Flow injection spectrophotometric determination of V(V) involving on-line separation using a poly(vinylidene fluoride-co-hexafluoropropylene)-based polymer inclusion membrane.

A poly(vinylidene fluoride-co-hexafluoropropylene)-based polymer inclusion membrane (PIM) using Cyphos® IL 101 (i.e. trihexyl(tetradecyl)phosphonium chloride) as the carrier and 2-nitrophenyl octyl ether as a plasticizer in a mass ratio of 55/35/10 was employed for the on-line extractive separation of V(V) prior to its spectrophotometric determination in a flow injection analysis (FIA) system using xylenol orange as the colorimetric reagent. The selectivity of the membrane allowed the determination of V(V) in sulfate solutions in the presence of a variety of cations and anions. The interference of molybdenum(VI) was eliminated by off-line extraction using the same PIM. A univariate sequential optimization of the newly developed FIA system was conducted and under optimal conditions the system is characterized by a linear concentration range of 0.5-8.0mgL-1, detection limit of 0.08mgL-1 and sample throughput of 4h-1. The relative standard deviation at the 3mgL-1 level of V(V) was 2.9% based on 8 replicate determinations. The membrane was stable, which was reflected by the standard deviation value for determinations over three consecutive days (24 determinations of 3mgL-1 V(V)) of 3.6%. The newly developed FIA system was applied to the determination of V(V) in water and dietary supplements samples and a good agreement with inductively coupled plasma optical emission spectrometry was observed.

Chemical characterisation and speciation of organic selenium in cultivated selenium-enriched Agaricus bisporus.

The selenium concentration in Agaricus bisporus cultivated in growth compost irrigated with sodium selenite solution increased by 28- and 43-fold compared to the control mushroom irrigated solely with water. Selenium contents of mushroom proteins increased from 13.8 to 60.1 and 14.1 to 137 µgSe/g in caps and stalks from control and selenised mushrooms, respectively. Selenocystine (SeCys; detected as [SeCys]2 dimer), selenomethionine (SeMet), and methyl-selenocysteine (MeSeCys) were separated, identified and quantified by liquid chromatography-electrospray ionisation-mass spectrometry from water solubilised and acetone precipitated proteins, and significant increases were observed for the selenised mushrooms. The maximum selenoamino acids concentration in caps and stalks of control/selenised mushrooms was 4.16/9.65 µg/g dried weight (DW) for SeCys, 0.08/0.58 µg/g DW for SeMet, and 0.031/0.10 µg/g DW for MeSeCys, respectively. The most notable result was the much higher levels of SeCys accumulated by A. bisporus compared to SeMet and MeSeCys, for both control and selenised A. bisporus.

Elemental and metabolite profiling of nickel hyperaccumulators from New Caledonia.

Leaf material from nine Ni hyperaccumulating species was collected in New Caledonia: Homalium kanaliense (Vieill.) Briq., Casearia silvana Schltr, Geissois hirsuta Brongn. & Gris, Hybanthus austrocaledonicus Seem, Psychotria douarrei (G. Beauvis.) Däniker, Pycnandra acuminata (Pierre ex Baill.) Swenson & Munzinger (syn Sebertia acuminata Pierre ex Baill.), Geissois pruinosa Brongn. & Gris, Homalium deplanchei (Viell) Warb. and Geissois bradfordii (H.C. Hopkins). The elemental concentration was determined by inductively-coupled plasma optical emission spectrometry (ICP-OES) and from these results it was found that the species contained Ni concentrations from to 250-28,000 mg/kg dry mass. Gas chromatography mass spectrometry (GC-MS)-based metabolite profiling was then used to analyse leaves of each species. The aim of this study was to target Ni-binding ligands through correlation analysis of the metabolite levels and leaf Ni concentration. Approximately 258 compounds were detected in each sample. As has been observed before, a correlation was found between the citric acid and Ni concentrations in the leaves for all species collected. However, the strongest Ni accumulator, P. douarrei, has been found to contain particularly high concentrations of malonic acid, suggesting an additional storage mechanism for Ni. A size exclusion chromatography separation protocol for the separation of Ni-complexes in P. acuminata sap was also applied to aqueous leaf extracts of each species. A number of metabolites were identified in complexes with Ni including Ni-malonate from P. douarrei. Furthermore, the levels for some metabolites were found to correlate with the leaf Ni concentration. These data show that Ni ions can be bound by a range of small molecules in Ni hyperaccumulation in plants.