The Estrogenic Acitivities Of Raw Water And Distribution Of The Phenolic EDCs In Drinking Water Treatment Processes Of W City Jiangsu Province

Environmental Endocrine Disrupting Chemicals (EDCs) raised great concern because of the ubiquitous distribution and adverse effects to human health. The detection methods of estrogenicity and phenolic EDCs in drinking water are not standardized in China yet, and limited studies concern on the occurrence and distribution of these compounds in the drinking water treatment processes. The objective of this study is to establish a method that combining solid phase extraction and liquid chromatography tandem mass spectrometer (SPE-LC-MS/MS) and applying the recombined yeast estrogen screen (YES assay) to assess the estrogenicity and phenolic EDCs in the raw water (Taihu Lake and Yangtze River) and effluent of each drinking water treatment process (both conventional and advanced processes) in Jiangsu province. To find out the main contributor to the estrogenicity among the phenolic EDCs and to provide scientific dada for improving the drinking water treatment processes.Part I Establish the detection method for phenolic EDCs in water using SPE-LC-MS/MSObjective: Establish a method that combining solid phase extraction and liquid chromatography tandem mass spectrometer (SPE-LC-MS/MS) to detect the phenolic EDCs in water. To provide scientific data for selecting raw water and improving drinking water treatment processes.Method:1. Prepare single standard and mixed standard series of the four phenolic EDCs (BPA, DES, OP, NP);2. Optimize the MRM (Multiple Reaction Model) parameters of LC-MS/MS;3. Optimize the gradient elution model;4. Assess the limit of detection, precision and accuracy of the method.5. Optimize the cartridge type, pH, ionic strength, eluent type and sampling speed.6. Apply the raw water, finished water and type water to assess the method.Results: The parameters of detection method are as following:Applicability:drinking water (river, lake water and tap water);Equipment: Ultra high performance liquid chromatography (Shimadzu SIL-30AC), triple quadrupole mass spectrometer (AB SCIEX (API 4000+)), column (Shim pack XR ODS ? (2.2 ?m) 75 L x 2.0);Water sample pretreatment:1. Cartridge type:Oasis HLB; 2.Condition:5 mL methanol, 5 mL ultrapure water (in turn); 3. pH: 6; 4. Ionic strength:0%; 5. Sampling speed: 4 mL/min; 6. Rinsing:1 mL ultrapure water; 7. Dry.-in Vacuum freeze drying machine,-40?,10 Pa, dry 2 h; 8. Eluent type:2 mL methanol+2 mL n-hexane+2 mL dichloromethane (in turn); 9. Enrichment: water bath 40? in nitrogen; 10. Dissolve:1 mL methanol (HPLC grade).Conclusion:According to the water sample pretreatment and detection parameters, the limit of detection are BPA:3.41 ng/L, DES:2.34 ng/L, OP:8.4 ng/L,NP:9.2 ng/L, precisions are within 10%, recoveries arrange from 70% to 120%, this established method can completely suitable for detecting phenolic EDCs in surface water.Part II The estrogenicity and phenolic EDCs in raw water of Taihu Lake and Yangtze River from Wuxi regionObjective:Assess the estrogencity and time and space distribution of nonvolatile organic compounds and the phenolic EDCs in Taihu Lake and Yangtze River from the region of W city. Estimate the effects to the Taihu Lake water of project "Water Diversion Project from Yangtze River to Taihu Lake (WDYT)", and to find out the main contributor to the estrogenicity among the four phenolic EDCs. Explore the effects of suspended particles to the phenolic EDCs. Thus, to provide scientific data for improving drinking water treatment processes and management of WDYT.Method: From December 2013 to August 2015, water samples were collected from Taihu Lake, Yangtze River and project WDYT. YES assay and LC-MS/MS were applied to analysis the estrogenicity and detect the phenolic EDCs. The effects of the suspended particles to the compounds were evaluated at the same time by applying the glass fiber.Results: The raw water of Taihu Lake and Yangtze River presented the estrogenicity at different extent (EEQs:<LOD?7.56 ng/L). The estrogenic strengths of XD raw water (< LOD?6.20 ng/L) were higher than CX (<LOD?2.96 ng/L), and the NQ raw water (<LOD ?0.33 ng/L) present the weakest estrogenicity. The estrogenicity of raw water presented seasonal variations: dry period> level period> wet period. Water parameters such as chemical oxygen demand, ammonia nitrogen, nitrite, total nitrogen and total organic carbon present well correlations with EEQs (all the P values are below 0.01). BPA was detected 98.9% among all the raw water samples with concentration (4-996 ng/L), and DES was 44.4% with concentration (< LOD?40.5 ng/L), OP and NP were not detected.The influence of project WDYT to Taihu Lake: The more the water quantity, the greater the estrogenicity; The closer to Wangyu River, the more intense the estrogenic activities and higher the concentrations of the phenolic EDCs.Conclusion:The raw water of Taihu Lake and Yangtze River presented the estrogenicity at different extent; The contribution ratio of DES are 30 times than BPA in raw water with DES (0?60.4%) and BPA (0?2.5%); The project WDYT presented great influence to the estrogenicity of Taihu Lake:the estrogenic activities of Taihu Lake water present positive relation with the water quantity that diverted. BPA can attach to the suspended particles in raw water.The safety threshold of estrogencity of drinking water is recommended as 0.68 ng/L (EEQs) in this study.Part ? Occurrence and distribution of estrogenicity and phenolic EDCs in the drinking water treatment processesObjective: Detect, analyze the occurrence and distribution of estrogenicity and phenolic EDCs in the drinking water treatment processes of the raw water from Yangtze River and Taihu Lake. To provide scientific data for improving drinking water treatment processes.Method:From January 2013 to August 2015, water samples were collected from each drinking water treatment process which takes source water from Taihu Lake and Yangtze River. YES assay and LC-MS/MS were applied to analysis the estrogenicity and detect the phenolic EDCs.Results: The results of YES assay showed that both the conventional and advanced water treatment processes can effectively reduce the EEQs. All the water samples do not present estrogenic activities at the finished treatment process, removal effeciencies were nearly 100%. Coagulation sedimentation and biodegradation can effectively reduce the EEQs, removal ratio close to 100%. At the membrane process, the EEQs slightly went up.The result of LC-MS/MS showed that BPA and DES were the main phenolic EDCs in the water samples. Both the conventional and advanced water treatment processes can effectively reduce the concentration of BPA and DES, removal effeciencies were nearly 100%. Coagulation sedimentation and biodegradation can effectively reduce the BPA concentration, removal ratio close to 100%. At the membrane process, the concentration of BPA raised.Conclusion:According to the results of this study both the conventional and advanced water treatment processes can effectively reduce the the EEQs of the raw water from Yangtze River and Taihu Lake.