吴敏, 李浩, 郎笛, 潘波. 环境持久性自由基对有机污染物环境行为的影响研究进展[J]. 化工进展, 2017, 36(11): 4243-4249.

References

[1] DUGAS T R,LOMNICKI S,CORMIER S A,et al. Addressing emerging risks:scientific and regulatory challenges associated with environmentally persistent free radicals[J]. International Journal of Environmental Research and Public Health,2016,13:573.
[2] INGRAM D,TAPLEY J,JACKSON R,et al. Paramagnetic resonance in carbonaceous solids[J]. Nature,1954,174:797-798.
[3] UEBERSFELD J,ÉTIENNE A,COMBRISSON J. Paramagnetic resonance,a new property of coal-like materials[J]. Nature,1954,174:614.
[4] TRUONG H,LOMNICKI S,DELLINGER B. Potential for misidentification of environmentally persistent free radicals as molecular pollutants in particulate matter[J]. Environmental Science & Technology,2010,44:1933-1939.
[5] VEJERANO E,LOMNICKI S,DELLINGER B. Formation and stabilization of combustion-generated environmentally persistent free radicals on an Fe(Ⅲ)₂O₃/silica surface[J]. Environmental Science & Technology,2010,45:589-594.
[6] DELLINGER B,LOMNICKI S,KHACHATRYAN L,et al. Formation and stabilization of persistent free radicals[J]. Proceedings of the Combustion Institute,2007,31:521-528.
[7] DELLINGER B,PRYOR W A,CUETO R,et al. Combustion-generated radicals and their role in the toxicity of fine particulate[J]. Organohalogen Compounds,2000,46:302-305.
[8] LI H,GUO H Y,PAN B,et al. Catechol degradation on hematite/silica-gas interface as affected by gas composition and the formation of environmentally persistent free radicals[J]. Sci. Rep.,2016,6:9.
[9] LI H,PAN B,LIAO S H,et al. Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation[J]. Environmental Pollution,2014,188:153-158.
[10] TOLLIN G,STEELINK C. Biological polymers related to catechol:electron paramagnetic resonance and infrared studies of melanin,tannin,lignin,humic acid and hydroxyquinones[J]. Biochimica et Biophysica Acta,1966,112:377-379.
[12] MASKOS Z,DELLINGER B. Radicals from the oxidative pyrolysis of tobacco[J]. Energy & Fuels,2008,22:1675-1679.
[13] BARRIQUELLO M F,SAAB S d C,CONSOLIN FILHO N,et al. Electron paramagnetic resonance characterization of a humic acid-type polymer model[J]. Journal of the Brazilian Chemical Society,2010,21:2302-2307.
[14] SARAVIA J,LEE G I,LOMNICKI S,et al. Particulate matter containing environmentally persistent free radicals and adverse infant respiratory health effects:a review[J]. Journal of Biochemical and Molecular Toxicology,2013,27:56-68.
[15] LIAO S H,PAN B,LI H,et al. Detecting free radicals in biochars and determining their ability to inhibit the germination and growth of corn,wheat and rice seedlings[J]. Environmental Science & Technology,2014,48:8581-8587.
[16] PETRAKIS L,GRANDY D W. Free radicals in coals and synthetic fuels[M]. New York:Elseivier Science Publishers Co. Inc.,1984.
[17] VALAVANIDIS A,IOPOULOS N,GOTSIS G,et al. Persistent free radicals,heavy metals and PAHs generated in particulate soot emissions and residue ash from controlled combustion of common types of plastic[J]. Journal of Hazardous Materials,2008,156:277-284.
[18] HALDORAI Y,HWANG S K,GOPALAN A I,et al. Direct electrochemistry of cytochrome c immobilized on titanium nitride/multi-walled carbon nanotube composite for amperometric nitrite biosensor[J]. Biosensors & Bioelectronics,2016,79:543-552.
[19] HON N S. Formation of free radicals in photo-irradiated cellulose. Ⅳ. Effect of ferric ions[J]. Journal of Applied Polymer Science,1975,19:2789-2797.
[20] MASKOS Z,KHACHATRYAN L,DELLINGER B. Precursors of radicals in tobacco smoke and the role of particulate matter in forming and stabilizing radicals[J]. Energy & Fuels,2005,19:2466-2473.
[21] SAKAGUCHI M,OHURA T,IWATA T,et al. Diblock copolymer of bacterial cellulose and poly(methyl methacrylate) initiated by chain-end-type radicals produced by mechanical scission of glycosidic linkages of bacterial cellulose[J]. Biomacromolecules,2010,11:3059-3066.
[22] YANG J,PAN B,LI H,et al. Degradation of p-nitrophenol on biochars:role of persistent free radicals[J]. Environmental Science & Technology,2016,50:694-700.
[23] DELA CRUZ A L N,COOK R L,DELLINGER B,et al. Assessment of environmentally persistent free radicals in soils and sediments from three superfund sites[J]. Environmental Science Processes & Impacts,2014,16:44-52.
[24] BALAKRISHNA S,LOMNICKI S,MCAVEY K M,et al. Environmentally persistent free radicals amplify ultrafine particle mediated cellular oxidative stress and cytotoxicity[J]. Particle and Fibre Toxicology,2009,6:11.
[25] LU S L,YI F,HAO X J,et al. Physicochemical properties and ability to generate free radicals of ambient coarse,fine,and ultrafine particles in the atmosphere of Xuanwei,China,an area of high lung cancer incidence[J]. Atmospheric Environment,2014,97:519-528.
[26] KUMAGAI Y,ARIMOTO T,SHINYASHIKI M,et al. Generation of reactive oxygen species during interaction of diesel exhaust particle components with NADPH-cytochrome P450 reductase and involvement of the bioactivation in the DNA damage[J]. Free Radical Biology and Medicine,1997,22:479-487.
[28] FAHMY B,DING L,YOU D,et al. In vitro and in vivo assessment of pulmonary risk associated with exposure to combustion generated fine particles[J]. Environmental Toxicology and Pharmacology,2010,29:173-182.
[29] PIGNATELLOJJ,XING B S. Mechanisms of slow sorption of organic chemicals to natural particles[J]. Environmental Science & Technology,1995,30:1-11.
[30] WEBER W J,HUANG W. A distributed reactivity model for sorption by soils and sediments. 4. Intraparticle heterogeneity and phase-distribution relationships under nonequilibrium conditions[J]. Environmental Science & Technology,1996,30:881-888.
[31] WATANABE A,MCPHAIL D B,MAIE N,et al. Electron spin resonance characteristics of humic acids from a wide range of soil types[J]. Organic Geochemistry,2005,36:981-990.
[32] PAUL A,STOSSER R,ZEHL A,et al. Nature and abundance of organic radicals in natural organic matter:effect of pH and irradiation[J]. Environmental Science & Technology,2006,40:5897-5903.
[33] SPAGNUOLO M,JACOBSON A R,BAVEYE P. Electron paramagnetic resonance analysis of the distribution of a hydrophobic spin probe in suspensions of humic acids,hectorite,and aluminum hydroxide-humate-hectorite complexes[J]. Environ. Toxicol. Chem.,2005,24:2435-2444.
[34] SPARKS D L. Soil physical chemistry[J]. Soil Science,1988,145:231-232.
[35] MCPHAIL D B,CHESHIRE M V. Effect of ascorbate reduction on the electron spin resonance spectra of humic acid radical components[M]//HAYES M H B,WILSON W S. Humic substance,peats and sludges:health and environmental aspects. Woodhead Pubishing,1997:63-72.
[36] SAAB S C,MARTIN N L. Studies of semiquinone free radicals by ESR in the whole soil,HA,FA and humin substances[J]. Journal of the Brazilian Chemical Society,2004,15:34-37.
[37] RIMMER D L. Free radicals,antioxidants,and soil organic matter recalcitrance[J]. European Journal of Soil Science,2006,57:91-94.
[38] COATES J D,COLE K A,CHAKRABORTY R,et al. Diversity and ubiquity of bacteria capable of utilizing humic substances as electron donors for anaerobic respiration[J]. Applied and Environmental Microbiology,2002,68:2445-2452.
[39] BOYD S A,MORTLAND M M. Radical formation and polymerization of chlorophenols and chloroanisole on copper(Ⅱ)-smectite[J]. Environmental Science & Technology,1986,20:1056-1058.
[40] RATASUK N,NANNY MA. Characterization and quantification of reversible redox sites in humic substances[J]. Environmental Science & Technology,2007,41:7844-7850.
[41] SQUADRITO G L,CUETO R,DELLINGER B,et al. Quinoid redox cycling as a mechanism for sustained free radical generation by inhaled airborne particulate matter[J]. Free Radical Biology and Medicine,2001,31:1132-1138.
[42] BARONTI S,VACCARI F P,MIGLIETTA F,et al. Impact of biochar application on plant water relations in Vitis vinifera (L.)[J]. Eur. J. Agron.,2014,53:38-44.
[43] MUKHERJEE A,ZIMMERMAN A R. Organic carbon and nutrient release from a range of laboratory-produced biochars and biochar-soil mixtures[J]. Geoderma,2013,193:122-130.
[44] CHEN W F,LI Y,ZHU D Q,et al. Dehydrochlorination of activated carbon-bound 1,1,2,2-tetrachloroethane:implications for carbonaceous material-based soil/sediment remediation[J]. Carbon,2014,78:578-588.
[45] FANG G D,GAO J,LIU C,et al. Key role of persistent free radicals in hydrogen peroxide activation by biochar:implications to organic contaminant degradation[J]. Environmental Science & Technology,2014,48:1902-1910.
[46] FANG G D,LIU C,GAO J,et al. Manipulation of persistent free radicals in biochar to activate persulfate for contaminant degradation[J]. Environmental Science & Technology,2015,49:5645-5653.
[47] FANG G D,LIU C,GAO J,et al. New insights into the mechanism of the catalytic decomposition of hydrogen peroxide by activated carbon:implications for degradation of diethyl phthalate[J]. Industrial & Engineering Chemistry Research,2014,53:19925-19933.
[48] LUO L S,WU D,DAI D J,et al. Synergistic effects of persistent free radicals and visible radiation on peroxymonosulfate activation by ferric citrate for the decomposition of organic contaminants[J]. Applied Catalysis B:Environmental,2017,205:404-411
[49] JIANG B,DAI D,YAO Y,et al. The coupling of hemin with persistent free radicals induces a nonradical mechanism for oxidation of pollutants[J]. Chemical Communications,2016,52:9566-9569.
[50] LOMNICKI S,TRUONG H,VEJERANO E,et al. Copper oxide-based model of persistent free radical formation on combustion-derived particulate matter[J]. Environmental Science & Technology,2008,42:4982-4988.
[51] GUO H Y,WEI C,LI H,et al. Decreased phenol degradation by hematite under UV irradiation on HMT-silica surface[J]. Environmental Chemistry,2016,35:273-279.
[52] 王婷,李浩,郭惠莹,等. 邻苯二酚-Fe₂O₃和邻苯二酚-CuO体系中持久性自由基的形成机制及特征[J]. 环境化学,2016,35(3):423-429. WANG T,LI H,GUO H Y,et al.The formation and characteristics of persistent free radicals in catechol-Fe₂O₃/silica and catechol-CuO/silica systems[J].Environmental Chemistry,2016,35(3):423-429.

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