Soil organic matter (SOM) anchors global terrestrial productivity and food and fiber supply. SOM retains water and soil nutrients and stores more global carbon than do plants and the atmosphere combined. SOM is also decomposed by microbes, returning CO 2 , a greenhouse gas, to the atmosphere. Unfortunately, soil carbon stocks have been widely lost or degraded through land use changes and unsustainable forest and agricultural practices.

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Soils retain large quantities of carbon, thereby slowing its return to the atmosphere. The mechanisms governing organic carbon sequestration in soil remain poorly understood, yet are integral to understanding soil-climate feedbacks. We evaluated the biochemistry of dissolved and solid organic carbon in potential source and sink horizons across a chronosequence of volcanic soils in Hawai'i. The soils are derived from similar basaltic parent material on gently sloping volcanic shield surfaces, support the same vegetation assemblage, and yet exhibit strong shifts in soil mineralogy and soil carbon content as a function of volcanic substrate age. Solid-state 13 carbon nuclear magnetic resonance spectra indicate that the most persistent mineral-bound carbon is comprised of partially oxidized aromatic compounds with strong chemical resemblance to dissolved organic matter derived from plant litter. A molecular mixing model indicates that protein, lipid, carbohydrate, and char content decreased whereas oxidized lignin and carboxyl/carbonyl content increased with increasing short-range order mineral content. When solutions rich in dissolved organic matter were passed through Bw-horizon mineral cores, aromatic compounds were preferentially sorbed with the greatest retention occurring in horizons containing the greatest amount of short-range ordered minerals. These minerals are reactive metastable nanocrystals that are most common in volcanic soils, but exist in smaller amounts in nearly all major soil classes. Our results indicate that long-term carbon storage in short-range ordered minerals occurs via chemical retention with dissolved aromatic acids derived from plant litter and carried along preferential flow-paths to deeper B horizons.

stable isotopes, differential scanning calorimetry (DSC), scanning transmission X-ray microscopy (STXM), near edge x-ray absorption fine structure spectroscopy (NEXAFS) 2 AbstractSoil carbon turnover models generally divide soil carbon into pools with varying intrinsic decomposition rates. While these decomposition rates are modified by factors such as temperature, texture, and moisture, they are rationalized by assuming chemical structure is a primary controller of decomposition. In the current work, we use Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy in combination with differential scanning calorimetry (DSC) and alkaline CuO oxidation to explore this assumption. Specifically, we examined material from the 2.3-2.6 kg L Therefore, our results demonstrate that C age is not necessarily related to molecular structure or thermodynamic stability, and we suggest that soil carbon models would benefit from viewing turnover rate as co-determined by the interaction between substrates, microbial actors and abiotic driving variables. Furthermore, assuming that old carbon is composed of complex or "recalcitrant" compounds will erroneously attribute a greater temperature sensitivity to those materials than they may actually possess.

Sequential density fractionation separated soil particles into ''light'' predominantly mineral-free organic matter vs. increasingly ''heavy'' organo-mineral particles in four soils of widely differing mineralogy. With increasing particle density C concentration decreased, implying that the soil organic matter (OM) accumulations were thinner. With thinner accumulations we saw evidence for both an increase in 14 C-based mean residence time (MRT) of the OM and a shift from plant to microbial origin.Evidence for the latter included: (1) a decrease in C/N, (2) a decrease in lignin phenols and an increase in their oxidation state, and (3) an increase in d 13 C and d 15 N. Although bulk-soil OM levels varied substantially across the four soils, trends in OM composition and MRT across the density fractions were similar. In the intermediate density fractions (*1.8-2.6 g cm -3 ), most of the reactive sites available for interaction with organic molecules were provided by aluminosilicate clays, and OM characteristics were consistent with a layered mode of OM accumulation. With increasing density (lower OM loading) within this range, OM showed evidence of an increasingly microbial origin. We hypothesize that this microbially derived OM was young at the time of attachment to the mineral surfaces but that it persisted due to both binding with mineral surfaces and protection beneath layers of younger, less microbially processed C. As a result of these processes, the OM increased in MRT, oxidation state, and degree of microbial processing in the sequentially denser intermediate fractions. Thus mineral surface chemistry is assumed to play little role in determining

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