Broad-spectrum determination of pesticides in groundwater by gas chromatography with electron capture detection, nitrogen-phosphorus detection, and tandem mass spectrometry.

Gas chromatography with electron capture detector (ECD), nitrogen-phosphorus detector (NPD), and tandem mass spectrometry (MS/MS) was used to identify 36 pesticides, widely used to control various pest and diseases in vegetables, in water after a preconcentration step on C18 cartridges. The recoveries obtained ranged from 70 to 135% at a fortification level of 100 ng/L with relative standard deviations of <36.2%. The limits of detection and quantitation were < or =48 and < or =160 ng/L, respectively. Important advantages of MS/MS over ECD and NPD in the determination of pesticides are also presented. The proposed analytical methodology was applied to the determination of pesticides in groundwater samples from an agricultural area, the Campo de Dalías (Almería, Spain). The most frequently encountered pesticides were endosulfan sulfate and metalaxyl, whereas the pesticide found at the highest concentration was fenamiphos.

Application of the Kohonen neural network in coastal water management: methodological development for the assessment and prediction of water quality.

Kohonen neural network (KNN) was applied to nutrient data (ammonia, nitrite, nitrate and phosphate) taken from coastal waters in a Spanish tourist area. The activation maps obtained were not sufficient to evaluate and predict the trophic status of coastal waters. To achieve this aim, a new methodology is proposed which uses as its starting point the activation maps obtained from KNN. Firstly, to evaluate the trophic status of the coastal waters, it consists of the development of a quadrat system which enables a better classification than the traditional classification based simply on standardized data. The new classification allows clear differentiation of water quality within the mesotrophic band. Secondly, and in order to use the activation maps as predictive tools, the trophic classification, obtained from activation maps, was transposed onto new activation maps. To do this, the activation maps of the sampling points which defined each trophic group were superimposed. To avoid unnecessary complexity and to facilitate the process, this superimposition was undertaken only where the frequency exceeded 0.05. In this way, four frequency maps related to the trophic status of coastal waters (potentially eutrophic, high mesotrophic, low mesotrophic and oligotrophic) were obtained. There was no loss of relevant information in the new maps thus obtained. These frequency maps served as the basis for the successful prediction of the trophic status of random samples of coastal waters. This methodology, based on KNN, is proposed as a tool to aid the decision-making in coastal water quality management.

Quantitative determination of endocrine- disrupting polychlorinated biphenyls and organochlorinated pesticides in human serum using gas chromatography with electron-capture detection and tandem mass spectrometry.

A sensitive, selective and reliable procedure was developed and validated to determine organochlorinated compounds, which have endocrine-disrupting effects, in human serum. Target compounds were selected between polychlorinated biphenyls and organochlorinated pesticides. Sample workup consisted of (1) extraction of serum with organic solvents, (2) clean-up of the organic extract using acid treatment with H(2)SO(4), (3) elution of the cleaned-up extract through a liquid column chromatographic system and (4) analysis of the fraction eluted by gas chromatography with electron capture detection (ECD) and tandem mass spectrometry (MS/MS) detection. Performance characteristics, such as linearity, sensitivity, precision, accuracy and recovery, of both chromatographic methods were studied. The proposed analytical methodology was applied to determine the target compounds in serum samples from women living in agricultural areas of Almería (Spain). The results show the advantage of MS/MS over ECD in the analysis of real human serum samples where matrix interferences can be confused with target pesticides.

Pesticide trace analysis using solid-phase extraction and gas chromatography with electron-capture and tandem mass spectrometric detection in water samples.

Gas chromatography (GC) with electron-capture detection (ECD), mass spectrometry (MS) and tandem mass spectrometry (MS-MS) were employed for the identification of 12 pesticides in water samples. For this purpose, a solid-phase extraction procedure with C18 cartridges was used, optimising the breakthrough volume and the saturation concentration. In GC-MS-MS, the lowest detectable concentrations for the pesticides were between 2 and 26 ng l(-1), recoveries ranged from 70 to 133% in water samples spiked at 100 ng l(-1) and the relative standard deviations were in the range 5.3 to 17.4%. The proposed analytical methodology was applied to analyse pesticides in wetland samples from Almería (Spain).

Use of the cross-section technique linked with multivariate calibration methods to resolve complex pesticide mixtures.

The potential of the cross-section (CS) approach in combination with the partial least squares (PLS) and principal component regression (PCR) was assessed in the resolution of a complex pesticide mixture showing twelve overlapped components in High Performance Liquid Chromatography with Diode Array Detection (HPLC-DAD). Careful selection of the CS through the three-dimensional (3D) (A, lambda, t) data matrix gave two-dimensional (2D) signals with the best sensitivity for the determination of each pesticide. In all cases, the application of the PLS method demonstrated a better quantitative prediction ability than that of the PCR method. The CS-PLS approach is a powerful analytical tool. Ten pesticides were well-resolved, while for the other two pesticides of the mixture prediction ability was poor, and they could not be determined, probably due to their low net analytical signal. The CS-PLS model was evaluated by predicting the concentrations of independent test set samples. Finally, the proposed model was successfully applied for the determination of these pesticides in groundwater.

First derivative of the ratio spectra method for resolving iodide and thiocyanate in binary mixtures.

A new method is described to analyse the binary mixture of iodide (I(-)) and thiocyanate (SCN(-)) ions, using the first derivative of the ratio spectra obtained by mathematical treatment of the data. The method is based on the formation of mixed ligand complexes between benzohydroxamic acid (BHA), vanadium (V) and I(-) or SCN(-) and their extraction in ammonium quaternary salt dissolved in toluene. Calibration graphs for 2-9 mug/ml of I(-) and for 2-6 mug ml of SCN(-) were established by measuring the analytical signals at 376 nm for I(-) and at 400.6 nm for SCN(-). The method has been applied for determining both ions in waste water of an power station at ng/ml levels after a preconcentration step with C(18), without any separation step.