Ultra-sensitive speciation analysis of tellurium by manganese and iron assisted photochemical vapor generation coupled to ICP-MS/MS.

Photochemical vapor generation (PVG) of Te4+ was undertaken with a simple reactor consisting of a polytetrafluoroethylene reaction coil wrapped around a low-pressure mercury tube lamp and using a flow-injection for sample delivery. The composition of a reaction medium, the influence of irradiation time and the effect of added sensitizers and interferents were investigated using high-resolution continuum source atomic absorption spectrometry and a miniature diffusion flame atomizer. A mixture of 5 M acetic acid and 3.5 M formic acid and sample flow rate of 4 mL min-1 permitting a 36 s irradiation time were found optimal for PVG of Te4+. The addition of 250 mg L-1 Mn2+ and 15 mg L-1 Fe2+ ions as sensitizers enhanced the overall PVG efficiency 2.75-fold to 50 ± 2%. In order to achieve higher sensitivity necessary for determination of Te in real environmental samples, PVG was coupled to inductively coupled plasma triple quadrupole mass spectrometer and detection was performed with O2 in the reaction cell utilizing a mass shift mode of measurement (m/z 128 → m/z 144) to ensure interference free ion detection. A limit of detection 1.3 ng L-1 and repeatability (RSD) 0.9% at 250 ng L-1 were achieved. This ultrasensitive methodology was validated for speciation analysis of Te in water samples of various matrix complexities (fresh water, well water, seawater and contaminated water). Since no response was observed from Te6+ under optimal PVG conditions, Te4+ was selectively determined by direct PVG. The sum of Te4+ and Te6+ was determined after pre-reduction of Te6+ in 6 M HCl (95 °C), evaporation to dryness and reconstitution in the reaction medium containing sensitizers. Very good accuracy was demonstrated by spiked recoveries for both Te4+ and total Te in water samples and also by total Te determination in fresh water Standard Reference Material NIST 1643f.

Allelic Diversity of Acetyl Coenzyme A Carboxylase accD/bccp Genes Implicated in Nuclear-Cytoplasmic Conflict in the Wild and Domesticated Pea (Pisum sp.).

Reproductive isolation is an important component of species differentiation. The plastid accD gene coding for the acetyl-CoA carboxylase subunit and the nuclear bccp gene coding for the biotin carboxyl carrier protein were identified as candidate genes governing nuclear-cytoplasmic incompatibility in peas. We examined the allelic diversity in a set of 195 geographically diverse samples of both cultivated (Pisum sativum, P. abyssinicum) and wild (P. fulvum and P. elatius) peas. Based on deduced protein sequences, we identified 34 accD and 31 bccp alleles that are partially geographically and genetically structured. The accD is highly variable due to insertions of tandem repeats. P. fulvum and P. abyssinicum have unique alleles and combinations of both genes. On the other hand, partial overlap was observed between P. sativum and P. elatius. Mapping of protein sequence polymorphisms to 3D structures revealed that most of the repeat and indel polymorphisms map to sequence regions that could not be modeled, consistent with this part of the protein being less constrained by requirements for precise folding than the enzymatically active domains. The results of this study are important not only from an evolutionary point of view but are also relevant for pea breeding when using more distant wild relatives.