| Phthalic Acid Esters(PAEs)are the most widely used plasticizers in the market,which can increase the flexibility and ductility of products,so they are widely used in various consumer products.PAEs has certain physiological toxicity,can enter the human body through inhalation,oral and skin contact,and harm human health.Skin,as an important exposure route,is receiving more and more attention because it can pass through the skin and directly enter human blood without intermediate steps compared with inhalation and oral exposure.Clothing is the closest contact with skin,affecting skin exposure.Therefore,it is necessary to explore the pollution characteristics of PAEs in clothing and the influence of clothing on skin exposure.On the basis of questionnaire survey,children’s intimate clothing was selected as the research object to explore the pollution characteristics of PAEs in clothing background,and the influence of accumulation conditions,washing conditions and drying conditions on the characteristics of PAEs in clothing.Clothing was worn on the child dummy to analyze the contamination characteristics of PAEs on the surface of each part of the child dummy.On this basis,according to the concentration of PAEs in the clothing and the concentration of PAEs on the dummy surface,the monte Carlo simulation method was used to compare and analyze the children’s skin exposure.(1)Based on the results of the questionnaire survey,60 samples of children’s intimate clothing of different types,materials,colors and with or without printing were purchased in this study.The detection rate of 11 kinds of PAEs was higher than 50%.The detection rates of Diethyl phthalate(DEP),Diisobutyl phthalate(Di BP),Di-n-butyl phthalate(Dn BP),Di(2-n-Butoxyethyl)phthalate(DBEP),Di(2-Ethylhexyl)phthalate(DEHP)and Dicyclohexyl phthalate(DCHP)ranged from 87% to 100%.The detection rates of Dimethyl phthalate(DMP),Bis(4-methyl-2-amyl)phthalate(BMPP),Dihexyl phthalate(DNHP),Butyl benzyl phthalate(BBz P)and Di-nonyl phthalate(DNP)ranged from 55% to 77%.DEHP,DBEP,DCHP and Dn BP are the most important PAEs in the background samples of children’s intimate clothing.(2)In the background samples of different types of clothing,the concentration of PAEs in vest,shorts and socks was relatively high.There was no significant difference in the concentration of Dn BP,DBEP and DEHP among different types of clothing(P<0.05).There were no significant differences in Di BP,Dn BP,BMPP,DBEP and DNP among different fabrics(P>0.05),DMP of polyester fiber and Modal material clothing was significantly higher than that of 100% cotton and blended clothing(P<0.05);The concentration of DEP in polyester fiber and blended clothing was significantly higher than that in 100% cotton and modal clothing(P<0.05);The DNHP and BBz P of blended fabric were significantly higher than those of 100% cotton,polyester and modal fabric(P<0.05);The concentration of DCHP and DEHP in 100% cotton material clothing was significantly higher than that in blended,polyester fiber and Modal material clothing(P<0.05).There were significant differences in DNHP and BBz P between light-colored and dark-colored groups(P<0.05).The median concentration levels of DMP,Di BP,Dn BP,DBEP and DEHP in printed clothing samples were 1.2-2.2 times higher than those in non-printed clothing samples.(3)A total of 108 samples of children’s intimate clothing were obtained under different conditions of accumulation and ventilation duration.The detection rates of Dn BP,Bis(2-methoxyethyl)phthalate(DMEP),BMPP,Bis(2-ethoxyethyl)phthalate(DEEP),BBz P,DBEP,DCHP,DEHP,Di-n-octyl phthalate(Dn OP)and DNP were higher than 50%.The PAEs detection rate and median concentration distribution of clothing samples accumulated for 3 and 7 days were higher than that of clothing samples accumulated for 1 day.Under different ventilation duration,the concentrations of Dn BP,BMPP,DEEP,DBEP,DCHP,DEHP,Dn OP and DNP in clothing samples with daily ventilation duration of 3 hours were significantly higher than those in clothing samples without ventilation(P<0.05).The concentrations of Dn BP,DEEP,DBEP and Dn OP in clothing samples with 9 hours of daily ventilation were significantly higher than those without ventilation(P<0.05).(4)72 and 36 children’s intimate clothing samples were obtained after washing and drying.After washing,the PAEs species decreased,and only the detection rate of BBz P,DBEP,DCHP,DEHP and Dn OP PAEs was higher than 50%.After drying in different directions,the detection rate of DEP,Di BP,Dn BP,BBz P,DBEP,DCHP,DEHP and Dn OP was higher than 50%.Compared with unwashed clothing samples,the concentration levels of DCHP,DEHP and Dn OP in unwashed clothing samples were significantly higher than those in washed clothing samples(P<0.05).DBEP in washed clothing samples was significantly higher than that in unwashed clothing samples(P<0.05).Different chemicals such as washing powder,detergent,and softener add have the same washing effect.The DEP,Dn BP,BBz P,DBEP,DCHP and DEHP of the clothes aired on shade side were significantly higher than those of the clothes aired on sunny side(P<0.05).(5)In this study,162 surface wipe samples of dummy models were collected,and the detection rates of 10 PAEs,including Dn BP,DMEP,BMPP,DEEP,BBz P,DBEP,DCHP,DEHP,Dn OP and DNP,were higher than 50%.The detection rates of DNP,DEHP and DEEP were all 100%.The median size order of PAEs was DEHP(687.14 μg/m2)>DCHP(666.70 μg/m2)>Dn OP(118.25 μg/m2)>DNP(101.49 μg/m2)>DEEP(84 μg/m2)>Dn BP(47.94 μg/m2)>DMEP(7.79 μg/m2)>BMPP(6.65 μg/m2)>DBEP(2.24 μg/m2)>BBz P(0.8 μg/m2).For different body parts,the concentrations of PAEs on the surface of the head and hands were higher.There was no significant difference in the PAEs of the dummy surface wipe samples under different accumulation time(P>0.05).The concentrations of DMEP,DEEP and DNP in the dummy surface wipe samples with air gap with clothing were significantly higher than those in the dummy surface wipe samples without air gap(P<0.05).(6)Monte Carlo simulation was used to assess skin exposure.The results of children’s skin exposure calculated based on the concentration of PAEs on the dummy surface showed that the head and torso were the two parts with the highest exposure,and the exposure amount of PAEs with low molecular weight was higher than that of PAEs with high molecular weight.On the contrary,the results of skin exposure based on the concentration of PAEs in clothing samples showed that the exposure of DBEP,DCHP and DEHP with relatively high molecular weight was higher than that of PAEs with low molecular weight.Autumn clothing and short sleeves contributed more to the exposure based on background samples of different types of clothing than other types of clothing.Under the condition of different accumulated durations,the skin exposure caused by Dn BP,DCHP,DEHP and Dn OP in the clothes sample is 3-26 time of that caused by the washed clothes.The total skin exposure of Dn BP,BBz P,DBEP,DCHP,DEHP and DNP in the clothes background samples is 1.6-24 times of that under the condition of different accumulated durations. |
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