Annealing of radiation damage in allanite and gadolinite

Samples of allanite and gadolinite with a range of alpha-recoil damage 0.1 to 3.0 dpa, were annealed in Ar and analysed by X-ray powder diffraction (XRD), high resolution transmission electron microscopy (HRTEM), infrared (IR) and differential thermal analysis (DTA). Samples that were fully metamict, and also amorphous regions of partially metamict samples, annealed according to the Ostwald step rule. After annealing, X-ray crystalline material still showed significantly damaged regions under transmission electron microscopy (TEM). Hydrothermal annealing of fully metamict gadolinite at 710° C and PH₂O=2.3 kbar resulted in direct recrystallization. Direct recrystallization, by heterogeneous nucleation, occurred also in samples with significant amount of relict crystalline material. Of two exotherms observed on DTA curves for fully metamict gadolinite only one, at 840° C, resulted from recrystallization. The second exotherm at 895° C was related to the transformation of a transitional, high-temperature γ-phase into gadolinite. The activation energy of recrystallization of partially metamict gadolinite is 0.58 eV. The same annealing path for fully metamict gadolinite and for the amorphous component of partially metamict allanite is consistent with the model of an aperiodic random network structure of metamict minerals.     

Energetics of radiation damage in natural zircon (ZrSiO4)

Transposed temperature drop calorimetry at 1000 °C was performed on natural zircons (ZrSiO₄) from Sri Lanka that were partially to completely metamict due to α-decay event damage (0.06 to 11.7×10¹⁵ α-decay events/mg). The enthalpy of annealing at room temperature (ΔH_anneal) varies sigmoidally as a function of radiation dose. ΔH_anneal reaches a saturation plateau at radiation doses greater than 5×10¹⁵ α-decay events/mg. The annealing of several samples to a crystalline structure with broadened diffraction peaks does not significantly affect the enthalpy of annealing. The large magnitude of the enthalpy of annealing plateau, ?59±3 kJ/mol, suggests that the damage to the structure is pervasive on the scale of Angstroms, consistent with the loss of mid-range order characteristic of a glass. The energetics are consistent with, but do not require, chemical heterogeneity caused by micro-domains of amorphous SiO₂-rich and ZrO₂-rich regions in the metamict state.     

Characterization of the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses

X-ray absorption spectroscopy using synchrotron radiation has been applied to the investigation of the coordination geometries around Y, Zr and Nb atoms in metamict zircon, gadolinite, fergusonite, euxenite and samarskite. EXAFS and XANES spectra of their crystalline counterparts and synthetic compounds including ZrO₂, Y₂O₃, YNbTiO₆, YNbO₄, LiNbO₃, and NiNb₂O₆ were also measured for comparison. Metamict zircon shows a significant decrease in its Zr-O bond distances accompanying an increase in distortion of the Zr-O coordination polyhedra as compared with crystalline zircon. On the contrary, the average Nb-O bond distances and the symmetry of the coordination polyhedra around the Nb atoms in metamict euxenite and samarskite resemble those in the crystalline euxenite. Compared with crystalline fergusonite, a decrease in the distortion of the Nb-O octahedra is observed in metamict fergusonite. The structures of the second nearest neighbors (the metal-metal interactions) are largely disrupted in the metamict specimens except for metamict zircon and samarskite with high trivalent iron concentration. Nb in metamict samarskite is in octahedral coordination by oxygen and is similar to that in euxenite.     

The structure of metamict zircon: A temperature-dependent EXAFS study

The thermal annealing (300–1700 K) of two metamict zircons (Ampagabe, Madagascar and Näegy, Japan) has been studied using X-Ray Diffraction (XRD) and Extended X-ray Absorption Fine Structure spectroscopy (EXAFS) at Zr K-edge. Two stages of thermal annealing within the aperiodic zircon are evidenced between 293 and 1700 K. The first stage (up to 600° C) shows a decrease of the a ₀-cell parameter from 6.674 (at 300° C) to 6.610 (at 600° C)± 0.005 Å. In that temperature range, the average local environment around Zr (presence of ^VIIZr and d(Zr-Zr) 3.3–3.6 Å) shows a weak, but significant increase of the Zr-Zr correlations located at 3.3–3.4 Å, undetectable by XRD. At temperatures up to 700° C (stage 2), the XRD-Bragg component arising from crystalline zircon increases in magnitude, whereas, Zr-K EXAFS analysis indicates a progressive ^VIIZr^VIIIZr transition, associated with a recovery of the crystalline zircon medium-range environment. For both techniques, the zircon structure is fully recovered at annealing temperatures up to 900° C.Electrostatic modelings suggest that the ^VIIIZr^VIIZr transition observed in zircon with increasing alpha-decay damage creates significantly overbonded oxygen atoms around Zr. With increasing temperature, those oxygen atoms are better bonded to ^VIIZr, due to the thermal expansion of the Zr-O bond. The congruent recovery of the zircon structure should therefore be favoured with increasing temperature. On the other hand, the metamict network can be also partially reorganized around 400–500° C, with the creation of Zr-rich domains, as measured by EXAFS. However, the growth of these domains after 3 hours annealing affects only minor portions of the aperiodic network. This model is corroborated by a similar thermal behaviour observed for a synthetic sol-gel of ZrO₂ · SiO₂ composition.     

Activation energy of annealed metamict gadolinite from 57Fe Mössbauer spectroscopy

Gadolinite, REE₂FeBe₂Si₂O₁₀, is commonly metamict. ⁵⁷Fe Mössbauer annealing studies of fully metamict gadolinite from Ytterby, Sweden, have been completed in argon atmosphere from 873 to 1473 K. This technique has rarely been employed in studies of metamict minerals. Changes in the experimental parameters of Mössbauer spectra are sensitive indicators of the thermal recrystallization process of metamict gadolinite and revealed two stages of the structural recovery: a major stage from 873 to 1073 K and a slower recovery stage from 1133 to 1473 K. These observations are confirmed by X-ray powder diffraction. In relation to the first stage, the exponential behaviour of the changes in the Mössbauer parameters can be used for deriving the activation energy E _a of the recrystallization process. The calculated value E _a =1.97 eV in argon atmosphere explains the common occurrence of gadolinite in the fully or partially metamict state. Results of Mössbauer spectroscopy suggest that the recrystallization of metamict gadolinite is a displacive transition that involves rotation and translation of SiO₄ and BeO₄ to their normal positions associated with removal of OH groups from the structure.     

Parascandolaite,KMgF3, a new perovskite-type fluoride from Vesuvius

The new mineral parascandolaite, isotypic to cubic perovskites, space group Pm \(\overline{3}\) m (no. 221) is the natural analog of the synthetic fluoride KMgF₃ and is related to neighborite, NaMgF₃. It was found as a volcanic sublimate at Vesuvius volcano on 1944 eruption lava scoria, associated with opal, cerussite, mimetite, phoenicochroite and coulsellite. It occurs as transparent colorless to white cubic crystals up to 0.5 mm in length with vitreous luster. The density measured by flotation in a diiodomethane–toluene mixture is 3.11(1) g/cm³; that calculated from the empirical formula and single-crystal X-ray data is 3.123 g/cm³. The mineral is isotropic with n = 1.395(5) (580 nm). The six strongest reflections in the X-ray powder diffraction pattern are: [d _obs in Å(I)(h k l)] 2.001(100)(2 0 0), 2.831(83)(1 1 0), 2.311(78)(1 1 1), 1.415(56)(2 2 0), 1.633(35)(2 1 1) and 1.206(22)(3 1 1). The unit-cell parameter is a = 4.0032(9) Å. The structure was refined to a final R(F) = 0.0149 for 35 independent observed reflections [I > 2σ(I)]. The mineral is named after the Italian mineralogist Antonio Parascandola (1902–1977).     

Iodine diagenesis in non-pelagic deep-sea sediments

Measurements of sediment geochemistry and porewater speciation have been made using eight cores containing turbidite sections from the Madeira and Nares Abyssal Plains. The results have been used to evaluate how the diagenetic chemistry of iodine in these sediments compares with that in sediments undergoing steady-state diagenesis. The behaviour of iodine is related to the development of a redox front within the turbidite, between the organic-rich anoxic sediment and its oxic cap, and the downward migration of the front through the turbidite with time. In contrast to the steady-state case, sediment I contents and I/ C ratios increase downwards through the oxidised section reaching a maximum at the redox front (up to ~ 100 μ/g I; molar I/C~ 20 × 10⁻⁴) below which values drop dramatically (I/C ~ 5 × 10⁻⁴). A strong iodate enrichment (up to ~3 μmol kg⁻¹) is observed in the oxidised section of the sediment. At the front interconversion of I⁻ and IO⁻₃ species occur and below the front porewater IO⁻₃ is absent and I~ concentrations increase with depth (as in other cases of anoxic diagenesis) up to ~ 10 μmol kg⁻. In the oxidised section of the sediment the I enrichment has been supplied by upward transport of iodide with the increasing I content, with depth being accounted for by progressive diagenetic enrichment with time.     

Microscope-photometric methods for non-destructive Fe2+ – Fe3+ determination in chloritoids (Fe2+, Mn2+, Mg)2 (Al,Fe3+)4 Si2O10(OH)4

Six natural chloritoid crystals with Fe²⁺ and Fe³⁺ contents ranging from 4.15 to 12.81 and from 0.411 to 0.849g-atoms/l, respectively, as determined by means of microprobe and Mössbauer techniques, served as reference material to develop non-destructive microscope-spectrophotometric methods for quantitative Fe²⁺ – Fe³⁺ determinations in chloritoids from unpolarized spectra of (001) platelets. Fe²⁺ concentrations in g-atom/l can be obtained from [ [Fe³⁺]=C₁xD₁/t where D₁ = log₁₀(I_0/I at 28,000 cm^-1 and t=crystal thickness in cm; C₁ is a conttant that may be influenced somewhat by experimental conditions and is found to be 0.002289 with the experimental set-up used in this study. Fe²⁺ concentrations in g-atom/l can be obtained from [Fe²⁺]=C₁xD₁/D₁-C₃ with D₂=log₁₀(I₀/I) at 16,300 cm^?1 and constants C₄ = 45.36 and C₅ = 3.540. Due to the uncertainties in absorbance measurements, D₁ and D₂ and the thickness measurements, the accuracies are ±0.05 and ±0.15 g-atom/l for [Fe³⁺] and [Fe²⁺], respectively. The determinations may be carried out on chloritoid grains in normal thin sections with an areal resolution of ～10 μm.     

High-pressure behaviour and equation of state of calcite, CaCO3

The high-pressure response of the cell parameters of calcite, CaCO₃, has been investigated by single crystal X-ray diffraction. The unit cell parameters have been refined from 0 to 1.435?GPa, and the linear and volume compressibilities have been measured as β _a =2.62(2)?×?10^?3?GPa^?1,β _c =7.94(7)?×?10^?3?GPa^?1, β _v =13.12?×?10^?3?GPa^?1. The bulk modulus has been obtained from a fit to the Birch-Murnaghan equation of state, giving K ₀=73.46?±?0.27?GPa and V ₀=367.789 ±?0.004?ų with K′=4. Combined with earlier data for magnesite, ankerite and dolomite, these data suggest that K ₀ V ₀ is a constant for the Ca-Mg rhombohedral carbonates.     

Estimating the Density and Compressibility of Seawater to High Temperatures Using the Pitzer Equations

The density and compressibility of seawater solutions from 0 to 95 °C have been examined using the Pitzer equations. The apparent molal volumes (X = V) and compressibilities (X = κ) are in the form $$ X_{\phi } = \bar{X}^{0} + A_{X} I/(1.2 \, m)\ln (1 + 1.2 \, I^{0.5} ) + \, 2{\text{RT }}m \, (\beta^{(0)X} + \beta^{(1)X} g(y) + C^{X} m) $$ where $ \bar{X}^{0} $ is the partial molal volume or compressibility, I is the ionic strength, m is the molality of sea salt, A_X is the Debye–Hückel slope for volume (X = V) or adiabatic compressibility (X = κ _s), and g(y) = (2/y ²)[1 ? (1 + y) exp(?y)] where y = 2I ^0.5. The values of the partial molal volume and compressibility ( $ \bar{X}^{0} $ ) and Pitzer parameters (β ^(0)X , β ^(1)X and C ^X ) are functions of temperature in the form $$ Y^{X} = \sum_{i} a_{i} (T-T_{\text{R}} )^{i} $$ where a _i are adjustable parameters, T is the absolute temperature in Kelvin, and T _R = 298.15 K is the reference temperature. The standard errors of the seawater fits for the specific volumes and adiabatic compressibilities are 5.35E?06 cm³ g^?1 and 1.0E?09 bar^?1, respectively. These equations can be combined with similar equations for the osmotic coefficient, enthalpy and heat capacity to define the thermodynamic properties of sea salt to high temperatures at one atm. The Pitzer equations for the major components of seawater have been used to estimate the density and compressibility of seawater to 95 °C. The results are in reasonable agreement with the measured values (0.010E?03 g cm^?3 for density and 0.050E?06 bar^?1 for compressibility) from 0 to 80 °C and salinities from 0 to 45 g kg^?1. The results make it possible to estimate the density and compressibility of all natural waters of known composition over a wide range of temperature and salinity.     

Dissociation constants of calcite and CaHC03+ from 0 to 50°C

From conductance measurements, the negative logarithm of the dissociation constant of the CaHCO₃₊ ion pair, pK(CaHCO₃⁺), is 0.7, 1.0 and 1.35 within ±0.05 units at 0, 25 and 60°C, respectively. A revaluation of published and unpublished data yields pK(CaCO₃⁰) ≈ 3.2 at 25°C. Use of these pK's to compute the dissociation constant of calcite (Kc) from published calcite solubility measurements in pure water gives pKc values which increase markedly with ionic strength. However, if the ion pairs are ignored, computed pKc values are nearly constant with ionic strength. All reasonable attempts to eliminate the trend in pKc by adjusting ion activity coefficients, and/or values of K(CaCO₃⁰) failed, so the dilemma remains. Kc values computed from the most reliable published calcite solubility data are in good agreement with such values based on solubility data measured in this study at 5, 15, 35 and 50°C. Study results ignoring ion pairs are accurately represented by the equation log Kc = 13.870 — (3059/T) ?0.04035T, and correspond to ?8.35, ?8.42, and ?8.635 at 0, 25 and 50°C, respectively. The logarithmic expression leads to ΔH_r^o = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔS_r^o = ?46.6 ± 1.0 cal/deg mol for the calcite dissociation reaction at 25°C. The dependence of Kc on temperature when CaCO₃⁰ and CaHCO₃⁺ are assumed, is described by log Kc = 13.543 ? (3000/T) ? 0.0401T which yields ?8.39, ?8.47, and -8.70 at 0, 25 and 50°C. This gives ΔH_r^o = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔS_r⁰ = ?47.4 ± 1.0 cal/deg mol at 25°C.     

Soft X-ray spectroscopy of ferrous silicates

Energy gaps and electrical conductivities in the ferrous silicates, Fe₂SiO₄ and FeSiO₃, depend primarily on Fe-O bonding and may be studied by ultraviolet and soft X-ray spectroscopy. We have measured FeL_II–III X-ray band spectra under conditions of “minimal” (I₄, at 4.0 keV) and “high” (I₁₀, at 10.0 keV) self absorption to determine 3d orbital energy levels, to delineate d states in the valence band, and to construct band gap models. Absorption spectra, I₄/I₁₀, were computed to determine vacant orbital levels in the gap. A difference function (I₄–I₁₀) has been proposed to identify X-radiation at photon energies above the measured L_III absorption edge, including high-energy, double-vacancy satellites and radiative transitions involving the anti-parallel (spin-down) d ⁶ electron in the ground state. The proposed band gap model for Fe₂SiO₄ is consistent with that of Nitsan and Shankland (1976), including an intrinsic transition of 6.5 eV and an energy gap of 7.8 eV. The 3d orbital energy level electronic structures are in general agreement with levels computed by Tossell et al. (1974) for [FeO₆]^10? in FeO using an SCF Xα cluster MO method. A high-energy, double-vacancy satellite was found at ～710.7 eV, and is presumed to originate from an L_IIIM_II,III initial state. The intensity of these satellites for the ferrous silicates and other iron compounds, and corresponding Fe L_II/L_III intensity ratios are correlated with differences in band gap magnitudes and gap structure. Fe L_II/L_III intensity ratios are not well correlated with iron oxidation state.     

The heat capacity of two natural chlorite group minerals derived from differential scanning calorimetry

The heat capacity of natural chamosite (X_Fe=0.889) and clinochlore (X_Fe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol^?1?K^?1 give: C _p,CA = 1224.3–10.685?×?10³?×?T ^??0.5???6.4389?× 10⁶?×T ^??2?+?8.0279?×?10⁸?×?T ^??3 and for the natural clinochlore (CE): C _p,CE = 1200.5–10.908?×?10³?×T ^??0.5?? 5.6941?×?10⁶?×?T ^??2?+?7.1166?×?10⁸?×?T ^??3. The corrected C _p-polynomial for pure end-member chamosite (Fe₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CAcor = 1248.3–11.116?× 10³?×?T ^??0.5???5.1623?×?10⁶?×?T ^??2?+?7.1867?×?10⁸×T ^??3 and the corrected C _p-polynomial for pure end-member clinochlore (Mg₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CEcor = 1191.3–10.665?×?10³?×?T ^??0.5???6.5136?×?10⁶?×?T ^??2?+ 7.7206?×?10⁸?×?T ^??3. The corrected C _p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C _p-polynomial for chamosite (C _p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C _p-polynomial (C _p,CAcor) is, however, in excellent agreement with the computed C _p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.     

Metamict transformations in some niobates and zircons according to X-ray absorption spectra

The niobium and zirconium L _III-absorption spectra in some niobates and zircons were obtained with a vacuum focusing crystal spectrometer. The effective charges of Nb and Zr in these minerals were derived from the X-ray absorption spectra. The fine structure of the absorption spectra and effective charges Nb and Zr in metamict, partly-metamict minerals and crystalline analogues made it possible to draw a conclusion as to the nature of the first coordination sphere of Nb and Zr during metamict decay and subsequent recrystallization under annealing of these minerals.     

The solubility of iron hydroxide in sodium chloride solutions

The solubility of iron(III) hydroxide as a function of pH was investigated in NaCl solutions at different temperatures (5–50°C) and ionic strengths (0–5 M). Our results at 25°C and 0.7 M in the acidic range are similar to the solubility in seawater. The results between 7.5 to 9 are constant (close to 10⁻¹¹ M) and are lower than those found in seawater (>10⁻¹⁰) in this pH range. The solubility subsequently increases as the pH increases from 9 to 12. The solubility between 6 and 7.5 has a change of slope that cannot be accounted for by changes in the speciation of Fe(III). This effect has been attributed to a solid-state transformation of Fe(OH)₃ to FeOOH. The effect of ionic strength from 0.1 to 5 M at a pH near 8 was quite small. The solubility at 5°C is considerably higher than at 25°C at neutral pH range. The effects of temperature and ionic strength on the solubility at low and high pH have been attributed to the effects on the solubility product and the formation of FeOH²⁺ and Fe(OH)₄⁻. The results have been used to determine the solubility products of Fe(OH)₃, K¹_Fe(OH)3 and hydrolysis constants, β¹₁, β¹₂, β¹₃, and β¹₄ as a function of temperature (T, K) and ionic strength (I):log K¹_Fe(OH)3 = −13.486 − 0.1856 I^0.5 + 0.3073 I + 5254/T (σ = 0.08)log β¹₁ = 2.517 − 0.8885 I^0.5 + 0.2139 I − 1320/T (σ = 0.03)log β¹₂ = 0.4511 − 0.3305 I^0.5 − 1996/T (σ = 0.1)log β¹₃ = −0.2965 − 0.7881 I^0.5 − 4086/T (σ = 0.6)log β¹₄ = 4.4466 − 0.8505 I^0.5 − 7980/T. (σ = 0.2)Both strong ethylenediaminetetraacetic acid and weak (HA) organic ligands greatly affect iron solubility. The additions of ethylenediaminetetraacetic acid and humic material were shown to increase the solubility near pH 8. The higher solubility of Fe(III) in seawater compared to 0.7 M NaCl may be caused by natural organic ligands.     

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.     

Solubility and complexing of Ni in the system NiO-H2O-HCl

The solubility of bunsenite (NiO) in Cl-bearing fluids in the range of 450°–700°C, 1–2 kbar was determined using the Ag + AgCl acid buffer technique. Based on the results of the experiments, it is concluded that the associated NiCl⁰₂ complex is the dominant Ni species in the fluid over the entire temperature-pressure range investigated. The temperature dependence of the equilibrium constant for the reaction NiO(s) + 2HCl⁰(aq) = NiCl⁰₂(aq) + H₂O is given by logK = ?4.17(±0.55) + 4629(±464)/T(K) at 1 kbar, and logK = ?4.75(±0.91) + 5933(±756)/T(K) at 2 kbar. The calculated difference in standard state Gibbs free energy of formation between NiCl⁰₂ and 2HCl⁰ in kcal is G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?20.77(±2.22) + 0.03264(±0.0026)T(K), at 1 kbar and G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?25.01(±1.35) + 0.03264(±0.0016)T(K) at 2 kbar. Comparison of the solubilities of Ni end-member minerals with those of Ca, Mn, Fe, and Mg indicates that nickel minerals generally are the least soluble at a given temperature and pressure. The relatively low solubility of Ni end-member minerals, combined with the relatively low concentration of Ni in most rocks, should result in a quite low mobility of Ni in hydrothermal fluids.     

Solubility and equilibrium constants of lead in carbonate solutions (25°C,I = 0.3 mol dm−3)

The solubilities of PbCO₃(s), 2PbCO₂·Pb(OH)₂(s), and of 3PbCO₃ 2Pb(OH)₂(s) have been studied at 25°C ± 0.1°C in solutions of the constant ionic strength I = 0.3 mol/dm³, consisting primarily of sodium perchlorate. A few experiments with hydrocerussite were performed in solutions of 0.1 M KNO₃. The concentrations of lead and hydrogen ions have been determined in solution in contact with the solid phase. From experimental data the following values for equilibrium constants are obtained: log [Pb²⁺]·pCO₂·[H⁺]^?2 = 5.20log [Pb²⁺]·pCO^0.67₂·[H⁺]^?2 = 6.80log [Pb₂₊]³·[CO^2?₃]²·[OH^?]² = ?44.08 (and ?44.8 forI = 0.1 M)log [PbCO⁰₃]·[Pb²⁺]^?1·[CO^2?₃]^?1 = 5.40log [Pb(CO₃)^2?₂]·[Pb₂₊]^?1·[CO^2?₃]^?2 = 8.86 The data indicate that hydrocerussite is the most stable solid phase in natural waters. Comparison with the literature and needs for further research are also presented.     

Radiological hazard assessment for building materials incorporating phosphogypsum made using Eshidiya mine rock in Jordan

The mean activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K in Eshidiya phosphogypsum samples were measured as 351.4 ± 23.4, 3.8 ± 0.3, and 120.7 ± 8.3 Bq kg^?1, respectively. The results show that the mean values of activity concentration of ²²⁶Ra, ²³²Th, and ⁴⁰K are in the lower range of typical values reported for phosphogypsum samples collected worldwide. Radiological hazard indices such as the radium-equivalent activity (Ra_eq), the gamma index (I _γ ) alpha index (I _α ), the absorbed gamma dose rate (D _in), and the corresponding annual effective dose (E _in) were assessed for building materials for dwellings. The results of assessment exhibit that all phosphogypsum samples are higher than the recommended safe limit for building materials for dwellings, except for the radium-equivalent activity (Ra_eq). Overall assessment, it can be concluded that the possibility of using Eshidiya phosphogypsum in building materials in proportions lower than 100 % will be safe. The mixture of phosphogypsum with normal gypsum can dilute the concentrations of natural radionuclides allowing the use of the mixed building materials to be safe from a radiological point of view.     

Static elasticity of cordierite I: Effect of heavy ion irradiation on the compressibility of hydrous cordierite

The effect of ion beam irradiations on the elastic properties of hydrous cordierite was investigated by means of Raman and X-ray diffraction experiments. Oriented single crystals were exposed to swift heavy ions (Au, Bi) of various specific energies (10.0–11.1 MeV/u and 80 MeV/u), applying fluences up to 5 × 10¹³ ions/cm². The determination of unit-cell constants yields a volume strain of 3.4 × 10^?3 up to the maximum fluence, which corresponds to a compression of non-irradiated cordierite at ~480 ± 10 MPa. The unit-cell contraction is anisotropic (e ₁ = 1.4 ± 0.1 × 10^?3, e ₂ = 1.5 ± 0.1 × 10^?3, and e ₃ = 7 ± 1 × 10^?4) with the c-axis to shrink only half as much as the axes within the ab-plane. The lattice elasticity for irradiated cordierite (? = 1 × 10¹² ions/cm²) was determined from single-crystal XRD measurements in the diamond anvil cell. The fitted third-order Birch–Murnaghan equation-of-state parameters of irradiated cordierite (V ₀ = 1548.41 ± 0.16 Å³, K ₀ = 117.1 ± 1.1 GPa, ?K/?P = ?0.6 ± 0.3) reveal a 10–11 % higher compressibility compared to non-irradiated cordierite. While the higher compressibility is attributed to the previously reported irradiation-induced loss of extra-framework H₂O, the anomalous elasticity as expressed by elastic softening (β _a ^?1 , β _b ^?1 , β _c ^?1  = 397 ± 9, 395 ± 28, 308 ± 11 GPa, ?(β ^?1)/?P = ?4.5 ± 2.7, ?6.6 ± 8.4, ?5.4 ± 3.0) appears to be related to the framework stability and to be independent of the water content in the channels and thus of the ion beam exposure.