MOE Key Laboratory of Aquatic Product Safety, School of Life Sciences, Sun Yat-Sen University, Guangzhou 510275, PR China.
Shenzhen Entry-Exit Inspection and Quarantine Bureau, Shenzhen 518045, PR China.
Anal Chim Acta. 2015 Mar 25;866:41-47. doi: 10.1016/j.aca.2015.02.011. Epub 2015 Feb 10.
In this study, a sample pretreatment method was developed for the determination of 13 endocrine disrupting chemicals (EDCs) in sediment samples based on the combination of subcritical water extraction (SWE) and dispersed liquid-liquid microextraction (DLLME). The subcritical water that provided by accelerated solvent extractor (ASE) was the sample solution (water) for the following DLLME and the soluble organic modifier that spiked in the subcritical water was also used as the disperser solvent for DLLME in succession. Thus, several important parameters that affected both SWE and DLLME were investigated, such as the extraction solvent for DLLME (chlorobenzene), extraction time for DLLME (30s), selection of organic modifier for SWE (acetone), volume of organic modifier (10%) and extraction temperature for SWE (150 °C). In addition, good chromatographic behavior was achieved for GC-MS after derivatisation by using N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA). As a result, proposed method sensitive and reliable with the limits of detection (LODs) ranging from 0.006 ng g(-1) (BPA) to 0.639 ng g(-1) (19-norethisterone) and the relative standard deviations (RSDs) between 1.5% (E2) and 15.0% (DES). Moreover, the proposed method was compared with direct ASE extraction that reported previously, and the results showed that SWE-DLLME was more promising with recoveries ranging from 42.3% (dienestrol) to 131.3% (4,5α-dihydrotestosterone), except for diethylstilbestrol (15.0%) and nonylphenols (29.8%). The proposed method was then successfully applied to determine 13 EDCs sediment of Humen outlet of the Pearl River, 12 of target compounds could be detected, and 10 could be quantitative analysis with the total concentration being 39.6 ng g(-1), and which indicated that the sediment of Humen outlet was heavily contaminated by EDCs.
本研究建立了一种基于亚临界水萃取（SWE）和分散液液微萃取（DLLME）相结合的沉积物样品中 13 种内分泌干扰化学物质（EDCs）的样品预处理方法。加速溶剂萃取仪（ASE）提供的亚临界水既是 DLLME 的样品溶液（水），也是连续加入的可溶性有机改性剂，也是 DLLME 的分散溶剂。因此，考察了影响 SWE 和 DLLME 的几个重要参数，如 DLLME 的萃取溶剂（氯苯）、DLLME 的萃取时间（30s）、SWE 的有机改性剂选择（丙酮）、有机改性剂的体积（10%）和 SWE 的萃取温度（150°C）。此外，通过使用 N,O-双（三甲基硅基）三氟乙酰胺（BSTFA）衍生化，GC-MS 获得了良好的色谱行为。结果表明，该方法灵敏度高、可靠，检出限（LOD）范围为 0.006ngg(-1)（BPA）至 0.639ngg(-1)（19-去甲睾酮），相对标准偏差（RSD）在 1.5%（E2）至 15.0%（DES）之间。此外，该方法与之前报道的直接 ASE 萃取进行了比较，结果表明，SWE-DLLME 更具潜力，回收率范围为 42.3%（双烯雌酚）至 131.3%（4,5α-二氢睾酮），除了己烯雌酚（15.0%）和壬基酚（29.8%）。该方法随后成功应用于珠江虎门出口沉积物中 13 种 EDCs 的测定，可检测到 12 种目标化合物，其中 10 种可进行定量分析，总浓度为 39.6ngg(-1)，表明虎门出口沉积物受到 EDCs 的严重污染。
