Structural characterization of high-pressure C–Na<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>5</Subscript> by single-crystal diffraction and <Superscript>29</Superscript>Si MAS NMR

Single crystals of C–Na₂Si₂O₅ have been synthesized from the hydrothermal recrystallization of a glass. The title compound is monoclinic, space group P2₁/c with Z= 8 and unit-cell parameters a= 4.8521 (4)Å, b=23.9793(16)Å, c=8.1410(6)Å, β=90.15(1)° and V=947.2(2)ų. The structure has been determined by direct methods and belongs to the group of phyllosilicates. It is based on layers of tetrahedra with elliptically six-membered rings in chair conformation. The sequence of directedness within a single ring is UDUDUD. The sheets are parallel to (010) with linking sodium cations in five- and sixfold coordination. Concerning the shape and the conformation of the rings, C–Na₂Si₂O₅ is closely related to β-Na₂Si₂O₅. However, both structures differ in the stacking sequences of the layers. A possible explanation for the frequently observed polysynthetic twinning of phase C is presented. In the ²⁹Si MAS-NMR spectrum of C–Na₂Si₂O₅ four well-resolved lines of equal intensity are observed at ?86.0, ?86.3, ?87.4, and ?88.2?ppm. The narrow range of isotropic chemical shifts reflects the great similarity of the environments of the different Si sites. This lack of pronounced differences in geometry renders a reliable assignment of the resonance lines to the individual sites on the basis of known empiric correlations and geometrical features impossible.     

Radiation-induced defects in euclase: formation of O<Superscript>−</Superscript> hole and Ti<Superscript>3+</Superscript> electron centers

Irradiation techniques are often applied to gem minerals for color enhancement purposes. Natural green, blue and colorless specimens of rare gemological quality euclase, BeAlSiO₄(OH), from Brazil were irradiated with gamma rays in the dose range from 10 to 500 kGy. Although the colors of the different specimens were not strongly influenced, two different irradiation-induced paramagnetic defect centers were found by electron paramagnetic resonance (EPR). The first one is an O⁻ hole center interacting with one Al neighbor and the second is a Ti³⁺ electron center. The EPR angular rotation patterns of both irradiation-induced defects were measured and analyzed. The results suggest that O⁻ hole centers are formed by dissociation of the hydroxyl ions, similar as in topaz crystals. In euclase the OH⁻ ions interconnect distorted Al octahedra and Be tetrahedra in O₅ positions. During irradiation, the electrons are captured by titanium ions (Ti⁴⁺ + e⁻), leading to the formation of paramagnetic Ti³⁺ ions. From the EPR rotation patterns it is clear that these ions substitute for Al ions. The spin Hamiltonian parameters of the irradiation-induced defects are analyzed and compared to similar defect centers in other mineral specimens. Thermal annealing experiments show that the O⁻ hole centers and Ti³⁺ electron centers are directly connected through the radiation process.     

Ab initio calculations on the O<Subscript>2</Subscript><Superscript>3−</Superscript>-Y<Superscript>3+</Superscript> center in CaF<Subscript>2</Subscript> and SrF<Subscript>2</Subscript>: its electronic structure and hyperfine constants

The O₂ ^3?-Y³⁺ center in fluorite-type structures (CaF₂ and SrF₂) has been investigated at the density functional theory (DFT) level using the CRYSTAL06 code. Our calculations were performed by means of the hybrid B3PW method in which the Hartree–Fock exchange is mixed with the DFT exchange functional, using Becke’s three parameter method, combined with the non-local correlation functionals by Perdew and Wang. Our calculations confirm the stability and the molecular character of the O₂ ^3?-Y³⁺ center. The unpaired electron is shown to be almost exclusively localized on and equally distributed between the two oxygen atoms that are separated by a bond distance of 2.47 Å in CaF₂ and 2.57 Å in SrF₂. The calculated ¹⁷O and ¹⁹F hyperfine constants for of the O₂ ^3?-Y³⁺ center are in good agreement with their corresponding experimental values reported by previous electron paramagnetic resonance and electron nuclear double resonance studies, while discrepancies are notable for the ⁸⁹Y hyperfine constants.     

Seasonal variations in sulfur isotopic composition of dissolved SO<Subscript>4</Subscript><Superscript>2−</Superscript> in the Aha Lake,Guiyang and their implications

The Aha Lake is a seasonal anoxic water system in the southwest of Guiyang City, Guizhou Province, China. Seasonal variations in SO42- concentrations and their isotopic compositions in lake water as well as in the tributaries were investigated in this study. The results showed that sulfate concentrations in river water range from 0.94 to 6.52 mmol/L and their δ34S values range from -14.9‰ and 0.9‰, while lake water has sulfate concentrations ranging from 1.91 to 2.79 mmol/L, and δ34S values from -9.8‰ to -5.9‰. It is suggested that coal mining drainage is the major source of SO42- in the Aha Lake. Rainfall, sewage discharge, sulfide oxidation and gypsum dissolution have made only limited contributions. Different depth-dependent distributions of dissolved SO42- and δ34S were de-veloped for both DB and LJK in summer and winter. Due to water overturn, δ34S values display homogenous vertical distributions in winter and spring. While in summer and autumn, significant positive shifts of δ34S were clearly ob-served in epilimnion and bottom strata as a result of water stratification. High δ34S values in epilimnion may result from the retention of rainwater during water stratification. Dissimilatory sulfate reduction by bacteria was thought to be responsible for the increase of δ34S value in hypolimnion.     

Kamarizaite,Fe<Stack><Subscript>3</Subscript><Superscript>3+</Superscript></Stack>(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>3</Subscript> · 3H<Subscript>2</Subscript>O,a new mineral species,arsenate analogue of tinticite

Kamarizaite, a new mineral species, has been identified in the dump of the Kamariza Mine, Lavrion mining district, Attica Region, Greece, in association with goethite, scorodite, and jarosite. It was named after type locality. Kamarizaite occurs as fine-grained monomineralic aggregates (up to 3 cm across) composed of platy crystals up to 1 μm in size and submicron kidney-shaped segregations. The new mineral is yellow to beige, with light yellow streak. The Mohs hardness is about 3. No cleavage is observed. The density measured by hydrostatic weighing is 3.16(1) g/cm³, and the calculated density is 3.12 g/cm³. The wavenumbers of absorption bands in the IR spectrum of kamarizaite are (cm^?1; s is strong band, w is weak band): 3552, 3315s, 3115, 1650w, 1620w, 1089, 911s, 888s, 870, 835s, 808s, 614w, 540, 500, 478, 429. According to TG and IR data, complete dehydration and dehydroxylation in vacuum (with a weight loss of 15.3(1)%) occurs in the temperature range 110–420°C. Mössbauer data indicate that all iron in kamarizaite is octahedrally coordinated Fe³⁺. Kamarizaite is optically biaxial, positive: n _min = 1.825, n _max = 1.835, n _mean = 1.83(1) (for a fine-grained aggregate). The chemical composition of kamarizaite (electron microprobe, average of four point analyses) is as follows, wt %: 0.35 CaO, 41.78 Fe₂O₃, 39.89 As₂O₅, 1.49 SO₃, 15.3 H₂O (from TG data); the total is 98.81. The empirical formula calculated on the basis of (AsO₄,SO₄)₂ is Ca_0.03Fe _2.86 ³⁺ (AsO₄)_1.90(SO₄)_0.10(OH)_2.74 · 3.27H₂O. The idealized formula is Fe ₃ ³⁺ (AsO₄)₂(OH)₃ · 3H₂O. Kamarizaite is an arsenate analogue of orthorhombic tinticite, space group Pccm, Pcc2, Pcmm, Pcm2₁, or Pc2m; a = 21.32(1), b = 13.666(6), c =15.80(1) Å, V= 4603.29(5) ų, Z= 16. The strongest reflections of the X-ray powder diffraction pattern [\(\bar d\), Å (I, %) (hkl)] are: 6.61 (37) (112, 120), 5.85 (52) (311), 3.947 (100) (004, 032, 511), 3.396 (37) (133, 431), 3.332 (60) (314), 3.085 (58) (621, 414, 324). The type material of kamarizaite is deposited in the Mineralogical Collection of Technische Universität Bergakademie Freiberg, Germany, inventory number 82199.     

The solubility of Gd<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and the hydrolysis of Gd<Superscript>3+</Superscript> in acidic solutions at 250°C and saturation vapor pressure

The solubility of Gd₂Ti₂O₇ ceramic in acidic solutions (HCl and HClO₄) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd₂Ti₂O_7(cr) + 3H⁺ = Gd³⁺ + TiO_2(cr) + 1.5 H₂O at pH < 3 and 0.5Gd₂Ti₂O₇(cr) + H⁺ + 0.5H₂O = Gd(OH) ₂ ⁺ TiO₂(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K ₍₁₎ ^o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd³⁺ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) ₂ ⁺ dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd³⁺. The second constant of Gd³⁺ hydrolysis was determined at 250°C as K ^o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd₂Ti₂O₇ solid phase were determined: S _298.15 ^o = 251.4 J/(mol K) and ΔfG _298.15 ^o = ?3630 ± 10 kJ/mol.     

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.     

Behaviour of Fe<Subscript>4</Subscript>O<Subscript>5</Subscript>–Mg<Subscript>2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions and their relation to coexisting Mg–Fe silicates and oxide phases

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe₄O₅–Mg₂Fe₂O₅ solid solutions and (2) to explore the phase relations involving (Mg,Fe)₂Fe₂O₅ (denoted as O₅-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O₅-phase coexists with Fe₂O₃, hp-(Mg,Fe)Fe₂O₄, (Mg,Fe)₃Fe₄O₉ or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O₅-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe³⁺-bearing phase B. However, (Mg,Fe)₂Fe₂O₅ does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe²⁺ and Fe³⁺ (at least ~?1.0 cations Fe per formula unit). Fe-L_2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe³⁺/Fe_tot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si⁴⁺?+?[6]Mg²⁺?=?2Fe³⁺. The ability to accommodate Fe²⁺ and Fe³⁺ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg₂Fe₂O₅ have been refined, yielding H°_1bar,298?=???1981.5 kJ mol^??1. Solid solution is complete across the Fe₄O₅–Mg₂Fe₂O₅ binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe²⁺ with silicates indicates that (Mg,Fe)₂Fe₂O₅ has a strong preference for Fe²⁺. Modelling of partitioning with olivine is consistent with the O₅-phase exhibiting ideal mixing behaviour. Mg–Fe²⁺ partitioning between (Mg,Fe)₂Fe₂O₅ and ringwoodite or wadsleyite is influenced by the presence of Fe³⁺ and OH incorporation in the silicate phases.     

Characterization,dissolution and solubility of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb<Subscript>x</Subscript>Ca<Subscript>1−x</Subscript>)<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>OH] at 25 °C and pH 2–9

Background

The interaction between Ca-HAP and Pb²⁺ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(Pb_xCa_1?x)₅(PO₄)₃(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (Pb_xCa_1?x)₅(PO₄)₃(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.

Results

Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (X_Pb) of the solids. For the solids with high X_Pb [(Pb_0.89Ca_0.11)₅(PO₄)₃OH], the aqueous Pb²⁺ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low X_Pb (0.00–0.80), the aqueous Pb²⁺ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.

Conclusions

The dissolution process of the solids with high X_Pb (0.89–1.00) was different from that of the solids with low X_Pb (0.00–0.80). The average K _sp values were estimated to be 10^?80.77±0.20 (10^?80.57–10^?80.96) for hydroxypyromorphite [Pb₅(PO₄)₃OH] and 10^?58.38±0.07 (10^?58.31–10^?58.46) for calcium hydroxyapatite [Ca₅(PO₄)₃OH]. The Gibbs free energies of formation (ΔG _f ^o ) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (X_Pb) of (Pb_xCa_1?x)₅(PO₄)₃(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (Pb_xCa_1?x)₅(PO₄)₃(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb₅(PO₄)₃OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (Pb_xCa_1?x)₅(PO₄)₃(OH) was in equilibrium with the Ca-rich aqueous solution.

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Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃OH] at 25??C and an initial pH of 2.00.

     

High-pressure X-ray diffraction and Raman spectroscopy of CaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-type β-CaCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

In situ high-pressure synchrotron X-ray diffraction and Raman spectroscopic studies of orthorhombic CaFe₂O₄-type β-CaCr₂O₄ chromite were carried out up to 16.2 and 32.0 GPa at room temperature using multi-anvil apparatus and diamond anvil cell, respectively. No phase transition was observed in this study. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a zero-pressure volume of V ₀ = 286.8(1) ų, an isothermal bulk modulus of K ₀ = 183(5) GPa and the first pressure derivative of isothermal bulk modulus K ₀′ = 4.1(8). Analyses of axial compressibilities show anisotropic elasticity for β-CaCr₂O₄ since the a-axis is more compressible than the b- and c-axis. Based on the obtained and previous results, the compressibility of several CaFe₂O₄-type phases was compared. The high-pressure Raman spectra of β-CaCr₂O₄ were analyzed to determine the pressure dependences and mode Grüneisen parameters of Raman-active bands. The thermal Grüneisen parameter of β-CaCr₂O₄ is determined to be 0.93(2), which is smaller than those of CaFe₂O₄-type CaAl₂O₄ and MgAl₂O₄.     

The thermal behaviour of γ-CaSO<Subscript>4</Subscript>

Thermal behaviour of γ-anhydrite (γ-CaSO₄, soluble anhydrite) has been investigated in situ real-time using laboratory parallel-beam X-ray powder diffraction data. Thermal expansion has been analysed from 303 to 569 K with temperature steps of 4 K. Lattice parameters and volume were fitted with a second-order polynomial to calculate thermal expansion coefficients. Thermal expansion of γ-anhydrite is anisotropic being larger along the c axis. Within the 343–383 K thermal range, γ-anhydrite has been found to partially re-hydrate to bassanite CaSO₄·0.5H₂O. At 455 K the transformation γ-CaSO₄ → β-CaSO₄, insoluble anhydrite, starts reaching completion at 653 K.     

Photoluminescence spectra of S<Subscript>2</Subscript><Superscript><Emphasis Type="Bold">−</Emphasis></Superscript> center in natural and heat-treated scapolites

The emission and excitation spectra of yellow luminescence due to S₂ ⁻ in scapolites (#1 from Canada and #2 from an unknown locality) were observed at 300, 80 and 10 K. Emission and excitation bands at 10 K showed vibronic structures with a series of maxima spaced 15–30 and 5–9 nm, respectively. The relative efficiency of yellow luminescence from scapolite #2 was increased up to 117 times by heat treatment at 1,000°C for 2 h in air. The enhancement of yellow luminescence by heat treatment was ascribed to the alteration of SO₃ ²⁻ and SO₄ ²⁻ to S₂ ⁻ in scapolite.     

Electrical conductivity,thermopower and <Superscript>57</Superscript>Fe Mössbauer spectroscopy of aegirine (NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)

DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi₂O₆) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity _DC was determined by extrapolating AC data to zero frequency. In both directions, the log _DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of E_A 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of _DC [001] with _DC(300 K) 2.0 × 10^{–6 –1}cm^–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to _DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () ^s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to _DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe²⁺ Fe³⁺ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. ⁵⁷Fe Mössbauer spectroscopy was applied to detect Fe²⁺ in addition to the dominating concentration of Fe³⁺.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Mineralogy,Mössbauer spectra and electrical conductivity of triphylite Li(Fe<Superscript>2+</Superscript>,Mn<Superscript>2+</Superscript>) PO<Subscript>4</Subscript>

The electrical conductivity of monocrystalline triphylite, Li(Fe²⁺,Mn²⁺)PO₄, with the orthorhombic olivine-type structure was measured parallel (∥) to the [010] direction and ∥ [001] (space group Pnma), between ～400 and ～700 K. Electrical measurements on triphylite are of technological interest because LiFePO₄ is a promising electrode material for rechargeable Li batteries. Triphylite was examined by electron microprobe, ICP atomic emission spectroscopy, X-ray diffraction, Mössbauer spectroscopy and microscopic analysis. The DC conductivity σ_DC was determined from AC impedance data (20 Hz–1 MHz) extrapolating to zero frequency. Triphylite shows σ_DC with activated behavior measured ∥ [010] between ～500 and ～700 K during the first heating up, with activation energy of E _A = 1.52 eV; on cooling E _A = 0.61 eV was found down to ～400 K and extrapolated σ_DC (295 K) ～10^?9 Ω^?1cm^?1; ∥ [001] E _A = 0.65 eV and extrapolated σ_DC(295 K) ～10^?9 to 10^?10 Ω^?1cm^?1, measured during the second heating cycle. The enhanced AC conductivity relative to σ_DC at lower temperatures indicates a hopping-type charge transport between localized levels. Conduction during the first heating up is ascribed to ionic Li⁺ hopping. DC polarization experiments showed conduction after the first heating up to be electronic related to lowered activation energy. Electronic conduction appears to be coupled with the presence of Li⁺ vacancies and Fe³⁺, formed by triphylite alteration. For comparison, σ_DC was measured on the synthetic compound LiMgPO₄ with olivine-type structure, where also an activated behavior of σ_DC with E _A ～1.45 eV was observed during heating and cooling due to ionic Li⁺ conduction; here no oxidation can occur associated with formation of trivalent cations.     

Assessment of NO<Subscript>3</Subscript><Superscript>−</Superscript> contamination in a karstic aquifer,with the use of geochemical data and spatial analysis

Kopaida plain is a cultivated region of Eastern Greece, with specific characteristic related with the paleogeographic evolution and the changes in land use. The present article examines the contamination that derives from nitrates, in terms of contaminant levels, definition of sources and spatial distribution of contaminant plume. For this purpose, 50 water samples were collected from the karstic aquifer and analyzed for 15 parameters including major ions, trace elements, physicochemical parameters, and stable isotopes. The assessment of the above parameter values along with the notes derived by the statistical process revealed the existence of nitrate contamination which has been spatial defined with the aid of spatial interpolation techniques. The correlation of NO₃ ⁻ concentrations with the stable isotope values, defined the infiltration conditions and showed contaminant transport. Nitrate values revealed the potential environmental threat for local people, as 10% of the samples exceeded the parametric value of 50 ppm and 54% of them are above 25 ppm, indicating no optimal quality conditions. The origin of nitrate contamination seems to derive exclusively from the application of N-fertilizers, since the rest of potential sources were not verified by analytical data and field works.     

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.     

Archaean fluid-assisted crustal cannibalism recorded by low δ<Superscript>18</Superscript>O and negative ε<Subscript>Hf(T)</Subscript> isotopic signatures of West Greenland granite zircon

The role of fluids during Archaean intra-crustal magmatism has been investigated via integrated SHRIMP U–Pb, δ¹⁸O and LA-MC-ICPMS ¹⁷⁶Hf isotopic zircon analysis. Six rock samples studied are all from the Nuuk region (southern West Greenland) including two ~3.69 Ga granitic and trondhjemitic gneisses, a 3.64 Ga granitic augen gneiss, a 2.82 Ga granodioritic Ikkattoq gneiss, a migmatite with late Neoarchaean neosome and a homogeneous granite of the 2.56 Ga Qôrqut Granite Complex (QGC). All zircon grains were thoroughly imaged to facilitate analysis of magmatic growth domains. Within the zircon analysed, there is no evidence for metamictization. Initial ε_Hf zircon values (n = 63) are largely sub-chondritic, indicating the granitic host magmas were generated by the remelting of older, un-radiogenic crustal components. Zircon from some granite samples displays more than one ²⁰⁷Pb/²⁰⁶Pb age, and correlated with ¹⁷⁶Hf/¹⁷⁷Hf compositions can trace multiple phases of remelting or recrystallization during the Archaean. Model ages calculated using Lu/Hf arrays for each sample indicate that the crustal parental rocks to the granites, granodiorites and trondhjemites segregated from a chondrite-like reservoir at an earlier time during the Archaean, corresponding to known formation periods of more primitive tonalite–trondhjemite–granodiorite (TTG) gneisses. Zircon from the ~3.69 Ga granite, the migmatite and QGC granite contains Eoarchaean cores with chondritic ¹⁷⁶Hf/¹⁷⁷Hf and mantle-like δ¹⁸O compositions. The age and geochemical signatures from these inherited components are identical to those of surrounding tonalitic gneisses, further suggesting genesis of these granites by remelting of broadly tonalitic protoliths. Zircon oxygen isotopic compositions (n = 62) over nine age populations (six igneous and three inherited) have weighted mean or mean δ¹⁸O values ranging from 5.8 ± 0.6 to 3.7 ± 0.5‰. The 3.64 Ga granitic augen gneiss sample displays the highest δ¹⁸O with a mildly supra-mantle composition of 5.8 ± 0.6‰. Inherited Eoarchaean TTG-derived zircon shows mantle-like values. Igneous zircon from all other samples, spanning more than a billion years of Archaean time, record low δ¹⁸O sub-mantle compositions. These are the first low δ¹⁸O signatures reported from Archaean zircon and represent low δ¹⁸O magmas formed by the remelting and metamorphism of older crustal rocks following high-temperature hydrothermal alteration by meteoric water. Meteoric fluid ingress coupled with crustal extension, associated high heat flow and intra-crustal melting are a viable mechanism for the production of the low δ¹⁸O granites, granodiorites and trondhjemites reported here. Both high and low δ¹⁸O magmas may have been generated in extensional environments and are distinct in composition from Phanerozoic I-type granitic plutonic systems, which are typified by increasing δ¹⁸O during intra-crustal reworking. This suggests that Archaean magmatic processes studied here were subtly different from those operating on the modern Earth and involved extensional tectonic regimes and the predominance of remelting of hydrothermally altered crystalline basement.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Yegorovite,Na<Subscript>4</Subscript>[Si<Subscript>4</Subscript>O<Subscript>8</Subscript>(OH)<Subscript>4</Subscript>]·7H<Subscript>2</Subscript>O,a new mineral from the Lovozero alkaline pluton,Kola Peninsula

A new mineral, yegorovite, has been identified in the late hydrothermal, low-temperature assemblage of the Palitra hyperalkaline pegmatite at Mt. Kedykverpakhk, Lovozero alkaline pluton, Kola Peninsula, Russia. The mineral is intimately associated with revdite and megacyclite, earlier natrosilite, microcline, and villiaumite. Yegorovite occurs as coarse, usually split prismatic (up to 0.05 × 0.15 × 1 mm) or lamellar (up to 0.05 × 0.7 × 0.8 mm) crystals. Polysynthetic twins and parallel intergrowths are typical. Mineral individuals are combined in bunches or chaotic groups (up to 2 mm); radial-lamellar clusters are less frequent. Yegorovite is colorless, transparent with vitreous luster. Cleavage is perfect parallel to (010) and (001). Fracture is splintery; crystals are readily split into acicular fragments. The Mohs hardness is ～2. Density is 1.90(2) g/cm³ (meas) and 1.92 g/cm³ (calc). Yegorovite is biaxial (?), with α = 1.474(2), β = 1.479(2), and γ = 1.482(2), 2V _meas > 70°, 2V _calc = 75°. The optical orientation is X ∧ a ～ 15°, Y = c, Z = b. The IR spectrum is given. The chemical composition determined using an electron microprobe (H₂O determined from total deficiency) is (wt %): 23.28 Na₂O, 45.45 SiO₂, 31.27 H₂O_calc; the total is 100.00. The empirical formula is Na_3.98Si_4.01O_8.02(OH)_3.98 · 7.205H₂O. The idealized formula is Na₄[Si₄O₈(OH)₄] · 7H₂O. Yegorovite is monoclinic, space group P2₁/c. The unit-cell dimensions are a = 9.874, b= 12.398, c = 14.897 Å, β = 104.68°, V = 1764.3 ų, Z = 4. The strongest reflections in the X-ray powder pattern (d, Å (I, %)([hkl]) are 7.21(70)[002], 6.21(72)[012, 020], 4.696(44)[022], 4.003(49)[211], 3.734(46)[\(\bar 2\) 13], 3.116(100)[024, 040], 2.463(38)[\(\bar 4\)02, \(\bar 2\)43]. The crystal structure was studied by single-crystal method, R _hkl = 0.0745. Yegorovite is a representative of a new structural type. Its structure consists of single chains of Si tetrahedrons [Si₄O₈(OH)₄]∞ and sixfold polyhedrons of two types: [NaO(OH)₂(H₂O)₃] and [NaO(OH)(H₂O)₄] centered by Na. The mineral was named in memory of Yu. K. Yegorov-Tismenko (1938–2007), outstanding Russian crystallographer and crystallochemist. The type material of yegorovite has been deposited at the Fersman Mineralogical Museum of Russian Academy of Sciences, Moscow.