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In order to study the emission characteristics of VOCs from the electronics-manufacturing industry and associated health risk assessment, ten typical electronics enterprises were selected to carry out sample collection and VOCs detection. Moreover, the impacts of VOCs on human health were evaluated by the US EPA and ACGIH methods. The results showed that: The concentrations of VOCs emitted from different types of electronic enterprises exhaust gas were different. The VOCs concentrations in the semiconductor devise and electronic terminal product were relatively higher than those in the display device and printed circuit board, and the VOCs concentrations were 13.41~13.63, 3.34~86.11, 7.86~9.75 and 4.31~4.67mg/m3, respectively. The main organic group in semiconductor devise exhaust gas was alkanes (70.56%~70.78%), and dimethylpentane (32.03%~33.60%) was the main VOCs species. The main organic group in display device exhaust gas and printed circuit board exhaust gas were both OVOCs, accounting for 93.48%~95.87% and 92.27%~93.05%, respectively. Additionally, the highest mass fraction were acetone (91.89%~94.99%) and isopropanol (80.36%~83.07%) in display device and printed circuit board. Due to the different production products, VOCs components were different in the electronic terminal product, but mainly OVOCs, aromatics and alkanes. The coefficient of divergence between different enterprises was 0.67~0.91, indicating that VOCs source profiles must not be similar. Total hazard ratio for non-cancer risk in semiconductor devise was the highest (484.35), followed by display device (447.46), electronic terminal product (11.74~87.35) and printed circuit boards (2.25), suggesting long-term exposure of various electronic industries would cause non-cancer health hazards. The LCRs from semiconductor devise (1.63×10-3) and electronic terminal product (1.64×10-4~5.16×10-3) were much higher, suggesting that these enterprises have a certain cancer risk. The LCRs from display device and printed circuit board were 1.74×10-5 and 1.40×10-5, indicating that these enterprises have a high probability cancer risk. The total Ei from electronic terminal product was the highest, while that from display device was the lowest. However, the Ei in different electronics industries were lower than 0.1, indicating that VOCs emitted from these industries may not generate many harmful effects to the workers. The results of the cancer risk assessment using the EPA and ACGIH methods vary significantly. This is mainly because two methods have different limiting indicators for the reference concentration of VOCs species exposure. But on the whole, the health risks from VOCs emitted in the electronic terminal product and semiconductor devise were much higher than in the other two industries. Therefore, to ensure the safety of workers, measures for controlling VOCs should be strengthened.

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为研究电子工业挥发性有机物(VOCs)排放特征及其健康风险影响,选取10家典型的电子企业,对其生产过程中产生的工艺废气进行样品采集和VOCs检测,并通过美国EPA和ACGIH方法评估其对人体健康的影响.结果表明:不同电子企业排气筒VOCs排放存在差异,半导体器件与电子终端产品行业VOCs浓度相对高于显示器及光电子器件与印制电路板行业,其VOCs浓度分别为13.41~13.63, 3.34~86.11, 7.86~9.75和4.31~4.67mg/m3;半导体器件排气筒废气中VOCs以烷烃为主(70.56%~70.78%),质量分数最高的VOCs物种为二甲基戊烷(32.03%~33.60%);显示器及光电子器件和印制电路板企业排气筒废气中VOCs均以OVOCs为主,质量分数分别为(93.48%~95.87%)和(92.27%~93.05%),且质量分数最高的分别为丙酮(91.89%~94.99%)和异丙醇(80.36%~83.07%);电子终端产品行业由于生产产品不同,导致排气筒废气中VOCs组分存在差异,但以OVOCs、芳香烃和烷烃为主;不同企业间分歧系数为0.67~0.91,即VOCs源成分谱必不相似;半导体器件的非致癌风险HR最高(484.35),其次为显示器及光电子器件(447.46)、电子终端产品(11.74~87.35)和印制电路板(2.25),即各电子行业长期暴露均会造成非致癌健康危害;半导体器件(1.63×10-3)、电子终端产品(1.64×10-4~5.16×10-3)行业LCR值较高,会产生确定的致癌风险;显示器及光电子器件、印制电路板行业LCR值分别为1.74×10-5和1.40×10-5,有大概率致癌风险;电子终端产品子行业的总Ei值相对较大,显示器及光电子器件行业的总Ei值最小,但所有电子行业的Ei值均低于0.1,表明电子行业VOCs排放可能不会对工人产生健康影响.EPA和ACGIH方法评估致癌风险的结果差异较大,主要是因为两种方法对VOCs物种暴露参考浓度的限定指标不同.但整体来看,电子终端企业产品及半导体器件行业排放的VOCs健康风险远高于其他两个子行业,因此,应重点加强两个行业VOCs管控以保护工人健康.

, correspAuthors=李国昊, authorNote=null, correspAuthorsNote=
*责任作者,研究员,
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吕喆(1992-),女,北京人,副研究员,博士,主要研究方向为大气污染防治.发表论文18篇. .

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吕喆(1992-),女,北京人,副研究员,博士,主要研究方向为大气污染防治.发表论文18篇. .

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吕喆(1992-),女,北京人,副研究员,博士,主要研究方向为大气污染防治.发表论文18篇. .

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Environmental Science and Managemant200732(10):37-41,44., articleTitle=Study on the emission of volatile organic compounds (VOCs) from semiconductor manufacture industry, refAbstract=null), Reference(id=1240689626260754446, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2012, volume=33, issue=9, pageStart=2967, pageEnd=2972, url=null, language=null, rfNumber=[35], rfOrder=54, authorNames=马英歌, journalName=环境科学, refType=null, unstructuredReference=马英歌. 印制电路板(PCB)厂挥发性有机物(VOCs)排放指示物筛选[J]. 环境科学201233(9):2967-2972., articleTitle=印制电路板(PCB)厂挥发性有机物(VOCs)排放指示物筛选, refAbstract=null), Reference(id=1240689626348834840, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2012, volume=33, issue=9, pageStart=2967, pageEnd=2972, url=null, language=null, rfNumber=[35], rfOrder=55, authorNames=Ma Y G, journalName=Environmental Science, refType=null, unstructuredReference=Ma Y G. Composition and characteristics of volatile organic chemicals emission from printed circuit board factories [J]. Environmental Science201233(9):2967-2972., articleTitle=Composition and characteristics of volatile organic chemicals emission from printed circuit board factories, refAbstract=null), Reference(id=1240689626457886750, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2020, volume=11, issue=5, pageStart=841, pageEnd=850, url=null, language=null, rfNumber=[36], rfOrder=56, authorNames=Zhang Y S, Li C, Yan Q S, journalName=Atmospheric Pollution Research, refType=null, unstructuredReference=Zhang Y SLi CYan Q S,et al. Typical industrial sector-based volatile organic compounds source profiles and ozone formation potentials in Zhengzhou,China. Atmospheric Pollution Research202011(5):841–850., articleTitle=Typical industrial sector-based volatile organic compounds source profiles and ozone formation potentials in Zhengzhou,China, refAbstract=null), Reference(id=1240689626558550055, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2018, volume=38, issue=2, pageStart=412, pageEnd=417, url=null, language=null, rfNumber=[37], rfOrder=57, authorNames=张伟, 姬亚芹, 张军, journalName=中国环境科学, refType=null, unstructuredReference=张伟,姬亚芹,张军,等. 辽宁省典型城市道路尘PM2.5成分谱研究[J]. 中国环境科学201838(2):412-417., articleTitle=辽宁省典型城市道路尘PM2.5成分谱研究, refAbstract=null), Reference(id=1240689626667601971, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2018, volume=38, issue=2, pageStart=412, pageEnd=417, url=null, language=null, rfNumber=[37], rfOrder=58, authorNames=Zhang W, Ji Y Q, Zhang J, journalName=China Environmental Science, refType=null, unstructuredReference=Zhang WJi Y QZhang J,et al. 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China Environmental Science201838(2):412-417., articleTitle=Study on the road dust source profile of PM2.5 in Liaoning Province typical cities, refAbstract=null), Reference(id=1240689626780848188, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2020, volume=40, issue=9, pageStart=3791, pageEnd=3800, url=null, language=null, rfNumber=[38], rfOrder=59, authorNames=冯旸, 刘锐源, 刘雷璐, journalName=中国环境科学, refType=null, unstructuredReference=冯旸,刘锐源,刘雷璐,等. 广州典型印刷企业VOCs排放特征及环境影响和健康风险评价[J]. 中国环境科学202040(9):3791-3800., articleTitle=广州典型印刷企业VOCs排放特征及环境影响和健康风险评价, refAbstract=null), Reference(id=1240689626894094406, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, doi=null, pmid=null, pmcid=null, year=2020, volume=40, issue=9, pageStart=3791, pageEnd=3800, url=null, language=null, rfNumber=[38], rfOrder=60, authorNames=Feng Y, Liu R Y, Liu L L, journalName=China Environmental Science, refType=null, unstructuredReference=Feng YLiu R YLiu L L,et al. VOCs emission characteristics,environmental impact and health risk assessment of typical printing enterprises in Guangzhou [J]. China Environmental Science202040(9):3791-3800., articleTitle=VOCs emission characteristics,environmental impact and health risk assessment of typical printing enterprises in Guangzhou, refAbstract=null)], funds=[Fund(id=1240689616165065036, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, awardId=Z181100005418015, language=CN, fundingSource=北京市科委“首都蓝天行动培育”专项(Z181100005418015), fundOrder=null, country=null), Fund(id=1240689616328642906, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, awardId=null, language=CN, fundingSource=O3与PM2.5复合污染协同防治预研项目, fundOrder=null, country=null)], companyList=[AuthorCompany(id=1240689605075325538, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, xref=null, ext=[AuthorCompanyExt(id=1240689605092102756, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, companyId=1240689605075325538, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Beijing Key Laboratory of Urban Atmospheric Volatile Organic Compounds Pollution Control and Application, National Engineering Research Center of Urban Environmental Pollution Control, Beijing Municipal Research Institute of Eco-Environmental Protection, Beijing 100037, China), AuthorCompanyExt(id=1240689605096297061, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, companyId=1240689605075325538, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=北京市生态环境保护科学研究院,国家城市环境污染控制工程技术研究中心,城市大气挥发性有机物污染防治技术与应用北京市重点实验室,北京 100037)])], figs=[ArticleFig(id=1240689610334982160, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.1, caption=The number and distribution of electronics-manufacturing industry enterprises in Beijing, figureFileSmall=7z2fg0pKeVWo9tAHgL/XYA==, figureFileBig=jaRjKrvRGPYv0pKUsWanHw==, tableContent=null), ArticleFig(id=1240689611740074010, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图1, caption=北京市电子工业企业数量及分布情况, figureFileSmall=7z2fg0pKeVWo9tAHgL/XYA==, figureFileBig=jaRjKrvRGPYv0pKUsWanHw==, tableContent=null), ArticleFig(id=1240689612079812662, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.2, caption=VOCs emission concentration of exhaust gas in different electronic enterprises, figureFileSmall=ukmbqhpozYv/vPYk5brB7A==, figureFileBig=E8JIpz25iGbGj2zJbcNjcg==, tableContent=null), ArticleFig(id=1240689612180475973, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图2, caption=不同电子企业排气筒VOCs排放浓度, figureFileSmall=ukmbqhpozYv/vPYk5brB7A==, figureFileBig=E8JIpz25iGbGj2zJbcNjcg==, tableContent=null), ArticleFig(id=1240689612281139282, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.3, caption=VOCs emission composition of electronic enterprises, figureFileSmall=MVhhFg2Ef46rYA2vK+kqgQ==, figureFileBig=miHRrXFVetBqdjSndwNk3Q==, tableContent=null), ArticleFig(id=1240689612457300076, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图3, caption=各电子企业VOCs排放组成, figureFileSmall=MVhhFg2Ef46rYA2vK+kqgQ==, figureFileBig=miHRrXFVetBqdjSndwNk3Q==, tableContent=null), ArticleFig(id=1240689612708958335, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.4, caption=Coefficient of divergence of VOCs source profiles in different electronic enterprises, figureFileSmall=Cdm5L7u3oKSpGV68xZDCRQ==, figureFileBig=SmM1oD2Hpwuan2BM5WZKEg==, tableContent=null), ArticleFig(id=1240689612876730508, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图4, caption=不同电子企业VOCs成分谱分歧系数, figureFileSmall=Cdm5L7u3oKSpGV68xZDCRQ==, figureFileBig=SmM1oD2Hpwuan2BM5WZKEg==, tableContent=null), ArticleFig(id=1240689613023531163, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.5, caption=VOCs source profiles of different electronics-manufacturing industries, figureFileSmall=TtFHI+KuhxV8q8HBcxpjpQ==, figureFileBig=sL7ivKk253aPaIByWOWq+g==, tableContent=null), ArticleFig(id=1240689613199691949, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图5, caption=不同电子行业VOCs成分谱, figureFileSmall=TtFHI+KuhxV8q8HBcxpjpQ==, figureFileBig=sL7ivKk253aPaIByWOWq+g==, tableContent=null), ArticleFig(id=1240689613342298293, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.6, caption=Non-cancer risks of VOCs in different electronics-manufacturing industries, figureFileSmall=bJz1ix8Dg7jZWnt7cYVrMw==, figureFileBig=lHHHI/NjYvOxxvM3Tvn7JA==, tableContent=null), ArticleFig(id=1240689613434572989, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图6, caption=不同电子行业VOCs的非致癌风险, figureFileSmall=bJz1ix8Dg7jZWnt7cYVrMw==, figureFileBig=lHHHI/NjYvOxxvM3Tvn7JA==, tableContent=null), ArticleFig(id=1240689613518459080, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.7, caption=Lifetime cancer risks of VOCs in different electronics-manufacturing industries, figureFileSmall=c2IltplaIvuCv6mNQ6MNUQ==, figureFileBig=Rv9G21SjI+m12u5ctRhcuQ==, tableContent=null), ArticleFig(id=1240689613661065426, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图7, caption=不同电子行业VOCs的终生癌风险, figureFileSmall=c2IltplaIvuCv6mNQ6MNUQ==, figureFileBig=Rv9G21SjI+m12u5ctRhcuQ==, tableContent=null), ArticleFig(id=1240689613765923040, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Fig.8, caption=Occupational exposure indexes of VOCs in different electronics-manufacturing industries, figureFileSmall=69s84IlGdjIyCbhEZ9NpAA==, figureFileBig=ALEgvPYNmg+KSSXIMF9WdA==, tableContent=null), ArticleFig(id=1240689613874974959, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=图8, caption=不同电子行业职业暴露指数, figureFileSmall=69s84IlGdjIyCbhEZ9NpAA==, figureFileBig=ALEgvPYNmg+KSSXIMF9WdA==, tableContent=null), ArticleFig(id=1240689613996609785, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Table 1, caption=

Electronics-manufacturing industry enterprise information in Beijing

, figureFileSmall=null, figureFileBig=null, tableContent=
企业编号行业类别主要产品采样位置废气处理设施样品数量
A企业半导体器件集成电路排气筒沸石转轮浓缩+RTO3
B企业半导体器件集成电路排气筒沸石转轮浓缩+RTO3
C企业显示器及光电子器件液晶面板排气筒沸石转轮浓缩+TO3
D企业显示器及光电子器件液晶面板排气筒沸石转轮浓缩+TO3
E企业印制电路板制造印制电路板排气筒活性炭吸附3
F企业印制电路板制造印制电路板排气筒活性炭吸附3
G企业电子终端产品控制板排气筒活性炭吸附脱附+RCO3
H企业电子终端产品音箱排气筒活性炭吸附3
I企业电子终端产品显示器排气筒活性炭吸附3
J企业电子终端产品医疗产品排气筒活性炭+UV光解3
), ArticleFig(id=1240689614143410442, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=表1, caption=

北京市电子工业企业信息

, figureFileSmall=null, figureFileBig=null, tableContent=
企业编号行业类别主要产品采样位置废气处理设施样品数量
A企业半导体器件集成电路排气筒沸石转轮浓缩+RTO3
B企业半导体器件集成电路排气筒沸石转轮浓缩+RTO3
C企业显示器及光电子器件液晶面板排气筒沸石转轮浓缩+TO3
D企业显示器及光电子器件液晶面板排气筒沸石转轮浓缩+TO3
E企业印制电路板制造印制电路板排气筒活性炭吸附3
F企业印制电路板制造印制电路板排气筒活性炭吸附3
G企业电子终端产品控制板排气筒活性炭吸附脱附+RCO3
H企业电子终端产品音箱排气筒活性炭吸附3
I企业电子终端产品显示器排气筒活性炭吸附3
J企业电子终端产品医疗产品排气筒活性炭+UV光解3
), ArticleFig(id=1240689614248268052, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Table 2, caption=

Health Risk Assessment Parameters

, figureFileSmall=null, figureFileBig=null, tableContent=
类别物种CASRfc(mg/m3)来源UR[(mg/m3)-1]来源TLV-TWA(10-6)
烷烃正戊烷109-66-01IRIS1000
异戊烷78-78-41000
正己烷110-54-30.7IRIS50
环己烷110-82-76IRIS100
庚烷142-82-50.4PPRTV400
2,2-二甲基丁烷75-83-2500
2,3-二甲基丁烷79-29-8500
2-甲基戊烷73513-42-5500
3-甲基戊烷96-14-0500
2-甲基庚烷592-27-8300
2-甲基己烷591-76-4400
3-甲基己烷589-34-4400
甲基环己烷108-87-23HEAST400
烯烃1,3-丁二烯106-99-00.002IRIS0.03IRIS2
1-丁烯106-98-9250
丙烯115-07-13Cal EPA500
芳香烃71-43-20.03IRIS0.0078IRIS0.5
甲苯108-88-35IRIS20
乙苯100-41-41IRIS0.0025OEHHA20
间、对二甲苯108-38-3/1330-20-70.217ATSDR100
邻二甲苯95-47-60.217ATSDR100
异丙苯98-82-80.4IRIS
正丙苯103-65-11X50
1,2,3-三甲基苯526-73-80.005PPRTV25
1,2,4-三甲基苯95-63-60.007PPRTV25
1,3,5-三甲基苯108-67-80.006PPRTV25
OVOCs丙酮67-64-131ATSDR500
异丙醇67-63-0200
丙烯醛107-02-80.00002IRIS
乙酸乙烯酯108-05-40.2IRIS10
甲基丙烯酸甲酯80-62-60.7IRIS50
丁醇35296-72-120
2-丁酮591-78-60.02IRIS200
乙酸丁酯123-86-4200
乙酸乙酯141-78-6400
卤代烃氯甲烷74-87-30.09IRIS50
氯仿67-66-30.098ATSDR0.023IRIS10
二氯甲烷75-09-20.6IRIS0.47IRIS50
三氯乙烯79-01-60.0019IRIS0.0041IRIS10
1,2-二氯丙烷78-87-50.004IRIS10
1,2-二氯乙烷107-06-20.007PPRTV0.026IRIS10
), ArticleFig(id=1240689614365708576, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=表2, caption=

健康风险评估参数

, figureFileSmall=null, figureFileBig=null, tableContent=
类别物种CASRfc(mg/m3)来源UR[(mg/m3)-1]来源TLV-TWA(10-6)
烷烃正戊烷109-66-01IRIS1000
异戊烷78-78-41000
正己烷110-54-30.7IRIS50
环己烷110-82-76IRIS100
庚烷142-82-50.4PPRTV400
2,2-二甲基丁烷75-83-2500
2,3-二甲基丁烷79-29-8500
2-甲基戊烷73513-42-5500
3-甲基戊烷96-14-0500
2-甲基庚烷592-27-8300
2-甲基己烷591-76-4400
3-甲基己烷589-34-4400
甲基环己烷108-87-23HEAST400
烯烃1,3-丁二烯106-99-00.002IRIS0.03IRIS2
1-丁烯106-98-9250
丙烯115-07-13Cal EPA500
芳香烃71-43-20.03IRIS0.0078IRIS0.5
甲苯108-88-35IRIS20
乙苯100-41-41IRIS0.0025OEHHA20
间、对二甲苯108-38-3/1330-20-70.217ATSDR100
邻二甲苯95-47-60.217ATSDR100
异丙苯98-82-80.4IRIS
正丙苯103-65-11X50
1,2,3-三甲基苯526-73-80.005PPRTV25
1,2,4-三甲基苯95-63-60.007PPRTV25
1,3,5-三甲基苯108-67-80.006PPRTV25
OVOCs丙酮67-64-131ATSDR500
异丙醇67-63-0200
丙烯醛107-02-80.00002IRIS
乙酸乙烯酯108-05-40.2IRIS10
甲基丙烯酸甲酯80-62-60.7IRIS50
丁醇35296-72-120
2-丁酮591-78-60.02IRIS200
乙酸丁酯123-86-4200
乙酸乙酯141-78-6400
卤代烃氯甲烷74-87-30.09IRIS50
氯仿67-66-30.098ATSDR0.023IRIS10
二氯甲烷75-09-20.6IRIS0.47IRIS50
三氯乙烯79-01-60.0019IRIS0.0041IRIS10
1,2-二氯丙烷78-87-50.004IRIS10
1,2-二氯乙烷107-06-20.007PPRTV0.026IRIS10
), ArticleFig(id=1240689614470566188, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=EN, label=Table 3, caption=

The top five species of VOCs mass fraction in each enterprise

, figureFileSmall=null, figureFileBig=null, tableContent=
企业特征VOCs
A二甲基戊烷(33.60%)、三氯乙烯(24.61%)、三甲基戊烷(16.87%)、正戊烷(8.14%)、2,3-二甲基丁烷(5.58%)
B二甲基戊烷(32.03%)、三氯乙烯(24.60%)、三甲基戊烷(17.17%)、正戊烷(8.63%)、2,3-二甲基丁烷(5.71%)
C丙酮(91.89%)、间/对二甲苯(2.43%)、乙酸丁酯(1.16%)、乙苯(0.95%)、1,3,5-三甲基苯(0.93%)
D丙酮(94.99%)、间/对二甲苯(1.82%)、1,3,5-三甲基苯(0.57%)、乙酸丁酯(0.56%)、乙苯(0.45%)
E异丙醇(80.36%)、乙醇(10.02%)、间/对二甲苯(3.37%)、丙酮(1.27%)、乙苯(1.11%)
F异丙醇(83.07%)、乙醇(6.40%)、丙酮(3.16%)、间/对二甲苯(3.06%)、乙苯(1.01%)
G乙醇(67.31%)、异丙醇(22.45%)、乙酸丁酯(5.74%)、间/对二甲苯(0.62%)、环己烷(0.62%)
H甲苯(82.08%)、2-丁酮(4.40%)、甲基丙烯酸甲酯(2.78%)、乙苯(2.25%)、间/对二甲苯(1.89%)
I二甲基戊烷(46.55%)、三氯乙烯(18.06%)、三甲基戊烷(9.7%)、异丙醇(7.85%)、正戊烷(5.82%)
J乙苯(46.42%)、乙酸丁酯(20.47%)、间/对二甲苯(14.29%)、邻二甲苯(10.37%)、甲苯(1.36%)
), ArticleFig(id=1240689614592201015, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1240689596632191993, language=CN, label=表3, caption=

各企业VOCs质量分数前5位物种

, figureFileSmall=null, figureFileBig=null, tableContent=
企业特征VOCs
A二甲基戊烷(33.60%)、三氯乙烯(24.61%)、三甲基戊烷(16.87%)、正戊烷(8.14%)、2,3-二甲基丁烷(5.58%)
B二甲基戊烷(32.03%)、三氯乙烯(24.60%)、三甲基戊烷(17.17%)、正戊烷(8.63%)、2,3-二甲基丁烷(5.71%)
C丙酮(91.89%)、间/对二甲苯(2.43%)、乙酸丁酯(1.16%)、乙苯(0.95%)、1,3,5-三甲基苯(0.93%)
D丙酮(94.99%)、间/对二甲苯(1.82%)、1,3,5-三甲基苯(0.57%)、乙酸丁酯(0.56%)、乙苯(0.45%)
E异丙醇(80.36%)、乙醇(10.02%)、间/对二甲苯(3.37%)、丙酮(1.27%)、乙苯(1.11%)
F异丙醇(83.07%)、乙醇(6.40%)、丙酮(3.16%)、间/对二甲苯(3.06%)、乙苯(1.01%)
G乙醇(67.31%)、异丙醇(22.45%)、乙酸丁酯(5.74%)、间/对二甲苯(0.62%)、环己烷(0.62%)
H甲苯(82.08%)、2-丁酮(4.40%)、甲基丙烯酸甲酯(2.78%)、乙苯(2.25%)、间/对二甲苯(1.89%)
I二甲基戊烷(46.55%)、三氯乙烯(18.06%)、三甲基戊烷(9.7%)、异丙醇(7.85%)、正戊烷(5.82%)
J乙苯(46.42%)、乙酸丁酯(20.47%)、间/对二甲苯(14.29%)、邻二甲苯(10.37%)、甲苯(1.36%)
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电子工业挥发性有机物排放及健康风险评价
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吕喆 , 李国昊 * , 白画画 , 刘晓宇 , 邵霞 , 聂磊
中国环境科学 | 环境毒理与健康 2025,45(2): 1074-1087
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中国环境科学 | 环境毒理与健康 2025, 45(2): 1074-1087
电子工业挥发性有机物排放及健康风险评价
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吕喆 , 李国昊* , 白画画, 刘晓宇, 邵霞, 聂磊
作者信息
  • 北京市生态环境保护科学研究院,国家城市环境污染控制工程技术研究中心,城市大气挥发性有机物污染防治技术与应用北京市重点实验室,北京 100037
  • 吕喆(1992-),女,北京人,副研究员,博士,主要研究方向为大气污染防治.发表论文18篇. .

通讯作者:

*责任作者,研究员,
Emission characteristics and health risk assessment of volatile organic compounds from electronics-manufacturing industry
Zhe LYU , Guo-hao LI* , Hua-hua BAI, Xiao-yu LIU, Xia SHAO, Lei NIE
Affiliations
  • Beijing Key Laboratory of Urban Atmospheric Volatile Organic Compounds Pollution Control and Application, National Engineering Research Center of Urban Environmental Pollution Control, Beijing Municipal Research Institute of Eco-Environmental Protection, Beijing 100037, China
出版时间: 2025-02-20
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为研究电子工业挥发性有机物(VOCs)排放特征及其健康风险影响,选取10家典型的电子企业,对其生产过程中产生的工艺废气进行样品采集和VOCs检测,并通过美国EPA和ACGIH方法评估其对人体健康的影响.结果表明:不同电子企业排气筒VOCs排放存在差异,半导体器件与电子终端产品行业VOCs浓度相对高于显示器及光电子器件与印制电路板行业,其VOCs浓度分别为13.41~13.63, 3.34~86.11, 7.86~9.75和4.31~4.67mg/m3;半导体器件排气筒废气中VOCs以烷烃为主(70.56%~70.78%),质量分数最高的VOCs物种为二甲基戊烷(32.03%~33.60%);显示器及光电子器件和印制电路板企业排气筒废气中VOCs均以OVOCs为主,质量分数分别为(93.48%~95.87%)和(92.27%~93.05%),且质量分数最高的分别为丙酮(91.89%~94.99%)和异丙醇(80.36%~83.07%);电子终端产品行业由于生产产品不同,导致排气筒废气中VOCs组分存在差异,但以OVOCs、芳香烃和烷烃为主;不同企业间分歧系数为0.67~0.91,即VOCs源成分谱必不相似;半导体器件的非致癌风险HR最高(484.35),其次为显示器及光电子器件(447.46)、电子终端产品(11.74~87.35)和印制电路板(2.25),即各电子行业长期暴露均会造成非致癌健康危害;半导体器件(1.63×10-3)、电子终端产品(1.64×10-4~5.16×10-3)行业LCR值较高,会产生确定的致癌风险;显示器及光电子器件、印制电路板行业LCR值分别为1.74×10-5和1.40×10-5,有大概率致癌风险;电子终端产品子行业的总Ei值相对较大,显示器及光电子器件行业的总Ei值最小,但所有电子行业的Ei值均低于0.1,表明电子行业VOCs排放可能不会对工人产生健康影响.EPA和ACGIH方法评估致癌风险的结果差异较大,主要是因为两种方法对VOCs物种暴露参考浓度的限定指标不同.但整体来看,电子终端企业产品及半导体器件行业排放的VOCs健康风险远高于其他两个子行业,因此,应重点加强两个行业VOCs管控以保护工人健康.

电子工业  /  挥发性有机物(VOCs)  /  排放特征  /  健康影响

In order to study the emission characteristics of VOCs from the electronics-manufacturing industry and associated health risk assessment, ten typical electronics enterprises were selected to carry out sample collection and VOCs detection. Moreover, the impacts of VOCs on human health were evaluated by the US EPA and ACGIH methods. The results showed that: The concentrations of VOCs emitted from different types of electronic enterprises exhaust gas were different. The VOCs concentrations in the semiconductor devise and electronic terminal product were relatively higher than those in the display device and printed circuit board, and the VOCs concentrations were 13.41~13.63, 3.34~86.11, 7.86~9.75 and 4.31~4.67mg/m3, respectively. The main organic group in semiconductor devise exhaust gas was alkanes (70.56%~70.78%), and dimethylpentane (32.03%~33.60%) was the main VOCs species. The main organic group in display device exhaust gas and printed circuit board exhaust gas were both OVOCs, accounting for 93.48%~95.87% and 92.27%~93.05%, respectively. Additionally, the highest mass fraction were acetone (91.89%~94.99%) and isopropanol (80.36%~83.07%) in display device and printed circuit board. Due to the different production products, VOCs components were different in the electronic terminal product, but mainly OVOCs, aromatics and alkanes. The coefficient of divergence between different enterprises was 0.67~0.91, indicating that VOCs source profiles must not be similar. Total hazard ratio for non-cancer risk in semiconductor devise was the highest (484.35), followed by display device (447.46), electronic terminal product (11.74~87.35) and printed circuit boards (2.25), suggesting long-term exposure of various electronic industries would cause non-cancer health hazards. The LCRs from semiconductor devise (1.63×10-3) and electronic terminal product (1.64×10-4~5.16×10-3) were much higher, suggesting that these enterprises have a certain cancer risk. The LCRs from display device and printed circuit board were 1.74×10-5 and 1.40×10-5, indicating that these enterprises have a high probability cancer risk. The total Ei from electronic terminal product was the highest, while that from display device was the lowest. However, the Ei in different electronics industries were lower than 0.1, indicating that VOCs emitted from these industries may not generate many harmful effects to the workers. The results of the cancer risk assessment using the EPA and ACGIH methods vary significantly. This is mainly because two methods have different limiting indicators for the reference concentration of VOCs species exposure. But on the whole, the health risks from VOCs emitted in the electronic terminal product and semiconductor devise were much higher than in the other two industries. Therefore, to ensure the safety of workers, measures for controlling VOCs should be strengthened.

electronic manufacturing industry  /  volatile organic compounds (VOCs)  /  emission characteristics  /  health impact
吕喆, 李国昊, 白画画, 刘晓宇, 邵霞, 聂磊. 电子工业挥发性有机物排放及健康风险评价. 中国环境科学, 2025 , 45 (2) : 1074 -1087 .
Zhe LYU, Guo-hao LI, Hua-hua BAI, Xiao-yu LIU, Xia SHAO, Lei NIE. Emission characteristics and health risk assessment of volatile organic compounds from electronics-manufacturing industry[J]. China Environmental Science, 2025 , 45 (2) : 1074 -1087 .
随着我国社会经济的快速发展和城市化进程的不断加快,以细颗粒物(PM2.5)和O3为特征的区域复合污染问题突出[1-3].为解决我国大气污染问题,国务院先后颁布实施了《大气污染防治行动计划》[4]、《打赢蓝天保卫战三年行动计划》[5]、《空气质量持续改善行动计划》[6]等一系列管控措施,2013~2022年,中国PM2.5平均浓度下降了57%,重污染天数减少93%[7],成为全世界空气质量改善速度最快的国家.然而,2022年京津冀及周边地区、汾渭平原PM2.5平均浓度为44与46µg/m3,O3日最大8h平均值第90百分位数浓度平均分别为179与167µg/m3,仍分别超过《环境空气质量标准》(GB3095-2012)[8]中污染物二级浓度限值的25.7%和31.4%、11.9%和4.4%.秋冬季PM2.5污染,夏季O3污染依然十分严重,区域重污染天气过程仍时有发生.因此,开展PM2.5和O3协同控制成为持续改善空气质量的迫切需要.挥发性有机化合物(VOCs)作为PM2.5和O3的重要前体物,通过控制其排放,可有效促进环境持续改善,减少人体健康影响[9-12].
北京作为中国首都,其空气质量受到全社会的关注.电子工业由于具有技术水平高、附加值高等特点,已经取代传统污染排放较大的工业,在北京获得较大发展.电子工业VOCs产生主要来自光刻、清洗、剥离、显影等环节,使用的原辅材料光刻胶、稀释剂、清洗剂和去除剂含有VOCs[13],2019年北京市电子工业VOCs排放量为1542t,主要来自显示器件、集成电路、电子专用材料制造与其他行业,分别占比71%、18%、3.2%和7.8%[14].电子工业VOCs具有种类繁多,成分复杂等特点,会对环境与人体健康均产生一定影响[15].因此,开展电子工业VOCs排放特征与健康影响研究具有十分重要的意义.
目前,众多学者对电子工业VOCs排放开展了研究.在排放量方面,2011~2016年我国显示器件行业VOCs排放量呈先增后降的趋势[16],而集成电路制造业VOCs排放量呈逐年上升的趋势[17],但是两个行业无组织排放量占比均呈逐年上升.在浓度组分特征方面,黄鹤雯等[18]对珠江三角洲地区电子设备制造业开展研究,发现其VOCs组分以OVOCs、芳香烃与烷烃为主,占比达90%左右.2000~2003年台湾某半导体工业园区内最丰富的VOCs物种是OVOCs和芳香烃,环境空气中测得的主要成分是异丙醇、丙酮、苯与甲苯[19].在健康方面,黄慧峰等[20]采用美国EPA方法评估企业喷粉工艺车间、UV漆喷涂工艺车间与PU漆喷涂工艺车间健康风险,发现三个车间均存在非致癌健康风险,且粉体喷涂替代UV和PU漆喷涂可以减少印制线路板生产过程中对环境与健康的影响.梁永锡等[21]和郭笑笑等[22]采用职业病危害因素调查方法,分别对广东省某市202家电子企业和天津市某电子元件制造企业开展调研,前者发现化学毒品总体超标率为3.82%,超标率排前3位的为苯乙烯(33.33%)、甲醛(8.00%)与三氯乙烯(7.32%),后者发现该企业主要职业病危害因素有二甲苯、异丙醇、丙酮、丁酮等.此外,也有学者对电子工业中VOCs的治理技术进行了综述[23].
目前,尚未有对电子工业各子行业VOCs排放特征和人体健康影响开展深入研究.因此,本研究选取北京市典型电子工业企业(半导体器件、显示器及光电子器件、印制电路板、电子终端产品)开展VOCs排放特征和健康影响研究,分析和比较不同电子工业子行业间的VOCs浓度和化学组分差异,整合各子行业VOCs排放成分谱.通过两种方式对电子工业企业工人暴露于排放的VOCs健康风险进行评估,健康风险评价包括非致癌和致癌风险(US EPA方法)以及职业暴露风险评价(ACGIH方法).本研究结果可为更好地理解电子工业VOCs排放特征,以及在公众健康方面的政策制定提供参考.
目前,北京市电子行业规模以上企业269家,多以设计与研发为主的总部企业或产品组装等非排污企业.根据环境统计数据,全市正常生产且涉气排放的电子工业企业有45家(图1),由电子元件(20.0%)、半导体器件(26.7%)、印制电路板(4.4%)、显示器及光电子器件(17.8%)、电子终端产品(31.1%)五大行业组成.此外,北京市电子工业企业主要集中在北京经济技术开发区,这是由于该区产业配套设施齐全,聚集高精尖技术人才,有利于产业发展.
综合考虑生产规模、产品类型、废气处理工艺等,本研究对北京市半导体器件、显示器及光电子器件、印制电路板、电子终端产品四大电子工业子行业的10家典型企业开展研究,企业具体信息见表1.
按照《固定污染源废气挥发性有机物的采样气袋法》(HJ 732-2014)[24]进行采样.排气筒废气样品经过硅烷化处理后的过滤头伸入排气筒,采用纯氮气抽真空清洗的10L聚四氟乙烯采样袋,流量为500mL/min,采样时间为10min.采样泵为北京市劳动保护科学研究所生产的QC-2型空气采样器,采样系统中所有连接管道均采用聚四氟乙烯材料,避免采样误差.采集样品时,企业正常生产,废气处理设施正常运行,烟气排放稳定.采样结束后,将聚四氟乙烯采样袋避光保存,随后导入预先清洗并抽至真空的SUMMA(3.2L)中保存.考虑单个样品带来的不确定性,每个采样点采集3个平行样品,采样间隔为1h.
样品组分分析采用美国EPA推荐的TO-15的方法,并采用三级冷阱预浓缩-二维GC-MS/FID系统进行定性与定量分析.气体样品首先经自动进样系统,通过快速连接头抽取400mL进入Entech 7100A预浓缩仪进行前处理.冷阱Module1为多孔玻璃微珠,能够去除水、N2和O2;冷阱Module2装有Tenax吸附剂,去除Ar、CH4、CO2和微量水分;冷阱Module3(空管)冷冻聚焦,将VOCs组分富集.聚焦冷冻完毕后,Module3快速升温使冷冻在毛细柱头的VOCs迅速汽化,在氦载气的推动下,解吸进入GC-MS/FID系统(Agilent 7890A/5975C)进行分离和定量.色谱柱信息:色谱柱包括总烃柱和甲烷柱,甲烷柱:3m×3mm的不锈钢柱,管内装有60目GDX104高分子多孔微球载体,总烃柱:1m×3mm的不锈钢柱,内装有60目的硅烷化玻璃微珠.GC-MS/FID系统的升温程序为:GC柱箱以35℃的初始温度保持5min;然后以5℃/min升温至160℃,保持2min;接着以20℃/min升温至220℃并保持5min,全程运行40min.载气为高纯氦气(纯度>99.999%),传输线温度为250℃.质谱条件:质谱检测器的离子源类型为电子轰击电离(EI),电离能量为70eV,离子源温度230℃,全扫描方式,扫描范围为20~200u.定量分析使用的外标气体为TO-15(Scott Gases,美国)和PAMS(Spectra gases,美国),前者包含63种化合物,后者包含56种VOCs.内标气体含有4种化合物,分别为溴氯甲烷、1,4-二氯苯、D5-氯苯、1-溴-4-氟苯(Spectra gases,美国).
按照美国EPA推荐的TO-15方法对SUMMA罐进行清洗.所有SUMMA罐均采用纯度>99.99%的氮气反复清洗3~4次,清洗后加压至6Pa以下,在实验室中保存24h,以避免罐内任何污染.同时,所有与烟气接触的管道均采用纯空气反复吹扫,以除去其表面存在的杂质.由于VOCs可以在一定温度下发生反应,因此避免太阳光的照射和保持房间温度必不可少.
为保证数据的有效性和可靠性,分别在样品采集过程与分析过程设置了全程序空白(同批次采样取1个气袋,在实验室注满氮气带到现场但不进行采样)与实验室空白(同批次采样取1个气袋,在实验室注满氮气).每10个样品分析1个全程序空白、1个实验室空白和1个平行样品,全程序空白和实验室空白样品中目标化合物的浓度应不高于方法检出限,平行样品中VOCs含量相对偏差在±25%以内.此外,仪器分析前绘制校准曲线,目标化合物相对响应因子的相对标准偏差在30%以内或曲线方程的相关系数不低于0.990,且每24h分析1次校准曲线中间浓度点,测定结果与初始浓度值得相对误差在±30%以内.
本研究采用分歧系数定量研究不同电子企业排气筒VOCs成分谱的相似程度,具体计算公式如下[25]
式中:CDjk表示两个源谱的分歧系数;n为参与计算的化学组分的总个数;CijCik分别为两个企业排气筒源成分谱中第i种化学组分的平均质量浓度,%.
本研究根据电子工业工人实际工作情况,评估可能导致癌症或非致癌(即指除癌症以外)的健康风险效应的VOCs慢性暴露的健康风险.
基于美国EPA方法,采用每日的环境浓度与各自的慢性非致癌吸入参考水平评估非致癌风险(HR),计算公式如下[26]
式中:HRi表示物种i的非致癌风险;Ci为物种i的暴露浓度,mg/m3;RfCi表示物种i通过慢性日均摄入剂量与参考浓度,mg/m3;CA为采样点中化合物i的环境浓度,mg/m3;ET代表暴露时间,h/d,本文依据工人实际工作时间,取8h/d进行计算;EF为暴露频率,d/a,根据企业实际生产情况,取值为300d/a;ED为持续暴露时间a,本研究取30a;AT为平均时间,a,非致癌风险和致癌风险的值分别取30a和70a[27].
本研究的RfC值主要来自综合风险信息系统(IRIS)与美国毒物与疾病登记署(ATSDR),对于这两个机构无法获得的RfC值,采用美国EPA健康影响评估汇总表(HEAST),美国EPA暂行同行评议毒性值(PPRTV),美国加利福尼亚州环保署(Cal EPA),或X附录(X Appendix PPRTV Screen),具体见表2.
此外,本研究基于美国EPA方法评估了终生致癌风险(LCR),即由于暴露导致终生患癌的概率增加,计算公式如下[26]
式中:LCRi表示物种i的终生致癌风险;URi代表物种i的单位吸入致癌风险,mg/m3,本研究UR值主要来自IRIS与加州环境健康危害评估办公室(OEHHA),取值参考表2.
采用ACGIH方法评估了电子工业企业VOCs排放对作业工人的致癌风险.职业暴露指数可以由下式计算[28]
式中:Ei为职业暴露指数;TLV-TWAi(Threshold limit values- Time weighted average)值为假设工人每天工作8h,一周工作5d的时间加权平均浓度,10-6,本研究中取值来自ACGIH,具体见表2.
对电子工业典型企业开展排气筒VOCs排放浓度测试,如图2所示.从行业角度分析,企业A和B排气筒来自半导体器件,其VOCs浓度为13.63,13.41mg/m3,这与武汉[29]半导体行业VOCs总浓度小于20mg/m3相一致.企业C和D排气筒来自显示器及光电子器件,其VOCs浓度为7.86,9.75mg/m3,与台湾[30]相关研究结果类似.E和F排气筒来自印制电路板制造,其VOCs浓度为4.67和4.31mg/m3,略低于肖景方等[31]的研究,其排气筒VOCs浓度为6.08~11.36mg/m3,这可能是由于使用的油墨有机成分及含量不同有关.企业G~J排气筒来自电子终端产品,其VOCs浓度为3.34~86.11mg/ m3,低于广东省[32]的相关研究(43.01~322.34mg/m3),这主要是由于所用原辅材料及末端治理设施不同导致的.半导体器件与电子终端产品VOCs浓度相对高于其他两个行业,主要是行业间原辅料使用、生产工艺、废气处理设施不同,导致其VOCs浓度存在一定差异.从企业角度来看,除电子终端产品外,其他3个行业内企业原辅材料使用与生产工艺相似、废气治理设施相同,因此VOC浓度差异不大;电子终端产品行业内企业VOCs浓度存在较大差异,主要是由于原辅材料使用不同与废气处理设施VOCs去除效率差异导致.E、F、H和I企业采用相同的废气治理设施(活性炭吸附),所以4家企业VOCs排放浓度主要受原辅材料影响,H企业为电子终端产品,VOCs浓度为15.19mg/m3,高于印制电路板企业E与F和同为电子终端产品企业I(3.34~4.67mg/m3),说明电子工业VOCs排放不能只关注末端控制,而是应该将末端控制为主转化为全过程控制(包括:原辅料使用、生产工艺等),全过程减少VOCs排放.
随着电子工业的发展,除国家层面外,北京、天津、上海、广东和江苏共5个省市发布与电子工业相关的VOCs排放标准,各标准中排气筒大气污染物排放浓度限值对非甲烷总烃的要求不同,其中最严格的排放限值为北京市地方标准[33](Ⅰ时段:20mg/m3,Ⅱ时段:10mg/m3).如图2所示,与Ⅰ时段的20mg/m3的标准限值相比,仅电子终端产品企业G排气筒VOCs排放浓度超标,即电子终端产品排气筒浓度达标率为75.00%,其他3个行业排气筒VOCs排放浓度达标率均为100.00%.与Ⅱ时段的10mg/m3标准限值相比,半导体器件排气筒VOCs浓度均超标;显示器及光电子器件、印制电路板排气筒VOCs排放浓度达标率均为100.00%;电子终端产品排气筒达标率较低,仅为25.00%.整体来看,电子终端产品排气筒VOCs浓度超标严重,其次为半导体器件,而显示器及光电子器件、印制电路板排气筒均可达标排放.本研究中,电子终端产品企业废气处理设施采用的是活性炭吸附、活性炭+UV光解或活性炭吸附脱附+RCO,以上废气处理设施VOCs去除效率较低,需要选择其他高效的VOCs废气处理设施.根据现场调研,参考《浙江省挥发性有机物污染防治可行技术指南 电子工业》,对于中、低浓度VOCs废气,建议优先采用吸附浓缩-燃烧技术处理,因此,根据企业实际情况,建议排气筒浓度超标企业采用沸石转轮吸附浓缩+催化燃烧工艺.半导体器件企业废气处理虽为沸石转轮浓缩+RTO,但是其排气筒浓度仍高于10mg/m3,考虑是由于废气处理设施未定期进行维护更新,建议企业定期对沸石进行高温或水洗再生,并按照生产情况,定时更换沸石,确保废气处理设施处理效率,使排气筒VOCs排放浓度达标.
本研究VOCs源成分谱共检测出51种组分,其中烷烃15种,烯烃6种,芳香烃14种,OVOCs10种,卤代烃6种,不同电子行业排气筒VOCs组分特征如图3所示.半导体器件A与B企业排气筒VOCs中,烷烃质量分数最高(70.78%和70.56%),其次为卤代烃(24.61%和24.60%),芳香烃(4.08%和4.30%)与OVOCs(0.54%和0.56%)占比较小,未检测出烯烃.这与徐捷等[34]和Shen等[29]的研究结果不一致,这两个研究中均为OVOCs的质量占比最高(91.29%~97.56%与61.60%~98.50%),且其质量分数远高于本研究,而烷烃与卤代烃质量分数较小.这可能是因为随着人们对环境与身体健康更加关注,碳氢清洗剂已经取代了传统溶剂型清洗剂,所以本研究中OVOCs质量分数较低.
针对显示器及光电子器件,企业C和D排放的VOCs以OVOCs为主,其质量分数为93.48%和95.87%,其次为芳香烃(6.06%和4.08%).这与Wang等[30]的研究结果较为相似,Wang等[30]发现陈列工程、彩膜工程与成盒工程中OVOCs质量分数最大(89.40%~98.93%),其次为芳香烃(0.31%~3.18%).乙醇和丙酮等作为清洗剂被广泛使用,因此本研究OVOCs质量分数较高.
印制电路板企业E、F排放的VOCs中,OVOCs质量分数最大(92.27%和93.05%),其次为芳香烃(7.62%和6.67%),烷烃最小(0.11%和0.11%).印制电路板VOCs组成与显示器及光电子器件较为相似,均以OVOCs为首要VOCs组分,芳香烃质量分数略高于显示器及光电子器件.这与马英歌等[35]的研究结果相似,其OVOCs质量分数为62.22%,芳香烃为31.82%;Shen等[29]研究结果表明,OVOCs(8.46%~67.28%)、烷烃(19.12%~74.63%)与卤代烃(7.35%~27.57%)为主要VOCs组分,与本研究结果存在一定差异;肖景方等[31]的研究中芳香烃占比(91.81%~95.39%)远高于本研究,这与该研究使用的原辅材料的有机成分及含量有关.
电子终端产品各企业排气筒VOCs组分排放特征存在差异,企业G排气筒废气中VOCs质量分数最高的是OVOCs(96.18%),其次为芳香烃(1.85%)与烷烃(1.42%).该结果与何梦林等[32]的研究结果相似,其OVOCs质量分数低于本研究(58.00%~65.00%),芳香烃(10.00%~40.00%)和烷烃(2.00%~31.00%)质量分数高于本研究.与企业G不同,企业H与J排气筒VOCs的特征组分主要为芳香烃(88.30%和76.40%),其次为OVOCs(10.12%和23.51%).这与马英歌等[35]研究结果中芳香烃占比最高(99.86%)相似.而企业I排气筒废气中烷烃占比最高(72.17%),其次为卤代烃(18.06%)和OVOCs(8.17%).该VOCs特征组分与Zhang等[36]研究结果较为相似,烷烃质量分数最高(68.95%),其次为OVOCs(19.63%)和卤代烃(5.02%),但质量分数存在一定差异.
表3展示了不同电子行业排气筒废气中VOCs质量分数位于前5的特征组分.对于半导体器件企业,质量分数最高的为二甲基戊烷,其次为三氯乙烯、三甲基戊烷、正戊烷和2,3-二甲基丁烷,其质量分数之和超过88%.二甲基戊烷为半导体器件企业排气筒排放的主要污染物,质量分数为32.03%和33.60%,主要是由于本研究中企业采用了碳氢清洗剂替代传统溶剂型清洗剂.该特征与徐捷等[34]和Shen等[29]研究结果不同,二者的研究结果中异丙醇(56.4%~98.3%与66.00%~89.79%)质量分数最高,主要是因为两者研究的企业仍使用以异丙醇为主要原料的溶剂型清洗剂对晶片表面进行清洗.
显示器及光电子器件企业排气筒废气中VOCs质量分数最高的是丙酮,其质量分数为91.89%和94.99%,这与Wang等[30]研究结果中乙醇(15.51%~74.73%)和丙酮(4.12%~42.38%)质量分数最高较为相似,主要是因为显示器及光电子器件的光刻环节中使用了清洗剂,而清洗剂中常用丙酮和乙醇作为溶剂使用.此外,间/对二甲苯、乙酸丁酯、乙苯和1,3,5-三甲基苯也是显示器及光电子器件企业排气筒废气中主要的VOCs组分,上述5种物质质量分数之和为97.36%和98.40%.
印制电路板企业排气筒废气中VOCs质量分数最高的前5个物种依次为异丙醇、乙醇、丙酮、间/对二甲苯和乙苯,其质量分数之和为96.13%和96.70%,与印制电路板行业常用的清洗剂主要组分相同.马英歌等[35]指出印制电路板企业VOCs质量分数前5种为丙酮(60.80%)、甲苯(14.20%)、间/对二甲苯(6.53%)、乙苯(3.98%)、邻二甲苯(1.99%),与本研究质量分数排名前5的物种有3种相同,但各物种质量分数存在差异.Shen等[29]研究发现丙酮为首要污染物(13.3%~62.4%),其质量分数高于本研究.而肖景方等[31]研究发现印制电路板排名前3的VOCs物种是二甲基己基苯(32.22%和36.18%)、异丙基甲基苯(18.26%和25.26%)与四甲苯(14.70%和20.72%),与本研究结果不同,主要是因为该研究只考虑了印制电路板中的防焊环节,因此其结果与使用的防焊油墨有机成分及含量有关.
电子终端产品企业G排气筒废气中,乙醇质量分数最大,其次为异丙醇、乙酸丁酯、间/对二甲苯和环己烷,其中乙醇和异丙醇来自电路板清洗,酯类、二甲苯等来自喷漆与烘干.这与何梦林等[32]研究结果中的手机喷漆有组织废气以乙酸乙酯为主(43.18%)、相机(26.15%)和笔记本电脑(40.36%)喷漆有组织废气以甲苯为主不同,但本研究前5的VOCs物种中除乙醇外,均在何梦林等[35]研究中检测出.电子终端产品企业H废气排气筒VOCs中质量分数最高的为甲苯,其次为2-丁酮、甲基丙烯酸甲酯、乙苯、间/对二甲苯;企业J废气排气筒VOCs中乙苯质量分数最高,其次为乙酸丁酯、间/对二甲苯、邻二甲苯与甲苯.与马英歌等[35]研究中甲苯(38.87%和14.75%)、乙苯(10.70%和13.55%)、间/对二甲苯(8.31%和19.81%)质量分数高的结果相似,主要是由于企业喷涂过程中使用的有机溶剂以苯系物溶剂为主.电子终端产品企业I排气筒废气VOCs质量分数最高的前5个物种为二甲基戊烷、三氯乙烯、三甲基戊烷、异丙醇与正戊烷,从原辅料VOCs组分来看,烷烃主要来自碳氢清洗剂.该排放特征与Zhang等[36]研究结果中乙醇(37.00%)、2,3-二甲基戊烷(20.00%)、环己烷(7.70%)、异丙醇(7.20%)、正十一烷(5.90%)存在相似性.综上,由于地域不同、产品不同,使用的原辅材料不同,其VOCs排放特征也各不相同,因此建立本地化电子行业源成分谱十分必要.
采用分歧系数定量评估电子行业成分谱的相似程度.有研究表明[37],当分歧系数介于0~0.2,则两个源成分谱必定相似;若介于0.2~0.5,则可能相似;若介于0.5~1.0,则源成分谱必然不相似.如图4所示,从行业角度分析,半导体器件企业A与B的分歧系数为0.03,介于0~0.2之间,说明2个企业的VOCs成分谱必定相似,可见2个企业工艺流程、VOCs原辅料使用等接近;显示器及光电子器件企业C与D、印制电路板企业E与F的分歧系数分别为0.40和0.36,介于0.2~0.5之间,说明其VOCs源成分谱可能相似;电子终端产品企业G~J之间的分歧系数为0.82~0.98,接近1.0,说明电子终端产品企业VOCs源成分谱必定不相似.从企业角度分析,排除行业内部企业间的源成分谱相似性,不同企业间分歧系数为0.67~0.91,即VOCs源成分谱必不相似.综上,除了半导体器件、显示器及光电子器件和印制电路板企业间排气筒VOCs源成分谱相似度较高,其他各企业间VOCs源成分谱相似度不高,一方面,电子终端产品企业受生产产品不同影响,其原辅材料使用不同,因此VOCs源成分谱相似度不高;另一方面,不同企业由于所属电子子行业不同,生产工艺、原辅材料、废气处理设施均不同,导致VOCs源成分谱不相似.
本研究,基于实测获得不同电子子行业VOCs排放数据,综合相似性分析结果,对除电子终端产品外的相同子行业VOCs组分检测结果进行算数平均和归一化处理,获得了电子行业VOCs成分谱,如图5所示,各电子行业VOCs质量百分比的标准偏差均较小,说明数据波动性小,差异较小.整体来看,电子终端产品企业由于其VOCs特征组分差异较大,后续讨论依然按照企业讨论.
利用美国EPA方法评估通过吸入途径暴露VOCs的潜在慢性健康效应(非致癌和致癌风险).本研究有28种VOCs用来评估非致癌风险,有研究表明[38],当非致癌风险HR<1时,非致癌风险的可能性很低;当非致癌风险HR>1时,长期暴露会造成非致癌健康危害.
图6所示,半导体器件的非致癌风险HR最高(484.35),为其他行业的1.08~215.27倍.半导体器件行业中,有4种VOCs风险值HR为0.1~1,表明对人体的非致癌风险不大,2种VOCs风险值HR>1,会危害人体健康.半导体器件行业中,卤代烃的总HR值远高于其他子行业,其中三氯乙烯的HR值最高(479.57),占了行业总HR的99.01%.因此,应该特别关注半导体行业中三氯乙烯的排放.显示器及光电子器件行业的非致癌风险HR次高(447.46),其中有3种VOCs风险值HR为0.1~1,2种VOCs风险值HR>1,表明有5种VOCs可能对人体产生非致癌风险.显示器及光电子器件子行业中,丙烯醛最值得关注,其HR值最大(443.03),占该行业总HR的99.01%.针对印制电路板行业,其HR较低,仅为2.25,可能是其相对较低的VOCs浓度导致.该行业中,有4种VOCs风险值HR为0.1~1,1种VOCs风险值HR>1,为1,3,5-三甲基苯(1.23),占总HR的54.67%.对于电子终端产品行业的G~J企业来说,风险值HR为0.1~1的VOCs分别有4种、7种、1种和3种;风险值HR>1的VOCs物种分别有3种、3种、1种和5种.各企业HR值最大的分别是1,3,5-三甲基苯(企业G和J)、2-丁酮和三氯乙烯,占总HR的60.56%和41.25%、50.44%、99.47%.整体来看,各行业总HR均大于1,即均会危害人体健康,因此开展电子行业VOCs排放管控工作十分必要.
本研究用7种VOCs用来评估终生致癌风险.按照Zhang等[28]研究结果,将致癌风险对人类健康影响程度分为4个等级:可忽略风险(<1×10-6)、小概率风险(1×10-6~1×10-5)、大概率风险(1×10-5~1×10-4)和确定的风险(>1×10-4).如图7所示,显示器及光电子器件、印制电路板行业总LCR值最小,为1.74×10-5和1.40×10-5,对人体有大概率致癌风险;半导体器件(1.63×10-3)、电子终端产品(1.64×10-4~5.16×10-3)行业LCR值较大,会对人体产生确定的致癌风险.整体来看,现有电子行业导致人体终生致癌风险较大.
半导体器件行业中,三氯乙烯(1.60×10-3)的LCR值大于1×10-4,表明三氯乙烯有确定的致癌风险;乙苯的LCR值介于1×10-5~1×10-4,即乙苯有大概率风险致癌;苯的LCR值最小(7.26×10-6),介于1×10-6~1×10-5,具有小概率致癌风险.对于显示器及光电子器件行业与印制电路板行业,只有乙苯被用来评估终生致癌风险,其LCR值分别为1.74×10-5和1.40×10-5,均在1×10-5~1×10-4范围内,被认为大概率具有致癌风险.电子终端产品行业中,企业G的1,3-丁二烯、乙苯和氯仿LCR值分别为2.99×10-5、8.08×10-5和5.36×10-5,其值介于1×10-5~1×10-4,说明这三种组分致癌风险概率大;企业H检测出了最多的致癌VOCs物种,其中二氯甲烷(5.03×10-3)与乙苯(1.00×10-4)对致癌具有确定的风险,LCR值>1×10-4.而1,2-二氯乙烷(3.28×10-5)与苯(3.45×10-6)LCR值介于1×10-5~1×10-4和1×10-6~1×10-5,即它们分别为对人体致癌有大概率风险和小概率风险;企业I中三氯乙烯LCR值大于1×10-4,认为其对人体致癌有确定的风险,而乙苯的LCR值较小,介于1×10-6~1×10-5,被认为对人体致癌有小概率风险;企业J不同企业I,乙苯的LCR值较高(1.47×10-3),对人体致癌有确定的风险,1,2-二氯乙烷的LCR值为2.99×10-5,介于1×10-5~1×10-4,对人体致癌有大概率风险.
本研究有39种VOCs被检测用来评估职业暴露致癌风险.如图8所示,各电子行业总Ei值为9.79×10-4~1.95×10-2,其中电子终端产品子行业(企业H)的总Ei值最大,是其他子行业的2.42~19.92倍,显示器及光电子器件行业的总Ei值最小,这与终生致癌风险研究结果类似.Zhang[28]等研究结果显示,当Ei值大于1时,认为VOCs排放会对工人产生潜在的健康风险.本研究中,所有子行业的Ei值均低于0.1,表明该地区排放的VOCs可能不会对工人产生有害影响.
进一步分析,半导体器件、电子终端产品(企业I)行业中卤代烃的Ei值最大,为6.68×10-3和1.21×10-3;显示器及光电子器件、印制电路板、电子终端产品(企业G)行业中Ei值最大的为OVOCs,其值为7.56×10-4~5.11×10-3;电子终端产品行业(企业H和J)中芳香烃的Ei值高于其他VOCs,分别为1.87×10-2和7.27×10-3.上述Ei值虽低于1,但是仍然应该重点关注.
综上,利用美国EPA和ACGIH方法评估健康风险的结果差异较大.US EPA方法在所有电子子行业均确认了VOCs暴露对工人的非致癌风险和致癌风险,但ACGIH方法结果显示,所有电子子行业均不存在职业暴露致癌风险.出现这种差异性的原因可能是因为两种方法对VOCs物种暴露参考浓度的限定指标不同.尽管这两种方法存在差异,但电子终端企业产品及半导体器件行业排放的VOCs健康风险远高于其他两个子行业,因此,为保证这两个行业的工作人员健康,应加强VOCs排放的管控.
3.1 不同电子工业有组织废气VOCs排放浓度由于原辅材料、生产工艺、产品不同,存在较大差异.半导体器件(13.41~13.63mg/m3)与电子终端产品行业(3.34~86.11mg/m3)VOCs浓度相对高于显示器及光电子器件(7.86~9.75mg/m3)与印制电路板行业(4.31~4.67mg/m3).与北京市电子工业标准中VOCs排放限值相比,电子终端产品排气筒VOCs排放超标严重,其次为半导体器件,显示器及光电子器件、印制电路板排气筒均可达标排放.
3.2 不同电子子行业排气筒废气中VOCs组分差异较大,半导体器件排气筒废气中VOCs以烷烃类为主,首要物种为二甲基戊烷;显示器即光电子器件和印制电路板企业排气筒废气中VOCs均以OVOCs为主,质量分数最高的物种分别为丙酮与异丙醇;电子终端产品VOCs组分存在差异,以OVOCs、芳香烃和烷烃为主.
3.3 除电子终端产品企业,其他3个电子子行业间分歧系数均小于0.5,即VOCs源成分谱相似;不同企业间分歧系数为0.67~0.91,即VOCs源成分谱必不相似,这主要是由于不同企业生产工艺、原辅材料、废气处理设施均不同,导致VOCs源成分谱不相似.
3.4 半导体器件和显示器及光电子器件行业的非致癌风险较高,总HR分别为484.35和447.46,电子终端产品和印制电路板总HR较小,分别为11.74~87.35与2.25,但整体看,各电子企业长期暴露均会造成非致癌健康危害.
3.5 半导体器件和电子终端产品行业LCR>1×10-4,即会对人体产生确定的致癌风险;显示器及光电子器件、印制电路板行业LCR值介于1×10-5~1×10-4之间,对人体有大概率致癌风险.
3.6 4个电子子行业的总Ei值为9.79×10-4~1.95×10-2,均小于0.1,表明VOCs排放不会对工人产生潜在的健康风险.
3.7 通过EPA和ACGIH方法评估的健康风险结果差异较大,这主要是由于不同方法对VOCs物种暴露参考浓度的限定指标存在差异.但整体来看,电子终端企业产品及半导体器件行业排放的VOCs健康风险远高于其他两个子行业.因此,加强控制这两个电子子行业VOCs排放十分必要.
  • 北京市科委“首都蓝天行动培育”专项(Z181100005418015)
  • O3与PM2.5复合污染协同防治预研项目
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  • 接收时间:2024-07-10
  • 首发时间:2026-03-17
  • 出版时间:2025-02-20
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  • 收稿日期:2024-07-10
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北京市科委“首都蓝天行动培育”专项(Z181100005418015)
O3与PM2.5复合污染协同防治预研项目
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    北京市生态环境保护科学研究院,国家城市环境污染控制工程技术研究中心,城市大气挥发性有机物污染防治技术与应用北京市重点实验室,北京 100037

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