EVALUATION OF HAND-HELD XRF FOR SCREENING WASTE ARTICLES FOR EXCEEDANCES OF LIMIT VALUES FOR BROMINATED FLAME RETARDANTS (WAFER)

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Resource or Project Abstract

Recent research has demonstrated the presence of restricted Persistent Organic Pollutant (POP) brominated flame retardants (BFRs) in items such as childrens? toys and food contact articles. As the presence of these contaminants in such items serves no useful purpose, they are thought to originate from the use of recycled plastics that were originally treated with BFRs. To address this issue, EU Regulation 850/2004 specifies low POP concentration limit (LPCL) values such that articles containing such BFRs (selected polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD)) at concentrations exceeding the LPCL (1,000 mg/kg) cannot be recycled and must be treated so that the BFR content of such articles is destroyed. Existing LPCLs for PBDEs cover those present in the Penta- and Octa-BDE formulations, but an LPCL for Deca-BDE at a similar concentration is scheduled for implementation from March 2019. Given widespread use of PBDEs and HBCDD in applications like electrical and electronic goods, polystyrene building insulation foam, seating foam and fabrics in homes, offices, and cars; monitoring compliance with LPCLs represents a substantial undertaking, compounded by conventional methods for measuring PBDEs and HBCDD being destructive, time-consuming, expensive, and incompatible with being conducted in situ at waste handling sites. Our principal objective was thus to evaluate the feasibility of using hand-held X-ray fluorescence (XRF) spectrometers to determine bromine in waste articles as a surrogate indicator of exceedance of LPCLs. Of particular concern is the incidence of false positives (where the concentration of bromine but not PBDEs or HBCDD exceeds the LPCL) and false negatives (where the concentration of PBDEs or HBCDD exceeds the LPCL but is not indicated by the bromine concentration recorded by XRF). False positives may occur when a BFR other than a PBDE or HBCDD (e.g. tetrabromobisphenol-A) is present above 1,000 mg/kg. We measured bromine in 769 waste articles and PBDEs and HBCDD in 538 of the same articles collected in Ireland between 2015 and 2016. These articles comprised waste electronic and electrical equipment (WEEE), polystyrene building insulation, end of life vehicle foams and fabrics, as well as waste carpets, curtains, furniture foams and fabrics. Measurements revealed concentrations of PBDEs and HBCDD exceeded existing LPCLs in 29/538 (5.4%) articles. Anticipating the introduction of an LPCL for Deca-BDE (BDE-209), we found the proportion of articles exceeding either existing LPCLs or the anticipated LPCL of 1,000 mg/kg for BDE-209 was 8.7 % (47/538). By comparison, false positives numbered 52 (9.7 %) when existing LPCLs only were considered, reducing to 34 (6.3 %) when the anticipated LPCL for BDE-209 was accounted for. No false negatives were detected. Based on our data, enforcement of existing LPCLs would prevent 97.9% of the estimated 17,721 kg/year of HBCDD, Penta- and Octa-BDEs generated currently in Ireland, as well as 13.0% of the 15,284 kg/year of BDE-209 generated from being recycled. Enforcement of an LPCL of 1,000 mg/kg for BDE-209, would prevent recycling of 98.1% of the 33,004 kg/year of PBDEs and HBCDD currently generated in Ireland. While false positives will lead to some articles being incorrectly prevented from being recycled, the absence of false negatives in this study, combined with the cost- and time-effectiveness of hand-held XRF relative to conventional methods for measuring PBDEs and HBCDD, renders hand-held XRF potentially feasible for large-scale monitoring of LPCL compliance. Despite this, use of hand-held XRF to screen individual waste articles may still be considered overly time-consuming by waste treatment professionals. Consequently, automation of the screening process using a ?fixed/bench-top? XRF instrument in conjunction with a conveyor belt carrying waste articles, is considered a feasible approach for large-scale waste handling operations ? albeit one requiring greater capital outlay. Short-term, approaches to minimise the number of articles requiring checking for compliance with LPCL values merit consideration. These involve using data from this project that show very low BFR concentrations and no exceedances of current or anticipated LPCLs for some waste categories such as extruded polystyrene (XPS) building insulation foam. On-site separation of XPS from expanded polystyrene (EPS) foam (for which 35 % of samples were found to exceed the LPCL for HBCDD), to allow recycling or reuse of XPS without checking for LPCL compliance would reduce the monitoring burden placed on the waste management industry.

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Contact Information for This Resource

Prof. Stuart Harrad
University of Birmingham

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Attachment Name and Download Link
Att 1    WAFER_Final_Report.docx   (0.21 Mb)
Att 2    WAFER_DATABASE.xlsx   (0.15 Mb)

Suggested Citation Information

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Author(s)Harrad, S.
Title Of WebsiteSecure Archive For Environmental Research Data
Publication InformationEVALUATION OF HAND-HELD XRF FOR SCREENING WASTE ARTICLES FOR EXCEEDANCES OF LIMIT VALUES FOR BROMINATED FLAME RETARDANTS (WAFER)
Name of OrganisationEnvironmental Protection Agency Ireland
Electronic Address or URL http://erc.epa.ie/safer/resource?id=0d00d379-0762-11e9-96ff-005056ae0019
Unique Identifier0d00d379-0762-11e9-96ff-005056ae0019
Date of AccessLast Updated on SAFER: 2019-03-25

An example of this citation in proper usage:

Harrad, S.   "EVALUATION OF HAND-HELD XRF FOR SCREENING WASTE ARTICLES FOR EXCEEDANCES OF LIMIT VALUES FOR BROMINATED FLAME RETARDANTS (WAFER)". Associated datasets and digitial information objects connected to this resource are available at: Secure Archive For Environmental Research Data (SAFER) managed by Environmental Protection Agency Ireland http://erc.epa.ie/safer/resource?id=0d00d379-0762-11e9-96ff-005056ae0019 (Last Accessed: 2019-03-25)

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Access Information For This Resource

SAFER-Data Display URL http://erc.epa.ie/safer/iso19115/display?isoID=3164
Resource KeywordsWaste plastics, brominated flame retardants, recycling,x-ray fluorescence
EPA/ERTDI/STRIVE Project Code2014-RE-MS-2
EPA/ERTDI/STRIVE Project ThemeWaste and Resource Management
Resource Availability: Any User Can Download Files From This Resource
Public-Open
Limitations on the use of this ResourceNONE
Number of Attached Files (Publicly and Openly Available for Download): 2
Project Start Date Monday 2nd February 2015 (02-02-2015)
Earliest Recorded Date within any attached datasets or digital objects Monday 2nd February 2015 (02-02-2015)
Most Recent Recorded Date within any attached datasets or digital objects Monday 31st July 2017 (31-07-2017)
Published on SAFERMonday 24th December 2018 (24-12-2018)
Date of Last EditMonday 24th December 2018 at 10:00:59 (24-12-2018)
Datasets or Files Updated On Monday 24th December 2018 at 10:00:59 (24-12-2018)

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Geographical and Spatial Information Related To This Resource

Description of Geographical Characteristics of This Project or Dataset
Data collected from waste sites at various locations across Ireland.

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Supplementary Information About This Resource

In this section some supplementary information about this resource is outlined. Lineage information helps us to understand why this project was carried out, what policy or research requirements did it fulfil, etc. Lineage is important in understanding the rationale behind the carrying out of a project or the collection of a specific dataset etc. Links to web sites, applications, papers, etc are outlined to provide you with additional information or supplementary reading about the project or dataset

Lineage information about this project or dataset
Dataset stems from a research project (WAFER) funded under the EPA's 2014 research call.
Supplementary Information
The following peer-reviewed papers have emerged from this research:
(1) M. Sharkey, M. A-E. Abdallah, D. S. Drage, S. Harrad, H. Berresheim, ?Portable X-ray fluorescence for the detection of POP-BFRs in waste plastics?, Science of the Total Environment, 639, 49?57 (2018).
(2) D. S. Drage, M. Sharkey, M. A-E. Abdallah, H. Berresheim, S. Harrad ?Brominated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and treatment options?, Science of The Total Environment, 625, 1535?1543 (2018).
(3) M. A-E. Abdallah, D. S. Drage, M. Sharkey, H. Berresheim, S. Harrad ?A rapid method for the determination of brominated flame retardant concentrations in plastics and textiles entering the waste stream?, Journal of Separation Science, 40, 3873?3881 (2017).
Links To Other Related Resources
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