Crystal Chemistry of Thallium in Marine Ferromanganese Deposits - Archive ouverte HAL
Article Dans Une Revue ACS Earth and Space Chemistry Année : 2022

Crystal Chemistry of Thallium in Marine Ferromanganese Deposits

Résumé

Our understanding of the up to seven orders of magnitude partitioning of thallium (Tl) between seawater and ferromanganese (FeMn) deposits rests upon two foundations: (1) being able to quantify the Tl(I)/Tl(III) ratio that reflects the extent of the oxidative scavenging of Tl by vernadite (δ-MnO2), the principle manganate mineral in oxic and suboxic environments, and (2) being able to determine the sorption sites and bonding environments of the Tl(I) and Tl(III) complexes on vernadite. We investigated these foundations by determining the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans at a Tl concentration ranging from several hundreds ppm (mg/kg) down to the low ppm level. Seventeen hydrogenetic crusts and eleven nodules from the Pacific, Atlantic, and Indian oceans and Baltic Sea were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and Tl L3-edge high energy-resolution XANES (HR-XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Tl concentration increases linearly from 1.5 to 319 ppm with the Mn/Fe ratio in Fe-vernadite from hydrogenetic crusts, whereas the percentage of Tl(III) to total Tl varies between 62% and 100% independent of both the Mn/Fe and Mn(III)/Mn(IV) 2 ratios. The data, complemented by molecular modeling of the Tl(III) coordination and by XANES calculations, suggest that the enrichment of Tl in Fe-vernadite is driven by (1) the oxidative uptake of octahedrally coordinated Tl(III) above the vacant Mn(IV) sites and on the layer edges of the vernadite layers, and (2) the sorption of Tl(I) on the crystallographic site of Ba at the surface of the vernadite layers, which is analog to the surface site of K. Thus, Tl has a high affinity for vernadite regardless of its oxidation state, and the lack of correlation between Tl(III) and the Mn/Fe ratio in FeMn crusts is explained by the affinity of Tl(I) for the Ba site. The Tl concentration varies between 2 and 112 ppm in surface and buried nodules independent of the Mn/Fe ratio, and the percentage of Tl(III) varies between 0% and 100%. Nodules subjected to sediment diagenesis with replacement of layered vernadite by tunneled todorokite are depleted in Tl and have more reduced thallium. Knowledge of the complex interplay of mineralogy, surface chemical processes, and crystallographic siting are required to understand the variability of Tl concentrations, redox state, and acquisition processes by marine FeMn deposits.
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hal-03688534 , version 1 (04-06-2022)

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Alain Manceau, Alexandre Simionovici, Nathaniel Findling, Pieter Glatzel, Blanka Detlefs, et al.. Crystal Chemistry of Thallium in Marine Ferromanganese Deposits. ACS Earth and Space Chemistry, 2022, 6 (5), pp.1269-1285. ⟨10.1021/acsearthspacechem.1c00447⟩. ⟨hal-03688534⟩
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