废旧轮胎翻新过程中多环芳烃排放及健康风险
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摘要
对废旧轮胎翻新过程(露天堆放、混炼、硫化、打磨过程)和工人宿舍楼的环境空气中16种PAHs的排放特征进行了分析,并对工人的职业健康风险进行了评价.结果表明,废旧轮胎翻新过程及宿舍楼空气中都检测出PAHs.混炼过程PAHs浓度最高,其次是露天堆放过程和硫化过程,打磨过程的PAHs浓度最低,而工人宿舍楼PAHs平均浓度为11.1 ng·m~(-3).所有采样点的菲、荧蒽、蒽和芘对PAHs的总浓度的贡献较大,且与总浓度的线性相关性较强.从环数分析发现各采样点的PAHs主要集中在三环和四环,二环、五环和六环占比不超过10%.通过PAHs的可能影响因数分析发现露天堆放和宿舍楼可能受燃烧源的影响,而混炼、硫化及打磨过程可能受胶油类的影响.主成分分析和聚类分析结果显示,废旧轮胎翻新过程各采样点和彼此间的空间位置会对多环芳烃的分布产生较大影响.健康风险评价结果表明:职业工人终身致癌危险度几率较小,职业工人的预期寿命损失影响也不大.
The emissions characteristics of 16 kinds of polycyclic aromatic hydrocarbons(PAHs) in ambient air during the waste tire retreading process(open-air storage,mixing,vulcanization,and grinding processes) and in workers' dormitory were analyzed.In addition,the occupational health risk of the workers was evaluated.Results showed that PAHs were detected in all retreading processes and in the workers' dormitory.The highest concentration site was the mixing process,followed by open-air storage and vulcanization process.The lowest concentration point was in the grinding process.The average concentration of PAHs in the workers' dormitory was 11.1 ng·m~(-3).The PAHs at all sampling points were largely phenanthrene(Phe),fluoranthene(Flu),anthracene(Ant),and pyrene(Pry),which also had a stronger linear correlation with the total PAH concentration.An analysis of the benzene rings showed that three ring and four ring were the majority,while two ring,five ring,and six ring components accounted for less than 10%.Results of the possible influencing factors of the PAHs revealed that the open-air storage and dormitory might be affected by a combustion source,but the mixing,vulcanization,and grinding processes might be affected by rubber oil.The principal component analysis(PCA) and cluster analysis showed that the spatial location of all sites would significantly influence the distribution of PAHs during the tire retreading process.The health risk assessment showed that occupational workers had a lower risk of lifelong cancer,and there was little influence on life expectancy.
The emissions characteristics of 16 kinds of polycyclic aromatic hydrocarbons(PAHs) in ambient air during the waste tire retreading process(open-air storage,mixing,vulcanization,and grinding processes) and in workers' dormitory were analyzed.In addition,the occupational health risk of the workers was evaluated.Results showed that PAHs were detected in all retreading processes and in the workers' dormitory.The highest concentration site was the mixing process,followed by open-air storage and vulcanization process.The lowest concentration point was in the grinding process.The average concentration of PAHs in the workers' dormitory was 11.1 ng·m~(-3).The PAHs at all sampling points were largely phenanthrene(Phe),fluoranthene(Flu),anthracene(Ant),and pyrene(Pry),which also had a stronger linear correlation with the total PAH concentration.An analysis of the benzene rings showed that three ring and four ring were the majority,while two ring,five ring,and six ring components accounted for less than 10%.Results of the possible influencing factors of the PAHs revealed that the open-air storage and dormitory might be affected by a combustion source,but the mixing,vulcanization,and grinding processes might be affected by rubber oil.The principal component analysis(PCA) and cluster analysis showed that the spatial location of all sites would significantly influence the distribution of PAHs during the tire retreading process.The health risk assessment showed that occupational workers had a lower risk of lifelong cancer,and there was little influence on life expectancy.
引文
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[21]谢忠麟.多环芳烃与橡胶制品[J].橡胶工业,2011,58(6):359-376.
[22]王震,董佳英.裂解气相色谱-质谱法和热失重法检验轮胎胎面胶成分[J].刑事技术,2014,39(4):14-17.Wang Z,Dong J Y.Analysis of tire tread rubber by TGA and PGC-MS[J].Forensic Science and Technology,2014,39(4):14-17.
[23]宋冠群,林金明.环境样品中多环芳烃的前处理技术[J].环境科学学报,2005,25(10):1287-1296.Song G Q,Lin J M.Sample pretreatment techniques for polycyclic aromatic hydrocarbons in environmental matrix[J].Acta Scientiae Circumstantiae,2005,25(10):1287-1296.
[24]吴水平,兰天,左谦,等.天津地区一些降尘中多环芳烃的含量与分布[J].环境科学学报,2004,24(6):1066-1073.Wu S P,Lan T,Zuo Q,et al.PAHs in the dust fallfrom tianjin area collected during winter and summer seasons[J].Acta Scientiae Circumstantiae,2004,24(6):1066-1073.
[25]Xiao R,Du X M,He X Z,et al.Vertical distribution of polycyclic aromatic hydrocarbons(PAHs)in Hunpu wastewaterirrigated area in northeast China under different land use patterns[J].Environmental Monitoring and Assessment,2008,142(1-3):23-34.
[26]Soclo H H,Garrigues P,Ewald M.Origin of polycyclic aromatic hydrocarbons(PAHs)in coastal marine sediments:case studies in Cotonou(Benin)and Aquitaine(France)Areas[J].Marine Pollution Bulletin,2000,40(5):387-396.
[27]Mai B X,Fu J M,Sheng G Y,et al.Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl River Delta,China[J].Environmental Pollution,2002,117(3):457-474.
[28]裴宜星.废轮胎回转窑热解油的应用研究[D].杭州:浙江大学,2006.43-44.Pei Y X.Properties and application of pyrolytic oil from pyrolysis of used tires in rotary kiln[D].Hangzhou:Zhejiang University,2006.43-44.
[29]Bosetti C,Boffetta P,La Vecchia C.Occupational exposures to polycyclic aromatic hydrocarbons,and respiratory and urinary tract cancers:a quantitative review to 2005[J].Annals of Oncology:Official Journal of the European Society for Medical Oncology,2006,18(3):431-446.
[30]Armstrong B,Hutchinson E,Unwin J,et al.Lung cancer risk after exposure to polycyclic aromatic hydrocarbons:a review and meta-analysis[J].Environmental Health Perspectives,2004,112(9):970-978.
[31]Mastrangelo G,Fadda E,Marzia V.Polycyclic aromatic hydrocarbons and cancer in man[J].Environmental Health Perspectives,1996,104(11):1166-1170.
[32]Mumford J L,He X Z,Chapman R S,et al.Lung cancer and indoor air pollution in Xuan Wei,China[J].Science,1987,235(4785):217-220.
[33]Zhou B,Zhao B.Population inhalation exposure to polycyclic aromatic hydrocarbons and associated lung cancer risk in Beijing region:Contributions of indoor and outdoor sources and exposures[J].Atmospheric Environment,2012,62(15):472-480.
[34]Jung K H,Yan B Z,Chillrud S N,et al.Assessment of benzo(a)pyrene-equivalent carcinogenicity and mutagenicity of residential indoor versus outdoor polycyclic aromatic hydrocarbons exposing young children in New York City[J].International Journal of Environmental Research and Public Health,2010,7(5):1889-1900.
[35]US EPA.EPA/600/P-95/002,Exposure factors handbooks[S].
[36]US EPA.EPA/540/1-89/002,Risk assessment guidance for superfund volume I human health evaluation manual(Part A)[S].
[37]US EPA.EPA/540/1-86/060,Super fund public health evaluation manual[S].
[38]杨宇,胡建英,陶澍.天津地区致癌风险的预期寿命损失分析[J].环境科学,2005,26(1):168-172.Yang Y,Hu J Y,Tao S.Loss of life expectancy analysis for cancer risk in Tianjin area[J].Environmental Science,2005,26(1):168-172.
[2]许冠英,彭晓春,周少奇,等.废旧轮胎回收利用对策[J].广州环境科学,2009,24(4):25-31.Xu G Y,Peng X C,Zhou S Q,et al.Recycling and control measures of scrap tires in Guandong[J].Guangzhou Environmental Sciences,2009,24(4):25-31.
[3]曹庆鑫.借助《准入条件》发布之机促进废轮胎综合利用行业整合重组[J].橡胶资源利用,2012,(4):9-11.
[4]李卓,赵磊,魏立超,等.美国废旧轮胎回收利用经验及对天津市的启示[J].资源节约与环保,2012(1):70-72.
[5]况敬静.安徽省淮河流域底泥中PAHs污染性状研究[D].淮南:安徽理工大学,2007.2.Kuang J J.Study on pollution characteristics of PAHs in sediments from Huaihe river valley in Anhui[D].Huainan:Anhui University of Science and Technology,2007.2.
[6]Boonyatumanond R,Murakami M,Wattayakorn G,et al.Sources of polycyclic aromatic hydrocarbons(PAHs)in street dust in a tropical Asian mega-city,Bangkok,Thailand.[J].Science of the Total Environment,2007,384(1-3):420-432.
[7]Atal A,Levendis Y A,Carlson J,et al.On the survivability and pyrosynthesis of PAH during combustion of pulverized coal and tire crumb[J].Combustion and Flame,1997,110(4):462-478.
[8]Chen S J,Su H B,Chang J E,et al.Emissions of polycyclic aromatic hydrocarbons(PAHs)from the pyrolysis of scrap tires[J].Atmospheric Environment,2007,41(6):1209-1220.
[9]Conesa J A,Gálvez A,Mateos F,et al.Organic and inorganic pollutants from cement kiln stack feeding alternative fuels[J].Journal of Hazardous Materials,2008,158(2-3):585-592.
[10]Monarca S,Feretti D,Zanardini A,et al.Monitoring airborne genotoxicants in the rubber industry using genotoxicity tests and chemical analyses[J].Mutation Research/genetic Toxicology and Environmental Mutagenesis,2001,490(2):159-169.
[11]Aylón E,Murillo R,Fernández-Colino A,et al.Emissions from the combustion of gas-phase products at tyre pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2007,79(1-2):210-214.
[12]Boffetta P,Jourenkova N,Gustavsson P.Cancer risk from occupational and environmental exposure to polycyclic aromatic hydrocarbons[J].Cancer Causes&Control,1997,8(3):444-472.
[13]董彩玉,苍飞飞.GC/MS内标法测定全钢载重子午线轮胎中的多环芳烃含量[J].轮胎工业,2013,33(2):119-123.Dong C Y,Cang F F.Determination of PAHs in truck and bus radial tire by GC/MS and internal standard method[J].Tire Industry,2013,33(2):119-123.
[14]贾敬香,潘铁英,杜一平,等.超声波萃取-GC/MS法测定橡胶轮胎中的多环芳烃[J].环境污染与防治,2008,30(3):54-56,61.Jia J X,Pan T Y,Du Y P,et al.Determination of polycyclic aromatic hydrocarbons in tyre using supersonic extraction coupled with gas chromatography/mass spectrometry[J].Environmental Pollution&Control,2008,30(3):54-56,61.
[15]周变红,张承中,王格慧.西安城区大气中多环芳烃的季节变化特征及健康风险评价[J].环境科学学报,2012,32(9):2324-2331.Zhou B H,Zhang C Z,Wang G H.Seasonal variation and health risk assessment of atmospheric polycyclic aromatic hydrocarbons(PAHs)in the urban area of Xi'an[J].Acta Scientiae Circumstantiae,2012,32(9):2324-2331.
[16]李志刚,周志华,李少艾,等.深圳市大气中多环芳烃的污染特征与来源识别[J].中国环境科学,2011,31(9):1409-1415.Li Z G,Zhou Z H,Li S A,et al.Pollutant characterization and source identification of polycyclic aromatic hydrocarbons(PAHs)in Shenzhen atmosphere[J].China Environmental Science,2011,31(9):1409-1415.
[17]赵淑莉,戴天有,段小丽,等.北京城市空气中多环芳烃的污染特征[J].环境科学研究,2007,20(3):16-20.Zhao S L,Dai T Y,Duan X L,et al.Pollution characterization of polycyclic aromatic hydrocarbons in Beijing ambient air[J].Research of Environmental Sciences,2007,20(3):16-20.
[18]彭华.郑州市环境空气中多环芳烃污染状况及变化规律的研究[J].中国环境监测,2008,24(4):75-78.Peng H.Study on the contamination of polycyclic aromatic hydrocarbons in the air of Zhengzhou city[J].Environmental Monitoring in China,2008,24(4):75-78.
[19]金银龙,李永红,常君瑞,等.我国五城市大气多环芳烃污染水平及健康风险评价[J].环境与健康杂志,2011,28(9):758-761.Jin Y L,Li Y H,Chang J R,et al.Atmospheric PAHs levels and health risk assessment in five cities of China[J].Journal of Environment and Health,2011,28(9):758-761.
[20]李军,张干,祁士华.广州市大气中多环芳烃分布特征、季节变化及其影响因素[J].环境科学,2004,25(3):7-13.Li J,Zhang G,Qi S H.Characteristics and seasonal variations and influence factors on polycyclic aromatic hydrocarbons in Guangzhou City[J].Environmental Science,2004,25(3):7-13.
[21]谢忠麟.多环芳烃与橡胶制品[J].橡胶工业,2011,58(6):359-376.
[22]王震,董佳英.裂解气相色谱-质谱法和热失重法检验轮胎胎面胶成分[J].刑事技术,2014,39(4):14-17.Wang Z,Dong J Y.Analysis of tire tread rubber by TGA and PGC-MS[J].Forensic Science and Technology,2014,39(4):14-17.
[23]宋冠群,林金明.环境样品中多环芳烃的前处理技术[J].环境科学学报,2005,25(10):1287-1296.Song G Q,Lin J M.Sample pretreatment techniques for polycyclic aromatic hydrocarbons in environmental matrix[J].Acta Scientiae Circumstantiae,2005,25(10):1287-1296.
[24]吴水平,兰天,左谦,等.天津地区一些降尘中多环芳烃的含量与分布[J].环境科学学报,2004,24(6):1066-1073.Wu S P,Lan T,Zuo Q,et al.PAHs in the dust fallfrom tianjin area collected during winter and summer seasons[J].Acta Scientiae Circumstantiae,2004,24(6):1066-1073.
[25]Xiao R,Du X M,He X Z,et al.Vertical distribution of polycyclic aromatic hydrocarbons(PAHs)in Hunpu wastewaterirrigated area in northeast China under different land use patterns[J].Environmental Monitoring and Assessment,2008,142(1-3):23-34.
[26]Soclo H H,Garrigues P,Ewald M.Origin of polycyclic aromatic hydrocarbons(PAHs)in coastal marine sediments:case studies in Cotonou(Benin)and Aquitaine(France)Areas[J].Marine Pollution Bulletin,2000,40(5):387-396.
[27]Mai B X,Fu J M,Sheng G Y,et al.Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl River Delta,China[J].Environmental Pollution,2002,117(3):457-474.
[28]裴宜星.废轮胎回转窑热解油的应用研究[D].杭州:浙江大学,2006.43-44.Pei Y X.Properties and application of pyrolytic oil from pyrolysis of used tires in rotary kiln[D].Hangzhou:Zhejiang University,2006.43-44.
[29]Bosetti C,Boffetta P,La Vecchia C.Occupational exposures to polycyclic aromatic hydrocarbons,and respiratory and urinary tract cancers:a quantitative review to 2005[J].Annals of Oncology:Official Journal of the European Society for Medical Oncology,2006,18(3):431-446.
[30]Armstrong B,Hutchinson E,Unwin J,et al.Lung cancer risk after exposure to polycyclic aromatic hydrocarbons:a review and meta-analysis[J].Environmental Health Perspectives,2004,112(9):970-978.
[31]Mastrangelo G,Fadda E,Marzia V.Polycyclic aromatic hydrocarbons and cancer in man[J].Environmental Health Perspectives,1996,104(11):1166-1170.
[32]Mumford J L,He X Z,Chapman R S,et al.Lung cancer and indoor air pollution in Xuan Wei,China[J].Science,1987,235(4785):217-220.
[33]Zhou B,Zhao B.Population inhalation exposure to polycyclic aromatic hydrocarbons and associated lung cancer risk in Beijing region:Contributions of indoor and outdoor sources and exposures[J].Atmospheric Environment,2012,62(15):472-480.
[34]Jung K H,Yan B Z,Chillrud S N,et al.Assessment of benzo(a)pyrene-equivalent carcinogenicity and mutagenicity of residential indoor versus outdoor polycyclic aromatic hydrocarbons exposing young children in New York City[J].International Journal of Environmental Research and Public Health,2010,7(5):1889-1900.
[35]US EPA.EPA/600/P-95/002,Exposure factors handbooks[S].
[36]US EPA.EPA/540/1-89/002,Risk assessment guidance for superfund volume I human health evaluation manual(Part A)[S].
[37]US EPA.EPA/540/1-86/060,Super fund public health evaluation manual[S].
[38]杨宇,胡建英,陶澍.天津地区致癌风险的预期寿命损失分析[J].环境科学,2005,26(1):168-172.Yang Y,Hu J Y,Tao S.Loss of life expectancy analysis for cancer risk in Tianjin area[J].Environmental Science,2005,26(1):168-172.