Evaluation of the state-of-the-art measurement capabilities for selected PBDEs and decaBB in plastic by the international intercomparison CCQM-P114

Abstract

An international intercomparison involving eight national metrology institutes (NMIs) was conducted to establish their current measurement capabilities for determining five selected congeners from the brominated flame retardant classes polybrominated diphenyl ethers and polybrominated biphenyls. A candidate reference material consisting of polypropylene fortified with technical mixtures of penta-, octa- and decabromo diphenyl ether and decabromo biphenyl, which was thoroughly assessed for material homogeneity and stability, was used as study material. The analytical procedures applied by the participants differed with regard to sample pre-treatment, extraction, clean-up, employed calibrants and type of calibration procedure as well as regarding analytical methods used for separation, identification and quantification of the flame retardant congeners (gas chromatography coupled to an electron capture detector (GC-ECD), gas chromatography-mass spectrometry in the electron ionisation mode (GC-EI-MS), gas chromatography-mass spectrometry in the electron capture negative ionisation mode (GC-ECNI-MS), and liquid chromatography-inductive coupled plasma-mass spectrometry (LC-ICP-MS)). The laboratory means agreed well with relative standard deviations of the mean of means of 1.9%, 4.8%, 5.5% and 5.4% for brominated diphenyl ether (BDE) 47, 183 and 209 and for the brominated biphenyl (BB) congener 209, respectively. For BDE 206, a relative standard deviation of 28.5% was obtained. For all five congeners, within-laboratory relative standard deviations of six measurements obtained under intermediate precision conditions were between 1% and 10%, and reported expanded measurements uncertainties typically ranged from 4% to 10% (8% to 14% for BDE 206). Furthermore, the results are in good agreement with those obtained in the characterization exercise for determining certified values for the flame retardant congeners in the same material. The results demonstrate the state-of-the-art measurement capabilities of NMIs for quantifying representative BDE congeners and BB 209 in a polymer. The outcome of this intercomparison (pilot study) in conjunction with possible improvements for employing exclusively calibrants with thoroughly assessed purity suggests that a key comparison aiming at underpinning calibration and measurement capability (CMC) claims of NMIs can be conducted.

Atomic spectrometry update. Industrial analysis: metals, chemicals and advanced materials

“…A new batch of a soil CRM is under preparation (NIST-SRM-4355A, Peruvian soil) and has been certified by Inn and colleagues using mass spectrometry. 198 A value for the upper limit (95% confidence) of 239 Pu in this material has been assigned at 54000 atoms/g. This measurement was extremely challenging and required careful consideration of a variety of parameters such as blanks, blank correction, isobaric interferences, instrument stability etc.…”

“…Analytical agreement between the participants was reported to be good with results obtained using ID-MS showing particularly good precision. Another inter-laboratory comparison organised by CCQM (CCQM-P114) involved eight national 239 Pu, 240 Pu Soil AMS Soil core samples from Hubei Province in China were investigated for 239 Pu + 240 Pu total activity and 240 Pu/ 239 Pu. 239 Pu, 240 U/ 238 U isotope ratios.…”

“…Another inter-laboratory comparison organised by CCQM (CCQM-P114) involved eight national 239 Pu, 240 Pu Soil AMS Soil core samples from Hubei Province in China were investigated for 239 Pu + 240 Pu total activity and 240 Pu/ 239 Pu. 239 Pu, 240 U/ 238 U isotope ratios. 226 Ra Natural waters and sediment pore water MS; ICP; -Thin film diffusive gradient sampling using a MnO 2 resin used to accumulate 226 Ra.…”

Recent developments in the analysis of polybrominated diphenyl ethers and polybrominated biphenyls in plastic

“…Because they are not chemically bound to the polymer, they are prone to volatilize and/or leach out into the air or aquatic environment from landfill (Talsness 2008, Zeleny et al 2010. PBDEs and PBBs appear to be lipophilic and bioaccumulative in wildlife and human, which leads to adverse physiological effects (Covaci et al 2007).…”

Pulsed glow discharge time of flight mass spectrometry for the screening of polymer-based coatings containing brominated flame retardants

“…Several analytical methods have been used for the analysis of BFRs, including gas and liquid chromatography coupled to mass spectrometry. [6][7][8] However, those reported methods have some analytical limitations, such as complex pre-treatment processes and long analysis time. Moreover, accurate quantification of BFRs in plastics can only be achieved if several challenges in the analysis are successfully handled, such as suitable grinding or milling of the sample, selective analytes extraction, as well as problems related to photolytic degradability or thermal instability.…”