Particle Size Distribution of Perfluoroalkyl Substances in Atmospheric Particulate Matter in Beijing
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摘要: 人为排放的持久性有机污染物倾向于在细级大气颗粒物中富集，但目前国内外关于大气颗粒物中全氟烷基化合物（PFASs）粒径分布在不同国家地区有显著差异，而在我国北京地区PFASs在不同粒径大气颗粒物中的富集能力尚不清楚。本文采用五级大流量主动分级采样器采集了北京市大气颗粒物样品，利用超声萃取结合高效液相色谱-电喷雾负电离源串联质谱测定PFASs含量，探讨了该地区大气颗粒物中PFASs的浓度水平和粒径分布特征，以及大气颗粒物浓度变化对PFASs浓度变化的影响。结果表明：研究区∑PFASs范围为10.1~62.9 pg/m3，76.4%~83.8%的PFASs集中分布在PM2.5颗粒物中，其中含量较高的PFOA、PFNA和PFDA在<0.25 μm细颗粒物中占比最高，分别为26.3%~43.7%、30.3%~68.6%和30.6%~49.7%；PFOS在<0.25 μm细颗粒物中没有检出，主要分布在1~2.5 μm和0.25~1 μm颗粒物中。此外，研究发现北京市霾天大气颗粒物中∑PFASs为晴天的3.5倍，且不同粒径大气颗粒物浓度变化对PFASs各化合物表现出不同的富集能力，其中PFOA、PFOS、PFNA和PFDA等中链PFASs更易富集。Abstract:
BACKGROUND Anthropogenic emissions of persistent organic pollutants (POPs) tend to be concentrated in fine-level atmospheric particles. However, there are significant differences in the particle size distribution of perfluoroalkyl compounds (PFASs) in atmospheric particulate matter in different countries and regions, and the enrichment capacity of PFASs in different size particulate matter in Beijing is still unclear. OBJECTIVES To reveal the concentration level and particle size distribution characteristics of perfluoroalkyl substances in atmospheric particulate matter in Beijing, by collecting samples using a five stage impactor sampler and to discuss the effects of atmospheric particulate matter concentration changes on the concentration of perfluoroalkyl substances under different sizes. METHODS The samples were pretreated by ultrasonic extraction, and the concentrations of PFASs were determined by High Performance Liquid Chromatography-Electrospray Negative Ionization Source Tandem Mass Spectrometry. RESULTS The concentrations of ∑PFASs are 10.1-62.9 pg/m3, and 76.4%-83.8% of PFASs are concentrated in PM2.5. PFOA, PFNA and PFDA have the highest concentration in the <0.25 μm particles, accounting for 26.3%-43.7%, 30.3%-68.6% and 30.6%-49.7%, respectively. PFOS is not detected in the fine particles (0.25 μm) and 68.9%-2.8% of PFOS are concentrated in the particles with sizes of 0.25-1 μm and 1-2.5 μm. CONCLUSIONS The ∑PFASs in the atmospheric particles of smog in Beijing are 3.5 times that of sunny days, and the changes of atmospheric particle concentration of different particle sizes show different enrichment ability for each compound of PFASs, among which PFOA, PFOS, PFNA and PFDA middle chain PFASs are enriched more easily. -
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表 1 北京市大气样品采集信息
Table 1. Sampling information in Beijing city
采样日期
(2014年)采样时间
(h)天气
状况室外温度
(℃)空气质量
等级AQI
指数10月9日 24 霾 13~22 严重污染 380 10月13日 24 晴 2~17 优 29 10月16日 24 晴 6~22 良 73 10月18日 24 晴 13~22 中度污染 194 10月21日 24 霾 7~17 重度污染 201 10月23日 24 霾 12~18 严重污染 263 10月31日 24 霾 8~17 良 67 注：AQI指数为空气污染指数，根据环境空气质量标准和各项污染物对人体健康、生态、环境的影响，将常规监测的几种空气污染物浓度简化成为单一的概念性指数值形式，它将空气污染程度和空气质量状况分级表示，适合于表示城市的短期空气质量状况和变化趋势。 
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表 2 大气样品中各PFASs的方法检出限、平均回收率及加标回收率
Table 2. Detection limits of the method and recoveries for individual PFASs in air samples
PFASs化合物 LOD
(pg/m3)平均回收率±
标准偏差(%)加标回收率±
标准偏差(%)同位素标记化合物 平均回收率±
标准偏差(%)PFHxA 0.005 103.2±11.3 97.5±13.6 13C2PFHxA 117.6±9.8 PFHpA 0.005 98.9±15.6 98.3±16.4 13C4PFOA 106.8±10.4 PFOA 0.005 104.3±12.7 117.5±11.9 13C5PFNA 115.5±15.1 PFNA 0.005 101.1±18.5 100.4±20.3 13C2PFDA 111.7±9.2 PFDA 0.023 99.3±13.8 98.9±14.1 13C2PFUnDA 104.5±12.6 PFUnDA 0.023 89.7±12.5 75.8±10.7 13C2PFDoDA 101.9±14.2 PFDoDA 0.005 102.5±9.8 120.3±12.9 13C4PFOS 121.6±16.3 PFTrDA 0.005 123.1±17.3 103.2±18.9 PFTeDA 0.005 102.6±14.0 87.1±17.4 PFHxDA 0.005 102.5±19.5 100.2±21.6 PFOcDA 0.005 92.6±11.4 107.7±15.1 PFOS 0.005 100.9±16.3 101.8±14.5 FOSA 0.006 93.6±13.2 90.5±12.7 N-EtFOSA 0.005 96.2±12.1 93.5±14.5
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表 3 北京市大气颗粒物中PFASs组成
Table 3. Composition of PFASs in atmospheric particulates in Beijing city
PFASs
化合物含量(pg/m3) 2014年
10月
9日2014年
10月
13日2014年
10月
16日2014年
10月
18日2014年
10月
21日2014年
10月
23日2014年
10月
31日PFOS 9.7 1.3 0.9 0.8 3.7 10.8 3.6 FOSA 0.1 0.1 0.0 0.0 0.1 0.2 0.1 N-EtFOSA 0.5 0.5 0.6 0.6 0.3 0.5 0.5 PFHxA 1.6 0.4 0.5 0.6 0.6 1.4 0.7 PFHpA 2.6 0.2 0.2 0.5 0.7 2.3 0.6 PFOA 22.5 3.7 3.7 3.9 8.9 32.0 11.7 PFNA 3.0 1.4 1.8 2.3 1.0 2.7 1.2 PFDA 5.6 0.6 0.7 0.9 1.0 4.9 1.0 PFUnDA 1.6 0.6 0.7 0.6 0.8 1.6 0.8 PFDoDA 2.3 0.3 0.5 0.7 0.5 2.2 0.4 PFTrDA 1.1 0.3 0.3 0.7 0.6 0.9 0.4 PFTeDA 1.4 0.4 0.7 0.7 0.5 1.6 0.3 PFHxDA 1.0 0.2 0.4 0.4 0.8 1.1 0.5 PFOcDA 0.9 0.2 0.1 0.7 0.2 0.7 0.1 ∑PFASs 54.0 10.1 11.0 13.4 19.7 62.9 21.9
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表 4 不同粒径下PFASs的q值
Table 4. q values of PFASs in different particle sizes
PFASs
化合物q值 ＞10 μm 2.5~
10 μm1~
2.5 μm0.25~
1 μm＜0.25 μm PFOS 4.44 4.26 2.36 2.52 - FOSA - 9.64 7.18 6.45 9.40 N-EtFOSA 10.21 - 6.22 - - PFHxA 5.17 4.96 4.60 5.28 - PFHpA 4.86 4.03 4.49 5.03 4.85 PFOA 2.75 2.16 2.19 2.35 1.85 PFNA 5.18 4.66 4.80 4.82 - PFDA 5.07 4.73 4.16 4.19 3.40 PFUnDA 7.84 6.76 5.45 5.22 4.78 PFDoDA 7.46 - 5.37 4.74 4.37 PFTrDA 6.26 5.47 7.29 6.09 5.41 PFTeDA - - 6.38 5.40 5.26 PFHxDA 6.04 4.09 6.31 5.74 5.61 PFOcDA 7.79 - - 5.73 6.09
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