1          Background

Polybrominated Diphenyl Ethers (PBDEs) are among the most common brominated flame retardants (FRs). They are mainly used in plastics, resins and textiles, as in plastic casings of electric and electronic devices such as computers and TVs, in printed circuit boards, as well as in protective clothing, textile covers and curtains. Today mainly DecaBDE is used while past usages included Penta and Octa-BDE.

PBDEs are considered to be persistent and partly bioaccumulative. On numerous occasions PBDEs have been found in aqueous systems, aquatic animals and mother’s milk. PentaBDE is considered very poisonous to water organisms. OctaBDE is classified as a reproductive toxin (category 2). The use of DecaBDE is currently being re-evaluated as part of an EU risk assessment. Potential endocrine activity is attributed to PBDE degradation products. Another point of discussion is the possible formation of especially polybrominated dibenzofurans in case of a fire in materials made less flammable by the incorporation of PBDEs.

The restriction 2003/11/EG (Restriction on the marketing and use of certain dangerous substances and preparations) by the European Parliament prescribes that the marketing of PentaBDE and OctaBDE is no longer allowed starting August 15th, 2004. As part of restriction 2002/95/EG (RoHS – Restriction of Hazardous Substances) the use of PBB and PBDE in new electrical and electronic devices is banned EU wide starting July 1^st, 2006. Currently there are discussions about exempting DecaBHD from the Directive.  Polybrominated diphenyl ethers (PBDEs) are classified as priority pollutant according to the EU water framework guideline 2000/60/EC.

2          Analytes

Polybrominated diphenyl ethers, totals and congeners

TriBDE	TetraBDE	PentaBDE	HexaBDE	HeptaBDE	OctaBDE	NonaBDE	DecaBDE
BDE-17	BDE-75	BDE-100	BDE-154	BDE-183	BDE-203	BDE-207	BDE-209
BDE-28	BDE-71	BDE-119	BDE-153	BDE-190
BDE-37	BDE-47	BDE-99	BDE-138
	BDE-49	BDE-85
	BDE-66	BDE-126
	BDE-77

The analysis is normally carried out according to the selection of PBDE compounds requested by the customer.

3          Test methods

Validated GC/MS GfA method using ¹³C₁₂-labelled internal standard substances

-  soxhlet extraction of the sample with toluene

-  addition of internal ¹³C₁₂-labelled PBDE standards (¹³C₁₂-TetraBDE, ¹³C₁₂-PentaBDE, ¹³C₁₂-HexaBDE, ¹³C₁₂-HeptaBDE, ¹³C₁₂-DecaBDE)

-  clean-up of the extract by column chromatography

-  analysis via capillary gas chromatography coupled with mass spectrometry (GC/MS)

-  identification via molecule or fragment ions

-  quantification of the native PBDE via the internal ¹³C-labelled standards

4          Quantification limits, sample quantity and shipment of samples

Matrix	Quantification limit	Sample quantity	Preferred sample container
sludge /sediment/soil	1 - 10 µg/kg	100 g sample	amber glass-/PE vessel
solutions (aq. matrix)	1 - 10 ng/l	2 x 1 l solution	amber glass vessel
Biological materials	1 - 10 µg/kg	100 g sample	amber glass-/PE vessel
Industrial materials	depends on matrix	after consultation	amber glass-/PE vessel

5          Pertinent Quality Assurance programs

-     QUASIMEME, UK: PBDE in fish, fish oil, sediment, sewage sludge; 2001/2002; 2004; 2005

-     Folkehelsa, Norway: PBDE, PCDF/D and PCB in chicken, trout, palm oil; 2004

-     DIN working group “brominated analysis” DIN NAW 1.3: PBDE in sediment and sewage sludge; 2005

-     Örebro University, Sweden: PBDE, PCDF/D and PCB in flue ash and fish; 2001/2002

-     APME, Brussels: PBB, PBDE and TBBPA in exhaust gases and E&E plastic shredder; 1996

6          Publications

-        Hamm, S., Maulshagen, A., Petersen, M., Fengler, S., Seel, P., Organohalogen Cmpds. 66 (2004) 1629-1634, PBDEs in Sewage Sludge and Effluents of Sewage Plants from a Central Region of Germany

-        Behnisch, P. A., Hosoe, K., Sakai, S.-J., Env. Intern. 29 (2003) 861-877, Brominated dioxin-like compounds: in vitro assessment in comparison to classical dioxin-like compounds and other polyaromatic compounds

-        Behnisch, P. A., Letcher, R. J., Environment International 29 (2003) 663-664, The state of the science and trends of brominated flame retardants in the environment: present knowledge and future directions

-        Hamm, S., Imai, T., Rothenbacher, K. P., Environ. Science Technol. 37 (3) (2003) 652-657, Comparison of the Recyclability of Flame-Retarded Plastics

-        Hamm, S., Strikkeling, M., Ranken, P. F., Rothenbacher, K. P., Chemosphere 44 (2001) 1353-1360, Determination of PBDEs and PBDD/Fs during the recycling of HIPS containing DecaBDE and antimony oxide

7          Contact

        Lars Reimann                                                                                      Dr. Stephan Hamm / Michaela Lichte
Eurofins Scientific                                                                               Eurofins / GfA
6555 Quince Road Suite 202                                                           Otto-Hahn-Straße 22,

        Memphis, TN 38119                                                                           48161 Münster

        U.S.A.                                                                                                     Germany

                Tel.:  +1 901.507.3959                                                                       ++49 (0) 25 34 / 80 70       

                Fax:  +1 901 272 2926                                                                        ++49 (0) 25 34 / 80 7-1 10
                e-mail:  LarsReimann@EurofinsUS.com                                              welcome@gfa-ms.de