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Spinel-structured hausmannite (Mn(II)Mn(III)2O4) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO2 formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment.more » « lessFree, publicly-accessible full text available July 1, 2026
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Two major barriers hinder the holistic understanding of subsurface critical zone (CZ) evolution and its impacts: (a) an inability to measure, define, and share information and (b) a societal structure that inhibits inclusivity and creativity. In contrast to the aboveground portion of the CZ, which is visible and measurable, the bottom boundary is difficult to access and quantify. In the context of these barriers, we aim to expand the spatial reach of the CZ by highlighting existing and effective tools for research as well as the “human reach” of CZ science by expanding who performs such science and who it benefits. We do so by exploring the diversity of vocabularies and techniques used in relevant disciplines, defining terminology, and prioritizing research questions that can be addressed. Specifically, we explore geochemical, geomorphological, geophysical, and ecological measurements and modeling tools to estimate CZ base and thickness. We also outline the importance of and approaches to developing a diverse CZ workforce that looks like and harnesses the creativity of the society it serves, addressing historical legacies of exclusion. Looking forward, we suggest that to grow CZ science, we must broaden the physical spaces studied and their relationships with inhabitants, measure the “deep” CZ and make data accessible, and address the bottlenecks of scaling and data‐model integration. What is needed—and what we have tried to outline—are common and fundamental structures that can be applied anywhere and used by the diversity of researchers involved in investigating and recording CZ processes from a myriad of perspectives.more » « less
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