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.

Metals associated with suspended sediments in lakes Erie and Ontario, 2000-2002.

Sediment traps were deployed in the three major basins of Lake Erie, and the central (Mississauga) basin of Lake Ontario, and refurbished seasonally over the period 2000-2002. In Lake Ontario, sediment down-flux rates and corresponding contaminant down-flux rates were highest in winter during periods of unstratified thermal conditions, and generally increased with depth due to the influence of resuspended bottom sediments during all sampling periods. Lake Ontario suspended sediments exhibited the highest concentrations of metals; concentrations of mercury and lead frequently exceeded guideline values for bottom sediments. Contaminant levels in Lake Ontario suspended sediments were similar to concentrations in bottom sediments in the same area. There was a spatial trend toward higher suspended sediment metals concentrations from the eastern basin to the western basin of Lake Erie, which is similar to the trend in bottom sediment contamination. In the eastern basin of Lake Erie, which is the deepest area of the lake, there was no trend in down-flux rate with depth in 2001; however, down-flux rates increased with depth in 2002. Suspended sediments in the western basin of Lake Erie were determined to be largely resuspended bottom sediments; all western basin samples collected in the study exceeded the guideline value for mercury (0.486 microg/g).