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Chemical and structural complexities in interstratified clay minerals arising from mineral transformations and evolving formation conditions should be recorded in their stable isotope signatures. This paper examines the controls on the stable hydrogen and oxygen isotope compositions of Fe3+-rich, glauconite-nontronite, talc-nontronite and talc-saponite from submarine hydrothermal sites, with a focus on the Red Sea Atlantis II Deep. Values of δ 18O became less positive in the order nontronite > glauconite-nontronite > talc-nontronite > talc-saponite, yielding oxygen isotope temperatures ranging from ∼40 °C for nontronite to ∼135–300 °C for talc-saponite. These clay minerals have low δ 2H, ranging from −145 to −127‰ for talc-nontronite, −135‰ for nontronite, −129 to −85‰ for glauconite-nontronite, and −95 to −59‰ for talc-saponite. The clay mineral-water hydrogen isotope fractionation is strongly affected by Fe3+ content, with increasing structural Fe3+ causing progressive weakening of O-H bonds. The large ionic radius and high charge of Fe3+ cause it to be more poorly shielded by surrounding oxygen from hydroxyl hydrogen relative to other octahedral or tetrahedral cations. The resulting lengthening of O-H bonds favours 1H over 2H. Our results confirm that Fe-rich phases, such as nontronite-glauconite, are produced at the lowest temperatures and Mg-rich phases, such as talc-saponite, are formed at the highest temperatures in seafloor hydrothermal environments. Evolving fluid chemistry and fluid pathways during clay mineral formation are also important. Glauconite layer formation from precursor nontronite likely occurred during diagenesis; redox changes causing Fe-reduction and an increase in layer charge facilitated interlayer K-fixation. Talc-saponite compositions vary with temperature and fluid chemistry, forming at variable sediment depths depending on access to the hottest hydrothermal fluids. • Fe3+ content controls δ 2H OH of seafloor Fe-rich hydrothermal, interstratified clay. • Large ionic radius and high charge of Fe3+ causes systematic decrease in clay δ 2H. • Seafloor clay δ 18O indicates lower temperature formation of Fe- versus Mg-rich phases. • Diagenetic glauconite-nontronite formed at ∼75 °C (Atlantis II Deep) from nontronite. • Talc-nontronite formed at ∼95 °C and talc-saponite at ∼240 °C (Atlantis II Deep). [ABSTRACT FROM AUTHOR]

Potassium metasomatism is a common geologic process occurring in a range of environments on Earth. K‐metasomatism can dramatically change the chemistry of large volumes of crust resulting in formation of abundant K‐rich feldspar while preserving original rock textures. Remote sensing of Mars has revealed the presence of rare but striking felspar‐rich terrains as well as K‐rich phyllosilicates such as illite or muscovite. Furthermore, the Curiosity Rover has detected evidence for K‐enrichment in rocks at Gale Crater. In this study, we use spectroscopic and remote sensing analyses of K‐metasomatized rocks on Earth as a comparison to K‐rich and/or possible granitic rocks on Mars. The results suggest that evidence for K‐feldspar rich, quartz‐bearing, and illite‐bearing rocks on Mars is consistent with K‐metasomatism. K‐rich rocks in Gale Crater have themselves likely not been metasomatized, but the abundant feldspar within them might have been derived from metasomatized crust. Plain Language Summary: Mars is a volcanic planet with a surface dominated by basalt and sedimentary rocks derived from basalt, similar to oceanic crust on Earth (though Mars' crust is thicker). For decades, Mars has been considered a "one plate planet" where plate tectonics never occurred and where continental type rocks never formed. Recent observations have, however, revealed enticing evidence that felsic "continental type" rocks containing K‐feldspar and quartz are present. Such rock units were recognized in Gale Crater based on their high potassium abundances. Granite‐type rocks detected from orbit using infrared data would also presumably be rich in potassium. However, rocks of the same composition can be made through aqueous alteration rather than from magma in the crust. This study shows a striking example of potassium enrichment and mineralogical changes in basaltic rocks on Earth caused entirely by low‐temperature hydrothermal brine in the crust. We use analogous remote sensing measurements to study these potassic rocks on Earth and compare the results to Mars. It appears that at least some of the felsic rock compositions on Mars were caused by metasomatism. Key Points: Subsurface brines can deposit significant potassium in volcanic rocks while preserving original texturesSpectral signatures of K‐metasomatism include K‐feldspar and illiteFelsic compositions on Mars might occur because of low‐temperate alteration by subsurface brines [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]

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]

Interest in mineral-microbe interaction has grown enormously over recent decades, providing information in a puzzle-like manner which points towards an ever increasingly intimate relationship between the two; a relationship that can be truly termed co-evolution. Clay minerals play a very central role in this co-evolving system. Some 20 years ago, clay scientists looked at clay mineral-microbe studies as a peripheral interest only. Now, can clay scientists think that they understand the formation of clay minerals throughout geological history if they do not include life in their models? The answer is probably no, but we do not yet know the relative weight of biological and inorganic factors involved in driving clay-mineral formation and transformation. Similarly, microbiologists are missing out important information if they do not investigate the influence and modifications that minerals, particularly clay minerals, have on microbial activity and evolution. This review attempts to describe the several points relating clay minerals and microorganisms that have been discovered so far. The information obtained is still very incomplete and many opportunities exist for clay scientists to help to write the real history of the biosphere. [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]

Saharan dust can travel long distances in different directions across the Atlantic and Europe, sometimes in episodes of high dust concentration. In recent years it has been discovered that Saharan dust aerosols can aggregate into large, approximately spherical particles of up to 100 μm generated within raindrops that then evaporate, so that the aggregate deposition takes place most times in dry conditions. These aerosol aggregates are an interesting phenomenon resulting from the interaction of mineral aerosols and atmospheric conditions. They have been termed “iberulites” due to their discovery and description from aerosol deposits in the Iberian Peninsula. Here, these aggregates are further investigated, in particular the role of the clay minerals in the aggregation process of aerosol particles. Iberulites, and common aerosol particles for reference, were studied from the following periods or single dust events and locations: June 1998 in Tenerife, Canary Islands; June 2001 to August 2002, Granada, Spain; 13–20 August 2012, Granada; and 1–6 June 2014, Granada. Their mineralogy, chemistry and texture were analysed using X-ray diffraction, electron microprobe analysis, SEM and TEM. The mineral composition and structure of the iberulites consists of quartz, carbonate and feldspar grains surrounded by a matrix of clay minerals (illite, smectite and kaolinite) that also surrounds the entire aggregate. Minor phases, also distributed homogenously within the iberulites, are sulfates and Fe oxides. Clays are apparently more abundant in the iberulites than in the total aerosol deposit, suggesting that iberulite formation concentrates clays. Details of the structure and composition of iberulites differ from descriptions of previous samples, which indicates dependence on dust sources and atmospheric conditions, possibly including anthropic activity. Iberulites are formed by coalescence of aerosol mineral particles captured by precursor water droplets. The concentration of clays in the iberulites is suggested to be the result of higher efficiency for clay capture than for the capture of larger mineral grains. The high hygroscopicity of clay minerals probably causes retention of water in the evaporation stage and some secondary minerals (mainly gypsum) are associated with clays. [ABSTRACT FROM AUTHOR]

Near-infrared remote sensing data of Mars have revealed thousands of ancient deposits of Fe/Mg-rich smectitic clay minerals within the crust with relevance to past habitability. Diagnostic metal–OH infrared spectroscopic absorptions used to interpret the mineralogy of these phyllosilicates occur at wavelengths of 2.27–2.32 μm, indicating variable Fe/Mg ratios in the clay structures. The objective of this work is to use these near infrared absorptions to constrain the mineralogy of smectites on Mars. Using Fe/Mg-rich seafloor clay minerals as mineralogical and spectroscopic analogs for Martian clay minerals, we show how crystal–chemical substitution and mixed layering affect the position of the diagnostic metal–OH spectral feature in smectitic clay minerals. Crystal-chemistry of smectites detected on Mars were quantitatively constrained with infrared data and categorized into four mineralogical groups. Possible alteration processes are constrained by comparisons of clay chemistry detected by remote sensing techniques to the chemistry of candidate protoliths. Of the four groups identified, three of them indicate significant segregation of Fe from Mg, suggestive of alteration under water-rich and/or oxidizing conditions on Mars. The fourth group (with low Fe/Mg ratios) may result from alteration in reducing or water-limited conditions, potentially in subsurface environments. Some samples are interstratified di–trioctahedral clay minerals that have characteristics of dioctahedral clay minerals but clear chemical evidence for trioctahedral sheets. Approximately 70% of smectite deposits previously detected on Mars are classified as Fe-rich (FeO/MgO > 10). Only 22% of detections are trioctahedral and relatively Mg-rich. An additional ∼8% are difficult to characterize, but might be very Fe-rich. The segregation of Fe from Mg in Martian clay minerals suggests that Mg should be enriched in other contemporaneous deposits such as chlorides and carbonates. [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]

Nuclear waste from thermal plants poses a lasting risk to the biosphere because of its long radioactive life. The planned definitive storage place for it is in deeply buried repositories. Such repositories would need to be both impermeable to water, and plastic during deformation, in order to avoid the formation of cracks that may allow water in. One of the clay minerals, smectite, has these two properties and is an ideal candidate as a sealing material or even host rock for nuclear waste repositories. The chemical stability of smectite in the repository environment is sufficient to maintain good sealing properties during the active life of the relevant radionuclides. [ABSTRACT FROM AUTHOR]

The Curiosity rover on Mars, landed in 2012, is capable of mineralogical investigation using X-ray diffraction, complementing the abundant infrared remote sensing data already available on clay minerals. We can, however, expect that the in situ X-ray diffraction information will convey a more complex picture than that inferred from infrared spectroscopy alone. CheMin has landed. [ABSTRACT FROM AUTHOR]

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]

Abstract: The preparation of ultra-thin clay mineral films promises to open novel applications for more sensitive sensors, stronger plastics and other unexpected functionalities. However, most natural and synthetic clay particles necessarily need often tedious preparation procedures to remove crystalline impurities and to obtain completely exfoliated forms. Furthermore, the wide range of particle sizes characteristic of commonly available synthetic and natural clays can lead to variable properties and unexpected reactions. Here we report the synthesis of a homogenous monolayer-thick Zn-smectite that will benefit specific applications requiring ultra-thin and monodispersed layered nanomaterials. Furthermore, the fast and easy preparation overcomes the problems associated with the processing of both currently available synthetic and natural smectites. XRD, FE-SEM, and TEM analyses show the synthetic Zn-smectites to be relatively impurity free. Electron microscopy imaging illustrates its nanometer-sized dimension and very thin sheet-like morphology. Based on light scattering and small angle X-ray scattering measurements, it has a narrow size distribution (ave. ∼70nm) and a molecular-level thickness (∼0.7nm), respectively. This nanostructure combined with the interesting properties of Zn is anticipated to yield novel applications as a clay-based nanomaterial. [Copyright &y& Elsevier]

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]

Many Plio-Pleistocene lake basins in eastern Africa associated with early hominins contained waters that were alkaline, enriched in silica due to weathering of volcaniclastics and hydrothermal activity, and evaporatively concentrated. Such conditions are favorable for the formation of silicate minerals precipitated from solution, or neoformed through alteration of detrital parent material. The most common authigenic silicates thus produced include the zeolite family of minerals and a number of clay minerals, particularly 2:1 clays of the illite and smectite families. Particularly in the absence of well-preserved paleoecological records, these minerals may provide important evidence of paleoenvironmental conditions. Stratigraphic variations in lacustrine authigenic silicates can give an indication of changes in cation proportions in paleolake waters over time. For example, in Pliocene deposits of the Baringo Basin, Kenya, fluctuations between phillipsite (K-rich) and analcime (Na-rich) facies suggest changing salinity levels because more saline waters have greater Na/K ratios. In one interval in the Chemeron Formation, analcimic muds are interbedded with freshwater diatomites, suggesting a link between high amplitude of environmental variability and peak orbital eccentricity ~2.6 Ma. In the Lake Magadi basin in southern Kenya, marked increases in zeolite abundance and greater dominance of Na-rich phases indicate hydrological closure and enhanced evaporative concentration suggesting a long-term increase in aridity accelerating ~380 ka. In short cores of the Chew Bahir basin of southern Ethiopia, greater analcime abundances and incipient low-temperature illitization of smectite (indicating greater K uptake in more saline waters) are associated with Late Pleistocene arid episodes such as the Younger Dryas. In the Olduvai Basin of northern Tanzania, fluctuations in the Al/Mg ratio of authigenic clay minerals record changes in salinity, as greater Mg is incorporated into clays during saline episodes. These clay mineral changes are accompanied by shifts in the oxygen isotope composition of structural oxygen, indicating equilibrium with variably saline waters. Both elemental and isotopic changes fluctuate over precessional timescales, suggesting orbital control of hydrologic balance ~1.8 Ma.Authigenic silicates can be an important source of paleolimnological data, particularly over the range of salinities between the relatively freshwater conditions under which biological proxies readily accumulate, and the extreme salinities associated with evaporites such as halite and trona (Na-carbonate). [ABSTRACT FROM AUTHOR]