The determination of manganese status in the Australian diet using neutron activation analysis

Fifty representative foods sampled Australia-wide from each of the State capitals were analysed for manganese by instrumental neutron activation analysis. Calculated daily intake of manganese for Australian diets was compared with recommendations by US authorities for the safe and adequate dietary intake of this essential trace element. The contribution of tea to adult daily intakes was determined.     

Kinetic studies of some substituted hexarhodium carbonyl clusters

Reactions of the halides X- (X- = chloride, bromide or iodide) with the substituted cluster Rh6(CO)15(PPh3) in oxygen-free chloroform lead to [Rh5(CO)14(PPh3)]-, Rh(CO)2(PPh3)2X and [Rh(CO)2X2]- in the molar ratios 2:1: approximately 13. Oxidation by the solvent is assumed to lead to most of the Rh(I) product, and the stoichiometry for reactions with I- can be defined as 4Rh6(CO)15(PPh3) + 27I- + 12CHCl3 --> 2[Rh5(CO)14(PPh3)]- + Rh(CO)2(PPh3)2I + 13[Rh(CO)2I2]- + 6C2H2Cl4 + 4CO + 12Cl-. This can be rationalized quite simply with the aid of a few generally justifiable assumptions. Rate constants for reactions with bromide increase to a limiting value with increasing [Br-] in a way that shows that breaking of one Rh-Rh bond, with an unusual closo to nido structural change, is rate determining. This opening of the cluster might be spontaneous or solvent induced. To complete the reaction, the bromide has to compete with the reverse nido to closo change. The same closo to nido change is also a major rate determining step for reactions with P(OPh)3 in oxygen-free solutions, and for reactions with bromide in oxygenated solutions in the presence of trifluoroacetic and some other acids. The limiting rates increase slightly with increasing basicity of the ligands P(p-XC6H4)3 along the series X = F3C, Cl, F, H and MeO. Activation parameters for these reactions are reported.     

Irradiation techniques for the release of bound heavy metals in natural waters and blood

Irradiation techniques are compared with conventional acid digestion procedures for the release of bound heavy metals in natural waters and in blood, before their determination by anodic stripping voltammetry. Ultra-violet irradiation of acidified water with a 550-W mercury vapour lamp releases bound zinc, cadmium, lead and copper after 4 h. The same results can be achieved with a 30-Mrad dose of high-energy γ-irradiation. These techniques are also effective for the release of metals in whole blood and blood plasma, where sample volumes as small as 200 μl are adequate in analyses for zinc, copper and lead. By comparison with acid digestion and solvent extraction methods, irradiation treatments offer the advantages of minimum sample manipulation and negligible reagent blanks.