摘要
卤系阻燃剂(HFRs)作为持久性有机污染物,因其生物蓄积性、长距离迁移性和潜在健康风险而备受关注。HFRs在土壤中通常以痕量水平存在,由于土壤基质复杂,干扰严重,且不同类别HFRs的极性、热稳定性等存在显著差异,给多类HFRs的同步准确分析带来挑战。在实际环境中HFRs常以复合污染形式存在,因此有必要建立多类HFRs同步提取、同时检测的分析方法,有效监测其在土壤环境中的残留水平。本文建立了一种适用于土壤中多溴联苯醚(PBDEs)、多溴联苯(PBBs)、德克隆(DPs)、多氯联苯(PCBs)等36种HFRs同时分析的方法,通过基质固相分散萃取(MSPDE)在样品中加入乙二胺基-N-丙基(PSA)和弗罗里硅土(Florisil)填料,可有效去除有机酸、色素、脂类和极性干扰物,减少基质干扰。样品经充分研磨5min后,采用加速溶剂萃取(ASE)在80℃温度和1500psi压力下,用正己烷-二氯甲烷(1∶1,V/V)静态萃取10min,循环2次。样品经提取净化后基质干扰显著减少,各化合物回收率能够达到60%以上。用硅藻土代替样品经同样的前处理过程,制备基质匹配溶液配制校准曲线,能有效减少实验流程中引入的干扰,经该曲线校正后顺式德克隆(Syn-DP)、反式德克隆(Anti-DP)、PBDE 206、PBDE209的回收率可达72.8%~123.5%。该方法PBBs、DPs、PCBs在10~500μg/L浓度范围内(PBDEs:50~500μg/L)线性关系良好,决定系数(R^(2))不小于0.998,检出限为0.15~4.5μg/kg。使用此方法对实际样品进行加标回收试验,回收率为65.9%~132.1%,相对标准偏差(RSD)为2.1%~24.3%,满足相关标准的要求,适用于大批量复杂样品的分析。
Halogenated flame retardants(HFRs)are persistent organic pollutants and have attracted much attention due to their bioaccumulation,long-range migration,and potential health risks.HFRs usually exist in trace levels in soil.Due to the complex soil matrix,severe interference,and significant differences in polarity,thermal stability,etc.among different types of HFRs,it brings challenges to the synchronous and accurate analysis of multiple types of HFRs.In the actual environment,HFRs often exist in the form of combined pollution.Therefore,it is necessary to establish an analytical method for the simultaneous extraction and detection of multiple HFRs to effectively monitor their residual levels in the soil environment.A method for the simultaneous analysis of 36 kinds of HFRs including polybrominated diphenyl ethers(PBDEs),polybrominated biphenyls(PBBs),dechlorane plus(DPs),polychlorinated biphenyls(PCBs)in soil has been established.By adding ethylenediamine-N-propyl(PSA)and Florisil to the sample through matrix solid-phase dispersion extraction(MSPDE),organic acids,pigments,lipids and polar interfering substances can be effectively removed,reducing matrix interference.After the samples were thoroughly ground for 5min,accelerated solvent extraction(ASE)was conducted at 80℃and 1500psi using n-hexane-dichloromethane(1∶1,V/V)as the extraction solvent,static extraction for 10min,and two extraction cycles.After extraction and purification of the samples,the matrix interference was significantly reduced,and the recovery of each compound was higher than 60%.Using diatomite instead of the sample and undergoing the same pretreatment process to prepare the matrix-matching solution for the calibration curve effectively reduced the interference introduced in the experimental process.After correction by this curve,the recoveries of Syn-DP,Anti-DP,PBDE 206,and PBDE209 reached 72.8%to 123.5%.This method had a good linear relationship among PBBs,DPs and PCBs within the concentration range of 10-500μg/L(PBDEs:50-500μg/L),with a coefficient of determination(R^(2))of no less than 0.998 and a detection limit of 0.15-4.5μg/kg.The method was applied to spiked actual samples,with recoveries ranging from 65.9%to 132.1%,and relative standard deviations(RSD)ranging from 2.1%to 24.3%,meeting the requirements of relevant standards and being suitable for the analysis of large quantities of complex samples.
作者
李晓亚
张永涛
左海英
张晶
LI Xiaoya;ZHANG Yongtao;ZUO Haiying;ZHANG Jing(Institute of Hydrogeology and Environmental Geology,Chinese Academy of Geological Sciences,Shijiazhuang 050061,China;Key Laboratory of Groundwater Contamination and Remediation,Hebei Province&China Geological Survey,Shijiazhuang 050061,China)
出处
《岩矿测试》
北大核心
2025年第4期612-627,共16页
Rock and Mineral Analysis
基金
中国地质科学院水文地质环境地质研究所基本科研业务费项目(SK202312)。
关键词
卤系阻燃剂
土壤
加速溶剂萃取
基质分散固相萃取
气相色谱-质谱法
halogenated flame retardants
soil
accelerated solvent extraction
matrix dispersion
gas chromatography–mass spectrometry
作者简介
第一作者:李晓亚,硕士,高级工程师,主要从事环境基质中有机污染物分析方法研究。E-mail:lixiaoya0527@126.com;通信作者:张永涛,正高级工程师,主要从事有机污染物分析方法研究。E-mail:icpzytws@126.com。
