Partitioning of lithium between smectite and solution: An experimental approach

Decarreau, A.; Vigier, Nathalie; Pálková, Helena; Petit, Sabine; Vieillard, Philippe; Fontaine, Claude

doi:10.1016/j.gca.2012.02.018

Cited by 43 publications

(37 citation statements)

References 32 publications

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“…As shown in Figure , the Lady Nye target also generally shows this enrichment of Li in the most Mg‐rich points. Clay minerals, in particular trioctahedral Mg‐rich smectites, can be effective at trapping Li, either adsorbed on their surface or within the crystal structure, most commonly substituting for Mg 2+ in octahedral sites, though presumably in interlayer space as well [ Starkey , ; Decarreau et al ., ]. Li‐bearing smectites have also been described from fluviolacustrine settings [ Starkey , , and references therein].…”

Section: Discussionmentioning

confidence: 99%

Chemistry of fracture‐filling raised ridges in Yellowknife Bay, Gale Crater: Window into past aqueous activity and habitability on Mars

et al. 2014

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The ChemCam instrument package on the Curiosity rover was used to characterize distinctive raised ridges in the Sheepbed mudstone, Yellowknife Bay formation, Gale Crater. The multilayered, fracture-filling ridges are more resistant to erosion than the Sheepbed mudstone rock in which they occur. The bulk average composition of the raised ridges is enriched in MgO by 1.2-1.7 times (average of 8.3-11.4 wt %; single-shot maximum of 17.0 wt %) over that of the mudstone. Al 2 O 3 is anticorrelated with MgO, while Li is somewhat enriched where MgO is highest. Some ridges show a variation in composition with different layers on a submillimeter scale. In particular, the McGrath target shows similar high-MgO resistant outer layers and a low-MgO, less resistant inner layer. This is consistent with the interpretation that the raised ridges are isopachous fracture-filling cements with a stratigraphy that likely reveals changes in fluid composition or depositional conditions over time. Overall, the average composition of the raised ridges is close to that of a Mg-and Fe-rich smectite, or saponite, which may also be the main clay mineral constituent of the host mudstone. These analyses provide evidence of diagenesis and aqueous activity in the early postdepositional history of the Yellowknife Bay formation, consistent with a low salinity to brackish fluid at near-neutral or slightly alkaline pH. The fluids that circulated through the fractures likely interacted with the Sheepbed mudstone and (or) other stratigraphically adjacent rock units of basaltic composition and leached Mg from them preferentially.

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Section: Discussionmentioning

confidence: 99%

Chemistry of fracture‐filling raised ridges in Yellowknife Bay, Gale Crater: Window into past aqueous activity and habitability on Mars

et al. 2014

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“…7f). These negative correlations could reflect the incorporation of light 6 Li isotope into octahedral sites of clay minerals, according to experimental studies on lithium isotopic fractionation during clay formation (Decarreau et al, 2012;Vigier et al, 2009). A previous study (Hosterman and Whitlow, 1983) found that rocks of the Marcellus Shale contain an average of 50% clay minerals, of which illite and smectite-illite mixed layers contribute up to 85%.…”

Section: Diagenesis Of Marcellus Shalementioning

confidence: 93%

Factors controlling Li concentration and isotopic composition in formation waters and host rocks of Marcellus Shale, Appalachian Basin

et al. 2016

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In this study, water and whole rock samples from hydraulically fractured wells in the Marcellus Shale (Middle Devonian), and water from conventional wells producing from Upper Devonian sandstones were analyzed for lithium concentrations and isotope ratios ( 7 Li). The distribution of lithium concentrations in different mineral groups was determined using sequential extraction. Structurally bound Li, predominantly in clays, accounted for 75-91 wt. % of total Li, whereas exchangeable sites and carbonate cement contain negligible Li (< 3%). Up to 20% of the Li is present in the oxidizable fraction (organic matter and sulfides). The δ 7 Li values for whole rock shale in Greene Co., Pennsylvania, and Tioga Co., New York, ranged from-2.3 to +4.3‰, similar to values reported for other shales in the literature. The  7 Li values in shale rocks with stratigraphic depth record progressive weathering of the source region; the most weathered and clay-rich strata with isotopically light Li are found closest to the top of the stratigraphic section. Diagenetic illite-smectite transition could also have partially affected the bulk Li content and isotope ratios of the Marcellus Shale. In Greene Co., southwest Pennsylvania, the Upper Devonian sandstone formation waters have  7 Li values of +14.6 ± 1.2 (2SD, n = 25), and are distinct from Marcellus Shale formation waters which have  7 Li of +10.0 ± 0.8 (2SD, n = 12). These two formation waters also maintain distinctive 87 Sr/ 86 Sr ratios suggesting hydrologic separation between these units. Applying temperature-dependent illitilization model to Marcellus Shale, we found that Li concentration in clay minerals increased with Li concentration in pore fluid during diagenetic illite-smectite transition. Samples from north central PA show a much smaller range in both δ 7 Li and 87 Sr/ 86 Sr than in southwest Pennsylvania. Spatial variations in Li and δ 7 Li values show that Marcellus formation waters are not homogeneous across the Appalachian Basin. Marcellus formation waters in the northeastern Pennsylvania portion of the basin show a much smaller range in both δ 7 Li and 87 Sr/ 86 Sr, suggesting long term, cross-formational fluid migration in this region. Assessing the impact of potential mixing of fresh water with deep formation water requires establishment of a geochemical and isotopic baseline in the shallow, fresh water aquifers, and site specific characterization of formation water, followed by long-term monitoring, particularly in regions of future shale gas development.

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“…From a structural point of view, the process has been well characterized using analytical tools such as XPS and the Rietveld analysis of neutron scattering data [ Gournis et al ., ]. The total occupancy of Li in octahedral positions has been determined by the analyses of the variations on cation exchange capacity (CEC) performed previously and after Li + inclusion to the structural lattice [ Tettenhorst , ; Schultz , ; Jaynes and Bigham , ; Theng et al ., ; Decarreau et al ., ]. Uptake of lithium by smectites may occur during the process of clay nucleation and growth (i.e., in hectorite), or by migration from the interlayer to either an octahedral position or to the ditrigonal cavities (i.e., in montmorillonites and beidellites), depending on the charge layer (Figure ).…”

Section: Methodsmentioning

confidence: 83%

“…Lithium (Li) isotope geochemistry investigations provide important information about the balance between silicate‐bearing minerals in source rocks and the geochemical processes associated with the weathering of primary silicates in aqueous environments [see, e.g., Chan et al ., ; Hathorne and James , ; Decarreau et al ., ; Ryu et al ., ]. Usually Li can be found, in the range of ppm, in almost all primary minerals present in basalt because of its small ionic radius, similar to Mg [ Seitz and Woodland , ; Seitz et al ., ; Tang et al ., ; Brant et al ., ].…”

Section: Introductionmentioning

confidence: 99%

Tracking the weathering of basalts on Mars using lithium isotope fractionation models

Fairén

Losa-Adams

Gil-Lozano

et al. 2015

Geochem Geophys Geosyst

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Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt‐forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium—7Li and 6Li—have a large relative mass difference (∼15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals—the source of Li—and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history.

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Partitioning of lithium between smectite and solution: An experimental approach

Cited by 43 publications

References 32 publications

Chemistry of fracture‐filling raised ridges in Yellowknife Bay, Gale Crater: Window into past aqueous activity and habitability on Mars

Chemistry of fracture‐filling raised ridges in Yellowknife Bay, Gale Crater: Window into past aqueous activity and habitability on Mars

Factors controlling Li concentration and isotopic composition in formation waters and host rocks of Marcellus Shale, Appalachian Basin

Tracking the weathering of basalts on Mars using lithium isotope fractionation models

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