Analytical Methods Of Phenolic Endocrine Disrupting Chemicals And Their Pollution Characteristics In Minjiang River Basin

ObjectiveTo establish analytical methods to detect eight phenolic endocrine disrupting chemicals?PEDCs?in water and fish sample respectively.Bisphenol A?BPA?,bisphenol B?BPB?,bisphenol F?BPF?,bisphenol S?BPS?,4-n-nonylphenol?4-n-NP?and4-nonylphenol?4-NP?,4-octylphenol?4-OP?,4-t-octylphenol?4-t-OP?were chosen to be detected.In this paper,the pollution characteristics of PEDCS in water and fish in Minjiang River basin were studied.Moreover,the risk of the eight PEDCS were evaluated preliminarily.Methods1.An analytical method of eight PEDCs in water was established:After optimizing the analysis and separation conditions and the pretreatment method of eight PEDCs,a qualitative and quantitative analytical method in water sample by ultra performance liquid chromatography-triple quadrupole mass spectrometry was established.Multi-response monitoring mode?MRM?was chosen in this method,and HSS T3 column was applied to separate the analytes under gradient elution conditions after enriching and purifying by ENVI^TM-18 SPE column.2.An analytical method of eight PEDCs in fish was established:A qualitative and quantitative analytical method by multi-response monitoring mode?MRM?in ultra performance liquid chromatography-triple quadrupole mass spectrometry was established.HSS T3 column was used to separate after extracting by ethyl acetate-cyclohexane?1:l?,purifying by gel permeation chromatography system and eluting by Biobead SX-3 at a flow rate of 3.0 mL/min.3.According to the stream trend of Minjiang River,17 monitoring points including the end of four major tributaries?Jian Stream,Futun Stream,Sha Stream and Dazhang Stream?,Minjiang main stream and Minjiang estuary were selected to collect water samples in the wet season?September?and the dry season?January?respectively.At the same time,26 fish samples including 11 species of fish collected at eight water collecting points in the Minjiang River Basin were determined in January 2018.The exposure concentration of eight PEDCs in water samples and fish samples was analyzed after detecting by established method.4.According to the WHO Principles and Methods for Chemical Risk Assessment in Food,the preliminary risk assessment of eight PEDCs in the Minjiang River basin was carried out to estimate the exposure risk on the basis of the above exposure experiment.Results1.An automatic solid phase extraction-ultra high performance liquid chromatography-triple quadrupole mass spectrometry method was established to determine the eight PEDCs in water.The eight PEDCs in water sample show good liner fit ranged from 0.1 to 40?g/L?r>0.990?with the detection limit of 0.0025⁰.0320ng/L.The average recoveries were in the range of 75.7%¹07.3%?n=6?with the RSD2.3%¹1.1%.2.Agelpermeationpurification-ultrahighperformanceliquid chromatography-triple quadrupole mass spectrometry method was established to determine the eight PEDCs in fish.The eight PEDCs in fish sample show good liner fit ranged from 0.1 to 40?g/L?r>0.990?with the detection limit of 0.48⁶.4ng/kg.The average recoveries were in the range of 70.2%¹12.1%?n=6?with the RSD 4.3%¹3.2%.3.The distribution characteristics of eight PEDCs in the water in Minjiang River basin:The detection range of BPA,4-NP,4-OP,4-t-OP,BPF,BPB,BPS and 4-n NP was4.59⁴13.95ng/L,12.34¹066.09ng/L,0.17¹0.61ng/L,3.46⁹4.63ng/L,ND³4.10ng/L,ND².53ng/L,ND¹4.31 ng/L and ND²3.98 ng/L,respectively.In the spatial and temporal distribution,the concentrations of the components between each two sample points were significantly different.The maximum concentration of 4-NP and BPA were all at the D03 sampling point in January.There was no significant difference?P>0.05?between the upper and lower reaches in the whole basin.In terms of time,4-NP,4-n-NP,4-OP,BPF,BPS and BPA were higher in September than in January.Among BPF and 4-NP;BPB and 4-NP,4-n-NP,4-OP;BPS and BPA,4-NP;BPA and 4-NP;4-NP and 4-n-NP,4-OP,4-t-OP,there were positive correlations between each two groups?P<0.05?.4.The distribution characteristics of eight PEDCs in the fish in Minjiang River basin:The detection range of BPA,4-NP,4-t-OP,BPF,BPB,BPS,4-OP and 4-n-NP in fish were 12.06⁴76.37ng/g,26.56⁶58.06ng/g,1.6⁸.80ng/g,ND²2.48 ng/g,ND⁸.65 ng/g,ND¹36.52 ng/g,ND⁸6.42 ng/g and ND⁰.32 ng/g,respectively.The detection rates of 4-NP,BPA,BPS,BPF,BPB,4-t-OP,4-OP 4-n-NP in fish offal were 100%,ranging from 31.69-820.07ng/g,9.82-584.58ng/g and0.31-286.77ng/g,respectively.The detection ranges of BPF,BPB,4-t-OP,4-OP and4-n-NP were 31.69⁸20.07ng/g,9.82⁵84.58ng/g,0.31²86.77ng/g,ND³5.26ng/g,ND⁸.73 ng/g,ND⁷0.21 ng/g,ND⁵9.61ng/g and ND¹1.45 ng/g,respectively.Among different species of fish,the concentrations of eight PEDCs were significantly different.The highest levels in chub was BPA with the content 476.37ng/g while the highest levels in Tilapia mossambica was 4-NP with the content 658 ng/g.The content of BPA and 4-NP in carp run the second with the content 621ng/g and 568ng/g,respectively.The results showed that BPF,BPS,BPA,4-NP,4-n-NP and 4-t-OP in the fish were all lower than that in the internal organs,and the difference was statistically significant?P<0.05?.The results of the comparison among the components showed that there was a positive correlation between BPF and 4-n-NP;BPB and 4-n-NP,4-OP;BPS and 4-n-NP;BPA and 4-NP;4-n-NP and 4-OP;4-OP and 4-t-OP?P<0.05?.There is a big difference between the components in the enrichment coefficient of eight PEDCS.The average concentration factor were in the range of 123⁷179.5.Preliminary risk assessment of eight PEDCs:According to the WHO Risk Assessment Principles and Methods for Chemical Risk Assessment in Foodstuffs,the amount of bisphenols and alkylphenols exposed by water and fish routes is low ignoring other factors,which indicates the risk is low.Conclusion1.The method to determine eight PEDCs in the water sample by automatic solid phase extraction-ultra performance liquid chromatography-triple quadrupole mass spectrometry and the method to determine eight PEDCs the fish sample by gel permeation and purification-ultra performance liquid chromatography-triple quadrupole mass spectrometry were established.Both methods showed good accuracy and repeatability and high sensitivity to meet the requirements of analytical methodologies and were suiTab.for the analysis and detection of real samples.2.The pollution characteristics of eight PEDCs in Minjiang River basin were studied for the first time.All of the eight PEDCs in water and fish samples in the Minjiang River basin were detected in different levels with significant difference in concentration between components,and the pollutants were mainly BPA and 4-NP.The difference of the eight PEDCs in water was obvious in seasons and collecting points while there was no significant difference between the upstream and downstream.Among different species of fish,the concentrations of eight PEDCs were significantly different.The concentrations of BPF,BPS,BPA,4-NP,4-n-NP,4-t-OP in fish are lower than that in fish viscera.The fish could enrich the PEDCs.3.The exposure level of eight PEDCs in water and fish in Minjiang River basin was lower than toxicity threshold.In the absence of other factors,the exposure of bisphenol A and alkyl phenol from water and fish routes is low and the risk is low.However,due to the widespread presence of PEDCs,exposure could expose through different channels,such as water and fish.Continued accumulation of exposure is still a risk to our health.