Comparison of different analytical procedures in the determination of trace elements in lichens

A BCR standard reference material of lichen (CRM 482) was used to validate an analytical procedure consisting of a microwave oven digestion associated with ICP-OES, ICP-MS and GFAAS techniques for the analysis of trace elements (Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in biomonitor samples. Two different acid mixtures were used: (a) 7 ml of HNO3, 1 ml of H2O2; (b) 7 ml of HNO3, 1 ml of H2O2 and 200 microl of HF; all digestions were carried out using 100-250 mg samples brought to a final volume of 50 ml. The validation of the procedure was carried out by two laboratories in terms of accuracy and precision; the former was estimated as percentage recovery by comparing experimental data with certificate values; the latter evaluated according to ISO standard 5725. Real lichen samples were analysed too with the procedures above described. In certified CRM 482 and real lichen samples the procedure with HF showed higher recovery values for Al, Ti, V, Ba and Fe than the procedure without HF. For all the other elements the two procedures gave comparable results both in terms of accuracy and precision. The recovery obtained with HF procedure for all the elements was generally better than 90-103%.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Levels of PCDD/Fs and trace elements in superficial soils of Pavia Province (Italy)

Trace elements and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in soils from rural and light-industrialized sites (n=168) of Province of Pavia (Northern Italy). Most of the trace element values fit in typical ranges of concentrations in soils and are similar to the ones reported for rural sites in Italy or sites with no direct anthropogenic impact. Total concentrations of 2,3,7,8 chlorine substituted PCDD/Fs in superficial soils ranged between 24.4 and 1287 pg g(-1) dw (0.5-28.9 pg WHO(98)-TEQ g(-1) dw). The North Eastern part of the Province presented significantly higher levels (p<0.001) than the rest of the Province for As, Cd, Hg, Pb, Zn and PCDD/Fs. While the existence of a defined heavy metal polluting source for this specific site has been suggested, in the case of PCDD/Fs, profiles were not linked to any specific emission source fingerprint. In the whole extension of Pavia Province, OCDD/F dominated the 2,3,7,8 chlorine substituted congener soil pattern, followed by the 1,2,3,4,6,7,8 hepta-CDD/F congener. Principal Component Analysis (PCA) showed that this profile could not be associated to any described PCDD/F emission source fingerprint and was relatively similar to the baseline deposition of sites with no direct impact of PCDD/F emission sources independently of land use.