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Keywords: Phyllosilicates; glauconite; nontronite; peak shift EN Phyllosilicates glauconite nontronite peak shift 1080 1090 11 06/01/22 20220601 NES 220601 Introduction Raman spectroscopy found widespread application in the rapid and non-destructive characterization of silicate minerals ([26]; [8]; [35]; [34]; [44]; [31]; [1]; [45], 2015; [30]). Concluding remarks In this study, Raman spectroscopy analysis of nontronite and glauconite-nontronite mixed-layer phases from deep-sea hydrothermal fields reveals that these phyllosilicates have diagnostic Raman spectral features that include a series of strong peaks in the low wavenumber region (<700 cm SP -1 sp ) and the hydroxyl domain (3500-3700 cm SP -1 sp ). To fill these knowledge gaps, this study reports a comprehensive Raman spectral characterization of nontronite and glauconite-nontronite mixed-layer phases (i.e., vertical mixing/interstratification of glauconite and nontronite layers) from seafloor hydrothermal fields. Chemistry/structure-dependent Raman spectral features of glauconite and nontronite For the analyzed nontronite and glauconite-nontronite mixed-layer samples, the covariations between Raman spectral properties and octahedral chemistry (Table 2; Figs. [Extracted from the article]

Fe(II) only occupies octahedral sites in phyllosilicates, whereas Fe(III) can occupy both octahedral and tetrahedral sites. The controls on Fe(III) distribution between tetrahedral and octahedral sites have been a matter of great interest to understand the interplay between formation environment (Fe abundance, redox conditions) and crystal-chemical factors (stability of the crystal lattice) during crystallization of Fe-phyllosilicates. Here, for the first time, we present a model of Fe(III) distribution in 2:1 phyllosilicates. We investigated 21 samples of 2:1 phyllosilicates of submarine hydrothermal origin using XRD, chemical analysis, and Mössbauer spectroscopy (and other supporting techniques not presented here). An additional data set of 49 analyses of 2:1 phyllosilicates from the literature was also used. Overall, the data cover a wide range of dioctahedral and trioctahedral phyllosilicates, including end-member minerals and interstratified phases. Dioctahedral phyllosilicates have a steric control whereby tetrahedral Fe(III) is only allowed if at least five out of six octahedral atoms are larger than Al (typically Fe[III], Fe[II], Mg) that produces an expanded structure where tetrahedral sites can accommodate Fe(III). After this threshold, further Fe(III) atoms occupy tetrahedral sites preferentially (~73% of further Fe[III] atoms) over octahedral sites. In trioctahedral 2:1 phyllosilicates there is no steric hindrance to tetrahedral Fe(III) because the crystal dimensions are such that tetrahedral sites can accommodate Fe(III). On average, Fe(III) enters tetrahedral and octahedral sites in similar proportion, and the only apparent control on tetrahedral Fe(III) abundance is Fe(III) availability during crystallization. This model allows to predict Fe(III) distribution between structural sites, provides an avenue for further exploration of the thermodynamic stability of phyllosilicates using cationic size, and provides a tool to better describe stability/reactivity of Fe-rich phyllosilicates, the most reactive of phyllosilicates and very relevant in geochemical and biological processes. [ABSTRACT FROM AUTHOR]

Abstract Phyllosilicate minerals have the potential to be used as indicators of past environmental conditions and climate. However, the appropriate use of this tool requires that the origin of the phyllosilicates be ascertained to correspond to the age under investigation, as mineralogical changes postdating it would lead to wrong conclusions. The soft sandstone of the Ashdown Formation (south-central and southeaster UK) contains fine-grained Al-phyllosilicates of limited interlayer expandability that have been described by other authors as vermiculite, smectite, interstratified illite-vermiculite and interstratified illite-smectite. The origin of these mineral phases is not yet agreed, with some authors reporting them as detrital and some as authigenic, generated by the weathering of detrital mica in the sandstone. In order to investigate whether or not these fine-grained minerals are detrital, four samples of the sandstone of variable softness were studied because they most likely had different clay content and because the different clay content could be possibly due to differential weathering. Investigation of mineralogy (X-ray diffraction), chemistry (bulk and SEM-EDS microanalysis) and rock fabric (image analysis of SEM micrographs) indicated that the sandstone consists of quartz, microcline, albite, anorthite, muscovite/illite, kaolinite, interstratified illite-smectite and smectite, where smectite layers expand only partially. Kaolinite is mainly detrital. Rock hardness was controlled by quartz abundance in the original sediment, not by later weathering. Alteration of the investigated sandstone samples after deposition was limited but reaction models are compatible with partial (<10 wt%) alteration of muscovite/illite to illite-smectite and smectite, and of microcline and plagioclase to kaolinite. Analysis of mineralogical data of the fraction <2 μm of the Ashdown Formation from the literature is compatible with this interpretation and indicates that the range of muscovite/illite alteration to interstratified illite-smectite and smectite varied widely (0–45% in the <2 μm size fraction) depending on location and depth. Highlights • Hardness of Sandstone from the Ashdown Formation (UK) follows quartz/clay ratio. • Quartz/clay ratio changes are controlled first by sedimentation, then by diagenesis. • The sandstone contains expandable clays of disputed origin. • Mineralogy and reaction models suggest that the expandable clays are authigenic. [ABSTRACT FROM AUTHOR]

Abstract A range of phyllosilicate compositions have been detected spectroscopically on Mars, but the largest fraction by far corresponds to clay minerals rich in Fe and Mg. Given that most of our understanding of Martian clays comes from remote sensing data, it is critically important to explore the details of how compositional variation affects spectral features of phyllosilicates. The greatest efforts have focused so far on near-infrared (NIR) spectroscopy. Recently, ambiguities have been detected in the NIR spectra of 2:1 phyllosilicates with intermediate Fe Mg content that preclude mineral and chemical discrimination. Such ambiguities highlight the relevance of exploring the visible spectral range as a complementary tool to characterize Martian phyllosilicates precisely. This article reports the investigation of laboratory reflectance spectra (330–800 nm) from 34 Earth analogues of Martian phyllosilicates with a wide range of Mg Fe composition, including nontronite, celadonite and saponite end-members, as well as interstratified glauconite-nontronite, talc-nontronite, and talc-saponite. The spectra indicated the presence of Fe(III) by absorption modulations and a decrease in total reflectance, especially in samples with tetrahedral Fe(III). Absorption bands at 370 and 420 nm were diagnostic of octahedrically and tetrahedrally coordinated Fe(III), respectively. Band amplitudes in the second derivative of the Kubelka-Munk function correlated positively with Fe(III) content (R 2 > 0.8). Standard color analyses of the visible reflectance spectra under the CIE illuminant D65 indicated that the CIELAB color parameter a * 10 was positively correlated with tetrahedral Fe(III), b * 10 was positively correlated with octahedral Fe(III), and L * 10 was negatively correlated with Fe(III) in both structural sites. Because Fe(II) was in relatively low amount, it did not provide clear spectral evidence. Multiple regression models using the amplitude of the diagnostic absorption bands predicted well absolute Fe content in the phyllosilicates (R 2 = 0.89) and the ratio Fe/(Fe + Mg + Al) (R 2 = 0.84). CIELAB color parameters improved the prediction of total Fe (R 2 = 0.92) and the ratio Fe/(Fe + Mg + Al) (R 2 = 0.93). Application of these analyses to Martian data has challenges set by Fe oxide dust coating and spatial and spectral resolution. However, these results mark an avenue to develop testable tools using visible-wavelength spectral data from both satellite and lander probes to help establishing Fe content and mineral identification of Martian phyllosilicates. Highlights • Visible-range spectra of phyllosilicates shaped by Fe content and site occupancy. • Phyllosilicate Fe content is predicted well by 2nd-derivative and color analyses. • Vis spectra from Martian rocks with phyllosilicates comparable to lab spectra. • 2nd-derivative and color analyses hopeful tool to estimate Fe in Martian clays. [ABSTRACT FROM AUTHOR]

On Earth, trioctahedral (Mg-rich) vermiculite occurs as a transient alteration product of Mg/Fe2+-mica and chlorite, pyroxene, olivine, amphibole and even plagioclase where there is a nearby Mg source, indicating mild/short-lived weathering or hydrothermal conditions. On Mars, the abundant mafic rocks and low water availability suggest the likelihood of widespread vermiculite formation from the Noachian to the early Hesperian. Although it can be challenging to identify vermiculite by remote sensing or in situ infrared spectroscopy alone, we show that numerous previous remote sensing results suggest that vermiculite is widespread on the martian surface and perhaps a more common mineral on that planet than on Earth. Investigation of rocks from Riotinto (SW Spain) provides an example of how chlorite alters to vermiculite in an acidic environment. Similar incomplete vermiculite replacements of Mg/Fe2+-mica, chlorite and mafic minerals could have resulted on Mars from acidic to neutral weathering at low water regimes. While possible bias exists towards remote sensing detection of vermiculite on Mars in sites (1) with advanced alteration and (2) where vermiculite is not mixed (at pixel level) with other phyllosilicates, we find that vermiculite occurs in Noachian terrains, in sites (wider than pixel level) where other phyllosilicates are detected, and that vermiculite has more Fe3+ than is typical on Earth. [Display omitted] • Vermiculite is a transient alteration product of mafic minerals, mica and chlorite. • Vermiculite is widespread on Mars and found in Noachian altered terrains. • The mineral might be more commonplace on Mars than on Earth. • Most identified vermiculite on Mars so far is Fe3+-rich. • Existing biases suggest more occurrences and wider composition range. [ABSTRACT FROM AUTHOR]

• Kaolinite transforms into Fe-smectite and Fe-illite in mangrove soils. • REE were not influenced by anthropic activity. • There is a trend of depletion of Heavy REE (HREE)in the normalized patterns. • Terrigenous kaolinite control the fractionation of light REE (LREE) over HREE. • Adsorption of HREE by 2:1 clays reduced the fractionation of LREE over HREE. Mangroves are intertidal tropical ecosystems influenced by marine and terrigenous input. They are important sinks of trace elements, like Rare Earth Elements (REE), which are recognized as excellent indicators of geochemical processes in estuaries. REE data of bulk soil samples from eight mangroves located along the Brazilian coast were correlated with quantitative clay mineral data based on XRD full-profile modelling. Kaolinite has been found to transform to Fe-illite in these mangroves. The clay assemblage was dominated by interstratified phases, including kaolinite-smectite (kaolinite and smectite-rich), illite–smectite and other illitic phases. REE concentrations in bulk soils were LREE > MREE > HREE (where L, M and H indicate light, medium and heavy). Multivariate statistical approach (PCA analysis) using clay mineral concentrations and proxies for relative REE concentrations ([La/Gd] N , [La/Yb] N and [Gd/Yb] N ratios) showed (r > 0.75) that fractionation of LREE over HREE was highest in mangroves where kaolinite, fed with the highly weathered sediments form the Neogene Barreiras Group, was most abundant (67–85% of all clay minerals), while REE fractionation decreased as the relative proportion of Fe-rich smectite increased (26–46 % of all clay minerals). Identified processes of REE control are: 1) Level of sediment weathering within the continent, where higher weathering implies higher kaolinite content and higher REE fractionation (LREE > MREE > HREE); 2) selective leaching of LREE from mangrove soils by saline water; 3) preferential adsorption of HREE by Fe-rich smectite and illite neoformed in the mangrove soils. It is possible to conclude that clay minerals exert an important control on REE fractionation in tropical mangroves. [ABSTRACT FROM AUTHOR]

The model of Fe3+ distribution between octahedra and tetrahedra in dioctahedral smectites by Decarreau and Petit (2014) used data from infrared analysis. From their own and other general evidence, the resulting data are likely to be affected by significant uncertainty. This aside, their model has limited application because it is based on synthetic smectites containing only Si, Al, and Fe3+. [ABSTRACT FROM AUTHOR]