Cadmium in the hyperaccumulating mushroom Thelephora penicillata: Intracellular speciation and isotopic composition.

Thelephora penicillata is an ectomycorrhizal mushroom that can accumulate extraordinarily high concentrations of Cd, As, Cu, and Zn in its fruit-bodies. To better understand its element accumulation ability, we compared the element concentrations in T. penicillata with 10 distinct ectomycorrhizal mushroom species growing at the same site (Karlina Pila, Czech Republic). On average, T. penicillata accumulated 330, 2130, 26, and 4 times more Cd, As, Cu, and Zn, respectively, than other mushrooms. Size-exclusion chromatography and an electrophoretic analysis of T. penicillata cell extracts indicate that intracellular Cd may be present mainly in >1 kDa, presumably compartmentalized, Cd species, and partially binding with 6-kDa cysteinyl-containing peptide(s) resembling metallothioneins. The cadmium isotopic composition of mushroom fruit-bodies, soil digests, and soil extracts was investigated by thermal ionization mass spectrometry (TIMS) with double spike correction. The isotopic composition (δ114/110Cd) of ectomycorrhizal mushrooms from Karlina Pila varied in a wide range of -0.37 to +0.14 ‰. However, remarkably low δ114/110Cd values were observed in the majority of the investigated mushrooms when compared to the relatively homogeneous Cd isotopic composition of bulk soil (δ114/110Cd = +0.09 ‰) and the comparatively heavy isotopic composition of soil extracts (mean δ114/110Cd values of +0.11 ± 0.01 ‰ and +0.22 ± 0.01 ‰, depending on the extraction method). The isotopic composition of Cd hyperaccumulated in T. penicillata essentially matched the mycoavailable soil Cd fraction. However, most isotopic data indicates isotopic fractionation at the soil/fruit-body interface, which could be of environmental significance.

Cadmium isotopic composition of biogenic certified reference materials determined by thermal ionization mass spectrometry with double spike correction.

A116Cd-106Cd double-spike method in combination with thermal ionization mass spectrometry (TIMS) was applied to obtain cadmium (Cd) mass fractions and stable isotope compositions in seven biogenic certified reference materials (pine needles, tomato leaves, spinach leaves, lichen, mussel tissue, oyster tissue, and pig kidney). This sample set was supplemented by the analysis of two manganese nodules and one soil reference material for which the Cd isotopic data has already been reported. The intermediate measurement precision of the whole protocol as determined for the NIST SRM 3108 Cd standard solution yields an excellent value of δ114/110Cd of -0.005 ± 0.029‰ (2SD, n = 47). The Cd isotopic compositions of the biogenic materials, reported as δ114/110Cd relative to NIST SRM 3108, range from -0.52 to +0.50‰. Plants show δ114/110Cd mean values ranging from -0.09 to +0.45‰ whereas the δ114/110Cd value of -0.17‰ was detected in the lichen and the values of -0.51, -0.52, and +0.47‰ were gathered for the oyster, mussel, and pig kidney tissues, respectively. The observed large variation of the δ114/110Cd values in the biogenic reference materials indicates a potential to use the natural mass-dependent Cd isotope fractionation in environmental, biogeochemical, and physiological studies.

Molybdenum-isotope signals and cerium anomalies in Palaeoproterozoic manganese ore survive high-grade metamorphism.

Molybdenum (Mo) and its isotopes have been used to retrieve palaeoenvironmental information on the ocean-atmosphere system through geological time. Their application has so far been restricted to rocks least affected by severe metamorphism and deformation, which may erase or alter palaeoenvironmental signals. Environmental Mo-isotope signatures can be retrieved if the more manganese (Mn)-enriched rocks are isotopically depleted and the maximum range of δ98Mo values is close to the ~2.7‰ Mo-isotope fractionation known from Mo sorption onto Mn oxides at low temperature. Here, we show that the Morro da Mina Mn-ore deposit in Minas Gerais, Brazil, contains Mn-silicate-carbonate ore and associated graphitic schist that likely preserve δ98Mo of Palaeoproterozoic seawater, despite a metamorphic overprint of at least 600 °C. The extent of Mo-isotope fractionation between the Mn-silicate-carbonate ore and the graphitic schist is similar to modern Mn-oxide precipitates and seawater. Differences in δ98Mo signals are broadly reflected in cerium (Ce) anomalies, which suggest an oxic-anoxic-stratified Palaeoproterozoic ocean.

Dissolution kinetics of Pd and Pt from automobile catalysts by naturally occurring complexing agents.

Powder samples prepared from gasoline (Pt, Pd, Rh, new GN/old GO) and diesel (Pt, new DN/old DO) catalysts and recycled catalyst NIST 2556 were tested using kinetic leaching experiments following 1, 12, 24, 48, 168, 360, 720 and 1440-h interactions with solutions of 20mM citric acid (CA), 20 mM Na(2)P(4)O(7) (NaPyr), 1 g L(-1) NaCl (NaCl), a fulvic acid solution (FA-DOC 50 mg L(-1)) and 20 mM CA at pH 3, 4, 5, 6, 7, 8 and 9. The mobilisation of platinum group elements (PGEs) was fastest in solutions of CA and NaPyr. In the other interactions (NaCl, FA), the release of PGEs was probably followed by immobilisation processes, and the interactions were not found to correspond to the simple release of PGEs into solution. Because of their low concentrations, the individual complexing agents did not have any effect on the speciation of Pd and Pt in the extracts; both metals are present in solution as the complexes Me(OH)(2), Me(OH)(+). Immobilisation can take place through the adsorption of the positively charged hydroxyl complexes or flocculation of fulvic acid, complexing the PGEs on the surface of the extracted catalysts. The calculated normalised bulk released NRi values are similar to the reaction rate highest in the solutions of CA and NaPyr.