对苯二胺类抗氧化剂及其氧化产物在道路尘土和附近表层土中的分布特征及人体暴露评估
Distribution Characteristics and Human Exposure Assessment of p-phenylenediamine (PPD) Antioxidants and Their Oxidation Products in Road Dust and Nearby Topsoil
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摘要: N,N'-取代对苯二胺(PPD)是一类广泛添加在橡胶轮胎中的抗氧化剂,能够随着橡胶轮胎的磨损,不断释放并积聚在道路尘土中。6PPD-Q(6PPD-quinone)是N-(1,3-二甲基丁基)-N'-苯基对苯二胺(6PPD)的臭氧化产物,近期由于其对银鲑鱼表现出的高毒性而备受人们关注。目前对于该类污染物的环境行为研究十分有限,给健康风险评估带来了极大的不确定性。本研究采集了大连市5个区域的尘土样品和表层土样品,研究了6种PPDs和6PPD-Q在不同区域样品中的分布特征。结果表明,6PPD、6PPD-Q、N,N'-二-2-萘基对苯二胺(DNPD)和N,N'-(1,4-二甲基戊基)-对苯二胺(77PD)在道路尘土样品中的检出率均为100%;而在表层土壤样品中,仅6PPD、6PPD-Q和77PD在70%以上的样品中有检出,所有样品中均未检测到N-苯基-N'-环己基-对苯二胺(CPPD)。6PPD-Q在大多数道路尘土中处于较高污染水平,浓度范围为0.12~52.21 ng·g-1(中值:7.18 ng·g-1)约占总质量浓度的34.10%,其次是DNPD和6PPD,二者浓度范围分别为0.61~113.83 ng·g-1(中值:2.54 ng·g-1)和0.21~27.26 ng·g-1(中值:1.83 ng·g-1)。6种PPDs总和(ΣPPDs)浓度范围为3.59~131.37 ng·g-1(中值:11.24 ng·g-1)。城市主干道尘土中ΣPPDs和6PPD-Q的浓度显著高于居民区尘土和居民广场尘土。居民区绿化带表层土中目标化合物检出率较低,农田表层土由于距离污染源较近,污染水平高于居民区绿化带。对3种尘土样品进行人体暴露评估,6种检测到的化合物中,6PPD-Q的暴露量最高;ΣPPDs和6PPD-Q经口摄入量远大于经皮肤摄入,ΣPPDs和6PPD-Q通过道路尘土的摄入量均表现为主干道>居民区道路>居民广场,其中,主干道尘土摄入量占70%以上。主干道、居民区道路和广场尘土样品中ΣPPDs的日摄入量分别为0.13、0.02、0.01 ng·kg-1·d-1,6PPD-Q的日摄入量分别为0.06、0.02、0.01 ng·kg-1·d-1。儿童对于ΣPPDs和6PPD-Q的日摄入量为0.20 ng·kg-1·d-1和0.11 ng·kg-1·d-1,约为成人的2倍。由于本研究选择的5个采样区域均与居民生活密切相关,道路尘土中6PPD-Q具有较高浓度可能会造成潜在的人体健康风险。Abstract: N,N'-substituted p-phenylenediamine (PPD) is widely used antioxidant in rubber tire, which may continuously release and accumulate in road dust with the tire wear. As an ozonation product of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), 6PPD-quinone (6PPD-Q) have attracted much attention currently due to the high toxicity to coho salmon. However, information on the environmental behavior of PPDs and 6PPD-Q remains limited. The present study collected dust and topsoil samples from five different urban areas in Dalian to investigate the distribution characteristics of six PPDs and 6PPD-Q. The results indicated that 6PPD, 6PPD-Q, N,N'-di-2-naphthyl-p-phenylenediamine (DNPD) and N,N'-(1,4-dimethylpentyl)-p-phenylenediamine (77PD) were detected in 100% of road dust samples. While, in topsoil samples, only 6PPD, 6PPD-Q, and 77PD were detected in more than 70% samples, N-phenyl-N'-cyclohexyl-p-phenylenediamine (CPPD) was not detected in all samples. 6PPD-Q was detected at higher level in most road dust samples, the concentrations ranged from 0.12 to 52.21 ng·g-1 (median:7.18 ng·g-1), which account for 34.10% of the total concentration, followed by DNPD and 6PPD, the concentrations ranged from 0.61 to 113.83 ng·g-1 (median:2.54 ng·g-1) and 0.21 to 27.26 ng·g-1 (median:1.83 ng·g-1), respectively. Total PPDs concentration (ΣPPDs) ranged from 3.59 to 131.37 ng·g-1 with the median concentration of 11.24 ng·g-1. ΣPPDs and 6PPD-Q in urban trunk dust were significantly higher than that in residential dust and residential plaza dust. A lower detection rate of each compound was observed in the topsoil collected from the residential green belt. However, the topsoil collected from agricultural land exhibited a higher level than that collected in the residential green belt due to its proximity to the source. The daily intake of each compound was calculated and the results showed that 6PPD-Q was at the highest exposure amount. Oral intake of ΣPPDs and 6PPD-Q was much greater than dermal intake. The intake of ΣPPDs and 6PPD-Q exhibited the same trend:trunk road > residential road > residential square. Compared with residential road and residential square road dust, exposure to urban trunk road dust accounting for more than 70% of the intake for ΣPPDs and 6PPD-Q. The daily intakes of ΣPPDs were 0.13, 0.02 and 0.01 ng·kg-1·d-1 and 6PPD-Q were 0.06, 0.02 and 0.01 ng·kg-1·d-1 for the main road, residential road and square dust samples, respectively. The intakes of ΣPPDs and 6PPD-Q for children was 0.20 ng·kg-1·d-1 and 0.11 ng·kg-1·d-1, which is nearly twice that of adults. The present study selected five sampling areas closely-related with resident life, and the high concentrations of 6PPD-Q in road dust may pose a potential human health risk.
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Key words:
- PPDs /
- 6PPD-Q /
- road dust /
- exposure assessment
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