Legacy Effects of Sorption Determine the Formation Efficiency of Mineral-Associated Soil Organic Matter.

Sorption of dissolved organic matter (DOM) is one major pathway in the formation of mineral-associated organic matter (MOM), but there is little information on how previous sorption events feedback to later ones by leaving their imprint on mineral surfaces and solutions ("legacy effect"). In order to conceptualize the role of legacy effects in MOM formation, we conducted sequential sorption experiments with kaolinite and gibbsite as minerals and DOM derived from forest floor materials. The MOM formation efficiency leveled off upon repeated addition of identical DOM solutions to minerals due to the retention of highly sorptive organic molecules (primarily aromatic, nitrogen-poor, hydrogen-poor, and oxygen-rich molecules), which decreased the sorption site availability and simultaneously modified the mineral surface charge. Organic-organic interactions as postulated in multilayer models played a negligible role in MOM formation. Continued exchange between DOM and MOM molecules upon repeated sorption altered the DOM composition but not the MOM formation efficiencies. Sorption-induced depletion of high-affinity compounds from solutions further decreased the MOM formation efficiencies to pristine minerals. Overall, the interplay between the differential sorptivities of DOM components and the mineral surface chemistry explains the legacy effects that contribute to the regulation of fluxes and the distribution of organic matter in the soil.

Sorption competition with natural organic matter as mechanism controlling silicon mobility in soil.

Growing evidence of silicon (Si) playing an important role in plant health and the global carbon cycle triggered research on its biogeochemistry. In terrestrial soil ecosystems, sorption of silicic acid (H4SiO4) to mineral surfaces is a main control on Si mobility. We examined the competitive sorption of Si, dissolved organic matter, and phosphorus in forest floor leachates (pH 4.1-4.7) to goethite, in order to assess its effects on Si mobility at weathering fronts in acidic topsoil, a decisive zone of nutrient turnover in soil. In batch sorption experiments, we varied the extent of competition between solutes by varying the amount of added goethite (α-FeOOH) and the Si pre-loading of the goethite surfaces. Results suggest weaker competitive strength of Si than of dissolved organic matter and ortho-phosphate. Under highly competitive conditions, hardly any dissolved Si (< 2%) but much of the dissolved organic carbon (48-80%) was sorbed. Pre-loading the goethite surfaces with monomeric Si hardly decreased the sorption of organic carbon and phosphate, whereas up to about 50% of the Si was released from surfaces into solutions, indicating competitive displacement from sorption sites. We conclude sorption competition with dissolved organic matter and other strongly sorbing solutes can promote Si leaching in soil. Such effects should thus be considered in conceptual models on soil Si transport, distribution, and phytoavailability.

Microbial and abiotic controls on mineral-associated organic matter in soil profiles along an ecosystem gradient.

Formation of mineral-organic associations is a key process in the global carbon cycle. Recent concepts propose litter quality-controlled microbial assimilation and direct sorption processes as main factors in transferring carbon from plant litter into mineral-organic associations. We explored the pathways of the formation of mineral-associated organic matter (MOM) in soil profiles along a 120-ky ecosystem gradient that developed under humid climate from the retreating Franz Josef Glacier in New Zealand. We determined the stocks of particulate and mineral-associated carbon, the isotope signature and microbial decomposability of organic matter, and plant and microbial biomarkers (lignin phenols, amino sugars and acids) in MOM. Results revealed that litter quality had little effect on the accumulation of mineral-associated carbon and that plant-derived carbon bypassed microbial assimilation at all soil depths. Seemingly, MOM forms by sorption of microbial as well as plant-derived compounds to minerals. The MOM in carbon-saturated topsoil was characterized by the steady exchange of older for recent carbon, while subsoil MOM arises from retention of organic matter transported with percolating water. Overall, MOM formation is not monocausal but involves various mechanisms and processes, with reactive minerals being effective filters capable of erasing chemical differences in organic matter inputs.

Variable silicon accumulation in plants affects terrestrial carbon cycling by controlling lignin synthesis.

Current climate and land-use changes affect regional and global cycles of silicon (Si), with yet uncertain consequences for ecosystems. The key role of Si in marine ecology by controlling algae growth is well recognized but research on terrestrial ecosystems neglected Si since not considered an essential plant nutrient. However, grasses and various other plants accumulate large amounts of Si, and recently it has been hypothesized that incorporation of Si as a structural plant component may substitute for the energetically more expensive biosynthesis of lignin. Herein, we provide evidence supporting this hypothesis. We demonstrate that in straw of rice (Oryza sativa) deriving from a large geographic gradient across South-East Asia, the Si concentrations (ranging from 1.6% to 10.7%) are negatively related to the concentrations of carbon (31.3% to 42.5%) and lignin-derived phenols (32 to 102 mg/g carbon). Less lignin may explain results of previous studies that Si-rich straw decomposes faster. Hence, Si seems a significant but hardly recognized factor in organic carbon cycling through grasslands and other ecosystems dominated by Si-accumulating plants.

A new conceptual model for the fate of lignin in decomposing plant litter.

Lignin is a main component of plant litter. Its degradation is thought to be critical for litter decomposition rates and the build-up of soil organic matter. We studied the relationships between lignin degradation and the production of dissolved organic carbon (DOC) and of CO2 during litter decomposition. Needle or leaf litter of five species (Norway spruce, Scots pine, mountain ash, European beech, sycamore maple) and of different decomposition stage (freshly fallen and up to 27 months of field exposure) was incubated in the laboratory for two years. Lignin degradation was followed with the CuO method. Strong lignin degradation occurred during the first 200 incubation days, as revealed by decreasing yields of lignin-derived phenols. Thereafter lignin degradation leveled off. This pattern was similar for fresh and decomposed litter, and it stands in contrast to the common view of limited lignin degradation in fresh litter. Dissolved organic carbon and CO2 also peaked in the first period of the incubation but were not interrelated. In the later phase of incubation, CO2 production was positively correlated with DOC amounts, suggesting that bioavailable, soluble compounds became a limiting factor for CO2 production. Lignin degradation occurred only when CO2 production was high, and not limited by bioavailable carbon. Thus carbon availability was the most important control on lignin degradation. In turn, lignin degradation could not explain differences in DOC and CO2 production over the study period. Our results challenge the traditional view regarding the fate and role of lignin during litter decomposition. Lignin degradation is controlled by the availability of easily decomposable carbon sources. Consequently, it occurs particularly in the initial phase of litter decomposition and is hampered at later stages if easily decomposable resources decline.