A sequential selective dissolution method to quantify storage and stability of organic carbon associated with Al and Fe hydroxide phases

Abstract

Stabilization of SOM (soil organic matter) is regulated in part by sorption and desorption reactions happening at mineral surfaces, as well as precipitation and dissolution of organo-metal complexes. Fe and Al hydroxides play a particularly significant role in SOM stabilization in soils due to their ubiquitous distribution and their highly reactive surface properties. Iron and Al hydroxides exist in soils across a wide spectrum of crystallinity, ranging from dissolved Fe and Al cations which combine with organics to form organo-metal precipitates to the more crystalline end members, goethite and gibbsite, which sorb SOM through a variety of molecular interactions. Though the importance of these sorption and precipitation reactions has long been recognized, the distribution of SOM among Fe and Al hydroxides of differing crystallinity has not been well quantified, nor has the timescale over which these stabilization mechanisms operate. In an attempt to measure the distribution of organic C among (i) Al- and Fe-humus complexes (ii) short-range-order (SRO) Al and Fe hydroxide surfaces and (iii) crystalline Fe oxyhydroxide surfaces, a single method combining several selective mineral dissolutions was applied to soils of four different geneses (a tropical forest Andisol, a temperate forest basaltic Mollisol, a Mediterranean coastal prairie Mollisol, and a northern mixed hardwood forest Spodosol). The traditional reactants used in selective dissolutions were replaced with carbon-free analogues so that the carbon released along with the Fe and Al at each stage of the selective dissolution process could be measured. Selective dissolutions were performed sequentially: Na-pyrophosphate (organo-Al and Fe complexes) followed by hydroxylamine (SRO Al and Fe hydroxides) followed by dithionite-HCl (crystalline Fe hydroxides). Carbon, Al, and Fe concentrations, as well as radiocarbon abundance were measured in the solutions yielded by each stage of the selective dissolution process. Results suggest that precipitation of organo-metal complexes (Na-pyrophosphate extractable C) often accounts for the largest pool of stabilized C among the three selectively dissolved pools, but these complexes were 14 C enriched in comparison to C from the other selectively dissolved pools and the residual C left on crystalline mineral surfaces after all three stages of selective dissolution. Hydroxylamine and dithionite-HCl extractable C pools were, on average, small and often below detection level in temperate soils. However, radiocarbon values for these C pools were generally depleted in comparison to other pools. These results suggest variation in organo-mineral complex stability is associated with degree of crystallinity of the mineral phase. Overall, this work suggests that sequential selective dissolution methods are a promising tool for characterizing the content and isotopic composition of soil C associated with distinct organo-mineral and organo-metal associations.