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Earth analogs are indispensable to investigate mineral assemblages on Mars because they enable detailed analysis of spectroscopic data from Mars and aid environmental interpretation. Samples from four sites in the Iberian Pyrite Belt (El Villar, Calañas, Quebrantahuesos, and Tharsis) were investigated using mineralogical, chemical, and spectroscopic techniques, with a focus on clay minerals and alteration environments. They represent Earth analogs of areas on Mars that underwent acidic alteration. X‑ray diffraction and transmittance mid-infrared data indicate that the rocks were subjected to several degrees of acid alteration corresponding to assemblages characterized by the following mixtures: (1) illite, chlorite, interstratified chlorite-vermiculite, kaolinite-smectite, and kaolinite; (2) illite, kaolinite, and alunite; and (3) jarosite and goethite. According to mineral stability data, these three assemblages correspond to pH values 7–5, 5–3, and <3, respectively. The lack of goethite in the illite-kaolinitealunite assemblage suggests an alteration in reducing conditions. Illite was progressively dissolved by acidic alteration but is sufficiently resilient not to be diagnostic of the intensity of the alteration. Illite and kaolinite were the two most abundant phyllosilicate minerals observed, and the main reaction involving phyllosilicates was the alteration of illite to kaolinite. Mixed-layer phases appeared mainly in the mildest degree of acid alteration, with few exceptions. This suggests a transition from a mechanism dominated by transformation to a mechanism dominated by dissolution-precipitation as the intensity of the acid alteration increases. Our results highlight the sparse kaolinite–alunite occurrences on Mars as worthy of specific investigation. Acid alteration on Mars is expected to be patchy and/or consisting of fine alteration rims. Alunite occurrences on Mars in the absence of goethite may indicate an acid alteration in reducing conditions. Kaolinite produced through acid alteration on Mars is expected to exist mainly as an end-member phase of low crystallinity, which would enhance IR absorption and increase its visibility. [ABSTRACT FROM AUTHOR]

Mangrove soils have peculiar chemical and physical conditions generated by the variable water salinity, cyclic tidal changes and intense biological activity that produce complex clay suites. In this study, the crystal-chemical characteristics of clay minerals from two mangrove soils were investigated in detail to further our understanding of the processes taking place. The two Brazilian mangroves are from zones of contrasting climatic type and continental sediment character: (1) tropical wet climate area receiving highly weathered sediments (Bragança, Pará State) and (2) mild semiarid climate area supplied with a mixture of highly and moderately weathered sediments (Acaraú, Ceará State). The investigation of the 2–0.2 μm and < 0.2 μm size fractions of the soils using XRD, Mössbauer spectroscopy, chemical analysis of individual mineral grains (TEM-EDS) and bulk samples (XRF) showed mineral assemblages composed by endmember and mixed-layer clay minerals. Three to four mineral phases were detected by XRD in each sample such as kaolinite-smectite minerals (K-S), illite-smectite (I-S) and Fe-rich illite, suggesting a progressive transformation via mixed-layering from detrital kaolinite (unstable in mangrove soil conditions) to K-S and I-S minerals rich in smectite, and then to Fe-rich illite. The chemical characterization corroborates this gradual transformation: there is an enrichment in K, Fe and Mg at the expense of Al in all samples. A solid-state reaction explains the sequential transformation, where crystal-chemical changes take place without complete disruption of the lattice. There is evidence of octahedral Fe reduction during the illitization stage, showing the influence of a reducing environment, from decaying organic matter and bacterial activity, on the clay minerals. The increase in layer charge is balanced by K and NH 4 ions, abundant in the interstitial water. Superior Fe-rich illite contents in Acaraú mangrove, compared to Bragança mangrove, are explained by high inputs of 2:1 clays from sediment source areas inland. The above clay mineral reactions shed light on the role of clays and the interaction between minerals and biotic components in mangrove soils. In addition, these reactions may influence the cycle of major elements in coastal ecosystem surrounding mangroves. [ABSTRACT FROM AUTHOR]

Most known clay mineral reactions are slow. Clay formation by weathering is recognized as faster (hundreds of thousands to few million years) than clay reverse weathering (few to tens My), even if the latter takes place in deep diagenetic conditions at temperatures above 100 °C. Identifying hot spots of fast clay retrograde reactions acting as effective potassium sinks would contribute to eliminating the present imbalance of the potassium budget towards release into the oceans. We have identified and modeled the reaction kaolinite + Fe + cations → Fe - illite occurring in Brazilian mangroves, which takes place through kaolinite-smectite and illite-smectite intermediates. The reaction is very fast, transforming 72–154 g m − 2 y − 1 of kaolinite into Fe-illite, or 16–38% of the newly sedimented kaolinite each year. This kaolinite-to-illite transformation is 10s–100s times faster than kaolinite formation by weathering. Extrapolation of the calculated potassium consumption to mangrove forests worldwide produces 0.6–3 × 10 12 g y − 1 , or 1–6% of the yearly potassium riverine input into the oceans. [ABSTRACT FROM AUTHOR]

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]

This study investigated soil clay mineralogy of mangrove forests along the Brazilian coast in eight regions of different environmental characteristics, with a focus on the crystallochemical features and genesis of 2:1 phyllosilicates. Samples from two different depths (0-30 and 60-90 cm) and two clay size fractions (<2 and <0.2 mm) were studied. The analytical tools used were x-ray diffraction, Fourier-transform infrared spectroscopy, and transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS). A complex assemblage was found in both fractions, including high proportions of kaolinite, illite (Fe-illite/glauconite), and smectite (Fe-beidellite, Fe-montmorillonite), minor amounts of gibbsite and quartz, and traces of K-feldspar, halloysite, and amphibole crystals (TEM-EDS data). Evidence of illite-smectite and possibly kaolinite-smectite mixed-layer phases was found in the <0.2-mm fraction. An authigenic transformation process likely taking place, from kaolinite to Fe-illite/glauconite, through transitory kaolinite- smectite and illite-smectite phases. The reaction is triggered by high Fe activity in solution generated by dissolution of Fe oxides and pyrite present in the sediment, at approximately neutral pH and high salt content in the water. Smectite illitization takes place by substitution of Al3+ for Si4+ in the tetrahedral sheet, of Fe and Mg2+ for Al3+ in the octahedral sheet, and progressive Fe reduction, all of which produces an increase in the layer charge and K uptake. The sequential nature of the transformation (kaolinite-smectite-illite) suggests a solid-state transformation process. Two unusual kaolinite-rich mangroves were found, indicating low reactivity or high deposition rate of continental sediments of soils derived from the Barreiras Group, dominated by kaolinite. [ABSTRACT FROM AUTHOR]

Abstract: The effect of oil on As(V) adsorption on clay minerals has been investigated using batch experiments at low and high pH, NaCl concentration and oil contents. Four clay minerals were chosen because of their abundance in sediments and their different crystal chemistry: illite, kaolinite, montmorillonite, and chlorite. The values for pH were 4 and 8 and salt concentrations were 0.001 and 0.7M NaCl to appreciate the effects of changing salinity, e.g. from fresh water to seawater conditions. For the coating experiments, a well-characterised oil was used to survey the main effects of complex organic mixtures on adsorption and oil to clay mineral (w/w) ratios were 0.0325 and 0.3250. As(V) adsorption increased with increasing NaCl concentration, suggesting that the mechanisms of As(V) adsorption are related to the formation of surface complexes in which Na+ ions act as bridges between the clay surface and the As(V) anions. Cation bridging is also indicated by zeta potential measurements which show that higher NaCl concentrations along with the presence of As(V) can cause the clay particles and adsorbed ions to have a more negative overall charge. Adsorption is lower at higher pH due to the reduced number of positively charged sites on the edge of clay mineral layers. Oil coating reduces As(V) adsorption by decreasing the available surface area of clay minerals, except in the case of oil-coated montmorillonite, where surface area following dispersion in water is increased. The main variables controlling As(V) adsorption are surface area and surface charge density, as confirmed by a simplified quantitative model. These findings advance our ability to predict the effects of complex pollution events in various freshwater and marine settings. [Copyright &y& Elsevier]

• 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]

Abstract: Aluminous clay deposits on Mars are recognized from remotely sensed infrared spectral features similar to those of montmorillonite, beidellite, and/or kaolinite. The nature of aluminous clay deposits on Mars is of interest because they likely indicate a different formation mechanism than that of Fe–Mg clays, which are widespread on Mars and likely alteration products of the Fe–Mg-rich basaltic crust. The near-infrared reflectance spectra of aluminous martian clay deposits frequently display characteristics typical of both montmorillonite and kaolinite. The question arises whether such mixed character is due to the existence of end-member phases or to kaolinite–smectite mixed-layer (K–S). The issue is relevant because K–S implies the existence of a smectite precursor that alters into kaolinite, and thus constrains the timing and intensity of the alteration processes that generates it. A mixture of kaolinite and smectite end-members may indicate locally heterogeneous alteration processes, or alternatively, could result from the physical mixing of altered materials of different provenance. A group of natural K–S samples and synthetic kaolinite/smectite mixtures of known proportion, all of which had been thoroughly characterized in previous work using several analytical techniques, were investigated here using near-infrared (NIR) spectroscopy. The NIR spectral features correlate well with their kaolinite–smectite relative proportions. The shape of spectral features attributed to Al–OH in K–S is subtly different from those in physical mixtures of kaolinite and smectite. Based on qualitative comparison, some regions on Mars appear to have spectral signatures similar to K–S. We also applied a quantitative technique using the second derivative of spectra. In this technique, plots of the height of the features at (λ=) 2.21μm (band present in kaolinite and montmorillonite) and 2.17μm (kaolinite only) were able to discriminate between K–S and kaolinite–smectite physical mixtures, as they generated correlations with different slopes. The method of discrimination was applied to Mars spectra, which resulted in reasonable evidence for the existence of K–S in Nili Fossae and Mawrth Vallis, and mixtures of end-members in Mawrth Vallis and Leighton Crater. This is one of the first times that evidence for mixed-layer clay minerals, and particularly K–S, on Mars has been gathered. The ability to detect mixed-layer clays is an important step forward for further development of our understanding of the processes that generated clay on Mars. [Copyright &y& Elsevier]

Investigates the formation of smectite under hydrothermal conditions in the aluminum-magnesium series. Types of smectite clays based on their charges; Models rationalizing kaolinite and smectite growth; Chemical analysis of gels; Difference in the growth rate of trioctahedral and dioctahedral smectite; Precursors to the growth of smectite.

The mechanism of kaolinite transformation into dickite has been investigating using 13 samples from the Frøy and Rind oil fields (Broad Fourteens basin, North Sea), 3 kaolinite specimens with different crystal order (KGa-2, Kaolinite API 17, Keokuk kaolinite), and 2 dickite-rich samples (Natural History Museum collection). Detailed analysis of XRD, thermal analysis, and SEM data show that: (1) as dickite content increases, there is also an increase of the crystal order of kaolinite; (2) in dickite-rich specimens kaolinite and dickite have crystals (or XRD-coherent domains) of the same size; (3) there is no specific dehydroxylation temperature for each polytype, rather particle size and crystal order control dehydroxylation temperature independently of polytype; (4) with progressive dickite content, the development of both particle size and the size of the coherent crystal domains within particles is greater in the c direction than in the a-b plane; (5) the growth of defect-free segments in the c direction is not connected with the growth in the a and b directions, as would be expected in crystallization from solution; (6) textural features indicate coalescence of kaolin plates with burial; (7) there is a very weak positive correlation between particle dimensions and relative kaolinite-dickite content. These results are interpreted as resulting from a double reaction taking place in the solid state with burial. Some kaolinite domains grow in size and crystal order while other domains are transformed into dickite. Presumably, also the dickite domains formed early in the transformation grow in crystal order. The transformation into dickite stops at 90-95% dickite because the remaining kaolinite domains are so large and stable that the stability increase produced by the polytype transformation would be negligible. [ABSTRACT FROM AUTHOR]

This study aims to contribute to a better understanding of the nature and evolution mechanism of interstratified clay minerals. We examined the <2µm or <0.2µm size fraction of interstratified kaolinite- smectite (K-S) formed by hydrothermal and hydrogenic alteration of volcanogenic material from a Tortonian clay deposit (Almería, Spain), a weathered Eocene volcanic ash (Yucatan, Mexico), and a weathered Jurassic bentonite (Northamptonshire, England). The methods used were X-ray diffraction analysis (XRD) of random and oriented preparations, thermogravimetry, chemical analysis, and 29Si MAS nuclear magnetic resonance. The proportions of kaolinite and smectite in K-S (%K) were determined by fitting the XRD patterns of ethylene-glycol-saturated samples with patterns calculated with the NEWMOD computer program. The obtained range of compositions is 0.85%K. A comparison of the results from the various techniques showed non-linear relationships, indicating that the layers in K-S are complex and hybrid in nature. The smectite-to-kaolinite reaction is a solid-state transformation proceeding through formation of kaolinite-like patches within the smectite layers. The process consists of several non-simultaneous stages: (1) removal of parts of the tetrahedral sheet, resulting in formation of kaolinite-like patches; (2) layer collapse to ∼7 Å where the kaolinite-like patches are sufficiently large; (3) Al for Mg substitution in the octahedral sheet, simultaneous or slightly delayed with respect to layer collapse, causing a layer-charge decrease and loss of interlayer cations; (4) Si for Al replacement in the tetrahedral sheet and further loss of interlayer cations. Iron remains in the kaolinite or is lost at the latest stages of the process. [ABSTRACT FROM AUTHOR]

Visible/Near Infrared Reflectance spectroscopy (350–2500 nm) is an efficient and effective tool to identify and semi-quantify clay minerals, Fe3+ (oxyhydr)oxides, and their crystal-chemistry/structure. Even so, there have been few studies systematically describing how spectroscopy can be applied to mineralogical evolution during weathering. This study investigated reflectance spectra of a long core of a thick basaltic weathering sequence in Hainan Island and a series of transformation products from montmorillonite to kaolinite to present spectral features associated with weathering trends. In combination with X-ray diffraction and geochemical results, mineralogical transitions and weathering intensity of the core samples were described from a spectroscopic perspective. Several different protoliths were spectroscopically recognized in the Hainan weathering sequence, consistent with geological observation and geochemical analysis. Overprinted on these multiple protoliths was a discernable weathering sequence observable by infrared spectroscopic methods. Clay minerals changed upwards in section from TOT type (nontronite) to TO type (kaolinite), and finally to O type (gibbsite) hydroxide clay-size particles as the result of gradual hydrolysis of silicates and leaching of mobile elements with weathering. The relative abundance of hydroxyl to interlayer water, observable by the band depth ratio of spectral absorptions around 1400 nm and 1900 nm (BD1400/BD1900), increased progressively and correlated positively with the chemical index of alteration and Al 2 O 3 concentration. The increasing BD1400/BD1900 index value with weathering was the result of gradual leaching of interlayer cations (e. g. Na+, K+), and their water complexes within interlayers, and gradual formation of M-OH layers by hydrolysis. Owing to leaching of Mg and release of Fe, the octahedral M-OH formed by hydrolysis was gradually dominated by Al-OH. Reflectance spectroscopy is a powerful tool to identify protolith changes in weathering sequences and for studying clay mineralogical transitions and weathering intensity. This spectroscopic approach could have great value for understanding weathering related to paleoclimate on Earth or other planets using field spectroscopy and remote sensing. • • Infrared reflectance spectroscopy was applied to a drill core through weathered rocks. • • Spectral indices of clay minerals were developed to characterize weathering trends. • • Ratios of spectral band depths measure interlayer water and hydroxyl content. • • These indices can be applied to remote sensing data of Mars. [ABSTRACT FROM AUTHOR]