Using Mg Isotopes to Trace Cyanobacterially Mediated Magnesium Carbonate Precipitation in Alkaline Lakes

This study assesses the potential use of Mg isotopes to trace Mg carbonate precipitation in natural waters. Salda Lake (SW Turkey) was chosen for this study because it is one of the few modern environments where hydrous Mg carbonates are the dominant precipitating minerals. Stromatolites, consisting mainly of hydromagnesite, are abundant in this lake. The Mg isotope composition of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments were measured. Because Salda Lake is located in a closed basin, mass balance requires that the Mg isotopic offset between Lake Salda water and precipitated hydromagnesite be comparable to the corresponding offset between Salda Lake and its water inputs. This is consistent with observations; a ??²⁶Mg offset of 0.8?C1.4??? is observed between Salda Lake water and it is the incoming streams and groundwaters, and precipitated hydromagnesite has a ??²⁶Mg 0.9?C1.1??? more negative than its corresponding fluid phase. This isotopic offset also matches closely that measured in the laboratory during both biotic and abiotic hydrous Mg carbonate precipitation by cyanobacteria (Mavromatis, V., Pearce, C., Shirokova, L. S., Bundeleva, I. A., Pokrovsky, O. S., Benezeth, P. and Oelkers, E.H.: Magnesium isotope fractionation during inorganic and cyanobacteria-induced hydrous magnesium carbonate precipitation, Geochim. Cosmochim. Acta, 2012a. 76, 161?C174). Batch reactor experiments performed in the presence of Salda Lake cyanobacteria and stromatolites resulted in the precipitation of dypingite (Mg₅(CO₃)₄(OH)₂·5(H₂O)) and hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O) with morphological features similar to those of natural samples. Concurrent abiotic control experiments did not exhibit carbonate precipitation demonstrating the critical role of cyanobacteria in the precipitation process.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

A study on the effects of drying conditions on the stability of NaNd(CO3)2·6H2O and NaEu(CO3)2·6H2O

The effect of different drying conditions on the stability of NaNd(CO₃)·6H₂O and NaEu(CO₃)·6H₂O and the identity of the decomposition product have been investigated. The rate of decomposition and the nature of the altered phases are dependant on the drying conditions used. When the phases are oven dried at 120 °C, the decomposition is immediate and the phase completely alters to Nd₂(CO₃)₃ or Eu₂(CO₃)₃ respectively. Under less severe drying conditions, the Na rare earth carbonate phases alter to Nd₂(CO₃)₃·8H₂O and Eu₂(CO₃)₃·8H₂O over a period of 24–48 h, but they can be kept indefinitely in a water saturated environment. The implications for using Nd and Eu as actinide analogues are discussed.     

Geochemical models of the impact of acidic groundwater and evaporative sulfate salts on Boulder Creek at Iron Mountain,California

During dry season baseflow conditions approximately 20% of the flow in Boulder Creek is comprised of acidic metals-bearing groundwater. Significant amounts of efflorescent salts accumulate around intermittent seeps and surface streams as a result of evaporation of acid rock drainage. Those salts include the Fe-sulfates — rhomboclase ((H₃O)Fe³⁺(SO₄)₂·3H₂O), ferricopiapite (Fe³⁺₅(SO₄)₆O(OH)·20H₂O), and bilinite (Fe²⁺Fe₂³⁺(SO₄)₄·22H₂O); Al-sulfates — alunogen (Al₂(SO₄)₃·17H₂O) and kalinite (KAl(SO₄)₂·11H₂O); and Ca- and Mg-sulfates — gypsum (CaSO₄·2H₂O), and hexahydrite (MgSO₄·6H₂O). The dissolution of evaporative sulfate salt accumulations during the first major storm of the wet season at Iron Mountain produces a characteristic hydrogeochemical response (so-called “rinse-out”) in surface waters that is subdued in later storms. Geochemical modeling shows that the solutes from relatively minor amounts of dissolved sulfate salts will maintain the pH of surface streams near 3.0 during a rainstorm. On a weight basis, Fe-sulfate salts are capable of producing more acidity than Al- or Mg-sulfate salts. The primary mechanism for the production of acidity from salts involves the hydrolysis of the dissolved dissolved metals, especially Fe³⁺. In addition to the lowering of pH values and providing dissolved Fe and Al to surface streams, the soluble salts appear to be a significant source of dissolved Cu, Zn, and other metals during the first significant storm of the season.     

Experimental determination of the solubility constant for magnesium chloride hydroxide hydrate (Mg3Cl(OH)5·4H2O, phase 5) at room temperature, and its importance to nuclear waste isolation in geological repositories in salt formations

In this study, the solubility constant of magnesium chloride hydroxide hydrate, Mg₃Cl(OH)₅·4H₂O, termed as phase 5, is determined from a series of solubility experiments in MgCl₂-NaCl solutions. The solubility constant in logarithmic units at 25 °C for the following reaction,

Mg₃Cl(OH)₅·4H₂O+5H⁺=3Mg²⁺+9H₂O(l)+Cl^-     

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano,Northern Tanzania

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na₂(CO₃), nyerereite Na₂Ca(CO₃)₂, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na₂(CO₃) · H₂O, trona Na₃(CO₃)(HCO₃) · 2H₂O, nahcolite Na(HCO₃), pirssonite Na₂Ca(CO₃)₂ · 2H₂O, calcite Ca(CO₃), and shortite Na₂Ca₂(CO₃)₃. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H₂O and CO₂ fugacity, and the ratio of Ca and Na activity in the Na₂O–CaO–CO₂–H₂O system.     

Crystal structure and refined formula of garyansellite Mg<Subscript>2</Subscript>Fe<Superscript>3+</Superscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH) · 2H<Subscript>2</Subscript>O

Single-crystal study of the structure (R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) ų, Z = 4. An idealized formula of garyansellite is Mg₂Fe³⁺(PO₄)₂(OH) · 2H₂O. Structurally the mineral is close to other members of the phosphoferrite–reddingite group. The structure contains layers of chains of M(2)O₄(OH)(H₂O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O₄(H₂O)₂ octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO₄ tetrahedra.     

Experimental investigations of the reaction path in the MgO–CO2–H2O system in solutions with various ionic strengths,and their applications to nuclear waste isolation

The reaction path in the MgO–CO₂–H₂O system at ambient temperatures and atmospheric CO₂ partial pressure(s), especially in high-ionic-strength brines, is of both geological interest and practical significance. Its practical importance lies mainly in the field of nuclear waste isolation. In the USA, industrial-grade MgO, consisting mainly of the mineral periclase, is the only engineered barrier certified by the Environmental Protection Agency (EPA) for emplacement in the Waste Isolation Pilot Plant (WIPP) for defense-related transuranic waste. The German Asse repository will employ a Mg(OH)₂-based engineered barrier consisting mainly of the mineral brucite. Therefore, the reaction of periclase or brucite with carbonated brines with high-ionic-strength is an important process likely to occur in nuclear waste repositories in salt formations where bulk MgO or Mg(OH)₂ will be employed as an engineered barrier. The reaction path in the system MgO–CO₂–H₂O in solutions with a wide range of ionic strengths was investigated experimentally in this study. The experimental results at ambient laboratory temperature and ambient laboratory atmospheric CO₂ partial pressure demonstrate that hydromagnesite (5424) (Mg₅(CO₃)₄(OH)₂ · 4H₂O) forms during the carbonation of brucite in a series of solutions with different ionic strengths. In Na–Mg–Cl-dominated brines such as Generic Weep Brine (GWB), a synthetic WIPP Salado Formation brine, Mg chloride hydroxide hydrate (Mg₃(OH)₅Cl · 4H₂O) also forms in addition to hydromagnesite (5424).     

A depositional model for hydromagnesite–magnesite playas near Atlin,British Columbia,Canada

This study formulates a comprehensive depositional model for hydromagnesite–magnesite playas. Mineralogical, isotopic and hydrogeochemical data are coupled with electron microscopy and field observations of the hydromagnesite–magnesite playas near Atlin, British Columbia, Canada. Four surface environments are recognized: wetlands, grasslands, localized mounds (metre‐scale) and amalgamated mounds composed primarily of hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O], which are interpreted to represent stages in playa genesis. Water chemistry, precipitation kinetics and depositional environment are primary controls on sediment mineralogy. At depth (average ≈ 2 m), Ca–Mg‐carbonate sediments overlay early Holocene glaciolacustrine sediments indicating deposition within a lake post‐deglaciation. This mineralogical change corresponds to a shift from siliciclastic to chemical carbonate deposition as the supply of fresh surface water (for example, glacier meltwater) ceased and was replaced by alkaline groundwater. Weathering of ultramafic bedrock in the region produces Mg–HCO₃ groundwater that concentrates by evaporation upon discharging into closed basins, occupied by the playas. An uppermost unit of Mg‐carbonate sediments (hydromagnesite mounds) overlies the Ca–Mg‐carbonate sediments. This second mineralogical shift corresponds to a change in the depositional environment from subaqueous to subaerial, occurring once sediments ‘emerged’ from the water surface. Capillary action and evaporation draw Mg–HCO₃ water up towards the ground surface, precipitating Mg‐carbonate minerals. Evaporation at the water table causes precipitation of lansfordite [MgCO₃·5H₂O] which partially cements pre‐existing sediments forming a hardpan. As carbonate deposition continues, the weight of the overlying sediments causes compaction and minor lateral movement of the mounds leading to amalgamation of localized mounds. Radiocarbon dating of buried vegetation at the Ca–Mg‐carbonate boundary indicates that there has been ca 8000 years of continuous Mg‐carbonate deposition at a rate of 0·4 mm yr^?1. The depositional model accounts for the many sedimentological, mineralogical and geochemical processes that occur in the four surface environments; elucidating past and present carbonate deposition.     

Spatial relationships of salt distribution and related physical changes of underlying rocks on naturally weathered sandstone exposures (Bohemian Switzerland National Park,Czech Republic)

Efflorescence, case hardening, and granular disintegration represent common weathering features of Upper Cretaceous quartz sandstones exposed in the Bohemian Switzerland National Park (NW Bohemia, Czech Republic). Salt species (sulphates: gypsum (CaSO₄·2H₂O), potassium alum (KAl(SO₄)₂·12H₂O), tschermigite (NH₄Al(SO₄)₂·12H₂O), alunite (K(Al₃(SO₄)₂(OH)₆), and alunogen (Al₂(SO₄)₃·17H₂O), minor nitrates: nitrammite (NH₄NO₃)) determined by X-ray diffraction exhibit vertical and geographic zoning. More soluble salts (chlorides, nitrates, tschermigite) crystallize preferentially on the cliffs exposed to the south, whereas the north face is characterized by the presence of less soluble phases: gypsum and K(Al₃(SO₄)₂(OH)₆. Vertical zoning of salt distribution on natural outcrops differs from the salt distribution in masonry. Salt distribution near the base of the cliff (profile to about 2–2.5 m above the ground) is affected by capillary rise from the ground level (first maximum of water-soluble salts at the level of 1–1.5 m above the ground) and by percolation of precipitation through the overhanging rock sequence (second maximum of 2–2.5 m above the ground). Percolation of salt solution from higher parts is affected by the asperity of the rock surface. The concentration of salts (determined by ion exchange chromatography) correlates to the changes of physical properties: bulk porosity, microporosity and water absorption. The porosity, microporosity, moisture content and absorption generally increase with the increasing volume of sulphates and nitrates.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

Uranium minerals from the San Marcos District, Chihuahua, Mexico

The mineralogy of the two uranium deposits (Victorino and San Marcos I) of Sierra San Marcos, located 30 km northwest of Chihuahua City, Mexico, was studied by optical microscopy, powder X-ray diffraction with Rietveld analysis, scanning electron microscopy with energy dispersive X-ray analysis, inductively coupled plasma spectrometry, and gamma spectrometry. At the San Marcos I deposit, uranophane Ca(UO₂)₂Si₂O₇·6(H₂O) (the dominant mineral at both deposits) and metatyuyamunite Ca(UO₂)(V₂O₈)·3(H₂O) were observed. Uranophane, uraninite (UO_2+x), masuyite Pb(UO₂)₃O₃(OH)·3(H₂O), and becquerelite Ca(UO₂)₆O₄(OH)₆ ·(8H₂O) are present at the Victorino deposit. Field observations, coupled with analytical data, suggest the following sequence of mineralization: (1) deposition of uraninite, (2) alteration of uraninite to masuyite, (3) deposition of uranophane, (4) micro-fracturing, (5) calcite deposition in the micro-fractures, and (6) formation of becquerelite. The investigated deposits were formed by high-to low-temperature hydrothermal activity during post-orogenic evolution of Sierra San Marcos. The secondary mineralization occurred through a combination of hydrothermal and supergene alteration events. Becquerelite was formed in situ by reaction of uraninite with geothermal carbonated solutions, which led to almost complete dissolution of the precursor uraninite. The Victorino deposit represents the second known occurrence of becquerelite in Mexico, the other being the uranium deposits at Peña Blanca in Chihuahua State.     

A Brine Evolution Model and Mineralogy of Chemical Sediments in a Volcanic Crater,Lake Kitagata,Uganda

Lake Kitagata, Uganda, is a hypersaline crater lake with Na–SO₄–Cl–HCO₃–CO₃ chemistry, high pH and relatively small amounts of SiO₂. EQL/EVP, a brine evaporation equilibrium model (Risacher and Clement 2001), was used to model the major ion chemistry of the evolving brine and the order and masses of chemically precipitated sediments. Chemical sediments in a 1.6-m-long sediment core from Lake Kitagata occur as primary chemical mud (calcite, magadiite [NaSi₇O₁₃(OH)₃·3H₂O], burkeite [Na₆(CO₃)(SO₄)₂]) and as diagenetic intrasediment growths (mirabilite (Na₂SO₄·10H₂O)). Predicted mineral assemblages formed by evaporative concentration were compared with those observed in salt crusts along the shoreline and in the core from the lake center. Most simulations match closely with observed natural assemblages. The dominant inflow water, groundwater, plays a significant role in driving the chemical evolution of Lake Kitagata water and mineral precipitation sequences. Simulated evaporation of Lake Kitagata waters cannot, however, explain the large masses of magadiite found in cores and the formation of burkeite earlier in the evaporation sequence than predicted. The masses and timing of formation of magadiite and burkeite may be explained by past groundwater inflow with higher alkalinity and SiO₂ concentrations than exist today.     

An assessment of Portland cement,cement kiln dust and Class C fly ash for the immobilization of Zn in contaminated soils

Zn-contaminated soils obtained from a steel company in the Republic of Korea were stabilized using Portland cement (PC), cement kiln dust (CKD) and Class C fly ash (FA). The effectiveness of the treatment was evaluated by the United States Environmental Protection Agency toxicity characteristic leaching procedure (TCLP) and the Universal Treatment Standard (UTS) of 4.3 mg/L. X-ray powder diffraction (XRPD) analyses were performed to investigate the crystalline phases associated with Zn immobilization. Scanning electron microscopy (SEM)–energy dispersive X-ray (EDX) analyses were utilized to support the XRPD results. The treatment results showed that the TCLP-Zn concentrations obtained from the 10 wt% PC and 15 wt% CKD treated samples were less than the UTS, after 7 days curing. However, the FA treatment (up to 30 wt%) was not effective in meeting the UTS even after 28 days curing. All PC–CKD treatment combinations were effective in reducing the TCLP-Zn concentrations below the UTS criteria. Moreover, a 20 wt% dose of a PC-FA treatment combination (75/25 PC-FA) was successful in reducing the TCLP-Zn concentrations below 4.3 mg/L after 1 day. The XRPD results showed that ettringite and Zn₆Al₂(OH)₁₆CO₃·4H₂O were the possible phases associated with Zn immobilization upon PC and CKD treatment. The SEM–EDX results confirmed the presence of ettringite, while Zn₆Al₂(OH)₁₆CO₃·4H₂O was not identified.     

Calcium and Magnesium‐bearing Sabugalite from the Tono Uranium Deposit,Central Japan

Calcium and magnesium‐bearing sabugalite occurs as aggregations of yellowish platy crystals in veinlets or druses in conglomerate from the oxidized parts of the Tono uranium deposit, Central Japan. X‐ray powder diffractometry of this mineral has reflections consistent with previous powder diffraction data of sabugalite. It is included in the monoclinic system with space group C2/m and calculated cell parameters of a = 19.68Å, b = 9.89Å, c = 9.82Å α = γ = 90°, β‐96.93° and V = 1897.83ų. Chemical analysis yields a formula of (Ca_0.10 Mg_0.09)_Σ0.19Al_0.53(UO₂)_2.04((PO₄)_1.99(AsO₄)_0.01)_Σ2.00·11.22H₂O. EMPA mapping shows that the mineral is compositionally uniform with no micron‐scale layering. Charge of cations including Ca and Mg in the cation‐H₂O layer is 1.98 being identical to that of autunite group minerals. This suggests that the charge balance in the cation‐H₂O layer of the mineral could be made by the alkaline earth or alkaline elements rather than by hydrogen ions.     

Thermochemical study of natural montmorillonite

The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ _f H _el ⁰ (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: ?5677.6 ± 7.6 kJ/mol for Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ (I), ?5614.3 ± 7.0 kJ/mol for Na_0.4K_0.1(Ca_0.1Mg_0.3Al_1.5Fe _0.1 ³⁺ )[Si_3.9Al_0.1O₁₀](OH)₂ (II), ?5719 ± 11 kJ/mol for K_0.1Ca_0.2Mg_0.2(Mg_0.6Al_1.3Fe _0.1 ³⁺ ) [Si_3.7Al_0.3O10](OH)₂ (III), and ?6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ · 2.6H₂O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H₂O) and dehydroxylation (166 ± 10 kJ per mole of H₂O) for Na-montmorillonite.     

Harkerite from the Alban Hills,Italy

Harkerite, found in metamorphic ejecta of the Alban Hills associated with cuspidine, grossular, phlogopite, vesuvian, biotite, and minor amounts of diopside, aegirinaugite, leucite, magnetite and calcito, shows cubic Laue symmetry m3m, possible space groups Fm3m, F432, F43m, a₀ = 14.82 Å.On the basis of isomorphous replacements suggested by the crystal structure analysis, chemical data may be represented by the formula: Ca₄₈Mg₁₆(AlSi₄O₁₆)₄(BO₃)₁₂(CO₃)₂₀ · 4H₂O. Refractive index n_D = 1.6490.The relations between harkerite from Albano, harkerite from Skye and other known harkerites and sakhaites are discussed.     

Solubility of Ca6[Al(OH)6]2(CrO4)3·26H2O,the chromate analog of ettringite; 5–75°C

Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O⇌6Ca²⁺+2Al(OH)⁻₄+3CrO²⁻₄+4OH⁻+26H₂O varies with pH unless a CaCrO_4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca²⁺+CrO²⁻₄=CaCrO_4(aq) was obtained by minimizing the variance in the IAP for Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log K_SP) of Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O at 25°C is −41.46±0.30. The temperature dependence of the log K_SP is log K_SP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG⁰_r,298 and ΔH⁰_r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol⁻¹. the values of ΔC⁰_P,r,298 and ΔS⁰_r,298 are −1506±140 and −534±83 J mol⁻¹ K⁻¹. Using these values and published standard state partial molal quantities for constituent ions, ΔG⁰_f,298=−15,131±19 kJ mol⁻¹, ΔH⁰_f,298=−17,330±8.6 kJ mol⁻¹, ΔS⁰₂₉₈=2.19±0.10 kJ mol⁻¹ K⁻¹, and ΔC⁰_Pf,298=2.12±0.53 kJ mol⁻¹ K⁻¹, were calculated.     

Kobyashevite, Cu5(SO4)2(OH)6·4H2O, a new devilline-group mineral from the Vishnevye Mountains, South Urals, Russia

A new mineral kobyashevite, Cu₅(SO₄)₂(OH)₆·4H₂O (IMA 2011–066), was found at the Kapital’naya mine, Vishnevye Mountains, South Urals, Russia. It is a supergene mineral that occurs in cavities of a calcite-quartz vein with pyrite and chalcopyrite. Kobyashevite forms elongated crystals up to 0.2 mm typically curved or split and combined into thin crusts up to 1?×?2 mm. Kobyashevite is bluish-green to turquoise-coloured. Lustre is vitreous. Mohs hardness is 2½. Cleavage is {010} distinct. D(calc.) is 3.16 g/cm³. Kobyashevite is optically biaxial (?), α 1.602(4), β 1.666(5), γ 1.679(5), 2 V(meas.) 50(10)°. The chemical composition (wt%, electron-microprobe data) is: CuO 57.72, ZnO 0.09, FeO 0.28, SO₃ 23.52, H₂O(calc.) 18.39, total 100.00. The empirical formula, calculated based on 18 O, is: Cu_4.96Fe_0.03Zn_0.01S_2.01O_8.04(OH)_5.96·4H₂O. Kobyashevite is triclinic, $ P\overline{\,1 } $ , a 6.0731(6), b 11.0597(13), c 5.5094(6)?Å, α 102.883(9)°, β 92.348(8)°, γ 92.597(9)°, V 359.87(7)?ų, Z?=?1. Strong reflections of the X-ray powder pattern [d,Å-I(hkl)] are: 10.84–100(010); 5.399–40(020); 5.178–12(110); 3.590–16(030); 2.691–16(20–1, 040, 002), 2.653–12(04–1, 02–2), 2.583–12(2–11, 201, 2–1–1), 2.425–12(03–2, 211, 131). The crystal structure (single-crystal X-ray data, R?=?0.0399) сontains [Cu₄(SO₄)₂(OH)₆] corrugated layers linked via isolated [CuO₂(H₂O)₄] octahedra; the structural formula is CuCu₄(SO₄)₂(OH)₆·4H₂O. Kobyashevite is a devilline-group member. It is named in memory of the Russian mineralogist Yuriy Stepanovich Kobyashev (1935–2009), a specialist on mineralogy of the Urals.     

Karchevskyite, [Mg18Al9(OH)54][Sr2(CO3,PO4)9(H2O,H3O)11], a new mineral species of the layered double hydroxide family

Karchevskyite, a new mineral related to the family of layered double hydroxides (LDHs), has been found in the Iron open pit at the Kovdor carbonatite massif, Kola Peninsula, Russia. The mineral occurs as spherulites of up to 1.5 mm in diameter composed of thin, curved lamellae. Dolomite, magnetite, quintinite-3T, strontium carbonate, and fluorapatite are associated minerals. Karchevskyite is white in aggregates and colorless in separate platelets. Its luster is vitreous with a pearly shine on the cleavage surface. The new mineral is nonfluorescent. The Mohs hardness is 2. The cleavage is eminent (micalike), parallel to {001}. The measured density is 2.21(2) g/cm³, and the calculated value is 2.18(1) g/cm³. Karchevskyite is colorless and nonpleochroic in immersion liquids. It is uniaxial, negative, ω = 1.542(2), and ? = 1.534(2). The chemical composition (electron microprobe, average of ten point analyses, standard deviation in parentheses, wt %) is as follows: 29.7(1.1) MgO, 18.3(0.7) Al₂O₃, 7.4(0.4) SrO, 0.2(0.1) CaO, 1.3(0.2) P₂O₅, 14.5(0.4) CO₂, and 28.6 H₂O (estimated by difference); the total is 100. The empirical formula calculated on the basis of nine Al atoms is Mg_18.00Al_9.00(OH)_54.00(Sr_1.79Mg_0.48Ca_0.09)_2.36 (Ca₃)_8.26(PO₄)_0.46(H₂O)_6.54(H₃O)_4.18. The idealized formula is [Mg₁₈Al₉(OH)₅₄][Sr₂(CO₃, PO₄)₉(H₂O, H₃O)₁₁]. The new mineral slowly dissolves in 10% HCl with weak effervescence. Karchevskyite is trigonal; possible space groups are P3, P3, P $ \overline 3 Karchevskyite, a new mineral related to the family of layered double hydroxides (LDHs), has been found in the Iron open pit at the Kovdor carbonatite massif, Kola Peninsula, Russia. The mineral occurs as spherulites of up to 1.5 mm in diameter composed of thin, curved lamellae. Dolomite, magnetite, quintinite-3T, strontium carbonate, and fluorapatite are associated minerals. Karchevskyite is white in aggregates and colorless in separate platelets. Its luster is vitreous with a pearly shine on the cleavage surface. The new mineral is nonfluorescent. The Mohs hardness is 2. The cleavage is eminent (micalike), parallel to {001}. The measured density is 2.21(2) g/cm³, and the calculated value is 2.18(1) g/cm³. Karchevskyite is colorless and nonpleochroic in immersion liquids. It is uniaxial, negative, ω = 1.542(2), and ɛ = 1.534(2). The chemical composition (electron microprobe, average of ten point analyses, standard deviation in parentheses, wt %) is as follows: 29.7(1.1) MgO, 18.3(0.7) Al₂O₃, 7.4(0.4) SrO, 0.2(0.1) CaO, 1.3(0.2) P₂O₅, 14.5(0.4) CO₂, and 28.6 H₂O (estimated by difference); the total is 100. The empirical formula calculated on the basis of nine Al atoms is Mg_18.00Al_9.00(OH)_54.00(Sr_1.79Mg_0.48Ca_0.09)_2.36 (Ca₃)_8.26(PO₄)_0.46(H₂O)_6.54(H₃O)_4.18. The idealized formula is [Mg₁₈Al₉(OH)₅₄][Sr₂(CO₃, PO₄)₉(H₂O, H₃O)₁₁]. The new mineral slowly dissolves in 10% HCl with weak effervescence. Karchevskyite is trigonal; possible space groups are P3, P3, P 1m, P31m, P312, P312, P3m1, or P3m1; unit-cell dimensions are a = 16.055(6), c = 25.66(1) ?, V = 5728(7) ?³, Z = 3. The strongest reflections in the X-ray powder diffraction pattern [d, (I, %)(hkl)] are: 8.52(10)(003), 6.41(4)(004), 5.13(3)(005), 4.27(6)(006), 3.665(9)(007), 3.547(9)(107), 3.081(6)(315). Wavenumbers of absorption bands in the infrared spectrum of the new mineral are (cm⁻¹; s is shoulder): 3470, 3420s, 3035, 2960s, 1650, 1426, 1366, 1024, 937, 860, 779, 678, 615s, 553, 449, 386. Results of thermogravimetric analysis: total weight loss is 42.0 wt %, with three stages of loss: 12.2%, maximum rate at 230°C; 6.1%, maximum rate at 320°C; and 23.7%, maximum rate at 440°C. Karchevskyite is a late-stage hydrothermal mineral. The mineral is named in memory of Russian mineralogist Pavel Karchevsky (1976–2002), who made a significant contribution to the study of carbonatites. The type material of karchevskyite is deposited at the Mineralogical Museum, Division of Mineralogy, St. Petersburg State University, and the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? S.N. Britvin, N.V. Chukanov, G.K. Bekenova, M.A. Yagovkina, A.V. Antonov, A.N. Bogdanova, N.I. Krasnova, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, No. 5, pp. 44–56. The new mineral karchevskyite and its name accepted by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, March 21, 2005. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, June 30, 2005.