色谱2024，Vol.42Issue(1)：64-74,11.DOI:10.3724/SP.J.1123.2023.04018
基于响应面法的基质固相分散萃取土壤中有机磷阻燃剂
Matrix solid-phase dispersion extraction of organophosphorus flame retardants in soil based on response surface methodology
摘要
Abstract
Organophosphorus flame retardants(OPFRs)are widely used in commercial prod-ucts owing to their exceptional flame-retarding and plasticizing properties.However,OPFRs are also well recognized as emerging persistent organic pollutants(POPs)because of their environ-mental persistence,biological concentration,and potential toxicity.Thus,the accurate detec-tion of OPFRs in environmental media is critical for analyzing their fate,transport,and ecologi-cal risk.However,very few OPFR detection methods are currently available,and the types of OPFRs detected may vary from site to site. In this study,matrix solid-phase dispersion extraction(MSPD),a simple,rapid,and versa-tile technique for preparing solid,semisolid,liquid,and viscous samples,was combined for the first time with gas chromatography-tandem mass spectrometry(GC-MS/MS)to analyze 10 OPFRs in soil,namely,tripropyl phosphate(TPrP),tri-n-butyl phosphate(TnBP),tri-iso-bu-tyl phosphate(TiBP),tris(2-chloroisopropyl)phosphate(TCIPP),tris(2-chloroethyl)phos-phate(TCEP),tris(1,3-dichloro-2-propyl)phosphate(TDCPP),triphenyl phosphate(TPHP),2-ethylhexyl diphenyl phosphate(EHDPP),triphenylphosphine oxide(TPPO),and trimethylphenyl phosphate(TCP).The GC-MS/MS system was equipped with a Bruker-5MS capillary column coupled with a triple quadrupole mass spectrometer operated in multiple reac-tion monitoring(MRM)mode.Prior to detection,a mixed standard solution was fortified with 10 ng of 13 C-PCB208 as an internal standard.The optimal conditions under which MSPD could achieve high selectivity for OPFRs were determined.In addition,single-factor analysis was used to examine the influence of the sorbent(i.e.,C18,PSA,Florisil,GCB,and multiwalled car-bon nanotubes(MWCNTs))as well as the dosage,type,and volume of the eluent on the ex-traction efficiency of the method for the 10 OPFRs.When GCB and ethyl acetate were used as the adsorbent and solvent,respectively,during elution,high extraction recoveries for the OP-FRs were achieved.Optimization via response surface methodology(RSM)was adopted to fur-ther analyze the impact of three key factors,namely,the adsorbent dosage,eluent volume,and grinding time,as well as their interactions,on OPFR recoveries.Under the optimal condi-tions of 0.3 g of GCB as the adsorbent,10 mL of ethyl acetate as the eluent,and 5 min of grinding time,the relative average recovery of the OPFRs was 87.5%.Furthermore,the 10 OP-FRs showed good linear relationships under five concentration gradients,with correlation coef-ficients greater than 0.998.The limits of detection(LODs)and quantification(LOQs)were cal-culated as signal-to-noise ratios(S/N)of 3 and 10,respectively,and found to be in the ranges of 0.006-0.161 and 0.020-0.531 ng/g,respectively.The performance of the proposed method was verified by determining the recoveries and relative standard deviations(RSDs)of the OP-FRs in soils spiked at low,medium,and high levels(10,20,and 100 ng/g,respectively).The recoveries of the OPFRs ranged from 70.4%to 115.4%,with RSDs ranging from 0.7%to 6.7%.Compared with the conventional accelerated solvent extraction(ASE)method,MSPD presents higher efficiency,simpler operation,and less solvent requirements.The developed method was applied to determine OPFRs in soil samples collected from different sites in Suzhou,including an electronics factory,an auto-repair factory,a paddy field,and a school field.The results re-vealed that the contents of OPFRs in the soils from the electronics and auto-repair factories were significantly higher than those in the soils from the paddy and school fields.The main pol-lutants in the soil samples collected from the electronics and auto-repair factories were TCIPP,TPPO,TCEP,and TDCPP.Moreover,the contents of these compounds were 5.30,4.44,4.54,and 4.20 ng/g,in soils from the electronics factory and 2.70,3.93,7.60,and 5.04 ng/g,in soils from the auto-repair factory.To the best of our knowledge,this study is the first to determine high concentrations of TPPO in industrial soils.Thus,the combination of MSPD and GC-MS/MS adopted in this study can provide useful insights into the detection of the 10 OPFRs in soil.关键词
气相色谱-串联质谱/基质固相分散萃取/响应面法/有机磷阻燃剂/土壤Key words
gas chromatography-tandem mass spectrometry(GC-MS/MS)/matrix solid-phase dispersion extraction(MSPD)/response surface methodology(RSM)/organophosphorus flame retardants(OPFRs)/soil分类
化学化工引用本文复制引用
王俊霞,徐思婕,孙悦莹,雷慧慧,程媛媛,王学东,张占恩..基于响应面法的基质固相分散萃取土壤中有机磷阻燃剂[J].色谱,2024,42(1):64-74,11.基金项目
国家自然科学基金项目(22076134,21876125,42207479) （22076134,21876125,42207479）
江苏省重点研发计划项目(BE2022733). National Natural Science Foundation of China(Nos.22076134,21876125,42207479) （BE2022733）
Jiangsu Provincial Key Research&Development Program(No.BE2022733). （No.BE2022733）
