Study On Traceability Of Perfluorinated Compounds In Groundwater System Of Chemical Industry Park

Perfluorinated compounds(PFCs),a new type of persistent organic pollutant in the environment,interior upholstery for the past 60 years because of their outstanding properties such as unique surface activity,thermal stability and acid resistance,have been widely used as carpet,paper,food packaging bags,fabric surface protection agent,chemical additives and other living and industrial areas,and people’s daily production and living are closely related.They have attracted more and more researchers’ intense attention because of their environmental persistence,bioaccumulation,global distribution and toxicity.Most of the PFCs will enter the water environment during the preparation and use,as well as the leakage and discharge of waste,and groundwater is also one of the terminal attributions of PFCs in the environment.At present,there are few researches on the pollution status of the groundwater system PFCs at home and abroad.Especially,for the traceability of PFCs in groundwater system,the research in this field is rare.Therefore,the research on traceability technology of PFCs in groundwater system of our country is of great significance.In this paper,two typical chemical industrial parks area of groundwater systems were studied,one in the upstream and another in the middle reaches of Xiaoqing River,as a new pollutant perfluorinated compound traceability research area.The experiment was conducted by using liquid chromatography-tandem mass spectrometry.Using liquid chromatography tandem mass spectrometry for experimental analysis,data processing and mapping using Spss、Excel、 Matlab、 Surfer、 ArcGIS software etc.Combined with the correlation analysis,principal component analysis(PCA),the nonnegative constraint factor rotation model(FA-NNC)and positive matrix factorization model(PMF)and other means to study the concentration and size distribution of groundwater system of PFCs,and the sources of pollution source tracking.The main conclusions are as follows:(1)Through systematic sampling and analysis,12 types of perfluorinated compounds(PFCs)in groundwater systems of a chemical park in the upper reaches of Xiaoqing River were studied(including Perfluorobutyric acid(PFBA),perfluoropentanoic acid(PFPeA),perfluorohexanoic acid(PFHxA),perfluoroheptanoic acid(PFHpA),perfluorooctanoic acid(PFOA),perfluorononanoic acid(PFNA),perfluorononanoic acid(PFDA),Perfluorodecanoic Acid(PFUnDA),Perfluorododecanoic Acid(PFDoDA),Perfluorobutane Sulfonic Acid(PFBS),Perfluorohexanesulfonic Acid(PFHxS),Perfluorooctane Sulfonate(PFOS)).The results showed that PFCs were detected in all groundwaters with concentrations of sum PFCs(∑PFCs)ranging from 0.15 to 768.5ng/L,104.6ng/L on average.The pollution of PFCs in groundwater is dominated by short and medium carbon chains,and the content of PFCs in long carbon chains is low with the detection rate below 8%.There are differences in the total amount and composition of PFCs at different sampling points,which may be caused by different sources of pollution.PFBA、PFOA、PFNA and PFOS were the predominant short/medium-chain PFCs in groundwater,with maximum concentrations of 50.35、566.25、104.83 and 145.64ng/L respectively.Concentrations of individual PFCs were compared with related criteria for drinking water.A total of 4 sites(11%)the greatest concentration of PFOA above the New Jersey guidance value for drinking water 40 ng/L.And most of groundwater samples PFCs concentration were below in the United States Drinking Water Standard.(2)The distribution characteristics of PFCs concentration in groundwater system in a chemical park in the middle reaches of Xiaoqing River were studied.The results showed that in the groundwater system in this area,the pollution of PFCs is very common,and contains high concentrations of PFCs,12 target compounds(including Perfluorobutyric acid(PFBA),perfluoropentanoic acid(PFPeA),perfluorohexanoic acid(PFHxA),perfluoroheptanoic acid(PFHpA),perfluorooctanoic acid(PFOA),perfluorononanoic acid(PFNA),perfluorononanoic acid(PFDA),Perfluorodecanoic Acid(PFUnDA),Perfluorododecanoic Acid(PFDoDA),Perfluorobutane Sulfonic Acid(PFBS),Perfluorohexanesulfonic Acid(PFHxS),Perfluorooctane Sulfonate(PFOS))are detected to varying degrees,the detection rate of ΣPFCs was 100%,the concentration of ΣPFCs was 1.36ng/L-232.39 μg/L,with a median of 187.6 ng/L.PFCs were detected at higher concentrations in the sampling sites near or immediately downstream of the plant and adjacent to the river.PFBA、PFPeA、PFHxA、PFHpA and PFOA were the major detected PFCs in all samples,the detection rate was more than 80%,the concentration of a few to several hundred μg/L.The highest concentration of PFOA was 203.7μg/L,which was 509 times higher than that of the U.S.temporary health counseling(400ng/L).C4-C7 perfluorocarboxylic acids PFBA、PFPeA、PFHxA、PFHpA maximum concentration values exceed the existing standard several times the drinking water.The maximum PFBA concentrations observed for C4 surrogates in this study were higher than those associated with PFBA,indicating a relatively high risk.Perfluorosulfonic compounds are below their guideline values.(3)The correlation analysis,principal component analysis(PCA)and positive matrix decomposition model(PMF)were used to trace the source of PFCs pollution in a chemical park groundwater system in the upper reaches of the Xiaoqing River.The results show that the main pollutants analyzed by the three models come from the potential three sources of pollution,namely pollution sources of fluoride processing agents,pollution sources of fabric finishing agents and pollution sources of domestic sewage,and the contribution rates of three pollution sources to PFCs pollution.They were 56%,28.3%,and 15.7%,respectively.(4)Using correlation analysis,principal component analysis(PCA)and non-negative constrained factor rotation model(FA-NNC)to trace the source of PFCs in groundwater systems in a chemical park in the middle reaches of the Xiaoqing River.The results show that the PFCs pollution source types obtained by the three methods are consistent with the composition of each pollution source PFCs,indicating that these three models can well analyze the PFCs pollution sources in the groundwater system in the study area.The traceability results show that there are mainly two types of characteristic pollution sources of groundwater system PFCs in a chemical industry park.They are fluorine chemical pollution sources,textile and paper finishing agent pollution sources,and the relative contribution rates of the two pollution sources to the antimony PFCs are 83.36% respectively.16.64%.