Hexabromocyclododecanes (HBCDs) are brominated aliphatic cyclic hydrocarbons used as flame retardants in thermal insulation building materials, upholstery textiles, and electronics. As a result of ...their widespread use and their physical and chemical properties, HBCDs are now ubiquitous contaminants in the environment and humans. This review summarizes HBCD concentrations in several environmental compartments and analyzes these data in terms of point sources versus diffuse sources, biomagnification potential, stereoisomer profiles, time trends, and global distribution. Generally, higher concentra tions were measured in samples (air, sediment, and fish) collected near point sources (plants producing or processing HBCDs), while lower concentrations were recorded in samples from locations with no obvious sources of HBCDs. High concentrations were measured in top predators, such as marine mammals and birds of prey (up to 9600 and 19 200 ng/g lipid weight, respectively), suggesting a biomagnification potential for HBCDs. Relatively low HBCD concentrations were reported in the few human studies conducted to date (median values varied between 0.35 and 1.1 ng/g lipid weight). HBCD levels in biota are increasing slowly and seem to reflect the local market demand. One important observation is the shift from the high percentage of the γ-HBCD stereoisomer in the technical products to a dominance of the α-HBCD stereoisomer in biological samples. A combination of factors such as variations in solubility, partitioning behavior, uptake, and, possibly, selective metabolism of individual isomers may explain the observed changes in stereoisomer patterns. Recommendations for further work include research on how HBCDs are transferred from products into the environment upon production, use, and disposal. Time trends need to be analyzed more in detail, including HBCD stereoisomers, and more data on terrestrial organisms are needed, especially for humans. Whenever possible, HBCDs should be analyzed as individual stereoisomers in order to address their fate and effects.
The environmental safety of decabromodiphenyl ether (BDE-209), a widely used flame retardant, has been the topic of controversial discussions during the past several years. Degradation of BDE-209 ...into lower brominated diphenyl ether congeners, exhibiting a higher bioaccumulation potential, has been a critical issue. Here, we report on the degradation of BDE-209 and the formation of octa- and nonabromodiphenyl ether congeners under anaerobic conditions. Sewage sludge collected from a mesophilic digester was used as the inoculum and incubated up to 238 days with and without a set of five primers. Following Soxhlet extraction and a liquid chromatography cleanup procedure, parent compounds and debromination products were analyzed by GC/HRMS. In experiments with primers, concentrations of BDE-209 decreased by 30% within 238 days. This corresponds to a pseudo-first-order degradation rate constant of 1 × 10-3 d-1. Without primers, the degradation rate constant was 50% lower. Formation of two nonabromodiphenyl ether and six octabromodiphenyl ether congeners proved that BDE-209 underwent reductive debromination in these experiments. Debromination occurred at the para and the meta positions, whereas debromination at the ortho position was not statistically significant. All three nonabromodiphenyl ether congeners (BDE-206, BDE-207, and BDE-208) were found to undergo reductive debromination as well. No significant change of the BDE-209 concentration and no formation of lower brominated congeners was observed in sterile control experiments. To our knowledge, this is the first report demonstrating microbially mediated reductive debromination of BDE-209 under anaerobic conditions.
With the increasing global legal and illegal trade of waste electrical and electronic equipment (WEEE) comes an equally increasing concern that poor WEEE recycling techniques, particularly in ...developing countries, are generating more and more environmental pollution that affects both ecosystems and the people living within or near the main recycling areas. This review presents data found in the scientific and grey literature about concentrations of lead (Pb), polybrominated diphenylethers (PBDEs), polychlorinated dioxins and furans as well as polybrominated dioxins and furans (PCDD/Fs and PBDD/Fs) monitored in various environmental compartments in China and India, two countries where informal WEEE recycling plays an important economic role. The data are compared with known concentration thresholds and other pollution level standards to provide an indication of the seriousness of the pollution levels in the study sites selected and further to indicate the potential negative impact of these pollutants on the ecosystems and humans affected. The review highlights very high levels of Pb, PBDEs, PCDD/Fs and PBDD/Fs in air, bottom ash, dust, soil, water and sediments in WEEE recycling areas of the two countries. The concentration levels found sometimes exceed the reference values for the sites under investigation and pollution observed in other industrial or urban areas by several orders of magnitude. These observations suggest a serious environmental and human health threat, which is backed up by other studies that have examined the impact of concentrations of these compounds in humans and other organisms. The risk to the population treating WEEE and to the surrounding environment increases with the lack of health and safety guidelines and improper recycling techniques such as dumping, dismantling, inappropriate shredding, burning and acid leaching. At a regional scale, the influence of pollutants generated by WEEE recycling sites is important due to the long-distance transport potential of some chemicals. Although the data presented are alarming, the situation could be improved relatively rapidly by the implementation of more benign recycling techniques and the development and enforcement of WEEE-related legislation at the national level, including prevention of unregulated WEEE exports from industrialised countries.
This study examined the emissions of powerful asthmatic agents called isocyanates from small-scale pyrolysis experiments of two common foams employed in mattress production such as flexible ...polyurethane foam (FPUF) and viscoelastic memory foam (VMF). A nitrogen atmosphere and five different temperatures, 300, 350, 400, 450 and 850 °C, were selected to carry out the experiments in order to evaluate the worst possible conditions for thermal degradation.
A similar trend for both materials was found. At lower temperatures, diisocyanates were the most important products whereas at 850 °C monoisocyanates, and mainly isocyanic acid released mainly from the thermal cracking of diisocyanates evolved directly from the polymer chains.
The total yields of isocyanates were in the range of 1.43–11.95 mg/m3 for FPUF at 300-850 °C and 0.05–6.13 mg/m3 for VMF, 300-850 °C. This difference could be a consequence of the lower amount of isocyanates employed in the VMF production which was confirmed by the nitrogen content of the foams, 5.95% FPUF vs. 3.34% in VMF.
Additionally, a qualitative search for so far unknown isocyanates was performed in samples from the pyrolysis of FPUF at 300, 400 and 850 °C. It was confirmed that six different aminoisocyanates at 300 °C were evolved, whereas at 400 and 850 °C only five of them were detected. The general trend observed was a decrease of the aminoisocyanate levels with increasing pyrolysis temperature.
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•Pyrolysis of flexible and viscoelastic memory foams was performed.•At 350-450 °C, diisocyanates are formed (around 0.1 μg/gsample).•At 850 °C, the emission factors of ICA and PHI 1 and 0.01 μg/gsample, respectively.•Isocyanate profiles observed agree with kinetic models proposed previously.•Six new aminoisocyanates have been found in the evolved gases from FPUF pyrolysis.
Two small-scale field studies were conducted to investigate the transfer of substances from products into dust due to direct and air-mediated transfer. The project focused on semivolatile organic ...compounds (SVOCs), which are frequently found in and re-emitted from dust. For the field studies, four artificial products containing deuterium-labeled SVOCs (eight phthalates and adipates) were installed in residential indoor environments. Two plastic products were installed vertically to investigate substance transfer due to evaporation into air. One plastic product and a carpet were installed horizontally to investigate the direct transfer from source to dust. A pyrethroid was intentionally released by spraying a commercial spray. Dust samples were collected from the floor, elevated surfaces in the room and the surfaces of the horizontally installed products. We observed that the dust concentrations of substances exclusively transferred via air were similar at different collection sites, but the concentrations of chemicals present in horizontal products were up to 3 orders of magnitude higher in dust deposited on the source. We conclude that direct transfer from source into dust substantially increases the final SVOC concentration in dust in contact with the source, regardless of the vapor pressure of investigated SVOCs, and may lead to larger human exposure.
Short-chain chlorinated paraffins (SCCPs) are of concern due to their potential for adverse health effects, bioaccumulation, persistence, and long-range transport. Data on concentrations of SCCPs in ...urban areas and underlying emissions are still scarce. In this study, we investigated the levels and spatial distribution of SCCPs in air, based on two separate, spatially resolved sampling campaigns in the city of Zurich, Switzerland. SCCP concentrations in air ranged from 1.8 to 17 ng·m–3 (spring 2011) and 1.1 to 42 ng·m–3 (spring 2013) with medians of 4.3 and 2.7 ng·m–3, respectively. Both data sets show that atmospheric SCCP levels in Zurich can vary substantially and may be influenced by a number of localized sources within this urban area. Additionally, continuous measurements of atmospheric concentrations performed at one representative sampling site in the city center from 2011 to 2013 showed strong seasonal variations with high SCCP concentrations in summer and lower levels in winter. A long-term dynamic multimedia environmental fate model was parametrized to simulate the seasonal trends of SCCP concentrations in air and to back-calculate urban emissions. Resulting annual SCCP emissions in the city of Zurich accounted for 218–321 kg, which indicates that large SCCP stocks are present in urban areas of industrialized countries.
N-nitrosodimethylamine (NDMA) is a potent carcinogen formed during chloramination of water and wastewater treatment plant effluents. A procedure is described for quantifying the concentration of the ...organic precursors of NDMA that could be formed during chlorination of wastewaters and natural waters. The method involves applying a high dose of monochloramine to a pH-buffered sample followed by a 10-day contact period, during which the monochloramine decays at a rate unrelated to the composition of the sample. Analyses of samples of municipal wastewater effluents and surface waters indicate that the method provides a robust and reproducible measurement of NDMA precursors over a wide range of conditions. A sensitive GC/CI/MS/MS analytical procedure for dimethylamine also is described and used to demonstrate that NDMA formation during chlorination of wastewater and natural waters cannot be explained by dimethylamine concentrations alone.
Monochloramine disinfection of drinking water can result in the formation of the potent carcinogen N-nitrosodimethylamine (NDMA). To assess NDMA precursor concentrations in natural waters, samples ...from lakes, reservoirs, groundwaters, and isolated natural organic matter were exposed to relatively high concentrations of monochloramine. After 1 week, the concentration of NDMA ranged from approximately 0.1 to 0.8 nM. Application of a sensitive new GC/MS/MS technique and amendment of a sample with the known NDMA precursor dimethylamine (DMA) prior to chloramination indicated that only a small fraction of the NDMA produced during chloramination could be attributable to DMA. Chloramination of isolated natural organic matter and application of solid-phase extraction prior to chloramination suggested that natural organic matter accounts for a significant fraction of the precursors. However, the concentrations of NDMA precursors were higher in the epilimnion than the hypolimnion of two stratified reservoirs despite similar concentrations of dissolved organic carbon throughout the water column. Experiments performed to simulate the formation of NDMA during conditions comparable to those encountered in water treatment and distribution systems that use chloramine indicated that the concentration of NDMA produced from naturally occurring precursors usually will be less than 0.1 nM. The results indicate that chloramination of natural organic matter alone is unlikely to produce NDMA levels exceeding the current regulations.
Poly- and perfluorinated alkyl substances (PFASs) are anthropogenic pollutants ubiquitously found in the environment. Volatile PFASs are likely transported atmospherically over long ranges, but ...identification and quantification of emission sources is a challenging task. In this work, special meteorological conditions were utilized to quantify atmospheric emissions of Zurich City, Switzerland with a dual approach of modeling and field measurements. During high pressure systems in summer, a stable nocturnal boundary layer is formed in which pollutants are enriched. For volatile PFASs, a diel pattern of high concentrations in the night and low concentrations during the day was observed in Zurich, which is likely due to the atmospheric boundary layer dynamics. These results enable to model the emission source strength of Zurich City with a multimedia mass balance model in an accompanying paper. Cluster analyses suggested that perfluorocarboxylates (PFCAs) are a result of degradation of volatile precursors and direct emissions.
► Atmospheric PFAS concentrations in Zurich increase during the night. ► Diel concentration dynamics are likely due to stable nocturnal boundary layer. ► City is a source of PFASs to the atmosphere. ► 8:2 FTOH concentrations are high: up to 1200 pg/m3. ► PFAA concentrations are correlated with ozone, not particulate matter.
Semivolatile PFAS concentrations follow a diel trend in Zurich City in stable summer conditions likely due to atmospheric boundary layer effects and urban emissions.
We aimed at demonstrating non-inferiority of bortezomib/cyclophosphamide/dexamethasone (VCD) compared to bortezomib/doxorubicin/dexamethasone (PAd) induction therapy with respect to very good partial ...response rates or better (⩾VGPR) in 504 newly diagnosed, transplant-eligible multiple myeloma patients. VCD was found to be non-inferior to PAd with respect to ⩾VGPR rates (37.0 versus 34.3%, P=0.001). The rates of progressive disease (PD) were 0.4% (VCD) versus 4.8% (PAd; P=0.003). In the PAd arm, 11 of 12 patients with PD had either renal impairment (creatinine ⩾2 mg/dl) at diagnosis or the cytogenetic abnormality gain 1q21, whereas no PD was observed in these subgroups in the VCD arm. Leukocytopenia/neutropenia (⩾3°) occurred more frequently in the VCD arm (35.2% versus 11.3%, P<0.001). Neuropathy rates (⩾2°) were higher in the PAd group (14.9 versus 8.4%, P=0.03). Serious adverse events, both overall and those related to thromboembolic events, were higher in the PAd group (32.7 versus 24.0%, P=0.04 and 2.8 versus 0.4%, P=0.04). Stem cell collection was not impeded by VCD. VCD is as effective as PAd in terms of achieving ⩾VGPR rates with fewer PD and has a favorable toxicity profile. Therefore, VCD is preferable to PAd as induction therapy.
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