Assessments of Organic Carbon Stabilization Using the Spectroscopic Characteristics of Humic Acids Separated from Soils of the Lena River Delta

In the Arctic zone, where up to 1024 × 1013 kg of organic matter is stored in permafrost-affected soils, soil organic matter consists of about 50% humic substances. Based on the analysis of the molecular composition of humic acids, we assessed the processes of accumulation of the key structural fragments, their transformations and the stabilization rates of carbon pools in soils in general. The landscape of the Lena River delta is the largest storage of stabilized organic matter in the Arctic. There is active accumulation and deposition of a significant amount of soil organic carbon from terrestrial ecosystems in a permafrost state. Under ongoing climate change, carbon emission fluxes into the atmosphere are estimated to be higher than the sequestration and storing of carbon compounds. Thus, investigation of soil organic matter stabilization mechanisms and rates is quite an urgent topic regarding polar soils. For study of molecular elemental composition, humic acids were separated from the soils of the Lena River delta. Key structural fragments of humic matter were identified and quantified by CP/MAS 13C NMR spectroscopy: carboxyl (–COOR); carbonyl (–C=O); CH3–; CH2–; CH-aliphatic; –C-OR alcohols, esters and carbohydrates; and the phenolic (Ar-OH), quinone (Ar = O) and aromatic (Ar–) groups as benchmark Cryosols of the Lena delta river terrestrial ecosystem. Under the conditions of thermodynamic evolutionary selection, during the change between the dry and wet seasons, up to 41% of aromatic and carboxyl fragments accumulated in humic acids. Data obtained showed that three main groups of carbon played the most important role in soil organic matter stabilization, namely C, H-alkyls ((CH2)n/CH/C and CH3), aromatic compounds (C-C/C-H, C-O) and an OCH group (OCH/OCq). The variations of these carbon species’ content in separated humics, with special reference to soil–permafrost organic profiles’ recalcitrance in the current environment, is discussed.

How do terrestrial plants access high molecular mass organic nitrogen, and why does it matter for soil organic matter stabilization?

Although there is increasing awareness of the potential role of organic N compounds (ON) in plant nutrition, its implications for soil organic matter (SOM) stabilization have hardly been discussed yet. The aim of this paper is therefore to gather the newest insights into plant use of high molecular mass organic N, its effect on root growth and anatomy, and finally, to discuss the implications of plant use of organic N for SOM stabilization. I propose that modified root growth due to the uptake of ON provides greater root and root-associated microbe input, leading to enhanced SOM stabilization. Finally, I discuss the role of the proposed framework in different ecosystems, and I encourage future studies combining plant N nutrition and SOM stabilization.

A molecular dynamic study of Soil Organic Matter stabilization mechanisms

<p>It is well known that some fractions of soil organic matter (SOM) can resist to physical and (bio)chemical degradation which can be attributed to factors ranging from molecular properties to the preference for digesting other molecular species by microorganisms. Some mechanisms, by which organic matter is protected, are often referred to as: physical stabilization through microaggregation, chemical stabilization by formation of SOM-mineral aggregates, and biochemical stabilization through the formation of recalcitrant SOM.</p><p>Protection mechanisms are responsible for the accumulation process of organic carbon, reducing the exposure of organic matter and making it less vulnerable to microbial, enzymatic or chemical attacks. In these mechanisms, water molecular bridges and metal cation bridges play a key role. Cation bridges serve as aggregation sites on humic substances, forming dense matter, in comparison to systems where bridges are missing. This effect is enhanced in systems with cations at higher oxidation states.</p><p>By using the modeler tool developed in our group (Vienna Soil–Organic–Matter Modeler, VSOMM2) (Escalona et al., 2021), we generated aggregate models of humic substances at atomistic scale reflecting the diversity in composition, size and conformations of the constituting molecules. Further, we built models of organo-clay aggregates using kaolinite and montmorillonite as typical soil minerals. This allowed a systematic study to understand the effect of the surrounding environment at microscopic scale, not fully accessible experimentally.</p><p>Molecular simulations of the adsorption process of SOM aggregates on the reactive surfaces of led to two observations: 1) the humic substances aggregates were able to interact with the reactive surfaces mainly via hydrogen bonds forming stable organic matter-clay complexes and 2) the aggregates subsequently lost rigidity and stability after metal cations removing, consequently leading to a gradual loss of humic substance molecules, evidencing the role of metal cations in the protection mechanism of soil organic matter aggregates and possibly explaining its recalcitrance (Galicia-Andrés et al., 2021).</p><p>References</p><ul><li>Escalona, Y., Petrov, D., & Oostenbrink, C. (2021). Vienna soil organic matter modeler 2 (VSOMM2). Journal of Molecular Graphics and Modelling, 103, 107817. https://doi.org/10.1016/j.jmgm.2020.107817</li> <li>Galicia-Andrés, E., Grančič, P., Gerzabek, M. H., Oostenbrink, C., & Tunega, D. (2021). Modeling of interactions in natural and synthetic organoclays. In I. C. Sainz Diaz (Ed.), Computational modeling in clay mineralogy.</li> </ul>