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MEKC coupling with LIF detection has been used for the determination of four aflatoxins (B(1), B(2), G(1) and G(2)). Separations were performed in an uncoated fused-silica capillary (70 cm x 75 microm id, 55 cm effective length), using 20 mM borate buffer with 30 mM SDS (pH 8.5) and 7% ACN. In order to increase sensitivity, an on-line preconcentration procedure was applied, based on sweeping, using the same separation buffer without SDS as solvent of the sample. The precision of the method was evaluated in terms of repeatability and intermediate precision and the results were acceptable in all cases (RSD<12%). With the on-line preconcentration LODs (obtained as 3 x S/N) were as low as 0.11, 0.52, 0.04 and 0.10 microg/L for G(2), G(1), B(2) and B(1), respectively. Recovery studies were developed with extracts of rice samples spiked with aflatoxins, being in the range between 93.0 and 105.4%. The method has also been applied to the determination of aflatoxins in rice samples, and the results compared with those obtained by a standard method, being in good agreement.

Peroxyoxalate chemiluminescence (PO-CL) is an indirect type of CL which allows the detection of native fluorophores or compounds derivatized with fluorescent labels. We propose a flow injection analysis (FIA) configuration based on the use of a two-injection valve system for the introduction of both PO and derivatized analyte solutions in the flow system, avoiding the problems arising from the use of organic solvents, such as acetonitrile, as no special tubes nor special pumps are required. Furthermore, the use of micellar media (sodium dodecyl sulphate, SDS) as a carrier and the addition of tetrahydrofurane (THF) in the PO solutions increase both the solubility and stability of POs, avoiding their rapid degradation in water. The proposed CL-FIA system has been applied to the determination of sulphadiazine (a sulphonamide mainly used in the treatment of urinary tract infections for human and veterinary use) using bis[2,4,6-trichlorophenyl]oxalate (TCPO) as CL precursor, H2O2 as oxidant, imidazole as a catalyst and fluorescamine as the fluorescent derivatizing agent. The optimization of variables was carried out by means of experimental designs and the method showed a LOQ of 379 microg l(-1) (calibration range 126-2000 microg l(-1)). It has been satisfactorily applied to the quantification of sulphadiazine in pills for human use and ampoules for veterinary use.

This paper presents two methods based on CZE-MS detection and CZE-MS/MS detection developed for the multiresidue determination of ten sulfonamides (sulfapyridine, sulfadoxin, sulfamethazine, sulfadimethoxine, sulfameter, sulfamerazine, sulfachlorpyridazine, sulfadiazine, sulfamethoxazole, and sulfamethizole) and a potentiator, trimethoprim (TMP), whose contents are regulated by the EU Council Regulation no. 2377/90 in animal edible tissues. Experimental designs were employed to optimize the electrospray conditions. MS/MS experiments using an IT as analyzer operating in multiple reaction monitoring (MRM) mode were carried out to achieve the minimum number of points according to the 2002/657/EC European Decision for unambiguous identification. The proposed procedures have been compared in terms of the performance characteristics and trueness. The limits of detection and quantification were in all cases lower than the maximum residue limits legislated for these compounds and the recoveries were satisfactory, being possible the application for their monitoring in foodstuff of animal origin and in environmental samples, allowing the determination of sulfonamides and TMP residues in meat and in superficial water in the low microg/L range.

A CZE method with UV-Vis detection has been established and validated for the determination of nine sulfonamides: sulfapyridine, sulfamethazine, sulfamerazine, sulfamether, sulfadiazine, sulfadimethoxine, sulfamethoxazole, sulfachlorpyridazine, and sulfamethizole. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 45 mM sodium phosphate and 10% methanol at pH 7.3, with temperature and voltage of 27 degrees C and 25 kV, respectively. p-Aminobenzoic acid was used as an internal standard . Taking into account the lack of sensitivity of the UV-Vis detection, the application of an on-line preconcentration methodology, such as large-volume sample stacking with polarity switching has been proposed. This procedure combined with a solvent extraction/SPE method applied for off-line preconcentration and cleanup provides a significant improvement in the LODs, ranging from 2.59 to 22.95 mug/L for the studied compounds; the quantification of these residues being possible below the levels established by EU legislation in animal food products, such as meat. Satisfactory recoveries were also obtained in the analysis of these compounds in ground water.

A new strategy is proposed for verifying if recovery factor is constant and independent of the real analyte content of samples. A signal-recovery function has been developed on the basis of measurement of spiked test samples before and after a pre-treatment step and considering, as starting point, a recent IUPAC recommendation which distinguishes between two terms--recovery factor, R, and apparent recovery, R*. Apparent recovery includes recovery factor and a new recovery term proposed in a previous paper by the authors, named calibration recovery, R(C). The signal-recovery function is obtained directly from the measured analytical signals instead of from the concentrations, simplifying the calculations. A linear signal-recovery curve indicates that the recovery factor is constant in the analyte concentration range studied experimentally and, in this way, a single recovery factor can be calculated. The usefulness of the proposed method has been shown by quantification of the pesticide carbaryl by two different flow-injection analysis methods with chemiluminescent detection based on the luminol and TCPO systems. Good results were obtained from both methods.

The determination of seven sulfonamides by means of HPLC with chemiluminescence detection is proposed for the first time. The analytes are derivatized with fluorescamine, separated and subsequently they participate in the post-column chemiluminescence (CL) peroxyoxalate system using imidazole as a catalyst. Among the different peroxyoxalates tested, bis[4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl] oxalate provides higher sensitivities and stabilities, avoiding precipitation problems. A rigorous optimization of the significant variables by means of experimental designs has been developed in order to reconcile the chromatographic conditions with the CL reaction. The method provides detection limits in the low microgl(-1) range and has been satisfactorily applied to the analysis of spiked raw milk samples.

A new formal strategy in the multidimensional optimisation of the experimental variables affecting the chemiluminescence (CL) detection in flow injection analysis (FIA) is proposed here. The strategy implies several steps, being the most significant: selection of the variables to be studied and their experimental domain; use of a screening design to detect significant variables and interactions into the experimental region; study of the main effect of variables and second-order interactions; and finally application of a Draper-Lin small composite design (orthogonal) to obtain the optimum values of the significant variables. The methodology is applied to the determination of methylamine by FIA based on the use of the peroxyoxalate CL (PO-CL) reaction. Considering the high number of experiments required due to the different chemical and instrumental variables to be taken account and their adequate compatibility to obtain maximum sensitivity, the methodology offers a rigorous study of the main effects and interactions, achieving a reduction of experimental work.