Martin Déborah E, Muselet Delphine, Kanso Hussein, Alnajjar Perla, Mexler Juliette, Le Roux Yves, Pak Lai Ting, Richard Antoine, Charlier Jean-Baptiste, Saaidi Pierre-Loïc
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, Univ Evry, Université Paris-Saclay, Evry, France.
Laboratoire Animal et Agroécosystèmes (L2A), Université de Lorraine, INRAE, 54500 Nancy, France; Ecole doctorale en Sciences et Technologie, Université Libanaise, Tripoli, Lebanon.
Sci Total Environ. 2024 Oct 20;948:174610. doi: 10.1016/j.scitotenv.2024.174610. Epub 2024 Jul 10.
Among the numerous organochlorines (OCs) applied in the French West Indies (FWI), chlordecone (hydrated form CClOH; CLD) still causes major environmental pollution nowadays. A recent report revealed the unexpected presence in FWI environment of transformation products (TPs) of CLD not routinely monitored due to a lack of commercial standards. Here, we present a method for surface waters and groundwaters to analyze CLD, its main TPs (hydroCLDs, chlordecol (CLDOH), 10-monohydroCLDOH and polychloroindenes) and other OCs. We developed an SPME-GC-SIM/MS method with a PDMS-DVB fiber. Since CLDOH-d commonly used as internal standard (IS) proved unsuitable, we synthesized several IS candidates, and finally identified 10-monohydro-5-methyl-chlordecol as a satisfactory IS for CLDOH and 10-monohydroCLDOH avoiding the use of C-labelled analogue. LODs for CLD and its TPs varied from 0.3 to 10 ng/L, equal to or below LODs of the two laboratories, BRGM (the French geological survey) and LDA26 (one of the French Departmental Analytical Laboratories), requested in FWI pollution monitoring that used liquid-liquid extractions and advanced facilities (LLE-GC-MS/MS and LLE-LC-MS/MS methods, respectively). Then, we extended the multi-residue method to 30 OCs (CLD and its TPs, mirex, β-HCH, lindane, dieldrin, aldrin, HCB, hexachlorobutadiene, TCE, PCE) and applied it to 30 surface and ground waters from FWI. While CLD, 8- and 10-monohydroCLD, CLDOH, 10-monohydroCLDOH, dieldrin, and β-HCH were detected and quantified, pentachloroindene, another CLD TP, was sporadically found in trace levels. A comparison with BRGM and LDA26 confirmed the interest of the SPME method. Results suggested an underestimation of CLDOH and an overestimation of high CLD concentrations with one of the currently used routine protocol. In light of these findings, previous temporal monitoring of environmental waters in FWI were re-examined and revealed some atypical values, which may indeed be due to analytical bias. These discrepancies call for intensified efforts to reliably quantify CLD and its TPs.
在法属西印度群岛（FWI）使用的众多有机氯化合物（OCs）中，十氯酮（水合形式CClOH；CLD）如今仍造成严重的环境污染。最近一份报告显示，由于缺乏商业标准，CLD的转化产物（TPs）意外出现在FWI环境中，而这些产物未被常规监测。在此，我们提出一种针对地表水和地下水的分析方法，用于分析CLD、其主要TPs（羟基十氯酮、氯代二醇（CLDOH）、10 - 单羟基CLDOH和多氯茚）以及其他OCs。我们开发了一种使用PDMS - DVB纤维的SPME - GC - SIM/MS方法。由于常用作内标（IS）的氘代CLDOH被证明不合适，我们合成了几种内标候选物，最终确定10 - 单羟基 - 5 - 甲基 - 氯代二醇是用于CLDOH和10 - 单羟基CLDOH的令人满意的内标，避免了使用碳标记类似物。CLD及其TPs的检测限在0.3至10 ng/L之间，等于或低于FWI污染监测中要求的两个实验室（法国地质调查局BRGM和法国省级分析实验室之一LDA26）的检测限，这两个实验室分别使用液 - 液萃取和先进设备（分别为LLE - GC - MS/MS和LLE - LC - MS/MS方法）。然后，我们将多残留方法扩展到30种OCs（CLD及其TPs、灭蚁灵、β - 六氯环己烷、林丹、狄氏剂、艾氏剂、六氯苯、六氯丁二烯、三氯乙烯、四氯乙烯），并将其应用于FWI的30份地表水和地下水中。虽然检测并定量了CLD、8 - 和10 - 单羟基CLD、CLDOH、10 - 单羟基CLDOH、狄氏剂和β - 六氯环己烷，但另一种CLD的TPs五氯茚偶尔在痕量水平被发现。与BRGM和LDA26的比较证实了SPME方法的优势。结果表明，目前使用的一种常规方案对CLDOH的估计偏低，对高CLD浓度的估计偏高。鉴于这些发现，对FWI环境水体以前的时间监测进行了重新审视，发现了一些非典型值，这可能确实是由于分析偏差导致的。这些差异要求加大力度可靠地定量CLD及其TPs。
