Detection of bromochloro alkanes in indoor dust using a novel CP-Seeker data integration tool
Bromochloro alkanes (BCAs) have been manufactured for use as flame retardants for decades and preliminary environmental risk screening suggests they are likely to behave similarly to polychlorinated alkanes (PCAs), subclasses of which are restricted as Stockholm Convention Persistent Organic Pollutants (POPs). BCAs have rarely been studied in the environment, though some evidence suggests they may migrate from treated-consumer materials into indoor dust, resulting in human exposure via inadvertent ingestion. In this study, BCA-C14 mixture standards were synthesized and used to validate an analytical method. This method relies on chloride-enhanced liquid chromatography-electrospray ionization-Orbitrap-high resolution mass spectrometry (LC-ESI-Orbitrap-HRMS) and a novel CP-Seeker integration software package for homologue detection and integration. Dust sample preparation via ultrasonic extraction, acidified silica clean-up and fractionation on neutral silica cartridges was found to be suitable for BCAs, with absolute recovery of individual homologues averaging 66 to 78% and coefficients of variation $\le$10% in replicated spiking experiments (n=3). In addition, a total of 59 indoor dust samples from six countries including Australia (n=10), Belgium (n=10), Colombia (n=10), Japan (n=10), Thailand (n=10) and the United States of America (n=9) were analysed for BCAs. BCAs were detected in seven samples from the USA, with carbon chain lengths of C8, C10, C12, C14, C16, C18, C24 to C28, C30 and C31 observed overall, though not detected in samples from any other countries. Bromination of detected homologues in the indoor dust samples ranged from Br1-4 as well as Br7, while chlorine numbers ranged from Cl2-11. BCA-C18 were the most frequently detected, observed in each of the USA samples, while the most prevalent halogenation degrees were homologues of Br2 and Cl4-5. Broad estimations of BCA concentrations in the dust samples indicated that levels may approach those of other flame retardants in at least some instances. These findings suggest that development of quantification strategies and further investigation of environmental occurrence and health implications are needed.
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