Local structure and speciation of platinum in fresh and road-aged North American sourced vehicle emissions catalysts: an X-ray absorption spectroscopic study.

Given emerging concerns about the bioavailability and toxicity of anthropogenic platinum compounds emitted into the environment from sources including vehicle emission catalysts (VEC), the platinum species present in selected North American sourced fresh and road-aged VEC were determined by Pt and Cl X-ray absorption spectroscopy. Detailed analysis of the Extended X-ray Absorption Fine Structure at the Pt L3 and L2 edges of the solid phase catalysts revealed mainly oxidic species in the fresh catalysts and metallic components dominant in the road-aged catalysts. In addition, some bimetallic components (Pt-Ni, Pt-Pd, Pt-Rh) were observed in the road-aged catalysts from supporting Ni-, Pd-, and Rh-K edge XAS studies. These detailed analyses allow for the significant conclusion that this study did not find any evidence for the presence of chloroplatinate species in the investigated solid phase of a Three Way Catalyst or Diesel Oxidation Catalysts.

Summary of historical terrestrial toxicity data for the brominated flame retardant tetrabromobisphenol A (TBBPA): effects on soil microorganisms, earthworms, and seedling emergence.

This article summarizes historical and recent research on the terrestrial toxicology of tetrabromobisphenol A (TBBPA). Despite its ubiquitous use and presence in the environment, little published data is available to evaluate the terrestrial ecotoxicity of TBBPA. The purposes of this paper are to enable broad access to a series of TBBPA ecotoxicity tests (nitrogen transformation, earthworm survival/reproduction, and seedling emergence/growth) that were conducted in support of regulatory risk assessments, and to summarize available research in the terrestrial toxicity of TBBPA. In these studies, no significant effect of TBBPA on nitrogen transformation was observed up to the highest concentration [1000 mg/kg dry weight (d.w.) soil]. The no-observed-effect concentrations (NOECs) for seedling emergence ranged from 20 to 5000 mg/kg d.w. Sensitivities were soybeans < corn ≈ onion ≈ tomato < ryegrass < cucumber; the most sensitive endpoints being seedling dry weight and height. The 28-day earthworm mortality NOEC was > 4840 mg/kg d.w. The most sensitive terrestrial endpoint was earthworm reproduction with a half maximal effective concentration (EC50) of 0.12 mg/kg d.w. soil. Based on this sensitive terrestrial endpoint, the EU derived a predicted no-effect concentration (PNEC) for soil of 0.012 mg/kg wet weight soil (EU 2008). We did not identify a more sensitive/lower point of departure for terrestrial toxicity endpoints in the published literature. On the basis of this PNEC, the EU concluded there was potential risk for environmental effects near TBBPA manufacturing sites, but no additional risk provided that no sewage sludge was applied to agricultural land (EU 2008).

Polybrominated diphenyl ether exposure to electronics recycling workers--a follow up study.

Workers at an electronics recycling plant have previously been shown to have elevated serum levels of polybrominated diphenyl ethers (PBDEs) compared to referents without occupational PBDE exposure. Subsequent structural changes and industrial hygiene measures at the plant were applied to improve the work environment. The present study aims to assess the impact of these work environment changes on the occupational exposure to PBDEs. Blood were drawn from the workers and analyzed at two different laboratories, and serum concentrations of several PBDE congeners were determined by GC/MS or GC/HRMS. Cross-sectional studies were performed prior to (in 1997; N=19) and after (in 2000; N=27) workplace improvements. Longitudinal studies were performed on twelve of the workers that were sampled at both occasions. Even though the amount of processed goods had doubled in 2000 as compared to 1997, there was a significant decrease in the serum levels of BDE-183 and BDE-209. For BDE-209 the levels observed in year 2000 were even lower than in referents with no occupational exposure. In contrast to the decrease of higher brominated diphenyl ethers, the concentrations of BDE-47 did not significantly change. For BDE-153, the cross-sectional study indicated no change, whereas the longitudinal follow up indicated a significant increase. This study shows that the industrial hygiene improvements clearly reduced the occupational exposure to BDE-183 and BDE-209 at the plant. Still, the levels of hexa- to nonaBDEs but not BDE-209 were elevated, compared to referents with no occupational exposure.

Comparison of the recyclability of flame-retarded plastics.

Mechanical recycling of plastics from waste from electrical and electronical equipment (WEEE) is increasingly expected by regulators and demanded by original equipment manufacturers (CEMs); however, mechanical recycling is generally recognized to be the most economically costly and technically challenging method of recovering WEEE plastics. With 12% of WEEE plastics requiring the use of flame-retardants in order to ensure appropriate levels of consumer fire safety, there is a distinct need for data from comparative tests on recyclability of various flame-retarded plastics. Ten commercially available flame-retarded plastic grades commonly used in electronic equipment (eight "halogen-free" grades and two grades containing brominated flame-retardants (BFRs)) were subjected to two different recycling scenarios. A standard recycling scenario was carried out by repeatedly extruding the materials and an accelerated hydrolysis scenario was carried out to study the influence of humidity from air during use on the process. Both, virgin and recycled materials were tested for a potential formation of polybrominated dibenzodioxins/furans (PBDD/Fs), their mechanical properties were assessed and the fire safety rating was determined. Results indicate that none of the tested materials showed a potential to form the PBDD/Fs regulated by the German Chemicals Banning Ordinance. The halogen-free plastic grades showed a significant deterioration of mechanical properties after recycling, whereas those plastics containing BFRs were able to pass all test criteria, thus maintaining their original properties. With respect to the fire safety rating, none of the eight tested halogen-free plastic grades could maintain their fire safety rating after five recycling loops, whereas both BFR plastics continued to achieve their fire safety ratings. Therefore the tested BFR containing plastic materials showed superior recycling properties compared to the tested halogen-free plastic grades with respect to all investigated parameters.