FP21 COMPARISON OF GC-(NCI)MS, GC-(ICP)MS AND GC-(EI)MS/MS FOR THE
DETERMINATION OF PBDEs IN WATER SAMPLES ACCORDING TO THE
REQUIREMENTS OF THE WATER FRAMEWORK DIRECTIVE (WFD). Adriana GonzalezGago, Daniel Proefrock and Andreas Prange. Helmholtz-Zentrum Geesthacht Zentrum für
Material- und Küstenforschung, Department of Marine Bioanalytical Chemistry, Max Planck
Str. 1, Geesthacht, Germany, D-21502; adriana.gonzalez@hzg.de
Polybrominated diphenyl ethers (PBDEs) are a family of chemicals that have been widely
used as flame retardants in a variety of polymeric materials and textiles. Owing to their
persistance and their ability to bioaccumulate and biomagnify, PBDEs have been spread all
around the world, being found in almost all environmental compartments. The extensive
contamination by PBDEs, together with their toxicity to living organisms, has led to their
classification as Persistent Organic Pollutants (POPs), substances from which human health
and the environment should be protected, according to the Stockholm Convention [1].
On a European level, PBDEs are regulated under the Water Framework Directive (WFD)
[2], which deals with the protection of water resources and aquatic environments. The WFD
includes some PBDEs (congeners 28, 47, 99, 100 153 and 154) in the list of priority
substances that need to be measured in surface waters and sets an Environmental Quality
Standard (EQS), or maximum allowable concentration, of 0.5 ng/L for the sum of the six priority
congeners [3]. Moreover, analytical methods must meet certain minimum performance criteria
in terms of uncertainty (≤ 50% at EQS, 95% confidence) and limits of quantification (LOQ ≤
30% of EQS) for a reliable determination of priority substances [4].
Most of the analytical methods developed and applied to the determination of PBDEs in
different environmental samples are based in their detection by Mass Spectrometry (MS),
since MS based methods usually provide adequate sensitivity and selectivity. However,
existing methods still need to be improved in order to be able to detect the overall very low
concentrations of PBDEs in water meeting the challenging requirements defined by the WFD.
According to this, different MS techniques were evaluated in terms of instrumental
capabilities for the sensitive and reliable determination of PBDEs. Three analytical methods
were developed based on the liquid-liquid extraction of the samples and measurement of the
extracts by GC-(NCI)MS, GC-(EI)MS/MS or GC-(ICP)MS. Different spikes (81Br-labelled
PBDEs or 13C-labelled) were selected allowing Isotope Dilution Mass Spectrometry (IDMS)
experiments, depending on the ionization source. Special attention has been paid to the GC(ICP)MS coupling for being a promising technique to meet the challenging requirements of the
WFD, as it shows good selectivity towards brominated compounds and high sensitivity in the
detection of bromine [5]. Furthermore, (ICP)MS has been used in combination with species
specific Isotope Dilution Analysis (IDA) for the determination of other priority pollutants showing
highly accurate and precise analytical results [6].
This work has been performed within the scope of an EMRP Researcher Grant for the
development of a traceable measurement approach for monitoring PBDEs in coastal water,
awarded in accordance with the EURAMET process to complement the JRP “Traceable
measurements for monitoring critical pollutants under the European Water Framework
Directive”.
[1] Stockholm Convention on Persistent Organic Pollutants, Stockholm 22 May 2001, adoption
of amendments to Annex A by decisions SC-4/14 and SC-4/18, Geneva 4-8 May 2009, United
Nations Environment Programme Reference: C.N.524.2009.TREATIES-4 (Depositary
Notification).
[2] Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000
establishing a framework for community action in the field of water policy. Off. J. Eur.
Commun., 22.12.2000, 327, 1-72.
[3] Directive 2008/105/EC of the European Parliament and of the Council of 16 December
2008 on environmental quality standards in the field of water policy, amending and
subsequently repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC,
84/491/EEC, 86/280/EEC and amending Directive 2000/60/EC of the European Parliament
and of the Council. Off. J. Eur. Union, 24.12.2008, 348, 84-97.
[4] Commission Directive 2009/90/EC of 31 July 2009 laying down, pursuant to Directive
2000/60/EC of the European Parliament and of the Council, technical specifications for
chemical analysis and monitoring of water status. Off. J. Eur. Union, 1.8.2009, 201, 36-38.
[5] R. F. Jr. Swarthout, J.R. Kucklick, W.C. Davis, J. Anal. At. Spectrom., 2008, 23, 1575-1580.
[6] B. Jackson, V. Taylor, R.A. Baker, E. Miller, Environ. Sci. Technol., 2009, 43, 2463-2469.