Improving the accuracy of hand-held X-ray fluorescence spectrometers as a tool for monitoring brominated flame retardants in waste polymers

Guzzonato, A.; Puype, Franky; Harrad, Stuart

doi:10.1016/j.chemosphere.2016.05.086

Cited by 24 publications

(12 citation statements)

References 26 publications

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“…Here, we employ XRF spectrometry to determine total Br among a wider range of plastic consumer products as a proxy for evaluating the abundance and distribution of BFRs in the indoor setting. The approach has been validated by independent analytical methods and with customized, polymeric standards containing specific BFRs (Guzzonato et al, 2016), and is gaining increasing application in the WEEE recycling industry as a practical solution to accurately and rapidly monitor for material compliance with limit concentrations (Löw, 2014;Gallen et al, 2014;Aldrian et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

Bromine in plastic consumer products – Evidence for the widespread recycling of electronic waste

Turner

Filella

2017

Science of The Total Environment

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A range of plastic consumer products and components thereof have been analysed by x-ray fluorescence (XRF) spectrometry in a low density mode for Br as a surrogate for brominated flame retardant (BFR) content. Bromine was detected in about 42% of 267 analyses performed on electronic (and electrical) samples and 18% of 789 analyses performed on non-electronic samples, with respective concentrations ranging from 1.8 to 171,000μgg and 2.6 to 28,500μgg. Amongst the electronic items, the highest concentrations of Br were encountered in relatively small appliances, many of which predated 2005 (e.g. a fan heater, boiler thermostat and smoke detector, and various rechargers, light bulb collars and printed circuit boards), and usually in association with Sb, a component of antimony oxide flame retardant synergists, and Pb, a heavy metal additive and contaminant. Amongst the non-electronic samples, Br concentrations were highest in items of jewellery, a coffee stirrer, a child's puzzle, a picture frame, and various clothes hangers, Christmas decorations and thermos cup lids, and were often associated with the presence of Sb and Pb. These observations, coupled with the presence of Br at concentrations below those required for flame-retardancy in a wider range of electronic and non-electronic items, are consistent with the widespread recycling of electronic plastic waste. That most Br-contaminated items were black suggests the current and recent demand for black plastics in particular is met, at least partially, through this route. Given many Br-contaminated items would evade the attention of the end-user and recycler, their disposal by conventional municipal means affords a course of BFR entry into the environment and, for food-contact items, a means of exposure to humans.

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Section: Introductionmentioning

confidence: 99%

Bromine in plastic consumer products – Evidence for the widespread recycling of electronic waste

Turner

Filella

2017

Science of The Total Environment

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“…In the present study, such constraints are circumvented by undertaking PBETs on larger and controlled quantities of microplastics that have been prepared from primary and secondary macroplastics in order to assess the potential for hazardous element exposure to sea birds. The samples for study were retrieved from local beaches and selected on the basis of non-compliance according to the Restriction of Hazardous Substances Directive on electronic plastics (RoHS, 2006); that is, in an homogeneous material of any new or recycled product, concentration limits are 100 g g -1 for Cd, 1000 g g -1 for Cr(VI), Hg and Pb, and 1000 g g -1 for specific brominated flame retardants and where total Br is a commonly employed proxy (Guzzonato et al, 2016). Additional, potentially hazardous elements were also considered that are commonly co-associated with RoHS-elements and that have restrictions on migration from plastics according to the original European toy safety standard, EN 71-3:1994 (Cordeiro et al, 2012); namely: As, Ba, Se and Sb.…”

Section: Introductionmentioning

confidence: 99%

Mobilisation kinetics of hazardous elements in marine plastics subject to an avian physiologically-based extraction test

Turner

2018

Environmental Pollution

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Samples of plastic collected from two beaches in southwest England (n = 185) have been analysed by XRF spectrometry for elements that are hazardous or restricted in synthetic polymers (namely, As, Ba, Br, Cd, Cr, Hg, Pb, Sb and Se). Overall, one or more restricted element was detected in 151 samples, with 15 cases exhibiting non-compliance with respect to the Restriction of Hazardous Substances (RoHS) Directive. Twelve plastics that were RoHS-non-compliant were subsequently processed into microplastic-sized fragments and subjected to an avian physiologically-based extraction test (PBET) that simulates the chemical conditions in the gizzard-proventriculus of the northern fulmar. Kinetic profiles of metal and metalloid mobilisation in the PBET were fitted using a pseudo-first-order diffusion model with rate constants ranging from ∼0.02 to 0.5 h, while profiles for Br were better fitted with a parabolic diffusion model and rate constants of 7.4-9.5 (μg L)h. Bioaccessibilities, based on maximum or equilibrium concentrations mobilised relative to total (XRF) concentrations, ranged from <1% for Cd and Se in polyethylene and polypropylene to over 10% for Br in a sample of expanded polystyrene and Pb in a sample of PVC. Calculations suggest that ingested plastic could contribute about 6% and 30% of a seabird's exposure to and accumulation of Pb and brominated compounds, respectively.

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“…Moreover, as alluded to above, while screening tools like hand-held X-ray fluorescence may provide an acceptable measure of Br in polymers, they do not provide information on the chemical form of that Br, in particular whether the Br detected arises from a regulated BFR. [13][14][15] As Sb 2 O 3 is widely used as a co-additive with PBDEs added to flame retardancy 16 but is not used in conjunction with other regulated BFRs, we hypothesise that detection in a given sample of both Br and Sb provides a simple indicator of whether the Br detected arises from the presence of PBDEs. We measured the concentrations of Br, Sb and WEEE related rare earth elements (REEs) in down-stream items (new food-contact articles and toys) that are likely to contain recycled fractions coming from different upper-level waste streams.…”

Section: Introductionmentioning

confidence: 99%

Evidence of bad recycling practices: BFRs in children's toys and food-contact articles

Guzzonato

Puype

Harrad

2017

Environ. Sci.: Processes Impacts

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Brominated flame retardants (BFRs) have been used intentionally in a wide range of plastics, but are now found in an even wider range of such materials (including children's toys and food contact articles) as a result of recycling practices that mix BFR-containing waste plastics with "virgin" materials. In this study Br was quantified in toy and food contact samples on the assumption that its concentration can be used as a metric for BFR contamination. Subsequently, compound specific determination of BFRs was performed to evaluate the validity of the aforementioned assumption, crucial to render rapid, inexpensive, in situ Br determination in non-laboratory environments (such as waste handling facilities) a viable option for sorting wastes according to their BFR content. We report semi-quantitative compound specific BFR concentrations to give an overview of the distribution of individual BFRs in the analyzed samples. Finally, we evaluated the correlations between waste electrical and electronic equipment (WEEE) related substances (Ca, Sb and rare earth elements (REEs)) and Br as a proxy for identifying poor sorting practices in different waste streams. 26 samples of toys, food-contact articles and WEEE were analyzed with a suite of different techniques in order to obtain comprehensive information about their elemental and molecular composition. The information obtained from principal component analysis about WEEE-related compounds provides new insights into the influence of sorting practices on the extent of products' contamination and bringing out polymer-related trends in the pollutants' signature. 61% of all samples were Br positive: of these samples, 45% had decaBDE concentrations exceeding the concentration limits for PBDEs and their main constituent polymer was - according to the REE signature of such samples - Acrylonitrile Butadiene Styrene (ABS), uses of which include copying equipment, laptops and computers. The ability to better track chemicals of concern and their trends in products is the main requirement for high-level management and control of material cycles to become non-toxic in the future as proposed in the EU's 7 Environmental Action Plan.

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Improving the accuracy of hand-held X-ray fluorescence spectrometers as a tool for monitoring brominated flame retardants in waste polymers

Cited by 24 publications

References 26 publications

Bromine in plastic consumer products – Evidence for the widespread recycling of electronic waste

Bromine in plastic consumer products – Evidence for the widespread recycling of electronic waste

Mobilisation kinetics of hazardous elements in marine plastics subject to an avian physiologically-based extraction test

Evidence of bad recycling practices: BFRs in children's toys and food-contact articles

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