Vibrational spectroscopic study of three Mg–Ni mineral series in white and greenish clay infillings of the New Caledonian Ni-silicate ores

This study presents and discusses infrared spectroscopic data of well characterised, naturally occurring trioctahedral layer silicates of the serpentine (Srp), talc (Tlc), and sepiolite (Sep) mineral groups, which are found in reactivated faults and sequences of white and green clay veins (deweylite and garnierite) of the New Caledonian Ni-silicate ores. Bands assigned to the OH stretching vibrations of these 1:1 and 2:1 layer silicates in both the fundamental and first overtone regions of mid- and near-infrared (MIR and NIR) spectra, respectively, are compared to those reported in the literature for synthetic Mg–Ni series of the Srp and Tlc mineral groups. They are also presented according to the sequences of infillings recognised in the white and green veins of the Ni-silicate ores. The study reveals that serpentine-like (SL) minerals of the first sequences of clay infillings are residues of larger crystals of serpentines (lizardite, chrysotile, and antigorite) and that the newly formed talc-like (TL) minerals and Sep are the main Ni-bearing carriers of the Ni-silicate ores. Decreasing crystal size and order in serpentine species have major effects on vibrational bands. They favour the broadening of the OH stretching bands, the degradation of the signals assigned to the interlayer OH, and the enhancement of the signal related to weakly bound water molecules. The replacement of Mg by Ni in octahedral sites of the 2:1 layer silicates (TL, Sep) of the greenish clay infillings can be traced by specific OH stretching bands related to the Mg3OH, Mg2NiOH, MgNi2OH, and Ni3OH configurations in the fundamental (MIR) and first overtone (NIR) regions of the spectra. The dominance of the Mg3OH and Ni3OH configurations with respect to mixed configurations in the Mg–Ni mineral series of the clay infillings (mostly in the dominant TL minerals) suggests that Mg and Ni segregation is related to separate Mg-rich and Ni-rich mineral phases rather than to a cationic clustering within the individual particles. This segregation of Mg and Ni in discrete mineral phases is related to Mg–Ni oscillatory zoning patterns (banded patterns) and is reproduced at the scale of the Ni-silicate ores between the white (deweylite) and greenish (garnierite) veins of the reactivated faults.

How Closely Is Potassium Mass Balance Related to Soil Test Changes?

The exchangeable fraction of soil potassium (K) has been viewed as the most important source of plant-available K, with other sources playing smaller roles that do not influence the predictive value of a soil test. Thus, as K mass balance changes, the soil test should change correspondingly to be associated with greater or reduced plant availability. However, soil test changes and the availability of K to plants are influenced by many other factors. This chapter reviews research on soil test K changes and the relation to crop uptake and yield. A mass-balance relationship is rarely achieved from the measurement of exchangeable K because of the potential for buffering of K removal from structural K in feldspars and from interlayer K in primary and secondary layer silicates. Similarly, surplus K additions can be fixed in interlayer positions in secondary layer silicates, or potentially sequestered in sparingly soluble neoformed secondary minerals, neither of which is measured as exchangeable K. In addition, soil moisture, temporal differences in exchangeable K with K uptake by crops, K leaching from residues, clay type, organic matter contribution to the soil CEC, and type of K amendment confound attempts to relate K additions and losses with an exchangeable K soil test. Research is needed to create regionally specific K soil test procedures that can predict crop response for a subset of clays and K-bearing minerals within specific cropping systems.

Swelling capacity of mixed talc-like/stevensite layers in white/green clay infillings (“deweylite”/ “garnierite”) from serpentine veins of faulted peridotites, New Caledonia

White (Mg-rich) and green (Ni-rich) clay infillings (“deweylite”/ “garnierite”) found in serpentine veins of faulted peridotite formations from New Caledonia consist of an intimate mixture of fine-grained and poorly ordered 1:1 and 2:1 layer silicates, commonly referred to as non-expandable serpentine-like (SL) and talc-like (TL) minerals. New data on the swelling and shrinking capacity of these layer silicates were gathered from X-ray diffraction (XRD) after saturation of the clay fractions with different cations (Ca2+, Li+, K+), ethylene glycol (EG) solvation, and heat treatments. Simultaneously, layer charge distribution and vacancy density, respectively, were investigated by FTIR spectroscopy on NH4-saturated clay fractions and XRD on Li-saturated clay fractions before and after heating (Hofmann Klemen treatment). Five clay infillings, with dominant 2:1 layer silicates and variable Ni contents, were selected for this study, from a large set of veinlets, according to their swelling capacity. The crystal chemistry of these samples was characterized by FTIR spectroscopy and bulk chemical analyses. The swelling ability of the clay infillings is attributed to the 2:1 layer silicates. It does not seem to be affected by the relative fraction of Mg and Ni in their octahedral sheets. In XRD patterns, the swelling ability is reflected by slight shifts of the basal reflection of the 2:1 layer silicates toward low angles for bulk samples and by splitting of the peak into two contributions for clay fractions saturated with Ca (or Li) and solvated with EG. The split increases with the swelling capacity of the sample. It originates mainly from octahedral-layer charge generated by vacant sites. Such results lead us to consider the 2:1 layer silicates of the infillings as an intimate mixture of non-expandable (TL) and expandable (stevensite) phases. In agreement with previous studies that suggested a contribution of hydrothermal processes in the alteration of serpentine species into 2:1 layer silicates, we propose that the proportion of expandable phases in the clay infillings (or vacancy sites in the octahedral sheets of the 2:1 layer silicates) could be used as an efficient means for assessing the temperature of their formation. Clay infillings mostly made of stevensite would have formed at ambient temperatures, whereas those consisting mainly of non-expandable TL would have formed at higher temperatures.

Smectite clay minerals reduce the acute toxicity of quaternary alkylammonium compounds towards potentially pathogenic bacterial taxa present in manure and soil

Quaternary alkylammonium compounds (QAACs) are a group of cationic surfactants which are disinfectants with numerous industrial and agricultural applications and frequently released into the environment. One recent hypothesis is that bacteria present in soil will be protected from acute toxic effects of QAACs in the presence of expandable layer silicates due to interlayer sorption. We therefore studied bacterial growth kinetics with high temporal resolution and determined minimal inhibitory concentrations (MICs) of two QAACs, benzyldimethyldodecylammonium chloride (BAC-C12) and didecyldimethylammonium chlorid (DADMAC-C10), for eight strains of different bacterial taxa (Escherichia coli, Acinetobacter, Enterococcus faecium, Enterococcus faecalis, and Pseudomonas fluorescens) in relation to QAAC sorption to smectite and kaolinite. The MICs of BAC-C12 and DADMAC-C10 were in the absence of smectite and kaolinite in the order of 10 to 30 µg mL−1 and 1.0 to 3.5 µg mL−1 for all strains except the more sensitive Acinetobacter strain. For all tested strains and both tested QAACs, the presence of smectite increased apparent MIC values while kaolinite had no effect on MICs. Sorption curves without bacteria showed that smectite sorbed larger amounts of QAACs than kaolinite. Correcting nominal QAAC concentrations employed in toxicity tests for QAAC sorption using the sorption curves explained well the observed shifts in apparent MICs. Transmission electron microscopy (TEM) demonstrated that the interlayer space of smectite expanded from 13.7 ± 1 Å to 19.9 ± 1.5 Å after addition of BAC-C12. This study provides first evidence that low charge 2:1 expandable layer silicates can play an important role for buffering QAAC toxicity in soils.

Asbestiform anthophyllite, tremolite, and related fibrous amphibole chemistry, both as primary and secondary mineralization in metamorphic facies in asbestos occurrences in North American deposit comparisons

<p>As we continue to investigate the asbestos-forming minerals and their associated geology as they occur in North America, we have found that subtle variations can make the standardization of what is and what is not asbestos more difficult. On the other hand, some geochemical trends recently observed have given us significant insight into what we can expect in the ground, which we hope will lend much-needed information to medical investigators to better understand the relationship of mineral morphologic and chemical differences and the ramifications to human health for those potentially exposed. In efforts to understand why certain minerals form in the asbestiform habit, mineralogists still cannot fully explain the cause-and-effect of this phenomenon. Although we know that there are chemical variances and pressure or temperature regimes that are conducive to the formation of asbestos, a complete and absolute picture of how and why amphibole forms fibers, or serpentine forms chrysotile scrolls remains elusive. Research indicates however that there are two primary ways that sheet silicates compensate for the fundamental misfit between their tetrahedral silica layers (T) and their octahedrally-coordinated cation layers (O) that is by either tetrahedral rotation /stretching or by bending or modulation of the layers in concert. Rotation or stretching occurs in both the 1:1 layer silicates (T-O) such as serpentines, and the 2:1 phyllosilicates (T-O-T) such as vermiculite or talc. The other primary means of misfit compensation is structural bending, with the obvious examples of antigorite or chrysotile. Although it was originally hypothesized as early as the 1950s that this curving or bending of the sheet structure was entirely due to the T-O misfit, more recent research points to the importance and variances of hydroxyl bonding in the chrysotile structure. A secondary mode of compensation for the fundamental misfit is by the addition or subtraction of silica tetrahedra or octahedral cations in modulated fashion, which affects the overall chemistry of the mineral as a whole. In polysomatic hydrous biopyriboles we see the importance of hydration alteration reactions in the transformation of chain zippers. Thusly, a wide variety of intergrowth microstructures appear in Mg-rich 1:1 modulated layer silicates, analogous to the hydrous biopyriboles as is common intimate intermixing in a polysomatic series. It is therefore common that the means by which all of our regulated asbestos minerals form is through the combined action of T-O misfit compensation and the action of water in the crystallizing or re-crystallizing process. </p>