Polybrominated diphenyl ethers (PBDEs) serve as flame retardants in many household materials such as electrical and electronic devices, furniture, textiles, plastics, and baby products. Though the use of PBDEs like penta-, octa- and deca-BDE greatly reduces the fire damage, indoor pollution by these toxic emissions is ever-growing. In fact, a boom in the global market projections of PBDEs threatens human health security. Therefore, efforts are made to minimize PBDEs pollution in USA and Europe by encouraging voluntary phasing out of the production or imposing compelled regulations through Stockholm Convention, but >500 kilotons of PBDEs still exist globally. Both ‘environmental persistence’ and ‘bioaccumulation tendencies’ are the hallmarks of PBDE toxicities; however, both these issues concerning household emissions of PBDEs have been least addressed theoretically or practically. Critical physiological functions, lipophilicity and toxicity, trophic transfer and tissue specificities are of utmost importance in the benefit/risk assessments of PBDEs. Since indoor debromination of deca-BDE often yields many products, a better understanding on their sorption propensity, environmental fate and human toxicities is critical in taking rigorous measures on the ever-growing global deca-BDE market. The data available in the literature on human toxicities of PBDEs have been validated following meta-analysis. In this direction, the intent of the present review was to provide a critical evaluation of the key aspects like compositional patterns/isomer ratios of PBDEs implicated in bioaccumulation, indoor PBDE emissions versus human exposure, secured technologies to deal with the toxic emissions, and human toxicity of PBDEs in relation to the number of bromine atoms. Finally, an emphasis has been made on the knowledge gaps and future research directions related to endurable flame retardants which could fit well into the benefit/risk strategy.

Polybrominated diphenyl ethers (PBDEs) undergo debromination when they were exposed in zerovalent metal or bimetallic systems. Yet their debromination pathways and mechanisms in these systems were not well understood. Here we reported the debromination pathways of three BDE congeners (BDE-21, 25 and 29) by nano-zerovalent iron (n-ZVI). All these BDE congeners have three bromine substituents that were located in ortho-, meta- and para-positions. Results demonstrated that BDE-21, 25 and 29 preferentially debrominate meta-, ortho- and para-bromines, respectively, suggesting that bromine substituent at each position (i.e. ortho-, meta- or para-) of PBDEs can be preferentially removed. Singly occupied molecular orbitals of BDE anions are well correlated with their actual debromination pathways, which successfully explain why these BDE congeners exhibit certain debromination pathways in n-ZVI system. In addition, microscale zerovalent zinc (m-ZVZ), iron-based bimetals (Fe/Ag and Fe/Pd) were also used to debrominate PBDEs, with BDE-21 as target pollutant. We found that the debromination pathways of BDE-21 in m-ZVZ and Fe/Ag systems are the same to those in n-ZVI system, but were partially different from those in Fe/Pd systems. The debromination of BDE-21 in Pd-H2 system as well as the solvent kinetic isotope effect in single metal and bimetallic systems suggests that H atom transfer is the dominant mechanism in Fe/Pd system, while e-transfer is still the dominant mechanism in Fe/Ag system.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal).This article has been retracted at the request of the authors due to the results of a detailed investigation of the data quality conducted by the Central Analytical Laboratory (CAL) after relocation to the University of Wisconsin (UW) – Wisconsin State Laboratory of Hygiene. Using a subset of the 30 samples with the highest bromide ion (Br-) concentrations, the CAL at UW found 6 samples that could not be verified or were incorrect. Because the extent of the incorrect data is unknown, the NADP Executive Committee voted unanimously in May 2019 to discontinue public access to these data, and they decided to sequester all Br- data prior to June 2018. These issues were not obvious to the authors when the paper was written.The authors apologize for the inconvenience caused.

Extensive studies have been conducted on the environmental degradation of multiwall carbon nanotubes (MWCNTs), but primarily focused on the extent and rate of MWCNTs mineralization. Few studies have explored possible structural changes that may occur to MWCNTs during natural or engineered processes. We systematically examined MWCNTs in oxidative coupling reactions in the presence of a common contaminant tetrabromobisphenol A (TBBPA). MWCNTs was modified by the radicals of TBBPA resulting from peroxidase-mediated coupling reaction. Interactions between TBBPA radicals and MWCNTs were definitely confirmed by analyzing the characteristic mass spectrometry response of bromine in TBBPA and the structures of MWCNTs. After reaction with TBBPA radicals for 60 min, the content of bromine contained in MWCNTs was 6.84(±0.12)%, a quantity equivalent to a 501.65(±2.19) mg loading of TBBPA per gram MWCNTs. Modified MWCNTs had better stability and smaller sizes than that of MWCNTs and TBBPA-adsorbed MWCNTs. Assessment using zebrafish embryos revealed that the modified MWCNTs passed through the chorion and entered the embryo inducing acute toxicity, while the MWCNTs/TBBPA-adsorbed MWCNTs was trapped by chorion. These findings indicated that MWCNTs was modified in peroxidase-mediated coupling reactions, and suggested that such modifications may have an influence on the ecological risks of MWCNTs.

Several pollutants, which include metals, are present in the Antarctic atmosphere, snow, marine and terrestrial organisms. This work reports the elements incorporated by Usnea sp thalli in Potter Peninsula, 25 de Mayo (King George) Island, South Shetlands, Antarctica. Geological origin was analyzed as possible sources of elements. For this purpose, correlations were done using a geochemical tracer, principal component analysis and enrichment factors were computed. Lithophile elements from particulate matter were present in most of the sampling sites. Bromine, Se and Hg showed the highest enrichment factors suggesting other sources than the particulate matter. Mercury values found in Usnea sp were in the same range as those reported for Deception Island (South Shetlands) and remote areas from the Patagonia Andes.

Open burning of electronic waste (e-waste) releases various metals and organohalogen compounds in the environment. Here we investigated the interplay of metals (Cu, Pb, Zn, Fe, Co, and Sr) and bromine (Br) in the formation of dioxin-related compounds (DRCs), including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs), as well as non-regulated DRCs such as polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and their monobrominated PCDD/Fs in soils sampled from open burning e-waste sites at Agbogbloshie in Accra, Ghana. The predominant DRCs were PBDFs, PCDFs, PCDDs, and DL-PCBs. Statistical analyzes, X-ray absorption spectroscopy, and the PCDF/PCDD ratio suggested possible formation paths of PCDD/Fs and DL-PCBs by catalytic behaviors of copper chlorides (CuCl, CuCl2, and Cu2(OH)3Cl) and thermal breakdown of polyvinyl chloride. Predominant formation of brominated furans may be derived from electron transfer from intermediates of PBDE to copper, Cu(II) → Cu(I). Lead chloride also contributed to generate DRCs and may become highly bioaccessible through the open burning of e-waste. The main zinc species (ZnCl2 and ZnS) suggested a possible relationship to generate DRCs and specific zinc source such as tire burning. Cu, Pb, Zn, and Br contained in various e-wastes, wires/cables, plastics, and tires strongly influenced generation of many DRCs.

Photosensitization of natural organic matter (NOM) is an important natural source of reactive bromine species (RBrS) in the environment. Up to now, quantitative information about RBrS was mainly based on model sensitizers. Whether the behavior of model compounds could represent those of complex NOM remains unknown. In this study, we employed a chemical probe (3,5-dimethyl-1-H-pyrazole) to measure RBrS in humic acid (HA)-containing solutions and investigated their influential factors. The formation rate, decay rate constant, steady-state concentration, and lifetimes of RBrS were 3.87(±0.16) × 10⁻¹³ mol L⁻¹·s⁻¹, 1.99(±0.20) × 10⁴ s⁻¹, 2.04(±0.13) × 10⁻¹⁷ mol L⁻¹, and 5.06(±1.05) × 10⁻⁵ s, respectively. Measured steady-state concentrations of RBrS were 3–5 orders of magnitude lower than those in model sensitizer system. Results showed that HA drove the RBrS generation, and about 0.12–0.70% of triplet-state HA (³HA*) would be transformed into RBrS. HA structures strongly affected this process. Phenolic-like groups suppressed the formation, while aromatic ketone-like moieties facilitated it. Last, HA also altered the transformation pathways. The contribution of ·OH dependent and direct oxidation pathways was almost equal, while the direct oxidation was predominant in the model system. Thus, careful consideration should be taken into photochemical formation of RBrS in NOM-involved solution, due to their complexity and multiple roles.

In this study, the degradation of eight bromophenols (BPs), including monobromophenols (2-BP, 3-BP, and 4-BP), dibromophenols (2,4-DBP, 2,6-DBP, and 3,5-DBP), a tribromophenol (2,4,6-TBP) and a pentabromophenol (PBP), by a Fe(VI) reaction process at a pH of 8.0 was systematically studied. It was concluded that their degradation rates increased with increasing Fe(VI) concentrations in solution. The removal of 2,4,6-TBP, 2-BP, and 2,6-DBP was faster than that of the other five BPs, which could be attributed to the position of the substituting Br atom. Moreover, the direct oxidation and coupling reactions greatly influenced the reactivity of the bromophenols with Fe(VI). The electron paramagnetic resonance (EPR) analysis confirmed the presence of hydroxyl radicals in present system. The oxidation reaction products of PBP and 2-BP were recognized by an electrospray time-of-flight mass spectrometer; hydroxylation, hydroxyl substitution, the cleavage of the C–C bond, direct oxidation and polymerization via an end linking mechanism were noticeably found in the reaction process, resulting in the formation of polymerization products and causing hydroxylation to occur. Theoretical calculations further determined the possible oxidation sites of 2-BP and PBP. This study may provide comprehensive and important information on the remediation of BPs by Fe(VI).

Chokka squid (Loligo reynaudii) from three sites along the South African coast were analyzed for halogenated natural products (HNPs) and anthropogenic persistent organic pollutants (POPs). HNPs were generally more than one order of magnitude more abundant than POPs. The most prevalent pollutant, i.e. the HNP 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1), was detected in all chokka squid samples with mean concentrations of 105, 98 and 45 ng/g lipid mass, respectively, at the Indian Ocean (site A), between both oceans (site B) and the South Atlantic Ocean (site C). In addition, bromine containing polyhalogenated 1′-methyl-1,2′-bipyrroles (PMBPs), 2,4,6-tribromophenol (2,4,6-TBP, up to 28 ng/g lipid mass), polybrominated methoxy diphenyl ethers, MHC-1, TBMP and other HNPs were also detected. Polychlorinated biphenyls (PCBs) were the predominant class of anthropogenic POPs. PCB 153 was the most abundant PCB congener in chokka squid from the Indian Ocean, and PCB 138 in samples from the South Atlantic Ocean and between both oceans.

Temuco is a mid-size city representative of severe wood smoke pollution in southern Chile; however, little is known about the indoor air quality in this region. A field measurement campaign at 63 households in the Temuco urban area was conducted in winter 2014 and is reported here. In this study, indoor and outdoor (24-hr) PM2.5 and its elemental composition were measured and compared. Infiltration parameters and outdoor/indoor contributions to indoor PM2.5 were also determined. A statistical evaluation of how various air quality interventions and household features influence indoor PM2.5 was also performed.This study determined median indoor and outdoor PM2.5 concentrations of 44.4 and 41.8 μg/m3, respectively. An average infiltration factor (0.62 ± 0.06) was estimated using sulfur as a tracer species. Using a simple mass balance approach, median indoor and outdoor contributions to indoor PM2.5 concentrations were then estimated as 12.5 and 26.5 μg/m3, respectively; therefore, 68% of indoor PM2.5 comes from outdoor infiltration. This high percentage is due to high outdoor pollution and relatively high household air exchange rates (median: 1.06 h−1).This study found that S, Br and Rb were dominated by outdoor contributions, while Si, Ca, Ti, Fe and As originated from indoor sources. Using continuous indoor and outdoor PM2.5 measurements, a median indoor source strength of 75 μg PM2.5/min was estimated for the diurnal period, similar to literature results. For the evening period, the median estimate rose to 135 μg PM2.5/min, reflecting a more intense wood burning associated to cooking and space heating at night.Statistical test results (at the 90% confidence level) support the ongoing woodstove replacement program (reducing emissions) and household weatherization subsidies (reducing heating demand) for improving indoor air quality in southern Chile, and suggest that a cookstove improvement program might be helpful as well.