Search

Global significance of iron (Fe) and aluminum (Al) for the storage of organic matter (OM) in soils and surface sediments is increasingly recognized. Yet specific metal phases involved or the mechanism behind metal–OM correlations frequently shown across soils remain unclear. We identified the allocation of major metal phases and OM to density fractions using 23 soil samples from five climate zones and five soil orders (Andisols, Spodosols, Inceptisols, Mollisols, Ultisols) from Asia and North America, including several subsurface horizons and both natural and managed soils. Each soil was separated into four to seven density fractions using sodium polytungstate with mechanical shaking, followed by the sequential extraction of each fraction with pyrophosphate (PP), acid oxalate (OX), and finally dithionite–citrate (DC) to estimate pedogenic metal phases of different solubility and crystallinity. The concentrations of Fe and Al (per fraction) extracted by each of the three reagents were generally higher in meso-density fractions (1.8–2.4 g cm -3) than in the lower- or higher-density fractions, showing a unique unimodal pattern along the particle density gradient for each soil. Across the studied soils, the maximum metal concentrations were always at the meso-density range within which PP-extractable metals peaked at 0.3–0.4 g cm -3 lower-density range relative to OX- and DC-extractable metals. Meso-density fractions, consisting largely of aggregated clusters based on SEM observation, accounted for on average 56 %–70 % of total extractable metals and OM present in these soils. The OM in meso-density fractions showed a 2–23 unit lower C : N ratio than the lowest-density fraction of the respective soil and thus appeared microbially processed relative to the original plant material. The amounts of PP- and OX-extractable metals correlated positively with co-dissolved C across the soils and, to some extent, across the density fractions within each soil. These results led to a hypothesis which involves two distinct levels of organo-metal interaction: (1) the formation of OM-rich, mixed metal phases with fixed OM : metal stoichiometry followed by (2) the development of meso-density microaggregates via "gluing" action of these organo-metallic phases by entraining other organic and mineral particles such as phyllosilicate clays. Given that OM is mainly located in meso-density fractions, a soil's capacity to protect OM may be controlled by the balance of three processes: (i) microbial processing of plant-derived OM, (ii) dissolution of metals, and (iii) the synthesis of organo-metallic phases and their association with clays to form meso-density microaggregates. The current hypothesis may help to fill the gap between well-studied molecular-scale interaction (e.g., OM adsorption on mineral surface, coprecipitation) and larger-scale processes such as aggregation, C accrual, and pedogenesis. [ABSTRACT FROM AUTHOR]