title: Fate of brominated flame retardants and organochlorine pesticides in urban soil: volatility and degradation.
abstract: As the uses of polybrominated diphenyl ethers (BDEs) are being phased out in many countries, soils could become a secondary emission source to the atmosphere. It is also anticipated that the demand for alternative brominated flame retardants (BFRs) will grow, but little is known about their environmental fate in soils. In this study, the volatility and degradation of BFRs and organochlorine pesticides (OCPs) in soil was investigated. A low organic carbon (5.6%) urban soil was spiked with a suite of BFRs and OCPs, followed by incubation under laboratory condition for 360 days. These included BDE- 17, -28, -47, -99; α- and β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), β-1,2,5,6-tetrabromocyclooctane (TBCO), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), OCPs: α-hexachlorocyclohexane (α-HCH) and (13)C(6)-α-HCH, trans-chlordane (TC), and (13)C(10)-TC. The volatility of spiked chemicals was investigated using a fugacity meter to measure the soil-air partition coefficient (K(SA)). K(SA) of some spiked BFRs and OCPs increased from Day 10 to 60 or 90 and leveled off afterward. This suggests that the volatility of BFRs and OCPs decreases over time as the chemicals become more strongly bound to the soil. Degradation of alternative BFRs (α- and β-TBECH, β-TBCO, DPTE), BDE-17, and α-HCH ((13)C-labeled and nonlabeled) was evident in soils over 360 days, but no degradation was observed for the BDE-28, -47, -99, and TC ((13)C-labeled and nonlabeled). A method to separate the enantiomers of α-TBECH and β-TBCO was developed and their degradation, along with α-HCH ((13)C-labeled and nonlabeled) was enantioselective. This is the first study which reports the enantioselective degradation of chiral BFRs in soils. Discrepancies between the enantiomer fraction (EF) of chemicals extracted from the soil by dichloromethane (DCM) and air were found. It is suggested that DCM removes both the sequestered and loosely bound fractions of chemicals in soil, whereas air accesses only the loosely bound fraction, and these two pools are subject to different degrees of enantioselective degradation. This calls for caution when interpreting EFs obtained from DCM extraction of soil with EFs in ambient air.
authors.affiliation: Centre for Atmospheric Research Experiments, Science and Technology Branch, Environment Canada, 6248 Eighth Line, Egbert, L0L 1N0 Ontario, Canada. fiona.wong@utoronto.ca
authors.forename: Fiona
authors.initials: F
authors.lastname: Wong
authors.forename: Perihan
authors.initials: P
authors.lastname: Kurt-Karakus
authors.forename: Terry F
authors.initials: TF
authors.lastname: Bidleman
mesh_terms: D000388:Air; D002947:Cities; D052918:Environmental Restoration and Remediation; D005411:Flame Retardants / Q000032:analysis*; D006207:Half-Life; D006842:Hydrocarbons, Brominated / Q000032:analysis* / Q000737:chemistry; D006843:Hydrocarbons, Chlorinated / Q000032:analysis* / Q000737:chemistry; D010575:Pesticides / Q000032:analysis*; D012989:Soil Pollutants / Q000032:analysis*; D013237:Stereoisomerism; D013997:Time Factors; D014835:Volatilization
chemical_list: D005411:Flame Retardants; D006842:Hydrocarbons, Brominated; D006843:Hydrocarbons, Chlorinated; D010575:Pesticides; D012989:Soil Pollutants