Rapid identification of polystyrene foam wastes containing hexabromocyclododecane or its alternative polymeric brominated flame retardant by X-ray fluorescence spectroscopy

Abstract

The brominated flame retardant hexabromocyclododecane (HBCDD) was added to Annex A of the list of persistent organic pollutants (POPs) of the Stockholm Convention. Thus, production and use of HBCDD will be banned, and the recycling of HBCDD-containing foam waste will be restricted. In reaction a special polymeric brominated flame retardant (PolyFR) was developed to replace HBCDD in expanded and extruded polystyrene foams for building and construction applications. A decision has to be made at some future time whether expanded and extruded polystyrene foam waste is to be subjected to incineration (with HBCDD) or to recycling (without HBCDD). Therefore, an appropriate and rapid field method is required to distinguish between foams containing HBCDD and foams free from HBCDD.

Here we present a screening method for identifying HBCDD containing expanded and extruded polystyrene foams. The test principle is based on the fact that PolyFR (a brominated polymeric macromolecule) is not extractable whereas HBCDD (a low molecular weight substance) is extractable. Following rapid extraction of HBCDD the brominated flame retardant is identified and quantified via bromine analysis using a handheld X-ray fluorescence instrument.

The method was applied successfully to 27 expanded and extruded polystyrene foam samples (foams and extruded polystyrene foam raw materials), which were provided without any information about the applied flame retardant. The presence of HBCDD was confirmed for all HBCDD-positive samples in the test. A robustness test revealed a high degree of correctness and a high repeatability for the test system: samples containing HBCDD and HBCDD-free samples were identified correctly with relative standard deviations of quantitative results below 14%. Moreover, X-ray fluorescence spectroscopy test results agree well with HBCDD determinations performed in a laboratory with a gas chromatograph coupled to a flame ionisation detector.

Keywords

PS foam EPS XPS HBCDD PolyFR demolition waste analysis POP

Get full access to this article

View all access options for this article.

References

Alaee

Arias

Sjodin

. (2003) An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release. Environment International 29: 683–689.

Allen

McClean

Stapleton

. (2008) Linking PBDEs in house dust to consumer products using X-ray fluorescence. Environmental Science & Technology 42: 4222–4228.

Allen

Stapleton

Vallarino

. (2013) Exposure to flame retardant chemicals on commercial airplanes. Environmental Health 12: 17.

Beach

Beaudoin

Beulich

. (2013) New class of brominated polymeric flame retardants for use in polystyrene foams. Cellular Polymers 32: 229–236.

Eljarrat

Barcelo

(2004) Sample handling and analysis of brominated flame retardants in soil and sludge samples. Trends in Analytical Chemistry 23: 727–736.

Environmental Protection Agency (2014) Flame retardant alternatives for hexabromocyclododecane (HBCD). Final Report. EPA Publication 740R14001. Washington, D.C.: US EPA Available at: http://www2.epa.gov/sites/production/files/2014-06/documents/hbcd_report.pdf (accessed 17 April 2015).

European Chemicals Agency (2015) Opinion on an Application for authorisation for hexabromocyclododecane (HBCDD), alpha-hexabromocyclododecane, beta-hexabromocyclododecane, gamma-hexabromocyclododecane. Use: manufacture of flame retarded expanded polystyrene (EPS) articles for use in building applications. ECHA/RAC/SEAC: AFA-O-0000004949-56-12/D. Helsinki, Finland: ECHA. Available at: http://echa.europa.eu/documents/10162/0144eda8-0377-4cc6-aa94-c0de9a5a9456 (accessed 17 April 2015).

European Union (2011) Commission Regulation (EU) No 143/2011 of 17 February 2011 amending Annex XIV to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (‘REACH’). Official Journal of the European Union L 44/2.

European Extruded Polystyrene Insulation Board Association (2014) Environmental product declaration on extruded polystyrene (XPS) foam insulation with HBCD flame retardant. Declaration No. EPD-EXI-20140154-IBE1-EN. Berlin, Germany: IBU. Available at: https://epd-online.com/PublishedEpd/Download/6484. (accessed 17 April 2015)

10.

Fromme

Hilger

Kopp

. (2014) Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and “novel” brominated flame retardants in house dust in Germany. Environment International 64: 61–68.

11.

Ghosal

Fang

(2015) Raman spectroscopy based identification of flame retardants in consumer products using an acquired reference spectral library. Talanta 132: 635–640.

12.

Kajiwara

Sueoka

Ohiwa

. (2009) Determination of flame-retardant hexabromocyclododecane diastereomers in textiles. Chemos-phere 74: 1485–1489.

13.

Kemmlein

Herzke D and Law RJ (2009) Brominated flame retardants in the European chemicals policy of REACH – Regulation and determination in materials. Journal of Chromatography A 1216: 320–333.

14.

Mark

Vehlow

Dresch

. (2015) Destruction of the flame retardant hexabromocyclododecane in a full-scale municipal solid waste incinerator. Waste Management & Research 33: 165–174.

15.

Rani

Shim

Han

. (2014) Hexabromocyclododecane in polystyrene based consumer products: An evidence of unregulated use. Chemosphere 110: 111–119.

16.

Schlummer

Gruber

Maurer

. (2007) Characterisation of polymer fractions from waste electrical and electronic equipment (WEEE) and implications for waste management. Chemosphere 67: 1866–1876.

17.

Schlummer

Maurer

Leitner

. (2006) Report: Recycling of flame-retarded plastics from waste electric and electronic equipment (WEEE). Waste Management & Research 24: 573–583.

18.

Takigami

Suzuki

Hirai

. (2009) Brominated flame retardants and other polyhalogenated compounds in indoor air and dust from two houses in Japan. Chemosphere 76: 270–277.

19.

Thuresson

Bjorklund

de Wit

(2012). Tri-decabrominated diphenyl ethers and hexabromocyclododecane in indoor air and dust from Stockholm microenvironments 1: Levels and profiles. Science of the Total Environment 414: 713–721.

20.

United Nations (2013) Stockholm Convention on Persistent Organic Pollutants. Depositary notifications: C.N.934.2013.TREATIES-XXVII.15. Amendment to Annex A. Geneva: United Nations. Available at: https://treaties.un.org/doc/Publication/CN/2013/CN.934.2013-Eng.pdf (accessed 17 April 2015).

21.

Weil

Levchik

(2007) Flame retardants for polystyrenes in commercial use or development. Journal of Fire Sciences 25: 241–265.

22.

Wolf

Molinari

(1973) True cosolvency. Acetone/diethylether/polystyrene. Die Makromolekulare Chemie 173: 241–245.

Supplementary Material

Please find the following supplemental material available below.

For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.

For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.

0.00 MB

0.07 MB