Flame retardants are common additives contained in a wide variety of consumer and industrial products, either applied to objects after the event or formulated into the products as part of production. The presence and impact of these substances in the environment has been part of a global research effort for decades. In response to environmental and health concerns plus increasing regulatory changes, traditional Brominated Flame Retardants (BFRs) such as PBDEs are being replaced with other flame retardants. In addition, new classes of flame retardants are under study. Many of these substances have been found in wastewater effluents and wildlife.
Announcing Advances in Flame Retardant Analysis
To support the efforts of federal and state agencies, regulators, and wastewater treatment plants as they continue to explore the presence of flame retardants, AXYS has developed a multi-residue method for Chlorinated and Brominated Flame Retardants, and two new methods for 13 priority Organophosphorus Flame Retardants (OPFRs). These new methods, along with our traditional offerings in PBDEs, HBCD, and TBBPA, provide comprehensive support to those involved in the study of Flame Retardants. We are able to measure trace levels in the environment, defining background levels and assessing temporal and spatial changes to provide insights in a variety of studies focused on:
- Removal efficiencies of flame retardants in water, wastewater, and solid waste treatment systems
- Toxic effects of flame retardants in the environment
- Point sources of flame retardants in the environment
- Risk assessment and remediation of flame retardants in the environment
A recent published study using these methods to measure analytes in influent, effluent and biosolids from samples collected from a secondary wastewater treatment system showed OPFRs had the highest concentration of any flame retardant.
Quantitative determination of 13 organophosphorous flame retardants and plasticizers in a wastewater treatment system by high performance liquid chromatography tandem mass spectrometry (2015) Journal of Chromatography A. Woudneh, M.B., Benskin, J.P., Wang, G., Grace, R., Hamilton, M.C., Cosgrove, J.R.
Comprehensive Methods for Chlorinated and Brominated Flame Retardants. AXYS has launched the first set of commercial multi-residue methods to monitor currently used flame retardants. This offering makes it possible to analyze 26 compounds together in a single method, creating a cost-effective solution for POTW – WWTPs, pollution monitoring agencies, and academics. The target analytes include flame retardants such as dechlorane plus and related compounds, tribromophenoxy compounds such as; ATE, BATE, and BTBPE as well as monoaromatics such as; HBB, PBEB, and PBT, as well as cycloaliphatic flame retardants such as TBECH. The methods have been validated in influent, effluent and biosolid matrices and provide a comprehensive and robust platform to probe the occurrence of these currently used contaminants in the environment. AXYS’ new methods have successfully measured these contaminants in influent, effluent and biosolids samples collected from a secondary wastewater treatment system. The findings will be presented in the upcoming Society of Environmental Toxicology and Chemistry conference in Salt Lake City, USA, 1-5 November 2015.
Analytes of Interest
Chemical name Short name CAS# Triethyl phosphate TEP 78−40−0 Tris(2-chloroethyl) phosphate TCEP 115−96−8 Tripropyl phosphate TPrP 513−08−6 Tris(2-chloroisopropyl) phosphate TCPP* 13674−84−5 Tetrakis(2-chlorethyl)dichloroisopentyldiphosphate V6 38051−10−4 Tris(1,3-dichloro-2-propyl) phosphate TDCPP 13674−87−8 Triphenyl phosphate TPP 115−86−6 Tris(2,3-dibromopropyl) phosphate TDBPP 126−72−7 Tributyl phosphate TBP 126−73−8 Tris(2-butoxyethyl) phosphate TBEP 78−51−3 Tricresyl phosphate * TCrP * 1330−78−5 2-Ethylhexyl-diphenyl phosphate EHDPP 1241−94−7 Tris(2-ethylhexyl) phosphate TEHP 78−42−2
* Analyte represents mixed isomers.
Organophosphate flame retardants (OPFRs) constitute a newer class of flame retardants, which are replacing traditional brominated flame retardants (BFRs) in response to regulatory changes. The global consumption of OPFRs has increased sharply in recent years, and their diffuse exposure patterns have triggered federal and state agencies, regulators, and wastewater treatment plants to explore the possible environmental effects of these substances.
AXYS is the first commercial lab to provide validated methods to measure phosphate-based flame retardants, with two new recently developed methods for 13 priority OPFRs in aqueous and solid samples, including wastewater treatment system samples.
Hexabromocyclododecane (HBCD or HBCDD) is a type of polybrominated flame retardant (PBFR) used in expandable polystyrene foams in domestic and industrial building insulation, packaging of industrial products, and bean bag filling. HBCD has been identified as a potential concern to the environment based on information regarding possible persistence, bioaccumulation in organisms, and potential to cause harm to aquatic life. This classification of HBCD has lead to a screening assessment by the government of Canada.
AXYS measures the three primary isomers: α-HBCD, β-HBCD and γ-HBCD in aqueous, solid, tissue and blood samples using LC-MS/MS.
Tetrabrominated bisphenol A (TBBPA) is synthetic compound consisting of 4 bromine atoms substituted on a Bisphenol A ring structure. TBBPA and its derivatives are a group of flame retardants widely used in electronic components, including printed circuit boards. When used as additive flame retardants, TBBPA and/or its derivatives may leach from the products into the environment.
AXYS measures TBBPA in aqueous, solid, biosolid, tissue, and blood serum samples using LC-MS/MS.
Polybrominated diphenyl ethers (PBDEs) are a set of 209 compounds consisting of 1--10 bromine atoms substituted on a diphenyl ether backbone. PBDEs were used widely as flame retardants in a variety of consumer and industrial products including furniture, electronics, insulation and more. Most PBDE residues in the environment result from the use of three commercial formulations of varying bromination levels: Penta, Octa and Deca. PBDEs are mostly persistent, bioaccumulative, and ubiquitous in the environment.
AXYS uses HRMS to analyze PDBEs with required measurements usually in the pg/L range for water, and the pg/g range for soils, sediments, biosolids, tissue, and serum. PBDEs are ubiquitous and therefore great care is required to reduce laboratory background levels, especially for low-level measurement in tissues and serum. AXYS has measured PBDEs since 1995, and our work has resulted in the development of EPA Method 1614-Draft, the only published reference method for PBDE measurement in these matrices at these levels.
Supporting SFEI’s regional monitoring program for water quality
AXYS has provided analysis of PBDE flame retardants for the San Francisco bay regional monitoring program since 2002. Samples included high volume (>100L) aqueous samples collected on XAD-2 and filters, grab aqueous samples in stormwater and tributary work, sediments samples and monitoring of multiple trophic levels. High volume samples have been used to generate PBDE data in the dissolved and suspended phases of the water samples. Sentence here about passive sampling experiences in the project.
Supporting Environment Canada’s National study of landfill leachates
During the period 2009-2010 AXYS provided flame retardant analysis for PBDEs, HBCDD, and TBBPA flame retardants to support Environment Canada’s Chemical Management Program (CMP) for monitoring landfill leachates.
Supporting Environment Canada’s Detroit River Monitoring Program
Under contract to Environment Canada, AXYS provided analysis of PBDE flame retardants using high volume aqueous samples collected on XAD-2 resin and filter.
Supporting California’s Ambient PBDE Air Monitoring Program
Under contract to California Air Resources Board and to support California’s ambient air monitoring program, AXYS provided analysis for PBDE flame retardants using air samples collected on PUF-XAD-PUF media.