CO2 mineral trapping comparison in different regions: predicted geochemical reactivity of the Precipice Sandstone reservoir and overlying Evergreen Formation

Injected CO2 streams may have geochemical reactivity to different rock types in a CO2 storage complex depending on solubility and formation water chemistry. The Precipice Sandstone and Evergreen Formation are a low-salinity reservoir-seal pair in the Surat Basin, Australia, targeted for potential CO2 storage. The kinetic geochemical CO2 reactivity of different rock Facies from three regions were predicted over 30 and 1000 year time periods. No material CO2 mineral trapping in the quartz-rich Precipice Sandstone reservoir was predicted, owing to the low rock reactivity. Predicted CO2 mineral trapping in the Evergreen Formation was more variable due to different amounts of more reactive feldspars, clays, calcite and siderite. Predicted mineral trapping as siderite and ankerite was between 0.03 and 8.4 kg/m3 CO2 and mainly depends on chlorite and plagioclase content. Predicted pH was between 5 and 7.5 after 1000 years. Pyrite precipitation was also predicted with SO2 present in the injectate. QEMSCAN and SEM-EDS spot imaging of samples from the seal containing natural fractures filled by siderite, pyrite, clays, ankerite, calcite, barite and apatite represent a natural analogue for natural mineral trapping. These are in good agreement with our model predictions. This study suggests that, from a geochemical perspective, the Precipice Sandstone is a suitable storage reservoir where mineral trapping would occur in the overlying Evergreen Formation.Supplementary material: [additional model input, characterisation and model images, and an excel file of QEMSCAN mineral and porosity components] is available at https://doi.org/10.6084/m9.figshare.c.5395393Thematic collection: This article is part of the Geoscience for CO2 storage collection available at: https://www.lyellcollection.org/cc/geoscience-for-co2-storage

Diagenetic formation of uranium-silica polymers in lake sediments over 3,300 years

The long-term fate of uranium-contaminated sediments, especially downstream former mining areas, is a widespread environmental challenge. Essential for their management is the proper understanding of uranium (U) immobilization mechanisms in reducing environments. In particular, the long-term behavior of noncrystalline U(IV) species and their possible evolution to more stable phases in subsurface conditions is poorly documented, which limits our ability to predict U long-term geochemical reactivity. Here, we report direct evidence for the evolution of U speciation over 3,300 y in naturally highly U-enriched sediments (350–760 µg ⋅ g−1 U) from Lake Nègre (Mercantour Massif, Mediterranean Alps, France) by combining U isotopic data (δ238U and (234U/238U)) with U L3-edge X-ray absorption fine structure spectroscopy. Constant isotopic ratios over the entire sediment core indicate stable U sources and accumulation modes, allowing for determination of the impact of aging on U speciation. We demonstrate that, after sediment deposition, mononuclear U(IV) species associated with organic matter transformed into authigenic polymeric U(IV)–silica species that might have partially converted to a nanocrystalline coffinite (UIVSiO4·nH2O)-like phase. This diagenetic transformation occurred in less than 700 y and is consistent with the high silica availability of sediments in which diatoms are abundant. It also yields consistency with laboratory studies that proposed the formation of colloidal polynuclear U(IV)–silica species, as precursors for coffinite formation. However, the incomplete transformation observed here only slightly reduces the potential lability of U, which could have important implications to evaluate the long-term management of U-contaminated sediments and, by extension, of U-bearing wastes in silica-rich subsurface environments.

Geochemical reaction mechanism discovery from molecular simulation

Environmental context Computational simulations are providing an increasingly useful way to isolate specific geochemical and environmental reactions and to test how important they are to the overall rate. In this review, we summarise a few ways that one can simulate a reaction and discuss each technique’s overall strengths and weaknesses. Selected case studies illustrate how these techniques have helped to improve our understanding for geochemical and environmental problems. Abstract Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. Some common methods are summarised that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and their strengths and weaknesses are also discussed. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineral surfaces, surface charging, crystal growth and dissolution, and electron transfer. The effect that molecular simulation has had on our understanding of geochemical reactivity is highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.