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).

Polybrominated diphenyl ethers (PBDEs) are aromatic compounds that containing bromine atoms, which possess high efficiency, good thermal stability. However, PBDEs had various known toxic effects and were characterized as persistent environmental pollutants. Exposure to a quinone-type metabolite of PBDEs (PBDEQ) is linked with excess production of intracellular reactive oxygen species (ROS) in our previous studies. Here, we observed that PBDEQ exposure led to ROS and mitochondrial dysfunction, which promoted canonical and non-canonical Nod-like receptor protein 3 (NLRP3) inflammasome activation. Further experiments demonstrated that PBDEQ exposure activated Toll-like receptors (TLRs), subsequently regulating nuclear factor kappa B (NF-κB) signaling. Moreover, lysosomal damage and K⁺ efflux were involved in PBDEQ-driven NLRP3 inflammasome activation. Our in vivo study also illustrated that PBDEQ administration induced liver inflammation in male C57BL/6J mice. Cumulatively, our current finding provided novel insights into PBDEQ-induced pro-inflammatory responses.

Air pollution remains a major global public health and environmental issue. We assessed the levels of PM₂.₅ and delineated the major sources in Makkah, Saudi Arabia. Fine particulate matter (PM₂.₅) sampling was performed from February 26, 2014–January 27, 2015 in four cycles/seasons. Samples were analyzed for black carbon (BC) and trace elements (TEs). PM₂.₅ source apportionment was performed by computing enrichment factors (EFs) and positive matrix factorization (PMF). Backward-in time trajectories were used to assess the long-range transport. Significant seasonal variations in PM₂.₅ were observed, Spring: 113 ± 67.1, Summer: 88.3 ± 36.4, Fall: 67.8 ± 24, and Winter: 67.6 ± 36.9 μg m⁻³. The 24-h PM₂.₅ exceeded the WHO (25 μg m⁻³) and Saudi Arabia's (35 μg m⁻³) guidelines, with an air quality index (AQI) of “unhealthy to hazardous” to human health. Most delta–C computations were below zero, indicating minor contributions from bio-mass burning. TEs were primarily Si, Ca, Fe, Al, S, K and Mg, suggesting major contributions from soil (Si, Ca, Fe, Al, Mg), and industrial and vehicular emissions (S, Ca, Al, Fe, K). EF defined two broad categories of TEs as: anthropogenic (Cu, Zn, Eu, Cl, Pb, S, Br and Lu), and earth-crust derived (Al, Si, Na, Mg, Rb, K, Zr, Ti, Fe, Mn, Sr, Y, Cr, Ga, Ca, Ni and Ce). Notably, all the anthropogenic TEs can be linked to industrial and vehicular emissions. PMF analysis defined four major sources as: vehicular emissions, 30.1%; industrial-mixed dust, 28.9%; soil/earth-crust, 24.7%; and fossil-fuels/oil combustion, 16.3%. Plots of wind trajectories indicated wind direction and regional transport as major influences on air pollution levels in Makkah. In collusion, anthropogenic emissions contributed >75% of the observed air pollution in Makkah. Developing strategies for reducing anthropogenic emissions are paramount to controlling particulate air pollution in this region.

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.

Samples of microplastic (n = 924) from two beaches in south west England have been analysed by field-portable-x-ray fluorescence (FP-XRF) spectrometry, configured in a low-density mode and with a small-spot facility, for the heavy metals, Cd and Pb, and the halogen, Br. Primary plastics in the form of pre-production pellets were the principal type of microplastic (>70%) on both beaches, with secondary, irregularly-shaped fragments representing the remainder of samples. Cadmium and Pb were detected in 6.9% and 7.5% of all microplastics, respectively, with concentrations of either metal that exceeded 103 μg g−1 usually encountered in red and yellow pellets or fragments. Respective correlations of Cd and Pb with Se and Cr were attributed to the presence of the coloured, inorganic pigments, cadmium sulphoselenide and lead chromate. Bromine, detected in 10.4% of microplastics and up to concentrations of about 13,000 μg g−1, was mainly encountered in neutrally-coloured pellets. Its strong correlation with Sb, whose oxides are effective fire suppressant synergists, suggests the presence of a variety of brominated flame retardants arising from the recycling of plastics originally used in casings for heat-generating electrical equipment. The maximum bioaccessible concentrations of Cd and Pb, evaluated using a physiological extraction based on the chemical characteristics of the proventriculus-gizzard of the northern fulmar, were about 50 μg g−1 and 8 μg g−1, respectively. These concentrations exceed those estimated for the diet of local seabirds by factors of about 50 and 4, respectively.

The relative significance of H-atom transfer versus electron transfer in the dehalogenation of halogenated organic compounds (HOCs) in bimetallic systems has long been debated. In this study, we have investigated this question through the case study of the debromination of 2, 2′, 4, 4’-tetrabromodiphenyl ether (BDE-47). The debromination rates of isomer products of BDE-47 by palladized nano zero-valent iron (n-ZVI/Pd) in the same reactor were compared. The results confirmed a shift in the debromination pathway of BDE-47 when treated with unpalladized nano zero-valent iron (n-ZVI) vs. treatment with n-ZVI/Pd. Study showed that BDEs could be rapidly debrominated in a palladium-H2 system, and the debromination pathway in this system is the same as that in the n-ZVI/Pd system. These results suggest that the H-atom species adsorbed on the surface of palladium are responsible for the enhanced reaction rates and the shift of the debromination pathway in the n-ZVI/Pd system. The Mulliken charges, calculated with density functional theory, on bromine atoms of PBDEs were directly correlated with the susceptibility to the e-transfer pathway in the n-ZVI system and inversely correlated with the susceptibility to the H-transfer pathway in n-ZVI/Pd system. These experimentally verified correlations in BDE-47 permit the prediction of the dominant debromination pathway in other BDEs.