Patricia Cava-Montesinos

Determination of arsenic and antimony in milk by hydride generation atomic fluorescence spectrometry.

A highly sensitive procedure has been developed for total arsenic and antimony determination in milk samples by hydride generation atomic fluorescence spectrometry after microwave-assisted sample digestion. The discrete introduction of 2 ml of digested sample in the automated continuous flow hydride generation system allows us to reduce drastically the sample and HCl consume and to determine several elements from a same sample digestion. The method provides detection limits of 0.006 and 0.003 ng ml(-1), a sensitivity of 2390 and 2840 fluorescence units per ng ml(-1) for As and Sb respectively, and average relative standard deviation of 2.3% for As and 4.8% for Sb. The analysis of cow milk samples, obtained from the Spanish market evidenced the presence of As at concentration levels from 3.4 to 11.6 ng g(-1) and Sb levels from 3.5 to 11.9 ng g(-1), thus in a proportion near to 1:1, which is in contrast with the 10:1 natural ratio between As and Sb and could evidence the effect of the introduction of new alloys and polymer materials in the industrial process of milk. The method was validated by the comparison of data found for commercial samples by using the proposed procedure and reference methods based on dry-ashing and AFS, and microwave-assisted digestion and inductively coupled plasma mass spectrometry determination.

Non-chromatographic speciation of toxic arsenic in fish

A rapid, sensitive and economic method has been developed for the direct determination of toxic species of arsenic present in fish and mussel samples. As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were determined by hydride generation-atomic fluorescence spectrometry using a series of proportional equations without the need of a chromatographic previous separation. The method is based on the extraction of arsenic species from fish through sonication with HNO(3) 3moll(-1) and 0.1% (m/v) Triton and washing of the solid phase with 0.1% (m/v) EDTA, followed by direct measurement of the corresponding hydrides in four different experimental conditions. The limit of detection of the method was 0.62ngg(-1) for As(III), 2.1ngg(-1) for As(V), 1.8ngg(-1) for MMA and 5.4ngg(-1) for DMA, in all cases expressed in terms of sample dry weight. The mean relative standard deviation values (R.S.D.) in actual sample analysis were: 6.8% for As(III), 10.3% for As(V), 8.5% for MMA and 7.4% for DMA at concentration levels from 0.08mgkg(-1) As(III) to 1.3mgkg(-1) DMA. Recovery studies provided percentages greater than 93% for all species in spiked samples. The analysis of SRM DORM-2 and CRM 627 certified materials evidenced that the method is suitable for the accurate determination of arsenic species in fish.

Determination of As, Sb, Se, Te and Bi in milk by slurry sampling hydride generation atomic fluorescence spectrometry.

A simple and fast analytical procedure has been developed for the determination of As, Sb, Se, Te and Bi in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS). Samples were treated with aqua regia for 10min in an ultrasound water bath and pre-reduced with KBr for total Se and Te determination or with KI and ascorbic acid for total As and Sb, the determination of Bi being possible in all with or without pre-reduction. Slurries of samples, in the presence of antifoam A, were treated with NaBH(4) in HCl medium to obtain the corresponding hydrides, and AFS measurements were processed in front of external calibrations prepared and measured in the same way as samples. Results obtained by the developed procedure compare well with those found after microwave-assisted complete digestion of samples. The proposed method is simple and fast, and only 1ml of milk is needed. The values obtained for detection limit are 2.5, 1.6, 3, 6 and 7ngl(-1) for As, Sb, Se, Te and Bi respectively in the diluted samples, with average relative standard deviation values of 3.8, 3.1, 1.9, 6.4 and 1.2% for three independent analysis of a series of commercially available samples of different origin. Data found in Spanish market samples varied from 3.2+/-0.3 to 11.3+/-0.2ngg(-1) As, from 3.1+/-0.2 to 11.6+/-0.4ngg(-1) Sb, from 10.7+/-0.5 to 25.5+/-0.4ngg(-1) Se, from 0.9+/-0.2 to 9.4+/-0.6ngg(-1) Te and from 11.5+/-0.1 to 27.7+/-0.4ngg(-1) Bi.

On-line speciation of mercury in fish by cold vapour atomic fluorescence through ultrasound-assisted extraction

A fully mechanized procedure has been developed for the speciation of mercury in fish samples by using cold vapour atomic fluorescence spectrometry (CV-AFS). Sample slurries in an acid mixture in the presence of a surfactant and with traces of K2Cr2O7, were injected into a flow system, sonicated and merged with 1 ml of an oxidant mixture of KBr/KBrO3 heated at 50 °C in a water bath and total Hg determined by CV-AFS. Sonicated sample slurries were also measured, in the absence of KBr/KBrO3, in order to obtain a second series of data which could be employed to establish the concentrations of free Hg(II). Different compositions of the acidic extractant solutions were evaluated by mixing HCl, HNO3, H2SO4 and H2O2. The best results were obtained for a diluted mixture of HCl 3 mol l−1, H2SO4 1.4 mol l−1, HNO3 0.11 mol l−1and H2O2 0.22 mol l−1. The method provides a detection limit of 7 µg kg−1 in dried sample and a mean relative standard deviation in actual samples of 6.8%. Quantitative recoveries were obtained for the determination of Hg and methylmercury (MeHg) in a SRM DORM-2 (dogfish muscle) and a SRM TORT-2 (lobster hepatopancreas) certified reference materials.

Speciation of selenium and tellurium in milk by hydride generation atomic fluorescence spectrometry

A simple, fast and highly sensitive method has been developed for the differentiation of Se and Te into their (IV) and (VI) oxidation states in milk samples by HG-AFS. This procedure involves a previous leaching of milk slurries by sonication with aqua regia for 10 min. Se(IV) and Te(IV) were determined by analysis of the samples without a pre-reduction step; being total Se and Te determined after reduction with KBr. The method provides limit of detection values (LOD) of 0.012 and 0.023 ng ml−1 for Se(IV) and Te(IV) respectively. Average relative standard deviation values of 10.5%, 3.9%, 12% and 12.5% were found for the determination of Se(IV), Se(VI), Te(IV) and Te(VI) in milk samples containing Se from 11.1 to 32.2 ng g−1 and Te from 1.1 to 10 ng g−1. Recovery experiments made on actual samples spiked with Se(IV), Se(VI), Te(IV) and Te(VI) evidenced that the sonication with aqua regia does not modify the oxidation state of the elements considered.

1,3-Oxazin-2-ones vs tetrahydrofurans by iodocyclisation of 2-alkoxycarbonylamino-3-alken-1-ols

Abstract Iodocyclisation of primary homoallylic alcohols 2a – d , containing either a 2- t -butoxy- or a benzyloxycarbonylamino group, was studied, in order to establish the nucleophilic group involved in cyclofunctionalisation. In fact, the N - t -Boc derivative 2a gave the oxazinone 3 , exclusively, whereas starting from the N -Cbz derivative 2b a diastereomeric mixture of substituted tetrahydrofurans 4 and 5 resulted in ratios depending upon the reaction conditions. These results were rationalised by means of computational methods. On the contrary, migration of both the t -butyl or benzyl group to the hydroxy group was observed when both 2c and 2d underwent cyclisation to give the corresponding 5-alkoxymethyl oxazolidin-2-ones 7a , b in low yield, but with high regio- and stereocontrol.