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To investigate the environmental behavior of organophosphate esters (OPEs) in the surroundings of the electronics industry, an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was used to determine the concentration levels of 18 OPEs in soil, atmospheric, and wastewater samples, which were collected from surrounding areas of typical electronic industry enterprises in Shenzhen. Correlation analysis and principal component analysis (PCA) were applied to identify pollution sources, and the health risk levels of people of different age groups were evaluated. The results indicated that the detection rates of 18 OPEs in various environmental media were found to range between 40.9% and 100.0%. In 34 soil samples, 21 atmospheric samples, and 30 wastewater samples, the mean concentrations of ∑18 OPEs were determined to be 283ng/g (12.2~857ng/g), 4.48×105 pg/m3(3.12×103~2.95×106 pg/m3), and 1.11×106 ng/L (5.39×105~2.73×106 ng/L), respectively. Tris(2,4-di-tert-butylphenyl)phosphate (AO168=O), tris(4-tert-butylphenyl) phosphate (T4tBPP), tris(2-chloropropyl) phosphate (TCPP), and bisphenol A bis(diphenyl phosphate) (BPADP) were identified as the predominant OPEs across all media. The correlation and principal component analysis (PCA) results demonstrated that OPE contamination in the vicinity of electronic industry enterprises was predominantly influenced by industrial production emissions and traffic-related discharges. Non-carcinogenic and carcinogenic health risks associated with multi-pathway exposure to OPEs in soil and atmospheric media across different age groups were found to remain within acceptable thresholds; however, the health risks posed by long-term cumulative OPE exposure were identified as requiring sustained scientific attention.

, correspAuthors=Ling-Chuan GUO, 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=Zhan-lu LÜ, Ling ZHENG, Ting-ting ZHU, Pu YE, Chun-yan GUI, Bin LUO, Ling-Chuan GUO), CN=ArticleExt(id=1234106410997436419, articleId=1234106407281283901, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=典型电子工业企业周边有机磷酸酯的环境污染特征及其人群健康风险评估, columnId=1234106394006311784, journalTitle=中国环境科学, columnName=环境毒理与健康, runingTitle=null, highlight=null, articleAbstract=

为探究有机磷酸酯(OPEs)在电子工业周边环境行为,采用超高效液相色谱-串联质谱联用仪(UPLC-MS/MS)测定深圳市典型电子行业企业周边环境土壤、大气和废水样品中18种OPEs的浓度水平,使用相关性分析和主成分分析解析其污染来源,并评估不同年龄段人群的健康风险水平.结果表明各环境介质中18种OPEs的检出率在40.9%~100.0%之间,在34个土壤样品、21个大气样品和30个废水样品中∑18OPEs的均值分别为283ng/g(12.2~857ng/g)、4.48×105pg/m3(3.12×103~2.95×106pg/m3)和1.11×106ng/L(5.39×105~2.73×106ng/L),三(2,4-二叔丁基苯基)磷酸酯(AO168=O)、三(4-叔丁基苯基)磷酸酯(T4tBPP)、磷酸三(2-氯丙基)酯(TCPP)和双酚A双(二苯基磷酸酯)(BPADP)是各介质中主要的OPEs;相关性和主成分分析结果表明,电子行业企业周边环境中OPEs污染主要受工业生产排放和交通排放的影响.不同年龄段人群经多种途径暴露于土壤和大气中OPEs的非致癌和致癌健康风险处于可接受水平,但OPEs长期累积暴露的健康风险依然不容忽视.

, correspAuthors=郭凌川, authorNote=null, correspAuthorsNote=
* 责任作者,副研究员,
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吕占禄(1985-),男,青海民和人,高级工程师,硕士,主要研究方向为环境健康风险调查与评估.发表论文30余篇..

, authorsList=吕占禄, 郑玲, 朱婷婷, 叶璞, 贵春燕, 罗斌, 郭凌川)}, authors=[Author(id=1234106412071178340, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=lv.zhanlu@craes.org.cn, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1234106412222173298, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, authorId=1234106412071178340, language=EN, stringName=Zhan-lu LÜ, firstName=Zhan-lu, middleName=null, lastName=LÜ, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, address=1.State Key Laboratory of Environmental Criteria and Risk Assessment, State Environmental Protection Key Laboratory of Ecological Effect and Risk Assessment of Chemicals, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
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2.兰州大学大气科学学院,半干旱气候变化教育部重点实验室,甘肃 兰州 730000, bio={"content":"

吕占禄(1985-),男,青海民和人,高级工程师,硕士,主要研究方向为环境健康风险调查与评估.发表论文30余篇..

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吕占禄(1985-),男,青海民和人,高级工程师,硕士,主要研究方向为环境健康风险调查与评估.发表论文30余篇..

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tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Fig.2, caption=Box plot of OPE component concentration levels in soil, atmosphere, and wastewater around the electronic industry(logarithmic conversion), figureFileSmall=Hdjbnox287I5cpTm+Em1Xg==, figureFileBig=vXGtYNOpFssxzc+G8L9eWg==, tableContent=null), ArticleFig(id=1234106420510118479, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=图2, caption=电子工业厂区周边土壤、大气和废水中OPEs组分浓度水平箱式图(经对数转换)

箱式图方框的上下缘表示不同环境介质OPEs水平的第75和第25百分位数,方框的水平线表示中位数,黑点代表异常值

, figureFileSmall=Hdjbnox287I5cpTm+Em1Xg==, figureFileBig=vXGtYNOpFssxzc+G8L9eWg==, tableContent=null), ArticleFig(id=1234106420623364693, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Fig.3, caption=Correlation analysis chart and principal component factor loading chart of OPEs in soil, atmosphere, and wastewater, figureFileSmall=0z5O2F65wCoMohUJyZ0DOQ==, figureFileBig=sBdMoIdI4i9rraVFP991PQ==, tableContent=null), ArticleFig(id=1234106420740805216, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=图3, caption=土壤、大气和废水中OPEs的相关性分析图和主成分因子载荷, figureFileSmall=0z5O2F65wCoMohUJyZ0DOQ==, figureFileBig=sBdMoIdI4i9rraVFP991PQ==, tableContent=null), ArticleFig(id=1234106420887605871, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Fig.4, caption=Hazard quotient heat map of population exposure to soil and atmospheric OPEs, figureFileSmall=NoukmLIW5qCBH+tRe5HFkg==, figureFileBig=uwtOAy9apbfAhqz0xyhJtQ==, tableContent=null), ArticleFig(id=1234106421164429947, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=图4, caption=人群暴露于土壤和大气各OPEs组分的危害商值热图(以均值计)

图(a)、(b)和(c)内有16个中条带(代表各OPEs组分,除RDT905和T4tBPP外),每个中条带内有6个小条带,每行从上至下分别代表0~3岁婴儿、3~6岁儿童、6~17岁青少年、成人、男性、女性

, figureFileSmall=NoukmLIW5qCBH+tRe5HFkg==, figureFileBig=uwtOAy9apbfAhqz0xyhJtQ==, tableContent=null), ArticleFig(id=1234106421307036294, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Fig.5, caption=Heat map of carcinogenic health risks of population exposure to soil and atmospheric OPEs, figureFileSmall=ZXCvTFVwmS0qq13TB6TB7g==, figureFileBig=XzVTDoGJhT4aU9PVN9O9OQ==, tableContent=null), ArticleFig(id=1234106421491585687, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=图5, caption=人群暴露于土壤和大气OPEs的致癌健康风险热图(以均值计)

图(A)和(C)内有3×4个中格,图(B)内有3×3个中格,每个中格内有6×4个小格,每行从上至下分别代表0~3岁婴儿、3~6岁儿童、6~17岁青少年、成人、男性、女性;每列从左至右分别代表LADD最小值、LADD均值、LADD中位数、LADD最大值

, figureFileSmall=ZXCvTFVwmS0qq13TB6TB7g==, figureFileBig=XzVTDoGJhT4aU9PVN9O9OQ==, tableContent=null), ArticleFig(id=1234106421625803425, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Fig.6, caption=Monte Carlo simulation of the comprehensive HQ and CR of adult exposure to soil and atmospheric OPEs, figureFileSmall=BbtEP5ff2eBtc2WH89LfuA==, figureFileBig=fh0CAWlIi3+f3HzZBoAW3g==, tableContent=null), ArticleFig(id=1234106421806158505, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=图6, caption=蒙特卡洛模拟成人暴露于土壤和大气OPEs的综合HQ和CR, figureFileSmall=BbtEP5ff2eBtc2WH89LfuA==, figureFileBig=fh0CAWlIi3+f3HzZBoAW3g==, tableContent=null), ArticleFig(id=1234106421965542067, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Table 1, caption=

Minimum detection limit, detection rate and spiked recovery rate of OPEs in various environmental media

, figureFileSmall=null, figureFileBig=null, tableContent=
OPEs定量下限(μg/L)检出率(%)加标回收率(%)
土壤大气废水
卤化OPEsIDDPP0.006100.0100.0100.079.6~92.0
BEHPP0.01994.1100.060.091.6~101.9
TCEP0.06797.195.5100.087.6~105.9
T4IPPP0.01997.190.926.783.2~103.1
TCPP0.028100.0100.0100.089.4~100.6
BPADP0.009100.0100.096.795.1~106.9
TDCPP0.08173.5100.083.385.9~97.7
RDP0.020100.095.590.088.5~104.6
V60.01161.840.980.089.8~106.6
CDP0.05285.386.453.388.8~106.6
RDT9050.01758.895.5100.084.9~102.7
非卤化OPEsTPhP0.11097.1100.090.097.1~103.9
TBP0.08488.295.593.389.1~105.3
2IPPDPP0.03488.281.860.088.3~103.7
TCrP0.01594.1100.063.395.1~100.9
4tBPDPP0.03079.486.470.088.8~103.2
T4tBPP0.06976.563.643.396.0~103.1
AO168=O0.029100.0100.0100.098.4~102.7
), ArticleFig(id=1234106422095565502, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=表1, caption=

各环境介质中OPEs的定量下限、检出率和加标回收率

, figureFileSmall=null, figureFileBig=null, tableContent=
OPEs定量下限(μg/L)检出率(%)加标回收率(%)
土壤大气废水
卤化OPEsIDDPP0.006100.0100.0100.079.6~92.0
BEHPP0.01994.1100.060.091.6~101.9
TCEP0.06797.195.5100.087.6~105.9
T4IPPP0.01997.190.926.783.2~103.1
TCPP0.028100.0100.0100.089.4~100.6
BPADP0.009100.0100.096.795.1~106.9
TDCPP0.08173.5100.083.385.9~97.7
RDP0.020100.095.590.088.5~104.6
V60.01161.840.980.089.8~106.6
CDP0.05285.386.453.388.8~106.6
RDT9050.01758.895.5100.084.9~102.7
非卤化OPEsTPhP0.11097.1100.090.097.1~103.9
TBP0.08488.295.593.389.1~105.3
2IPPDPP0.03488.281.860.088.3~103.7
TCrP0.01594.1100.063.395.1~100.9
4tBPDPP0.03079.486.470.088.8~103.2
T4tBPP0.06976.563.643.396.0~103.1
AO168=O0.029100.0100.0100.098.4~102.7
), ArticleFig(id=1234106422267531979, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Table 2, caption=

Toxicity parameters related to different exposure pathways of OPEs

, figureFileSmall=null, figureFileBig=null, tableContent=
OPEsCAS号致癌等级*RfD[mg/(kg·d)]SF[kg·d/mg]来源
经口暴露经皮暴露吸入暴露经口暴露经皮暴露吸入暴露
卤化OPEsIDDPP29761-21-50.500.200.16EPA
BEHPP298-07-70.050.020.13EPA
TCEP51805-45-9可能对人类致癌0.0070.0070.0070.0200.0200.020[59]
T4IPPP68937-41-70.500.200.20EPA
TCPP13674-84-50.010.130.70EPA
BPADP5945-33-50.200.200.20EPA
TDCPP13674-87-8已知人类致癌物0.020.460.520.0310.0310.031[60]
RDP57583-54-70.500.200.49EPA
V638051-10-40.200.200.17EPA
CDP26444-49-50.140.140.14EPA
RDT90552186-00-2
非卤化OPEsTPHP115-86-60.070.070.07[61]
TBP126-73-80.31.02.8EPA
2IPPDPP64532-94-11.00.5EPA
TCrP1330-78-50.0130.0130.013[62]
4tBPDPP981-40-81.580.791.58EPA
T4tBPP78-33-1
AO168=O31570-04-40.60.20.2EPA
), ArticleFig(id=1234106422405944018, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=表2, caption=

OPEs不同暴露途径的相关毒性参数

, figureFileSmall=null, figureFileBig=null, tableContent=
OPEsCAS号致癌等级*RfD[mg/(kg·d)]SF[kg·d/mg]来源
经口暴露经皮暴露吸入暴露经口暴露经皮暴露吸入暴露
卤化OPEsIDDPP29761-21-50.500.200.16EPA
BEHPP298-07-70.050.020.13EPA
TCEP51805-45-9可能对人类致癌0.0070.0070.0070.0200.0200.020[59]
T4IPPP68937-41-70.500.200.20EPA
TCPP13674-84-50.010.130.70EPA
BPADP5945-33-50.200.200.20EPA
TDCPP13674-87-8已知人类致癌物0.020.460.520.0310.0310.031[60]
RDP57583-54-70.500.200.49EPA
V638051-10-40.200.200.17EPA
CDP26444-49-50.140.140.14EPA
RDT90552186-00-2
非卤化OPEsTPHP115-86-60.070.070.07[61]
TBP126-73-80.31.02.8EPA
2IPPDPP64532-94-11.00.5EPA
TCrP1330-78-50.0130.0130.013[62]
4tBPDPP981-40-81.580.791.58EPA
T4tBPP78-33-1
AO168=O31570-04-40.60.20.2EPA
), ArticleFig(id=1234106422565327580, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Table 3, caption=

Concentration of the OPEs in soil, atmosphere and wastewater around the electronic industry

, figureFileSmall=null, figureFileBig=null, tableContent=
OPEs土壤OPEs(n=34)(ng/g)大气OPEs(n=21)(pg/m3)废水OPEs(n=30)(ng/L)
平均数中位数范围平均数中位数范围平均数中位数范围
卤化OPEsIDDPP2.60×10-18.00×10-21.00×10-2~2.95184.0103.04.20~2.13×103475.0421.073.3~1.31×103
BEHPP4.70×10-11.00×10-1n.d.~6.81317.098.82.70~3.12×103437.0366.0n.d.~2.32×103
TCEP2.933.20n.d.~10.81.31×1043.33×103n.d.~1.36×1057.06×1045.14×1041.13×104~3.34×105
T4IPPP1.033.50×10-1n.d.~7.84323.0115.0n.d.~3.77×1031441.00×10-2n.d.~1.25×103
TCPP6.203.721.30×10-1~83.17.64×1041.79×10447.4~6.42×1051.67×1051.13×1052.08×104~6.30×105
BPADP29.95.293.10×10-1~2123.45×103710.051.4~2.97×1042.94×103400.0n.d.~2.67×104
TDCPP3.00×10-11.40×10-1n.d.~2.314.79×103587.061.8~6.71×1046.24×1033.88×103n.d.~2.67×104
RDP8.692.90×10-13.00×10-2~97.1472.074.9n.d.~3.37×103685.0314.0n.d.~8.40×103
V64.00×10-21.00×10-2n.d.~3.00×10-1125.01.00×10-2n.d.~2.47×1032.99×1031.10×103n.d.~2.70×104
CDP4.10×10-12.60×10-1n.d.~2.572.32×103226.0n.d.~1.85×1041.97×1031.34×103n.d.~9.67×103
RDT9053.00×10-21.00×10-2n.d.~3.10×10-1339.050.2n.d.~5.31×1035.17×1034.47×10379.6~3.44×104
11卤化OPEs50.318.41.02~3171.02×1052.83×104196~8.42×1052.58×1052.01×1057.87×104~8.67×105
非卤化OPEsTPhP7.341.06n.d.~68.11.02×1042.62×10342.7~5.02×1048.70×1035.05×103n.d.~3.13×104
TBP1.60×10-19.00×10-2n.d.~1.893.37×103232.0n.d.~6.10×1048.37×1045.84×103n.d.~2.14×106
2IPPDPP7.30×10-18.00×10-2n.d.~16.3375.089.8n.d.~5.35×103338.0183.0n.d.~1.79×103
TCrP5.589.00×10-2n.d.~183241.084.52.50~1.59×103135.081.9n.d.~704
4tBPDPP2.10×10-13.00×10-2n.d.~2.57168.049.7n.d.~9112.42×103202.0n.d.~4.30×104
T4tBPP113.056.6n.d.~3971.14×1056.51×104n.d.~5.48×1052.32×1053.00×10-2n.d.~6.12×105
AO168=O107.090.79.30~2982.18×1051.06×1052.85×103~2.04×1065.22×1055.06×1053.18×105~6.95×105
7非卤化OPEs233.0158.09.85~8333.47×1052.29×1052.93×103~2.11×1068.49×1056.00×1053.27×105~2.62×106
总计18OPEs283.0252.012.2~8574.48×1052.87×1053.12×103~2.95×1061.11×1061.12×1065.39×105~2.73×106
), ArticleFig(id=1234106423957836516, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=表3, caption=

电子工业厂区周边土壤、大气和废水中OPEs含量

, figureFileSmall=null, figureFileBig=null, tableContent=
OPEs土壤OPEs(n=34)(ng/g)大气OPEs(n=21)(pg/m3)废水OPEs(n=30)(ng/L)
平均数中位数范围平均数中位数范围平均数中位数范围
卤化OPEsIDDPP2.60×10-18.00×10-21.00×10-2~2.95184.0103.04.20~2.13×103475.0421.073.3~1.31×103
BEHPP4.70×10-11.00×10-1n.d.~6.81317.098.82.70~3.12×103437.0366.0n.d.~2.32×103
TCEP2.933.20n.d.~10.81.31×1043.33×103n.d.~1.36×1057.06×1045.14×1041.13×104~3.34×105
T4IPPP1.033.50×10-1n.d.~7.84323.0115.0n.d.~3.77×1031441.00×10-2n.d.~1.25×103
TCPP6.203.721.30×10-1~83.17.64×1041.79×10447.4~6.42×1051.67×1051.13×1052.08×104~6.30×105
BPADP29.95.293.10×10-1~2123.45×103710.051.4~2.97×1042.94×103400.0n.d.~2.67×104
TDCPP3.00×10-11.40×10-1n.d.~2.314.79×103587.061.8~6.71×1046.24×1033.88×103n.d.~2.67×104
RDP8.692.90×10-13.00×10-2~97.1472.074.9n.d.~3.37×103685.0314.0n.d.~8.40×103
V64.00×10-21.00×10-2n.d.~3.00×10-1125.01.00×10-2n.d.~2.47×1032.99×1031.10×103n.d.~2.70×104
CDP4.10×10-12.60×10-1n.d.~2.572.32×103226.0n.d.~1.85×1041.97×1031.34×103n.d.~9.67×103
RDT9053.00×10-21.00×10-2n.d.~3.10×10-1339.050.2n.d.~5.31×1035.17×1034.47×10379.6~3.44×104
11卤化OPEs50.318.41.02~3171.02×1052.83×104196~8.42×1052.58×1052.01×1057.87×104~8.67×105
非卤化OPEsTPhP7.341.06n.d.~68.11.02×1042.62×10342.7~5.02×1048.70×1035.05×103n.d.~3.13×104
TBP1.60×10-19.00×10-2n.d.~1.893.37×103232.0n.d.~6.10×1048.37×1045.84×103n.d.~2.14×106
2IPPDPP7.30×10-18.00×10-2n.d.~16.3375.089.8n.d.~5.35×103338.0183.0n.d.~1.79×103
TCrP5.589.00×10-2n.d.~183241.084.52.50~1.59×103135.081.9n.d.~704
4tBPDPP2.10×10-13.00×10-2n.d.~2.57168.049.7n.d.~9112.42×103202.0n.d.~4.30×104
T4tBPP113.056.6n.d.~3971.14×1056.51×104n.d.~5.48×1052.32×1053.00×10-2n.d.~6.12×105
AO168=O107.090.79.30~2982.18×1051.06×1052.85×103~2.04×1065.22×1055.06×1053.18×105~6.95×105
7非卤化OPEs233.0158.09.85~8333.47×1052.29×1052.93×103~2.11×1068.49×1056.00×1053.27×105~2.62×106
总计18OPEs283.0252.012.2~8574.48×1052.87×1053.12×103~2.95×1061.11×1061.12×1065.39×105~2.73×106
), ArticleFig(id=1234106424083665644, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=EN, label=Table 4, caption=

Total OPEs pollution levels in soil, air and wastewater both domestically and internationally

, figureFileSmall=null, figureFileBig=null, tableContent=
样品类型地区采样区域样品量(个)均值中位数
土壤样品(ng/g)本文电子工业厂区周边34283252
中国广州[52]公园土壤1187.075.0
稻田/菜地土壤13120.0110.0
越南[37]电子废物回收区土壤10620.0110.0
中国华南地区[12]电子垃圾拆解厂区土壤241.20×104
电子垃圾拆解厂周边地表土壤83256.0
中国广东省清远市[23]电子废物处理车间室内粉尘111.82×103
加拿大[24]废弃电器和电子设备室内粉尘241.10×105
中国重庆[38]农业区蔬菜731.417.7
大气样品(pg/m3)本文电子工业厂区周边214.48×1052.87×105
天津城市地区562.18×1031.59×103
中国京津冀地区[40]北京城市地区561.16×103987.0
石家庄城市地区561.50×1031.41×103
中国华南地区[42]电子垃圾清运园区181.30×108
电子垃圾清运园区周边地区187.40×104
中国华东地区[41]宝山区大551.94×1041.66×104
徐家汇区616.60×1034.40×103
南海永兴岛[43]永兴岛1003.80×10-1330.0
废水样品(ng/L)本文电子工业厂区301.11×1061.12×106
中国珠江三角洲地区[46]污水处理厂采集的出水样品
中国广西壮族自治区南宁[47]灌溉水110.0
雨水84.0
), ArticleFig(id=1234106424192717555, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106407281283901, language=CN, label=表4, caption=

国内外环境土壤、大气和废水中总OPEs污染水平

, figureFileSmall=null, figureFileBig=null, tableContent=
样品类型地区采样区域样品量(个)均值中位数
土壤样品(ng/g)本文电子工业厂区周边34283252
中国广州[52]公园土壤1187.075.0
稻田/菜地土壤13120.0110.0
越南[37]电子废物回收区土壤10620.0110.0
中国华南地区[12]电子垃圾拆解厂区土壤241.20×104
电子垃圾拆解厂周边地表土壤83256.0
中国广东省清远市[23]电子废物处理车间室内粉尘111.82×103
加拿大[24]废弃电器和电子设备室内粉尘241.10×105
中国重庆[38]农业区蔬菜731.417.7
大气样品(pg/m3)本文电子工业厂区周边214.48×1052.87×105
天津城市地区562.18×1031.59×103
中国京津冀地区[40]北京城市地区561.16×103987.0
石家庄城市地区561.50×1031.41×103
中国华南地区[42]电子垃圾清运园区181.30×108
电子垃圾清运园区周边地区187.40×104
中国华东地区[41]宝山区大551.94×1041.66×104
徐家汇区616.60×1034.40×103
南海永兴岛[43]永兴岛1003.80×10-1330.0
废水样品(ng/L)本文电子工业厂区301.11×1061.12×106
中国珠江三角洲地区[46]污水处理厂采集的出水样品
中国广西壮族自治区南宁[47]灌溉水110.0
雨水84.0
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典型电子工业企业周边有机磷酸酯的环境污染特征及其人群健康风险评估
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吕占禄 1, 2 , 郑玲 1 , 朱婷婷 3 , 叶璞 3 , 贵春燕 1, 4 , 罗斌 4 , 郭凌川 1, *
中国环境科学 | 环境毒理与健康 2025,45(6): 3460-3471
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中国环境科学 | 环境毒理与健康 2025, 45(6): 3460-3471
典型电子工业企业周边有机磷酸酯的环境污染特征及其人群健康风险评估
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吕占禄1, 2 , 郑玲1, 朱婷婷3, 叶璞3, 贵春燕1, 4, 罗斌4, 郭凌川1, *
作者信息
  • 1.中国环境科学研究院,环境基准标准与风险管控全国重点实验室,国家环境保护化学品生态效应与风险评估重点实验室,北京 100012
  • 2.兰州大学大气科学学院,半干旱气候变化教育部重点实验室,甘肃 兰州 730000
  • 3.深圳市环境科学研究院,国家环境保护饮用水水源地管理技术重点实验室,深圳市水环境中新型污染物检测与控制重点实验室,广东 深圳 518001
  • 4.兰州大学公共卫生学院,劳动卫生与环境卫生学研究所,甘肃 兰州 730000
  • 吕占禄(1985-),男,青海民和人,高级工程师,硕士,主要研究方向为环境健康风险调查与评估.发表论文30余篇..

通讯作者:

* 责任作者,副研究员,
The pollution characteristics and population health risk assessment of organopho sphorus esters around the typical electronic industry
Zhan-lu LÜ1, 2 , Ling ZHENG1, Ting-ting ZHU3, Pu YE3, Chun-yan GUI1, 4, Bin LUO4, Ling-Chuan GUO1, *
Affiliations
  • 1.State Key Laboratory of Environmental Criteria and Risk Assessment, State Environmental Protection Key Laboratory of Ecological Effect and Risk Assessment of Chemicals, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
  • 2.Key Laboratory of Semi-Arid Climate Change of Ministry of Education, College of Atmospheric Sciences, Lanzhou University, Lanzhou 730000, China
  • 3.State Environmental Protection Key Laboratory of Drinking Water Source Management and Technology, Shenzhen Key Laboratory of Emerging Contaminants Detection and Control inWater Environment, Guangdong Engineering Research Center of Low Energy Sewage Treatment, Shenzhen Academy of Environmental Sciences, Shenzhen 518001, China
  • 4.Institute of Occupational Health and Environmental Health, School of Public Health, Lanzhou University, Lanzhou 730000, China
出版时间: 2025-06-20
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为探究有机磷酸酯(OPEs)在电子工业周边环境行为,采用超高效液相色谱-串联质谱联用仪(UPLC-MS/MS)测定深圳市典型电子行业企业周边环境土壤、大气和废水样品中18种OPEs的浓度水平,使用相关性分析和主成分分析解析其污染来源,并评估不同年龄段人群的健康风险水平.结果表明各环境介质中18种OPEs的检出率在40.9%~100.0%之间,在34个土壤样品、21个大气样品和30个废水样品中∑18OPEs的均值分别为283ng/g(12.2~857ng/g)、4.48×105pg/m3(3.12×103~2.95×106pg/m3)和1.11×106ng/L(5.39×105~2.73×106ng/L),三(2,4-二叔丁基苯基)磷酸酯(AO168=O)、三(4-叔丁基苯基)磷酸酯(T4tBPP)、磷酸三(2-氯丙基)酯(TCPP)和双酚A双(二苯基磷酸酯)(BPADP)是各介质中主要的OPEs;相关性和主成分分析结果表明,电子行业企业周边环境中OPEs污染主要受工业生产排放和交通排放的影响.不同年龄段人群经多种途径暴露于土壤和大气中OPEs的非致癌和致癌健康风险处于可接受水平,但OPEs长期累积暴露的健康风险依然不容忽视.

有机磷酸酯  /  电子工业  /  污染特征  /  来源分析  /  健康风险评估

To investigate the environmental behavior of organophosphate esters (OPEs) in the surroundings of the electronics industry, an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was used to determine the concentration levels of 18 OPEs in soil, atmospheric, and wastewater samples, which were collected from surrounding areas of typical electronic industry enterprises in Shenzhen. Correlation analysis and principal component analysis (PCA) were applied to identify pollution sources, and the health risk levels of people of different age groups were evaluated. The results indicated that the detection rates of 18 OPEs in various environmental media were found to range between 40.9% and 100.0%. In 34 soil samples, 21 atmospheric samples, and 30 wastewater samples, the mean concentrations of ∑18 OPEs were determined to be 283ng/g (12.2~857ng/g), 4.48×105 pg/m3(3.12×103~2.95×106 pg/m3), and 1.11×106 ng/L (5.39×105~2.73×106 ng/L), respectively. Tris(2,4-di-tert-butylphenyl)phosphate (AO168=O), tris(4-tert-butylphenyl) phosphate (T4tBPP), tris(2-chloropropyl) phosphate (TCPP), and bisphenol A bis(diphenyl phosphate) (BPADP) were identified as the predominant OPEs across all media. The correlation and principal component analysis (PCA) results demonstrated that OPE contamination in the vicinity of electronic industry enterprises was predominantly influenced by industrial production emissions and traffic-related discharges. Non-carcinogenic and carcinogenic health risks associated with multi-pathway exposure to OPEs in soil and atmospheric media across different age groups were found to remain within acceptable thresholds; however, the health risks posed by long-term cumulative OPE exposure were identified as requiring sustained scientific attention.

organophosphorus esters  /  electronics industry  /  pollution characteristics  /  source analysis  /  health risk assessment
吕占禄, 郑玲, 朱婷婷, 叶璞, 贵春燕, 罗斌, 郭凌川. 典型电子工业企业周边有机磷酸酯的环境污染特征及其人群健康风险评估. 中国环境科学, 2025 , 45 (6) : 3460 -3471 .
Zhan-lu LÜ, Ling ZHENG, Ting-ting ZHU, Pu YE, Chun-yan GUI, Bin LUO, Ling-Chuan GUO. The pollution characteristics and population health risk assessment of organopho sphorus esters around the typical electronic industry[J]. China Environmental Science, 2025 , 45 (6) : 3460 -3471 .
有机磷酸酯(OPEs)作为传统溴系阻燃剂的替代产品,通过物理混合的方式被广泛添加到电子设备、纺织品、塑料材料、乳胶漆、地板蜡和胶水等产品中,还被用作增塑剂和消泡剂[1-2],在产品生产和使用过程中OPEs极易通过磨损、浸出、溶解和挥发等多种方式释放进入周边环境中[3-4].目前,OPEs作为备受国际社会关注的新污染物,已在环境空气(室内/室外)[5-6]、水体(饮用水/地表水)[7-8]、灰尘(室内/车内)[9-10]、土壤(底泥/淤泥)[11-12]、食物[13-14]和人体生物样品(头发/血清)[15-16]等介质中广泛检出.由于OPEs具有心脏、神经、生殖、内分泌干扰和致癌等毒性[17-19],OPEs环境暴露严重威胁着生物体和人类健康.
电子工业作为国家战略性新兴行业,在电子产品的生产和使用、危废处理等工序是OPEs排放的重要来源,排放的OPEs具有局部浓度高、排放量大、组分复杂、不同工艺产生的组成与浓度差异大等特点[20].目前,众多学者对电子工业OPEs排放开展了研究,在中国华南地区[21]和越南[22]电子垃圾拆解区、广东清远[23]和加拿大[24]废弃电器和电子设备室内粉尘,以及中国华南地区[25]电子垃圾清运园区周边土壤、大气、灰尘、血清和人类头发中OPEs的健康风险均不可忽视.
目前,尚未有对电子工业厂区周边多介质中OPEs的污染特征和人体健康影响开展深入研究.因此,本文选取深圳市正常运行且废气和废水排放量较大的电子工业企业作为研究对象,采集环境土壤、废水和空气样品,测定18种OPEs组分的含量,分析比较环境介质中OPEs的污染特征,识别行业特征OPEs,评估周边居民暴露的健康风险,为我国OPEs控制、治理及相关行业标准的制修订提供参考,也有助于制定保护公共健康的风险防控策略.
本文选择深圳市电子工业企业相对集中的宝安区、龙岗区和龙华区典型的电子工业企业作为研究对象,采集企业周边50~100m范围以内的0~20cm表层土壤、厂区楼顶的大气以及经过厂区废水处理设施处置后的废水,共采集85个环境样品,包括土壤样品34个、大气样品21个和废水样品30个(图1).样品采集严格参照相关技术规范[26-28]进行.
土壤样品(10.0g)经冷冻干燥后,用二氯甲烷索氏提取24h.提取前,在每个样品中加入已知量的5.0μL(200.0ng/μL)TCEP-d12作为替代标准品.提取液经旋转蒸发器(Heidolph 4000,德国)吹干,用0.5mL的正己烷复溶后,由固相萃取柱(Supelclean Envi Florisil,1.0g,6.0mL,SUPELCO,美国)萃取.固相萃取柱预先用6.0mL乙酸乙酯、6.0mL正己烷/二氯甲烷(8:2,V/V)和10.0mL正己烷活化.用6.0mL正己烷:二氯甲烷(8:2,V/V)淋洗固相萃取柱后,用20.0mL乙酸乙酯洗脱目标物,氮吹至干.目标物用200.0μL异辛烷复溶待测.
大气滤膜样品用正己烷和丙酮的混合物(1:1)索氏提取48h.提取前,加入替代标准品(TPPd21, TNBP-d27和TCIPP-d18).提取液浓缩至1.0mL后,用固相萃取柱(Supelclean ENVI-Florisil, 3.0mL, 0.5kg)萃取.固相萃取柱预先用5.0mL己烷和5.0mL的己烷:二氯甲烷(1:1,V/V)淋洗,用8.0mL乙酸乙酯洗脱目标物,氮吹近干.目标物用300μL异辛烷复溶,加入内标(TCEP-d12)待测.
废水样品按照文献[29-30]中描述的方法制备.1L水样通过玻璃纤维过滤器(GF/F,孔径:0.7μm,Whatman,美国)过滤,然后加入10ng的氘化的替代标准(同大气),用固相萃取柱(Oasis HLB,200mg,6mL,Waters,美国)进行固相萃取.固相萃取柱预先4mL乙酸乙酯、4mL甲醇和4mL纯水活化,流速为4mL/min.水样通过后,用6mL乙酸乙酯以1mL/min的流速洗脱,氮吹近干.目标物用100μL异辛烷复溶,加入将加入内标(TCEP-d12)待测.
OPEs分析均由气相色谱/单四极杆串联质谱(Agilent 7890A-7000A)中进行,采用DB5-MS毛细管柱(30m×0.25mm和0.25 μm膜厚度).传输线和离子源的温度分别保持在280℃和230℃.柱温箱温度从60℃开始,持续1min,以30℃/min的速率增加至220℃(保持0min),然后以5℃/min的速率(保持15min)增加至300℃[31].共检测18种国内外研究重点关注的OPEs,包括IDDPP、BEHPP、TCEP、T4IPPP、TCPP、BPADP、TDCPP、RDP、V6、CDP、RDT905、TPhP、TBP、2IPPDPP、TCrP、4tBPDPP、T4tBPP、AO168=O.其中非卤化OPEs 11种,卤化OPEs 7种,各OPEs定量下限和检出率具体见表1.
现场空白、程序空白和平行样品作为质量控制措施.每批10个样品中分别分析1个程序空白和1个溶剂空白,每个取样程序同时处理3个现场空白.实验室质控采用加标回收、重复测试和设置最低检测限值的方式,同时设置实验检测空白.样品中目标OPEs的浓度通过减去同一批空白样品的浓度进行校正.本次检测的加标回收率在79.3%~106.6%之间(表1).在分析过程中,进行每日校准,在相对误差在±10.0%内的每10个样品插入中间浓度校准.另外,每10个样品分析1个平行样品;平行样品的相对标准偏差控制在±8.0%以内.每种OPEs的定量下限计算为标准品的3倍信噪比.
采用SPSS 26.0、R 4.1.2和Graphpad Prism 8.0.2等软件对数据进行统计分析与图的绘制.采用Pearman相关系数分析各环境介质中18种OPEs组分之间的相关性;采用因子分析主成分,检验水准为α=0.05.
本文采用美国环保署健康风险评估“四步法”模型和相关技术指南[32],评估不同年龄段人群(0~<3岁婴幼儿、3~<6岁儿童、6~17岁青少年、成人、男性和女性)经手口摄入、皮肤接触和呼吸吸入土壤中OPEs,经呼吸吸入和皮肤接触大气中OPEs造成的综合潜在健康风险.暴露参数参考《中国人群暴露参数手册(成人卷)》《中国人群暴露参数手册(儿童卷)0~5岁》和《中国人群暴露参数手册(儿童卷)6~17岁》及国际权威组织或机构的推荐值.TCEP、TDCPP、TPhP和TCrP的参考剂量(RfD)综合国内外文献分析筛选确定[33-34].使用Oracle Crystal Ball中蒙特卡洛模型对OPEs健康风险进行定量的不确定性分析[35].OPEs不同暴露途径的相关毒性参数见表2.
18种OPEs组分在电子工业厂区周边环境土壤、大气和废水中广泛存在,各介质中均有不同浓度的检出.土壤、大气和废水中OPEs各组分的检出率范围分别是58.8%~100.0%、40.9%~100.0%和58.8%~100.0%;各介质中∑18OPEs的浓度水平有差异,且具有统计学意义(KWH统计量=68.7,P<0.001)(表3).
34个土壤样品中∑18OPEs浓度范围为12.2~857ng/g(均值283ng/g和中值252ng/g),浓度中位数最高的前三种卤化OPEs分别为BPADP、TCPP和TCEP,其中位数分别为5.29ng/g(3.10×10-1~212ng/g)、3.72ng/g(1.30×10-1~83.1ng/g)和3.20ng/g (n.d.~10.8ng/g);前三种非卤化OPEs分别为AO168=O、T4tBPP和TPHP,其中位数分别为90.7ng/g (9.30~298ng/g)、56.6ng/g(n.d.~397ng/g)和1.06ng/g (n.d.~68.1ng/g).与国内外其他地区相比(表4),本文中∑18OPEs浓度水平高于中国广州公园[36]和农田土壤样品[36];与越南电子废物回收区土壤[37]、中国华南地区电子垃圾拆解厂周边地表土壤[12]等浓度中位数水平接近,表明电子产品制造及拆除活动中阻燃剂、增塑剂等有机溶剂的使用及排放使得周边土壤中OPEs的累积[12].本文∑18OPEs浓度远远低于中国华南地区电子垃圾拆解厂区土壤样品[12]、中国广东省清远市电子废物处理车间室内粉尘样品[23]、加拿大废弃电器和电子设备室内粉尘样品等[24],说明电子垃圾拆解活动相比其他制造过程更易释放OPEs.虽然农业区蔬菜样品OPEs浓度[38]低于本文企业周边土壤OPEs浓度,但有研究表明农作物吸收和积累是将污染物转移到食物链中的重要步骤[39].同时,本文区属于工业区、居民区和农业种植区纵横交错区域,当地农作物中的OPEs污染与随之造成的健康风险仍需引起关注.
21个大气样品中∑18OPEs浓度范围为3.12×103~2.95×106pg/m3(均值4.48×105pg/m3和中值2.87×105pg/m3),浓度最高的前3种卤化OPEs分别为TCPP、TCEP和BPADP,其中位数分别为1.79×104pg/m3(47.4~6.42×105pg/m3)、3.33×103pg/m3(n.d.~1.36×10pg/m35)和710pg/m3(51.4~2.97×104pg/m3);前3种非卤化OPEs分别为AO168=O、T4tBPP和TPhP,其中位数分别为1.06×105pg/m3(2.85×103~2.04×106pg/m3)、6.51×104pg/m3(n.d.~5.48×105pg/m3)和2.62×103pg/m3(42.7~5.02×104pg/m3).与国内外其他地区相比(表4),本文中∑18OPEs浓度水平高于中国京津冀地区城市大气[40]和中国华东地区大气[41];比中国华南地区电子垃圾清运园区大气样品(中位数1.30×108pg/m3)低3个数量级,但高于电子垃圾清运园区周边地区大气样品(中位数7.40×104pg/m3)[42].而与南海永兴岛偏远地区的大气样品(中位数330pg/m3)[43]相比,本文中OPEs浓度远高于偏远地区.Suhring等[44]通过监测加拿大和北极空气样品发现OPEs具有远程大气输送的潜力.Zhang等[43,45]也认为正是由于OPEs可以进行远程大气输送,使得中国南海永兴岛OPEs检测结果呈现季节性变化.
30个废水样品中∑18OPEs浓度范围为5.39×105~2.73×106ng/L(均值1.11×106ng/L和中值1.12×106ng/L),浓度最高的前三种卤化OPEs分别为TCPP、TCEP和RDT905,其中位数分别为1.13×105ng/L(2.08×104~6.30×105ng/L)、5.14×104ng/L(1.13×104~3.34×105ng/L)和4.47×103ng/L(79.6~3.44×104ng/L);前3种非卤化OPEs分别为AO168=O、TBP和TPHP,其中位数分别为5.06×105ng/L(3.18×105~6.95×105ng/L)、5.84×103ng/L(n.d.~2.14×106ng/L)和5.05×103ng/L(n.d.~3.13×104ng/L).与国内外其他地区相比(表4),本文中∑18OPEs浓度水平远远高于中国珠江三角洲地区污水处理厂采集的出水样品(范围65.8~2.84×103ng/L)[46]和中国广西壮族自治区南宁市灌溉水(均值110ng/L)、雨水样品(均值84.0ng/L)[47].前人在瑞典和德国的研究已发现污水处理厂是生活水域中OPEs的来源,流出的废水通常含有较高水平的OPEs,且卤化的OPEs不易被污泥去除或降解[48-49].此外有研究表明,在最常检出的OPEs中,TCPP被归类为不易生物降解,而TBP等物质在水环境中的半衰期为几天[50],在废水中发现更高水平的TCPP与本文一致.同时有证据证明烷基磷酸盐的生物降解潜力随着其链长的增加而降低,其持久性随着其苯基取代基的数量和大小的增加而增加[51],氯化OPEs比烷基和芳基磷酸盐更耐降解[50],在本文中AO168=O在非卤化OPEs组分中显示出更高的浓度水平,卤代OPEs对人群造成的潜在持久性的健康危害需要重点关注.
电子工业厂区周边土壤、大气和废水中18种OPEs组分的占比有所差别(图2).土壤中相对丰度最高的3种依次是T4tBPP、AO168=O和BPADP,分别占∑18OPEs的39.9%、37.8%和10.6%;大气中AO168=O(48.7%)、T4tBPP(25.4%)和TCPP(17.1%)相对丰度最高,废水中AO168=O(47.0%)、T4tBPP(20.9%)和TCPP(15.0%)在样品中相对丰度最高.可见,AO168=O在土壤、大气和废水中占比均较高,平均占比达到44.5%,可作为电子工业厂区周边环境介质中特征OPEs污染物.AO168=O是AO168的主要氧化产物,而这种氧化生成的有机磷酸酯在工业应用上没有或者仅有极少的应用,被认为是新型OPEs.Liu等[53]在室内灰尘里发现了高水平的AO168=O,认为该新型OPEs是前人研究中可能被忽视的OPEs的来源.新型OPEs在环境介质中的高浓度和高检出率使其成为OPEs类污染物研究的新焦点.
土壤中OPEs组分之间的Pearson相关分析和主成分分析结果如图3(a)和(b)所示.
大多数OPEs之间存在较强的正相关关系.影响土壤中OPEs分布的主成分有2个,贡献了54.3%的OPEs来源.PC1(34.6%)中T4IPPP、T4tBPP、4tBPDPP和AO168=O具有较高的载荷.2IPPDPP、4tBPDPP、AO168作为抗氧化剂常被用于塑料外壳、塑料包装袋、聚丙烯(PP)薄膜等塑料制品中[54],而AO168=O是AO168的主要氧化产物,会在加工、挤压、储存和阳光照射之后产生[55].PC1代表了电子产品生产活动中阻燃剂、增塑剂和抗氧化剂等有机溶剂产生的副产物经大气沉降并长期在土壤中累积.PC2(19.7%)中TDCPP、CDP、IDDPP、TCEP、RDT905、V6和TCPP具有较高的载荷.TDCPP主要用作增塑剂、油漆和消泡剂等.TCIPP和TCEP是聚氨酯泡沫中主要的OPEs[56],PC2可认为是在塑料制品的生产和应用过程中产生的物质.
大气中OPEs组分之间的Pearson相关分析和主成分分析结果如图3(c)和(d)所示.部分OPEs之间存在较强相关关系.影响大气中OPEs分布的主成分有2个,贡献了70.3%的OPEs来源.PC1(52.2%)中BEHPP、T4IPPP、TCPP、TDCPP、V6、RDT905、TBP和AO168=O具有较高的载荷.研究显示目前一些商业OPEs混合物可能含有多种OPEs作为杂质或副产物,导致高度相关的发生[57].TBP、TCPP等多种OPEs组分作为抗氧化剂和抗磨剂,常被添加到润滑剂和液压油中,较容易通过挥发作用释放至大气[58].PC1代表了工业生产或使用机溶剂副产物的排放.PC2(18.1%)中IDDPP、2IPPDPP、TPhP、RDP具有较高的载荷.TPhP被广泛应用于飞机发动机和车辆发动机,特别是重型建筑机械和卡车中使用的柴油发动机[47],已被建议作为柴油车的排放指标[59].PC2代表交通排放.
废水中OPEs组分含量之间的Pearson相关分析和主成分分析结果如图3(e)和(f)所示.大多数OPEs之间存在较强的相关关系.影响废水中OPEs分布的主成分有2个,贡献了44.1%的OPEs来源.PC1(28.8%)中T4tBPP、AO168=O具有较高的载荷.AO168=O是AO168的主要氧化产物,AO168是目前使用最广泛的OPEs,广泛用于除氯化塑料以外的所有塑料制品的生产[53].PC1代表了电子工业中生产或使用塑料制品的排放.PC2(15.3%)中TPhP、TCPP、TCrP、2IPPDPP、CDP具有较高的载荷.TPhP可以作为电子废物分解过程的指标[42].PC2代表电子拆解过程的排放.
不同年龄段人群经多种途径暴露于土壤和大气中OPEs的非致癌健康风险以综合危害商(HQ)定量表征(图4).0~<3岁婴幼儿、3~<6岁儿童、6~17岁青少年、成人暴露于∑16OPEs的HQ均值分别为4.98×10-3(6.88×10-6~4.42×10-2)、4.35×10-3(5.90×10-6~3.86×10-2)、3.28×10-3(4.46×10-6~2.91×10-2)、5.39×10-4(7.58×10-7~4.72×10-3),其中,男性和女性暴露于∑16OPEs的HQ均值分别为5.31×10-4(7.46×10-7~4.70×10-3)和5.43×10-4(7.65×10-7~4.83×10-3),HQ值均小于1.0,提示不同年龄段人群经多种途径暴露于土壤和大气中OPEs的非致癌健康风险处于可接受水平.结果显示不同年龄段人群的HQ存在较大差异,HQ从高到低分别是0~3岁婴幼儿、3~6岁儿童、6~17岁青少年、成人.成人性别存在差异,女性HQ值略高于男性.暴露于大气OPEs的HQ比土壤OPEs高2~3个数量级,卤化OPEs的HQ均值高于非卤化OPEs的HQ均值.在OPEs各组分中TCPP的非致癌健康风险最高,TCEP的非致癌健康风险也明显高于其他组分.
不同年龄段人群经多种途径暴露于土壤和大气中OPEs的致癌健康风险以综合风险值(CR)定量表征(图5).0~<3岁婴幼儿、3~<6岁儿童、6~17岁青少年、成人暴露于∑2OPEs的CR均值分别为1.57×10-8(7.39×10-11~1.83×10-7)、1.37×10-8(6.42×10-11~1.60×10-7)、1.03×10-8(4.84×10-11~1.20×10-7)和6.88×10-9(3.24×10-11~8.00×10-8),其中,男性和女性暴露于∑2OPEs的CR均值分别为6.78×10-9(3.19×10-11~7.89×10-8)和6.92×10-9(3.26×10-11~8.05×10-8).CR值均小于1.0×10-6,提示不同年龄段人群经多种途径暴露于土壤和大气中OPEs的致癌健康风险处于可接受水平.结果显示土壤和大气OPEs污染导致不同年龄段人群的致癌健康风险存在较大差异,致癌健康风险从高到低分别是0~<3岁婴幼儿、3~<6岁儿童、6~17岁青少年、成人.成人性别存在差异,女性致癌健康风险略高于男性.暴露于大气OPEs的致癌健康风险比土壤OPEs高2~3个数量级,TCEP的致癌健康风险高于TDCPP的致癌健康风险.
进一步分析OPEs健康风险评估的不确定性和敏感性[35].通过蒙特卡洛模拟成人暴露于土壤和大气OPEs的综合HQ和CR的概率分布(图6).结果显示,成人暴露于OPEs的综合HQ值远低于1.0,综合CR值远低于1.0×10-6,表明暴露于OPEs的非致癌和致癌健康风险均较低,但脆弱人群的OPEs暴露风险情况仍需注意防控.
对于成人暴露于OPEs非致癌健康风险的敏感度,大气OPEs浓度(35.21%)和暴露期(23.53%)是增加综合HQ值的最主要因素,而RfD值(-25.92%)作用相反.对于成人暴露于OPEs致癌健康风险的敏感度,暴露期(28.77%)和大气OPEs浓度(14.45%)是增加综合CR值的最主要因素,而致癌效应平均时间(-25.92%)作用相反.
3.1 电子工业企业周边环境土壤、大气和废水中广泛检出OPEs,AO168=O、T4tBPP、TCPP、和BPADP是主要组分,AO168=O可作为电子工业特征OPEs污染物.
3.2 电子工业企业周边环境介质中OPEs主要来源于工业生产和交通排放.
3.3 不同年龄段人群(0~3岁婴幼儿、3~6岁儿童、6~17岁青少年、成人、男性和女性)经手口摄入、皮肤接触和呼吸吸入途径暴露土壤和大气中OPEs的非致癌和致癌健康风险处于人群可接受水平,但OPEs长期累积暴露的健康风险依然不容忽视.
3.4 成人暴露于土壤和大气OPEs总的非致癌和致癌风险的不确定性均在可接受水平.
  • 中央级公益性科研院所基本科研业务费专项(2023YSKY-35)
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2025年第45卷第6期
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  • 接收时间:2024-10-09
  • 首发时间:2026-02-27
  • 出版时间:2025-06-20
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  • 收稿日期:2024-10-09
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中央级公益性科研院所基本科研业务费专项(2023YSKY-35)
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    1.中国环境科学研究院,环境基准标准与风险管控全国重点实验室,国家环境保护化学品生态效应与风险评估重点实验室,北京 100012
    2.兰州大学大气科学学院,半干旱气候变化教育部重点实验室,甘肃 兰州 730000
    3.深圳市环境科学研究院,国家环境保护饮用水水源地管理技术重点实验室,深圳市水环境中新型污染物检测与控制重点实验室,广东 深圳 518001
    4.兰州大学公共卫生学院,劳动卫生与环境卫生学研究所,甘肃 兰州 730000

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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