The formation of fine-grained magnetite (~0.1 μm) at pH 7 and 25°C from aeration of Fe(II) chloride solutions is presented. The magnetite converted at 105°C to maghemite with poorly developed superstructure lines. Under the experimental conditions employed, as the initial [Cl]/[Fe] ratio was increased from the stoichiometric value of 2, the final product contained increasing amounts of lepidocrocite. The degree of crystallinity of this phase, as measured by the width at half height of the 020 X-ray diffraction peak, also increased with this ratio. The hydrolysis rate (base consumption to maintain pH) showed a plateau whose position and extent changed with the initial [Cl]/[Fe] ratio. Through this plateau region the Eh decreased to a minimum value the position of which was directly related to the [Cl]/[Fe] value. The formation of lepidocrocite rather than magnetite is likely due to the high [Cl] where there would be increased difficulty for neighboring OH to condense and eliminate H2O. The formation of Fe-O-Fe bonds in this condensation would be impeded by Cl substitution for OH either in the first formed green rust stage or during its oxidation.

Diffractograms of lepidocrocites formed from the oxidation of Fe(II) chloride solutions at pH 7 and 25°C showed differential line broadening with (0k0) reflections being much sharper than (hk0) or (hkl). As the initial [Cl]/[Fe] ratio was increased from 2, crystallinity increased in all axial directions, as defined by the width at half height of diffraction peaks. At [Cl]/[Fe] ratios greater than ~8, the crystallinity did not increase further, and for reflections involving the a-axis direction, it appeared to decrease. Increased [Cl]/[Fe] ratios changed the rate of the oxidation/hydrolysis reactions. These variations reflect changes in the stability and/or composition of the intermediate green rust phase, (Fe(II)Fe(III) hydroxychloride) in the high [Cl] environment. The influence of the [Cl]/[Fe] ratio was related to the experimental conditions employed, especially where they influenced the rate of oxidation.

Imogolite is a tubular aluminosilicate which is common in Andosols and Spodosols. The high pH at point-of-zero charge at the outer parts of the tube and the anomalously high chloride adsorption of imogolite suggested that there may be structural charge associated with this mineral. The structural charge may arise because of changes in bond valence imposed by the incorporation of orthosilicate anions in a gibbsite-type sheet. By using a Basic Stem Model approach, it is shown that the surface charge properties of imogolite are explained if the mean Al-O bond valence of the outer -Al2OH groups is higher than the inner -Al2OHSiO3 groups. Hence, a weak positive charge is developed on the outer tube walls whereas a negative charge develops in the tubular pores. The best model fits were obtained where either one or two units of structural charge per unit cell of tube were assumed. The model may also explain why imogolite tubes are normally aggregated in large bundles in close hexagonal packing, because bound counterions may hold the tubes together. However, to arrive at good model descriptions, the deprotonation of -Al2OH groups must occur at a higher pH than that expected when assuming that all surface oxygens form two hydrogen bridges with H2O. A more precise structure of imogolite is required to test fully this hypothesis.

The application of Raman spectroscopy to the study of the mixed cationic Pb-Cu and Pb-Cu-Ag minerals: boleite, cumengeite and diaboleite has enabled their molecular structures to be compared. Each of these three minerals shows different hydroxyl-stretching vibrational patterns, but some similarity exists in the Raman spectra of the hydroxyl-deformation modes. The low-wavenumber region is characterized by the bands assigned to the cation-chloride stretching and bending modes. Phosgenite is also a mixed chloride-carbonate mineral and a comparison is made with the molecular structure of the aforementioned minerals. Raman spectroscopy lends itself to the study of these types of minerals in complex mineral systems of secondary mineral formation.

The new mineral therasiaite, ideally (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, was found in a mediumtemperature (∼250°C) intracrater active fumarole at La Fossa crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as brown to dark brown equant to short prismatic crystals up to 0.1 mm in length, in association with salammoniac, kremersite and adranosite. The mineral is monoclinic, space group: Cc (no. 9) with a = 18.284(4), b = 12.073(2), c = 9.535(2) Å, β = 108.10(3)°, V = 2000.6(7) Å3 and Z = 4. The six strongest reflections in the X-ray powder diffraction pattern are: [dobs in Å(I)(hkl)] 2.812(100)(23), 2.664(77)(13), 3.297(28)(33), 3.208(14)(2), 3.008(12)(040), 2.942(11)(331). The empirical formula (based on 17 anions per formula unit (p.f.u.)) is (NH4)2.68K1.32Na2.04Fe1.76Al0.12Mn0.12S2.98O11.95Cl5.05. The measured density is 2.41(1) g cm−3, dcalc = 2.395 g cm−3. The mineral is biaxial (−) with α= 1.585(3) β = 1.615(3) and γ = 1.630(3) (white light). Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.0240 for 5574 independent observed reflections [I > 2σ(I)]. The structure of therasiaite displays a novel topology and contains two independent, distorted octahedral Fe sites, with the Fe atoms in oxidation state 3+ and 2+, respectively, each surrounded by three Cl atoms and three oxygens of the sulfate ions. The Fe octahedra and the three independent sulfate anions are connected to form chains running along [001]. Voids between the chains are occupied by three independent ammonium ions (partially replaced by K+), one K+ and two Na+ ions. The formula resulting from the structure refinement is [(NH4)2.25K0.75]KNa2Fe2(SO4)3Cl5.

Some of the physical, chemical and mineralogical characteristics of Portland cement and related materials relevant to nuclear waste immobilization are defined. The ability to condition and maintain a high aqueous pH is undoubtedly the most important factor: it precipitates many species as hydrous oxides or hydroxides. However, in the longer term, many species – cationic as well as anionic – react with one or more cement components forming solubility-limiting phases. Progress on characterization of these phases is outlined. Many of the host phases have natural equivalents and this gives comfort in respect of their likely persistence over geological time. The emerging picture of immobilization in cement suggests that cement compositions can be tailored in terms of pH, Eh and internal chemistry so as to maximize immobilization potential. Nickel, uranium and chromium and chloride are used as examples.

A new mineral chrysothallite K6Cu6Tl3+Cl17(OH)4·H2O was found in two active fumaroles, Glavnaya Tenoritovaya and Pyatno, at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Chrysothallite seems to be a product of the interactions involving high-temperature sublimate minerals, fumarolic gas and atmospheric water vapour at temperatures not higher than 150ºC. It is associated with belloite, avdoninite, chlorothionite, sanguite, eriochalcite, mitscherlichite, sylvite, carnallite and kainite at Glavnaya Tenoritovaya and with belloite, avdoninite, chlorothionite, eriochalcite, atacamite, halite, kröhnkite, natrochalcite, gypsum and antlerite at Pyatno. The mineral forms equant-to-thick tabular crystals up to 0.05 mm, typically combined in clusters or crusts up to 1 mm across. Crystal forms are: {001}, {100}, {110}, {101} and {102}. Chrysothallite is transparent, bright golden-yellow to light yellow in finely crystalline aggregates. The lustre is vitreous. The mineral is brittle. Cleavage was not observed, the fracture is uneven. Dmeas = 2.95(2), Dcalc = 2.97 g cm–3. Chrysothallite is optically uniaxial (+), ω = 1.720(5), ε = 1.732(5). The Raman spectrum is given. The chemical composition (wt.%, electron-microprobe data, H2O calculated based on the crystal structure data) is: K 15.92, Cu 24.56, Zn 1.38, Tl 13.28, Cl 40.32, H2O(calc.) 3.49, total 98.95. The empirical formula, calculated on the basis of 17 Cl + 5 O a.p.f.u., is: K6.09(Cu5.78Zn0.32)Σ6.10Tl0.97Cl17[(OH)3.80O0.20]·H2O. Chrysothallite is tetragonal, I4/mmm, a = 11.3689(7), c = 26.207(2) Å, V = 3387.3(4) Å3, Z = 4. The strongest reflections of the powder X-ray pattern [d, Å (I)(hkl)] are: 13.20(44)(002); 6.88(100)(112); 5.16(30)(202, 114); 4.027(25)(220); 3.471(28)(206), 3.153(30)(314), 3.075(47)(305), 2.771(38)(316). The crystal structure (solved from single-crystal X-ray diffraction data, R = 0.0898) is unique. Its basic structural unit is a (001) layer of edge-sharing distorted CuCl4(OH)2 octahedra. Two Tl3+ cations occupy the centre of isolated TlCl6 and TlCl4(H2O)2 octahedra connected to each other and to the Cu polyhedral layers via KCl6 and KCl9 polyhedra. The name reflects the bright golden-yellow colour of the mineral (from the Greek χρυσος, gold) and the presence of thallium. Chrysothallite is the second known mineral with species-defining trivalent thallium.

Isotopic and geochemical evidence of paleoclimates, especially for the last glaciation, has been obtained from deep confined groundwaters of southern India. The δ13C, δ18O, chloride, and deuterium analyses of groundwaters show distinct excursions inferred to be related to climatic variations. The arid climatic episode associated with the last glaciation (18,000 ± 2000 yr B.P.) is conspicuously identified by signatures of relatively enriched δ13C (−10 to −12‰ PDB) and δ18O (−5.3 to −4.8‰ SMOW) values, and high chloride concentration (80 to 160 mg/l). The transition from an arid to humid period ca. 12,000–8000 yr B.P. is shown by a decreasing trend in the δ13C (−9.5 to −17‰) and δ18O (−4.5 to −6.3‰) contents of groundwaters. The late Holocene (since 4000 yr B.P.), marked by a more humid but unstable climate, is identified by further depletion of δ13C (−13 to −20‰) and δ18O (−5.2 to −6.3‰). Similar variation between δ18O and chloride values in confined groundwaters further demonstrates two distinct climatic excursions (arid and humid) governed by the “amount effect.” This is the first time that isotopic and geochemical signatures related to changing paleoclimates have been identified in the confined groundwaters of the southern Indian landmass.

Echinoderms are exclusively marine, osmoconformer invertebrates. Their distribution patterns are strongly influenced by salinity. Nevertheless, several species of the phylum inhabit the challenging intertidal zone, characterized by steep and fast salinity fluctuations. This study evaluated the response of coelomic fluid ionic concentrations (sodium, chloride, magnesium and potassium) of the intertidal sea cucumber Holothuria grisea to hypo- and hypersaline challenges. A stepwise protocol was performed for the whole animal exposure to both anisosmotic conditions: from 35 to 15 psu along 8 h, and from 35 to 45 psu along 6 h, to simulate intertidal conditions. Tissue water regulation by the longitudinal muscle, oesophagus and posterior intestine was also evaluated, upon hypo- and hyper-osmotic shocks of 20 and 50% of intensity with respect to the isosmotic control. Ionic gradients were observed between coelomic fluid and external water, mainly for potassium and magnesium, but also sodium, and in a greater extent under hyposaline conditions than under hypersaline exposure. Consistently, H. grisea shows retracted tube feet in 15 psu, but a more relaxed appearance and exposed tube feet in 45 psu. In addition, H. grisea showed greater capacity for tissue water maintenance during hyper- than in hyposmotic conditions. Holothuria grisea shows an avoidance behaviour in low salinity (thus sustaining ionic gradients), preventing its tissues from intense swelling. This strategy allows it to dwell in the intertidal region.

Protein nanofibrils with 10–20 nm diameters were formed by heating whey protein solution at pH 2·0. Nanofibrils solution was deacidified slowly through dialysis followed by adding different amounts of CaCl2 (0–80 mM) into the dialysis water resulting in formation of a soft viscoelastic gel over time. The gel fabricated from the nanofibrils solution dialyzed against distilled water with 0 mM CaCl2 had zero ash content. Fourier transform infra-red spectroscopy revealed a change in the pattern of hydrogen bond formation in gel network by calcium chloride. The higher the ash content of gels, the lower was the storage modulus and fracture stress of samples. Gels with higher ash contents had a more porous microstructure which was attributed to the diminished hydrophobic interactions and hydrogen bonding among nanofibrils by the action of chloride. Higher ash contents also led to higher water holding capacity of gels which was attributed to the influence of the strongly hydrated calcium ions that interacted with the non-charged regions of proteins via site-specific interactions.

Various Mars missions have detected Cl atoms, chlorides and perchlorates in martian surface materials. The global soils, in particular, always contain significant levels of observable Cl. Direct evidence points to this Cl being in the form of both chlorides and perchlorates, and possibly also chlorates and other oxychlorines. The most widespread measurements have been of Cl atoms, and cannot discern the chemical form. However, from separate evidence of perchlorate obtained at high latitudes (Phoenix lander) and low latitudes (Curiosity rover), it is likely that perchlorates are widespread, albeit in varying proportions relative to the total amount of ubiquitous Cl.

In 2014, Khan et al. presented evidence that soil exchangeable K (Exch-K) increases over time without addition of potassium (K) to the soil despite the removal of K in crops on a soil rich in montmorillonite and illite. The authors term this behavior ‘The potassium paradox’. From their review of the literature, the authors also report a lack of crop response to potassium chloride (KCl) fertilization. Close evaluation of these findings reveals that their observations can be interpreted and predicted using current knowledge of K in soil chemistry and its uptake by plants, and there is no paradox in K behavior in the soil–plant system. There is also no evidence of a detrimental effect of KCl on crop yield or quality. Their conclusion that the widely used Exch-K soil test is inadequate for managing K fertilization is discussed and some possible modifications to improve its performance are included. We believe that measurement of Exch-K is an essential and valuable tool and its use should be continued, along with improvements in recommending K fertilizer application.

Le but de ce travail est une contribution à l’étude de l’efficacité d’utilisation dutraitement de phosphatation au zinc pour la lutte contre la corrosion des armatures dansle béton. Pour réaliser cette conversion chimique superficielle, des échantillons en acierrond à béton ont subi une phosphatation cristalline dans un bain de phosphate de zincmodifié par des ions Ni2+. Par suite, nous avons évalué leur comportement à lacorrosion dans une solution simulée du béton au moyen de différentes techniquesélectrochimiques. Les résultats obtenus montrent que le traitement de phosphatation permetd’améliorer d’une manière significative la résistance à la corrosion de l’acier. En effet,les échantillons phosphatés, par rapport à ceux non phosphatés, présentent des valeurs depotentiel de corrosion et de piqûration plus nobles ainsi que des densités de courant decorrosion plus faibles. Les mesures d’impédances confirment cette tendance, les spectresobtenus montrent une nette augmentation de la résistance de transfert de chargesconjointement à une diminution de la capacité de la double couche électrochimique deséchantillons traités. Cette action protectrice est due au fait que la couche de phosphateobtenue joue le rôle de barrière physique face à la diffusion des ions chlorures d’unepart, sa dissolution en surface dans la solution simulée fortement alcaline libère lesions PO43- rentrant dans la réaction de formation d’un film depassivation jouant le rôle de barrière chimique face à l’amorçage de la corrosion parpiqûres, d’autre part.

GABA-induced whole-cell currents were measured in rod bipolar cells dissociated from the adult rat retina. The patch-clamp electrode contained nystatin, which made the cell membrane electrically permeable without rupture, thus retarding the rate of diffusion of Cl– ions from the patch pipette to the cell interior. The reversal potential of the GABA-induced currents was around –70 mV at an extracellular Cl-–concentration of 149 mM. We conclude that GABA generates hyperpolarizing responses in rod bipolar cells of the rat retina.