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New materials based on molecularly imprinted polymers (MIPs) have been developed for use as sorbents in solid phase extraction to preconcentrate some urea herbicides. In the preconcentration step, different molecularly imprinted polymers were tested using methacrylic acid (MAA) and 2-(trifluoromethyl)acrylic acid (TFMAA) as functional monomers, and linuron and isoproturon as templates. The best results were obtained when the polymer was synthesised using MAA with isoproturon as template. Another parameter evaluated was the way in which the polymer was obtained. We observed that the imprinted polymers obtained by precipitation displayed a greater capacity to retain the phenylureas. Studies conducted using scanning electron microscopy (SEM) revealed that the bulk polymerisation method is far from ideal owing to the random shape and size distribution of the particles obtained, whereas when polymerisation was carried out in precipitation microspheres were obtained. In order to confirm the interaction between the functional monomer and the template, 1H NMR (CD2Cl2) analyses were conducted. The results obtained suggest that the hydrogen and/or nitrogen of the amino group of the template would be involved in the formation of hydrogen bonds with the functional monomer. The imprinted polymer obtained by precipitation polymerisation with MAA as functional monomer and isoproturon as template can be applied to preconcentrate phenylureas when the sample is dissolved in toluene. The proposed methodology was employed to evaluate polymer selectivity towards humic acids and towards other herbicides.

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A sensitive analytical method based on liquid chromatography-electrospray ionisation mass spectrometry (LC-ESI-MS) has been developed for the determination of seven endocrine-disrupting compounds: 4-n-nonylphenol (NP), 4-tert-butylphenol (t-BP), bisphenol A (BPA), 2,4-dichlorophenol (DCP), 2,4,5-trichlorophenol (TCP), pentachlorophenol (PCP) and 4-tert-butylbenzoic acid (BBA) in water samples. To achieve a good LC separation, acidification of the LC mobile phase was necessary, but this led to MS signal suppression for the less acidic compounds. In order to enhance the sensitivity for these analytes, post-column addition of different bases such as ammonia, trimethylamine, and 1,8-diazabicyclo-(5,4,0)undec-7-en (DBU) was evaluated. The post-column addition of base is proposed here to raise effluent pH, helping in the ionisation process of the compounds with higher pKa values (t-BP, BPA, DCP and NP). The use of DBU, diluted in MeOH, proved to be the most efficient post-column reagent for enhancing the MS signal. The signal-to-noise ratios for t-BP and NP increased by more than 200-fold and 35-fold, respectively, whereas for DCP and BPA an increase of about 10-fold was achieved. This strategy permitted direct determination of the seven compounds at low ppb levels. For application to real water samples, an extraction and preconcentration step using the solid-phase extraction (SPE) technique was carried out. The applicability of three solid-phase materials--Bond Elut C18, and two polymeric sorbents: LiChrolut EN and Oasis HLB--and the optimization of other SPE parameters such as the elution solvent and sample volume used, were studied in order to maximize extraction efficiency. Oasis HLB provided the best results, obtaining--with the proposed SPE procedure--satisfactory percentage recoveries for all compounds (70-110%) with the exception of NP, for which a recovery of 54% was achieved. Application of the whole method, SPE-LC-(ESI)-MS, to natural waters permitted low nanogram-per-liter determination of all seven compounds.

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