Manganese Oxide-Mediated Reactions with Olivine Dissolution Products: A Double-Edged Sword for Ocean Alkalinity Enhancement

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Mar 1, 2026, 6:02:35 PM (3 days ago) Mar 1
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https://pubs.acs.org/doi/abs/10.1021/acs.est.5c16120

Authors: Wen Zhuang, Feng Li, Tianqiang Zhu, Liwen Zheng, Minghao Zhu, Jihua Liu

24 February 2026

Abstract 
Olivine-based ocean alkalinity enhancement (OAE) is a promising carbon dioxide removal strategy, yet interactions with layered manganese oxides─ubiquitous minerals controlling trace metal biogeochemistry in marine sediments─remain poorly understood. We investigated these mechanisms using synthetic birnessite, a natural analogue of hexagonal layered Mn oxides, in controlled laboratory experiments in seawater under three scenarios reflecting different OAE deployment strategies: direct olivine-birnessite contact, exposure to simulated olivine leachate, and repeated alkaline inputs. Results revealed a dual role for birnessite. It accelerated olivine dissolution through proton-releasing cation exchange and surface-mediated Fe(II) oxidation. However, this proton generation consumed alkalinity, diminishing carbon sequestration efficiency. Regarding trace metals, birnessite efficiently scavenged Ni (>50%) and Co (>99%) but markedly enhanced Cr mobility (reaching ∼0.05 μmol kg–1), likely via oxidation to more toxic Cr(VI). Crucially, sustained Fe(II) supply mitigated this risk by reducing >50% of Cr(VI) back to Cr(III). Birnessite maintained structural stability throughout. While natural sediment systems are expected to introduce additional complexities, our findings underscore potential environmental trade-offs: Cr(VI) accumulation could exceed ecological thresholds in poorly flushed environments. This study provides foundational mechanistic insights into olivine-sediment interactions, establishing key parameters for modeling OAE safety in complex marine environments.

Source: ACS Publications 
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