Identification and Simultaneous Optimisation of Tunisian Clay Properties: Preliminary Study for the Ceramic Products

The relationship between composition and physical parameters such as specific surface area, cationic exchange capacity and plasticity is studied with the aim of developing regression models that would permit the prediction of clay properties. These models could be useful for mineralogists and industrial applications. Nineteen representative clay samples were collected from Jebel Ressas in north-eastern Tunisia. Mineralogical data show that clay samples cover a very large variety of minerals. The main clay mineral is illite (50–60 wt%), secondary minerals including quartz, calcite and minor amounts of Na-feldspar. This study reveals that the average amount of silica (SiO₂) and alumina (Al₂O₃) are 51.9 and 19.6 wt%, respectively. The contents of lime (CaO) and iron (Fe₂O₃) vary between 4 and 8 wt% whereas the amount of alkalis (Na₂O + K₂O) is on average 4.1 wt%. The grain size data indicates a significant amount of silt fraction, and the fraction <2 µm varies between 23 and 35 wt%. Values for plasticity index range from 16 to 28 wt%. The cation exchange capacity and the specific surface values are 34.1–45.7 meq/100 g of air-dried clay and 302–374 m²/g, respectively. Lastly, regression models are used to correlate the properties with the mineralogical and chemical compositions. The significance and the validity of models were confirmed by statistical analysis and verification experiments. The regression models can be used to select the clay properties (plasticity index, cation exchange capacity and specific surface) in relation with clay minerals proportions and the finer fraction amounts.     

Rare metal mineralization of calcite carbonatites from the Cape Verde Archipelago

Rare metal mineralization of oceanic carbonatites was studied for the first time by the example of calcite carbonatite from Fogo Island in the Cape Verde Archipelago. The following evolutionary sequence of rare metal minerals was established: zirconolite-Th-calciobetafite-betafite + Th-pyrochlore-thorite + Ti-Zr-Nb silicates + zircon.Schematic reactions were proposed for zirconolite transformation to secondary phases: (Ca,Th,U)Zr(Ti,Nb)₂O₇ (zirconolite) + SiO₂ + Ca(F,OH)₂ → ZrSiO₄ (zircon) + (Ca,Th,U)₂(Ti,Nb)₂O₆(OH,F) (Th-calciobetafite) and (Ca,Th,U)₂(Ti,Nb)₂O₆(OH,F) + Na₂Si₂O₅ → ThSiO₄ (thorite) + (Ca,Na,Th)₂(Nb,Ti)₂O₆(OH,F) (Th-pyrochlore), where SiO₂, Ca(F,OH)₂, and Na₂Si₂O₅ are the components of melt-solution coexisting with the carbonatite.It was shown that the distribution and behavior of rare and radioactive elements in oceanic carbonatites show the same tendencies as in continental carbonatites. The contents and distribution of Ti, Ta, and Th in zirconolites and pyrochlores from oceanic and continental carbonatites are different: the minerals of oceanic carbonatites are enriched in Ti and Th and strongly depleted in Ta.     

A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO₂, 8 wt.% Cr₂O₃ and 4 wt.% ZrO₂, representing a solid solution of andradite (Ca₃Fe³⁺ ₂Si₃O₁₂ ≈46 mol%), uvarovite (Ca₃Cr₂Si₃O₁₂ ≈23 mol%), grossular (Ca₃Al₂Si₃O₁₂ ≈10 mol%), schorlomite (Ca₃Ti₂[Si,(Fe³⁺,Al³⁺)₂]O₁₂ ≈15 mol%), and kimzeyite (Ca₃Zr₂[Si,Al₂]₃O₁₂ ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al³⁺, Fe³⁺ and Ti⁴⁺. Cr³⁺ and Zr⁴⁺ are found at the octahedral site along with Fe³⁺, Al³⁺ and Ti⁴⁺. The measured H₂O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca_2.99Mg_0.03)_Σ=3.02(Fe³⁺ _0.67Cr_0.54Al_0.33Ti_0.29Zr_0.15)_Σ=1.98(Si_2.42Ti_0.24Fe_0.18Al_0.14)_Σ=2.98O₁₂OH_0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.     

Crystal structure of K-substituted gonnardite: separation of local water–cation assemblages

K-substituted gonnardite, K_2.18Na_0.04Ca_0.02[Al_2.26Si_2.74O₁₀]·2.2H₂O, was studied by X-ray powder diffraction method. The structure was refined with the Rietveld technique in the tetragonal space group $I\overline{4} 2d$ with a = 13.65409(16), c = 6.56928(11) Å, V = 1224.74(2) ų, Z = 4. Most of K⁺ cations (1.94 apfu) statistically occupy three nearest positions to be considered as the split one. “Excess” cations are located in the position non-typical for K⁺. Statistics in the cation distribution is defined by the occupation of the additional position. Based on a crystal chemical positional model (C₂R₂A₂) [T₅O₁₀], the separation of the local water–cation assemblages from an average statistical pattern has been suggested.     

Cancrinite and cancrisilite in the Khibina-Lovozero alkaline complex: Thermochemical and thermal data

The paper presents the results of a thermochemical and thermal study of cancrinite, (Na_6.93Ca_0.545K_0.01)_Σ7.485[(Si_6.47Al_5.48Fe_0.05)_Σ12O₂₄](CO₃)_1.25 · 2.30 H₂O, and cancrisilite, (Na_7.17 Ca_0.01)_Σ7.18[(Si_7.26Al_4.70Fe_0.04)_Σ12O₂₄][(CO₃)_1.05(OH)_0.21(PO₄)_0.04(SO₄)_0.01] · 2.635 H₂O, from the Khibina-Lovozero Complex, Kola Peninsula, Russia. Stages of the thermal decomposition of these minerals were studied using IR spectroscopy. The enthalpies of formation of the minerals from elements were determined by melt drop solution calorimetry: Δ _f H _el ⁰ (298.15 K) = ?14 490 ± 16 kJ/mol for cancrinite and ?14302 ± 17 kJ/mol for cancrisilite. The values of Δ _f H _el ⁰ (298.15 K), S ^o(298.15 K), and Δ _f H _el ⁰ (298.15 K) are determined for cancrinite and cancrisilite of theoretical composition.     

Geochemical alterations in surface waters of Govind Ballabh Pant Sagar,Northern Coalfield,India

Major ions showed high concentrations, ionic strength and chemical activity in the surface waters of Govind Ballabh Pant Sagar reservoir. Various geochemical ratios showed the dominance of silicate over carbonate weathering and major ions such as Na⁺ + K⁺ account for about 52 % of the cation budget. The high Na⁺ and K⁺ showed sedimentation of rock/coal particles consisting of highly weathered silicate minerals contributed by the discharge of mine water, fly ash mixing during transportation, etc. Further, Ca²⁺ + Mg²⁺/Na⁺ + K⁺ ratio was <1 (0.92) indicating the occurrence of silicate weathering in the reservoir catchment. The comparative assessment showed that the proportion of Ca²⁺ + Mg²⁺/Na⁺ + K⁺ tends to be lower along the coal mining belts compared to non-coal mining regions in the world. The Ca²⁺/SO₄ ^2? ratio <1 revealed not only H₂CO₃ but H₂SO₄ also acting as a source of protons for rock weathering. The cause underlying these differences can be related directly to geological substrate and anthropogenic activities.     

Comparative compressibilities of majorite-type garnets

Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg_2.84Fe_0.10Ca_0,06) Al₂Si₃O₁₂], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg₃(MgSi)Si₃O₁₂], calcium-bearing majorite [(Ca_0.49Mg_2.51)(MgSi)Si₃0₁₂], sodium majorite [(Na_1.88Mgp_0.12)(Mg_0.06Si_1.94)Si₃O₁₂], and an intermediate composition [(Na_0.37Mg_2.48)(Mg_0.13Al_1.07 Si₀₈₀) Si₃O₁₂]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.     

Kyanoxalite,a new cancrinite-group mineral species with extraframework oxalate anion from the Lovozero alkaline pluton,Kola Peninsula

Kyanoxalite, a new member of the cancrinite group, has been identified in hydrothermally altered hyperalkaline rocks and pegmatites of the Lovozero alkaline pluton, Kola Peninsula, Russia. It was found at Mount Karnasurt (holotype) in association with nepheline, aegirine, sodalite, nosean, albite, lomonosovite, murmanite, fluorapatite, loparite, and natrolite and at Mt. Alluaiv. Kyanoxalite is transparent, ranging in color from bright light blue, greenish light blue and grayish light blue to colorless. The new mineral is brittle, with a perfect cleavage parallel to (100). Mohs hardness is 5–5.5. The measured and calculated densitiesare 2.30(1) and 2.327 g/cm³, respectively. Kyanoxalite is uniaxial, negative, ω = 1.794(1), ɛ = 1.491(1). It is pleochroic from colorless along E to light blue along O. The IR spectrum indicates the presence of oxalate anions C₂O₄²⁻ and water molecules in the absence of CO₃²⁻ Oxalate ions are confirmed by anion chromatography. The chemical composition (electron microprobe; water was determined by a modified Penfield method and carbon was determined by selective sorption from annealing products) is as follows, wt %: 19.70 Na₂O, 1.92 K₂O, 0.17 CaO, 27.41 Al₂O₃, 38.68 SiO₂, 0.64 P₂O₅, 1.05 SO₃, 3.23 C₂O₃, 8.42 H₂O; the total is 101.18. The empirical formula (Z = 1) is (Na_6.45K_0.41Ca_0.03)_Σ6.89(Si_6.53Al_5.46O₂₄)[(C₂O₄)_0.455(SO₄)_0.13(PO₄)_0.09(OH)_0.01]_Σ0.68 · 4.74H₂O. The idealized formula is Na₇(Al₅₋₆Si₆₋₇O₂₄)(C₂O₄)_0.5−1 · 5H₂O. Kyanoxalite is hexagonal, the space group is P6₃, a = 12.744(8), c = 5.213(6) -ray powder diffraction pattern are as follows, [d, [A] (I, %)(hkl)]: 6.39(44) (110), 4.73 (92) (101), 3.679 (72) (300), 3.264 (100) (211, 121), 2.760 (29) (400), 2.618 (36) (002), 2.216, (29) (302, 330). According to the X-ray single crystal study (R = 0.033), two independent C₂O₄ groups statistically occupy the sites on the axis 6₃. The new mineral is the first natural silicate with an additional organic anion and is the most hydrated member of the cancrinite group. Its name reflects the color (κɛανgoΣς is light blue in Greek) and the species-forming role of oxalate anions. The holotype is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration no. 3735/1.     

Mayenite-supergroup minerals from burned dump of the Chelyabinsk Coal Basin

Three minerals of the mayenite supergroup have been found in fluorellestadite-bearing metacarbonate rock (former fragment of petrified wood of ankeritic composition) from the dump at the Baturinskaya-Vostochnaya-1-2 mine. These are eltyubyuite Ca₁₂Fe1°Si₄O3₂Cl6, its fluorine analog Ca₁₂Fe₁₀³⁺Si₄O₃₀F₁₀, and chlormayenite-wadalite Ca₁₂(Al,Fe)₁₄O₃₂Cl₂-Ca₁₂(Al,Fe)₁₀Si₄O₃₂Cl₂. The first two phases occur in the reaction mantle around hematite, magnesioferrite, and Ca-ferrite aggregates (“calciohexaferrite” CaFe₁₂O₁₉, “grandiferrite” CaFe₄O₇, and “dorrite phase” Ca₂(Fe₅^3 +Mn0^0.5Mg_0.5)(Si_0.5Fe_5.5³⁺)O₂₀) and, rarely, as individuals in grained aggregates of fluorellestadite-cuspidine (± lar- nite ± rusinovite Ca₁₀(Si₂O₇)₃Cl₂). Assemblages of zoned chlormayenite-wadalite crystals are found in grained aggregates of fluorellestadite- cuspidine, which lack Ca-ferrite. Also, harmunite CaFe₂O₄, chlorellestadite, fluorapatite, anhydrite, rondorfite CasMg(SiO₄)₄Cl₂, fluorine analog of rondorfite CasMg(SiO₄)₄F₂, “Mg-cuspidine” Ca_3.5(Mg,Fe)_0.5(Si₂O₇)F₂, fluorite, barioferrite BaFe₁₂O₁9, zhangpeishanite BaFCl, and other rare phases are identified in this rock. Data on the chemical composition and Raman spectroscopy of the mayenite-supergroup minerals are given. The genesis of metacarbonate rock is considered in detail: “oxidizing calcination” of Ca-Fe-carbonates with the formation of hematite and lime; reaction between hematite and lime with the formation of different Ca-ferrites; formation of larnite as a result of reaction between SiO₂ and lime or CaCO₃; and reactionary impact of hot Cl-F-S-bearing gases on early assemblages. Eltyubyuite and its fluorine analog crystallized at the stages of gas impact. It is presumed that the maximum temperature during the formation of rock reached 1200–1230 °C. © 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.     

Comprehensive physicochemical study of dioctahedral palygorskite-rich clay from Marrakech High Atlas (Morocco)

This study is devoted to the physicochemical and mineralogical characterizations of palygorskite from Marrakech High Atlas, Morocco. The raw clay and its Na⁺-saturated <2 μm fraction were characterized using chemical, structural, and thermal analytical techniques. Measurements of specific surface area and porous volume are reported. The clay fraction was found to be made up of 95 % of palygorskite and 5 % of sepiolite. An original feature of this palygorskite is its deficiency in zeolitic H₂O. The half-cell structural formula of its dehydrated form was determined on the basis of 21 oxygens to be (Si_7.92Al_0.08)(Mg_2.15Al_1.4Fe_0.4Ti_0.05 $ \square_{1} $ )(Ca_0.03Na_0.08K_0.04)O₂₁, while the hydrated form could be formulated as (Si_7.97Al_0.03)(Mg_2.17Al_1.46Fe_0.40Ti_0.05)(Ca_0.03Na_0.07K_0,03)O_20.18(OH)_1.94(OH₂)_3.88·2.43 H₂O. These formulas show that the (Al³⁺+Fe³⁺)/Mg²⁺ ratio is around 0.84, revealing a pronounced dioctahedral character. Further, inside its octahedral sheet, it was determined that the inner M₁ sites are occupied by vacancies, whereas the M₂ sites are shared between 90 % of trivalent cations (78 % for Al³⁺ and 22 % for Fe³⁺), 7.5 % of Mg²⁺, and 2.5 % of Ti⁴⁺, all of them linked to 1.94 of structural hydroxyls. The two remaining Mg²⁺ by half-cell occupy edge M₃ sites and are coordinated to 3.88 molecules of OH₂. Channels of this palygorskite are deficient in zeolitic H₂O since they contain only 2.43 H₂O molecules. A correlation was found between these results and the observation of very intense and well-resolved FTIR bands arising from dioctahedral domains (mainly Al₂OH, Fe₂OH, and AlFeOH) along with very small responses from a trioctahedral domain (Mg₃OH). Accordingly, a schematic representation of the composition of the octahedral sheet was proposed. The cation exchange capacity, specific surface area, and total pore volume were also assessed to be ca. 21.2 meq/100 g, 116 m²/g, and 0.458 cm³/g, respectively.     

Impact of anthropogenic activities on the chemistry and quality of groundwater: a case study from a terrain near Zarand City, Kerman Province, SE Iran

Groundwater of an aquifer located in the vicinity of a large coal washery near Zarand City, Iran consists of two hydrochemically differing facies, which have been informally designated as groundwater (A) and groundwater (B). Groundwater (A) is native, brackish in composition and is characterized by Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and SO₄ ^2? > HCO₃ ^? > Cl^? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, and values of chloro-alkaline indices, C ratio and Na⁺/Cl^? molar ratio indicate that in the groundwater (A), the ionic load of Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ^2? and HCO₃ ^? is derived essentially from weathering of both carbonates and aluminosilicates and direct cation and reverse cation–anion exchange reactions. Groundwater (B) is the polluted variant of the groundwater (A), brackish to saline in composition, and unlike the groundwater (A), consists of HCO₃ ^? as the dominant anion. In comparison with the groundwater (A), the groundwater (B) contains higher concentrations of all ions, and its average ionic load (av. = 59.74 me/L) is 1.43 times higher than that of the groundwater (A) (av. = 41.54 me/L). Additional concentrations of Ca²⁺, Mg²⁺, K⁺, SO₄ ^2?, Cl^? and HCO₃ ^? in the groundwater (B) are provided mainly by downward infiltrating water from the coal washery tailings pond and reverse cation–anion exchange reaction between tailings pond water and exchanger of the aquifer matrix during non-conservative mixing process of groundwater (A) and tailings pond water. Certain additional concentrations of Na⁺, K⁺ and NO₃ ^? in the groundwater (B) are provided by other anthropogenic sources. Quality wise, both groundwaters are marginally suitable for cultivation of salt-tolerant crops only.     

Compositional limits and analogs of monoclinic triple-chain silicates

Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg₁₀Si₁₂O₃₂(OH)₄), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na₄Mg₈Si₁₂O₃₂(OH)₄. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO₂, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F⁻ for OH⁻, Mn²⁺, Ca²⁺, or Fe²⁺ for Mg²⁺, and 2Li⁺ for Mg²⁺ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na₄Mg₈Si₁₂O₃₂(OH)₄, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na₄Mg₈Si₁₂O₃₂F₄ at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na⁺ for Na⁺ + H⁺ and of Mg²⁺ + vacancy for 2Na⁺. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na_2.5Mg₈Si₁₂O_30.5(OH)_5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na_1.1Mg_9.4Si₁₂O_31.9(OH)_4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na₄Mg₈Si₁₂O₃₂(OH)₄–Ca₂Mg₈Si₁₂O₃₂(OH)₄ where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na_0.7Ca_1.8Mg_7.8Si₁₂O_31.9(OH)_4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.     

Hydro-chemical analysis and ionic flux of meltwater runoff from Khangri Glacier,West Kameng,Arunachal Himalaya,India

The detailed hydro-chemical study of meltwater draining from Khangri glacier Arunachal Pradesh has been carried out to evaluate the major ion chemistry and weathering processes in the drainage basin. The investigative results shows that the meltwater is almost neutral to slightly acidic in nature with Mg–HCO₃-dominated hydro-chemical facies. In glacial meltwater, Ca^+?2 is the most dominated cation followed by Mg⁺², Na⁺, and K⁺, while HCO₃^? is the most dominant anion followed by SO₄^2?, NO₃^?, and Cl^?. The dominant cations such as Ca⁺² and Mg⁺² show a good relation with the minerals abundance of the rocks. Calcite (CaCO₃) and biotite [K(Mg,Fe)₃AlSi₃O₁₀(F,OH)₂] are the most abundant minerals in the deformed carbonate-rich metasedimentary rocks near to the snout with some K feldspar (KAlSi₃O₈) and quartz (SiO₂). This suggests Ca⁺² have definitely entered into the water due to the dissolution of calcite and Ca feldspar (CaAl₂Si₂O₈), while one of the source of Mg⁺² is biotite. Na feldspar (NaAlSi₃O₈) has contributed towards the availability of sodium ion, while potassium ion is derived from the chemical weathering of K feldspar and biotite. The chemical weathering is the foremost mechanism controlling the hydro-chemistry of the Khangri glacier because of the least anthropogenic interferences. The mineralogy of surrounding rocks is studied to understand better, the rock–water interaction processes, and their contribution towards ionic concentration of meltwater. The meltwater discharge and individual ion flux of the catchment area have also been calculated, to determine the ionic denudation rate for the ablation season. The high elemental ratio of (Ca?+?Mg)/(Na?+?K) (7.91?±?0.39 mg/l) and low elemental ratio of (Na?+?K)/total cations (0.11?±?0.004) indicate that the chemical composition of meltwater is mainly controlled by carbonate weathering and moderately by silicate weathering. The scatter plot result between (Ca?+?Mg) and total cations confirms that carbonate weathering is a major source of dissolved ions in Khangri glacier meltwater. In addition, the statistical analysis was also used to determine the correlation between physical parameters of glacier meltwater which controlled the solute dynamics.     

Mechanism and numerical simulation of multicomponent solute transport in sodic soils reclaimed by calcium sulfate

The mechanism for reclaiming sodic soils using calcium sulfate (CaSO₄) could provide a theoretical basis for the field application of CaSO₄ substitutes, including the by-products of flue gas desulfurization (BFGD), fly ash, and phosphorus gypsum. In this study, Ca²⁺ application experiment was conducted to analyze the dynamic changes of the cations in the reclamation of sodic soils with CaSO₄. A multicomponent solute transport model (UNSATCHEM) that considers ion adsorption exchange and dynamic changes in the soil’s hydraulic conductivity was subsequently used to simulate and predict the movement of ions. The Ca²⁺ application experiment consisted of four treatments with four CaSO₄ concentrations (0.5, 1, 1.5, and 2 g L^?1). When the Ca²⁺ concentrations in the supplied water were 14.71, 22.06, and 29.41 mmol L^?1, Ca²⁺ achieved penetration, and this process was faster when the Ca²⁺ concentration in the supplied water was higher. Ca²⁺ did not achieve penetration when the Ca²⁺ concentration was 7.35 mmol L^?1. UNSATCHEM was able to simulate the transportation mechanism of Ca²⁺ and Na⁺ in the soil solution in the Ca²⁺ application experiment, the adsorption and exchange between the Na⁺ in the soil colloid and Ca²⁺ in the soil solution, and the precipitation and dissolution of CaSO₄ with a high degree of accuracy. Sodic soil reclamation with CaSO₄ was not a short-term process. Compared with applying CaSO₄ only once, applying CaSO₄ in batches decreased the accumulation of soil salts and promoted its dissolution.     

Crystal chemistry, surface morphology and X-ray photoelectron spectroscopy of Fe-rich osumilite from Mt. Arci, Sardinia (Italy)

Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K_0.729)_C (Na_0.029)_B (Si_10.498 Al_1.502)_T1 (Al_2.706 Fe _0.294 ²⁺ )_T2 (Mg_0.735 Mn_0.091 Fe _1.184 ²⁺ )_AO₃₀. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe²⁺ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si_2p, Al_2p, Mg_1s and Fe_2p core levels, suggests that Fe presents Fe²⁺ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si⁴⁺ and Si¹⁺ components, respectively, both in tetrahedral coordination. The binding energy of Al_2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L_2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site.     

X-ray single-crystal and Raman study of (Na<Subscript>0.86</Subscript>Mg<Subscript>0.14</Subscript>)(Mg<Subscript>0.57</Subscript>Ti<Subscript>0.43</Subscript>)Si<Subscript>2</Subscript>O<Subscript>6</Subscript>, a new pyroxene synthesized at 7 GPa and 1700 °C

A new pyroxene with formula (Na_0.86Mg_0.14)(Mg_0.57Ti_0.43)Si₂O₆, synthesized in a high-pressure toroidal ‘anvil-with-hole’ apparatus at P = 7 GPa and T = 1700 °C, was characterized by X-ray single-crystal diffraction and Raman spectroscopy. The compound was found to be monoclinic (R1 = 2.56 %), space group C2/c, with lattice parameters a = 9.687(2), b = 8.814(1), c = 5.290(1) Å, β = 107.853(2)°, V = 430.08(1) ų. The coexistence of Mg and Ti⁴⁺ at the M1 site does not induce strong modifications either to the M1 site or to the adjacent M2 site. The Raman spectrum of synthetic Na–Ti-pyroxene was obtained for the first time and compared with that of Mg₂Si₂O₆ (with very low concentrations of Na and Ti). The structural characterization of the Na–Ti–Mg-pyroxene is important, because the study of its thermodynamic constants provides new constraints on thermobarometry of the upper mantle assemblages.     

Hydrogeochemistry and quality of groundwater of coastal unconfined aquifer in Amol–Ghaemshahr plain,Mazandaran Province,Northern Iran

Groundwater of the unconfined aquifer (1,100 sq. km) of a two-tier coastal aquifer located in the Amol–Ghaemshahr plain, Mazandaran Province, Northern Iran, is classified into fresh and brackish water types. Fresh groundwater (FGW) samples (n = 36) are characterized by Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ and HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, values of the C-ratio (av. = 0.89) and CAI and values of the molar ratios of Ca²⁺/HCO₃ ^?, Ca²⁺/SO₄ ^2?, Mg²⁺/HCO₃ ^? and Mg²⁺/SO₄ ^2? indicate that the ionic load in the FGW is derived essentially from carbonic acid-aided weathering of carbonates and aluminosilicates, saline/sea water trapped in the aquifer sediments (now admixed with the groundwater) and ion exchange reactions. Values of the CAI and Na⁺/Cl^? molar ratio suggest that the part of the Ca²⁺ (±Mg²⁺) content in 23 FGW samples is derived from clay minerals of the aquifer matrix, and part of the Na⁺ content in 20, 12, and 3 FGW samples is derived, respectively, from alkali feldspar weathering, clay minerals of the aquifer matrix and rain water and/or halite. Brackish groundwater (BGW) samples (n = 4) contain Cl^? as the dominant anion and their average total ionic concentration (38.65 meq/L) is 1.79 times higher than that of the FGW samples (21.50 meq/L). BGW pockets were generated by non-conservative mixing of FGW with the upconed saline water from the underlying saline groundwater zone of the semi-confined aquifer along bore wells involved in excessive extraction of groundwater from the unconfined aquifer. Groundwater belongs essentially to “high salinity, low sodium” irrigation water class.     

The Al (Nb,Ta) Ti(in−2) substitution in titanite: the emergence of a new species?

Summary The highest (Nb, Ta) content ever encountered in titanite is reported from the Maríkov 11 pegmatite in northern Moravia, Czech Republic. This dike is a member of a pegmatite swarm of the beryl-columbite subtype, metamorphosed under conditions of the amphibolite facies. The pegmatite carries, i.a., rare tantalian rutile intergrown with titanian ixiolite, titanian columbite-tantalite, fersmite and microlite. Fissures generated in the Nb, Ta oxide minerals during deformation are filled with titanite, formed by reaction of the oxide minerals with metamorphic pore fluids. The titanite displays limited degrees of substitutions Na(Ta > Nb)(CaTi)_–1, (Ta > Nb)₄Ti_–4Si_–1 and AI(OH, F)(TiO)_–1, but an extensive (and occasionally the sole significant) substitution (Al > Fe³⁺)(Ta > Nb)Ti_–2, responsible for widespread oscillatory zoning. This substitution reduces the proportion of the titanite componentsensu stricto, CaTiSiO₄,O, to less than 50 mole % in many analyzed spots. The extreme composition corresponds to (Ca_0.994Na_0.011)(Ti_0.436Sn_0.007Al_0.280Fe³⁺ _0.006Ta_0.199Nb_0.079)Si_0.988O₄(O_0.974F_0.026). However, so far this substitution fails to generate compositions that would define a new species.

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Zusammenfassung Die AI(Nb, Ta)Ti_–2 Substitution im Titanit: Auftauchen einer neuen Mineralspecies? Die höchsten (Nb, Ta) Gehalte, die jemals für Titanit gefunden wurden, werden für den Maríkov II Pegmatit in Nordmähren, Tschechei, berichtet. Der Intrusivgang ist Teil eines Amphibolit-faziell überprägten Pegmatitschwarms vom Beryll-Columbit Subtypus Der Pegmatit führt u.a. seltene tantalbetonte Rutile verwachsen mit titanbetontem Ixiolith, titanbetontem Columbit-Tantalit, Fersmit and Mikrolith. Deformationsbedingte Frakturen in den (Nb, Ta) Oxiden sind mit Titanit, als Folge der Reaktion der metamorphen Porenlösungen mit den Oxidmineralen, verkittet. Titanit zeigt begrenzte Substitutionen Na(Ta > Nb)(CaTi)_–1,(Ta > Nb)₄Ti_–4Si_–1 and Al(OH, F)(TiO)_–1, aber extensive (und gelegentlich einzig bedeutsame) Substitution (Al >> Fe³⁺)(Ta > Nb)Ti_–2, die eine weitverbreitete, oszillierende Zonierung hervorruft. Diese Substitution verringert den Anteil der Titanit-Komponentesensu stricto, CaTiSiO,O, auf weniger als 50 Mol% in vielen Analysen. Die Extremzusammensetzung entspricht Ca_0.994Na_0.11) (T_10.436Sn_0.007Al_0.280Fe³⁺ _0.006Ta_0.199Nb_0.079)Si_0.988O₄(O_0.974F_0.026). Das AusmaB dieser Substitution ist unzureichend, um eine neue Mineralspecies zu definieren.

     

The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.