Chemical characteristics of coastal rainwater from Puducherry to Neithavasal,Southeastern coast of India

The chemistry of the rainwater indirectly reflects the composition of the ions in the atmosphere. The study of the rainwater gains its own importance as it forms the basis for the agricultural, domestic and drinking water. Twelve rainwater samples were collected along the southeastern coast of India during southwest monsoon. The samples were analyzed for the major anions (Cl^?, SO₄ ^2?, PO₄ ^3? and HCO₃ ^?) and cations (Na⁺, K⁺, Ca²⁺ and Mg²⁺). The majority of the samples reflect acidic pH. The general dominance of the cations is in the order of Na⁺ > Ca²⁺ > K⁺ > Mg²⁺ and that of anions is HCO₃ ^? > Cl^? > SO₄ ^2? > PO₄ ^3?. The water is classified as calcium bicarbonate to sodium bicarbonate type. The decrease of pH value also increases the pCO₂. In order to study the impact of acidic and alkaline species on rainwater, correlation coefficients were determined for establishing the relationship between different ions. Good correlation was established between cations, and sulfate has no correlation with other ions and pH. Factor analysis reveals that land use pattern, marine source and methanogenesis from the tidal influenced mangroves play a major role in determining the rainwater chemistry of the region.     

Geochemistry and stable isotope investigation of acid mine drainage associated with abandoned coal mines in central Montana,USA

The Great Falls-Lewistown Coal Field (GFLCF) in central Montana contains over 400 abandoned underground coal mines, many of which are discharging acidic water with serious environmental consequences. Areas of the mines that are completely submerged by groundwater have circum-neutral pH and relatively low concentrations of metals, whereas areas that are only partially flooded or freely draining have acidic pH (< 3) and high concentrations of metals. The pH of the mine drains either decreases or increases after discharging to the surface, depending on the initial ratio of acidity (mainly Al and Fe²⁺) to alkalinity (mainly HCO₃^?). In acidic, Fe-rich waters, oxidation of Fe²⁺ after exposure to air is microbially catalyzed and follows zero-order kinetics, with computed rate constants falling in the range of 0.97 to 1.25 mmol L^? 1 h^? 1. In contrast, Fe²⁺ oxidation in near-neutral pH waters appears to be first-order with respect to Fe²⁺ concentration, although insufficient data were collected to constrain the rate law expression. Rates of Fe²⁺ oxidation in the field are dependent on temperature such that lower Fe²⁺ concentrations were measured in down-gradient waters during the day, and higher concentrations at night. Diel cycles in dissolved concentrations of Zn and other trace metals (Mn, Ni) were also noted for down-gradient waters that were net alkaline, but not in the acidic drains.The coal seams of the GFLCF and overlying Cretaceous sandstones form a perched aquifer that lies ~ 50 m above the regional water table situated in the underlying Madison Limestone. The δD and δ¹⁸O values of flooded mine waters suggest local derivation from meteoric water that has been partially evaporated in agricultural soils overlying the coal mines. The S and O isotopic composition of dissolved sulfate in the low pH mine drains is consistent with oxidation of biogenic pyrite in coal under aerated conditions. A clear distinction exists between the isotopic composition of sulfate in the acid mine waters and sulfate in the adjacent sedimentary aquifers, making it theoretically possible to determine if acid drainage from the coal mines has leaked into the underlying Madison aquifer.     

Proton and metal ion binding to natural organic polyelectrolytes—II. Preliminary investigation with a peat and a humic acid

A unified physico-chemical model, based on a modified Henderson-Hasselbalch equation, for the analysis of ion complexation reactions involving charged polymeric systems is presented and verified. In this model pH = pK_a+p(ΔK_a) + log(α/1 − α) where K_a is the intrinsic acid dissociation constant of the ionizable functional groups on the polymer, ΔK_a is the deviation of the intrinsic constant due to electrostatic interaction between the hydrogen ion and the polyanion, and alpha (α) is the polyacid degree of ionization. Using this approach pK_a values for repeating acidic units of polyacrylic (PAA) and polymethacrylic (PMA) acids were found to be 4.25 ± 0.03 and 4.8 ± 0.1, respectively. The polyion electrostatic deviation term derived from the potentiometric titration data (i.e. p(ΔK_a)) is used to calculate metal ion concentration at the complexation site on the surface of the polyanion. Intrinsic cobalt-polycarboxylate binding constants (7.5 for PAA and 5.6 for PMA), obtained using this procedure, are consistent with the range of published binding constants for cobalt-monomer carboxylate complexes. In two phase systems incorporation of a Donnan membrane potential term allows determination of the intrinsic pK_a of a cross-linked PMA gel, pK_a = 4.83, in excellent agreement with the value obtained for the linear polyelectrolyte and the monomer. Similarly, the intrinsic stability constant for cobalt ion binding to a PMA-gel (β_CoPMA+ = 11) was found to be in agreement with the linear polyelectrolyte analogue and the published data for cobalt-carboxylate monodentate complexes.     

Influence of different strain rates on hydro-mechanical behaviour of reconstituted unsaturated soil

The hydro-mechanical behaviour of a reconstituted unsaturated soil under different suctions and strain rates was studied through various rate-controlled unsaturated/undrained triaxial tests. The fully saturated reconstituted specimens were desaturated to four different initial suctions (s₀?=?0, 100 kPa, 200 kPa and 300 kPa) and then triaxially sheared (conventional triaxial compression) at three different strain rates in undrained conditions (\(\dot{\varepsilon }_{1} = 0.001\) h^?1, 0.01 h^?1, and 0.1 h^?1). The observed hydro-mechanical behaviour during shearing including the volumetric strain, deviatoric stress, degree of saturation and suction is presented and discussed in this paper. The results indicate that when the strain rate rises at the given initial suctions (or pore water pressures), the maximum deviatoric stress (q_max), critical net stress ratio (M) and critical state suction (s_c) increase but the degree of saturation (S_rc) and volumetric strain at the critical state (ε^c_v ) reduce. The critical effective stress ratio (M′) is not dependent on the strain rate for saturated and unsaturated samples. The critical state lines for unsaturated soils with the constant strain rates are parallel with each other in the e???lnp′ space.

     

Experimental study of octanol–water partition coefficients for2,4,6-trichlorophenol and pentachlorophenol: Derivation of an empirical model of chlorophenol partitioning behaviour

The octanol–water partition coefficients (log K_ow) of 2,4,6-trichlorophenol and pentachlorophenol were determined as functions of pH, ionic strength and aqueous metal content. For both chlorophenols, the log K_ow exhibits pH dependence in the range pK_a−1<pH<pK_a+3. At lower and higher pH values, the behaviour of the chlorophenols is independent of pH. The present data, in conjunction with that of pre-existing data, indicate that a linear relationship exists between log K_ow and log ionic strength of the aqueous solution for pentachlorophenol, and the data also suggest that aqueous metal–chlorophenolate complexation can significantly alter the partitioning behaviour. The data reported here was used to obtain an empirical model of the partitioning behaviour based on speciation of the aqueous chlorophenol. The model requires knowledge of the low pH partitioning behaviour, as well as the acidity constant for the particular chlorophenol of interest. Although K_ow values have been measured as a function of pH and/or ionic strength for only pentachlorophenol, the input parameters for our empirical model are readily accessible in the literature for many chlorophenols. The model greatly expands our ability to quantify the hydrophobicity of chlorophenols, enabling accurate estimations of the pH and ionic strength dependencies of the partitioning behaviour over a wide range of pH and ionic strength values of environmental interest.     

Assessment of hydrogeochemical processes in a coastal region: Application of multivariate statistical model

Hydrogeochemical studies have been carried out in a coastal region, using multivariate statistical model, for better understanding the controlling processes that influence the aquifer chemistry. Two principal components (PC1 and PC2) are extracted from the data set of chemical variables (pH, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO ₃ ^? , Cl^?, SO ₄ ^2? , NO ₃ ^? and F^?), which account for 79% of the total variation in the quality of groundwater. The PC1 (salinity controlled process) includes the concentrations of TDS, Mg²⁺, Na⁺, K⁺, Cl^?, SO ₄ ^2? and NO ₃ ^? , while the PC2 (alkalinity controlled process) comprises the concentrations of pH, HCO ₃ ^? and F^?. The spatial distribution of PC scores identifies the locations of high salinity and alkalinity processes. The first process corresponds to the influences of geogenic, anthropogenic and marine sources, and the second one to the influence of water-soil-rock interaction. Thus, the present study shows the usefulness of multivariate statistical model as an effective means of interpretation of spatial controlling processes of groundwater chemistry.     

Thermoelasticity and high-<Emphasis Type="Italic">T</Emphasis> behaviour of anthophyllite

The thermoelastic behaviour of anthophyllite has been determined for a natural crystal with crystal-chemical formula ^ANa_0.01 ^B(Mg_1.30Mn_0.57Ca_0.09Na_0.04) ^C(Mg_4.95Fe_0.02Al_0.03) ^T(Si_8.00)O₂₂ ^W(OH)₂ using single-crystal X-ray diffraction to 973 K. The best model for fitting the thermal expansion data is that of Berman (J Petrol 29:445–522, 1988) in which the coefficient of volume thermal expansion varies linearly with T as α _V,T  = a ₁ + 2a ₂ (T − T ₀): α₂₉₈ = a ₁ = 3.40(6) × 10⁻⁵ K⁻¹, a ₂ = 5.1(1.0) × 10⁻⁹ K⁻². The corresponding axial thermal expansion coefficients for this linear model are: α _a ,₂₉₈ = 1.21(2) × 10⁻⁵ K⁻¹, a _2,a  = 5.2(4) × 10⁻⁹ K⁻²; α _b ,₂₉₈ = 9.2(1) × 10⁻⁶ K⁻¹, a _2,b  = 7(2) × 10⁻¹⁰ K⁻². α _c ,₂₉₈ = 1.26(3) × 10⁻⁵ K⁻¹, a _2,c  = 1.3(6) × 10⁻⁹ K⁻². The thermoelastic behaviour of anthophyllite differs from that of most monoclinic (C2/m) amphiboles: (a) the ε ₁ − ε ₂ plane of the unit-strain ellipsoid, which is normal to b in anthophyllite but usually at a high angle to c in monoclinic amphiboles; (b) the strain components are ε ₁ ≫ ε ₂ > ε ₃ in anthophyllite, but ε ₁ ~ ε ₂ ≫ ε ₃ in monoclinic amphiboles. The strain behaviour of anthophyllite is similar to that of synthetic C2/m ^ANa ^B(LiMg) ^CMg₅ ^TSi₈ O₂₂ ^W(OH)₂, suggesting that high contents of small cations at the B-site may be primarily responsible for the much higher thermal expansion ⊥(100). Refined values for site-scattering at M4 decrease from 31.64 epfu at 298 K to 30.81 epfu at 973 K, which couples with similar increases of those of M1 and M2 sites. These changes in site scattering are interpreted in terms of Mn ↔ Mg exchange involving M1,2 ↔ M4, which was first detected at 673 K.     

In situ high-temperature powder X-ray diffraction study on the spinel solid solutions (Mg1?xMnx)Cr2O4

Using a conventional high-T furnace, the solid solutions between magnesiochromite and manganochromite, (Mg_1−x Mn _x )Cr₂O₄ with x = 0.00, 0.19, 0.44, 0.61, 0.77 and 1.00, were synthesized at 1,473 K for 48 h in open air. The ambient powder X-ray diffraction data suggest that the V–x relationship of the spinels does not show significant deviation from the Vegard’s law. In situ high-T powder X-ray diffraction measurements were taken up to 1,273 K at ambient pressure. For the investigated temperature range, the unit-cell parameters of the spinels increase smoothly with temperature increment, indicating no sign of cation redistribution between the tetrahedral and octahedral sites. The V–T data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (a_T = a₀ + a₁ T + a₂ T ^{- 2} \alpha_{T} = a_{0} + a_{1} T + a_{2} T^{ - 2} ), which yielded insignificant a ₂ values. The effect of the composition on a ₀ is adequately described by the equation a ₀ = [17.7(8) − 2.4(1) × x] 10⁻⁶ K⁻¹, whereas that on a ₁ by the equation a ₁ = [8.6(9) + 2.1(11) × x] 10⁻⁹ K⁻².     

Acidic deposition impacts mediated by sulfur cycling in a coastal plain forest ecosystem

Deposition in the New Jersey Pinelands was very acidic (pH=4.17) and contained high levels of SO₂ ⁻² based on bulk deposition measurementsfrom July 1984–July 1986. Streamwater over the same interval in undisturbed watersheds was less acidic (pH =4.52) and had proportionately less SO₄ ⁻². A preliminary alkalinity budget for undisturbed watersheds suggested that SO₄ ⁻² retention within Pinelands watersheds accounted for a large portion of the total alkalinity generated and thereby lessened the impact of acidic deposition on surface waters. The only process capable of explaining the retention of SO₄ ⁻² was microbial sulfate reduction in the extensive wetlands surrounding Pinelands streams which occurred at high rates.     

Fluoride-bearing groundwater in Gummanampadu Sub-basin, Guntur District, Andhra Pradesh, India

The functional factors responsible for fluoride (F^?)-bearing groundwater used for drinking as well as for cooking in the area of Gummanampadu Sub-basin, Guntur District, Andhra Pradesh, India are discussed. The study area is a part of an Archean Gneissic Complex, consisting of banded-biotite-hornblende-gneisses, over which the Proterozoic Cumbhum quartzites, shales, phyllites, and dolomitic limestones occur. The chemistry of groundwater is dominated by carbonates (HCO₃ ^? and CO₃ ^2?) at a higher pH. This results in a higher total alkalinity over total hardness, causing an excess alkalinity. Sodium ion is dominated among the cations (Ca²⁺, Mg²⁺, and K⁺). The concentration of F^? (2.1–3.7 mg/L) is higher than that of desirable national limit (1.2 mg/L) prescribed for drinking purpose. A significant positive correlation exists between F^? and pH as well as that between F^? and HCO₃ ^? + CO₃ ^2?. This indicates that the alkaline condition is the prime conducive factor for dissolving F^?-bearing minerals more effectively leading to a higher concentration of F^? in the groundwater. Furthermore, a positive chloro-alkaline index reflects the ion exchange, and an oversaturation with respect to CaCO₃ indicates the evaporation. In addition, a negative relation between the well depth and F^? shows the effect of solubility and/or leaching of salts in different depth levels. These factors regulate the concentration of F^? in the groundwater. On the other hand, a positive correlation of F^? with SO₄ ^2? as well as with K⁺ shows the human land use activities (namely, use of chemical fertilizers, disposal of domestic wastes, etc.), which add F^? to the groundwater. A significant number of the residents of the study area suffer from the health disorders related to fluorosis, which is a consequence of higher concentration of F^? in the drinking water. Thus, this study emphasizes the need for supply of safe drinking water, nutritional diet, rainwater-harvesting structures, and public education to realize “health for all” motto of World Health Organization.     

Inorganic speciation of dissolved elements in seawater: the influence of pH on concentration ratios

Assessments of inorganic elemental speciation in seawater span the past four decades. Experimentation, compilation and critical review of equilibrium data over the past forty years have, in particular, considerably improved our understanding of cation hydrolysis and the complexation of cations by carbonate ions in solution. Through experimental investigations and critical evaluation it is now known that more than forty elements have seawater speciation schemes that are strongly influenced by pH. In the present work, the speciation of the elements in seawater is summarized in a manner that highlights the significance of pH variations. For elements that have pH-dependent species concentration ratios, this work summarizes equilibrium data (S = 35, t = 25°C) that can be used to assess regions of dominance and relative species concentrations. Concentration ratios of complex species are expressed in the form log[A]/[B] = pH - C where brackets denote species concentrations in solution, A and B are species important at higher (A) and lower (B) solution pH, and C is a constant dependent on salinity, temperature and pressure. In the case of equilibria involving complex oxy-anions (MO _x (OH) _y ) or hydroxy complexes (M(OH) _n ), C is written as pK _n = -log K _n or pK _n * = -log K _n * respectively, where K _n and K _n * are equilibrium constants. For equilibria involving carbonate complexation, the constant C is written as pQ = -log(K ₂ ^l K _n [HCO₃ ^-]) where K ₂ ^l is the HCO₃ ^- dissociation constant, K _n is a cation complexation constant and [HCO₃ ^-] is approximated as 1.9 × 10^-3 molar. Equilibrium data expressed in this manner clearly show dominant species transitions, ranges of dominance, and relative concentrations at any pH.     

Reaction time scales for sulphate reduction in sediments of acidic pit lakes and its relation to in-lake acidity neutralisation

Sulphate reduction is a key reaction to remove acidity from water bodies affected by acid mine drainage. In this study, ³⁵SSO₄²⁻ reduction rates determined in sediments from a variety of acidic lignite pit lakes have been compiled. The rates decreased with pH and are strongly dependent on carbon substrate. The rates were fitted to a Monod model adapted to the specific conditions of acidic pit lakes (APL) sediments: i) sulphate reduction rate is independent from sulphate concentration due to the high concentration typically observed in APL systems (10–30 mM), ii) the observed pH dependency of sulphate reduction was accounted for by an inhibition function F_inihibt which considers the occurrence of low cell numbers of sulphate reducing bacteria at pH values < 4.75. Simulated steady-state sulphate reduction rates are predicting measured rates at carbon substrate concentrations of <10 μM. Estimated steady-state reaction time scales range between 2.4 h at pH 7 and 41 h at pH 3 at a carbon half-saturation constant of K_C−S = 100 μM and are increasing with increasing K_C−S values. Time scales at low pH are too long to allow for significant generation of alkalinity during the time of residence of groundwater passing through the top and hence most reactive zone of APL sediments which has important implications for the remediation of acidic pit lakes.     

Kinetics of Au (III) extraction by DBC from hydrochloric solution using Lewis cell

The kinetics of forward extraction [AuCl₄]^? from aqua regia medium by diethylene glycol dibutyl ether (DBC) have been investigated by the Lewis cell (LC) technique. At first gold extraction has been carried out under different experimental conditions for achieving the stoichiometry coefficients and the value of the extraction equilibrium constant (K = 0.1). For kinetic data treatment, flux ‘F’ method has been applied. Reaction order with respect to DBC, pH and [AuCl₄]^? was determined and then the rate constant was calculated. The rate of gold extraction from 2 M chloride medium can be expressed as F = 10^0.88[AuCl₄^?]^1.25 [DBC]^0.4 [H⁺]^?0.22. Kinetics data were treated by EVIEWS software and coefficients were obtained. The comparison of manual and software results indicated that the results had good conformity. Influence of temperature was studied and then activation energy, E_a, (11.17 kJ/mol), activation enthalpy (11.66 kJ/mol) and entropy (?187 J/mol K) were calculated by using Arrhenius and activation complex theory respectively. E_a value (< 20.9 kJ/mol) indicates that, the extraction of gold (III) in the investigated system is controlled by diffusion process.     

Is bicarbonate directly used as substrate to participate in photosynthetic oxygen evolution

If the photosynthetic organisms assimilated only CO₂ in the Archean atmosphere, hydroxide ion in the Archean seawater would not increase. If plants would not consume bicarbonate as a direct substrate during photosynthesis, it is difficult to explain the evolution of Earth's environment. To date, it is generally accepted that photosynthetic O₂ evolution of plants come from water photolysis. However, it should be debated by evaluating the effect of bicarbonate in photosynthetic O₂ evolution, analyzing the role of carbonic anhydrase (CA) in photosynthetic O₂ evolution, and the relationship between thylakoid CA and photosynthetic O₂ evolution. In the paper, I propose that bicarbonate is directly used as substrate to participate in photosynthetic O₂ evolution. The rationality of bicarbonate photolysis of plants is discussed from the thermodynamics and evolution of Earth's environment. The isotopic evidence that bicarbonate is not the direct substrate of photosynthetic O₂ release is reexamined, and the new explanation of bicarbonate photolysis in photosynthetic O₂ evolution is proposed.

     

Untersuchungen über das Gleichgewicht zwischen K-Feldspat,Quarz und Muskovit und die Anwendung auf Fragen der Gesteinsbildung bei tieferen Temperaturen

During equilibration of K-feldspar, quartz and muscovite with dilute KCl-solutions, the change in pH of the solution was measured as a function of time. The resulting equilibrium constant, K _T = ^aK + /^aH +, is 10^4.21±0.06, 10^5.86±0.03 and 10^6.01±0.03 at 300, 60 and 30° C respectively (standard states at 1 bar) and are consistent with the best higher temperature data. At 30° C this constant is consistent with the ^aK + /^aH + ratio of seawater. From K _T and the activity of K ⁺ in seawater, a pH of 8.2 is calculated, essentially identical with the pH which results from dissolution of CaCO₃ under atmospheric CO₂-pressure. Consequently, detrital K-feldspar, quartz, muscovite, and calcite are stable in seawater. Apparently, the seawater pH is controlled by CaCO₃ as well as K-feldspar, quartz and muscovite. Independently both equilibria show virtually the same pH, within the variability due to disordering, solid solution and surface energy effects.Assuming that the K-concentrations of pore solutions vary between about 4000 and 40 ppm, these solutions have alkalic pH-values in the temperature range between 30 and 300° C if K-feldspar, quartz and muscovite are present. In limestones the pH is fixed by the dissociation of CaCO₃; the occasionally observed formation of K-feldspar in these rocks requires a minimum K-concentration of approximately 4 ppm.

---

---

Die Untersuchungen wurden am Department of Mineralogy and Geochemistry der Pennsylvania State University durchgeführt. Der erste Autor (H. E. Usdowski) bedankt sich für die freundliche Aufnahme und die ausgezeichneten Arbeitsmöglichkeiten. Besonderer Dank gilt Dr. George Helz für viele Diskussionen und manche Hilfe im Labor. Die Deutsche Forschungsgemeinschaft hat die Untersuchungen durch einen Forschungsauftrag unterstützt.     

The airborne contagiousness of respiratory viruses: A comparative analysis and implications for mitigation

The infectious emission rate is a fundamental input parameter for airborne transmission risk assessment, but data are limited due to reliance on estimates from chance superspreading events. This study assesses the strength of a predictive estimation approach developed by the authors for SARS-CoV-2 and uses novel estimates to compare the contagiousness of respiratory pathogens. We applied the approach to SARS-CoV-1, SARS-CoV-2, MERS, measles virus, adenovirus, rhinovirus, coxsackievirus, seasonal influenza virus and Mycobacterium tuberculosis (TB) and compared quanta emission rate (ER_q) estimates to literature values. We calculated infection risk in a prototypical classroom and barracks to assess the relative ability of ventilation to mitigate airborne transmission. Our median standing and speaking ER_q estimate for SARS-CoV-2 (2.7 quanta h^?1) is similar to active, untreated TB (3.1 quanta h^?1), higher than seasonal influenza (0.17 quanta h^?1), and lower than measles virus (15 quanta h^?1). We calculated event reproduction numbers above 1 for SARS-CoV-2, measles virus, and untreated TB in both the classroom and barracks for an activity level of standing and speaking at low, medium and high ventilation rates of 2.3, 6.6 and 14 L per second per person (L s^–1 p^–1), respectively. Our predictive ER_q estimates are consistent with the range of values reported over decades of research. In congregate settings, current ventilation standards are unlikely to control the spread of viruses with upper quartile ER_q values above 10 quanta h^?1, such as SARS-CoV-2, indicating the need for additional control measures.     

Equations of state of magnesium silicates anhydrous B and superhydrous B

High-pressure single crystal X-ray diffraction experiments of phase anhydrous B and superhydrous B have been carried out to 7.3 and 7.7?GPa, respectively, at room temperature. Fitting a third-order Birch-Murnaghan equation of state to the P-V data yields values of V ₀?=?838.86?±?0.04?ų, K_T,0?=?151.5?±?0.9?GPa and K′?=?5.5?±?0.3 for Anhy-B and V ₀?=?624.71?± 0.03?ų, K_T,0?=?142.6?±?0.8?GPa and K′?=?5.8?±?0.2 for Shy-B. A similar analysis of the axial compressibilities in Anhy-B reveals that the c-axis is most compressible (K_c?=?137?±?3?GPa), the b-axis is least compressible (K_b?=?175?±?4?GPa), and the a-axis is intermediate (K_a?=?148?±?1?GPa). In Shy-B, the a-axis is most compressible (K_a?=?135?±?1?GPa), followed by the b- and c-axes which have similar compressibilities (K_b?=?146?±?3?GPa; K_c?=?148?±?3?GPa). The fact that the b-axis of Shy-B is approximately 16% more compressible than Anhy-B is primarily due to differences in the O-T layer in which the H atoms are located and the linkages with the adjacent O layers. The rigid edge-sharing chains of MgO₆ and SiO₆ octahedra in the O layer control compressibility along the a- and c-axes in both structures. The net result is a reduction in the overall anisotropic compression from ～22% in Anhy-B to ～9% in Shy-B.     

The thermoelastic behavior of clintonite up to 10?GPa and 1,000°C

The thermoelastic behavior of a natural clintonite-1M [with composition: Ca_1.01(Mg_2.29Al_0.59Fe_0.12)_Σ3.00(Si_1.20Al_2.80)_Σ4.00O₁₀(OH)₂] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 457.1(2) ?³, K _T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K _T0(a) = 0.0023(1) GPa⁻¹; β(b) = 1/3K _T0(b) = 0.0018(1) GPa⁻¹; β(c) = 1/K _T0(c) = 0.0072(3) GPa⁻¹]. The β-angle increases in response to the applied P, with: β_P = β₀ + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K _T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α₀ + α₁ T ^−1/2. The refined parameters for clintonite are as follows: α₀ = 2.78(4) 10⁻⁵°C⁻¹ and α₁ = −4.4(6) 10⁻⁵°C^1/2 for the unit-cell volume; α₀(a) = 1.01(2) 10⁻⁵°C⁻¹ and α₁(a) = −1.8(3) 10⁻⁵°C^1/2 for the a-axis; α₀(b) = 1.07(1) 10⁻⁵°C⁻¹ and α₁(b) = −2.3(2) 10⁻⁵°C^1/2 for the b-axis; and α₀(c) = 0.64(2) 10⁻⁵°C⁻¹ and α₁(c) = −7.3(30) 10⁻⁶°C^1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.     

Elasticity and equation of state of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>

A single crystal X-ray diffraction study on lithium tetraborate Li₂B₄O₇ (diomignite, space group I4₁ cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I4₁ cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V ₀  = 923.21(6) ų, K ₀  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a ₀  = 9.4747(3) Å, K _0a  = 73.3(9) GPa, K′ _a  = 5.1(3) and c ₀  = 10.2838(4) Å, K _0c  = 24.6(3) GPa, K′ _c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li₂B₄O₇ is very large with the zero-pressure compressibility ratio β _0c /β _0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B₄O₇]²⁻ forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B₄O₇]²⁻ units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).