A. Domínguez-Vidal

Investigation by ICP-MS of trace element levels in vegetable edible oils produced in Spain

The content of trace elements (Ag, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Ti, Tl and V) in edible oils (virgin olive, olive, pomace-olive, sunflower, soybean and corn) from Spain was determined, using inductively-coupled plasma-mass spectrometry (ICP-MS) after microwave digestion, employing only nitric acid in this step. The method has been validated by using both an oil reference material and recovery experiments over different oil samples, obtaining satisfactory results in all cases. Inter-day repeatabilities lower than 10% were observed for all of the analysed elements in the different kinds of oil samples. Studying the content of trace elements, in order to detect tendencies in the samples of the same type of oil, principal components analysis was used. Promising groupings were observed using a model with two principal components and retaining 75.3% of the variance.

Ion mobility spectrometry of volatile compounds from Iberian pig fat for fast feeding regime authentication.

Characteristic ion mobility spectra for volatile compounds present in fat were used to authenticate the feeding regime of Iberian pigs. Volatile compounds were obtained by heating the solid samples at 150 degrees C for 40 min. This produced a headspace that was introduced in the spectrometer ionization chamber by means of a highly purified nitrogen stream. The spectra thus, obtained for the fat samples were processed chemometrically in order to assess their usefulness for discriminating meat from free-range pigs fed on pasture and acorns and confined pigs fed with commercial feed including high-oleic acid products. Principal component analysis was used as both an exploratory tool and a variable reduction method, and linear discriminant analysis was employed to classify 65 subcutaneous fat samples according to pig feeding regime. Only 2.3% of the samples from pigs reared in confinement were misclassified. 95.5% of the free-range samples were correctly predicted.

Fast flow-injection fluorimetric determination of amiloride by using a solid sensing zone

A rapid and simple flow-through solid phase spectrofluorimetric system is described in this paper for the determination of the diuretic amiloride in physiological fluid (serum) and pharmaceuticals. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric transduction. Amiloride was transitorily retained on cationic exchanger gel Sephadex SP-C25 placed in the detection area into the cell. The determination is carried out without any derivatization reaction, by measuring directly the intrinsic fluorescence of the analyte and using the peak height as analytical signal. The wavelengths of excitation and emission were 291 and 419 nm, respectively. Amiloride could be determined in the concentration ranges of 10-600 and 4-250 mugl(-1) at a sampling rate of 24 and 30 h(-1), respectively with detection limits of 0.92 and 0.33 mugl(-1) for 100, and 600 mul of sample volume injected, respectively. The relative standard deviations for ten independent determinations were better than 0.65%. The method was satisfactorily applied to the determination of amiloride in spiked biological fluids (serum) and pharmaceutical preparations without any pretreatment of the samples.

Feasibility study on the use of infrared spectroscopy for the direct authentication of Iberian pig fattening diet

The feasibility of using both middle- and near-infrared spectroscopy for discrimination between subcutaneous fat of Iberian pigs reared on different fattening diets has been evaluated. The sample set was formed by subcutaneous fat of pigs fattened outdoors (extensively) with natural resources (montanera) and pigs fattened on commercial feeds, either with standard feed or with especial formulations with higher content in oleic acid (HO-formulated feed). Linear discriminant analysis was used to classify the samples according to the fattening diet using the scores obtained from principal component analysis of near- and middle-infrared spectra as variables to construct the discriminant functions. The most influential variables were identified using a stepwise procedure. The discriminant potential of each spectral region was investigated. Best results were obtained with the combination of both regions with 91.7% of the standard feed and 100% of montanera and HO-formulated feed samples correctly classified. Chemical explanations are provided based on the correlation of these variables with fatty acid content in the samples.

Environmental Water Samples Analysis of Pesticides by Means of Chemometrics Combined with Fluorimetric Multioptosensing

A single flow-through optosensor spectrofluorimetric system is proposed for the resolution of mixtures of three pesticides, α-naphthol, o-phenylphenol and thiabendazole, at μg l−1 levels using a partial least-squares (PLS) calibration approach. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric detection using C18 silicagel as an active sorbent substrate in the flow cell. By using 20% methanol-water (v:v) solution as carrier solution, the multisensor responds linearly in the measuring range without requiring additional reagents or derivatization. First derivative emission spectra of the corresponding analytes recorded during the process of retention-elution were used to provide multivariate data. The different kinetic on the retention process of the analytes on the sensing zone allows the selection of a time matrix for each analyte providing best results in the PLS approach. Accurate prediction results were obtained for the three analytes with RMSEP values of 1.86%, 3.34% and 0.50% were obtained for α-naphtol, o-phenylphenol and thiabendazole respectively. In the analysis of environmental waters samples, a mean recovery of 103% was obtained.

Renaissance patinas in Úbeda (Spain): mineralogic, petrographic and spectroscopic study

Different analytical techniques were used for microstructural and compositional analysis of the ochre-coloured patinas that appear on the calcarenite substrate of monuments in the historical settings of Úbeda and Baeza (Spain). Optical microscopy, scanning electron microscopy–energy dispersive x-ray spectrometry (SEM-EDX), x-ray diffraction, Raman spectroscopy and attenuated total reflection–Fourier transform infrared spectroscopy (ATR-FTIR) were employed and a critical comparison of their experimental requirements, strengths and weaknesses is presented. The study focussed on two churches in Úbeda where patinas were widespread in ornamental elements. These films contained calcite as the principal component, and traces of dolomite and feldspars. Clear identification of calcium oxalate, mainly in the form of whewellite, was achieved by infrared and Raman spectroscopic studies. Results from texture, distribution and composition of the patinas in ornamental elements suggest that ancient treatments were applied for protection of Renaissance façades and consolidation of weathered older façades. The patinas were seldom found on supporting elements. Their different composition, apatite was found together with oxalates, and location may suggest a biogenic origin here. Gypsum crusts were sometimes found over the patinas.

Determination of triamterene by transitory retention in a continuous flow solid phase system with fluorimetric transduction

A rapid and simple flow-through solid phase espectrofluorimetric system (sensor) is described in this paper for the determination of the diuretic triamterene at ng ml(-1) level in physiological fluids and in pharmaceuticals. This sensor is based on the transitory retention of the analyte on the cationic ion-exchanger gel Sephadex SP C-25 placed into a quartz flow-cell in the detection zone itself of a spectrofluorimeter and the continuous monitorization of its intrinsic fluorescence. The spectrofluorimeter was tuned at 240 (excitation) and 440 nm (emission). A transitory signal was obtained because the carrier solution used also eluted the analyte from the sensing zone and no derivatization reactions were needed. Triamterene could be determined in the concentration ranges of 10-400 and 2.5-80 ng ml(-1) with detection limits of 0.95 and 0.17 ng ml(-1) for 300 and 1000 microl of sample volume, respectively. The relative standard deviations (RSD) for ten independent determinations and at three concentration levels of standards solutions were lower than 0.90 for 300 microl and 0.45 for 1000 microl. The RSDs for the determination of triamterene in serum samples and pharmaceuticals were lower than 3.3 and 2.6%, respectively. The method was satisfactorily applied to the determination of triamterene in human serum and pharmaceuticals.

Assessment of dentifrice adulteration with diethylene glycol by means of ATR-FTIR spectroscopy and chemometrics.

A direct and fast method for determination of the adulterant diethylene glycol (DEG) in toothpaste and gel dentifrices combining attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy with partial least squares (PLS) regression has been proposed. Considering the high heterogeneity of dentifrices available in the market, the possibility of reducing the number of calibration samples for PLS was evaluated. Similar prediction performance was achieved by both employing a large calibration set of 20 dentifrices spiked with different amounts of DEG and a reduced calibration set of seven ones selected by means of hierarchical cluster analysis (HCA). The feasibility of using the simple calibration model to predict DEG adulteration in a wide variety of unknown dentifrice samples increases the applicability of the proposed method. With this approach, DEG was quantified with a root mean squared error of prediction value of 1.1% for a validation set of 40 different dentifrices containing DEG in the range 0-16% (w:w).

Near-infrared spectroscopy and X-ray fluorescence data fusion for olive leaf analysis and crop nutritional status determination

Leaf analysis is a useful way of diagnosing the nutritional status of the plants and therefore fast methods of analysis are demanded to aid in fertilization management decisions. In this work, a strategy based on the combined use of near-infrared spectroscopy (NIR) and portable energy dispersive X-Ray Fluorescence (EDXRF) is proposed as a suitable cheap and rapid alternative to traditional wet analytical methodologies. The approach has the major benefit of minimal sample preparation since leaves need to be only dried and ground. The ability of both techniques individually and applying two strategies of data fusion for the prediction of the most important plant nutrients, namely N, P, K, Ca, Mg, Mn, Zn, and B was tested. Predictive models were constructed using Partial Least Squares (PLS) to correlate the spectra with the nutrient contents. Models of unequal prediction performance in terms of the ratio of predictive deviation (RPD) were obtained for the different parameters when considering both techniques separately. Low-level data fusion, which consists of a concatenation of the raw data from both techniques, showed little improvement and even decreased the predictive ability for some elements. Better results were obtained with mid-level data fusion, that is, merging data after a feature extraction step performed by means of Principal components analysis (PCA). The results show that a fair quantitative prediction is possible for Ca, K and Mn with RPDs ≥ 2 for external validation, whereas models for N and P allowed a semiquantitative estimation. Mg and B models were less satisfactory and can be used only for distinguish between low and high levels, while Zn content cannot be predicted. Finally, the potential of the fusion of FT-NIR and EDXRF spectroscopic data for the fast screening of olive crop nutritional status has been tested. Deficiencies in important elements like N and K has been successfully detected.