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Soil organic matter (OM) can be stabilized against decomposition by association with minerals, by its inherent recalcitrance and by occlusion in aggregates. However, the relative contribution of these factors to OM stabilization is yet unknown. We analyzed pool size and isotopic composition (14C, 13C) of mineral-protected and recalcitrant OM in 12 subsurface horizons from 10 acidic forest soils. The results were related to properties of the mineral phase and to OM composition as revealed by CPMAS 13C-NMR and CuO oxidation. Stable OM was defined as that material which survived treatment of soils with 6 wt% sodium hypochlorite (NaOCl). Mineral-protected OM was extracted by subsequent dissolution of minerals by 10% hydrofluoric acid (HF). Organic matter resistant against NaOCl and insoluble in HF was considered as recalcitrant OM. Hypochlorite removed primarily 14C-modern OM. Of the stable organic carbon (OC), amounting to 2.4–20.6 g kg−1 soil, mineral dissolution released on average 73%. Poorly crystalline Fe and Al phases (Feo, Alo) and crystalline Fe oxides (Fed−o) explained 86% of the variability of mineral-protected OC. Atomic Cp/(Fe+Al)p ratios of 1.3–6.5 suggest that a portion of stable OM was associated with polymeric Fe and Al species. Recalcitrant OC (0.4–6.5 g kg−1 soil) contributed on average 27% to stable OC and the amount was not correlated with any mineralogical property. Recalcitrant OC had lower Δ14C and δ 13C values than mineral-protected OC and was mainly composed of aliphatic (56%) and O-alkyl (13%) C moieties. Lignin phenols were only present in small amounts in either mineral-protected or recalcitrant OM (mean 4.3 and 0.2 g kg−1 OC). The results confirm that stabilization of OM by interaction with poorly crystalline minerals and polymeric metal species is the most important mechanism for preservation of OM in these acid subsoil horizons. [ABSTRACT FROM AUTHOR]

Ferric iron (Fe III ) solid phases serve many functions in soils and sediments, which include providing sorption sites for soil organic matter, nutrients, and pollutants. The reactivity of Fe solid phases depends on the mineral structure, including the overall crystallinity. In redox-active soils and sediments, repeated reductive dissolution with subsequent exposure to aqueous ferrous iron (Fe 2+ ) and oxidative re-precipitation can alter Fe phase crystallinity and reactivity. However, the trajectory of Fe mineral transformation under redox fluctuations is unclear and has been reported to result in both increases and decreases in Fe phase crystallinity. Several factors such as water budget, organic matter input, redox dynamics as well as the initial Fe phase composition might play a role. The objective of our study was to examine if Fe minerals in soils that differ in porosity-dependent water leaching rate and initial Fe phase crystallinity, demonstrate distinct mineral transformations when subjected to redox fluctuations. We sampled paired plots of two soil types under similar management but with different water leaching rates and contrasting Fe oxide crystallinity — an Alisol rich in crystalline Fe phases and an Andosol rich in short-range-ordered (SRO) Fe phases. The two soils were either exposed to several decades of redox fluctuations during rice paddy cultivation (paddy) or to predominantly oxic conditions in neighboring vegetable gardens (non-paddy). Paddy soils are uniquely suited for this type of study because they are regularly submerged and develop regular redox fluctuations. We also incubated the non-paddy soils in the laboratory for one year through eight anoxic/oxic cycles and monitored the aqueous soil geochemistry. Mössbauer spectroscopy was then used to evaluate Fe mineral speciation in field soils (paddy and non-paddy) and laboratory incubations. In the field soils, we found that redox fluctuation had contrasting effects on Fe oxide crystallinity, with crystallinity being lower in the Alisol paddy soil and higher in the Andosol paddy soil than in their corresponding non-paddy controls. In the laboratory incubation experiment, Eh, pH and dissolved Fe 2+ responded as anticipated, with elevated Fe 2+ concentrations during the anoxic periods as well as low Eh and high pH. Mössbauer measurements suggest the fluctuating redox incubation was beginning to alter Fe oxide crystallinity along the same trajectory as observed in the field, but the changes were within the range of fitting errors. We propose that reductive dissolution of crystalline Fe oxides prevails in the soil rich in crystalline Fe oxides (Alisol) and that re-precipitation as SRO Fe oxides is favored by constrained leaching, which leads to the observed decrease in Fe oxide crystallinity. In the soil rich in SRO Fe phases (Andosol), preferential reductive dissolution of SRO Fe oxides coupled with stronger leaching of dissolved Fe 2+ causes the observed relative increase in crystallinity of the remaining Fe oxides. The observed increase in Fe oxide crystallinity may further be a result of Fe(II)-catalyzed re-crystallization of SRO Fe oxides. These findings indicate that, besides other factors, the Fe mineral composition of the initial soil or sediment as well as the leaching rate likely influence the trajectory of Fe oxide evolution under alternating redox-conditions. [ABSTRACT FROM AUTHOR]

Abstract: The mechanisms of organic matter (OM) stabilization and possible organic–mineral interactions in alkaline soils rich in Ca (calcareous soils) were investigated. We sampled soils that developed over a period of 70 years under natural succession from homogeneous calcareous and organic-free substrate resulting from industrial production. We took advantage of a shift from non-woody to woody angiosperm vegetation with increasing soil age and tracked lignin as an indicator of the fate of plant residues. Using density separation in combination with ultrasonic dispersion, four fractions were obtained: (1) free particulate OM (FPOM), (2) OM occluded within soil aggregates (OPOM), (3) heavy fraction with a density of 1.6–2.2gcm−3 and (4) heavy fraction with a density >2.2gcm−3. The fractions were analysed for C, N, CuO oxidation products and mineral composition. Accumulation of OM by occlusion within aggregates contributed little (4–16%) to the total organic C in the soils. The dominant portion of organic C was in the fractions >1.6gcm−3. Lignin phenols in the fractions >1.6gcm−3 showed the most intensive diagenetic alteration as reflected in small yields of vanillic, syringic and cinnamic (VSC) lignin and stronger oxidation of the side chains of vanillyl phenols. In contrast to the POM fractions, the fractions >1.6gcm−3 from the older sites conserved the non-woody angiosperm lignin signature of the former vegetation, indicating slower OM turnover. The mineral composition of the two heavy fractions clearly differed, with layered double hydroxides (i.e., hydrotalcite and hydrocalumite) dominating the fractions >1.6gcm−3 and calcite dominating the fractions >2.2gcm−3. We conclude that partly degraded lignin, enriched in acidic groups, accumulated in the fraction 1.6–2.2gcm−3, due to preferential adsorption to the positively charged layered double hydroxides. Although representing only a small portion of the soil mineral assemblage, layered double hydroxides seem to be of significant relevance for OM accumulation. Over the years, the fraction 1.6–2.2gcm−3 comprised the largest single pool of organic C. Compared with the 1.6–2.2gcm−3 fraction, the >2.2gcm−3 fraction had a much smaller carbon concentrations. The lignin in that fraction showed by far the strongest oxidative alteration of all the fractions. We assume that partly degraded lignin components, not adsorbed to layered double hydroxides, undergo further microbial oxidation until they form complexes with calcite. Consequently, we conclude that in these calcareous soils accumulation of OM is mainly due to the attachment of partly oxidized OM to positively charged clays, resulting in stabilization against further decomposition, thus slowing down turnover. To a minor extent, calcite is also involved in the stabilization of the plant residues. [Copyright &y& Elsevier]

Abstract: In arable farming systems, the term ‘subsoil’ refers to the soil beneath the tilled or formerly tilled soil horizon whereas the latter one is denoted as ‘topsoil’. To date, most agronomic and plant nutrition studies have widely neglected subsoil processes involved in nutrient acquisition by crop roots. Based on our current knowledge it can be assumed that subsoil properties such as comparatively high bulk density, low air permeability, and poverty of organic matter, nutrients and microbial biomass are obviously adverse for nutrient acquisition, and sometimes subsoils provide as little as less than 10% of annual nutrient uptake in fertilised arable fields. Nevertheless, there is also strong evidence indicating that subsoil can contribute to more than two-thirds of the plant nutrition of N, P and K, especially when the topsoil is dry or nutrient-depleted. Based on the existing literature, nutrient acquisition from arable subsoils may be conceptualised into three major process components: (I) mobilisation from the subsoil, (II) translocation to the shoot and long-term accumulation in the Ap horizon and (III) re-allocation to the subsoil. The quantitative estimation of nutrient acquisition from the subsoil requires the linking of field experiments with mathematical modelling approaches on different spatial scales including Process Based Models for the field scale and Functional–Structural Plant Models for the plant scale. Possibilities to modify subsoil properties by means of agronomic management are limited, but ‘subsoiling’ – i.e. deep mechanical loosening – as well as the promotion of biopore formation are two potential strategies for increasing access to subsoil resources for crop roots in arable soils. The quantitative role of biopores in the nutrient acquisition from the subsoil is still unclear, and more research is needed to determine the bioaccessibility of nutrients in subsoil horizons. [Copyright &y& Elsevier]

Abstract: Paddy soils make up the largest anthropogenic wetlands on earth. They may originate from any type of soil in pedological terms, but are highly modified by anthropogenic activities. The formation of these Anthrosols is induced by tilling the wet soil (puddling), and the flooding and drainage regime associated with the development of a plough pan and specific redoximorphic features. Redox potential oscillations due to paddy management control microbial community structure and function and thus short-term biogeochemical processes. After flooding, microbial reduction processes sequentially use NO3 −, Mn4+, Fe3+, SO4 2 − as electron acceptors, accompanied by the emission of the trace gases N2O, N2, H2S, CH4 and — due to reduction-induced increasing pH — NH3. This results in N losses and low N fertilizer use efficiency. However, transport of atmospheric O2 to the roots via the rice plant''s aerenchyma modifies conditions in the rhizosphere, leading to nitrification and methane oxidation, and precipitation of Mn and Fe oxides. High concentrations and fluxes of dissolved organic matter (DOM) in paddy soils from plant debris trigger microbial activity and thus the emission of greenhouse gases. Retention of DOM by soil minerals and its subsequent stabilisation against microbial decay depend on the redox state (e.g. DOM precipitation by Fe2+ under anaerobic conditions). Oscillation in redox conditions may enhance retention and stabilisation of DOM by Fe oxyhydroxides. Induced by the periodic short-term redox cycles, paddy management over long periods has strong effects on long-term biogeochemical processes. Frequent irrigation intensifies mineral weathering and leaching processes. High concentrations of DOM during flooding seasons enhance the changes and the release of structural iron in clay minerals, and support the formation of ferrihydrite. Repeated redox alternations lead to a translocation of iron in various directions, and particularly increase the crystallinity of iron oxides. This results also in higher total iron oxide contents in paddy compared to non-paddy soils. The large accumulation of soil organic matter (SOM) observed in some, but not all paddy soils, is considered to be due to high input of plant residues and charred material associated with retarded decomposition under anaerobic conditions. There is also evidence of SOM stabilisation via occlusion into aggregates and phytoliths as well as interactions with clay minerals and iron oxides. SOM accumulation in paddy subsoils can be explained by downward movement of DOM and its stabilisation by interaction with iron oxides. A specific feature of paddy soils is the coupling of organic matter turnover with mineral transformations and fluxes, which seem to be intensified by the alternating redox conditions with increasing age of paddy soil development. Bioavailability of soil organic N is strongly coupled to SOM cycling and is a crucial parameter determining crop yield. Anaerobic conditions inhibit N mineralization, with a high risk of gaseous N losses. In paddy soils the management-induced, microbially mediated redox processes control the dynamics of soil minerals and soil organic matter, which are strongly related to the microbial accessibility of C and N, but also of Fe. [Copyright &y& Elsevier]