Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals.

Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using (14)CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle.

Study of the mechanisms of cadmium biosorption by dealginated seaweed waste.

The ability of dealginated seaweed waste, a waste material derived from the commercial processing of seaweed for alginate production, to remove cadmium from solution was determined. Cadmium sorption was found to be rapid (91% removal within 5 min), achieving a residual concentration of 0.8 mg L-1 after 1-h contact time from an initial solution concentration of 10 mg L-1. The binding of cadmium by dealginate was found to be pH dependent, optimal sorption occurring at around pH 6-8. The mechanism of cadmium ion binding by dealginate was investigated by a number of techniques. Potentiometric titration of the dealginate revealed two distinct pKa values, the first having a value similar to carboxyl groups and the second comparable with that of saturated thiols and amines. Esterification of the dealginate resulted in the subsequent reduction in cadmium sorption (95% to 17%), indicating that carboxyl groups are largely responsible for sorption. Evidence from FT-IR spectra confirmed the presence of carboxyl groups in untreated dealginate, while the number of carboxyl groups was markedly reduced in the esterified sample. Furthermore, the FT-IR spectrum for dealginate was found to be similar to that previously reported for mannuronic acid-rich calcium alginate. Determination of a molar ratio in the displacement of calcium by cadmium on dealginate further supported the presence of an ion-exchange relationship. The ion-exchange constant was calculated to be 0.329 x 10(-6). The speciation of cadmium in solution both before and after sorption was determined by an ion-selective electrode (ISE) technique. The findings of this study suggest that the sorption of cadmium by dealginate is mainly due to an ion-exchange mechanism.