Diastereomer- and enantiomer-selective accumulation and depuration of 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexanes (DBE-DBCHs) and 1,2,5,6-tetrabromocyclooctanes (TBCOs) in earthworms (Eisenia fetida).

Due to the regulation of hexabromocyclododecane (HBCD), much attention has been paid to its potential substitutes, 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane (DBE-DBCH) and 1,2,5,6-tetrabromocyclooctane (TBCO). DBE-DBCH and TBCO contain several diastereomers and enantiomers, which may exhibit different environmental behaviors and biological effects. In this study, the accumulation and depuration of individual DBE-DBCH and TBCO diastereomers by earthworms (Eisenia fetida) from diastereomer-contaminated soils were evaluated. The accumulation and depuration kinetics of DBE-DBCH and TBCO diastereomers followed one-compartment first-order kinetics. The biota soil accumulation factor (BSAF) of ß-DBE-DBCH (2.74 goc glip-1) was 1.26 times that of α-DBE-DBCH (2.18 goc glip-1), while the BSAF of ß-TBCO (2.15 goc glip-1) was 1.62 times that of α-TBCO (1.3 goc glip-1), showing the diastereomer-specific accumulation of DBE-DBCH and TBCO. DBE-DBCH and TBCO diastereomers appeared to be transformed in earthworm-soil systems; however, no evidence of bioisomerization of the four diastereomers in earthworms was found, and no potential metabolites of debromination and hydroxylation were detected. Furthermore, the selective enrichment of E1-α-DBE-DBCH and E1-ß-DBE-DBCH (E1 represents the first enantiomer eluted) occurred in earthworms as the enantiomer fractions (EFs) for α-DBE-DBCH (0.562-0.763) and ß-DBE-DBCH (0.516-0.647) were significantly greater than those in the technical products (0.501 for α-DBE-DBCH and 0.497 for ß-DBE-DBCH, p < 0.05), especially in the depuration stage. The results demonstrated the diastereomer- and enantiomer-selective accumulation of DBE-DBCH and the diastereomer-selective accumulation of TBCO in the earthworm.

Distribution and bioaccessibility of polycyclic aromatic hydrocarbons in industrially contaminated site soils as affected by thermal treatment.

Thermal treatment can not only efficiently remove volatile pollutants but also distinctly alter the speciation of organic carbon (C) and the behaviors of residual pollutants in contaminated soils. Here we examined the distribution and bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in industrially contaminated site soils affected by thermal treatment (temperature ranging of 105-650 â„ƒ) using synchrotron-based infrared microspectroscopy and n-butanol extraction (a mild solvent extractant). In the pristine soils, the sequestration and distribution of PAHs were simultaneously controlled by aromatic C, aliphatic C and clay minerals. Desorption efficiency of PAHs was substantially increased with increasing temperature, whereas the residual PAHs were strongly immobilized within their binding sites evidenced by their dramatically decreased bioaccessibility. Aliphatic and carboxylic C were gradually decomposed and/or carbonized with increasing temperature. In contrast, aromatic C remained relatively recalcitrant during the thermal treatment and was the key controlling factor for the desorption of residual PAHs in the soils with either thermal treatment or n-butanol extraction. This study is the first to visualize the changes in the binding sites and bioaccessibility of PAHs induced by thermal treatment, which have important implications for understanding the sequestration mechanisms of organic pollutants in soil and optimizing the remediation technique.