Arsenic hyperaccumulator Pteris vittata shows reduced biomass in soils with high arsenic and low nutrient availability, leading to increased arsenic leaching from soil.

Plant-soil interactions affect arsenic and nutrient availability in arsenic-contaminated soils, with implications for arsenic uptake and tolerance in plants, and leaching from soil. In 22-week column experiments, we grew the arsenic hyperaccumulating fern Pteris vittata in a coarse- and a medium-textured soil to determine the effects of phosphorus fertilization and mycorrhizal fungi inoculation on P. vittata arsenic uptake and arsenic leaching. We investigated soil arsenic speciation using synchrotron-based spectromicroscopy. Greater soil arsenic availability and lower nutrient content in the coarse-textured soil were associated with greater fern arsenic uptake, lower biomass (apparently a metabolic cost of tolerance), and arsenic leaching from soil, due to lower transpiration. P. vittata hyperaccumulated arsenic from coarse- but not medium-textured soil. Mass of plant-accumulated arsenic was 1.2 to 2.4 times greater, but aboveground biomass was 74% smaller, in ferns growing in coarse-textured soil. In the presence of ferns, mean arsenic loss by leaching was 195% greater from coarse- compared to the medium-textured soil, and lower across both soils compared to the absence of ferns. In the medium-textured soil arsenic concentrations in leachate were higher in the presence of ferns. Fern arsenic uptake was always greater than loss by leaching. Most arsenic (>66%) accumulated in P. vittata appeared of rhizosphere origin. In the medium-textured soil with more clay and higher nutrient content, successful iron scavenging increased arsenic release from soil for leaching, but transpiration curtailed leaching.

Synthetic iron (hydr)oxide-glucose associations in subsurface soil: Effects on decomposability of mineral associated carbon.

Soils are a globally important reservoir of organic carbon. There is a growing understanding that interactions with soil mineral phases contribute to the accumulation and retention of otherwise degradable organic matter (OM) in soils and sediments. However, the bioavailability of organic compounds in mineral-organic-associations (MOAs), especially under varying environmental conditions is not well known. To assess the impact of mineral association and warming on the decomposition of an easily respirable organic substrate (glucose), we conducted a series of laboratory incubations at different temperatures with field-collected soils from 10 to 20cm, 50-60cm, and 80-90cm depth. We added 13C-labeled glucose either directly to native soil or sorbed to one of two synthetic iron (hydr)oxide phases (goethite and ferrihydrite) that differ in crystallinity and affinity for sorbing glucose. We found that: (1) association with the Fe (hydr)oxide minerals reduced the decomposition rate of glucose by >99.5% relative to rate of decomposition for free glucose in soil; (2) the respiration rate per gram carbon did not differ appreciably with depth, suggesting a similar degree of decomposability for native C across depths and that under the incubation conditions total carbon availability represents the principal limitation on respiration under these conditions as opposed to reduced abundance of decomposers or moisture and oxygen limitations; (3) addition of free glucose enhanced native carbon respiration at all soil depths with the largest effect at 50-60cm; (4) in general respiration of the organo-mineral complex (glucose and iron-(hydr)oxide) was less temperature sensitive than was respiration of native carbon; (5) the addition of organic free mineral decreased the rate of soil respiration in the intermediate 50-60cm depth soil. The results emphasize the key role of MOAs in regulating the fluxes of carbon from soils to the atmosphere and in turn the stocks of soil carbon.

Mn(III) center availability as a rate controlling factor in the oxidation of phenol and sulfide on delta-MnO2.

Manganese oxides are involved in many environmentally important redox reactions. This work focuses primarily on the reaction of phenol and sulfide with delta-MnO2 (birnessite) and the inhibitory effect of pyrophosphate on these reactions. The reactions were modeled in terms of Mn(III) center surface availability. The model partitioned the observed rate constants between two different hypothetical reaction pathways. One of these pathways was deemed to be dependent on Mn(III) center concentration, while the other was Mn(III) center independent. The relative contribution of each pathway was then calculated based on the equilibrium concentration of free Mn(III) centers at a given pyrophosphate concentration. Using this approach it was possible to model the observed pyrophosphate effects and to predict inhibition with respect to reactant concentration. Finally, the effects of pyrophosphate and orthophosphate on the reaction of sulfide and hydroquinone with delta-MnO2 were observed and compared to previously published observations. The observed orthophosphate and pyrophosphate effects were consistent with the two reaction pathway model in terms of Mn(III) center complexation. These findings have important implications for modeling and understanding the fate and transport of redox reactive material.