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In order to identify the pollution characteristics and carcinogenic risk of oxygenated polycyclic aromatic hydrocarbons(OPAHs)in the environmental media in the coking plants, vegetation, soil and ambient air samples were collected in JD and PF coking plants. Four species of OPAHs, including 1-acenaphthenone(1-ANO), 9-fluorenone(9-FLU), 9, 10-anthraquinone(9, 10-ATQ), and benzanthrone(BZO), were detected using gas chromatography-mass spectrometry detector(GC-MSD). The results showed that the concentrations of Σ4OPAHs in vegetations, soils, and ambient air in PF plant were higher than those in JD plant, respectively, and 9-FLU and 9, 10-ATQ were dominated in the environmental media in both plants. The fugacity of ambient air-soil showed that 9-FLU was in equilibrium between the air and soil, and 9, 10-ATQ released from soil into the air in PF plant. Human health risks were assessed for adults through ingestion, dermal contact and inhalation. The carcinogenic risks of OPAHs in the soils in JD and PF plants were acceptable for adults, and the carcinogenic risks of OPAHs in the ambient air in both plants were also acceptable for adults. The results provide a basis for the formulation of OPAH prevention and control measures.

, correspAuthors=Xiao-feng LIU, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Yu-huan CHENG, Xiao-feng LIU, Xin TAN, Xin-yang LI, Kun WANG), CN=ArticleExt(id=1241116672422114061, articleId=1241116665669284251, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=焦化厂4种含氧多环芳烃特征及健康风险评估, columnId=1234106394006311784, journalTitle=中国环境科学, columnName=环境毒理与健康, runingTitle=null, highlight=null, articleAbstract=

为明确焦化厂区环境介质中含氧多环芳烃(OPAHs)的污染特征和致癌风险,采集JD和PF焦化厂植物、土壤和环境空气样品,利用气相色谱-质谱联用仪(GC-MSD)测试其中1-苊酮(1-ANO)、9-芴酮(9-FLU)、蒽醌(9,10-ATQ)和苯并蒽酮(BZO)4种OPAHs浓度.结果表明:PF厂植物、土壤和环境空气中Σ4OPAHs的浓度均高于JD厂,且两厂环境介质中均是9-FLU和9,10-ATQ占主导地位.环境空气-土壤的逸度研究表明PF厂9-FLU处于平衡状态,9,10-ATQ由土壤释放到环境空气中.通过摄入、皮肤接触和吸入3种途径对成人进行了人体健康风险评估,发现JD和PF厂土壤中OPAHs对成人的致癌风险均是可接受的,厂区环境空气中OPAHs的致癌风险对成人也是可接受的.研究结果为OPAHs防控措施的制定提供依据.

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* 责任作者,副教授,
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程玉环(2000-),女,山西省晋城市人,太原理工大学硕士研究生,主要从事大气环境化学研究..

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程玉环(2000-),女,山西省晋城市人,太原理工大学硕士研究生,主要从事大气环境化学研究..

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程玉环(2000-),女,山西省晋城市人,太原理工大学硕士研究生,主要从事大气环境化学研究..

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Science of the Total Environment2019653:423-430., articleTitle=Spatial,seasonal and particle size dependent variations of PAH contamination in indoor dust and the corresponding human health risk, refAbstract=null)], funds=[Fund(id=1241116681121099946, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, awardId=202203021211182, language=CN, fundingSource=山西省基础研究计划项目(202203021211182), fundOrder=null, country=null), Fund(id=1241116681209180334, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, awardId=2021-052, language=CN, fundingSource=山西省回国留学人员科研资助项目(2021-052), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241116672736686886, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, xref=null, ext=[AuthorCompanyExt(id=1241116672745075494, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, companyId=1241116672736686886, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=College of Environment and Ecology, Taiyuan University of Technology, Taiyuan 030024, China), AuthorCompanyExt(id=1241116672749269799, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, companyId=1241116672736686886, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=太原理工大学环境与生态学院,山西 太原 030024)])], figs=[ArticleFig(id=1241116677358809120, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Fig.1, caption=Locations of coking plants and sampling sites, figureFileSmall=Wtf1nZZcDpdtlRkFuGANtg==, figureFileBig=wOu6MB/rCQWOJ57WY4TkHA==, tableContent=null), ArticleFig(id=1241116677472055335, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=图1, caption=焦化厂采样点位, figureFileSmall=Wtf1nZZcDpdtlRkFuGANtg==, figureFileBig=wOu6MB/rCQWOJ57WY4TkHA==, tableContent=null), ArticleFig(id=1241116677782433844, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Fig.2, caption=Distribution characteristics of individual OPAH in environmental media in coking plants, figureFileSmall=OoE8zlJUdwy94maSv8zukQ==, figureFileBig=b6LpqhIDgbzFG/nBAnCohg==, tableContent=null), ArticleFig(id=1241116677908262978, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=图2, caption=焦化厂区环境介质中单体OPAH的分布特征, figureFileSmall=OoE8zlJUdwy94maSv8zukQ==, figureFileBig=b6LpqhIDgbzFG/nBAnCohg==, tableContent=null), ArticleFig(id=1241116678008926280, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Fig.3, caption=Gas-particle partition of OPAHs in ambient air in coking plants, figureFileSmall=zMXTgmB3fT9s/URhKX0HAQ==, figureFileBig=k4oG799uaj6s8lyUNJfzKQ==, tableContent=null), ArticleFig(id=1241116678113783885, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=图3, caption=焦化厂区环境空气中OPAHs的气固分布, figureFileSmall=zMXTgmB3fT9s/URhKX0HAQ==, figureFileBig=k4oG799uaj6s8lyUNJfzKQ==, tableContent=null), ArticleFig(id=1241116678235418707, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Fig.4, caption=ILCR assessment of OPAHs for adults in coking plant soils, figureFileSmall=RAZ7PTfrHPGp/tB5iunByw==, figureFileBig=PkEYN8mMhpVGHWgO6T1w5g==, tableContent=null), ArticleFig(id=1241116678327693401, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=图4, caption=焦化厂区土壤中OPAHs成人的ILCR评估, figureFileSmall=RAZ7PTfrHPGp/tB5iunByw==, figureFileBig=PkEYN8mMhpVGHWgO6T1w5g==, tableContent=null), ArticleFig(id=1241116678424162399, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Table 1, caption=

Description of the sampling sites

, figureFileSmall=null, figureFileBig=null, tableContent=
采样位置采样点特征
JD焦化厂J1焦炉焦侧,烟气脱硫脱硝装置附近
J2办公区,临近厂区外交通要道
J3焦炉西侧
J4焦炉机侧,焦炉和化工生产加工区之间
J5焦炉东侧
PF焦化厂P1焦炉焦侧,烟气脱硫脱硝装置和化工生产加工区之间
P2办公区
P3焦炉东北面草地
P4化工生产加工区
P5焦炉东南面绿化带,在东门道路一侧
P6焦炉西南面,煤场附近
城市对照点Park焦化厂西北约9km的公园内
), ArticleFig(id=1241116678508048488, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=表1, caption=

采样点描述

, figureFileSmall=null, figureFileBig=null, tableContent=
采样位置采样点特征
JD焦化厂J1焦炉焦侧,烟气脱硫脱硝装置附近
J2办公区,临近厂区外交通要道
J3焦炉西侧
J4焦炉机侧,焦炉和化工生产加工区之间
J5焦炉东侧
PF焦化厂P1焦炉焦侧,烟气脱硫脱硝装置和化工生产加工区之间
P2办公区
P3焦炉东北面草地
P4化工生产加工区
P5焦炉东南面绿化带,在东门道路一侧
P6焦炉西南面,煤场附近
城市对照点Park焦化厂西北约9km的公园内
), ArticleFig(id=1241116678600323180, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Table 2, caption=

Parameters of the formulas for calculating ILCR values of OPAHs in soil and ambient air

, figureFileSmall=null, figureFileBig=null, tableContent=
参数描述单位成人参考文献
EF暴露频率d/a350[31]
BW体重kg60.6[29]
IR*摄入率mg/d100[31]
SA*表面积cm2/d6032[31]
AF*皮肤粘附因子mg/cm20.07[31]
ED暴露时间a26[31]
AT平均时间d25550[31]
PEF*颗粒物排放系数m3/kg1.36×109[31]
ET*暴露时间h/h24/24[27]
CSF*癌症斜率系数(kg·d)/mg7.3[27]
ABS*真皮吸收分数-0.13[27]
IUR*吸入风险m3/mg1.1[27]
GIABS*胃肠道吸收的分数-1[27]
), ArticleFig(id=1241116678688403570, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=表2, caption=

土壤和环境空气中OPAHs的ILCR值计算公式的参数

, figureFileSmall=null, figureFileBig=null, tableContent=
参数描述单位成人参考文献
EF暴露频率d/a350[31]
BW体重kg60.6[29]
IR*摄入率mg/d100[31]
SA*表面积cm2/d6032[31]
AF*皮肤粘附因子mg/cm20.07[31]
ED暴露时间a26[31]
AT平均时间d25550[31]
PEF*颗粒物排放系数m3/kg1.36×109[31]
ET*暴露时间h/h24/24[27]
CSF*癌症斜率系数(kg·d)/mg7.3[27]
ABS*真皮吸收分数-0.13[27]
IUR*吸入风险m3/mg1.1[27]
GIABS*胃肠道吸收的分数-1[27]
), ArticleFig(id=1241116678801649786, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Table 3, caption=

The OPAH concentrations in the environmental media in the coking plants

, figureFileSmall=null, figureFileBig=null, tableContent=
位置植物(ng/g)土壤(ng/g)环境空气(ng/m3)
气相颗粒相
1-ANO9-FLU9,10-ATQBZO4OPAHs1-ANO9-FLU9,10-ATQBZO4OPAHs1-ANO9-FLU9,10-ATQBZO4OPAHs1-ANO9-FLU9,10-ATQBZO4OPAHs
JDMean5.6598.5631.7710.36146.351.987.655.143.5718.342.944.800.5808.3301.064.391.096.55
SD0.8431.178.652.8043.010.573.202.112.268.142.414.510.2407.15
PFMean6.19144.9643.1915.58209.925.6410.726.104.8527.314.2617.030.35021.6304.1419.346.1729.65
SD4.1752.5029.329.7381.514.065.083.142.7314.472.353.320.0602.93
城市对照点8.5010.4613.065.7237.741.282.621.620.826.34
), ArticleFig(id=1241116678910701698, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=表3, caption=

焦化厂区环境介质OPAHs的浓度

, figureFileSmall=null, figureFileBig=null, tableContent=
位置植物(ng/g)土壤(ng/g)环境空气(ng/m3)
气相颗粒相
1-ANO9-FLU9,10-ATQBZO4OPAHs1-ANO9-FLU9,10-ATQBZO4OPAHs1-ANO9-FLU9,10-ATQBZO4OPAHs1-ANO9-FLU9,10-ATQBZO4OPAHs
JDMean5.6598.5631.7710.36146.351.987.655.143.5718.342.944.800.5808.3301.064.391.096.55
SD0.8431.178.652.8043.010.573.202.112.268.142.414.510.2407.15
PFMean6.19144.9643.1915.58209.925.6410.726.104.8527.314.2617.030.35021.6304.1419.346.1729.65
SD4.1752.5029.329.7381.514.065.083.142.7314.472.353.320.0602.93
城市对照点8.5010.4613.065.7237.741.282.621.620.826.34
), ArticleFig(id=1241116679002976391, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Table 4, caption=

Concentrations of ΣOPAHs in different types of soils at home and abroad(ng/g)

, figureFileSmall=null, figureFileBig=null, tableContent=
土壤类型位置种类浓度参考文献
工业区焦化厂山西(JD)410.20~26.49本研究
山西(PF)49.31~44.73本研究
山西758.4[37]
法国(Neuves-Maisons)8113120[39]
法国(Homécourt)8543360[39]
瑞典13106760[38]
非焦化厂澳大利亚7377~11536[40]
泰国1521~208[41]
德国柏林1816208[42]
瑞典13426660[38]
乌兹别克斯坦1262~1893[23]
交通公共汽车站比拉特讷格尔292.2~123[26]
城市城市青岛79.45[25]
加德满都292.4~178[26]
曼谷1512~269[41]
布拉迪斯拉发1488~2692[43]
), ArticleFig(id=1241116679095251084, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=表4, caption=

国内外不同类型土壤中OPAHs的浓度水平(ng/g)

, figureFileSmall=null, figureFileBig=null, tableContent=
土壤类型位置种类浓度参考文献
工业区焦化厂山西(JD)410.20~26.49本研究
山西(PF)49.31~44.73本研究
山西758.4[37]
法国(Neuves-Maisons)8113120[39]
法国(Homécourt)8543360[39]
瑞典13106760[38]
非焦化厂澳大利亚7377~11536[40]
泰国1521~208[41]
德国柏林1816208[42]
瑞典13426660[38]
乌兹别克斯坦1262~1893[23]
交通公共汽车站比拉特讷格尔292.2~123[26]
城市城市青岛79.45[25]
加德满都292.4~178[26]
曼谷1512~269[41]
布拉迪斯拉发1488~2692[43]
), ArticleFig(id=1241116679200108689, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Table 5, caption=

Concentrations of ΣOPAHs in ambient air at different locations at home and abroad(ng/m3

, figureFileSmall=null, figureFileBig=null, tableContent=
场地类型位置采样时间种类类型浓度文献
工业区焦化厂山西(JD)2021年11月4TSP+气相14.88本研究
山西(PF)2021年11月4TSP+气相51.28本研究
非焦化厂清远市2009年夏季6PM2.50.519~0.930[44]
清远市2010年冬季6PM2.50.695~1.246[44]
广东2019年12月12TSP2.24~17.0[45]
海南2019年3月12TSP0.216~1.84[45]
山东青岛2019年供暖期6气相2.657±0.919[46]
2020年非供暖期1.583±0.998
交通多伦多2016~2017年7气相3.92±1.21[47]
天津2016年11月4PM2.518.44±20.41[52]
城市天津2021年冬季5PM2.5+气相3.68~18.60[48]
天津2021年秋季5PM2.5+气相4.00~13.30[48]
北京2012~2013年5PM2.555.9[10]
法国南部城市2004年8PM10+气相6.286[51]
德国奥格2008年冬季7PM2.53.2[49]
斯堡2007年夏季7PM2.50.66[49]
韩国首尔2020年冬季10PM2.59.40±2.50[50]
2020年秋季10PM2.54.33±0.80[50]
2020年春季10PM2.53.70±0.24[50]
2020年夏季10PM2.53.58±0.78[50]
), ArticleFig(id=1241116680689086616, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=表5, caption=

国内外不同地区环境空气中OPAHs的浓度水平(ng/m3

, figureFileSmall=null, figureFileBig=null, tableContent=
场地类型位置采样时间种类类型浓度文献
工业区焦化厂山西(JD)2021年11月4TSP+气相14.88本研究
山西(PF)2021年11月4TSP+气相51.28本研究
非焦化厂清远市2009年夏季6PM2.50.519~0.930[44]
清远市2010年冬季6PM2.50.695~1.246[44]
广东2019年12月12TSP2.24~17.0[45]
海南2019年3月12TSP0.216~1.84[45]
山东青岛2019年供暖期6气相2.657±0.919[46]
2020年非供暖期1.583±0.998
交通多伦多2016~2017年7气相3.92±1.21[47]
天津2016年11月4PM2.518.44±20.41[52]
城市天津2021年冬季5PM2.5+气相3.68~18.60[48]
天津2021年秋季5PM2.5+气相4.00~13.30[48]
北京2012~2013年5PM2.555.9[10]
法国南部城市2004年8PM10+气相6.286[51]
德国奥格2008年冬季7PM2.53.2[49]
斯堡2007年夏季7PM2.50.66[49]
韩国首尔2020年冬季10PM2.59.40±2.50[50]
2020年秋季10PM2.54.33±0.80[50]
2020年春季10PM2.53.70±0.24[50]
2020年夏季10PM2.53.58±0.78[50]
), ArticleFig(id=1241116680831692960, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=EN, label=Table 6, caption=

Ratios of individual OPAH to pPAH in different medium in coking plants and from emission sources[9,53,56]

, figureFileSmall=null, figureFileBig=null, tableContent=
环境介质和排放源9-FLU/Flu9,10-ATQ/Ant文献
植物(JD厂)0.140.49本研究
植物(PF厂)0.170.51本研究
土壤(JD厂)0.250.37本研究
土壤(PF厂)0.430.30本研究
环境空气(JD厂)0.020.15本研究
环境空气(PF厂)0.150.11本研究
木材燃烧0.790.42[9]
煤球燃烧4.31.7[9]
煤饼燃烧0.390.12[9]
秸秆焚烧0.40±0.180.89±0.41[53]
煤燃烧0.25±0.250.14±0.08[53]
柴油车尾气0.50~0.790.68~1.01[56]
), ArticleFig(id=1241116680961716386, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116665669284251, language=CN, label=表6, caption=

焦化厂区环境介质和排放源[9,53,56]中单体OPAH与pPAH的比值

, figureFileSmall=null, figureFileBig=null, tableContent=
环境介质和排放源9-FLU/Flu9,10-ATQ/Ant文献
植物(JD厂)0.140.49本研究
植物(PF厂)0.170.51本研究
土壤(JD厂)0.250.37本研究
土壤(PF厂)0.430.30本研究
环境空气(JD厂)0.020.15本研究
环境空气(PF厂)0.150.11本研究
木材燃烧0.790.42[9]
煤球燃烧4.31.7[9]
煤饼燃烧0.390.12[9]
秸秆焚烧0.40±0.180.89±0.41[53]
煤燃烧0.25±0.250.14±0.08[53]
柴油车尾气0.50~0.790.68~1.01[56]
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焦化厂4种含氧多环芳烃特征及健康风险评估
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程玉环 , 刘效峰 * , 谭欣 , 李欣泱 , 王昆
中国环境科学 | 环境毒理与健康 2025,45(3): 1647-1656
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中国环境科学 | 环境毒理与健康 2025, 45(3): 1647-1656
焦化厂4种含氧多环芳烃特征及健康风险评估
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程玉环 , 刘效峰* , 谭欣, 李欣泱, 王昆
作者信息
  • 太原理工大学环境与生态学院,山西 太原 030024
  • 程玉环(2000-),女,山西省晋城市人,太原理工大学硕士研究生,主要从事大气环境化学研究..

通讯作者:

* 责任作者,副教授,
Characteristics and health risk of four oxygenated polycyclic aromatic hydrocarbons in coking plants
Yu-huan CHENG , Xiao-feng LIU* , Xin TAN, Xin-yang LI, Kun WANG
Affiliations
  • College of Environment and Ecology, Taiyuan University of Technology, Taiyuan 030024, China
出版时间: 2025-03-20
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为明确焦化厂区环境介质中含氧多环芳烃(OPAHs)的污染特征和致癌风险,采集JD和PF焦化厂植物、土壤和环境空气样品,利用气相色谱-质谱联用仪(GC-MSD)测试其中1-苊酮(1-ANO)、9-芴酮(9-FLU)、蒽醌(9,10-ATQ)和苯并蒽酮(BZO)4种OPAHs浓度.结果表明:PF厂植物、土壤和环境空气中Σ4OPAHs的浓度均高于JD厂,且两厂环境介质中均是9-FLU和9,10-ATQ占主导地位.环境空气-土壤的逸度研究表明PF厂9-FLU处于平衡状态,9,10-ATQ由土壤释放到环境空气中.通过摄入、皮肤接触和吸入3种途径对成人进行了人体健康风险评估,发现JD和PF厂土壤中OPAHs对成人的致癌风险均是可接受的,厂区环境空气中OPAHs的致癌风险对成人也是可接受的.研究结果为OPAHs防控措施的制定提供依据.

炼焦  /  含氧多环芳烃  /  环境介质  /  迁移转化  /  健康风险评价

In order to identify the pollution characteristics and carcinogenic risk of oxygenated polycyclic aromatic hydrocarbons(OPAHs)in the environmental media in the coking plants, vegetation, soil and ambient air samples were collected in JD and PF coking plants. Four species of OPAHs, including 1-acenaphthenone(1-ANO), 9-fluorenone(9-FLU), 9, 10-anthraquinone(9, 10-ATQ), and benzanthrone(BZO), were detected using gas chromatography-mass spectrometry detector(GC-MSD). The results showed that the concentrations of Σ4OPAHs in vegetations, soils, and ambient air in PF plant were higher than those in JD plant, respectively, and 9-FLU and 9, 10-ATQ were dominated in the environmental media in both plants. The fugacity of ambient air-soil showed that 9-FLU was in equilibrium between the air and soil, and 9, 10-ATQ released from soil into the air in PF plant. Human health risks were assessed for adults through ingestion, dermal contact and inhalation. The carcinogenic risks of OPAHs in the soils in JD and PF plants were acceptable for adults, and the carcinogenic risks of OPAHs in the ambient air in both plants were also acceptable for adults. The results provide a basis for the formulation of OPAH prevention and control measures.

coking  /  oxygenated polycyclic aromatic hydrocarbons  /  environmental media  /  migration and transformation  /  health risk assessment
程玉环, 刘效峰, 谭欣, 李欣泱, 王昆. 焦化厂4种含氧多环芳烃特征及健康风险评估. 中国环境科学, 2025 , 45 (3) : 1647 -1656 .
Yu-huan CHENG, Xiao-feng LIU, Xin TAN, Xin-yang LI, Kun WANG. Characteristics and health risk of four oxygenated polycyclic aromatic hydrocarbons in coking plants[J]. China Environmental Science, 2025 , 45 (3) : 1647 -1656 .
含氧多环芳烃(OPAHs)是母体多环芳烃(pPAHs)的衍生物,是一类广泛存在于大气的有机污染物[1].pPAHs具有致癌性、致畸性和致突变性三致特性,与pPAHs相比OPAHs毒性表现出了相似或更高的特性[2],且OPAHs在环境中也具有持久性,是许多生物和化学降解的最终产物,近年来越来越受到了广泛关注[3-5].
OPAHs属于半挥发性有机污染物,以气相和颗粒相两种状态存在,对人体肺泡组织和血液系统造成影响[4].一些OPAHs,如多环芳香醌,可以产生活性氧,导致氧化应激,从而造成过敏性疾病[5-6].OPAHs与pPAHs相比有更高的分子量和更低的蒸气压,更易吸附在颗粒物上[7-8],具有更高的毒性.OPAHs来源复杂,可以通过煤炭、生物质等燃烧直接排放[9-10],也可以由pPAHs光解、与大气中O3、OH和NOx等发生均相或非均相反应后二次形成[4,11-12].煤炭燃烧气固相9-FLU、9,10-ATQ和BZO的排放因子分别为4.10~14.9mg/kg、0.23~4.97mg/kg和0.01~1.70mg/kg[13].韩国首尔PM10中春夏秋冬4季检测到9-FLU和9,10-ATQ[14].环境空气中pPAHs及其衍生物通过干湿沉降进入土壤表层[15],造成土壤污染,植物也可以从土壤中吸收pPAHs[16],土壤中蒽(Ant)可转化为9,10-ATQ并发生累积[17].
煤焦化是隔绝空气高温条件下的煤转化过程,是pPAHs的重要来源之一[18-20].2017年中国大陆pPAHs的排放量为100.09Gg,工业pPAHs排放的比例从2007年的19.5%增加到2017年的29.26%[21]. 2017年山西省工业pPAHs排放量为4.99Gg,炼焦和工业煤燃烧排放pPAHs占工业源排放总量的95.6%[21].OPAHs可以从污染源直接排放,也可由pPAHs转化形成,焦化厂区是介于排放源和城市之间的特殊区域,故本文以焦化厂区环境介质为研究对象,探讨OPAHs的迁移转化,评估OPAHs对人体健康的潜在致癌风险.研究结果提供了焦化厂区OPAHs污染状况的基础数据,为OPAHs防控措施的制定提供依据.
本研究选择山西省2个典型焦化厂(JD和PF),JD焦化厂成立于2015年,有2座高度为6.98m的顶装焦炉,结焦时间为22h,焦炭产量每年150万t,PF焦化厂成立于2009年,有4座高度为6.25m的捣固焦炉,结焦时间为25.5h,焦炭产量每年200万t.于2021年11月采集两焦化厂厂区植物、土壤和环境空气样品及城市对照点植物、土壤样品,采样点位置和描述参考文献[22],见图1表1.采集J1和P1点环境空气样品,利用青岛崂应中流量采样器(Type 2050),使用聚氨酯泡沫(PUFs)和石英纤维滤膜(QFFs)同时采集气相和颗粒相样品,每个样品采集时长为10h,共采集12个样品(气相和颗粒相各6个),采样后用铝箔纸包裹并密封.由于0~10cm表层土壤中OPAHs的浓度高于10~20cm[23],故本研究在J3、J4、P1、P2、P5点采集0~10cm的表层土壤样品,放于密封袋中.采集J2、J4、J5、P3、P4、P5、P6点植物叶片,包括冬青、大叶黄杨、金叶女贞,采样后立即用袋子封装,带回实验室后用超纯水浸泡10min,去除叶面尘数次再用蒸馏水冲洗,避光自然风干.环境空气样品(包括PUFs和QFFs)、土壤样品、植物样品均密封后保存在-20℃的冰箱中.
环境空气、土壤和植物样品的前处理和测试在中国科学院地球环境研究所完成,方法参考文献[2224].为保证测试量将每个焦化厂环境空气颗粒相样品合并后测试,样品前处理:首先,QFFs中加入D代混标(苊-D10-D12、苯并苝-D12、蒽醌-D8),再加入15mL二氯甲烷(DCM)超声萃取30min,重复3次,利用旋转蒸发仪将萃取液旋蒸至小于2mL;其次,将浓缩萃取液通过3g活化过的硅胶进行洗脱,用15mL正己烷(HEX):二氯甲烷(DCM)(体积比,7:3)混合液洗脱pPAHs,再用8mL DCM以及5mL丙酮(ACE)洗脱OPAHs;最后,利用正戊烷和含有5% H2O的二甲基甲酰胺(DMF)纯化洗脱后的含pPAHs的混合液,吹氮浓缩,加入六甲基苯,定容至100µL待上机测定.在PUFs中加入D代混标,使用DCM索氏抽提48h,确保所有目标物可以全部溶于DCM中,其他过程与QFFs相同.土壤和植物样品各称取10g粉碎研磨,土壤样品加入10mLDCM,超声萃取60min,重复3次,其他前处理过程分别与QFFs、PUFs相同.利用Agilent 7890A-5975C气相色谱-质谱联用仪(GC-MSD)测试样品中的1-苊酮(1-ANO)、9-芴酮(9-FLU)、蒽醌(9,10-ATQ)和苯并蒽酮(BZO)4种OPAHs.选择EI模式(电子轰击源),高纯氦气载气,运行电压是70eV,进样口、传导管和四级杆的温度分别为280℃、310℃和150℃.升温程序为:初始温度50℃维持2min,然后以15℃/min的速率升温至120℃,再以5℃/min的速率升温至300℃并维持16min.蒽醌-D8的平均回收率为63%.
逸度是对化学物质从一种介质转移到另一种介质潜力的测量,可以用来表示OPAHs在空气和土壤介质之间移动的净方向[22,25-26].OPAHs在环境空气的逸度值(fa)、土壤中的逸度值(fs)以及土壤-空气的逸度比(ff)据式(1)~(3)计算[25].
式中:CsCa分别为目标化合物在土壤中的浓度(ng/g)和环境空气中气相OPAH的浓度(ng/m3);Koa为辛醇-空气分配系数;φom为土壤中有机质分数,这里假设为1.7倍总有机碳(TOC)分数,TOC的测定见本课题组其他成果[22]ρs为土壤固体密度,1.78× 106g/m3R为气体常数,8.314Pa·m3/(mol·K);T为平均气温,K.
采用终生癌症风险增量(ILCR)评价焦化厂OPAHs对人类的潜在致癌风险,成人在摄入(ILCRing)、皮肤接触(ILCRder)、吸入(ILCRinh)3个途径致癌风险的计算见式(4)~(7)[27].通过毒性当量因子(TEF)将OPAHs的浓度转化为苯并[a]芘毒性等效浓度(B(a)Peq)[27],其计算见公式(8):
式中:CSeq为致癌OPAHs当量浓度的总和(ng/g).据式(4)~(7)计算土壤中OPAHs的ILCR值,参数见表2.参考文献[28]利用式(4)计算环境空气中OPAHs的致癌风险,其中CSF为3.14(kg·d)/mg[28],IR为15.7m3/d[29],其他参数见表2.Ci为单体OPAH的浓度,TEFi为单体OPAHs对应的TEF值[30],本研究中9-FLU、9,10-ATQ和BZO的TEF值分别为0.002、0.004和0.0039[30].
表3所示,JD和PF焦化厂植物叶片中Σ4OPAHs的平均浓度分别为(146.35±43.01)ng/g和(209.92±81.51)ng/g,显著高于焦化厂所在城市对照点植物中Σ4OPAHs的浓度(37.74ng/g).炼焦是pPAHs的重要排放源,装煤和出焦过程16种pPAHs的排放因子分别为346.132,93.173µg/kg[19,32],气相pPAHs通过角质层或气孔扩散到植物叶片中,而颗粒相pPAHs沉积在叶片表面,可能扩散到植物角质层中,被吸附到亲脂性组织或渗透到叶子中[33],故高pPAHs排放是造成焦化厂植物中OPAHs浓度远高于城市对照点的原因.PF焦化厂植物叶片中Σ4OPAHs浓度是JD厂的1.43倍,这是由于不同焦炉高度和装煤方式pPAHs的排放量不同.研究表明,顶装焦炉无组织排放pPAHs浓度低于捣鼓(侧装)焦炉[18,32],焦炉高度越低有机碳排放因子越高[19].PF厂焦炉高度为6.25m,装煤方式为侧装,JD厂焦炉高度为6.98m,装煤方式为顶装,故PF焦化厂pPAHs的排放高于JD厂,所以PF焦化厂植物中OPAHs浓度高于JD厂.研究发现,青藏高原东南部G318高速公路苔藓中Σ6OPAHs的浓度为2.76~12.3ng/g[34],青藏高原苔藓、北极植物、南极苔藓中Σ8OPAHs的浓度分别为5.56~88.5ng/g、0~14.8ng/g、7.99~16.0ng/g[35].
显然,焦化厂植物中OPAHs的浓度远高于交通源及三极地区,这与炼焦过程pPAHs排放量较高有关.
图2所示,JD和PF焦化厂区植物中单体OPAH分布特征一致,单体OPAH占Σ4OPAHs比例的顺序为:9-FLU>9,10-ATQ>BZO>1-ANO,且JD和PF焦化厂植物中9-FLU和9,10-ATQ二者占Σ4OPAHs的比例分别为89.06%和89.63%,远高于城市对照点(62.33%).这可能是由于焦化厂区植物主要受到炼焦过程排放的影响,而城市对照点位于焦化厂西北约9km的公园里,受到城区商业和居民活动等人类活动的影响[22].研究表明青藏高原东南部G318高速公路苔藓中OPAHs的主要组分为9-FLU和9,10-ATQ[34],青藏高原苔藓、北极植物、南极苔藓中9-FLU是OPAHs含量最高的化合物(35.3%~53.8%),其次是9,10-ATQ(14.3%~21.3%)[35].JD和PF焦化厂植物中含量最高的单体OPAH与之前的研究基本一致[34-35].
JD和PF焦化厂土壤中Σ4OPAHs的平均浓度分别为(18.34±8.14)ng/g和(27.31±14.47)ng/g,PF焦化厂土壤中OPAHs的浓度明显高于JD厂,并且均高于城市对照点土壤中Σ4OPAHs的浓度(6.34ng/g),见表3.这是由于炼焦过程是pPAHs的重要排放源,且PF焦化厂pPAHs的排放量高于JD厂,pPAHs经过二次转化形成PAHs衍生物[10],这些污染物通过干湿沉降进入土壤[36],进而影响土壤中污染物的浓度.另外,PF厂建于2009年,JD厂建于2015年,两厂不同的生产时间也会影响OPAHs在土壤中的积累水平.Liu等[22]研究表明PF焦化厂土壤中16种pPAHs的平均浓度(2501.27ng/g)高于JD厂(1402.24ng/g),本研究中PF焦化厂土壤中Σ4OPAHs的平均浓度高于JD厂,与pPAHs特征一致.JD焦化厂土壤中9-FLU和9,10-ATQ的浓度分别为7.65ng/g和5.14ng/g,pPAHs中Flu和Ant的浓度分别为28.14ng/g和12.77ng/g[22]. PF厂土壤中9-FLU和9,10-ATQ分别为10.72ng/g和6.10ng/g,pPAHs中Flu和Ant的浓度分别为75.60ng/g和60.00ng/g[22],显然JD和PF焦化厂土壤中Flu和Ant的平均浓度显著高于对应OPAHs的平均浓度.
表4可以看出,国内外工业区、交通及城市土壤均不同程度受到OPAHs的污染.由表4可知,焦化厂与其他非焦化厂工业区土壤中OPAHs均处于较高的污染水平,总体而言工业区土壤中OPAHs浓度高于交通和城市土壤[25-2637-40].JD和PF焦化厂土壤中OPAHs的浓度低于山西另一焦化厂(58.4ng/g)[37],一方面由于该焦化厂土壤研究了7种OPAHs的总浓度,JD和PF厂则是4种PAHs的总浓度,另一方面可能是由于生产规模和管理模式的差异.JD和PF焦化厂土壤中OPAHs的浓度亦低于国外工业区土壤[23,37-42],其中9-FLU(JD为7.65ng/g,PF为10.72ng/g)低于瑞典焦化厂(48000ng/g)[38]、澳大利亚工业区(783ng/g)[40]、瑞典工业区(83000ng/g)[38]、乌兹别克斯坦工业区表层土(20~810ng/g)[23],9,10-ATQ(JD为5.14ng/g,PF为6.10ng/g)低于瑞典工业区(51000ng/g)[38]和与瑞典焦化厂(6400ng/g)[38]等工业区.不同城市土壤中OPAHs具有显著差异[25-264143],JD和PF厂土壤中9,10-ATQ与青岛城市土壤(6.70ng/g)[25]相近.
图2所示,JD和PF焦化厂区土壤中单体OPAH分布特征基本一致,且与城市对照点基本一致,9-FLU占Σ4OPAHs的比例最高,JD和PF厂分别为41.69%和39.27%,其次为9,10-ATQ,占比为28.03%和22.34%.研究发现,瑞典某焦化厂土壤中9-FLU占Σ13OPAHs的比例为45%,是含量最高的化合物[38],曼谷0~5cm层土壤中9-FLU占Σ15OPAH的比例为16%,是OPAHs中含量较高的化合物[41],这与JD和PF焦化厂中含量最高的化合物相同.瑞典工业区土壤中9-FLU和9,10-ATQ的占Σ13OPAH为31%[38],斯洛伐克布拉迪斯拉发大多数表层土壤中,9-FLU和9,10-ATQ占Σ9OPAH比例分别为20%和25%[43],JD和PF焦化厂土壤中9-FLU和9,10-ATQ也具有很高的比例.
表3可见,JD和PF焦化厂环境空气中Σ4OPAHs (气固相之和)的浓度分别为14.88ng/m3和51.28ng/m3,PF焦化厂Σ4OPAHs平均浓度是JD的3.45倍.表5列出了国内外不同地区环境空气中OPAHs的浓度水平.显然,不同地区、不同时间环境空气中OPAHs浓度有较大差异.JD和PF焦化厂环境空气中OPAHs的浓度高于其他没有焦化厂的工业区,也高于交通和部分城市采样点[44-50].9,10-ATQ和9-FLU是JD和PF焦化厂环境空气中占比较高的两种OPAHs. JD和PF焦化厂中9,10-ATQ的浓度分别为4.97ng/m3和19.69ng/m3,均高于清远市(夏季69.8~145pg/m3,冬季204~285pg/m3)[44]和山东青岛(供暖期1.41ng/m3,非供暖期1.02ng/m3)[46]等工业区.JD和PF焦化厂中9-FLU的浓度分别为5.86ng/m3和21.17ng/m3,也高于清远市(夏季11.4~59.7pg/m3,冬季35.5~49.5pg/m3)[44]和山东青岛(供暖期0.21ng/m3,非供暖期0.29ng/m3)[46]等工业区,且高于多伦多交通站点(2.47ng/m3)的浓度[47].
图2所示,JD和PF焦化厂区环境空气中单体OPAH(气固相之和)分布特征基本一致.JD厂环境空气中9-FLU和9,10-ATQ占Σ4OPAHs的比例之和为72.88%,PF厂为79.67%.山东青岛的工业区环境空气中9,10-ATQ是OPAHs中比例最高的化合物,供暖期和非供暖期占比分别为53%和64%[46].天津市秋冬季环境空气PM2.5中OPAHs占比较高的为9,10-ATQ和BZO,气相中9-FLU的占比最高[48].兰州市不同功能区环境空气中OPAHs占比最高的均为9-FLU、9,10-ATQ和BZO,这3种OPAHs占Σ8OPAHs的比例为51.8%~94.9%[4].因此焦化厂环境空气中主要的单体OPAH与其他区域环境空气的相似[4,46,48].
图3所示,两个焦化厂环境空气中单体OPAH具有相同的气固分布特征,1-ANO和9-FLU等分子量较低的化合物主要存在于气相,9,10-ATQ和BZO等分子量较高的化合物主要存在于颗粒相.焦化厂环境空气中单体OPAH在颗粒相的占比呈现出随分子量的增大而逐渐增大的变化趋势,这是由于分子量高的物质具有较低的蒸气压,更难从颗粒相迁移到气相中[4].JD和PF焦化厂中9-FLU在颗粒相的占比分别为18.09%和19.56%.这与城市环境空气中单体OPAH的气固分布特征基本一致,天津市环境空气中9-FLU在PM2.5中的占比秋季和冬季分别为0.2%~5.0%和3.8%~100.0%[48],法国南部城市环境空气中9-FLU在PM10中占比为4%[51].JD厂环境空气中9,10-ATQ和BZO的占比为88.33%和100.00%,PF厂的占比为98.22%和100.00%,与城市环境空气的研究结果基本一致[48,51].天津市秋季环境空气PM2.5中9,10-ATQ和BZO的占比分别为0.5%~69.3%和51.6%~98.6%[48],冬季分别为76.5%~99.1%和89.9%~99.9%[48],法国南部城市环境空气中9,10-ATQ和BZO在PM10的占比为71%和100%[51].
图2所示,JD和PF焦化厂植物、土壤、环境空气中单体OPAH的分布特征基本一致,9-FLU占比最高,其次为9,10-ATQ,说明焦化厂不同介质中OPAHs的来源基本一致.炼焦生产是隔绝空气高温条件下煤的干馏过程,9-FLU和9,10-ATQ占Σ4OPAHs的比例较高,这可以部分归因于固体燃料的不完全燃烧[53].
1-ANO、9-FLU、9,10-ATQ和BZO对应的pPAHs分别是苊烯(Acy)+苊(Ace)、芴(Flu)、Ant和苯并[a]蒽(BaA).OPAH与对应pPAH的比值可用于确定OPAHs的来源,如9-FLU/Flu、9,10-ATQ/Ant、苯并[a]蒽-7,12-二酮(BaAQ)/BaA和1,8-萘二甲酸酐(1,8-NA)/(Acy+Ace)[15,54-55].如表6所示,Shen等[9]发现,木材燃烧、煤球燃烧和煤饼燃烧中9-FLU/Flu分别为0.79、4.3和0.39,9,10-ATQ/Ant分别为0.42、1.7和0.12,Shen等[53]发现秸秆燃烧9-FLU/Flu和9,10-ATQ/Ant分别为0.40±0.18和0.89±0.41,煤燃烧分别为0.25±0.25和0.14±0.08,Li等[56]研究发现以柴油为燃料的机动车尾气中9-FLU/Flu和9,10-ATQ/Ant分别为0.50~0.79和0.68~1.01.本研究利用9-FLU/Flu、9,10-ATQ/Ant值解析焦化厂区环境介质中OPAHs的来源,Flu和Ant的浓度数据来源于本课题组的其他研究.从表6可以看出,JD和PF焦化厂环境介质中9-FLU/Flu值范围为0.02~0.43,与煤饼燃烧(0.39)、秸秆燃烧(0.40±0.18)、煤燃烧(0.25±0.25)及柴油车尾气(0.50~0.79)该比值接近[9,53,56],9,10-ATQ/Ant值范围为0.11~0.51,与木材燃烧(0.42)、煤饼燃烧(0.12)及煤燃烧(0.14±0.08)该比值接近[9,53].由于焦化厂区几乎没有木材燃烧和秸秆燃烧源,且煤炭使用主要是煤焦化过程,因此焦化厂区OPAHs主要来自于煤焦化和柴油车尾气.
焦化厂区环境介质中OPAH与pPAH比值与其他区域有明显差异[11,41].表6中JD和PF厂土壤中9-FLU/Flu分别为0.25和0.43,9,10-ATQ/Ant分别为0.37和0.30,明显低于Bandowe等[41]研究的曼谷土壤中9-FLU/Flu值(12)和9,10-ATQ/Ant值(7),这可能是由于曼谷地区温度高,使pPAH光化学和微生物活性降解速率加快,加强了OPAHs的形成和积累.Wei等[11]研究发现中国西安三月环境空气中9-FLU/Flu为0.770、9,10-ATQ/Ant为0.287,表6中JD和PF厂环境空气中9-FLU/Flu分别为0.02和0.15、9,10-ATQ/Ant分别为0.15和0.11,焦化厂环境空气中这两个比值较低,这可能是由于炼焦过程排放的pPAHs浓度较高造成的[18-19].
空气和土壤逸度比可以推断出污染物在空气和土壤介质之间移动的净方向[25-2657].逸度比ff为0.5时表示OPAHs在环境空气和土壤之间平衡,ff>0.5表示OPAHs从土壤净挥发到空气中,ff<0.5表示OPAHs从空气净沉积到土壤中[57].由于计算的不确定性,ff在0.50±0.35的范围(即0.15~0.85)被认为与平衡没有显著差异,ff>0.85表示OPAHs从土壤释放到空气中,ff<0.15表示OPAHs从空气向土壤的净沉积[25,57].
PF焦化厂中的9-FLU的逸度比为0.77,表明该物质处于平衡状态,9,10-ATQ的逸度比为0.96,表明9,10-ATQ是从土壤释放到空气.Liu等[22]发现焦化厂区大多数pPAHs的主要迁移过程是从土壤到空气的净挥发,本研究9,10-ATQ的迁移过程与pPAHs一致.Qi等[25]研究发现山东青岛城市、农村和崂山山顶OPAHs(包括BaAQ、BZO、9-甲醛菲(PHE-9-ALD)、1,4-蒽醌(1,4-ATQ)、9,10-ATQ、9-FLU和1-萘甲醛(NAP-1-ALD))的ff <0.15,OPAHs倾向于从空气沉积到土壤[25],这与本研究结果不同,因此焦化厂区环境空气-土壤的迁移转化具有不同于城市、农村的独特特征.
本研究对接触焦化厂土壤中OPAHs的成人进行了健康风险评估,由于TEF数据不全,故仅对9-FLU、9,10-ATQ和BZO进行了健康风险评估.研究表明,ILCR<10-6表示污染物对人类健康风险是安全的,在10-4和10-6之间表示具有潜在风险,>10-4则表示具有高风险[30,58].如图4所示,JD和PF焦化厂区土壤中成人OPAHs的平均致癌风险分别为3.31×10-7和4.30×10-7,故OPAHs对成人的致癌风险是可以接受的.图4显示PF焦化厂土壤中OPAHs的致癌风险是JD厂的1.30倍,这可能是由于PF厂土壤中OPAHs浓度较高.3种暴露途径中,JD和PF厂成人OPAHs摄入风险占总暴露风险的比例均为64.56%,皮肤接触风险与摄入风险处于同一个数量级,吸入风险远低于前两者,与Ren等[27]的研究结果基本一致.Ren等[27]研究了华南某城市土壤中PAHs及其衍生物的致癌风险,成人的平均ILCR为4.09×10−7,其中ILCRing占总ILCR的64.6%.由于皮肤接触和摄入是焦化厂土壤中OPAHs致癌风险的主要途径,故焦化厂工作人员应在皮肤接触和摄入这2方面注意防护,以便减少OPAHs对身体的伤害.
本研究计算了焦化厂环境空气中OPAHs对成人的致癌风险,结果显示JD和PF厂OPAHs的致癌风险分别为6.93×10-9和3.18×10-8,均小于1.0×10-6,不存在致癌风险.PF厂环境空气中OPAHs对成人的致癌风险高于JD厂,是JD厂的4.58倍,这是由于PF厂环境空气中OPAHs的浓度高于JD厂.焦化厂需制定相关的污染防治措施加强对人体健康的保护.
3.1 JD焦化厂区植物、土壤和环境空气中Σ4OPAHs的平均浓度分别为(146.35±43.01)ng/g,(18.34±8.14)ng/g和14.88ng/m3,PF厂分别为(209.92±81.51)ng/g,(27.31±14.47)ng/g和51.28ng/m3. JD厂植物、土壤和环境空气中Σ4OPAHs浓度均高于PF厂,且两厂环境介质中9-FLU和9,10-ATQ占比最高,占Σ4OPAHs的61.61%~89.63%.
3.2 环境空气-土壤逸度系数结果表明PF焦化厂区9-FLU在环境空气和土壤间处于平衡状态,9,10-ATQ由土壤释放到环境空气中.PF焦化厂9,10-ATQ在环境空气-土壤的迁移过程与pPAHs的迁移过程一致,均是从土壤到空气的净挥发,具有不同于城市、农村OPAHs迁移转化的独特特征.
3.3 焦化厂土壤中OPAHs对成人的健康风险评估结果表明,PF厂致癌风险高于JD厂,两厂土壤中OPAHs对成人的致癌风险均是可以接受的,且皮肤接触和摄入风险较高,这2者是引起致癌风险的主要途径.焦化厂环境空气中OPAHs对成人的致癌风险是可以接受的.焦化厂需要制定相关的污染防治措施从而加强对人体健康的保护.
  • 山西省基础研究计划项目(202203021211182)
  • 山西省回国留学人员科研资助项目(2021-052)
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    太原理工大学环境与生态学院,山西 太原 030024

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