深圳城市大气PM_(2.5)中金属元素的在线测量与来源特征
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摘要
大气PM_(2.5)中很多金属元素危害人体健康,且具有源示踪性,因此,开展PM_(2.5)中金属在线监测对污染来源分析和大气污染防治有着重要意义.本研究于2017年4—5月使用美国Cooper环境空气多金属在线监测仪对深圳城市大气PM_(2.5)中金属元素进行连续观测.与同步离线采样测量的金属数据进行比对表明,10种元素(K、Zn、Cu、Mn、Fe、V、Ni、Ti、Pb、Cr)呈现良好的相关性,因而用于后续分析.观测期间大气PM_(2.5)的平均浓度24.8μg·m~(-3),其中10种金属元素总浓度为0.72μg·m~(-3),占比2.9%.Mn、Fe、Cu、Zn和Ti的浓度日变化显示了日间高、夜间低的特征,表明受到本地人为源的显著影响;而K、Pb、Cr浓度日变化无明显波动,说明受区域传输影响较大;Ni与V日变化趋势一致,主要来源为船舶排放.主成分因子分析结果表明,观测期间PM_(2.5)中金属污染来源主要为交通和扬尘源、工业排放/废物燃烧和船舶污染,方差贡献依次为54.3%、19.8%和8.8%.
Some metals in PM_(2.5) are harmful to human health and can be tracers to some particular pollution sources. Therefore, it is very important to carry out on-line monitoring of metals in atmospheric PM_(2.5) for analysis of pollution sources and prevention of atmospheric pollution. In this study, the Cooper automated multi-metals monitor was used to continuously observe the metals in the atmospheric PM_(2.5) in Shenzhen from April to May in 2017. The comparisons with simultaneous off-line sampling and measurement of metal data indicated that 10 elements(K, Zn, Cu, Mn, Fe, V, Ni, Ti, Pb, Cr) exhibited good correlation and were therefore used for subsequent analysis. During the observation period, the average concentration of PM_(2.5) was 24.8 μg·m~(-3), and the total concentration of 10 metal elements was 0.72 μg·m~(-3), accounting for 2.9% of the total. The diurnal variation of Mn, Fe, Cu, Zn, and Ti showed the characteristics of higher in the daytime and lower in the evening, indicating that they were significantly influenced by the anthropogenic activities, while the diurnal variation of K, Pb, and Cr concentrations did not show significant fluctuations, indicating mainly affected by regional transport. The diurnal variation of Ni was consistent with V, implying their main source was ship emissions. The results of principal component analysis showed that the sources of metal pollution in PM_(2.5) during the observation period were mainly traffic/dust, industrial emissions/waste burning, and ship emissions, contributing 54.3%, 19.8%, and 8.8%, respectively.
Some metals in PM_(2.5) are harmful to human health and can be tracers to some particular pollution sources. Therefore, it is very important to carry out on-line monitoring of metals in atmospheric PM_(2.5) for analysis of pollution sources and prevention of atmospheric pollution. In this study, the Cooper automated multi-metals monitor was used to continuously observe the metals in the atmospheric PM_(2.5) in Shenzhen from April to May in 2017. The comparisons with simultaneous off-line sampling and measurement of metal data indicated that 10 elements(K, Zn, Cu, Mn, Fe, V, Ni, Ti, Pb, Cr) exhibited good correlation and were therefore used for subsequent analysis. During the observation period, the average concentration of PM_(2.5) was 24.8 μg·m~(-3), and the total concentration of 10 metal elements was 0.72 μg·m~(-3), accounting for 2.9% of the total. The diurnal variation of Mn, Fe, Cu, Zn, and Ti showed the characteristics of higher in the daytime and lower in the evening, indicating that they were significantly influenced by the anthropogenic activities, while the diurnal variation of K, Pb, and Cr concentrations did not show significant fluctuations, indicating mainly affected by regional transport. The diurnal variation of Ni was consistent with V, implying their main source was ship emissions. The results of principal component analysis showed that the sources of metal pollution in PM_(2.5) during the observation period were mainly traffic/dust, industrial emissions/waste burning, and ship emissions, contributing 54.3%, 19.8%, and 8.8%, respectively.
引文
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Ogulei D,Hopke P K,Zhou L,et al.2005.Receptor modeling for multiple time resolved species:The Baltimore supersite[J]. Atmospheric Environment,39(20):3751-3762
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齐冰,杜荣光,于之锋,等.2015.杭州地区大气细颗粒物浓度变化特征分析[J].环境化学,34 (1):77-82
Richard A,Gianini M F D,Mohr C,et al.2011.Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland[J].Atmospheric Chemistry & Physics,11(17):8945-8963
Samet J M,Dominici F,Curriero F C,et al.2000.Fine particulate air pollution and mortality in 20 U.S.cites,1987-1994[J].The New England Journal of Medicine,343(24):1742-1749
谭吉华,段菁春.2013.中国大气颗粒物重金属污染、来源及控制建议[J].中国科学院大学学报,30(2):145-155
Tremper A H,Font A, Priestman M,et al.2017.Field and laboratory evaluation of a high time resolution x-ray fluorescence instrument for determining the elemental composition of ambient aerosols[J].Atmospheric Measurement Techniques,11(6): 3541-3557
USEPA (United States Environmental Protection Agency).1990.The clean air act amendments of 1990 list of hazardous air pollutants [OL].2017-12-15,http: //www. epa. gov/ttnatw01/ orig189
王晓浩,赵倩彪,崔虎雄.2015.基于在线监测的上海郊区冬季PM2.5来源解析[J].南京大学学报(自然科学),51(3):517-523
Watson J G.2002.Visibility:science and regulation[J].Journal of the Air & Waste Management Association,52(6):628- 713
谢华林,张萍,贺惠,等.2002.大气颗粒物中重金属元素在不同粒径上的形态分布[J].环境工程,20(6):55-57
许栩楠,曾立民,张远航,等.2016.北京市怀柔区冬季大气重金属污染状况分析[J].环境化学,35(12):2460-2468
杨怀金,杨德容,叶芝祥,等.2016.成都西南郊区春季PM2.5中元素特征及重金属潜在生态风险评价[J].环境科学,37(12):4490-4503
Yuan Z,Lau A K H,Zhang H,et al.2006.Identification and spatiotemporal variations of dominant PM10, sources over Hong Kong[J].Atmospheric Environment,40(10):1803-1815
周雪明,郑乃嘉,李英红,等.2017.2011—2012北京大气PM2.5中重金属的污染特征与来源分析[J].环境科学,38 (10):4054-4060
庄马展.2016.厦门大气PM2.5中元素特征及重金属健康风险评价[J].环境化学,35(8):1723-1732
Zou B B,Huang X F,Zhang B,et al.2017.Source apportionment of PM2.5,pollution in an industrial city in southern China[J]. Atmospheric Pollution Research,8(6):1193-1202
Balasubramanian R,Qian W B.2004.Characterization and source identification of airborne trace metals in Singapore[J].Journal of Environmental Monitoring,6(10):813-818
Bullock K R,Norris D G A,Mcdow S R,et al.2008.Evaluation of the CMB and PMF models using organic molecular markers in fine particulate matter collected during the Pittsburgh Air Quality Study[J].Atmospheric Environment,42(29):6897-6904
Cao J J,Lee S C,Ho K F,et al.2004.Spatial and seasonal variations of atmospheric organic carbon and elemental carbon in Pearl River Delta Region,China[J].Atmospheric Environment,38:4447-4456
Dall′Osto M,Querol X,Amato F,et al.2013.Hourly elemental concentrations in PM2.5 aerosols sampled simultaneously at urban background and road site during SAPUSS-diurnal variations and PMF receptor modelling[J].Atmospheric Chemistry & Physics,13(8):4375-4392
方凤满.2010.中国大气颗粒物中金属元素环境地球化学行为研究[J].生态环境学报,19(4):979-984
Furger M,Minguillón M C,Yadav V,et al.2017.Elemental composition of ambient aerosols measured with high temporal resolution using an online XRF spectrometer[J].Atmospheric Measurement Techniques,10(6):1-26
Gietl J K,Lawrence R,Thorpe A J,et al.2010.Identification of brake wear particles and derivation of a quantitative tracer for brake dust at a major road[J].Atmospheric Environment,44(2):141-146
Hagler G S, Bergin M H, Salmon L G,et al.2006.Source areas and chemical composition of fine particulate matter in the Pearl River Delta region of China[J].Atmospheric Environment,40:3802-3815
Haritash A K, Kaushik C P.2007.Assessment of seasonal enrichment of heavy metals in respirable suspended particulate matter of a sub-urban Indian City[J].Environmental Monitoring & Assessment,128(1/3):411-420
黄晓锋,云慧,宫照恒,等.2014.深圳大气PM2.5来源解析与二次有机气溶胶估算[J].中国科学:地球科学,44(4):723-734
Jeong C H,Wang J M,Evans G J.2016.Source apportionment of urban particulate matter using hourly resolved trace metals,organics,and inorganic aerosol components[J].Atmospheric Chemistry & Physics,1-32
Jeong J H,Shon Z H,Kang M,et al.2017.Comparison of source apportionment of PM2.5,using receptor models in the main hub port city of East Asia:Busan[J].Atmospheric Environment,148:115-127
Li L,Tan Q,Zhang Y,et al.2017.Characteristics and source apportionment of PM2.5 during persistent extreme haze events in Chengdu,southwest China[J]. Environmental Pollution,230:718-729
Li H,Huang X,Cao L,et al.2018.Development of an on-line measurement system for water-soluble organic matter in PM 2.5 and its application in China[J].Journal of Environmental Sciences, 69:33-40
李丽娟,温彦平,彭林,等.2014.太原市采暖季PM2.5中元素特征及重金属健康风险评价[J].环境科学,35(12):4431-4438
刘佳,翟崇治,许丽萍,等.2015.灰霾天气下重庆地区秋冬金属污染特征及来源分析[J].生态环境学报,24(10):1689-1694
Ogulei D,Hopke P K,Zhou L,et al.2005.Receptor modeling for multiple time resolved species:The Baltimore supersite[J]. Atmospheric Environment,39(20):3751-3762
Pancras J P,Ondov J M,Poor N,et al.2006.Identification of sources and estimation of emission profiles from highly time-resolved pollutant measurements in Tampa,FL[J].Atmospheric Environment,40(2):467-481
Pant P,Harrison R M.2012.Critical review of receptor modelling for particulate matter:A case study of India[J].Atmospheric Environment,49(3):1-12
Park S,Cho S,Jo M,et al.2014.Field evaluation of a near-real time elemental monitor and identification of element sources observed at an air monitoring supersite in Korea[J].Atmospheric Pollution Research,5(1):119-128
Pope C A,Dockery D W.2006.Health effects of fine particulate air pollution: lines that connect[J].Journal of the Air & Waste Management Association,56(6):709-742
齐冰,杜荣光,于之锋,等.2015.杭州地区大气细颗粒物浓度变化特征分析[J].环境化学,34 (1):77-82
Richard A,Gianini M F D,Mohr C,et al.2011.Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland[J].Atmospheric Chemistry & Physics,11(17):8945-8963
Samet J M,Dominici F,Curriero F C,et al.2000.Fine particulate air pollution and mortality in 20 U.S.cites,1987-1994[J].The New England Journal of Medicine,343(24):1742-1749
谭吉华,段菁春.2013.中国大气颗粒物重金属污染、来源及控制建议[J].中国科学院大学学报,30(2):145-155
Tremper A H,Font A, Priestman M,et al.2017.Field and laboratory evaluation of a high time resolution x-ray fluorescence instrument for determining the elemental composition of ambient aerosols[J].Atmospheric Measurement Techniques,11(6): 3541-3557
USEPA (United States Environmental Protection Agency).1990.The clean air act amendments of 1990 list of hazardous air pollutants [OL].2017-12-15,http: //www. epa. gov/ttnatw01/ orig189
王晓浩,赵倩彪,崔虎雄.2015.基于在线监测的上海郊区冬季PM2.5来源解析[J].南京大学学报(自然科学),51(3):517-523
Watson J G.2002.Visibility:science and regulation[J].Journal of the Air & Waste Management Association,52(6):628- 713
谢华林,张萍,贺惠,等.2002.大气颗粒物中重金属元素在不同粒径上的形态分布[J].环境工程,20(6):55-57
许栩楠,曾立民,张远航,等.2016.北京市怀柔区冬季大气重金属污染状况分析[J].环境化学,35(12):2460-2468
杨怀金,杨德容,叶芝祥,等.2016.成都西南郊区春季PM2.5中元素特征及重金属潜在生态风险评价[J].环境科学,37(12):4490-4503
Yuan Z,Lau A K H,Zhang H,et al.2006.Identification and spatiotemporal variations of dominant PM10, sources over Hong Kong[J].Atmospheric Environment,40(10):1803-1815
周雪明,郑乃嘉,李英红,等.2017.2011—2012北京大气PM2.5中重金属的污染特征与来源分析[J].环境科学,38 (10):4054-4060
庄马展.2016.厦门大气PM2.5中元素特征及重金属健康风险评价[J].环境化学,35(8):1723-1732
Zou B B,Huang X F,Zhang B,et al.2017.Source apportionment of PM2.5,pollution in an industrial city in southern China[J]. Atmospheric Pollution Research,8(6):1193-1202