| Brominated flame retardants?BFRs?and organophosphorus flame retardant?OPFRs?have been widely used in various products to prevent combustion and to delay the spread of fire after ignition.These chemicals are mostly additives that can be easily released from products during their manufacture,usage,and disposal,and pose adverse effects on environmental and human health.As a result,they have been found extensively in the environment worldwide.Atmosphere is an important medium of pollutants,playing a significant role in their occurrence,transportation,distribution,and human exposure.Currently,little information is available on the occurrence,emissions,and potential health impact of organic flame retardants from industrial activities,which are significant potential sources of these chemicals.In this study,total suspended particles?TSPs?,fine particles(PM2.5)and gaseous samples were collected in a number of industrial parks in an urban region and e-waste recycling parks in a rural region in the Pearl River Delta,South China.Concentrations,compositions,and spatial distributions of BFRs and OPFRs in the air were investigated.The emission inventories of BFRs and OPFRs from these parks were estimated.Correlations among BFRs,OPFRs and polycyclic aromatic hydrocarbons?PAHs?,organic carbon?OC?,elemental carbon?EC?in the particles were performed to explore the emission mechanisms of BFRs and OPFRs.Metal and water-soluble ions in airborne particles were also analyzed.Moreover,Cytotoxicities of size-fraction inhalable airborne particles from industrial parks to A549 cell lines were conducted.Human exposure and cancer risks of toxic metals were assessed.Such an effort would be helpful to understand the atmospheric contamination of BFRs and OPFRs related to industrial emissions,their sources in the air,transport,potential impact on human health,and China's fulfillment of international conventions.Concentrations of BFRs in urban industrial parks were lower than in e-waste parks.Decabromodiphenyl ethane?DBDPE?and PBDEs were the primary BFRs in air from different industrial/commercial activities in both urban and e-waste region.The median concentrations of PBDEs and DBDPE in TSP in the urban region were184 and 414 pg/m3 respectively;While in PM2.5 were 40.2 and 63.4 pg/m3.The levels of brominated BDEs in gaseous samples were in general low?median=5.72 pg/m3?.High concentrations of PBDEs in airborne particles were related with manufacture of machinery,electronics,decorative materials and vehicles in urban region while DBDPE was associated only with the manufacture of the first two ones.In the e-waste region,the median concentrations of PBDEs and DBDPE in TSP were 411 and 193pg/m3 and levels of PBDEs and DBDPE in PM2.5 were 201 and 93.2 pg/m3,respectively.Only penta-BDEs?median=42.4 pg/m3?were detected in gaseous samples,which presented a higher concentration than urban region.Overall,levels of DBDPE were higher than PBDEs in the urban region while levels of DBDPE were lower than PBDEs in the e-waste region.The median concentrations of BTBPE in TSP and PM2.5.5 from urban region were 9.54 and 2.78 pg/m3,respectively,whereas e-waste recycling region exhibited higher levels(8.63–345 pg/m3 in TSP and 9.30–279 pg/m3 in PM2.5).The dominating PBDE congener was BDE209 in particles from both,urban and e-waste regions,but more BDE209 may have been degraded in the e-waste region.The profiles of penta-BDEs were similar in each sampling site of the urban region.Nevertheless,profiles of penta-BDEs from the e-waste sites were different,which can point to the direct emission from the recycling process.According to the Junge-Pankow model,PBDEs in most urban parks were absorbed in organic phase of particles while in the e-waste region were adsorbed on the surface of particles.DBDPE?median=5819 g/yr?presented higher emissions than PBDEs?median=1555 g/yr?in the urban region while PBDEs?median=7350 g/yr?showed higher emissions than DBDPE?median=2656 g/yr?in the e-waste region.BTBPE was probably emitted from diffuse sources in the urban region while from point sources in e-waste region.The median emission of BTBPE from e-waste parks was233 g/yr.Strong correlation between BDE209 and DBDPE were found in both TSP and PM2.5 in the urban region,which indicates that PBDEs are still employed in different industrial/commercial activities there.Regarding BDE209 and BTBPE,no correlations were found in PM2.5 but significant ones were found in TSP.This result indicated DBDPE and BDE209 being emitted together with fine particles in different industrial/commercial activities.Moreover,correlations among BDE209 and PAHs,OC or EC were hardly found,which indicated that BDE209 was weakly related with combustion or pyrolysis processes in industrial/commercial activities.Contrarily,combustion or pyrolysis of e-waste played a significant role in emitting BFRs emissions.Concentrations of OPFRs in urban parks and e-waste parks were comparable.Levels of OPFRs in PM2.5 ranged from 519 to 62747 pg/m3,with a median of 2854pg/m3 in the urban region.High levels of OPFRs in PM2.5 were found near the manufacturing of electronic,plastic,and waste recycling,electroplating industries while lower OPFRs were prone to be detected in PM2.5 around manufacturing of machinery,paper,clothing and furniture industries.The dominating OPFRs in PM2.5from the whole urban region were TCIPP?average percentage=35.7%?and TMPP?19.6%?.However,TPHP?32.3–54.1%?,TNBP?16.7–88.0%?and EHDPP?11.2–31.8%?presented high percentages in PM2.5 at industrial sites which related with manufacturing of machinery and clothing,household products and furniture,formal waste recycling and leather,respectively.Concentrations of OPFRs in the e-waste region ranged from 775 to 13823 pg/m3?median=3321 pg/m3?and TPHP,TCIPP,TMPP were the most abundant OPFRs?41.4%,25.9%and 16.5%,respectively?.The median emission rate of OPFRs associated with PM2.5 was 73 kg/yr?8.8–546 kg/yr?in the urban region,which is higher than BFRs.The emission rates of OPFRs in the e-waste region?27–45 kg/yr,median=33 kg/yr?were lower.Correlations among most OPFRs in the urban region were weak which may result from different OPFRs being employed in different parks or OPFRs being influenced by different atmospheric conditions.Significant correlations were found between TNBP and Cl-OPFRs,in both urban and e-waste regions,which imply the direct emission of Cl-OPFRs.Most of OPFRs presented no significant correlation with PAHs,OC and EC except EHDPP and TEHP in both urban and e-waste regions,which indicates EHDPP and TEHP can be more related with combustion or pyrolysis processes in industrial parks.The principal trace metals in airborne particles were Ni,Cu,Mo,Mn,Pb and Ti in the urban region.Median concentrations of principal trace metals ranged from 94.3to 326 ng/m3 in TSP and from 31.8 to 70.6 ng/m3 in PM2.5.Ni,Pb and Mn are the most toxic ones among principal trace metals.High levels of Ni,Pb and Mn were associated with manufacture and wholesale of electronics,manufacture of leathers and manufacture of electronics,respectively.Cu,Pb and Ti were the primary trace metals in particles from the e-waste region.Median concentrations of Cu,Pb and Ti were respectively 235,113,16.3 ng/m3 in TSP and 104,88.1,11.4 ng/m3 in PM2.5.Median concentrations of water-soluble ions in particles were ordered as NO3->SO42->NH4+>Cl-in the urban region and NO3->NH4+>SO42->Cl-in the e-waste region.Ammonium tended to combine with SO42-in urban region,yet prone to react with NO3-in the e-waste region.Size-fractioned inhalable particles presented similar cytotoxicities to A549 cell lines while large-size particles?5.8–10?m?exhibited higher cytotoxicity.Particles which were related with manufacture of machinery and leather,waste incineration power plant presented higher cytotoxicities to A549 cell lines.BFRs and most of OPFRs in airborne particles were less harmful to A549 cell lines yet water-soluble ions,PAHs and EC may play more significant role in presenting cytotoxicities of particles.People from the urban region were exposed to the highest levels of Pb,Mn and Ni in PM2.5 via inhalation.On the contrast,only Pb exhibited high exposure to human in the e-waste region.Similarly,Cr?VI?presented a high median value of human exposure both in urban and e-waste regions,even that it was detected only in68.2%samples from the urban region and 25%samples from the e-waste region.Chromium?VI?and As presented the highest human carcinogenic risks both in urban and e-waste regions.The median values of human carcinogenic risks for Cr?VI?and As were 2.27×10-5 and 1.47×10-66 in the urban region;1.99×10-5 and 1.89×10-6 in the e-waste region,respectively.Carcinogenic risks of Cr?VI?and As surpassed the US EPA acceptable threshold(10-6)both in urban and e-waste regions. |
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