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.

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.

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.

The Qinling subspecies of giant panda (Ailuropoda melanoleuca qinlingensis), is highly endangered; fewer than 350 individuals still inhabit Qinling Mountains. Previous research revealed captive pandas were exposed to bromine, so we hypothesized that captive pandas were exposed to and affected by polybrominated diphenyl ethers (PBDEs). To test this hypothesis, we tested blood and feces of captive and wild pandas, their drinking water, food (bamboo leaves) from SWARC (Shaanxi Wild Animal Research Center)and FNNR (Foping National Nature Reserve) and supplemental feedstuff given to captive panda at SWARC. We found 13 congeners of PBDEs in fecal samples, of which BDE47, BDE66, BDE71, BDE99, and BDE154 were the dominant, total PBDE concentration in feces of captive pandas was 255% higher than in wild pandas. We found nine PBDEs congeners in blood samples: BDE153 and BDE183 were the predominant congers. PBDEs in blood from captive pandas were significantly higher than in wild pandas. The total concentration of PBDEs were 5473 and 4835 (pg.g) in Fargesia qinlingensis, were 2192 and 1414 (pg.g) in Bashannia fargesii (2192, 1414 pg g), 0.066, 0.038 (pg/ml) in drinking water, and 28.8 (pg.g) in supplemental feedstuff for captive and wild pandas, which indicate that the PBDEs came from its bamboo feed, especially from Bashannia fargesii. Our results demonstrate that BDE99 and BDE47 could be threatening the pandas’ health especially for captive panda and there are potential health risks from PBDEs for pandas. In the short term, this risk may be ameliorated by strict control of food quality. In the long term, however, reducing air, water and soil contamination so as to improve environmental quality can best reduce these risks to meet the international standard such as Stockholm Convention.

To reveal the emission patterns of brominated flame retardants (BFRs) in the Beijiang River, South China, concentrations of polybrominated diphenyl ethers (PBDEs) and phenolic BFRs (2,4,6-tribromophenol (TBP), pentabromophenol (PeBP), tetrabromobisphenol A (TBBPA)), and bisphenol A (BPA) in water and sediments were simultaneously measured, and the geographic information system (GIS) were applied to analyse their emission patterns. Results showed that PBDEs, TBP, PeBP, TBBPA and BPA were ubiquitous in the water and sediment samples collected from the Beijiang River. However, most of the concentrations were very low or below the detection limits (DL). In water, Σ20PBDEs (sum of all 20 PBDEs congeners) levels ranged from < DL to 232 pg L−1, with the predominant congeners containing low bromine contents. The levels of TBP, PeBP, TBBPA and BPA in water were lower than 810 pg L−1. In sediments, Σ20PBDEs varied from 260 to 5640 pg g−1 dry weight (d.w.), with the predominant congeners containing high bromine contents. The levels of TBP, PeBP, TBBPA and BPA were lower than 600 pg g−1 d.w.. Risk assessments indicated that the water and sediments at the sampling locations imposed no estrogenic risk (E2EQ < 1.0 ng E2 L−1), and the eco-toxicity assessment at three trophic levels also showed no risk at all sampling sites in water (RQTotal < 1.0), but with a potential eco-toxicity at some sampling points in sediments (1.0<RQTotal < 10.0).

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).

Ionic liquids (ILs) are extensively used in several chemistry fields. And research about the effects of ILs on soil microbes is needed. In this study, brown soil was exposed to 1-butyl-3-methylimidazolium bromide ([C₄mim]Br), 1-hexyl-3-methylimidazolium bromide ([C₆mim]Br) and 1-decyl-3-methylimidazolium bromide ([C₁₀mim]Br). The toxicities of the three ILs are evaluated by measuring the soil culturable microbial number, enzyme activity, microbial diversity and, abundance of the ammonia monooxygenase (amoA) genes of ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). Results showed that all tested ILs caused a decrease in culturable microbial abundance. Tested ILs exposure inhibit urease activity and promote acid phosphatase and β-glucosidase activities. Tested ILs reduced soil microbial diversity and the abundances of AOB-amoA and AOA-amoA genes significantly. After a comparison of the integrated biomarker response (IBR) index, the toxicities of tested ILs to soil microorganisms were as follows: [C₁₀mim]Br > [C₆mim]Br > [C₄mim]Br. Among all collected biomarkers, the abundance of the AOA-amoA gene was the most sensitive one and was easily affected after ILs exposure.

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.

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.

Samples of plastic collected from two beaches in southwest England (n = 185) have been analysed by XRF spectrometry for elements that are hazardous or restricted in synthetic polymers (namely, As, Ba, Br, Cd, Cr, Hg, Pb, Sb and Se). Overall, one or more restricted element was detected in 151 samples, with 15 cases exhibiting non-compliance with respect to the Restriction of Hazardous Substances (RoHS) Directive. Twelve plastics that were RoHS-non-compliant were subsequently processed into microplastic-sized fragments and subjected to an avian physiologically-based extraction test (PBET) that simulates the chemical conditions in the gizzard-proventriculus of the northern fulmar. Kinetic profiles of metal and metalloid mobilisation in the PBET were fitted using a pseudo-first-order diffusion model with rate constants ranging from ∼0.02 to 0.5 h−1, while profiles for Br were better fitted with a parabolic diffusion model and rate constants of 7.4–9.5 (μg L−1)−1h−1/2. Bioaccessibilities, based on maximum or equilibrium concentrations mobilised relative to total (XRF) concentrations, ranged from <1% for Cd and Se in polyethylene and polypropylene to over 10% for Br in a sample of expanded polystyrene and Pb in a sample of PVC. Calculations suggest that ingested plastic could contribute about 6% and 30% of a seabird's exposure to and accumulation of Pb and brominated compounds, respectively.