Testing And Exposure Assessment Of Bisphenol A And Alkylphenols

The influence of environment endocrine(内分泌)interference to the person and the animal was becoming an international popular problem.Particularly,the environment estrogen(雌激素)initiated and interfered endogenesis estrogen by combining with estrogenic receptor or influencing the way of cell signal conduction or the other ways,which has esteogen-like action,brings hazard to the mankind and the animal.BPA was key raw material of making epoxide resin,polycarbonate,polystyrene resin,which was used to the stabilizing of agent phenol formaldehyde resin,bactericidal agen,antioxidanK polyvinyl chloride,dye.The alkylphenol NP,OP was widely used to elasticizer,technica grade abstergent,pesticide emulsifies,trimming Iin the spinning and weaving,ect.People usually use some articles,whose raw material was BPA,NP and OP, BPA,NP and OP were often migrated and contaminate living environment .Especially,BPAn,NP and OP were migrated to food when food packing has BPA,NP and OP,enter a human body directly,endanger mankind's health.Our country is important country using BPA,NP and OP,if we didn't control strictly,the pollution problem of the BPA,NP and OP would be very serious.For the sake of the protection our country people health and the industry benefits of the nations, we carried on detection technique,organism marker and migration of plastic products of BPA,NP and OP,and make a comprehensive comment to the BPA,NP and OP in the meantime,mainly include several aspects as follows:(1)The detection technique of the BPA,NP and OP in the canned foodIn this study,the comprehensive analytical methods based on Ultra-high Pressure Liquid Chromatography-mass/mass(UPLC-MS/MS)or high performance liquid chromatography fluorescence detection(HPLC-FLD)with solid phase extraction,Liquid liquid Extraction before have been established for determination of BPA,NP and OP in food samplesBPA,NP and OP was extracted with methanol,the residue was dissolved in alkaline solution,acidized,extracted by dichloroacetamide from the foods and the extract was concentrated.Clean-up of samples was performed on an NH₂ column solid extraction cartridges.The UPLC separation was performed on a Acquity UPLC^TM BEH,C₁8 column(particle diameter 1.7μm) with a gradient elution system of methanol-water as the mobile phase.triple-quadrupole mass spectrometry analyzer was performed for the qualitative and quantitative analyse of LC-MS/MS system.The limit of detection of BPA,NP and OP was 0.22-0.35μg/kg,0.031-0.05Oμg/kg and 0.08-0.12μg/kg;The limit of quantification of BPA,,NP and OP was0.55-0.80μg/kg,0.10-0.94μg/kg and 0.20-0.30μg/kg;The Recoveries of BPA,NP and OP were 70.0-123%,70.2-125%and 71.2-133%;The precision was 7.06-17.6%,3.98-18.9%and 6.91-19.2%,respectively.The HPLC separation was performed on Waters XTerra^? MS C₁8 column with a gradient elution system of methanol-water as the mobile phase and fluorescence detector with the excitation and emission wavelength at 225 nm and 310nm respectively were used for the determination..The limit of detection of BPA,NP and OP was 0.52-0.91μg/kg,0.10-0.52μg/kg and 0.14-0.53μg/kg;The limit of quantification of BPA,NP and OP was 1.18-2.70μg/kg,0.28-2.15μg/kg and 0.35-1.87μg/kg;The Recoveries of BPA,NP and OP were 70.1-90.2%,80.1-122%and 72.1-126%;The precision was 5.61-11.2%,2.35-8.88%and 5.61-12.3%,respectively.The two methods both may detect the BPA,NP and OP at the time,The results showed that the method is with high sensitivity,accuracy,precision,specificity.the method is suitable for the determination of BPA,NP and OP in can food.30 food samples from Beijing's markets were determined by using the improved methods,the method is simple,the result is accurate,credibility.(2)The study of biomarker-human urine The BPA,NP and OP is esteogen-like "endocrine chemical materials".the general people contacted with the BPA,NP and OP through using plastics packing material,the can food,abstergent,ect.The metabolic product in urine is mainly glucoside conjugate and sulphate conjugate.In this study,we detected BPA,NP and OP in the urine of health crowd.The urine samples was de-conjugated by addingβ-glucuronidase and sulfatase,after the enzymatic treatment,the samples was subjected to the OASIS HLB column solid extraction cartridges to Clean-up and concentrate.A comprehensive analytical method based on Ultra-high Pressure Liquid Chromatography-mass/mass(UPLC-MS/MS)or high performance liquid chromatography fluorescence detection(HPLC-FLD) has been established for the determination of BPA,NP and OP in urine.UPLC-MS/MS:The limit of detection of BPA,OP and NP was 0.41,0.20 and 0.50μg/L;The limit of quantification of BPA,OP and NP was 1.02,0.85 and 1.28μg/L;The Recoveries of BPA,OP and NP were 72.3-109%,71.2-114%,76.6-116%;The precision was 12.5-14.1%,10.0-14.0%,7.12-15.5%,respectively.HPLC-FL:The limit of detection of BPA,OP and NP was 3.71,4.90 and 7.50μg/L;The limit of quantification of BPA,OP and NP was 11.9,15.7 and 21.3μg/L;The Recoveries of BPA,OP and NP were 70.2-95.7%,73.2-108%and 76.3-109%;The precision was 8.81-10.7%,9.31-14.5%and 6.65-15.5% respectively.60 urine samples were determined by using these two methods,the method is sensitivity,selectivity and good reproducibility.(3) The migration experiment research of the plastics product BPA,OP and NP were one kind of environment estrogen,which were used to make non-ion surface activity agent,elasticizer,polycarbonate,epoxy resin,polysulfone resin,polyphenyl Ether resin,selectron,ect.They were generally used to make plastic products,tableware,coating,ect.According to documents,many plastic products may dissolute a little BPA,OP and NP,brought threat to the human body health and pollute the environment,influence directly the person's healthy.This study investigated migration circumstance,respectively,under different test conditions:the different simulant:Distilled water,3%acetic acids,4%acetic, acids,15%alcohol,20%alcohol,65%alcohol,hexane;the different temperature: 25°C,40°C,60°C,80°C,100°C;The Different soaks time:12h,24h and 48h.The result show,when the simulant is 65%alcohol,at 60°C,soak for 3 hours,the amount of migration is greatest.A UPLC-MS/MS method was developed for quantifying levels of BPA,OP and NP in plastic products.The limit of detection of BPA,OP and NP was 0.25-0.38μg/L,0.10-0.22μg/Land 0.20-0.30μg/L;The limit of quantification of BPA,OP and NP was 0.70-1.01μg/L.0.50-0.74μg/L and 0.75-0.80μg/L;The Recoveries of BPA,OP and NP were 80.1-105%,80.8-112%and 80.5-110%.The precision was 5.02-10.9%.4.66-13.5%and 4.73-10.4%respectively.A HPLC-FL method was developed for detecting levels of BPA,OP and NP in plastic products.The limit of detection of BPA,OP and NP was 1.55-2.75μg/L,1.00-1.60μg/Land 1.00-1.84μg/L;The 1imit of quantification of BPA,OP and NP was 4.03-5.00μg/L,2.85-3.41μg/L and 2.75-4.05μg/L;The Recoveries of BPA,OP and NP were 80.9-107%,80.4-108%and 80.4-107%.The precision was 4.24-11.5%,4.93-12.4%and 3.64-9.88%respectively.The experiment showed that the amount of migration is greatest when the sample was soaked in 65%alcohol(60°C)for 3 hours.The method was sensitivity,selectivity,accurate and credibility.(4) The determination and the exposure assessment of the BPA,NP and OP Using the improved methods established in this work,the BPA,NP and OP in vegetable,fish,meat can food samples from Beijing's markets were determined.We collect 30 can food samples(10 vegetable samples,10 vegetable samples and 10 vegetable samples).11 samples of the total were found to contain BPA,its level is 0.180-12.3μg/kg;27 samples of the total were found to contain NP,its level is 1.35-100μg/kg;6 samples of the total were found to contain OP,its level is 0.05 -23.5μg/kg.The results demonstrated the widespread occurrence of NP in can food.60 urine samples were determined by using the method,the method is sensitivity,selectivity and good reproducibility.8 samples of the total were found to contain BPA(13.3%),its level is0.515-49.5μg/ml;29 samples of the total were found to contain NP(48.3%),its level is 2.32-28.5 ng/m1;17 samples of the total were found to contain NP(28.3%),its level is 0.720-15.2ng/ml.The female detection ratios was higher the male detection ratios.The detection ratios increased with the age increase.15 plastics product samples(plastics box,baby's bottle,water cup and lubricator)were determined 13 samples of the total were found to contain BPA,its level is 10.3-1004ng/L;14 samples of the total were found to contain NP,its level is 103 -9875ng/L;5 samples of the total were found to contain OP,its level is 1.02-12.1 ng/L.The results demonstrated many samples contained BPA,NP and OP,and NP was resided widely in can food and plastic products.