Sampling and analytical methods Sampling

Brown ampere bottles should be used which had been threefold rinsed successively with acetone and Milli Q-water and finally heated at 250 °C over night. Each glass bottle must be rinsed at least twice with the water of the site. The water will be immediately adjusted to pH 2-3 with sulphuric acid (50 %, v/v). During the transport the samples will be cooled with an ice bath and the enrichment may be carried out the next two days.

Sample preparation

Prior to analysis, the extraction techniques proposed in the recent papers are the following : liquid-liquid extraction with or without derivatization, SPE with or without derivatization.

Different derivatization techniques are used: MSTFA (N-methyl-N-trimethylsilyltrifluor-acetamide), TMSI (Trimethylsilylimidazole), DTE (Dithioerytrol), PFB (Pentafluorobenzyl bromide).

Analytical procedures

At this time any normalized method is existing for the determinations in routine laboratories of these emerging compounds. The identification and the quantification are carried out by liquid or gas chromatography coupled with mass spectrometry or tandem mass spectrometry with an electrospray ionization source (Table 7.6). In the particular case of estrogens, two analytical methods are proposed for their determination: 1. gas chromatography coupled with a mass spectrometer and 2. liquid chromatography coupled with triple quadrupole mass spectrometer.

The advantage of the second is the absence of a time-consuming derivatization step prior to the analysis. The most common methods used for these determinations are the following:

- SPE/GC-MS with derivatization for steroids and bisphenol A - SPE/LC-MS for bisphenol A

- SPE/LC-MS with derivatization for steroids

- SPE/GC-MS for alkylphenolcarboxylates with derivatization

- SPE/LC-MS/MS for alkylphenolethoxylates and alkylphenolcarboxylates - SPE/LC-MS/MS for pharmaceuticals

Table 7.6. Examples of analytical methods used for monitoring emerging substances.

Compounds Sample

pretreatment

Extraction method Elution solvent Derivatization Separation LOQ ng/l

Ref.

Bisphenol A Filtration SPE/clean-up silica gel

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