Potential phytoavailability of anthropogenic cobalt in soils as measured by isotope dilution techniques.

Isotope dilution is a useful technique to determine the potential phytoavailability of an element in soil. This method involves equilibrating an isotope with soil and then sampling the labile metal pool by analysis of the soil solution (E value) or plants growing in the soil (L value). The work reported here was conducted to evaluate the distribution coefficient (Kd), and the potential phytoavailability (E value) of cobalt (Co) in eight soils subjected to the atmospheric deposition of anthropogenic Co. Multiple regression analyses demonstrated that the K(d) of isotopically exchangeable Co in these soils was best modelled with two parameters: soil pH and organic carbon (OC) content (log Kd=0.85(pH)+1.1(logOC)-5.0, R2=0.94, p<0.01). Cobalt E values ranged from 1.5 to 37% of total soil Co concentrations. No evidence was obtained to suggest that Co(III), if present, was isotopically exchangeable in these soils and it was concluded that the Co E values consisted solely of Co(II). Cobalt L values, measured with Triticum aestivum L. (46 days), of two of these soils (varying in soil pH, e.g. 5.0 and 7.2) were statistically (p<0.05) different to E values. However, when changes of bulk soil pH on Co E values were considered, the two values were statistically (p<0.05) similar indicating that processes affecting soil pH during plant growth can alter isotopically exchangeable concentrations of Co.

Anion exchange liquid chromatography--inductively coupled plasma-mass spectrometry detection of the Co2+, Cu2+, Fe3+ and Ni2+ complexes of mugineic and deoxymugineic acid.

Phytosiderophores, such as mugineic and deoxymugineic acid, are produced by graminaceous plant species in response to Fe deficiency conditions normally experienced in calcareous and alkaline non-calcareous soils. As these phytosiderophores have the ability to form thermodynamically stable complexes with other metal cations present in the growing medium, they have also been implicated in the transport and bioavailability of these metals in the environment. However, routine analytical methodology to detect the various metal complexes formed by these phytosiderophores is lacking. Therefore, as these complexes are negatively charged over a wide range of pH values, anion exchange liquid chromatography (AE LC) coupled to inductively coupled plasma-mass spectrometry (ICP-MS) was investigated as a means to separate and quantify these complexes. The metal-phytosiderophore complexes were prepared at pH 7 and separated by NaOH or NH4NO3 gradient elution on a Dionex AS11 anion exchange column. Of the metals tested only the Co2+ and Ni2+ complexes of mugineic and deoxymugineic acid were detected when using a 0-20mM NaOH gradient elution profile. However, the phytosiderophore complexes of Cu2+ and Fe3+ were also detected when using NH4NO3 as the mobile phase at pH 7. Base-assisted hydrolysis of the latter two complexes is proposed to explain their apparent 'instability' in the high pH NaOH mobile phase. The absolute detection limits of the developed methodologies for these metal complexes ranged from 0.1 to 2.8pmol. As phytosiderophore complexes with Cd2+ and Zn2+ were not detected, it was concluded that the dissociation kinetics of these metal-phytosiderophore complexes were too rapid for these complexes to be observed in the present chromatographic conditions.

Performance of diffusion gradient in thin films to evaluate the toxic fraction of copper to Daphnia magna.

This study investigates the relevance of the diffusion gradient in thin films technique (DGT) to measure copper's induced lethality on Daphnia magna in natural water spiked with various organic ligands. Ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and glycine were used as artificial organic ligands in controlled solutions of mineral water. With EDTA, DGT measurement makes it possible to predict the toxicity of the mixture because Cu-EDTA complexes are inert, whereas DGT is of no help in the case of NTA, because Cu-NTA complexes are fully labile. The Cu-glycine complexes appear as partly labile and toxic. Humic acids as well as fresh and aged algae extracts also were used as models for natural dissolved organic matters. All three of them form copper complexes that are not toxic to Daphnia magna and appear as partly labile with open-pored DGT. However, the use of restricted gels in DGT greatly reduces the contribution of labile complexes, at least for humic acids and aged algae copper complexes. The DGT with restrictive gels, therefore, appears to be a powerful tool for measuring bioavailable copper in natural water bodies, especially when the dissolved organic matter mostly is of humic origin. The DGTs potential ability to mimic the lability induced by the biological uptake also is discussed.

Uptake, localization, and speciation of cobalt in Triticum aestivum L. (wheat) and Lycopersicon esculentum M. (tomato).

The root-to-shoot transfer, localization, and chemical speciation of Co were investigated in a monocotyledon (Triticum aestivum L., wheat) and a dicotyledon (Lycopersicon esculentum M., tomato) plant species grown in nutrient solution at low (5 muM) and high (20 muM) Co(II) concentrations. Cobalt was measured in the roots and shoots by inductively coupled plasma-mass spectrometry. X-ray absorption spectroscopy measurements were used to identify the chemical structure of Co within the plants and Co distribution in the leaves was determined by micro-PIXE (particle induced X-ray emission). Although the root-to-shoot transport was higher for tomato plants exposed to excess Co, both plants appeared as excluders. The oxidation state of Co(II) was not transformed by either plant in the roots or shoots and Co appeared to be present as Co(II) in a complex with carboxylate containing organic acids. Cobalt was also essentially located in the vascular system of both plant species indicating that neither responded to Co toxicity via sequestration in epidermal or trichome tissues as has been observed for other metals in metal hyperaccumulating plants.

Assessment of isotope exchange methodology to determine the sorption coefficient and isotopically exchangeable concentration of selenium in soils and sediments.

Isotope exchange methodology is invaluable to determine the solution-solid-phase distribution (Kd) and isotopically exchangeable concentration (Evalue) of elements in soils and sediments. This work examined the use of species-specific stable isotope exchange techniques to determine the Kd and E value of selenium (Se), as selenite (SeO3) and selenate (SeO4), in nine soils and sediments varying in concentration and source of Se. High-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was used to quantify the isotope (e.g., 76Se, 78Se, 80Se, and 82Se) concentrations of the soluble Se oxyanions. The two Se oxyanions were detected in the solution phase of all of the soils and sediments. However, upon spiking the suspensions with stable isotope-labeled 78SeO3 and 76SeO4, it was observed that isotope self-exchange was insignificant to the derivation of Se oxyanion Kd and E values during 24 h (and up to 120 h in four of the samples). These results demonstrate that valid determinations of the Evalue of Se necessitate that the Se oxyanions are speciated in solution. This is clearly evident for these soils and sediments where it was observed that the Evalues of SeO3 and SeO4 represented, respectively, 5-97% and 3-95% of the total Se E value.