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Methods for the determination of phenolic brominated flame retardants, and by-products, formulation intermediates and decomposition products of brominated flame retardants in water.

Journal of chromatography. A (2008-09-03)
P López, S A Brandsma, P E G Leonards, J De Boer
ABSTRACT

Brominated flame retardants (BFRs) are the chemicals of high importance within the REAch framework. In addition to polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA), other BFRs such as bromophenols, intermediates in FR formulation like bromoanilines, and their brominated and non-brominated by-products such as bromoanisoles, bromotoluenes, bromoalkanes and 1,5,9-cyclododecatriene, respectively should be monitored and controlled because of their toxicity and their very low odour and taste thresholds, below sub-nanogram-per liter levels. In the present study several analytical methods for the simultaneous determination, i.e., combining one single sample treatment and one analysis step, of these compounds in water have been developed, optimized and evaluated. The methods involve a (pre-concentration)-extraction technique, such as liquid-liquid (LLE), solid-phase (SPE), headspace (HS) extraction or solid-phase microextraction (SPME), followed by gas chromatography (GC)-mass spectrometry (MS) analysis with either electron capture negative ionization (ECNI) or electron impact (EI) as ionization techniques. ECNI is more sensitive than EI for analytes with more than one bromine atom. HS and SPME were previously optimized by means of a multifactorial experimental design. Extraction temperature and the liquid/headspace volume ratio were the most significant factors in HS extraction. In SPME, the variables studied were the nature of the fiber, the mode of extraction and the extraction temperature. Polydimethylsiloxane (PDMS) fibers appeared to be more suitable than carboxen-polydimethylsiloxane (CAR-PDMS) for the analysis of the target compounds with more than one bromine atom. The extraction of 2,4-dibromoaniline was only achieved in a direct immersion mode, in which the optimal extraction temperature was 60 degrees C. The methods LLE-GC-(ECNI)MS, LLE-GC-(EI)MS, SPE-GC-(ECNI)MS, SPE-GC-(EI)MS, HS-GC-(EI)MS and SPME-GC-(EI)MS were evaluated in terms of linearity, precision, detection limits and trueness. All methods, with the exception of HS-GC-(EI)MS, were linear in a range of at least two orders of magnitude, giving recoveries above 75% and detection limits at the low ng/L level for most of the target analytes. SPE-GC-(ECNI)MS is the most sensitive and reliable method for the determination of most of the bromine compounds, whereas SPE-GC-(EI)MS is the most suitable to quantify the three isomers of 1,5,9-cyclododecatriene. Both methods together with SPME-GC-(EI)MS (for qualitative confirmation) were applied to water samples from the Western Scheldt (The Netherlands), where 2,6-dibromophenol and 2,4,6-tribromoanisole could be detected at levels higher than their respective odour thresholds.

MATERIALS
Product Number
Brand
Product Description

Supelco
Carboxen® 569, glass TD tube, fritted, O.D. × L 1/4 in. × 3 1/2 in., preconditioned, pkg of 10 ea
Supelco
2,3,4,5,6-Pentabromotoluene, analytical standard
Supelco
Carboxen® 569, O.D. × L 1/4 in. × 3 1/2, glass TD tube, fritted, Sealed with Brass Endcaps, preconditioned, pkg of 10 ea
Supelco
ORBO 90 Carboxen® 564 (20/45), 160/80 mg, W,F,F separators, O.D. × L 6 mm × 75 mm, pkg of 25 ea, for analyte group MEK (methylethyl ketone)
Supelco
ORBO 78 HBr on Carboxen® 564 specially cleaned (20/45), 400/200 mg, W,W,W separators, O.D. × L 6 mm × 110 mm, pkg of 25 ea
Supelco
SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), for use with autosampler, needle size 23 ga, metal alloy fiber, fiber L 1 cm
Supelco
SPME fiber assembly Carboxen/Polydimethylsiloxane (CAR/PDMS), df 85 μm (CAR/PDMS), for use with autosampler, needle size 23 ga, metal alloy fiber
Supelco
SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), for use with autosampler, needle size 23 ga, metal alloy fiber, fiber L 2 cm
Supelco
SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), needle size 23 ga, StableFlex, for use with autosampler
Supelco
SPME fiber assembly Carboxen/Polydimethylsiloxane (CAR/PDMS), df 85 μm (CAR/PDMS), needle size 23 ga, StableFlex, for use with autosampler
Supelco
SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), needle size 23 ga, StableFlex, for use with manual holder/autosampler, fiber L 2 cm
Supelco
Tenax® TA / Carboxen® 1018, glass TD tube, preconditioned, O.D. × L 1/4 in. × 3 1/2 in., Sealed with (Swagelok® End-Fittings), pkg of 10 ea
Supelco
Carboxen® Adsorbent, matrix Carboxen® 572, 20-45 mesh, bottle of 10 g
Supelco
Carboxen® 1000 Reversible SPE Tube, 200 mg/mL, pk 30
Supelco
Carboxen® Adsorbent, matrix Carboxen® 569, 20-45 mesh, bottle of 500 g
Supelco
ORBO-93 Sorbent Tube, ORBO tube I.D. × L 6 mm × 95 mm, Bed B 90 mg, Bed A 180 mg, 60/80 mesh, pkg of 25 ea
Supelco
Carboxen® 572 for Tobacco Smoke, Adsorbent Bed Wt: 300 mg, cartridge size 3 mL, pkg of 50 ea
Supelco
Carboxen® 572 for Tobacco Smoke, Adsorbent Bed Wt: (300 mg), cartridge volume 3 mL, pkg of 10 ea
Supelco
Carboxen® Adsorbent, matrix Carboxen® 564, 20-45 mesh, pack of 144 × 290 mg
Supelco
Carboxen®-1006 PLOT Capillary GC Column, L × I.D. 30 m × 0.32 mm, average thickness 15 μm
Supelco
Carboxen® Adsorbent, matrix Carboxen® 1003, 40-60 mesh, bottle of 10 g
Supelco
SPME Portable Field Sampler, coating CAR/PDMS
Supelco
SPME fiber assembly Carboxen/Polydimethylsiloxane (CAR/PDMS), df 75 μm (CAR/PDMS), needle size 23 ga, for use with manual holder
Supelco
SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), needle size 24 ga, for use with manual holder
Supelco
Carboxen® Adsorbent, matrix Carboxen® 1000, 40-60 mesh, bottle of 50 g
Supelco
SPME fiber assembly Carboxen/Polydimethylsiloxane (CAR/PDMS), df 85 μm (CAR/PDMS), needle size 24 ga, StableFlex, for use with autosampler
Supelco
Carboxen® Adsorbent, matrix Carboxen® 1000, 60-80 mesh, bottle of 10 g
Supelco
Carboxen®-1010 PLOT Capillary GC Column, L × I.D. 30 m × 0.32 mm, average thickness 15 μm
Supelco
Carboxen®-1010 PLOT Capillary GC Column, L × I.D. 30 m × 0.53 mm, average thickness 30 μm
Supelco
Carboxen® Adsorbent, matrix Carboxen® 569, 20-45 mesh, bottle of 10 g