微波辅助提取GC-MS/MS测定复杂基质底泥中德克隆类化合物及处理效果初探  

Determination of Dechlorane Plus Compounds in Complex Matrix Sludge by GC-MS/MS with Microwave-Assisted Extraction and Evaluation of Treatment Efficiency

作　　者：朱帅[1,2] 沈亚婷 潘萌[1] 贾静[1] 杨志鹏[1] 曹建华[2] 王玉[1] ZHU Shuai;SHEN Yating;PAN Meng;JIA Jing;YANG Zhipeng;CAO Jianhua;WANG Yu(National Research Center for Geoanalysis,Beijing 100037,China;Institute of Karst Geology,Chinese Academy of Geological Sciences,Guilin 541004,China)

机构地区：[1]国家地质实验测试中心,北京100037 [2]中国地质科学院岩溶地质研究所,广西桂林541004

出　　处：《岩矿测试》2025年第2期290-304,共15页Rock and Mineral Analysis

基　　金：国家重点研发计划项目(2022YFC3700803);中国地质科学院基本科研业务费项目(CSJ-2023-03);中国地质调查局地质调查项目(DD20230454)。

摘　　要：德克隆类物质在污泥样品中以痕量水平(ng/g级)存在,加之污泥基质复杂,对污泥中德克隆类化合物的分析带来极大挑战。鉴于此,本文建立了微波辅助提取与气相色谱-三重四极杆串联质谱(GC-MS/MS)相结合,测定污水处理厂底泥中德克隆类化合物的分析方法。底泥样品采用微波辅助提取在线净化的方法,以丙酮-正己烷(1∶1,V/V)作为提取溶剂,在120℃温度和1500W功率条件下,该方法能够高效地从基质复杂的底泥样品中提取出德克隆类化合物,提取回收率超过80%。样品提取后,利用石墨化碳黑(GCB)和乙二胺基-N-丙基(PSA)固相萃取柱进一步净化,可有效地去除色素、脂类和非极性干扰物,减少基质干扰。借助质谱多反应监测(MRM)模式,针对目标化合物的特定离子对进行选择性监测,排除其他干扰离子的影响,从而实现了对德克隆类化合物的准确定量。该方法在5~400ng/mL浓度范围内线性关系良好,相关系数(r)不小于0.998,检出限为0.017~0.040ng/g。在低、中、高三个浓度水平底泥基质中,德克隆类化合物的平均回收率分别为79.8%~99.5%、86.2%~104.8%、91.2%~106.1%,相对标准偏差(RSD)<7%。将该方法应用于实际底泥样品的检测,在11个污水处理厂底泥中均检出德克隆类化合物,且含量较高(31.4~195.6ng/g)。底泥中顺式德克隆(syn-DP)异构体比例的平均值f_(syn)=0.27,低于德克隆(DP)产品的f_(syn)值,这是由于底泥对反式德克隆(anti-DP)的吸附性更强,或底泥中的顺式德克隆(syn-DP)优先发生了生物降解。初步比较了11个污水处理厂采用不同的污水处理工艺处理底泥中德克隆化合物的效果,与活性污泥法水处理相比,采用A2/O工艺处理的德克隆类化合物的浓度显著降低,f_(syn)值显著增高,但其影响机制仍待深入探究。Dechlorane plus compounds are present at trace levels(ng/g)in sludge samples.The complex sludge matrix poses a significant challenge for the analysis of these compounds.To address this issue,we established an analytical method for determining dechlorane plus compounds in the sludge of sewage treatment plants,combining microwave-assisted extraction with gas chromatography-triple quadrupole tandem mass spectrometry.Sludge samples were processed using microwave-assisted extraction with online purification,and using acetone-n-hexane(1∶1,V/V)as the extraction solvent.After extraction,GCB/PSA solid-phase extraction columns were used for further purification to reduce matrix interference.The multiple reaction monitoring(MRM)mode of mass spectrometry was employed for accurate quantification.This method demonstrated good linearity(r≥0.998)in the 5-400ng/mL range,with a detection limit of 0.017-0.040ng/g.The average recoveries were 79.8%-99.5%,86.2%-104.8%and 91.2%-106.1%at low,medium and high concentrations,respectively,with relative standard deviations(RSDs)of<7%.When applied to 11 sewage treatment plants,dechlorane plus compounds were detected,and the contents were relatively high(31.4-195.6ng/g).In sludge,average f_(syn) of syn-DP was 0.27,lower than that of DP products.This is due to stronger anti-DP adsorption or preferential syn-DP biodegradation.When the A^(2)/O process was adopted,the concentration of dechlorane plus compounds was significantly reduced,and the f_(syn) value was significantly increased,but the influencing mechanism still needs to be further explored.

关 键 词：德克隆化合物 污泥 微波辅助提取 气相色谱-三重四极杆串联质谱法 污水处理厂 顺式德克隆(syn-DP)异构体比例(f_(syn)) 

分 类 号：O657.63[理学—分析化学] X832[理学—化学]