Department of Analytical Chemistry, Nutrition and Food Sciences, IIAA - Institute for Food Analysis and Research, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain.
FI-TRACE Group, Department of Chemistry, Faculty of Science, University of the Balearic Islands, Carretera de Valldemossa km 7.5, E-07122 Palma de Mallorca, Illes Balears, Spain.
Sci Total Environ. 2017 Feb 15;580:540-549. doi: 10.1016/j.scitotenv.2016.11.210. Epub 2016 Dec 18.
This paper reports the evaluation of in-vitro physiologically relevant extraction tests for ascertainment of the bioaccessible fractions of emerging flame retardants from indoor dust in the gastric and gastrointestinal compartments. Standardized bioaccessibility tests under both fasting (UBM-like test) and fed (FOREhST test) conditions simulating the macronutrient composition of an average child diet were harnessed for investigation of the oral bioaccessibility of chlorinated organophosphate esters, namely, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCP), in household and automobile cabin dust samples with varying concentration levels of contaminants. Minimal processing of the biomimetic extracts (only protein precipitation using acetonitrile) was proven feasible by analysis with liquid chromatography-mass spectrometric detection (LC-MS/MS). An inversely proportional relationship was identified between log K and oral bioaccessibility concentrations for TCEP, TCPP and TDCP in both dust samples with maximum bioaccessibility fractions for TCEP within the range of 50-103%. Non-bioaccessible fractions were determined by matrix-solid phase dispersion. Limits of quantification of LC-MS/MS in surrogate digestive fluids ranging from 0.4-0.8ng/mL suffice for determination of freely dissolved fractions of the two less hydrophobic species. Our results indicate that lipophilic food commodities used under fed-state gastrointestinal extraction conditions do not increase availability of TCEP, TCPP and TDCP in body fluids, and therefore conservative conditions in human health risk explorations for the target moderately polar flame retardants might be obtained with simplified tests under fasting conditions. This also holds true for the UBM/FOREhST bioaccessibility data for SRM 2585 (organic contaminants in house dust). Estimated average daily intake doses for toddlers incorporating oral bioaccessibility data afforded body burdens for the three chlorinated alkyl phosphates of ca. 3000 to 700 times below reference dose values, which indicate that long-term exposure to chlorinated organophosphate esters via accidental ingestion of indoor dust does not pose health risks to toddlers.
本文报告了评估体内生理相关提取试验以确定室内灰尘中新兴阻燃剂的生物可及分数的情况，这些试验在胃和胃肠道部分中模拟了空腹（UBM 样试验）和进食（FOREhST 试验）条件下的标准生物可及性试验，以研究氯代有机磷酸酯，即三（2-氯乙基）磷酸酯（TCEP）、三（1-氯-2-丙基）磷酸酯（TCPP）和三（1,3-二氯-2-丙基）磷酸酯（TDCP）在家庭和汽车舱灰尘样本中的口服生物可及性，这些样本中含有不同浓度水平的污染物。通过使用液相色谱-质谱检测（LC-MS/MS）对仿生提取物（仅使用乙腈进行蛋白质沉淀）进行分析，证明了最小程度的处理是可行的。在这两种灰尘样本中，TCEP、TCPP 和 TDCP 的 log K 值与口服生物可及性浓度呈反比关系，最大生物可及性分数 TCEP 范围为 50-103%。非生物可及性分数通过基质固相分散法确定。LC-MS/MS 在替代消化液中的定量限范围为 0.4-0.8ng/mL，足以测定两种疏水性较低的物质的自由溶解分数。我们的结果表明，在进食状态下的胃肠道提取条件下使用的亲脂性食物不会增加 TCEP、TCPP 和 TDCP 在体液中的可用性，因此对于目标中极性阻燃剂，简化空腹条件下的简化试验可能会获得保守的人体健康风险探索结果。这对于 UBM/FOREhST 生物可及性数据对于 SRM 2585（室内灰尘中的有机污染物）也是如此。将口服生物可及性数据纳入幼儿估计的每日平均摄入量剂量，可得到三种氯化烷基磷酸酯的约 3000 至 7000 倍的身体负担，低于参考剂量值，这表明通过意外摄入室内灰尘长期接触氯化有机磷酸酯不会对幼儿构成健康风险。
