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The aim of this study was to further our understanding of the pedogenic and lacustrine modification of clay minerals. Some of these modifications are of special interest because they constitute reverse weathering reactions, rare in surface environments, and because there is not yet an accurate assessment of their global relevance in mineralogical and geochemical cycles. For this study, two sections from the Central System in Spain were selected. Both are sections through the Uppper Cenomanian-Turonian mixed clastic and carbonate succession, containing both calcite and dolomite, in the Sierra de Guadarrama. Mid-Turonian sea level fall resulted in the formation of a coastal plain environment in which extensive pedogenesis occurred around saline lagoons. The mineralogical changes that have occurred as a result of sedimentation in saline lagoons and as a consequence of pedogenesis are described. Textural relationships indicate that the dolomite cement pre-dates the calcite. Silicate minerals are represented by quartz, kaolinite, illite-smectite, illite, minor plagioclase and alkali feldspar, and trace chlorite and palygorskite. There is a positive correlation between the intensity of pedogenesis and the proportion of illite in the clay assemblage in one of the sections, indicating pedogenic illitisation. In this section, the intensity of the illitisation process increases up, reaching a maximum where pedogenesis is most intense in the middle part, and then decreases as marine influence increases towards the top of the Alcorlo Formation and the overlying marine Tranquera Formation. The clay assemblages are consistent with a slow transformation process from kaolinite to illite by way of illite-smectite, taking place under surface conditions. The illitisation process has resulted in a less Fe-rich, more Mg-, and Al-rich illite than the majority of previously documented cases in the near surface. Formation of Al-rich illite is not therefore restricted to the deep subsurface. The mechanism for low temperature illitisation involves enhanced layer charge resulting from Mg 2 + substitution for Al 3 + (or Fe 3 + ) and Fe 3 + to Fe 2 + reduction. Mg 2 + enrichment may have occurred principally in saline lagoons or lakes, while Fe 3 + to Fe 2 + reduction occurred as a result of wetting and drying in a pedogenic environment. So far as it has been possible to establish, this dual mechanism has not previously been documented. This study indicates clearly that the dolomite and calcite are authigenic cements that precipitated in a clastic sediment, probably soon after deposition. Dolomitisation and Mg enrichment of the clay may have occurred at the same time. Seawater is the most probable source of Mg. [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]

Iron electronic transitions produce intense colors in minerals with moderate to high Fe content, which phenomenon allows using color and visible spectroscopy to identify and quantify Fe-bearing minerals. This approach is especially useful for Mars investigation due to the limited analytical instruments available at Mars. The challenges are: (1) overlap between Fe electronic absorption bands of Fe-bearing minerals, (2) band wavelengths are modified by chemical and structural variables, and (3) particle size effects can modify mineral color. The magnitude of these difficulties, however, depends on the mineral mixture investigated. In this study, we further probe the potential of visible-range data for investigation of Fe-minerals. The samples were mineral mixtures from the Riotinto area (SW Spain) that resulted from acidic alteration and contained Fe in oxy-hydroxides, hydroxysulfates and phyllosilicates. Samples were studied using visible/near-infrared spectroscopy, X-ray diffraction and thermogravimetry. The wavelength range 320–1000 nm was investigated using spectral second derivatives and CIELAB color parameters. Hematite was readily detected, below X-ray diffraction detection limits, from the band at 520–560 nm. Jarosite was readily identified by the combined presence of bands at ~390 and ~ 440 nm. Thermogravimetric and CIELAB color analyses indicated goethite as the most common Fe-rich mineral in the samples. Correlations between CIELAB color parameters were controlled by goethite, where jarosite-rich specimens aligned with the correlations but some samples containing hematite plotted outside them. Quantification of goethite was attempted as calibrated against thermogravimetric data. Calibration was not possible below ~10 wt% goethite. Above this value, results from spectral second derivatives allowed quantification up to the maximum goethite content of ~35 wt% (linear correlation with R2 = 0.89). Goethite quantification with CIELAB color parameters was hindered by hematite. In samples with very low or no hematite, goethite quantification was possible with parameters L * 10 (R2 = 0.83) and h ab,10 (R2 = 0.65), also up to ~35 wt% goethite. Consequently, if accurate calibration is possible and depending on mineral mixture components, spectroscopic and CIELAB color parameters should allow goethite quantification in a wide concentration range. • Hematite detectability in mineral mixtures is high due to absorption at 520–560 nm. • Jarosite is also readily detectable due to the combined bands at 390 and 440 nm. • Goethite and jarosite share color characteristics determined with CIELAB parameters. • Hematite modifies CIELAB color characteristics of goethite-jarosite mixtures. • Goethite quantification is possible by spectral and color methods to at least 35 wt%. [ABSTRACT FROM AUTHOR]