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Using high-resolution mass spectrometry, we identified tri(2,4-di-t-butylphenyl) phosphate (TDTBPP) in e-waste dust. This is a previously unsuspected pollutant that had not been reported before in the environment. To assess its abundance in the environment, we measured its concentration in e-waste dust, house dust, sediment from the Chicago Ship and Sanitary Canal, Indiana Harbor water filters, and filters from high-volume air samplers deployed in Chicago, IL. To provide a context for interpreting these quantitative results, we also measured the concentrations of triphenyl phosphate (TPhP), a structurally similar compound, in these samples. Median concentrations of TDTBPP and TPhP were 14 400 and 41 500 ng/g, respectively, in e-waste dust and 4900 and 2100 ng/g, respectively, in house dust. TDTBPP was detected in sediment, water, and air with median concentrations of 527 ng/g, 3700 pg/L, and 149 pg/m 3 , respectively. TDTBPP concentrations were generally higher or comparable to those of TPhP in all media analyzed, except for the e-waste dust. Exposure from dust ingestion and dermal absorption in the e-waste recycling facility and in homes was calculated. TDTBPP exposure was 571 ng/kg bw/day in the ewaste recycling facility (pro-rated for an 8-h shift), and 536 ng/kg bw and 7550 ng/kg bw/day for adults and toddlers, respectively, in residential environments.

For the first time, we present an analytical method to simultaneously extract, fractionate, and quantify four groups of semi-volatile organic compounds (SVOCs) in silicone wristbands, including 35 polybrominated diphenyl ethers (PBDEs), 10 novel flame retardants (NFRs), 19 organophosphate esters (OPEs), and 13 polycyclic aromatic hydrocarbons (PAHs). Wristbands were extracted using ultrasonication, and cleaned and fractionated on two multi-layer columns: one consisting of neutral alumina, neutral silica and Florisil, and the other consisting of neutral alumina, neutral silica, and acidic silica. Method accuracy and precision were validated using spiked wristband samples (n = 8) and procedural blanks (n = 7). Average matrix spike percent recoveries for all target analytes were within 57 -107% with relative standard errors < 20%, with a few exceptions. This method was applied to analyze thirteen wristbands worn by ten participants for seven days; three participants wore two wristbands to evaluate duplicate samples. Percent recoveries of surrogate standards for all four groups of analytes in these wristbands were all within the 80 -120% range with a few exceptions: recoveries for 13 C 12 BDE-209 and for 13 C 12 -triphenyl phosphate ranged from 35 -62% and 69 -176%, respectively. The majority of target analytes were detected in at least half of worn wristbands. The levels of total PBDEs, NFRs, OPEs and PAHs in deployed wristbands ranged from 28.4 to 412 ng, 40.7 to 625 ng, 2,440 to 9,580 ng, and 76.2 to 1,240 ng, respectively.We developed an efficient method for the determination of a total of 77 analytes, including 35 PBDEs, 10 NFRs, 19 OPEs, and 13 PAHs, in silicone wristbands. This method offers a solution to chromatographic interferences associated with siloxanes from the wristband Romanak et al. Highlights •Silicone wristbands are a novel tool for assessing personal exposures • This is the first method for simultaneous quantitative analysis of 77 SVOCs 35 PBDEs, 9 NFRs, 19 OPEs, and 13 PAHs were simultaneously extracted and analyzed Romanak et al. •

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Use of brominated flame retardants (BFRs) in soft furnishings has occurred for over thirty years with the phase out of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) only relatively recently begun. As products treated with BFRs reach the end of their lifecycle they enter the waste stream, thereby constituting an important and increasing reservoir of these chemicals. This review highlights the dearth of data on the extent and potential mechanisms of BFR emissions from waste soft furnishings. However, insights into what may occur are provided by scrutiny of the larger (though still incomplete) database related to BFR emissions from electronic waste (e-waste). In many countries, municipal landfills have historically been the primary disposal method of waste consumer products and therefore represent a substantial reservoir of BFRs. Published data for BFR emissions to both air and water from landfill and other waste disposal routes are collated, presented and reviewed. Reported concentrations of PBDEs in landfill leachate range considerably from <1ngL(-1) to 133,000ngΣPBDEL(-1). In addition to direct migration of BFRs from waste materials; there is evidence that some higher brominated flame retardants are able to undergo degradation and debromination during waste treatment, that in some instances may lead to the formation of more toxic and bioavailable compounds. We propose that waste soft furnishings be treated with the same concern as e-waste, given its potential as a reservoir and source of environmental contamination with BFRs.

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