Identification of tetramethylarsonium in rice grains with elevated arsenic content.

Tetramethylarsonium has for the first time been identified in a commercially grown food product, rice, constituting up to 5.8% of the total arsenic in the rice.

Identification of Sb(V) complexes in biological and food matrixes and their stibine formation efficiency during hydride generation with ICPMS detection.

Several studies have described the synthetic preparation of Sb(V) complexes with organic ligands, but only recently was such a complex identified to exist in beverages stored in PET containers. In the present study, we have investigated by using HPLC-ICPMS and HPLC-ES-MS(/MS), the formation of Sb(V) complexes in various biological (urine) and food matrixes (yoghurt and juice) spiked with noncomplexed inorganic Sb(V). Our results show that Sb(V) complex formation is matrix dependent and that several Sb(V) complexes form to a considerable extent in these matrixes. The results also suggest that the existence of Sb(V) complexes in natural samples may have previously been overlooked due to analytical method limitations, mainly chromatographic, but also detection limitations when hydride generation is used. To overcome some of these limitations, we have developed chromatographic methods suitable for preserving Sb-organic ligand complexes during their separation. When applying this mild nondestructive chromatographic method, we were able to identify novel Sb complexes in yoghurt spiked with inorganic Sb(V), i.e., 1:1 Sb(V)-citrate, 1:1 Sb(V)-lactate, 1:2 Sb(V)-lactate, and other Sb(V)-lactate complexes. This is the first characterization of Sb(V)-lactate complexes. Detailed studies on the hydride generation (HG) efficiency of Sb(V) complexes showed that Sb(V) complexes of high stability, such as Sb(V)-citrate, Sb(V)-(adenosine)n and Sb(V)-(lactate)n (n = 1 or 2), are nondetectable by HG-ICPMS. Furthermore, Sb(V) complexes formed in natural biological and food matrixes were only partly detectable by HG-ICPMS, confirming limitations of analytical methods based on HG volatilization and subsequent stibine detection in natural samples containing complexing ligands with affinity toward Sb(V).

Arsinothioyl-sugars produced by in vitro incubation of seaweed extract with liver cytosol analysed by HPLC coupled simultaneously to ES-MS and ICP-MS.

It has been shown, that in vitro incubation of Laminaria digitata extract (containing mainly As-sugar 1 (glycerol-arsenoribose) and As-sugar 3 (sulfonate-arsenoribose)) with liver cytosol, produced the same two arsenicals, as when L. digitata extract was treated with H(2)S. By parallel use of HPLC-ICP-MS and HPLC-ES-MS the compounds displayed mainly m/z 345 and m/z 409. A pure As-sugar 1 standard was obtained, and a standard of arsinothioyl-sugar 1 (m/z 345) was produced, by purging a solution of As-sugar 1 with gaseous H(2)S. The identity of arsinothioyl-sugar 1 was characterised by ES-MS, 1D and 2D NMR. Arsinothioyl-sugar 1 showed the same chromatographic behaviour and MS characteristics as one of the two arsenic-containing compounds (m/z 345) produced by incubation of L. digitata extracts with liver cytosol, and as the product of the incubation of As-sugar 1 with liver cytosol (HPLC-ICP-MS, HPLC-ES-MS). Assuming that As-sugar 3 reacts in a similar way to As-sugar 1 with H(2)S, it is most likely that the second unknown (m/z 409) is arsinothioyl-sugar 3. The degradation of As-sugar 1 in acidic solution (100 mM HCl) was followed by (1)H-NMR, and the relative slow degradation (t(1/2)= 17 h) suggests that arsenosugars are taken up from the stomach in their original chemical form, hence the study of arsenosugar incubation in tissue is highly relevant. The arsinothioyls are a new group of organoarsenicals, which have only recently been identified in nature. Here, arsinothioyl sugars are detected for the first time. The in vitro formation of arsinothioyl-sugars in liver cytosol suggests that arsinothioyls may be of large biochemical and toxicological importance.

Sulfur-containing arsenical mistaken for dimethylarsinous acid [DMA(III)] and identified as a natural metabolite in urine: major implications for studies on arsenic metabolism and toxicity.

It is vital that methylated trivalent arsenicals [MA(III) and DMA(III)] are described and characterized unequivocally due to their high toxicity. Two different ways of generating the methylated trivalent arsenicals have been practiced-reduction of the methylated pentavalent arsenical either by the sodium-metabisulfite (Na(2)S(2)O(5))/sodium thiosulfate (Na(2)S(2)O(3)) reagent (method A) or by KI, H(2)SO(4), and SO(2) (method B). The shared identity between the products of the two synthetic methods has never been questioned or proven. Here, we characterize and identify the arsenic species formed when reducing DMA(V) by method A or B. Dimethylarsinous acid [DMA(III)] was formed when reducing DMA(V) by method B, but DMA(III) was not the main product of the reaction by method A. The product was revealed by HPLC-ICP-MS coupled simultaneously to HPLC-ES-MS and ES-Q-TOF-MS to have the molecular formula C(2)H(7)OSAs. The structure was further confirmed by (1)H NMR, and ab initio tautomeric energy calculations showed it to be present as Me(2)As(=S)OH (dimethylarsinothioic acid). Dimethylarsinothioic acid was also identified as a metabolite in urine and in wool extract from sheep naturally consuming large amounts of arsenosugars (35 mg of As daily) through their major food source, seaweed.

Arsenic accumulation and speciation analysis in wool from sheep exposed to arsenosugars.

Wool or hair fibre is a metabolically dead material after it has left the epidermis. During growth the fibre in the root is a metabolically very active organ, which is highly influenced by the health status of the living being. Arsenic is one of the elements that is easily taken up by the cells of the root and stored in the fibre afterwards. Here we show that arsenic can quantitatively be extracted by boiling the wool fibre or hair in water. The high intake of arsenic species by the sheep of North Ronaldsay (the seaweed-eating sheep) leads to a high arsenic concentration in wool (mean 5.2+/-2.3 mug g(-1)). The wool of lambs of these sheep, which are not exposed to seaweed, contains about 10 times less arsenic, which is still elevated compared to uncontaminated wool. The arsenic species identified in wool extract are arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMA(V)) and monomethylarsonious acid (MMA(III)) as minor species. The major species is dimethylated arsenic DMA in its tri- and pentavalent form (dimethylarsinous acid (DMA(III)) and dimethylarsinic acid (DMA(V))) accounting for 85% of the specified arsenic in the wool which reflects the amount of dimethylated species (i.e. the arsenoribofuranosides) taken up by seaweed being the main food source of the sheep. However, there are unknown arsenic species in the extract, which are not eluting from a strong anion exchange column. In vitro incubation experiments with this kind of wool showed that it has reducing properties but no demethylation was recorded. The absorption ability of the wool for methylated arsenic species is negligible, while inorganic arsenic is easier to be absorbed in the fibre (11-17%). This means that the species integrity is only guaranteed in terms of the degree of methylation but not in terms of their redox status.