Joanna Kuc,

Adam Grochowalski


Methods of sample preparation with a particular emphasis on extraction and purification techniques are described. Gas and liquid chromatography techniques applied for the determination of hexabromocyclododecane are presented. Issues relating to the determination of this compound in food samples are discussed.

Słowa kluczowe: BFRs, HBCD, food analysis, GC-MS, LC-MS

Marvin C.H., Tomy G.T., Armitage J.M., Arnot J.A., McCarty L., Covaci A., Palace V., Hexabromocyclododecane: Current understanding of chemistry, environmental fate and toxicology and implications for global management, Environmental Science & Technology, vol. 45, 2011, 8613-8623.

Smith K., Liu C-H., El-Hiti G.A., Kang G.S., Jonas E., Clement S.G., Checquer A.D., Howarth O.W., Hursthouse M.B., Coles S.J., An extensive study of bromination of cis, trans- 1,5,9-cyclododecatriene: product structures and conformations, Organic & Biomolecular Chemistry, vol. 3, 2005, 1880-1892.

Heeb N.V., Schweizer W.B., Kohler M., Gerecke A.C., Structure elucidation of hexabromocyclododecanes – a class of compounds with a complex stereochemistry, Chemosphere, vol. 61, 2005, 65-73.

Heeb N.V., Schweizer W.B., Mattrel P., Haag R., Gerecke A.C., Kohler M., Schmid P., Zennegg M., Wolfensberger M., Solid-state conformations and absolute configurations of (+) and (–) a-, b-, and g-hexabromocyclododecanes (HBCDs), Chemosphere, vol. 68, 2007, 940-950.

Arsenault G., Konstantinov A., Marvin C.H., MacInnis G., McAlees A., McCrindle R., Riddell N., Tomy G.T., Yeo B., Synthesis of the two minor isomers, delta- and epsilon- 1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane, Chemosphere, vol. 68, 2007, 887-92.

Troitzsch J., Overview of flame retardants, Chimica Oggi/Chemistry Today, vol. 16, 1998, 1-19.

Priority Existing Chemical Assessment Report No. 34 Hexabromocyclododecane, Sydney 2012.

TemaNord 2008:520. Hexabromocyclododecane as a possible global POP, Copenhagen 2007.

Proposal for Harmonised Classification and Labelling Based on the CLP Regulation (EC) No 1272/2008, Annex VI, Part 2. Hexabromocyclododecane, Swedish Chemicals Agency 2009.

ECHA European Chemical Agency. Doc:ED/67/2008, Inclusion of substances of very high concern in candidate list, Helsinki, 28 October 2008.

ACCBFRIP American Chemistry Council Brominated Flame Retardant Industry Panel, 2005, HPV data summary and test plan for hexabromocyclododecane (HBCD), CAS No. 3194556, 20 December 2001, Updated March 2005, Arlington (VA).

BSEF Bromine Science and Environmental Forum. Factsheet, Brominated Flame Retardant, Hexabromocyclododecane, October 2012.

EUMEPS Healthy building with EPS, Belgium, August 2002.

EUMEPS Behavior of EPS in case of fire, Belgium, August 2002.

de Wit C.A., An overview of brominated flame retardants in the environment, Chemosphere, vol. 46, 2002, 583-624.

Remberger M., Sternbeck J., Palm A., Kaj L., Strömberg K., Brorström-Lundén E., The environmental occurrence of hexabromocyclododecane in Sweden, Chemosphere, vol. 54, 2004, 9-21.

Kajiwara N., Sueoka M., Ohiwa T., Takigami H., Determination of flame-retardant hexabromocyclododecane diastereomers in textiles, Chemosphere, vol. 74, 2009, 1485-1489.

Vilaplana F., Karlsson P., Ribes-Greus A., Ivarsson P., Karlsson S., Analysis of brominated flame retardants in styrenic polymers: Comparison of the extraction efficiency of ultrasonication, microwave-assisted extraction and pressurised liquid extraction, Journal of Chromatography A, vol. 1196–1197, 2008, 139-146.

de Wit C.A., Herzke D., Vorkamp K., Brominated flame retardants in the Arctic environment – trends and new candidates, Science of the Total Environment, vol. 408, 2010, 2885-2918.

Peled M., Scharia R., Sondack D., Thermal rearrangement of hexabromocyclododecane (HBCD), [in] Advances in Organobromine Chemistry II. Ed., Desmurs J-R., Gérard B. and Goldstein MJ. Elsevier, Amsterdam 1995, 92-99.

Great Lakes Chemical Corporation, Material Safety Data Sheet. Great Lakes CD-75-P, CD-75PM and CD-75PC, West Lafayette (IN): Great Lakes Chemical Corporation. MSDS Number: 00177. Effective Date: 10/14/2005.

Stenzel J.I., Nixon W.B., Hexabromocyclododecane (HBCD): Determination of the vapor pressure using a spinning rotor gauge, Wildlife international Ltd. 1997, Easton, Maryland. 439C-117, pp. 44.

EBFRIP European Brominated Flame Retardant Industry Panel. 2004a, Determination of water solubility of hexabromocyclododecane (HBCD) using a generator column method, Easton (MD): Wildlife International, Ltd. Project No. 439C-138.

Veith G.D., DeFoe D.L., Bergstedt B.V., Measuring and estimating the bioconcentration factor of chemicals in fish, Journal of the Fisheries Research Board of Canada, vol. 36, 1979, 1040-1048.

Hayward S.J., Lei Y.D., Wania F., Comparative evaluation of three HPLC-based KOW estimation methods for highly hydrophobic organic compounds: polybrominated diphenyl ethers and hexabromocyclododecane, Environmental Toxicology and Chemistry, vol. 25, 2006, 2018-2027.

EUROPEAN CENTRE FOR ENVIRONMENT AND HEALTH BONN OFFICE Hazard assessment: five substances proposed for POPs protocol of CLRTAP, 13th Meeting of the Task Force on Health in Bonn, April 2010.

ECB – SUMMARY FACT SHEET PBT WORKING GROUP – PBT LIST NO. 58, Results of the evaluation of the PBT/VPVB properties of hexabromocyclododecane, 1st Draft, March, 2008.

Alaee M., Arias P., Sjödin A., and Bergman A., An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release, Environment International, vol. 29, 2003, 683-689.

Covaci A., Gerecke A.C., Law R.J., Voorspoels S., Kohler M., Heeb N.V., Leslie H., Allchin C.R., and De Boer J., Hexabromocyclododecanes (HBCDs) in the environment and humans: a review, Environmental Science & Technology, vol. 40, 2006, 3679-3688.

de Wit C.A., Alaee M., Muir D.C.C., Levels and trends of brominated flame retardants in the Arctic, Chemosphere, vol. 64, 2006, 209.

Kohler M., Zennegg M., Bogdal C., Gerecke A.C., Schmid P., Heeb N.V., Sturm M., Vonmont H., Kohler H.P., Giger W., Temporal trends, congener patterns, and sources of octa-, nona-, and decabromodiphenyl ethers (PBDE) and hexabromocyclododecanes (HBCD) in Swiss lake sediments, Environmental Science & Technology, vol. 42, 2008, 6378- 6384.

Thomsen C., Froshaug M., Broadwell S.L., Becher G., Brominated flame retardants in breast milk from Norway, Organohalogen Compound, vol. 67, 2005, 509-512.

Thomsen C., Stigum H., Froshaug M., Broadwell S.L., Becher G., Eggesbo M., Determinants of brominated flame retardants in breast milk from a large scale Norwegian study, Environment International, vol. 36, 2010, 68-74.

Janak K., Covaci A., Voorspoels S., Becher G., Hexabromocyclododecane in marine species from the Western Scheldt Estuary: diastereoisomer- and enantiomer-specific accumulation, Environment Science & Technology, vol. 39, 2005, 1987-1994.

Law R.J., Herzke D., Harrad S., Morris S., Bersuder P., Allchin C.R., Levels and trends of HBCD and BDEs in the European and Asian environments with some information for other BFRs, Chemosphere, vol. 73, 2008, 223-241.

Shaw S.D., Berger M.L., Brenner D., Kannan K., Lohmann N., Papke O., Bioaccumulation of polybrominated diphenyl ethers and hexabromocyclododecane in the northwest Atlantic marine food web, Science of the Total Environment, vol. 407, 2009, 3323-3329.

Nakagawa R., Murata S., Ashizuka Y., Shintani Y., Hori T., Tsutsumi T., Hexabromocyclododecane determination in seafood samples collected from Japanese coastal areas, Chemosphere, vol. 81, 2010, 445-452.

Rawn D.F.K., Sadler A., Quade S.C., Sun W.F., Lau B.P., Kosarac I., Hayward S., Ryan J.J., Brominated flame retardants in Canadian chicken egg yolks, Food Additive & Contaminants: part A, vol. 28, 2011, 807-815.

Hu D., Hu X., Li J., Wang P., Guo S., Determinations of hexabromocyclododecane (HBCD) isomers in plastic products from china by LC-MS/MS, Journal of Liquid Chromatography & Related Technologies, vol. 35, 2012, 558-572.

Xu W., Wang X., Cai Z., Analytical chemistry of the persistent organic pollutants identified in the Stockholm Convention: A review, Analytica Chimica Acta, vol. 790, 2013, 1-13.

Namieśnik J., Jakość wyników analitycznych, [in] Ocena i kontrola jakości wyników pomiarów analitycznych, Wydawnictwo Naukowo-Techniczne, Warszawa 2007.

Curren M.S.S., King J.W., Chapter 25: Sampling and sample preparation for food analysis, [in] Comprehensive Analytical Chemistry XXWIZ, J. Pawliszyn (Ed.) 2002 Elsevier Science B.V.

Luque de Castro M.D., Priego-Capote F., Soxhlet extraction: Past and present panacea, Journal of Chromatography A, vol. 1217, 2010, 2383-2389.

US EPA (1996), Method 3540C: soxhlet extraction.

Frederiksen M., Vorkamp K., Svensmark B., Method development for simultaneous analysis of HBCD, TBBPA, and dimethyl-TBBPA in marine biota from Greenland and the Faroe Islands, International Journal of Environmental Analytical Chemistry, vol. 87, 2007, 1095-1109.

Hu X., Hu D., Song Q., Li J., Wang P., Determinations of hexabromocyclododecane (HBCD) isomers in channel catfish, crayfish, hen eggs and fish feeds from China by isotopic dilution LC-MS/MS, Chemosphere, vol. 82, 2011, 698-707.

US EPA (2007). Method 3545A: pressurized fluid extraction (PFE).

US EPA (2007). Method 3562: supercritical fluid extraction of polychlorinated biphenyls (PCBs) and organochlorine pesticides.

US EPA (2007). Method 3546: microwave extraction.

US EPA (2007). Method 3550C: ultrasonic extraction.

Accelerated Solvent Extraction (ASE®) Sample Preparation Techniques for Food and Animal Feed Samples, Technical Note 209, DIONEX, ThermoSc.

Haukås M., E.Mariussena, Ruus A., Tollefsen K.E., Accumulation and disposition of hexabromocyclododecane (HBCD) in juvenile rainbow trout (Oncorhynchus mykiss), Aquatic Toxicology, vol. 95, 2009, 144-151.

Altwaiq A., Wolf M., van Eldik R., Extraction of brominated flame retardants from polymeric waste material using different solvents and supercritical carbon dioxide, Analytica Chimica Acta, vol. 491, 2003, 111-123.

Eskilsson C.S., Björklund E., Analytical-scale microwave-assisted extraction, Journal Chromatography A, vol. 902, 2000, 227-250.

Ganzler K., Salgo A., Valko K., Microwave Extraction: A Novel Sample Preparation Method for Chromatography, Journal of Chromatography, vol. 371, 1986, 299-306.

Tadeo J.L., Sánchez-Brunete C., Albero B., García-Valcárcel A.I., Application of ultrasound- -assisted extraction to the determination of contaminants in food and soil samples, Journal of Chromatography A, vol. 1217, 2010, 2415-2440.

Luque-Garcia J.L., Luque de Castro M.D., Ultrasound: a powerful tool for leaching, Trends in Analytical Chemistry, vol. 22, 2003, 41-47.

Moore J.C., Gel permeation chromatography. I. A new method for molecular weight distribution of high polymers, Journal of Polymer Science, vol. 2, 1964, 835-843.

Kuc J., Grochowalski A., Isolation of hexabromocyclododecane from fat matrix using size exclusion chromatography, Czasopismo Techniczne, 2-Ch/2012.

Gómara B., Lebrón-Aguilar R., Quintanilla-Lópezb J.E., González M.J., Development of a new method for the enantiomer specific determination of HBCD using an ion trap mass spectrometer, Analytica Chimica Acta, vol. 605, 2007, 53-60.

Esslinger S., Becker R., Jung C., Schröter-Kermani C., Bremser W., Nehls I., Chemosphere, vol. 83, 2011, 161-167.

Bergqvist P.-A., Strandberg B., Bergek S., Rappe C., Lipid reduction during the analyses of PCDDs, PCDFs and PCBs in environmental samples using semipermeable membrane technique, Organohalogen Compounds, 11, 1993, 41-44.

Kuc J., Grochowalski A., Mach S., Placha D., Level of hexabromocyclododecane isomers in the tissue of selected commonly consumed fish in Central European countries, Acta Chromatografica DOI:10.1556/AChrom.26.2014.4.1 online preview.

Schecter A., Szabo D.T., Miller J., Gent T.L., Malik-Bass N., Petersen M., Paepke O., Colacino J.A., Hynan L.S., Harris T.R., Malla S., Birnbaum L.S., Hexabromocyclododecane (HBCD) Stereoisomers in U.S. Food from Dallas, Texas, Environ Health Perspective, vol. 120, 2012, 1260-1264.

Frederiksen M., Vorkamp K., Bossi R., Svensmark B., Analysis of HBCD and TBBPA by GC-MS versus LC-MS-MS – indications of systematic differences in obtained results, 4th International Symposium On Flame Retardants BRF2007, Amsterdam, Netherlands 2007.

Haug L.S., Thomsen C., Liane V.H., and Becher G., Comparison of GC and LC determinations of hexabromocyclododecane in biological samples – results from two interlaboratory comparison studies, Chemosphere, vol. 71, 2008, 1087-1092.

Barontini F., Cozzani V., Cuzzola A., Petarca L., Investigation of hexabromocyclododecane thermal degradation pathways by gas chromatography/mass spectrometry, Rapid Communication of Mass Spectrometry, vol. 15, 2001, 690-698.

Covaci A., Voorspoels S., de Boer J., Determination of brominated flame retardants, with emphasis on polybrominated diphenyl ethers (PBDEs) in environmental and human samples – A review, Environment International, vol. 29, 2003, 735-756.

Guerra P., Eljarrat E., Barceló D., Determination of halogenated flame retardants by liquid chromatography coupled to mass spectrometry, Trends in Analytical Chemistry, vol. 30, 2011, 842-855.

Budakowski W., Tomy G., Congener-specific analysis of hexabromocyclododecane by high-performance liquid chromatography/electrospray tandem mass spectrometry, Rapid Communication of Mass Spectrometry, vol. 17, 2003, 1399-1404.

Morris S., Bersuder P., Allchin C.R., Zegers B., Boon J.P., Leonards P.E.G., de Boer J., Determination of the brominated flame retardant, hexabromocyclododecane in sediment and biota by liquid chromatography electrospray ionisation mass spectroscopy, Trends in Analytical Chemistry, vol. 25, 2006, 343-349.