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Volatile organic compounds(VOCs)were identified as chemicals that caused odor pollution in cars. Nanostructured water ion(EWNS)technology was demonstrated to be capable of producing large amounts of hydroxyl radicals to degrade VOCs, though systematic research on odor VOC removal had not been conducted. In this study, VOCs components from 9cars were first analyzed offline using TD-GC-MS, and the main odor VOCs in actual car interiors were determined through the comprehensive scoring method. A mixture gas containing the average concentration ratio of detected odor VOCs was then introduced into the experimental vehicle, where degradation efficiency was evaluated using EWNS technology. Human health risk assessment was also performed. The results revealed that aliphatic compounds were detected most frequently(7species)in car interior VOCs, while aromatic compounds were found to have the highest detection rate and concentration. Through odor identification scoring, xylene, toluene, ethyl acetate, o-xylene, n-butanol, and hexanal were selected as representative odor VOCs. After EWNS treatment, significant removal effects were observed for all representative odor VOCs, with toluene removal rate being recorded at 92.8%. However, EWNS degradation efficiency was found to vary with placement locations in the vehicle, where better removal effects were achieved in rear positions compared to front positions, potentially associated with hydroxyl radical diffusion efficiency. Meanwhile, the carcinogenic risks of benzene and ethylbenzene were significantly reduced, transitioning from carcinogenic risk to risk-free status.

, correspAuthors=Xiao-bing PANG, 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=Zi-han SUN, Geng WANG, Peng-kai TANG, Chao HUANG, Zhi-biao YANG, Xiao-bing PANG), CN=ArticleExt(id=1241057228728365166, articleId=1241057223422571194, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=小客车室内异味VOCs的治理及健康风险评估, columnId=1234106388364981004, journalTitle=中国环境科学, columnName=大气污染与控制, runingTitle=null, highlight=null, articleAbstract=

挥发性有机物(VOCs)是造成汽车室内异味污染的重要物质之一,纳米结构水离子(EWNS)技术可产生大量羟基自由基降解VOCs,但对于异味VOCs的去除缺少系统研究.使用TD-GC-MS对9辆汽车进行VOCs成分离线分析,根据综合评分法确定实际车内的主要异味VOCs.后在实验车内添加依据检出异味VOCs的平均浓度比配置的混标气体,使用EWNS进行降解,测定其对异味VOCs的降解效率,并进行人体健康风险评估.结果表明,车内VOCs中脂肪族化合物数量最多(7种)而芳香族化合物的检出率和检出浓度最高,通过异味识别综合得分排名情况选择间二甲苯、甲苯、乙酸乙酯、邻二甲苯、正丁醇和正己醛为代表性异味VOCs.经过EWNS治理后,对各代表性异味VOCs物质有明显的去除效果,其中对甲苯去除达到92.8%.然而EWNS在车内的放置位置不同,降解效率存在一定的差异,后排的去除效果优于前排,可能与羟基自由基的扩散效率有关.同时,苯和乙苯的致癌风险显著降低,从致癌风险下降到无风险.

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* 责任作者,教授,
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孙孜涵(2001-),男,安徽宿州人,浙江工业大学硕士研究生,主要从事大气环境的监测与研究..

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孙孜涵(2001-),男,安徽宿州人,浙江工业大学硕士研究生,主要从事大气环境的监测与研究..

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孙孜涵(2001-),男,安徽宿州人,浙江工业大学硕士研究生,主要从事大气环境的监测与研究..

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Science of the Total Environment2019693:133417., articleTitle=Emission characteristics and associated health risk assessment of volatile organic compounds from a typical coking wastewater treatment plant, refAbstract=null)], funds=[Fund(id=1241057240896041899, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, awardId=42327806, language=CN, fundingSource=国家自然科学基金资助项目(42327806), fundOrder=null, country=null), Fund(id=1241057241009288112, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, awardId=2022C03073, language=CN, fundingSource=浙江省领雁计划项目(2022C03073), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241057230502555805, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, xref=1., ext=[AuthorCompanyExt(id=1241057230510944416, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, companyId=1241057230502555805, 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articleId=1241057223422571194, language=EN, label=Fig.2, caption=Schematic diagram of cabin air sampling in test vehicles, figureFileSmall=jQim/uU2C8FGhliI6pw9+A==, figureFileBig=CTMXMFcBhYbTqez8TmFSgA==, tableContent=null), ArticleFig(id=1241057236924035806, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=图2, caption=测试车辆室内空气采样示意, figureFileSmall=jQim/uU2C8FGhliI6pw9+A==, figureFileBig=CTMXMFcBhYbTqez8TmFSgA==, tableContent=null), ArticleFig(id=1241057237007921894, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=EN, label=Fig.3, caption=Organic compounds speciation profile in vehicle cabin, figureFileSmall=bBMCt0ujgXfFWvIcS6SHxQ==, figureFileBig=EdnHbs3elWkP5KiqBomPOg==, tableContent=null), ArticleFig(id=1241057237116973802, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=图3, caption=车舱中有机物种类分布, 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tableContent=null), ArticleFig(id=1241057239482561338, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=EN, label=Table 1, caption=

The compilation of experimental vehicle baseline parameters

, figureFileSmall=null, figureFileBig=null, tableContent=
车辆编号品牌使用年限
(月)
行驶里程
(km)
内饰材质
测试车辆1特斯拉3335000皮革
测试车辆2沃尔沃2430000皮革
测试车辆3奔驰2440000皮革
测试车辆4奥迪7271000皮革
测试车辆5丰田4880000皮革
测试车辆6雷克萨斯1810000皮革
测试车辆7宝马1816000皮革
测试车辆8福特67000皮革
测试车辆9奔驰1226000皮革
实验车辆1比亚迪<1<100皮革
实验车辆2比亚迪<1<100皮革
), ArticleFig(id=1241057239616779080, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=表1, caption=

实验车辆基本信息汇总

, figureFileSmall=null, figureFileBig=null, tableContent=
车辆编号品牌使用年限
(月)
行驶里程
(km)
内饰材质
测试车辆1特斯拉3335000皮革
测试车辆2沃尔沃2430000皮革
测试车辆3奔驰2440000皮革
测试车辆4奥迪7271000皮革
测试车辆5丰田4880000皮革
测试车辆6雷克萨斯1810000皮革
测试车辆7宝马1816000皮革
测试车辆8福特67000皮革
测试车辆9奔驰1226000皮革
实验车辆1比亚迪<1<100皮革
实验车辆2比亚迪<1<100皮革
), ArticleFig(id=1241057239759385429, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=EN, label=Table 2, caption=

The analytical parameters for TD-GC-MS system configuration

, figureFileSmall=null, figureFileBig=null, tableContent=
TDGCMS
参数参数参数
吹扫时间(min)2进样口温度(℃)200接口温度(℃)280
样品解析时间(min)10分流比20:1离子源温度(℃)250
样品解析温度(℃)320载气流速(mL/min)1.0扫描模式全扫描
冷阱吹扫时间(min)2溶剂延迟时间(min)0扫描范围(amu)26~250
冷阱解析时间(min)5
冷阱加热速率(℃/min)40
冷阱低温(℃)-30
冷阱高温(℃)325
), ArticleFig(id=1241057239901991775, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=表2, caption=

TD-GC-MS联用仪分析条件参数

, figureFileSmall=null, figureFileBig=null, tableContent=
TDGCMS
参数参数参数
吹扫时间(min)2进样口温度(℃)200接口温度(℃)280
样品解析时间(min)10分流比20:1离子源温度(℃)250
样品解析温度(℃)320载气流速(mL/min)1.0扫描模式全扫描
冷阱吹扫时间(min)2溶剂延迟时间(min)0扫描范围(amu)26~250
冷阱解析时间(min)5
冷阱加热速率(℃/min)40
冷阱低温(℃)-30
冷阱高温(℃)325
), ArticleFig(id=1241057240048792429, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=EN, label=Table 3, caption=

Screening indexes and grading criteria for each pollutant

, figureFileSmall=null, figureFileBig=null, tableContent=
赋值
r
嗅阈值r1
(mg/m3
浓度r2
(µg/m3
挥发性r3
(kPa2
检出率r4
(%)
1>1000~50<10-50~20
21~10050~10010-5~120~40
310-2~1100~1501~1040~60
410-3~10-2150~20010~10060~80
5<10-4>200>10080~100
), ArticleFig(id=1241057240191398774, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=表3, caption=

各污染物筛选指标与赋分标准

, figureFileSmall=null, figureFileBig=null, tableContent=
赋值
r
嗅阈值r1
(mg/m3
浓度r2
(µg/m3
挥发性r3
(kPa2
检出率r4
(%)
1>1000~50<10-50~20
21~10050~10010-5~120~40
310-2~1100~1501~1040~60
410-3~10-2150~20010~10060~80
5<10-4>200>10080~100
), ArticleFig(id=1241057240304644987, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=EN, label=Table 4, caption=

Comprehensive odor recognition scoring ranking of detected compounds

, figureFileSmall=null, figureFileBig=null, tableContent=
排名物质嗅阈值
(mg/m3
浓度
(µg/m3
挥发性
(kPa)
检出率
(%)
分值
1间二甲苯9.1×10-2175.121.161003.50
2甲苯9.8×10-2280.313.801003.45
3乙酸乙酯0.84175.041.59×1011003.30
4邻二甲苯2.80102.358.01×10-11002.94
5正丁醇6.60×10-2133.698.20×10-11002.92
6正己醛1.25×10-331.581.451002.89
7异辛醇5.41×10-254.705.50×101802.89
8乙苯8.06×10-163.801.231002.84
9乙酸丁酯1.16×10-298.312.00702.84
10壬醇5.80×10-371.808.40×10-1502.83
11乙醇1.07115.105.66702.69
129.4257.171.33×1011002.64
13正己烷5.7768.403.00×101702.54
14丁二烯1.63×10-260.708.25×10-1702.46
15三甲苯9.12×10-117.101.93502.31
16甲基环己烷6.57×10-132.305.73502.31
17甲基异丁基甲酮1.10×10-140.342.66502.21
18甲基叔丁基醚/28.803.27×101502.11
19十一烷6.0755.907.50×10-2602.08
20三甲基庚烷9.5144.802.61702.03
21丙二醇5.44×10-118.809.60×10-2502.03
22异戊烷4.1945.307.93×101502.01
23正丁烷3.11×10389.901.42×101501.96
24苯甲醛9.9512.361.29×10-11001.95
252,2-二甲基丙醚2.75×10-1/38.108.33501.88
263-乙基-3甲基庚烷9.5366.103.47×10-1501.88
27乙二醇1.3016.601.30501.83
28苯乙酮/16.274.90×10-2601.75
), ArticleFig(id=1241057240422085508, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=表4, caption=

检出物异味识别综合得分排名

, figureFileSmall=null, figureFileBig=null, tableContent=
排名物质嗅阈值
(mg/m3
浓度
(µg/m3
挥发性
(kPa)
检出率
(%)
分值
1间二甲苯9.1×10-2175.121.161003.50
2甲苯9.8×10-2280.313.801003.45
3乙酸乙酯0.84175.041.59×1011003.30
4邻二甲苯2.80102.358.01×10-11002.94
5正丁醇6.60×10-2133.698.20×10-11002.92
6正己醛1.25×10-331.581.451002.89
7异辛醇5.41×10-254.705.50×101802.89
8乙苯8.06×10-163.801.231002.84
9乙酸丁酯1.16×10-298.312.00702.84
10壬醇5.80×10-371.808.40×10-1502.83
11乙醇1.07115.105.66702.69
129.4257.171.33×1011002.64
13正己烷5.7768.403.00×101702.54
14丁二烯1.63×10-260.708.25×10-1702.46
15三甲苯9.12×10-117.101.93502.31
16甲基环己烷6.57×10-132.305.73502.31
17甲基异丁基甲酮1.10×10-140.342.66502.21
18甲基叔丁基醚/28.803.27×101502.11
19十一烷6.0755.907.50×10-2602.08
20三甲基庚烷9.5144.802.61702.03
21丙二醇5.44×10-118.809.60×10-2502.03
22异戊烷4.1945.307.93×101502.01
23正丁烷3.11×10389.901.42×101501.96
24苯甲醛9.9512.361.29×10-11001.95
252,2-二甲基丙醚2.75×10-1/38.108.33501.88
263-乙基-3甲基庚烷9.5366.103.47×10-1501.88
27乙二醇1.3016.601.30501.83
28苯乙酮/16.274.90×10-2601.75
), ArticleFig(id=1241057240585663378, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=EN, label=Table 5, caption=

Comparative analysis of removal efficiency based on installation positions and EWNS quantity(%)

, figureFileSmall=null, figureFileBig=null, tableContent=
物质去除率
1台
(前排通风口)
2台
(前排通风口)
1台
(后排通风口)
2台
(后排通风口)
正己醛70.8282.3375.1986.12
甲苯73.5187.2980.3892.87
正丁醇72.9084.1479.2290.53
间二甲苯73.0686.9378.9091.42
邻二甲苯75.2888.1180.1490.31
乙酸乙酯72.3986.9579.3492.44
), ArticleFig(id=1241057240719881117, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057223422571194, language=CN, label=表5, caption=

不同放置位置及EWNS数量的去除效率对比(%)

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物质去除率
1台
(前排通风口)
2台
(前排通风口)
1台
(后排通风口)
2台
(后排通风口)
正己醛70.8282.3375.1986.12
甲苯73.5187.2980.3892.87
正丁醇72.9084.1479.2290.53
间二甲苯73.0686.9378.9091.42
邻二甲苯75.2888.1180.1490.31
乙酸乙酯72.3986.9579.3492.44
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小客车室内异味VOCs的治理及健康风险评估
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孙孜涵 1 , 王耕 1 , 唐鹏凯 1 , 黄超 2 , 杨智表 2 , 庞小兵 1, *
中国环境科学 | 大气污染与控制 2025,45(5): 2369-2376
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中国环境科学 | 大气污染与控制 2025, 45(5): 2369-2376
小客车室内异味VOCs的治理及健康风险评估
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孙孜涵1 , 王耕1, 唐鹏凯1, 黄超2, 杨智表2, 庞小兵1, *
作者信息
  • 1.浙江工业大学环境学院,浙江 杭州 310014
  • 2.松下家电(中国)有限公司,浙江 杭州 310018
  • 孙孜涵(2001-),男,安徽宿州人,浙江工业大学硕士研究生,主要从事大气环境的监测与研究..

通讯作者:

* 责任作者,教授,
Odor-causing VOC remediation and health risk assessment in passenger vehicles
Zi-han SUN1 , Geng WANG1, Peng-kai TANG1, Chao HUANG2, Zhi-biao YANG2, Xiao-bing PANG1, *
Affiliations
  • 1.College of Environment, Zhejiang University of Technology, Hangzhou 310014, China
  • 2.Panasonic Home Appliances(China)Co., Ltd., Hangzhou 310018, China
出版时间: 2025-05-20
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挥发性有机物(VOCs)是造成汽车室内异味污染的重要物质之一,纳米结构水离子(EWNS)技术可产生大量羟基自由基降解VOCs,但对于异味VOCs的去除缺少系统研究.使用TD-GC-MS对9辆汽车进行VOCs成分离线分析,根据综合评分法确定实际车内的主要异味VOCs.后在实验车内添加依据检出异味VOCs的平均浓度比配置的混标气体,使用EWNS进行降解,测定其对异味VOCs的降解效率,并进行人体健康风险评估.结果表明,车内VOCs中脂肪族化合物数量最多(7种)而芳香族化合物的检出率和检出浓度最高,通过异味识别综合得分排名情况选择间二甲苯、甲苯、乙酸乙酯、邻二甲苯、正丁醇和正己醛为代表性异味VOCs.经过EWNS治理后,对各代表性异味VOCs物质有明显的去除效果,其中对甲苯去除达到92.8%.然而EWNS在车内的放置位置不同,降解效率存在一定的差异,后排的去除效果优于前排,可能与羟基自由基的扩散效率有关.同时,苯和乙苯的致癌风险显著降低,从致癌风险下降到无风险.

汽车室内VOCs  /  纳米结构水离子(EWSN)  /  健康风险评估  /  治理方法  /  异味识别

Volatile organic compounds(VOCs)were identified as chemicals that caused odor pollution in cars. Nanostructured water ion(EWNS)technology was demonstrated to be capable of producing large amounts of hydroxyl radicals to degrade VOCs, though systematic research on odor VOC removal had not been conducted. In this study, VOCs components from 9cars were first analyzed offline using TD-GC-MS, and the main odor VOCs in actual car interiors were determined through the comprehensive scoring method. A mixture gas containing the average concentration ratio of detected odor VOCs was then introduced into the experimental vehicle, where degradation efficiency was evaluated using EWNS technology. Human health risk assessment was also performed. The results revealed that aliphatic compounds were detected most frequently(7species)in car interior VOCs, while aromatic compounds were found to have the highest detection rate and concentration. Through odor identification scoring, xylene, toluene, ethyl acetate, o-xylene, n-butanol, and hexanal were selected as representative odor VOCs. After EWNS treatment, significant removal effects were observed for all representative odor VOCs, with toluene removal rate being recorded at 92.8%. However, EWNS degradation efficiency was found to vary with placement locations in the vehicle, where better removal effects were achieved in rear positions compared to front positions, potentially associated with hydroxyl radical diffusion efficiency. Meanwhile, the carcinogenic risks of benzene and ethylbenzene were significantly reduced, transitioning from carcinogenic risk to risk-free status.

automotive interior VOCs  /  EWSN  /  health risk assessment  /  governance methods  /  odor recognition
孙孜涵, 王耕, 唐鹏凯, 黄超, 杨智表, 庞小兵. 小客车室内异味VOCs的治理及健康风险评估. 中国环境科学, 2025 , 45 (5) : 2369 -2376 .
Zi-han SUN, Geng WANG, Peng-kai TANG, Chao HUANG, Zhi-biao YANG, Xiao-bing PANG. Odor-causing VOC remediation and health risk assessment in passenger vehicles[J]. China Environmental Science, 2025 , 45 (5) : 2369 -2376 .
国家促消费政策持续发力激发汽车市场潜能,2023年全国机动车保有量突破4.40亿辆.但汽车内部空间狭小且密闭,易积聚污染物,常伴有严重的异味污染与健康风险.异味物质主要是挥发性有机物(VOCs),主要来源于汽车内饰材料的释放、燃料系统的蒸发排放以及空调系统的使用[1-2],包括苯系物、烷烃化合物和有机醇、醚、酯等,可损害人体神经与血液系统,引发一系列疾病[3-4].因此,治理汽车室内的异味VOCs对改善车辆室内空气质量和降低健康风险具有重要意义.
车载空气净化器是治理汽车室内空气污染物的主流方式,主要治理技术有机械过滤技术和负离子技术[5].活性炭吸附技术是应用最为广泛的机械过滤技术,研究表明,活性炭对苯系物的吸附性能显著[6],每克吸附剂的吸附量可达39.1mg,兼具成本低、耐腐蚀且吸附性强等优势[7],但其吸附效率易受湿度与污染物浓度影响,饱和后需更换材料,增加运维成本,且可能引发微生物二次污染[8].负离子净化技术的原理是基于带负电荷的粒子对具有相反极性的颗粒物进行中和与沉降.车载负离子净化器因无需耗材和成本较低等优点受到市场追捧[9],但其净化物质较为单一,只针对颗粒物等具有去除效果且效率较低,还会产生其他离子、O3等副产物.其对于不同粒径颗粒物的去除效率在14.5%~67.7%之间[10].两种较为主流的治理技术受限于汽车室内环境的复杂性或VOCs多样性的影响,难以有效的治理汽车室内VOCs.纳米结构活性水离子(EWNS)技术作为一种新兴的空气净化技术,在环境温度下通过高压放电释放等离子体,通过荷电效应、静电力作用和化学反应等机理能够有效降解有机污染物、沉淀颗粒物和生物气溶胶[8].研究表明,EWNS通过生成纳米级带电水雾,与悬浮颗粒物(如PM2.5、PM10)发生碰撞凝聚,显著提升颗粒物沉降效率[11];在除菌与细菌灭活方面,EWNS技术可通过活性氧介导的氧化损伤机制,实现大于99%的细菌灭活率,有着显著的应用效果[12-13].此外,EWNS也易空气中的水分子发生反应产生活性较强的羟基自由基,可与VOCs进行反应.然而,目前没有研究将此技术应用于车内的VOCs的治理,尤其是危害更大的异味VOCs.因此有必要进行EWNS技术在汽车内部对VOCs的应用研究.
基于此,本文研究采用热脱附气相色谱质谱联用法(TD-GC-MS)方法对9辆测试车辆内的VOCs进行离线采样分析,综合嗅阈值、检出浓度、检出率等指标进行主要异味VOCs物质筛选.在实验车辆内通入固定浓度的异味VOCs混合气体后,打开EWNS装置进行异味VOCs治理.比较治理前后的异味VOCs的去除效率,综合分析EWNS在实际车辆内对异味VOCs的治理能力.本文研究为研制新型车载式空气净化装置,改善汽车室内环境的空气质量提供重要数据支撑.
实验设备主要有:热解析仪(英国Marks公司,型号TD100-xr);气相色谱-质谱联用仪(美国Agilent公司,GC-MS型号8860-5570B,Agilent公司生产的色谱柱,尺寸为60m×0.25mm×1.4μm,型号DB-624);Scalpha C300组合吸附管(莱创公司);便携式多通道气体自动采样器(定时启动,可实现连续自动恒流采样);VOC环境舱;零空气雾化发生装置;EWNS净化装置(日本松下公司).
EWNS是一种以静电雾化理论为基础的新型环保装置[14]图1).装置尺寸为105mm×74mm×230mm(长×宽×高),工作电压为12V,在5~40℃的温度范围和20%RH~85%RH的湿度范围内均可正常工作.运行时,空气中的水蒸气液化成水滴聚集在Peltier冷却电极上.其下方连有冷凝电极和接地感应电极,两电极间通入5450V高压形成静电场,移动电荷在电场力作用下聚集在液体表面,后受液体剪切应力作用形成泰勒锥.泰勒锥顶端产生含有离子的射流,随着电场强度的增加,射流持续分散为细小雾滴,最终分裂成为包含电子和大量活性氧(ROS)等成分的纳米级的带电水微粒[15].ROS中含有大量的羟基自由基(OH·),会与VOCs等有机物进行反应,使其分解或失去活性以达到治理效果.该装置每秒可释放多达4.8万亿个OH·,覆盖距离可达10m以上.
表1为实验车辆基本信息,9辆测试车辆均为M1类机动车,对其进行车舱内空气VOCs成分检测.所有车辆维护与运行状况良好,无燃油泄漏等机械问题.采样时,车舱内无香烟烟雾和香薰等物质干扰且与后备箱互不连通,密闭性较强.2辆实验车辆为相同品牌型号的轿车(内饰相同,行驶公里数均小于100km),分别作为EWNS治理的实验组与对照组.为保证EWSN发生装置的稳定运行,设定车舱环境温度为20℃,内循环送风.
本研究全程在静态条件下进行测试,以减少环境温度、湿度和空气压力等因素的影响[16].采样前,将可开启的车门与车窗全部打开并静置6h并确认汽车内部构件无表面覆盖物.采样时,汽车处于完全封闭状态,采样流量为60mL/min,流量稳定,使用一级皂膜流量计校准前后误差小于5%,采样时间为60min,连续采集4根样品.采样全程使用远程终端单元控制现场设备和大气自动采样设备,减少因人为操作或密封不完全而带来的影响.实时记录采样时车内外的环境温度、湿度及气压.如图2所示,全自动气体采样器放置在后排座椅下方,采样器连接聚四氟乙烯管进行定时采样,采样点位于前排座椅连线的中点,与座椅头枕的高度保持一致.进行异味VOCs治理时,根据检出异味VOCs的最大浓度值作为治理的起始浓度,预先设定采样时间与零空气鼓泡装置发生时间,通过零空气鼓泡装置向车内鼓入固定浓度的异味VOCs物质,鼓泡结束后立即采样.在收集车内空气样本后,通过精确的空气样本分析和质控流程来定性VOCs成分及其定量VOCs的浓度水平,尽可能减少车辆在准备阶段和采样过程中外界大气污染物的引入[17].EWNS工作时会产生O3前体物,经检测,O3浓度在4h的工作时间之内其浓度远低于EPA标准[18],无需增加臭氧过滤装置进行去除.
采用美国EPA检测空气中有毒害挥发性(非极性和弱极性)有机物的标准方法和光化学评估监测站分析样品.根据物质的保留时间和全扫描结果使用Qualitative Analysis 10.0软件(安捷伦公司)与NIST 15谱库(匹配度大于80%)对检出化合物进行定性,使用外标法对检出化合物进行定量.质量控制方参照之前的研究[19],TO-15和PAMS标气浓度均为1×10-6,使用动态校准稀释仪(雪迪龙公司)将其稀释至3×10-9、5×10-9、10×10-9、20×10-9和30×10-9等5个梯度,分别绘制标准曲线.TD-GC-MS分析VOC样品的分析条件如表2所示.用甲苯的标准曲线计算在标准气体之外但满足总挥发性有机物定义要求的VOCs的浓度[19].
车内异味是多种气态物质混合作用的结果,本研究采样综合评分法进行异味物质的识别与筛选.该方法进行多要素的综合评价,是应用最为广泛的污染物筛选方法之一[20].本研究以嗅阈值、物质浓度、检出率和挥发性等为筛选指标,遵循检出率高、浓度水平高、嗅阈值低且具有一定挥发性的筛选原则进行异味物质识别.不同指标对异味影响的重要程度不同,其中:嗅阈值>物质浓度>挥发性>检出率.各指标的权重系数采用模糊层次分析法进行确定(表3),通过赋值的方法计算异味物质的综合得分,得分越高,异味风险越大.其中,嗅阈值参考日本测定的223种化学物质嗅阈值数据表,挥发性用25 ℃下的蒸气压值表示,具体数据参考ChemBlink化学品数据库、化源网等相关网站.
式中:r为各筛选指标的赋分值(表3);Y得分为污染物的综合得分.
健康风险评估是指将污染物对人体产生的不良影响进行定性与定量的分析,是联系环境污染与人体健康的表征手段[21].本研究采用美国环保署提出的评价方法(EPA-540-R-070-002)对检出的VOCs进行健康风险评估.
非致癌风险评价用危害指数(HI)表示,指由于吸入途径暴露造成的长期摄入量与参考剂量的比值,是以每日暴露的剂量来预测长期暴露在此剂量下不会产生任何危害的效应[22].计算公式如下:
式中:EC为非致癌暴露浓度,μg/m3;CA为物质组分的环境浓度,μg/m3;ET为暴露时间,h/d,本研究取2.0h/d;EF为暴露频率,d/a,本研究取300d/a;ED为暴露周期,a,本研究取10a;AT为平均时间,本研究取10a×365d×24h[23];Rfc为单位吸入非致癌风险浓度,mg/m3,本研究采用EPA IRIS(综合风险信息系统)提供的推荐值;致癌风险由风险值(Risk)表示,由呼吸途径导致致癌风险的参考摄入量(或致癌强度系数)与终生平均暴露浓度的乘积表示
式中:IRU为单位吸入致癌风险浓度,μg/m3,本研究采用EPA IRIS(综合风险信息系统)提供的推荐值.
通过离线采样分析发现在所有测试车辆中共检出80余种VOCs,与已有研究中检出的VOCs数量相近[24].根据化学结构将检出物质分为五类,组成分布如图3所示.烷烯烃类化合物是车内主要的VOCs,占比为28.6%,包括6种烷烃,1种环烷烃和1种烯烃.苯系物和醇类化合物均有6种成分,占比为21.4%.醛类化合物和酮类化合物仅含有2种,分别为己醛、苯甲醛、2-丁酮、甲基异丁基甲酮,其余化合物为酯类和醚类.通常情况下,检出率大于50%的物质被认为是值得关注的物质[17],因此下文着重讨论在车内存在的这类物质.
图4所示,苯、甲苯、乙苯、间二甲苯、邻二甲苯、苯甲醛、乙酸乙酯、正己醛、壬醛等9种物质的检出率均为100%,有19种VOCs的检出率大于50%.各检出物种类中,苯系物检出浓度最高,其中甲苯检出浓度为180μg/m3,间二甲苯检出浓度为175.72μg/m3.这是因为车内的中控台和仪表板主要使用聚氨酯(PU)、聚丙烯(PP)、聚氯乙烯(PVC)等聚合物材料制成,内饰和座椅等是由织物、橡胶材料与粘合材料组成,这些合成材料在生产过程中会引入苯系物,其随着车辆使用时温度的变化和材料老化过程持续释放至车内.此外,汽车内部是一个狭小的空间,经长时间密闭或高温暴晒后也会加剧苯系物的释放,从而威胁到人体健康[25].作为应用最为广泛的酯类物质,乙酸乙酯常作为溶剂应用于人造皮革、粘合剂、涂料等产品,是整车工艺以及内饰材料中的重要物质[26].
值得注意的是,由于TD-GC-MS法对于某些极性极强的小分子有机物(如甲醛,有机酸等)的检测敏感性较低,检测能力很弱,这可能会导致车内部分异味物质无法被识别,从而限制本研究的检测结果.
准确识别车内产生异味的物质是控制并解决车内异味的首要前提.车内VOCs的浓度水平并非是异味产生的唯一要素,还要取决于物质本身的嗅阈值,挥发性等因素.综合评分法是整合上述因素的异味物质识别方法,能够量化VOCs的异味分值.表4是车内检出物质经过综合评分法计算后的排名情况.间二甲苯、甲苯、乙酸乙酯、邻二甲苯、正丁醇和正己醛异味得分较高,位于所有检出物质的前六位.甲苯和间二甲苯检出浓度较高,且甲苯嗅阈值为0.098mg/m3,间二甲苯嗅阈值为0.091mg/m3,二者均有较低的嗅阈值,在较低浓度的情况下即可被人体感知,且其气味会随着浓度的升高大幅上升.此外,其还具有较强的挥发性,能够在车厢中迅速扩散,造成车内异味污染.研究表明,VOCs气味的产生可能与其所带官能团和分子尺寸有关,小分子尺寸的酸和羰基化合物可能会有明显的气味,己醛便属于此类物质[27].此外,乙酸乙酯,异辛醇等物质也会引起嗅觉发应,但其反应机理尚不清晰[28].
车厢内空气环境较为复杂,值得注意的是,其他物质如正己烷、正丁烷等烷烃类的检出浓度整体较高,但其综合排名得分并不靠前,这是因为其具有较高的嗅阈值,不易产生异味,但其并非没有异味贡献,研究表明,大多VOCs之间有相互加成的作用,相互作用后可能也会对整体空气质量状态产生较大影响[29].
图5比较了车内异味VOCs在EWNS干预和自然衰减条件下的浓度衰减特征.在自然衰减条件下,各物质浓度随时间缓慢而稳定地衰减.在4h内,正己醛浓度降低42.7%、乙酸乙酯浓度降低36.4%、正丁醇浓度降低35.0%、邻二甲苯浓度降低36.0%、间、对二甲苯浓度降低40.2%、甲苯浓度降低35.7%.在打开EWNS的条件下,各物质的浓度衰减速率明显变快.在相同的时间里,正己醛、乙酸乙酯、正丁醇、邻二甲苯、间、对二甲苯、甲苯等物质在EWNS干预下浓度分别下降92.8%、92.4%、91.4%、90.5%、90.3%、86.1%.分别是自然衰减条件下的2.17、2.54、2.61、2.51、2.25与2.41倍,说明EWNS对异味VOCs具有显著的去除效果.
羟基自由基作为一种强氧化剂,化学性质非常活泼,主要通过抽取氢原子或加成到不饱和键等路径与上述异味VOCs进行反应,使这些有机物的破裂和氧化使其分解或失去活性.具体而言,对于甲苯、间、对二甲苯、邻二甲苯等苯系物,OH·加成到苯环上形成羟基取代的羟基苯自由基或对甲基上的氢原子进行攻击抽取,达到降解效果[30].正己醛含有极性较强的羰基(C=O),正丁醇含有较高反应活性的羟基(-OH),乙酸乙酯含有易受攻击的C–H键,OH·均可对于其相邻点位的α-氢进行抽取形成其他自由基,后被氧化或分解[31].EWNS对各物质的去除效率不同,其中,正己醛>乙酸乙酯>正丁醇>甲苯>二甲苯,这可能与氢键能和化合物的结构特性有关.研究表明,氢键能较低的化合物更容易与OH·发生反应,α-氢的键能通常较低,特别是位于羰基或羟基附近的氢原子.因此,正己醛、正丁醇等物质更容易发生与羟基自由基的反应,而芳香环上的氢原子键能较高,故甲苯、二甲苯的降解速度相对较慢[32].本研究对于EWNS处理VOCs的过程中可能会产生的副产物尚不明确,需要更加深入的研究.
表5为不同数量和放置位置的EWNS对于VOCs的去除效率对比.由表可知,两台EWNS有着更好的治理效果,但这并非同样适用于其他车辆,而是取决于装置数量和汽车体积的关系.后排通风口处的治理效果优于前排通风口,这可能是因为后排通风口处于车体的中间位置且高度更高,更有利于OH·在车内循环流动,其次,车厢后排的空间大于前排,其释放出的VOCs物质也会更多,OH·更易在后排发生反应.此外,购买成本也会影响人们的选择,在决定使用数量时,应综合考虑处理效率和经济成本之间的关系[33].
为进一步研究测试车辆空气中VOCs等污染物可能对人体健康产生的影响,对车内检出物质进行健康风险评估.依据检出物质的浓度与EPA优控物质进行筛选,共选取10种异味VOCs作为评估物质.国际癌症研究机构(IARC)认定苯为1类致癌物(对人确定为致癌物)、乙苯为2类致癌物(对人可能致癌);其余物质等为3类致癌物(对人类致癌性可疑)[34].基于此,本研究对苯和乙苯进行致癌风险评价,当致癌风险指数Risk<1×10-6时,表明对人体危害较低或者是在可接受风险之内;当Risk>1×10-4时,表明致癌风险较大,需采取一定措施进行风险的降低与规避;当1×10-6<Risk<1×10-4时,表明可能存在一定的致癌风险,需引起足够重视[23].对其他物质进行非致癌风险评价.当非致癌风险HI>1时,污染物对人体具有非致癌性危害,存在不良影响.
图6为治理前后各VOCs健康风险变化图.治理前,苯的Risk范围在1.42×10-5~3.05×10-5之间,平均系数为1.84×10-5;乙苯的Risk范围在6.89×10-6~1.09×10-5之间,平均系数为8.89×10-6.苯的致癌风险系数大于乙苯,但都在1×10-6~1×10-4之间,这表明均可能存在不同程度的致癌风险.治理后二者Risk值均小于1×10-6.甲苯的非致癌风险远小于1,不会对人体造成危害.间、对二甲苯的HI范围在0.69~1.16之间,平均系数为0.78;邻二甲苯的HI范围在0.4~1.03之间,平均系数为0.58.间、对二甲苯和邻二甲苯的平均非致癌风险系数和最小致癌风险系数均不到基准值,但最大风险系数分别是基准值的1.56倍和1.43倍,会对人体健康造成危害.治理后,各物质的健康风险均下降至可控范围之内,不会对人体健康造成损害.
3.1 小客车车舱内VOCs成分复杂,共检出80余种物质.有28种VOCs物质检出率大于50%.包括烷烯烃化合物(28.6%)、苯系物(21.4%)、醛酮化合物(14.3%)、醇类化合物(21.4%)和其他化合物(14.3%).苯系物、酯类物质和烷烃物质为检出浓度较高的物质.根据异味识别综合得分排名结果,间二甲苯、甲苯、乙酸乙酯、邻二甲苯、异辛醇和正己醛等为车舱内代表性异味VOCs,烷烃检出浓度虽高,但因其较高的嗅阈值而不被认为是代表性异味VOCs.
3.2 EWNS对异味VOCs的去除率高达90%以上,具有显著去除效果.该装置尺寸小巧便携,在常温常压下即可运行,对布置场地要求不高,可作为一种减少人体短期暴露于高浓度VOCs危害的解决方案.
3.3 车内苯和乙苯的致癌风险系数均在1×10-6~1×10-4之间,可能存在一定的致癌风险,间二甲苯和邻二甲苯可能会对人体健康造成非致癌危害,经治理后均下降至安全范围.但仍需定期对车辆进行通风和清洁.
  • 国家自然科学基金资助项目(42327806)
  • 浙江省领雁计划项目(2022C03073)
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2025年第45卷第5期
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  • 接收时间:2024-09-26
  • 首发时间:2026-03-18
  • 出版时间:2025-05-20
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  • 收稿日期:2024-09-26
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国家自然科学基金资助项目(42327806)
浙江省领雁计划项目(2022C03073)
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    1.浙江工业大学环境学院,浙江 杭州 310014
    2.松下家电(中国)有限公司,浙江 杭州 310018

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