Halogenated Flame Retardants Research Articles

Synergistic flame retardant effect of carbon nanohorns and ammonium polyphosphate as a novel flame retardant system for cotton fabrics

The development of environmentally friendly flame retardants that can achieve high efficiency for textiles at low addition levels is of great significance to human life and environmental protection. Halogen flame retardants have long dominated in flame retardant applications. However, there are increasing calls to ban its use because of the threat they pose to human health and the environment. Herein, this work investigated the potential of a novel carbonaceous nanomaterials-single-walled carbon nanohorns (SWCNHs) coating material for flame retardancy of cotton fabrics. The unique combination of SWCNHs and ammonium polyphosphate (APP) in a single halogen-free nanocoating has a synergistic effect, which endows cotton fabric with prominent fire resistance. When the addition amount of SWCNHs was 0.15 %, the limit oxygen index (LOI) could reach 27.5 ± 0.83 %, and the damage length decreased from 30 ± 0.01 % cm to 6.5 ± 0.06 % cm. SEM results showed that Cotton-APP/SWCNHs (0.15) still displayed well-preserved woven structure after the vertical flammability test. Additionally, the pHRR and THR of Cotton-APP/SWCNHs (0.15) were markedly decreased by 92.22 % and 58.44 %, respectively in the cone calorimeter test. Meanwhile, the flame retardant mechanism analysis confirmed that the incorporation of SWCNHs into the APP coatings promoted the formation of dense and stable graphitized carbon layer on the surface of the cotton fabric, and effectively prevented the generation of combustible volatiles, thus enhancing the flame retardant performance of cotton fabrics. This work provides a new insight into developing carbon nanomaterials for flame retardant polymeric materials and extending the application of SWCNHs.

Comprehensive characterization of halogenated flame retardants and organophosphate esters in settled dust from informal e-waste and end-of-life vehicle processing sites in Vietnam: Occurrence, source estimation, and risk assessment

Information about the co-occurrence of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) in the environment of informal waste processing areas is still limited, especially in emerging and developing countries. In this study, OPEs and HFRs including polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and chlorinated flame retardants (CFRs) were determined in settled dust from Vietnamese e-waste recycling (WR) and vehicle processing (VP) workshops. Pollutant concentrations decreased in the order: OPEs (median 1500; range 230–410,000 ng/g) ≈ PBDEs (1200; 58–250,000) > NBFRs (140; not detected – 250,000) > CFRs (13; 0.39–2200). HFR and OPE levels in the WR workshops for e-waste and obsolete plastic were significantly higher than in the VP workshops. Decabromodiphenyl ether and decabromodiphenyl ethane are major HFRs, accounting for 60 ± 26% and 25 ± 29% of total HFRs, respectively. Triphenyl phosphate, tris(2-chloroisopropyl) phosphate, and tris(1,3-dichloroisopropyl) phosphate dominated the OPE profiles, accounting for 30 ± 25%, 25 ± 16%, and 24 ± 18% of total OPEs, respectively. The OPE profiles differed between WR and VP dust samples, implying different usage patterns of these substances in polymer materials for electric/electronic appliance and automotive industries. Human health risk related to dust-bound HFRs and OPEs in the study areas was low.

Halogenated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and preliminary assessment of temporal trends

Halogenated flame retardants (HFRs) were measured in 470 waste plastic articles from Ireland between 2019 and 2020. We identified articles containing concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and tetrabromobisphenol-A (TBBP-A) exceeding European Union limits. Enforcement of existing limits of 1000 mg/kg will render an estimated 3.1% (2800 t) of articles in the waste categories studied unrecyclable, increasing to: 4.0, 4.9, and 5.6% if limits were reduced to 500, 200, and 100 mg/kg respectively. Meanwhile, enforcing limits of 1,000, 500, 200, and 100 mg/kg will respectively remove 78, 82, 84, and 85% of PBDEs, HBCDD, and TBBP-A present in such waste. Other FRs targeted were detected infrequently and predominantly at very low concentrations. However, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was detected in 3 display/IT product samples at 14,000 to 32,000 mg/kg, indicating elevated concentrations of FRs used as alternatives to PBDEs and HBCDD, will likely increase in future. Comparison with data for Ireland in 2015–16, revealed concentrations and exceedances of limits for PBDEs, HBCDD, and TBBP-A were similar or have declined. For end-of-life vehicle fabrics and foams, HBCDD and ΣPBDE concentrations declined significantly (p < 0.05) since 2015–16. Moreover, ΣPBDE concentrations in waste small domestic appliances are significantly lower in 2019–20, with a similarly significant decline for TBBP-A in waste IT and telecommunications articles. In contrast, HBCDD concentrations in waste extruded polystyrene increased significantly between 2015–16 and 2019–20. For other waste categories studied, no statistically significant temporal trends are evident (p > 0.05). Fewer samples exceeded PBDE and HBCDD limits in 2019–20 (7.8%) than 2015–16 (8.7%), while exceedances for TBBP-A fell from 2.4% in 2015–16 to 0.57% in 2019–20. While comparison between the 2015–16 and 2019-20 datasets provide a preliminary indication of changes, further monitoring is required if the impact of legislation designed to eliminate HFRs from the waste stream is to be fully evaluated.

Environmentally relevant exposure to TBBPA and its analogues may not drastically affect human early cardiac development

Tetrabromobisphenol A (TBBPA) and its substitutes and derivatives have been widely used as halogenated flame retardants (HFRs), in the past few decades. As a consequence, these compounds are frequently detected in the environment, as well as human bodily fluids, especially umbilical cord blood and breast milk. This has raised awareness of their potential risks to fetuses and infants. In this study, we employed human embryonic stem cell differentiation models to assess the potential developmental toxicity of six TBBPA-like compounds, at human relevant nanomolar concentrations. To mimic early embryonic development, we utilized embryoid body-based 3D differentiation in presence of the six HFRs. Transcriptomics data showed that HFR exposure over 16 days of differentiation only interfered with the expression of a few genes, indicating those six HFRs may not have specific tissue/organ targets during embryonic development. Nevertheless, further analyses revealed that some cardiac-related genes were dysregulated. Since the heart is also the first organ to develop, we employed a cardiac differentiation model to analyze the six HFRs’ potential developmental toxicity in more depth. Overall, HFRs of interest did not significantly disturb the canonical WNT pathway, which is an essential signal transduction pathway for cardiac development. In addition, the six HFRs showed only mild changes in gene expression levels for cardiomyocyte markers, such as NKX2.5, MYH7, and MYL4, as well as a significant down-regulation of some but not all the epicardial and smooth muscle cell markers selected. Taken together, our results show that the six studied HFRs, at human relevant concentrations, may impose negligible effects on embryogenesis and heart development. Nevertheless, higher exposure doses might affect the early stages of heart development.

Developmental toxicity of TCBPA on the nervous and cardiovascular systems of zebrafish (Danio rerio): A combination of transcriptomic and metabolomics

Tetrachlorobisphenol A (TCBPA), a widely used halogenated flame retardant, is frequently detected in environmental compartments and human samples. However, unknown developmental toxicity and mechanisms limit the entire understanding of its effects. In this study, zebrafish (Danio rerio) embryos were exposed to various concentrations of TCBPA while a combination of transcriptomics, behavioral and biochemical analyzes as well as metabolomics were applied to decipher its toxic effects and the potential mechanisms. We found that TCBPA could interfere with nervous and cardiovascular development through focal adhesion and extracellular matrix-receptor (ECM-receptor) interaction pathways through transcriptomic analysis. Behavioral and biochemical analysis results indicated abnormal swimming behavior of zebrafish larvae. Morphological observations revealed that TCBPA could cause the loss of head blood vessels. Metabolomic analysis showed that arginine-related metabolic pathways were one of the main pathways leading to TCBPA developmental toxicity. Our study demonstrated that by using omics, TCBPA was shown to have neurological and cardiovascular developmental toxicity and the underlying mechanisms were uncovered and major pathways identified.

Temporal Trends of Alternative Halogenated Flame Retardants in Humpback Dolphins from the South China Sea.

Increasing human activities are altering marine ecosystems, which may have ramifications for predator feeding ecology and, thus, the degree of contaminant exposure. We conducted the first investigation of spatiotemporal trends for nine alternative halogenated flame retardants (AHFRs) and their relations with dietary variations in 128 humpback dolphins that were stranded along the northern South China Sea during 2003-2020. We detected the highest levels of seven major AHFRs in humpback dolphins compared with the results reported in cetaceans globally, indicating high AHFR contamination in coastal regions of South China. Dolphins that were stranded near urban regions generally contained higher AHFR concentrations than those that were stranded near rural areas, mirroring the environmental trends of AHFRs occurring in this area. Model-generated diet estimates suggested that humpback dolphins have reduced their consumption of high trophic-level prey in recent years, likely attributable to overfishing-induced prey decline in this region. After adjusting AHFR concentrations due to diet changes, the temporal trends of AHFR contamination in humpback dolphins were only slightly altered. Our results suggest that increasing discharges of AHFRs into the South China Sea during the 2000s and 2010s may have had a greater influence on AHFR trends in humpback dolphins than dietary shifts.

Historical record of legacy and alternative halogenated flame retardants in dated sediment from a highly industrialized saltwater lake in Korea

Legacy and alternative halogenated flame retardants (HFRs), such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and dechlorane plus (DP), were measured in dated sediments from a highly industrialized lake in Korea. All HFRs were detected in almost all of the sediment depth layers for more than 70 years, indicating a history of long-term contamination. Similar historical trends in PBDEs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and DP were observed in dated sediments, whereas decabromodiphenylethane (DBDPE), and 2-ethylhexyl-2,3,4,5-octabromo-1,3,3-trimethyl-1-phenylindane (OBIND) concentrations sharply increased since the 1990s. Moreover, the concentration ratios of DBDPE/BDE 209 increased from the early 1990s to the present. Our findings suggest that DBDPE and OBIND have been used as HFR alternatives. The historical record of the concentrations and profiles of legacy and alternative HFRs corresponded with industrial activities, consumption of FRs, and coastal development activities. Inventories of legacy and alternative HFRs were similar to those reported for highly industrialized regions around the globe.

Persistent organic pollutant exposures among Greenlandic adults in relation to lifestyle and diet: New data from the ACCEPT cohort

High concentrations of persistent organic pollutants (POPs) in blood of the Greenlandic population are well known. The exposure is mainly through traditional food intake, including marine mammals and seabirds.The present study aimed to follow up on POP concentrations (organochlorine pesticides, polychlorinated biphenyls, per- and polyfluoroalkyl substances, and halogenated flame retardants (HFRs)) and relations to lifestyle and diet of the mothers included in the Greenlandic ACCEPT cohort (3–5 years after inclusion in 2013–15) and to include the children's fathers. This new data collection in 2019–20 included blood samples for measurement of POP concentrations and lifestyle and food frequency questionnaires from 101 mothers and 76 fathers aged 24–55 years living in Nuuk, Sisimiut, and Ilulissat, Greenland.The mothers' intra-individual median percentage decrease in POP concentrations from inclusion to this follow-up (3–5 years later) was 16–58%, except for mirex (0% change). Median concentrations of POPs were 1.4–4.6 times higher in fathers than in mothers. The POPs differed by residential town with generally higher concentrations in Ilulissat compared to Sisimiut and Nuuk. We report, for the first time, novel HFRs in human samples from Greenland. However, concentrations were low and only dechlorane plus (with its anti-isomer) was detected in >50% of the samples.Most POPs correlated positively with age and n-3/n-6 fatty acid ratio. The lipophilic POPs correlated positively with the percentage of life lived in Greenland, whereas few POPs correlated positively with BMI, income (personal and household), education, and alcohol intake.The POPs generally associated positively with the intake of marine mammals, seabirds, and dried fish, while few POPs associated positively with Greenlandic fish intake. In contrast, POPs generally associated negatively with imported meat products intake.The study findings may be of interest for future dietary recommendations in Greenland. We discuss the potential explanations for the findings and suggestions for future research.

Mass Spectrometric Identification of Pollutants in the Environment: A Personal and Bibliometric Perspective.

The nontarget identification of unsuspected organic pollutants in the environment is a topic of current interest, but it is not a new idea. Our laboratory has been engaged in this work for 50 years, and thus, it is timely to ask if our nontarget identifications of pollutants have mattered? The tool used to answer this question is the citation chronologies of several sets of nontarget identification papers we have published. Our papers on polycyclic aromatic hydrocarbons (1800 citations since 1972) and on halogenated flame retardants in the Great Lakes (800 citations since 2005) have clearly led to further work on the environmental sources and fates of these compounds. On the other hand, our papers on trifluoromethyl chlorobenzene derivatives in the Niagara River (170 citations since 1982) and on several alkyl phenols in the Detroit River (90 citations since 1991) have not led to further work. The attention that our identifications of polycyclic aromatic hydrocarbons and unusual flame retardants received was probably due to the known toxicity and environmental persistence of some of these compounds. On the other hand, our identifications of some compounds in the Niagara and Detroit Rivers may have been too site specific to attract much attention. We suggest that simply publishing lists of newly identified compounds in the environment, even if they have been well-characterized, is not necessarily enough. Readers need a reason to focus on a particular result; probably, the most significant reasons for such attention are a compound's toxicity and environmental persistence.

Low-level alternative halogenated flame retardants (AHFRs) in indoor dust from Adelaide, South Australia decades since national legislative control on polybrominated diphenyl ethers (PBDEs)

Since commercial polybrominated diphenyl ethers (PBDEs) have been globally banned or restricted in 2000s, alternative halogenated flame retardants (AHFRs) appear increasingly dominant over PBDEs in many countries/regions. In this study, low levels of AHFRs were unexpectedly observed in the indoor dust from Adelaide, South Australia. Anti-dechlorane plus (anti-DP) was the most frequently detected AHFR with a median concentration of 1.28 ng/g, while other AFHRs were less detected (detection frequency < 50%). The levels of ΣPBDEs (496 ng/g, median) and ΣAHFRs (160 ng/g) and the ratio of ΣAHFRs/ΣPBDEs (0.32) were much lower than those investigated in Australian indoor dust previously. The findings were different to the trend for PBDEs and AHFRs from other countries over the past two decades. No significant correlation was determined between DP and PBDE congeners, indicating their different sources in dust. The human exposure assessment suggested that dust ingestion was the predominant pathway of PBDEs and AHFRs exposure for toddlers, while dermal absorption may be the dominant pathway for adults. The estimated daily intake (EDI) suggested low health risks via dust ingestion and dermal contact for general populations in Adelaide. This study contributes to the knowledge on region-specific FR contamination in indoor environments and related human exposure risk.

Habitat-dependent trophic transfer of legacy and emerging halogenated flame retardants in estuarine and coastal food webs near a source region

With the phase-out of legacy halogenated flame retardants (HFRs), such as decabromodiphenyl ether (BDE-209), emerging ones, such as decabromodiphenyl ethane (DBDPE), are being widely produced. We conducted field campaigns to assess the trophic transfer of legacy and emerging HFRs in estuarine and coastal food webs of Laizhou Bay, which are located near the largest HFR manufacturing base in China. Seawater, sediment, plankton, invertebrates, and fish were collected from both sites. BDE-209 was the predominant compound in the estuary, whereas DBDPE was the main contributor to HFRs in the bay, followed by BDE-209. Invertebrates, especially bivalves and sea cucumbers, showed higher levels of BDE-209 and DBDPE than fish. The HFR levels in the organisms of the two coastal zones were comparable to each other, although their concentrations in the estuarine water were one order of magnitude higher than those in the bay. The HFR profiles in benthic organisms were similar to those in the sediments, indicating that the bioaccumulation of HFRs in coastal food webs depended on the habitat. The ΣHFR concentrations followed the order filter-feeding > carnivorous for invertebrates, and demersal non-migratory fish showed higher HFR levels than oceanodromous fish. The trophic magnification factors estimated for BDE-209, dechlorane plus, and DBDPE were lower than 1, suggesting biodilution potential in both food webs, whereas several PBDE congeners exhibited biomagnification capacity. Feeding habits, habitats, hydrophobicity, bioavailability, and metabolism may be the main factors impacting the bioaccumulation of HFRs in organisms in estuarine–coastal ecosystems of northern China.

Exposure of e-waste dismantlers from a formal recycling facility in Spain to inhalable organophosphate and halogenated flame retardants

Concentration levels of 16 organophosphate esters (OPEs) and 18 halogenated flame retardants (HFRs) were measured in airborne fine particulate matter (PM2.5) from an e-waste dismantling facility in Catalonia (Spain) to assess their occurrence, profiles and potential health risks. Three different areas from the facility were studied, including an area for cathodic ray-tube (CRT) TV dismantling, a grinding area, and the outdoor background. OPEs and HFRs were detected in all samples, with concentrations between 10.4 and 110 ng/m3 for OPEs and from 0.72 to 2213 ng/m3 for HFRs. The compounds with highest concentrations in both working areas were triphenyl phosphate (TPHP) and tris(2-chloroisopropyl) phosphate (TCIPP) for OPEs and decabromodiphenyl ether (BDE-209) for HFRs. Higher concentration levels were found in the CRT area compared to the grinding one, probably due to the lower ventilation and different types of e-waste being processed. OPEs were also detected in the solid e-waste from the facility, highlighting the need to evaluate pollutant levels in e-waste before proceeding to its re-use. Estimated daily intakes via inhalation during workday were calculated, as well as carcinogenic and non-carcinogenic health risks, these being 25 and 50 times lower than threshold risk values in the worst cases, respectively. However, this calculated risk only considers the workday exposure via inhalation, while other routes of exposure (e.g., ingestion, dermal) could bring these values closer to threshold values.

Industrial Production of Organophosphate Flame Retardants (OPFRs): Big Knowledge Gaps Need to Be Filled?

Since the phase-out of traditional halogenated flame retardants (HFRs), interests of research are gradually being shifted to organophosphate flame retardants (OPFRs), and this can be reflected by the increasing number of publications on OPFRs year by year. Here, an extensive survey is conducted in an attempt to generate a list of OPFRs that are being produced in factories, and to investigate the annual production volume (APV). This survey suggests that at least n = 56 OPFR monomers and n = 62 OPFR mixtures are being currently produced in 367 factories around the world, and 201 out of them are in Mainland China. APV of OPFRs was estimated as 598,422 metric tons, and this number could be underestimated due to the limitation of available information. We also notice that current researches are confined to a limited number of OPFRs, especially for OP esters (OPEs), and other OPFRs with different structures from OPEs has been rarely studied. Based on all the collected datasets, we provide five recommendations for how to proceed with future research to more comprehensively understand the currently-produced OPFRs in the environment.

Oxygen vacancies enriched Bi2WO6 for enhanced decabromodiphenyl ether photodegradation via C-Br bond activation

CBr bond activation is a critical step in the degradation of organic halogenated pollutants. Herein, by introducing oxygen vacancies with different concentration gradients into Bi2WO6, the CBr bond in decabromodiphenyl ether (BDE209) is activated, so that BDE209 is successfully dehalogenated under visible light. The study shows that the degradation rate of BDE209 on Bi2WO6 is determined by both interface defects and crystallinity. Good crystallinity is conducive to the generation and separation of photogenerated electrons and holes, and an appropriate defect concentration can promote the C-Br activation of BDE209. In addition, through the tracking analysis of the degradation products of BDE209, the content of the meta-debromination products of BDE209 on Bi2WO6 is significantly higher than that of the ortho- and para-debromination products, indicating that the reduction reaction is a position selective multi-electron mechanism. The study shows that oxygen vacancy assisted debromination is an excellent strategy for photocatalytic treatment of halogenated flame retardant pollutants.

Halogenated Flame Retardants in Irish Waste Polymers: Concentrations, Legislative Compliance, and Temporal Trends

Halogenated Flame Retardants in Irish Waste Polymers: Concentrations, Legislative Compliance, and Temporal Trends

Elevated Concentrations of Halogenated Flame Retardants in Waste Childcare Articles from Ireland

Elevated Concentrations of Halogenated Flame Retardants in Waste Childcare Articles from Ireland

Occurrence and Health Risks of Halogenated Flame Retardants in Soils: Association with E-Waste Dismantling, Urbanization and Industrialization

Occurrence and Health Risks of Halogenated Flame Retardants in Soils: Association with E-Waste Dismantling, Urbanization and Industrialization

Halogenated Flame Retardant Exposure Pathways in Urban-Adapted Gulls: Are Atmospheric Routes Underestimated?

Halogenated Flame Retardant Exposure Pathways in Urban-Adapted Gulls: Are Atmospheric Routes Underestimated?

Modification of Glass/Polyester Laminates with Flame Retardants.

This paper presents a review of flame retardants used for glass/polyester laminates. It concerns flame retardants withdrawn from use such as compounds containing halogen atoms and flame retardants currently used in the industry, such as inorganic hydroxides, phosphorus and nitrogen-containing compounds, antimony, and boron compounds, as well as tin–zinc compounds. Attention is also drawn to the use of nanoclays and the production of nanocomposites, intumescent flame retardant systems, and mats, as well as polyhedral oligomeric silsesquioxanes. The paper discusses the action mechanism of particular flame retardants and presents their advantages and disadvantages.

Phototransformation of tetrabromobisphenol A in saline water under simulated sunlight irradiation

The widespread use of halogenated flame retardants in recent years has led to the accumulation of TBBPA in water, which may cause potential harm to living organisms. The phototransformation of the flame retardant TBBPA in alkaline saline water under simulated sunlight irradiation was investigated. The effects of abiotic factors such as the initial concentration of TBBPA, chloride ion concentration, solution pH, inorganic anions and cations, dissolved organic matter (DOM) were studied. The results showed that the phototransformation rate of TBBPA accelerated with the decrease of the initial concentration of TBBPA, the increase of chloride ion concentration and solution pH. The scavenging experiments showed that •OH, 1O2, O2•- and 3TBBPA* all participated in the phototransformation of TBBPA. The presence of NO3−, CO32−, SO42−, Mg2+, Ca2+, Fe3+ and fulvic acid (FA) all inhibited the phototransformation of TBBPA in the present study. The phototransformation products of TBBPA were detected by liquid chromatography-mass spectrometry (LC-MS), and the phototransformation pathways were proposed. This is the first report on the photo-induced generation of halogen exchange products from TBBPA in saline solutions, which will contribute to a better understanding of the environmental behavior and risks of BFRs in water.