Retrospective analysis of "new" flame retardants in the global atmosphere under the GAPS Network.

A retrospective analysis was conducted on air samples that were collected in 2005 under the Global Atmospheric Passive Sampling (GAPS) Network around the time period when the Stockholm Convention on Persistent Organic Pollutants came into force. Results are presented for several new flame retardants, including hexabromocyclododecane (HBCD), which was recently listed under the Convention (2013). These results represent the first global-scale distributions in air for these compounds. The targeted compounds are shown to have unique global distributions in air, which highlights the challenges in understanding the sources and environmental fate of each chemical, and ultimately in their assessments as persistent organic pollutants. The study also demonstrates the feasibility of using the PUF disk passive air sampler to study these new flame retardants in air, many of which exist entirely in the particle-phase as demonstrated in this study using a KOA-based partitioning model.

Determination of cyclic volatile methylsiloxanes in water, sediment, soil, biota, and biosolid using large-volume injection-gas chromatography-mass spectrometry.

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid-solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI-GC-MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS's associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4°C were stable within 29d; however, significant depletion of D6 (60-70%) occurred only after 3d. Whereas cVMS in sewage influent and effluent were stable at 4°C within 21d. cVMS in sediment sealed in amber glass jars at -20°C and in pentane extracts in vials at -15°C were stable during 1month under both storage conditions.

Atmospheric concentrations of halogenated flame retardants at two remote locations: the Canadian High Arctic and the Tibetan Plateau.

Atmospheric concentrations of halogenated flame retardants (FRs) were monitored for approximately one year at two remote stations, namely Nam Co on the Tibetan Plateau and Alert in the Canadian High Arctic. BDE-47 and 99 were the dominant polybrominated diphenyl ether (PBDE) congeners at both sites. Atmospheric PBDE concentrations in Nam Co were generally lower than those at Alert. While significant seasonal variations were observed for PBDEs at Alert, the FR concentrations at Nam Co showed no significant seasonality, even though air masses originated from distinctly different regions during different seasons. This suggests that FRs in Tibet do not have regional sources, but are reflective of truly global background contamination. Three new FRs, namely 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate (EHTeBB) and bis(2-ethyl-1-hexyl)tetrabromophthalate (TBPH) were detected at relatively high concentrations at both sites. This is the first report of these FRs in the remote global atmosphere and suggests significant potential for long-range atmospheric transport.