Soil, the largest terrestrial carbon reservoir, is central to climate change and relevant feedback to environmental health. Minerals are the essential components that contribute to over 60% of soil carbon storage. However, how the interactions between minerals and organic carbon shape the carbon transformation and stability remains poorly understood. Herein, we critically review the primary interactions between organic carbon and soil minerals and the relevant mechanisms, including sorption, redox reaction, co-precipitation, dissolution, polymerization, and catalytic reaction. These interactions, highly complex with the combination of multiple processes, greatly affect the stability of organic carbon through the following processes: (1) formation or deconstruction of the mineral-organic carbon association; (2) oxidative transformation of the organic carbon with minerals; (3) catalytic polymerization of organic carbon with minerals; and (4) varying association stability of organic carbon according to the mineral transformation. Several pieces of evidence related to the carbon turnover and stability during the interaction with soil minerals in the real eco-environment are then demonstrated. We also highlight the current research gaps and outline research priorities, which may map future directions for a deeper mechanisms-based understanding of the soil carbon storage capacity considering its interactions with minerals. 

Mineral-mediated stability of organic carbon in soil and relevant interaction mechanisms

A novel oxalated zero-valent iron nanoparticle for Pb(II) removal from aqueous solution: Performance and synergistic mechanisms

The comprehensive understanding of contaminant interfacial behavior strongly depends on the in situ characterization technique, which is still a great challenge. In this study, we constructed a device integrated with open-circuit potentialand attenuated total reflectance Fourier transform infrared (OCP-ATR-FTIR) spectroscopy to simultaneously monitor the electrochemical and infrared spectral information on the interfacial reaction for the process analysis, taking the competitive adsorption of hexavalent chromium (Cr(VI)) and oxalate on hematite nanocubes (HNC) as an example. The synchronous OCP and infrared results revealed that Cr(VI) interacted with HNC via bidentate binuclear inner-sphere coordination, accompanied by electron transfer from HNC to Cr(VI), while oxalate was adsorbed on HNC through bidentate mononuclear side-on inner-sphere coordination with electron transfer from HNC to oxalate, and also outer-sphere coordination with negative charge accumulation. When oxalate was added to HNC with preadsorbed Cr(VI), oxalate would occupy the inner-sphere adsorption sites and thus cause the detaching of preadsorbed Cr(VI) from HNC. This study provides a promising in situ characterization technique for real-time interfacial reaction monitoring and also sheds light on the competitive adsorption mechanism of oxalate and Cr(VI) on the mineral surface.

Construction of an OCP-ATR-FTIR Spectroscopy Device to In Situ Monitor the Interfacial Reaction of Contaminants: Competitive Adsorption of Cr(VI) and Oxalate on Hematite.

Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g mg−1 min−1) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g mg−1 min−1 and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal. 

Oxalate modification enabled advanced phosphate removal of nZVI: In Situ formed surface ternary complex and altered multi-stage adsorption process

Green rust sulfate transformation under the impact of Cr(VI) and oxalic acid: Mechanism and environmental significance

Oxalate, a typical natural ligand, plays a significant role in promoting iron dissolution from iron (oxyhydr)oxide minerals to improve iron bioavailability in nature. However, the mechanism of oxalate promoted iron...

Oxalate Promoted Iron Dissolution of Hematite via Proton Coupled Electron Transfer

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Oxalate Promoted Iron Dissolution of Hematite via Proton Coupled Electron Transfer