Flame Retardants

Enzymes, being remarkable catalysts, are capable of accepting a wide range of complex molecules as substrates and catalyze a variety of reactions with a high degree of chemo-, stereo- and regioselectivity in most of the reactions. Biocatalysis can be used in both simple and complex chemical transformations without the need for tedious protection and deprotection chemistry that is very common in traditional organic synthesis. This current review highlights the applicability of one class of biocatalysts viz.…

This review summarises current knowledge about production volumes, physico-chemical properties, analysis, environmental occurrence, fate and behaviour and human exposure to the "novel" brominated flame retardants (NBFRs). We define the term NBFRs as relating to BFRs which are new to the market or newly/recently observed in the environment. Restrictions and bans on the use of some polybrominated diphenyl ether (PBDE) formulations, in many jurisdictions, have created a market for the use of NBFRs. To date, most data on NBFRs have arisen as additional information generated by research designed principally to study more "traditional" BFRs, such as PBDEs. This has led to a wide variety of analytical approaches for sample extraction, extract purification and instrumental analysis of NBFRs. An overview of environmental occurrence in abiotic matrices, aquatic biota, terrestrial biota and birds is presented. Evidence concerning the metabolism and absorption of different NBFRs is reviewed. Human exposure to NBFRs via different exposure pathways is discussed, and research gaps related to analysis, environmental sources, fate, and behaviour and human exposure are identified.

Tetrabromobisphenol A (TBBPA) is a ubiquitous flame retardant. A high-throughput immunoassay would allow for monitoring of human and environmental exposures as a part of risk assessment. Naturally occurring antibodies in camelids that are devoid of light chain, show great promise as an efficient tool in monitoring environmental contaminants, but they have been rarely used for small molecules. An alpaca was immunized with a TBBPA hapten coupled to thyroglobulin and a variable domain of heavy chain antibody (VHH) T3-15 highly selective for TBBPA was isolated from a phage displayed VHH library using heterologous coating antigens. Compared to the VHHs isolated using homologous antigens, VHH T3-15 had about a 10-fold improvement in sensitivity in an immunoassay. This assay, under the optimized conditions of 10% methanol in the assay buffer (pH 7.4), had an IC50 for TBBPA of 0.40 ng mL(-1) and negligible cross reactivity (<0.1%) with other tested analogues. After heating the VHH at 90 ...

Many xenobiotic compounds with endocrine disrupting activity have been described since the late eighties. These compounds are able to interact with natural hormone systems and potentially induce deleterious effects in wildlife, notably piscine species. However, while the characterization of endocrine disruptors with "dioxin-like", estrogenic or androgenic activities is relatively well established, little is known about environmentally relevant pollutants that may act at thyroid system level. Iodothyronine deiodinases, the key enzymes in the activation and inactivation of thyroid hormones, have been suggested as suitable biomarkers for thyroid metabolism disruption. The present article reviews the biotic and abiotic factors that are able to modulate deiodinases in teleosts, a representative model organism for vertebrates. Data show that deiodinases are highly sensitive to several physiological and physical variables, so they should be taken into account to establish natural...

From 2011-2013, a large-scale ecotoxicological study was conducted in several Chesapeake Bay tributaries (Susquehanna River and flats, the Back, Baltimore Harbor/Patapsco River, Anacostia/ middle Potomac, Elizabeth and James Rivers), and Poplar Island as a mid-Bay reference site. Osprey (Pandion haliaetus) diet and the transfer of contaminants from fish to osprey eggs were evaluated. The most bioaccumulative compounds (biomagnification factor >5) included p,p'-DDE, total PCBs, total PBDEs, and BDE congeners 47, 99, 100 and 154. This analysis suggested that alternative-brominated flame-retardants and other compounds (methoxytriclosan) are not appreciably biomagnifying. A multivariate analysis of similarity indicated major differences in patterns among study sites were driven by PCB congeners 105, 128, 156, 170/190 and 189, and PBDE congeners 99 and 209. An integrative redundancy analysis showed that osprey eggs from Baltimore Harbor/Patapsco River and the Elizabeth Rivers had ...

Organophosphate esters (OPEs) are used as flame retardants, plasticizers, and as hydraulic fluids. They are present in indoor environments in high concentrations compared with other flame retardants, and human exposure is ubiquitous. In this study we provide data for estimating dermal uptake for eight OPEs and ranking in OPEs risk assessment. Dermal uptake and percutaneous penetration of the OPEs were studied in a Franz diffusion cell system using human skin dosed with a mixture of OPEs in an ethanol:toluene (4:1) solution. Large variation in penetration profiles was observed between the OPEs. The chlorinated OPEs tris(2-chloroisopropyl) phosphate (TCIPP), and in particular tris(2-chloroethyl) phosphate (TCEP), penetrated the skin quite rapidly while tris(1,3-dichlor-2-propyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) tended to build up in the skin tissue and only smaller amounts permeated through the skin. For tris(isobutyl) phosphate (TIBP), tris(n-butyl) phosphate (TNBP),...