3 research outputs found
Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter
Abstract Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxidesâcollectively referred to as âoxidesâ hereafterâare prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline ÎŽ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate (âO horizon leachateâ hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopyânear-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOMâHMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 Ă 102 Όg C mâ2), DOM desorptionâassessed by 0.1 M NaH2PO4 extractionâis lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 Ă 102 Όg C mâ2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOMâHMO complexes may be more vulnerable to reductive dissolution than DOMâgoethite complexes
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