Soil polycyclic aromatic hydrocarbons (PAHs) generated from industrial processes are highly spatially heterologous, with limited quantitative studies on their main influencing factors. The present study evaluated the soil PAHs in three types of industrial parks (a petrochemical industrial park, a brominated flame retardant manufacturing park, and an e-waste dismantling park) and their surroundings. The total concentrations of 16 PAHs in the parks were 340–2.43 × 10³, 26.2–2.63 × 10³, and 394–2.01 × 10⁴ ng/g, which were significantly higher than those in the surrounding areas by 1–2 orders of magnitude, respectively. The highest soil PAH contamination was observed in the e-waste dismantling park. Nap can be considered as characteristic pollutant in the petrochemical industrial park, while Phe in the flame retardant manufacturing park and e-waste dismantling park. Low molecular weight PAHs (2–3 rings) predominated in the petrochemical industrial park (73.0%) and the surrounding area of brominated flame retardant manufacturing park (80.3%). However, high molecular weight PAHs (4–6 rings) were enriched in the other sampling sites, indicating distinct sources and determinants of soil PAHs. Source apportionment results suggested that PAHs in the parks were mainly derived from the leakage of petroleum products in the petroleum manufacturing process and pyrolysis or combustion of fossil fuels. Contrarily, the PAHs in the surrounding areas could have been derived from the historical coal combustion and traffic emissions. Source emissions, wind direction, and local topography influenced the PAH spatial distributions.

1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane (DBE-DBCH) is a brominated flame retardant used in commercial and industrial applications. The use of DBE-DBCH containing products has resulted in an increased release into the environment. However, limited information is available on the long-term effects of DBE-DBCH and its effects in aquatic invertebrates. Thus, the present study was aimed at determining how DBE-DBCH diastereomers (αβ and γδ) affects aquatic invertebrates using Daphnia magna as a model organism. Survival, reproduction, feeding, swimming behavior and toxicogenomic responses to environmental relevant concentrations of DBE-DBCH were analyzed. Chronic exposure to DBE-DBCH resulted in decreased lifespan, and reduced fecundity. Expression of genes involved in reproductive processes, vtg1 and jhe, were also inhibited. DBE-DBCH also induced hypoxia by inhibiting the transcription of genes involved in heme biosynthesis and oxygen transport. Furthermore, DBE-DBCH also inhibited feeding resulting in emptiness of the alimentary canal. Increased expression of the stress response biomarkers was observed following DBE-DBCH exposure. In addition, DBE-DBCH diastereomers also altered the swimming behavior of Daphnia magna. The present study demonstrates that DBE-DBCH cause multiple deleterious effects on Daphnia magna, including effects on reproduction and hormonal systems. These endocrine disrupting effects are in agreement with effects observed on vertebrates. Furthermore, as is the case in vertebrates, DBE-DBCH γδ exerted stronger effects than DBE-DBCH αβ on Daphnia magna. This indicate that DBE-DBCH γδ has properties making it more toxic to all so far studied animals than DBE-DBCH αβ.

As an emerging brominated flame retardant (BFR), tetrabromobisphenol S (TBBPS) has been frequently detected in the environmental media and organisms. Knowledges on the transformation and fate of TBBPS in both environment and engineering systems are essential to its ecological risk assessment. Herein, we reported the photochemical decomposition of TBBPS in aqueous solution upon 254 nm ultraviolet irradiation (UV₂₅₄). Results show that TBBPS was highly photoreactive, most likely due to the presence of four ortho-bromine substituents. The molar absorption coefficient and quantum yield of TBBPS were found to be pH-dependent, with the monoanionic form being most photoreactive. A series of photoproducts were identified by solid phase extraction (SPE) combined with liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI(+)-MS/MS. The photolysis of TBBPS likely proceeded through photonucleophilic substitution, photoreductive debromination, and β-scission reactions. A ketocarbene, possibly derived from the lower lying excited triplet state, was proposed to be involved in the photolysis of TBBPS. Ion chromatography analysis revealed that debromination occurred quickly, and the yield of bromide (Br⁻) approached 100% after 90 min irradiation. The presence of SRNOM and MRNOM inhibited the photodegradation rate of TBBPS, which is likely due to the light-screening and physical quenching effects of natural organic matter (NOM). Our results reveal that photolysis is an important process for the attenuation of TBBPS in aquatic system; however, naturally occurring species such as NOM can appreciably retard the decay of TBBPS.

As a novel brominated flame retardant (NBFR), decabromodiphenyl ethane (DBDPE) has been poorly understood for the environmental fate and toxicity in terrestrial invertebrates. For the first time, the bioaccumulation, elimination, metabolism and detoxification of DBDPE in earthworms as well as its potential impacts on soil microbes were investigated. The results showed much higher DBDPE concentrations in casts than in earthworms. The bioaccumulation factor (BAF) and elimination rate constant (kₑ) values were 0.028–0.213 (gdw, worm/gdw, soil) and 0.323–0.452 (day⁻¹), respectively. The detoxifying enzymes (CYP450 and GST) could be induced by DBDPE within the range of exposure dosage, and the activities were significantly increased at 21 d (p < 0.05). The results were identified by GC-ECNI-MS, and it showed that at least eleven unknown peaks were separately observed in the earthworms, which were the biotransformation products of DBDPE in earthworms. Additionally, the damages, including skin shrinkage, setae impairment, and intercellular vacuolization, were clearly observed by SEM/TEM. Based on these data, DBDPE could accumulate in earthworms, yet, with low bioaccumulation ability. Moreover, DBDPE exposure resulted in minimal harmful impacts on microbial activities including microbial biomass C (MBC), Microbial basal respiration (MBR), Urease (US) activity and fluorescein diacetate hydrolase (FDA) activity (p < 0.05). Our findings would provide some essential information for interpreting the ecological risks of DBDPE in soil.

Halogenated flame retardants (HFRs) are ubiquitous in the environment, but little information is available about the bioaccumulation of HFRs in mangrove plants. In this study, three mangrove plant species were collected from Futian National Nature Reserve of Shenzhen City, South China to investigate the bioaccumulation of polybrominated diphenyl ethers (PBDEs) and several alternative halogenated flame retardants (AHFRs), including decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HBB), pentabromotoluene (PBT), tetrabromop-xylene (pTBX), pentabromoethylbenzene (PBEB) and dechlorane plus (DP). The mean concentrations of PBDEs, DBDPE, BTBPE, pTBX, PBT, PBEB, HBB and DP in mangrove plant species were 2010, 1870, 36.2, 18.7, 40.1, 17.8, 9.68 and 120 pg g⁻¹ dry weight, respectively. PBDEs were the dominant HFRs in mangrove plant tissues, followed by DBDPE. The relative abundance of BDE 209 in three mangrove plant tissues were much lower than those in sediments. Significant negative relationships between log root bioaccumulation factors and log Kₒw, and between log TFᵣ₋ₛ (from root to stem) and log Kₒw were observed, indicating that HFRs with low hydrophobicity were easily absorbed by mangrove roots and stems. A positive correlation between log TFₛ₋ₗ (from stem to leaf) and log Kₒw were found, suggesting that air-leaf exchange may occur in mangrove plants. This study highlights the uptake of HFRs by mangrove plants, which can be used as remediation for HFRs contamination in the environment.

A substantial increase in the usage of organophosphate esters (OPEs) as flame retardants and plasticizers in rubbers, textiles, upholstered furniture, lacquers, plastics, building materials and electronic equipment has resulted in their increasing concentrations in the environment over time. However, little is known about the concentrations and fate of OPEs and their metabolites (mOPEs) in biota, including chicken eggs. The aim of this study was to understand the spatial variation in the concentrations in chicken eggs and the partitioning between yolk and albumin. In total, 153 chicken eggs were purchased across Australia and analysed for 9 OPEs and 11 mOPE. Most of the compounds were found to be deposited in egg yolk, where diphenyl phosphate (DPHP, 3.8 ng/g wet weight, median) and tris(2-chloroisopropyl) phosphate (TCIPP, 1.8 ng/g wet weight, median) were predominant mOPE and OPE, respectively. Moreover, no spatial differences in concentrations of OPEs and mOPEs in eggs purchased from different locations were found in this study. Although comparable levels of ∑OPEs were detected in egg yolk and albumin, much higher concentrations of ∑mOPEs were found in yolk than albumin. Meanwhile, a negative correlation (R² = 0.964, p = 0.018) was found between the molecular mass of analytes and partitioning coefficient of Cyₒₗₖ/Cyₒₗₖ₊ₐₗbᵤₘᵢₙ (defined as chemical concentration in egg yolk divided by the sum of chemical concentrations in both yolk and albumin). These results indicate that n-octanol/water partition coefficients (log KOW) may not be a crucial factor in the distribution of OPEs and mOPEs between egg yolk and albumin, which is important in understanding distribution of emerging organic contaminants in biota.

Endocrine-disrupting chemicals (EDCs) are compounds that interfere with the expression, synthesis, and activity of hormones in organisms. They are released into the environment from flame retardants and products containing plasticizers. Persistent pesticides, such as dichlorodiphenyltrichloroethane (DDT) and hexachlorobenzene, also disrupt the endocrine system through interaction with hormone receptors. Endogenous hormones, such as 17β-estradiol (E2), are released in the urine and feces of farm animals and seep into terrestrial and aquatic ecosystems through sewage. Pigs are widely used as animal models to determine the effects of EDCs because they are physiologically, biochemically, and histologically similar to humans. EDCs primarily disrupt the reproductive and nervous systems of pigs. Moreover, embryonic development during the prenatal and early postnatal periods is particularly sensitive to EDCs. Mycotoxins, such as zearalenone, are food contaminants that alter hormonal activities in pigs. Mycotoxins also alter the innate immune system in pigs, making them vulnerable to diseases. It has been reported that farm animals are exposed to various types of EDCs, which accumulate in tissues, such as those of gonads, livers, and intestines. There is a lack of an integrated understanding of the impact of EDCs on porcine reproduction and development. Thus, this article aims to provide a comprehensive review of literature regarding the effects of EDCs in pigs.

Passive samplers are useful tools for monitoring hydrophobic, persistent, and potentially bioaccumulative contaminants in the environment. In this study, low density polyethylene passive samplers were deployed in urban-influenced and background nearshore freshwaters of northwestern Lake Ontario and analyzed for a broad range of both legacy halogenated organic contaminants (HOCs) and halogenated flame retardants (HFRs). Non-targeted analysis was conducted for screening additional halogenated substances. For most compounds, concentrations were greatest in the industrialized Hamilton Harbour and more generally at sites that have stronger influences of wastewater effluent discharges and stormwater run-off through rivers and creeks. Polychlorinated biphenyls (PCBs) remain the dominant class of HOCs in water, with dissolved-phase concentrations ranging from 10 to 4100 pg/L (ΣPCBs), followed by polybrominated diphenylethers (ΣPBDEs; 14–960 pg/L) and the organochlorine pesticides (OCPs; 22–290 pg/L). Several non-PBDE brominated flame retardants (nBFRs) and chlorinated Dechlorane-related compounds were detected, with hexabromocyclododecanes (ΣHBCDD; sum of 3 diastereoisomers) the most abundant (1.0–21 pg/L). Non-targeted screening of samples by high resolution mass spectrometry using Kendrick mass defect plots for data analysis indicated that several other halogenated compounds were present in waters at relatively high abundances compared to the flame retardants, based on semi-quantitative estimates. These included methyl-triclosan, four halogenated anisoles (2,4,6-tribromoanisole, dimethyl-trichloroanisole, pentachloroanisole, and pentachlorothioanisole), and pentachloro-aniline. Dissolved-phase methyl-triclosan was estimated to contribute up to approximately 40% of the summed target HOC concentrations. Polyethylene passive samplers provided an excellent medium for both non-targeted screening of HOCs not currently included in monitoring programs and tracking brominated and chlorinated chemicals slated for reductions in uses and emissions through international (Stockholm Convention) and binational (Great Lakes) agreements.

Assessing the fate of both legacy and newer persistent organic pollutants (POPs) is an ongoing challenge. Top predators, including seabirds, are effective monitors of POPs because they forage over a range of marine habitats, integrating signals over space and time. However, migration patterns can make unravelling contaminant sources, and potentially assessments of the effectiveness of regulations, challenging if chemicals are acquired at distant sites. In 2014, we fitted geolocators on ancient murrelets (Synthliboramphus antiqueus) at four colonies on the Pacific Coast of Canada to obtain movement data throughout an annual cycle. All birds underwent a post-breeding moult in the Bering Sea. Around one-third then returned to overwinter on the British Columbia (BC) coast while the rest migrated to overwinter in waters along the north Asian coast. Such a stark difference in migration destination provided an opportunity to examine the influence of wintering location on contaminant signals. In summer 2015, we collected blood samples from returned geo-tagged birds and analyzed them for a suite of contaminants, including polybrominated diphenyl ethers (PBDEs), non-PBDE halogenated flame retardants, perfluoroalkyl substances (PFASs), organochlorines, and mercury. Feathers were also collected and analyzed for stable isotopes (δ¹³C, δ¹⁵N, and δ³⁴S). We found no significant differences in blood concentrations of any contaminant between murrelets from the two different overwinter areas, a result that indicates relatively rapid clearance of POPs accumulated during winter. Spatial variation in diet (i.e., δ¹³C) was associated with both BDE-47 and -99 concentrations. However, individual variation in trophic level had little influence on concentrations of any other examined contaminants. Thus, blood from these murrelets is a good indicator of recent, local contaminants, as most signals appear independent of overwintering location.

Food products are inevitably contaminated by flame retardants throughout their lifecycle (i.e., during production, use, and disposal). In order to evaluate the dietary intake of legacy and emerging halogenated flame retardants (HFRs) in typical market food in China, we investigate the distribution and profile of 27 legacy polybrominated diphenyl ethers (PBDEs) and 16 emerging HFRs (EHFRs) in 9 food categories (meat, poultry, aquatic food, eggs, dairy products, cereals, vegetables, nuts and fruits, and sugar). A total of 105 food samples collected from three markets in Nanjing, eastern China were included for evaluation. The highest concentrations of PBDEs and EHFRs were found in aquatic foods (means of 0.834 ng/g wet weight (ww) and 0.348 ng/g ww, respectively), and the lowest concentrations were found in sugar (means of 0.020 ng/g ww for PBDEs and 0.014 ng/g ww for EHFRs). 2,2′,4-tribromodiphenyl ether (BDE-17), a legacy HFR, and hexabromobenzene (HBBz), an EHFR, were the predominant pollutants in the investigated food samples. Concentrations of HBBz and 2,3-dibromopropyl tribromophenyl ether (DPTE) were comparable to those of some PBDEs in certain food samples. The concentrations of the total EHFRs and total PBDEs found in animal-based food samples were significantly greater than those in plant-based food samples. Comparison of the estimated total dietary intake of HFRs and their corresponding non-cancer reference dose (United States Environmental Protection Agency) suggests a low overall health risk. To the best of our knowledge, the present study is the first to simultaneously determine 27 PBDEs and 16 EHFRs in representative foods from Chinese markets. BDE-17, HBBz, and DPTE were the predominant congeners among the 43 investigated HFRs and meat and aquatic foods were the primary sources of PBDEs and EHFRs to the total local dietary intake.