Rapid Determination of Selected PFAS in Textiles Entering the Waste Stream.

Due to new European legislation, products entering the waste stream containing some perfluoro alkyl substances (PFAS) are subject to "low persistent organic pollutant concentration limits". Concentrations of restricted PFAS must be below this limit for them to be legally recycled or disposed of. A rapid extraction and clean-up method was developed for the determination of 21 PFAS in various polymers used in soft furnishings and upholstery. The optimised method used vortexing and ultrasonication in methanol (0.1% NH4OH), followed by a dilution and syringe filter clean-up step. PFAS were subsequently determined via UPLC-TripleTOF/MS. Good recoveries (80-120%) of target analytes were obtained with tall and narrow chromatogram peaks. The method was validated using control matrix samples spiked with target analytes. Repeated measurements of concentrations of target compounds showed good agreement with the spiked concentrations demonstrating good accuracy and precision. The resultant extracts provided low noise levels resulting in low limits of quantification ranging from 0.1 to 0.4 mg/kg. The developed method was applied successfully to real consumer products and it provided various advantages over traditional methods, including a substantially reduced analysis time, consumables and solvent consumption, and a high sample throughput which is critical to comply with implemented and proposed legislation.

Elevated concentrations of halogenated flame retardants in waste childcare articles from Ireland.

Concentrations of legacy and alternative halogenated flame retardants (HFRs) including chlorinated organophosphate esters (Cl-OPEs), were measured in waste childcare articles (n = 275 for Cl-OPEs, n = 187 for other HFRs) from the Republic of Ireland between 2019 and 2020. Articles studied comprised foams and fabrics from: child car seats, cot mattresses, changing mats, pushchairs, prams, and related items. Fifteen articles (7.7%) exceeded the European Union limit value of 1000 mg/kg for polybrominated diphenyl ethers (PBDEs) (all due to BDE-209), an additional 15 exceeded the limit for hexabromocyclododecane (HBCDD), with 7 articles exceeding the limit for both PBDEs and HBCDD. An even greater proportion of articles contained concentrations exceeding 1000 mg/kg for: tris(1-chloro-2-propyl) phosphate (TCIPP) (n = 73, 27%) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (n = 58, 21%), with concentrations greater than 1000 mg/kg also observed for: tris(2-chloroethyl) phosphate (TCEP) (n = 14, 5.1% articles), 2-ethylhexyl tetrabromobenzoate (EH-TBB) (n = 7, 3.7%), decabromodiphenyl ethane (DBDPE), and bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP) (both n = 5, 2.7%). Overall, 120 samples contained at least one HFR at a concentration exceeding 1000 mg/kg. In addition to the waste management implications of our findings, our data raise concerns about child exposure to HFRs during the use phase of these everyday items.

Chlorinated organophosphate esters in Irish waste foams and fabrics: Concentrations, preliminary assessment of temporal trends and evaluation of the impact of a concentration limit value.

Concentrations of the chlorinated organophosphate esters (Cl-OPEs): tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were measured in 273 waste synthetic foam and fabric articles collected in Ireland between 2019 and 2020. Articles examined comprised: polystyrene building insulation foam, as well as foam fillings and fabric coverings from furniture, mattresses, end-of-life vehicles, curtains, and carpets. Cl-OPEs were also measured in 156 samples from the same categories (except for building insulation foam) collected in 2015-16. Concentrations of TCIPP and TDCIPP in most samples exceeded those of TCEP; with those of TCIPP and TDCIPP generally and for some waste categories significantly (p < 0.05) higher in samples collected in 2019-20. Given potential future restrictions on use of these Cl-OPEs, we identified articles containing concentrations that exceeded 1000 mg/kg, in line with a similar limit that at the time of sample collection existed for some brominated flame retardants within the European Union. In 2019-20, 82 articles contained at least one Cl-OPE above 1000 mg/kg, with at least one article exceeding this concentration in each waste category examined. By comparison, only 28 samples collected in 2015-16, contained at least one Cl-OPE >1000 mg/kg, and articles exceeding this concentration were restricted to furniture and mattress foam, along with foams and fabrics from end-of-life vehicles. In the event of the introduction of such a limit on Cl-OPE concentrations in waste, it will result in 7200 t/year of such waste (24 % of the total) being rendered unrecyclable, while removing 98 % of the estimated ∼147,000 kg/year of Cl-OPEs from the recycling stream.

POP-BFRs in consumer products: Evolution of the efficacy of XRF screening for legislative compliance over a 5-year interval and future trends.

In 2015-16, a study of approximately 500 waste plastic articles showed that portable X-ray fluorescence (XRF) was up to 95 % effective in screening for compliance with low persistent organic pollutant (POP) concentration limits (LPCLs) on brominated flame retardants (BFRs) in waste. The present study conducted in 2019-20 mirrors that conducted five years prior on a similar number and range of articles, testing the hypothesis that increased use of alternative BFRs as replacements for POP-BFRs will reduce the effectiveness of XRF as a tool for monitoring compliance with LPCLs. In comparing the results, the overall screening efficacy for LPCL compliance reduced from ~95 % to ~88 %, due in part to decreased prevalence of POP-BFRs and potentially increased presence of alternative flame retardants, particularly in goods with shorter lifecycles such as electronics. We additionally examined the impacts of a number of modifications to the XRF measurement protocol on its efficacy, including: using elemental Sb as a qualifier in detecting POP-BFRs in hard plastics; reduced XRF analysis time; and the elimination of background interference using a test stand. The rate at which hard plastics from electronic waste may be analysed by XRF can be substantially improved by reducing analysis time to 5 s, with minimal increase in false exceedances of the LPCL. Monitoring Sb does not appear an effective qualifier for the presence of POP-BFRs, as Sb seems to be used with a range of BFRs. Use of the test stand, while reducing interference, appeared to reduce accuracy when screening low density and thin samples. Despite a seeming increased use of alternative BFRs, screening of waste for compliance with LPCLs using rapid and low-cost screening methods such as portable XRF is still necessary as methods such as GC-MS cannot be scaled up to match the quantities of waste requiring screening.

Halogenated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and preliminary assessment of temporal trends.

Halogenated flame retardants (HFRs) were measured in 470 waste plastic articles from Ireland between 2019 and 2020. We identified articles containing concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and tetrabromobisphenol-A (TBBP-A) exceeding European Union limits. Enforcement of existing limits of 1000 mg/kg will render an estimated 3.1% (2800 t) of articles in the waste categories studied unrecyclable, increasing to: 4.0, 4.9, and 5.6% if limits were reduced to 500, 200, and 100 mg/kg respectively. Meanwhile, enforcing limits of 1,000, 500, 200, and 100 mg/kg will respectively remove 78, 82, 84, and 85% of PBDEs, HBCDD, and TBBP-A present in such waste. Other FRs targeted were detected infrequently and predominantly at very low concentrations. However, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was detected in 3 display/IT product samples at 14,000 to 32,000 mg/kg, indicating elevated concentrations of FRs used as alternatives to PBDEs and HBCDD, will likely increase in future. Comparison with data for Ireland in 2015-16, revealed concentrations and exceedances of limits for PBDEs, HBCDD, and TBBP-A were similar or have declined. For end-of-life vehicle fabrics and foams, HBCDD and ΣPBDE concentrations declined significantly (p < 0.05) since 2015-16. Moreover, ΣPBDE concentrations in waste small domestic appliances are significantly lower in 2019-20, with a similarly significant decline for TBBP-A in waste IT and telecommunications articles. In contrast, HBCDD concentrations in waste extruded polystyrene increased significantly between 2015-16 and 2019-20. For other waste categories studied, no statistically significant temporal trends are evident (p > 0.05). Fewer samples exceeded PBDE and HBCDD limits in 2019-20 (7.8%) than 2015-16 (8.7%), while exceedances for TBBP-A fell from 2.4% in 2015-16 to 0.57% in 2019-20. While comparison between the 2015-16 and 2019-20 datasets provide a preliminary indication of changes, further monitoring is required if the impact of legislation designed to eliminate HFRs from the waste stream is to be fully evaluated.

Phasing-out of legacy brominated flame retardants: The UNEP Stockholm Convention and other legislative action worldwide.

Due to their toxicity and persistence, several families of brominated flame retardants (BFRs) have been listed as persistent organic pollutants (POPs) in the Stockholm Convention, a multilateral treaty overseen by the United Nations Environment Programme. This treaty mandates that parties who have signed must take administrative and legislative actions to prevent the environmental impacts that POPs pose, both within their jurisdictions and in the global environment. The specific BFRs listed in the Stockholm Convention are Polybrominated Diphenyl Ethers (PBDEs), Hexabromocyclododecane (HBCDD), and Hexabromobiphenyl (HBB), chemicals which must therefore be heavily restricted within the jurisdictions of the signatories. As an example, within the EU, hexabromobiphenyl (HBB), the PBDE commercial mixtures, and HBCDD are almost entirely prohibited in terms of both production and use in commercial goods. Waste articles containing excess concentrations of these BFRs are similarly restricted and must be disposed of in a manner that destroys or irreversible transforms the BFR in question. In some cases, specific exemptions for these limits are defined by the Convention for certain parties: for example, Penta- and Octa-BDE can be present in waste materials for recycling until 2030, while Deca-BDE can be applied to some aviation and automotive applications until 2036. However, in such cases, very specific criteria and guidelines apply for their use and/or production. Worldwide, China, Japan, India, and the United States of America have made significant advances in the regulation of POPs, in line with the provisions of the Stockholm Convention. China has established concentration limits for Penta- and Octa-BDEs in electronic goods. It is also currently availing of an exemption to allow for the use of HBCDD and has not yet ratified the Convention with regards to Deca-BDE. Japan meanwhile has classified HBB and Penta-/Octa-BDE compounds as Class I Specified Chemical Substances which virtually prohibits the manufacture, import, and use of these chemicals in all applications. India has banned the manufacture, trade, import, and use of HBB, HBCDD and some PBDEs, and has established concentration limits for all PBDEs in certain electrical goods. Finally, the United States has no federal mandate for the restriction of POPs and has not ratified the annexes to the Convention requiring them to do so. However, thirteen states have implemented their own state-wide concentration limits on a variety of flame retarding chemicals in various commercial applications. Though these limits worldwide are a very positive step for the removal of POP-BFRs from the environment, the increased use of replacement flame retardants renders such legislation only partially effective. The lack of effective screening mechanisms in waste management facilities means that BFR-treated plastics can be inadvertently recycled and remain in circulation. The rise in the use of novel BFRs (NBFRs) can furthermore hinder screening methods currently being developed and the additives themselves may pose similar issues to their predecessors owing to their similar chemical properties. Thus, restrictions on current BFRs will result in the use of new flame retardants, which may in turn be banned and replaced once again. Further research into and development of methods to screen for hazardous chemicals in end of life materials is therefore of the utmost importance. This must be coupled with pro-active legislation that eliminates the need for using such persistent and potentially harmful chemicals in the future.

Perfluoroalkyl substances and brominated flame retardants in landfill-related air, soil, and groundwater from Ireland.

Between November 2018 and January 2019, samples of air and soil were collected from locations downwind and upwind of 10 landfills across the Republic of Ireland. Samples of groundwater (n = 10) were also collected from locations with links traceable to the studied landfills. Concentrations of perfluoroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs), hexabromocyclodecane (HBCDD), and decabromodiphenyl ethane (DBDPE) determined in air and soil samples were not significantly different (p > 0.05) between downwind and upwind locations. The arithmetic mean concentration of PFOA in groundwater sourced from landfills (n = 4) that were not fully lined (69 ng/L) exceeded that in groundwater samples sourced from lined landfills (n = 6; 4.1 ng/L), with the difference, however being not statistically significant (p > 0.1). A positive correlation (p = 0.014) was observed between concentrations of PFOA in groundwater in our study and those reported previously in leachate from the same landfills. However, this correlation was driven substantially by one landfill which displayed the highest concentrations in both groundwater and leachate and no significant correlation (p > 0.1) was observed between log-transformed concentrations of PFOA in groundwater and leachate. DBDPE was detected in groundwater for the first time anywhere, in all samples at concentrations (median = 9.4 ng/L; arithmetic mean = 78 ng/L) that exceeded those of any other BFRs or PFASs targeted in this study. This likely reflects its recent use as a "drop-in" replacement for the recently restricted Decabromodiphenyl ether product. Overall, our data suggest that the 10 landfills studied do not exert a discernible influence on local air and soil concentrations of BFRs and PFASs. In contrast, while not of immediate concern, our data suggest that further more detailed study of the impact of landfill emissions on concentrations of DBDPE and PFOA is advisable.

Brominated flame retardants and perfluoroalkyl substances in landfill leachate from Ireland.

Between June and November 2017, leachate samples were collected from 40 landfills across the Republic of Ireland. Concentrations of perfluoroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDD) determined in these samples were within the range previously reported in other countries. Average concentrations of PFASs exceeded those of PBDEs and HBCDD; likely due to the higher water solubility of PFASs. Log-transformed concentrations of BDEs-47, 100, 153, and 183, as well as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorobutane sulfonate (PFBS) were significantly (p < 0.05) higher in leachate from newer, lined landfills than in samples from unlined landfills. These higher concentrations in lined landfills are likely related to the fact that lined landfills are found to retain organic matter leading to a higher organic content of leachate from such landfills. This is evidenced by the significant (p < 0.05) correlation between log-transformed concentrations in leachate of most of the same contaminants and those of chemical oxygen demand (COD). Concentrations of the less water-soluble, higher molecular weight BDE-209 were not correlated with leachate COD, nor landfill age or the presence of a landfill liner. This suggests that the presence of BDE-209 in landfill leachate is driven more by physical abrasion of particles and fibres from waste articles, than dissolution into the aqueous phase. The higher concentrations of some PFASs and PBDEs in leachate from lined landfills present a challenge with respect to leachate disposal, when leachate is sent to wastewater treatment plants that do not necessarily have mechanisms in place to remove or destroy these chemicals prior to discharge into the environment. Moreover, the presence of these persistent organic chemicals in leachate from unlined landfills raises concerns about releases to the environment including groundwater over the lifetime of such landfills and beyond.

Brominated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and treatment options.

A comprehensive survey was performed to construct an inventory of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) associated with waste polymers in Ireland. Based on our data, ~2200 t/yr of waste generated in Ireland exceeds "Low POP Concentration Limits" (LPCLs) set by the European Commission, of 1000 mg/kg of PBDEs (BDE-209 excluded) and HBCDD - collectively referred to as POP-BFRs. Waste articles containing concentrations exceeding the LPCL values require special treatment to remove POP-BFRs before they can be recycled. Waste articles exceeding LPCLs in our study consist primarily of expanded polystyrene used as building insulation (44%), waste furniture foams and fabrics (41%), with waste electrical and electronic equipment (WEEE) accounting for 13% and end of life vehicle waste contributing 1.7%. The recent listing of Deca-BDE under the Stockholm Convention means that a similar LPCL for its principal congener (BDE-209) is likely. Our data show that enforcement of an LPCL of 1000 mg/kg for BDE-209 would result in a further 1650 t/year of waste articles requiring special treatment. Our data show there to be 17,125 kg of POP-BFRs associated with waste polymers generated annually in Ireland. Enforcement of current LPCL values would prevent approximately 98% of these POP-BFRs from entering recycled goods. Introduction and enforcement of a similar LPCL for BDE-209 would prevent 93% of the 15,518 kg/yr of BDE-209 associated with Irish waste polymers from entering the recycling stream.

Portable X-ray fluorescence for the detection of POP-BFRs in waste plastics.

The purpose of this study was to establish the efficacy of portable X-ray fluorescence (XRF) instrumentation as a screening tool for a variety of end of life plastics which may contain excess amounts of brominated flame retardants (BFRs), in compliance with European Union (EU) and United Nations Environment Programme (UNEP) legislative limits (low POP concentration limits - LPCLs). 555 samples of waste plastics were collected from eight waste and recycling sites in Ireland, including waste electrical and electronic equipment (WEEE), textiles, polyurethane foams (PUFs), and expanded polystyrene foams. Samples were screened for bromine content, in situ using a Niton™ XL3T GOLDD XRF analyser, the results of which were statistically compared to mass spectrometry (MS)-based measurements of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBP-A) concentrations in the same samples. Regression between XRF and MS for WEEE samples shows that, despite an overall favourable trend, large deviations occur for a cluster of samples indicative of other bromine-based compounds in some samples; even compensating for false-positives due to background interference from electronic components, XRF tends to over-estimate MS-determined BFR concentrations in the 100 to 10,000 mg kg-1 range. Substantial deviations were additionally found between results for PUFs, textiles and polystyrene samples, with the XRF over-estimating BFR concentrations by a factor of up to 1.9; this is likely due to matrix effects influencing XRF measurements. However, expanded (EPS) and extruded polystyrene (XPS) yielded much more reliable estimations of BFR-content due to a dominance of HBCDD in these materials. XRF proved much more reliable as a "pass/fail" screening tool for LPCL compliance (including a prospective LPCL on Deca-BDE based on REACH). Using a conservative threshold of BFR content exceeding legislative limits (710 mg kg-1 bromine attributed to Penta-BDE), XRF mistakenly identifies only 6 % of samples (34/555) as exceeding legislative limits.

Hexabromocyclododecane in polystyrene packaging: A downside of recycling?

While there are no regulatory fire safety obligations for polystyrene (PS) when used as packaging material, concerns exist that such packaging material may contain the flame retardant hexabromocyclododecane (HBCDD) as a result of uncontrolled recycling activities. To evaluate these concerns, we collected 50 samples of PS packaging materials from the UK and 20 from Ireland. HBCDD was detected in 63 (90%) of samples, with concentrations in 4 samples from Ireland exceeding the EU's low POP concentration limit (LPCL) of 0.1% above which articles may not be recycled. Moreover, 2 further samples contained HBCDD >0.01%. While our samples were obtained in the 12 month period prior to the March 2016 introduction of the EU's 0.01% concentration limit above which articles may not be placed on the market, our data suggest that continued monitoring is required to assess compliance with this limit value. Ratios of α vs. γ-HBCDD in our EPS packaging samples (average = 0.63) exceeded significantly (p = 0.025) those in EPS building insulation material samples (average = 0.24) reported previously for Ireland. This shift towards α-HBCDD in packaging EPS is consistent with the additional thermal processing experienced by recycled PS and suggests the source of HBCDD in PS packaging is recycled PS insulation foam. This is of concern owing to the higher bioavailability and lower metabolic clearance of α-HBCDD compared to the ß- and γ-isomers.

A rapid method for the determination of brominated flame retardant concentrations in plastics and textiles entering the waste stream.

Due to new European legislation, products going to waste are subject to 'low persistent organic pollutant concentration limits'. Concentrations of restricted brominated flame retardants in waste products must be determined. A rapid extraction and clean-up method was developed for determination of brominated flame retardants in various plastics and textiles. The optimised method used vortexing and ultrasonication in dichloromethane followed by sulfuric acid clean-up to determine target compounds. Poly-brominated diphenyl ethers were determined by gas chromatography with mass spectrometry and hexabromocyclododecane by liquid chromatography with tandem mass spectrometry. Good recoveries of target analytes were obtained after three extraction cycles. The method was validated using poly-propylene and poly-ethylene certified reference materials as well as previously characterised textiles, expanded and extruded poly-styrene samples. Measured concentrations of target compounds showed good agreement with the certified values indicating good accuracy and precision. Clean extracts provided low noise levels resulting in low limits of quantification (0.8-1.5 ng/g for poly-brominated diphenyl ethers and 0.3 ng/g for α-, ß- and γ-hexabromocyclododecane). The developed method was applied successfully to real consumer products entering the waste stream and it provided various advantages over traditional methods, including reduced analysis time, solvent consumption, minimal sample contamination and high sample throughput, which is crucial to comply with the implemented legislation.