The effect of liquid composition on the partitioning of Ni between olivine and silicate melt

We report the results of experiments designed to separate the effects of temperature and pressure from liquid composition on the partitioning of Ni between olivine and liquid, \(D_{\text{Ni}}^{\text{ol/liq}}\). Experiments were performed from 1300 to 1600 °C and 1 atm to 3.0 GPa, using mid-ocean ridge basalt (MORB) glass surrounded by powdered olivine in graphite–Pt double capsules at high pressure and powdered MORB in crucibles fabricated from single crystals of San Carlos olivine at one atmosphere. In these experiments, pressure and temperature were varied in such a way that we produced a series of liquids, each with an approximately constant composition (~12, ~15, and ~21 wt% MgO). Previously, we used a similar approach to show that \(D_{\text{Ni}}^{\text{ol/liq}}\) for a liquid with ~18 wt% MgO is a strong function of temperature. Combining the new data presented here with our previous results allows us to separate the effects of temperature from composition. We fit our data based on a Ni–Mg exchange reaction, which yields \(\ln \left( {D_{\text{Ni}}^{\text{molar}} } \right) = \frac{{ -\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{RT} + \frac{{\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{R} - \ln \left( {\frac{{X_{\text{MgO}}^{\text{liq}} }}{{X_{{{\text{MgSi}}_{ 0. 5} {\text{O}}_{ 2} }}^{\text{ol}} }}} \right).\) Each subset of constant composition experiments displays roughly the same temperature dependence of \(D_{\text{Ni}}^{\text{ol/liq}}\) (i.e.,\(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\)) as previously reported for liquids with ~18 wt% MgO. Fitting new data presented here (15 experiments) in conjunction with our 13 previously published experiments (those with ~18 wt% MgO in the silicate liquid) to the above expression gives \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 3641 ± 396 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 1.597 ± 0.229. Adding data from the literature yields \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 4505 ± 196 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 2.075 ± 0.120, a set of coefficients that leads to a predictive equation for \(D_{\text{Ni}}^{\text{ol/liq}}\) applicable to a wide range of melt compositions. We use the results of our work to model the melting of peridotite beneath lithosphere of varying thickness and show that: (1) a positive correlation between NiO in magnesian olivine phenocrysts and lithospheric thickness is expected given a temperature-dependent \(D_{\text{Ni}}^{\text{ol/liq}} ,\) and (2) the magnitude of the slope for natural samples is consistent with our experimentally determined temperature dependence. Alternative processes to generate the positive correlation between NiO in magnesian olivines and lithospheric thickness, such as the melting of olivine-free pyroxenite, are possible, but they are not required to explain the observed correlation of NiO concentration in initially crystallizing olivine with lithospheric thickness.     

Strain responses of frozen clay with thermal gradient under triaxial creep

Thermal gradient is one of the main features for the temperature distribution in artificial frozen shaft lining (FSL). The time-dependent strain responses and the corresponding heterogeneity characteristics of frozen soils with thermal gradient are of potential significance for stability assessment and prediction of FSL, especially of the FSL embedded in thick alluvium. A series of triaxial creep tests were carried out on frozen saturated clay under various thermal gradients and creep stresses. The experimental results indicated that the triaxial creep curves for frozen clay with thermal gradient exhibit viscous characteristics, and the creep rate \(\Delta \varepsilon_{\text{a}} /\Delta t\) decreases with the increase in creep time \(t\) and decrease in thermal gradient. The stress–strain curve under different \(t\) showed that the creep stress has a marked growth when axial strain \(\varepsilon_{\text{a}} \le 1\,\%\). However, when \(\varepsilon_{\text{a}} \ge 1\,\%\), the growth rate decreases gradually. The deviation between measured radial strain \(\varepsilon_{\text{r}}^{\text{m}}\) under the middle specimen section height SSH and the calculated radial strain \(\varepsilon_{\text{r}}^{\text{c}}\) from the volumetric strain increases following a unified equation with the increase in axial strain. The radial strain \(\varepsilon_{\text{r}}^{\text{f}}\) for frozen clay with thermal gradient after experiment increases with the increase in SSH, and the slope of \( \varepsilon_{\text{r}}^{\text{f}} - {\text{SSH}} \) curve is significantly dependent on the thermal gradient and creep stress. The variation of \(\varepsilon_{\text{r}}^{\text{m}} - \varepsilon_{\text{r}}^{\text{c }}\) during experiment and \(\varepsilon_{\text{r}}^{\text{f}}\) distribution after experiment are the macro-responses of internal micro-heterogeneities in frozen soils induced from thermal gradient, and are closely related to strain rate and its variation. These observations and findings provide an insight into the creep mechanism and the estimation method of creep deformation for frozen soils with thermal gradient.     

Stress-dependent hydraulic properties of clayey-silt aquitards in eastern Australia

Clayey-silt aquitards account for 60 % of the ~100-m-thick alluvial sediment sequence in the Gunnedah area of eastern Australia. To better understand the stress-dependent hydraulic properties of these low-permeability units, oedometer test data presented for the first time in this study have been integrated with geotechnical centrifuge permeameter tests. Estimates of vertical pre-consolidation effective stress (\(\sigma_{\text{p}}^{'}\)), vertical in situ effective stress (\(\sigma_{\text{i}}^{'}\)), and over-consolidation ratio (OCR) were used to determine whether centrifugation stresses caused compression of core samples, and the degree to which vertical hydraulic conductivity (K _v) assessments were representative of the core samples tested. Results suggest that minimally disturbed drill core from semi-consolidated sediments (e.g., alluvial, colluvial, and eolian deposits) evaluated in this study should have target centrifugation stress less than \(\sigma_{\text{p}}^{'}, \) where OCR < 1 and \(\sigma_{\text{i}}^{'}\) where OCR > 1 to avoid significant changes in hydraulic properties during plastic straining. The results also imply that the stress-dependent response of aquitards is critical to understand the sensitivity of groundwater resources in areas with multiple stakeholders such as mining, coal seam gas, and agriculture developments. Groundwater in alluvial sediments that is essential for irrigation, water supply, and base flows to rivers must be sufficiently disconnected from groundwater in coal seams that are depressurized for extraction of energy resources.     

The high-pressure stability of chlorite and other hydrates in subduction mélanges: experiments in the system Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

The solubility of chromium in chlorite as a function of pressure, temperature, and bulk composition was investigated in the system Cr₂O₃–MgO–Al₂O₃–SiO₂–H₂O, and its effect on phase relations evaluated. Three different compositions with X _Cr = Cr/(Cr + Al) = 0.075, 0.25, and 0.5 respectively, were investigated at 1.5–6.5 GPa, 650–900 °C. Cr-chlorite only occurs in the bulk composition with X _Cr = 0.075; otherwise, spinel and garnet are the major aluminous phases. In the experiments, Cr-chlorite coexists with enstatite up to 3.5 GPa, 800–850 °C, and with forsterite, pyrope, and spinel at higher pressure. At P > 5 GPa other hydrates occur: a Cr-bearing phase-HAPY (Mg_2.2Al_1.5Cr_0.1Si_1.1O₆(OH)₂) is stable in assemblage with pyrope, forsterite, and spinel; Mg-sursassite coexists at 6.0 GPa, 650 °C with forsterite and spinel and a new Cr-bearing phase, named 11.5 Å phase (Mg:Al:Si = 6.3:1.2:2.4) after the first diffraction peak observed in high-resolution X-ray diffraction pattern. Cr affects the stability of chlorite by shifting its breakdown reactions toward higher temperature, but Cr solubility at high pressure is reduced compared with the solubility observed in low-pressure occurrences in hydrothermal environments. Chromium partitions generally according to \(X_{\text{Cr}}^{\text{spinel}}\) ? \(X_{\text{Cr}}^{\text{opx}}\) > \(X_{\text{Cr}}^{\text{chlorite}}\) ≥ \(X_{\text{Cr}}^{\text{HAPY}}\) > \(X_{\text{Cr}}^{\text{garnet}}\). At 5 GPa, 750 °C (bulk with X _Cr = 0.075) equilibrium values are \(X_{\text{Cr}}^{\text{spinel}}\) = 0.27, \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.08, \(X_{\text{Cr}}^{\text{garnet}}\) = 0.05; at 5.4 GPa, 720 °C \(X_{\text{Cr}}^{\text{spinel}}\) = 0.33, \(X_{\text{Cr}}^{\text{HAPY}}\) = 0.06, and \(X_{\text{Cr}}^{\text{garnet}}\) = 0.04; and at 3.5 GPa, 850 °C \(X_{\text{Cr}}^{\text{opx}}\) = 0.12 and \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.07. Results on Cr–Al partitioning between spinel and garnet suggest that at low temperature the spinel- to garnet-peridotite transition has a negative slope of 0.5 GPa/100 °C. The formation of phase-HAPY, in assemblage with garnet and spinel, at pressures above chlorite breakdown, provides a viable mechanism to promote H₂O transport in metasomatized ultramafic mélanges of subduction channels.     

Semi-empirical model for retrieval of soil moisture using RISAT-1 C-Band SAR data over a sub-tropical semi-arid area of Rewari district,Haryana (India)

We have estimated soil moisture (SM) by using circular horizontal polarization backscattering coefficient (\(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\)), differences of circular vertical and horizontal \(\sigma ^{\mathrm{o}} \, (\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}})\) from FRS-1 data of Radar Imaging Satellite (RISAT-1) and surface roughness in terms of RMS height (\({\hbox {RMS}}_{\mathrm{height}}\)). We examined the performance of FRS-1 in retrieving SM under wheat crop at tillering stage. Results revealed that it is possible to develop a good semi-empirical model (SEM) to estimate SM of the upper soil layer using RISAT-1 SAR data rather than using existing empirical model based on only single parameter, i.e., \(\sigma ^{\mathrm{o}}\). Near surface SM measurements were related to \(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\), \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}}\) derived using 5.35 GHz (C-band) image of RISAT-1 and \({\hbox {RMS}}_{\mathrm{height}}\). The roughness component derived in terms of \({\hbox {RMS}}_{\mathrm{height}}\) showed a good positive correlation with \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}} \, (R^{2} = 0.65)\). By considering all the major influencing factors (\(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\), \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}}\), and \({\hbox {RMS}}_{\mathrm{height}}\)), an SEM was developed where SM (volumetric) predicted values depend on \(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\), \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}}\), and \({\hbox {RMS}}_{\mathrm{height}}\). This SEM showed \(R^{2}\) of 0.87 and adjusted \(R^{2}\) of 0.85, multiple R=0.94 and with standard error of 0.05 at 95% confidence level. Validation of the SM derived from semi-empirical model with observed measurement (\({\hbox {SM}}_{\mathrm{Observed}}\)) showed root mean square error (RMSE) = 0.06, relative-RMSE (R-RMSE) = 0.18, mean absolute error (MAE) = 0.04, normalized RMSE (NRMSE) = 0.17, Nash–Sutcliffe efficiency (NSE) = 0.91 (\({\approx } 1\)), index of agreement (d) = 1, coefficient of determination \((R^{2}) = 0.87\), mean bias error (MBE) = 0.04, standard error of estimate (SEE) = 0.10, volume error (VE) = 0.15, variance of the distribution of differences \(({\hbox {S}}_{\mathrm{d}}^{2}) = 0.004\). The developed SEM showed better performance in estimating SM than Topp empirical model which is based only on \(\sigma ^{\mathrm{o}}\). By using the developed SEM, top soil SM can be estimated with low mean absolute percent error (MAPE) = 1.39 and can be used for operational applications.     

Cu diffusivity in granitic melts with application to the formation of porphyry Cu deposits

We report new experimental data of Cu diffusivity in granite porphyry melts with 0.01 and 3.9 wt% H₂O at 0.15–1.0 GPa and 973–1523 K. A diffusion couple method was used for the nominally anhydrous granitic melt, whereas a Cu diffusion-in method using Pt₉₅Cu₅ as the source of Cu was applied to the hydrous granitic melt. The diffusion couple experiments also generate Cu diffusion-out profiles due to Cu loss to Pt capsule walls. Cu diffusivities were extracted from error function fits of the Cu concentration profiles measured by LA-ICP-MS. At 1 GPa, we obtain \({D_{{\text{Cu, dry, 1 GPa}}}}=\exp \left[ {( - {\text{13.89}} \pm {\text{0.42}}) - \frac{{{\text{12878}} \pm {\text{540}}}}{T}} \right],\) and \({D_{{\text{Cu, 3}}{\text{.9 wt\% }}{{\text{H}}_{\text{2}}}{\text{O}},{\text{ 1 GPa}}}}=\exp \left[ {( - 16.31 \pm 1.30) - \frac{{{\text{8148}} \pm {\text{1670}}}}{T}} \right],\) where D is Cu diffusivity in m²/s and T is temperature in K. The above expressions are in good agreement with a recent study on Cu diffusion in rhyolitic melt using the approach of Cu₂S dissolution. The observed pressure effect over 0.15–1.0 GPa can be described by an activation volume of 5.9 cm³/mol for Cu diffusion. Comparison of Cu diffusivity to alkali diffusivity and its variation with melt composition implies fourfold-coordinated Cu⁺ in silicate melts. Our experimental results indicate that in the formation of porphyry Cu deposits, the diffusive transport of magmatic Cu to sulfide liquids or fluid bubbles is highly efficient. The obtained Cu diffusivity data can also be used to assess whether equilibrium Cu partitioning can be reached within certain experimental durations.     

New paleomagnetic results on $$\sim $$2367 Ma Dharwar giant dyke swarm,Dharwar craton,southern India: implications for Paleoproterozoic continental reconstruction

Here we report new paleomagnetic results and precise paleopole position of the extensional study on \(\sim \)2367 Ma mafic giant radiating dyke swarm in the Dharwar craton, southern India. We have sampled 29 sites on 12 dykes from NE–SW Karimnagar–Hyderabad dykes and Dhone–Gooty sector dykes, eastern Dharwar craton to provide unambiguous paleomagnetism evidence on the spectacular radiating dyke swarm and thereby strengthening the presence of single magmatic event at \(\sim \)2367 Ma. A total of 158 samples were subjected to detailed alternating field and thermal demagnetization techniques and the results are presented here along with previously reported data on the same dyke swarm. The remanent magnetic directions are showing two components, viz., seven sites representing four dykes show component (A) with mean declination of \(94{{}^{\circ }}\) and mean inclination of \(-\,70{{}^{\circ }}\) (\(\hbox {k}=87\), \(\upalpha _{95}=10{{}^{\circ }}\)) and corresponding paleopole at \(16{{}^{\circ }}\hbox {N}\), \(41{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=15{{}^{\circ }}\) and \(\hbox {dm}=17{{}^{\circ }}\)) and 22 sites representing 8 dykes yielded a component (B) with mean declination of \(41{{}^{\circ }}\) and mean inclination of \(-\,21{{}^{\circ }}\) (\(\hbox {k}=41\), \(\upalpha _{95}=9{{}^{\circ }}\)) with a paleopole at \(41{{}^{\circ }}\hbox {N}\), \(200{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=5{{}^{\circ }}\) and \(\hbox {dm}=10{{}^{\circ }}\)). Component (A) results are similar to the previously reported directions from the \(\sim \)2367 Ma dyke swarm, which have been confirmed fairly reliably to be of primary origin. The component (B) directions appear to be strongly overprinted by the 2080 Ma event. The grand mean for the primary component (A) combined with earlier reported studies gives mean declination of \(97{{}^{\circ }}\) and mean inclination of \(-\,79{{}^{\circ }}\) (\(\hbox {k}=55\), \(\upalpha _{95}=3{{}^{\circ }}\)) with a paleopole at \(15{{}^{\circ }}\hbox {N}\), \(57{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=5{{}^{\circ }}\), \(\hbox {dm}=6{{}^{\circ }}\)). Paleogeographical position for the Dharwar craton at \(\sim \)2367 Ma suggests that there may be a chance to possible spatial link between Dharwar dykes of Dharwar craton (India), Widgemooltha and Erayinia dykes of Yilgarn craton (Australia), Sebanga Poort Dykes of Zimbabwe craton (Africa) and Karelian dykes of Kola-Karelia craton (Baltica Shield).     

Characteristics of surface ozone in Agra,a sub-urban site in Indo-Gangetic Plain

In the present study, measurements of surface ozone (\(\hbox {O}_{3}\)) and its precursors (NO and \(\hbox {NO}_{2}\)) were carried out at a sub-urban site of Agra (\(27{^{\circ }}10'\hbox {N}\), \(78{^{\circ }}05'\hbox {E}\)), India during May 2012–May 2013. During the study period, average concentrations of \(\hbox {O}_{3}\), NO, and \(\hbox {NO}_{2}\) were \(39.6 \pm 25.3\), \(0.8 \pm 0.8\) and \(9.1 \pm 6.6 \, \hbox {ppb}\), respectively. \(\hbox {O}_{3}\) showed distinct seasonal variation in peak value of diurnal variation: summer \({>}\) post-monsoon \({>}\) winter \({>}\) monsoon. However, \(\hbox {NO}_{2}\) showed highest levels in winter and lowest in monsoon. The average positive rate of change of \(\hbox {O}_{3}\) (08:00–11:00 hr) was highest in April (16.3 ppb/hr) and lowest in August (1.1 ppb/hr), while average negative rate of change of \(\hbox {O}_{3}\) (17:00–19:00 hr) was highest in December (–13.2 ppb/hr) and lowest in July (–1.1 ppb/hr). An attempt was made to identify the \(\hbox {VOC--NO}_{\mathrm{x}}\) sensitivity of the site using \(\hbox {O}_{3}/\hbox {HNO}_{3}\) ratio as photochemical indicator. Most of the days this ratio was above the threshold value (12–16), which suggests \(\hbox {NO}_{\mathrm{x}}\) sensitivity of the site. The episodic event of ozone was characterized through meteorological parameters and precursors concentration. Fine particles (\(\hbox {PM}_{2.5}\)) cause loss of ozone through heterogeneous reactions on their surface and reduction in solar radiation. In the study, statistical analyses were used to estimate the amount of ozone loss.     

Principle of Formation of the Earth’s Crust under Natural Stress Conditions

This article formulates the experimentally substantiated physical principle that the natural stress condition of the Earth’s crust is formed due to the superposition of stress fields, which is caused by the gravitational forces of the Earth and by tectonic and astrophysical forces that are produced by physical processes in space. The natural stress field is represented by the stress tensor regulatory components: \(\sigma _{z}^{{\text{N}}}\) = \( - \gamma H + {{\sigma }_{{zT}}} + {{\sigma }_{{z{\text{AF}}}}}\), \(\sigma _{x}^{{\text{N}}}\) = \( - \lambda \gamma H + {{\sigma }_{{xT}}} + {{\sigma }_{{x{\text{AF}}}}}\), \(\sigma _{y}^{{\text{N}}}\) = \( - \lambda \gamma H + {{\sigma }_{{yT}}} + {{\sigma }_{{y{\text{AF}}}}}\).     

Separation of Cu<Superscript>2+</Superscript> and Pb<Superscript>2+</Superscript> by tetraethylenepentamine-modified sugarcane bagasse fixed-bed column: selective adsorption and kinetics

Tetraethylenepentamine-modified sugarcane bagasse (SCB) was prepared to improve its adsorption capacity and selectivity toward Cu²⁺. Adsorption performances of the modified sorbent for Cu²⁺ were studied in batch system. Separation of Cu²⁺ from Pb²⁺ by the modified sorbent fixed-bed column were studied under dynamic system with initial molar concentration ratio \(\left( {C_{0}^{\text{Cu}} /C_{0}^{\text{Pb}} } \right)\) ranging from 1:1 to 1:100. The amount of Cu²⁺ and Pb²⁺ adsorbed on the saturated column was calculated by the elution curve. Batch experimental results showed that the adsorption capacity of the sorbent for Cu²⁺ increased from 0.12 to 0.21 mmol g^?1 after modification. Dynamic adsorption results showed that the modified SCB had higher adsorption affinity toward Cu²⁺ than Pb²⁺. 0.07 mmol g^?1 of adsorbed Pb²⁺ was pushed off by Cu²⁺ during the competitive adsorption process at \(C_{0}^{\text{Cu}} /C_{0}^{\text{Pb}} = {\text{1:1}}.\) The breakthrough curves and adsorption kinetics of Cu²⁺ in the column could be fitted well by the Yoon–Nelson and modified Yoon–Nelson model, respectively. According to the elution curve, the amount of Cu²⁺ adsorbed on the fixed-bed column were 0.16, 0.16 and 0.15 mmol g^?1, while that of Pb²⁺ were 0.0016, 0.0051 and 0.0094 mmol g^?1 when \(C_{0}^{\text{Cu}} /C_{0}^{\text{Pb}}\) increased from 1:1 to 1:10 and 1:100. Cu²⁺ could be selectively adsorbed and separated from Pb²⁺ by using the modified sorbent fixed-bed column.     

The effect of silica activity on the diffusion of Ni and Co in olivine

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg₂SiO₄) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO₂ and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D _M (M = Ni or Co) for the combined data set can be fitted to the equation:

$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$

with E_a(Ni) = ? 284.3 kJ mol^?1 and E_a(Co) = ? 275.9 kJ mol^?1, with an uncertainty of ±10.2 kJ mol^?1. This equation fits the data (24 experiments) to ±0.1 in log D _M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg_1.8Fe_0.2SiO₄ at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe³⁺ in the Fe-bearing olivines. However, the dependence on fO₂ is small, with D \(\propto\) (fO₂)^0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO₂ magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO₂ magmas, such as tholeiitic basalts, at equal temperatures and fO₂.

     

Theoretical calculation of equilibrium Mg isotope fractionation between silicate melt and its vapor

Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO₃ and Mg₂SiO₄ melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ²⁵Mg values in the MgSiO₃ and Mg₂SiO₄ melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ²⁶Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO₃ and Mg₂SiO₄ melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope ²⁴Mg and m′ is the mass of the heavier isotope, ²⁵Mg or ²⁶Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.     

Appraisal of groundwater quality in a crystalline aquifer: a chemometric approach

The purpose of this study is to assess the groundwater quality and identify the processes that control the groundwater chemistry in a crystalline aquifer. A total of 72 groundwater samples were collected during pre- and post-monsoon seasons in the year 2014 in a semi-arid region of Gooty Mandal, Anantapur district, Andhra Pradesh, India. The study utilized chemometric analysis like basic statistics, Pearson’s correlation coefficient (r), principal component analysis (PCA), Gibbs ratio, and index of base exchange to understand the mechanism of controlling the groundwater chemistry in the study area. The results reveal that groundwater in the study area is neutral to slightly alkaline in nature. The order of dominance of cations is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ while for anions, it is \( {\mathrm{HCO}}_3^{-}>{\mathrm{Cl}}^{-} \)>\( {\mathrm{NO}}_3^{-} \)>\( {\mathrm{SO}}_4^{2-} \)>\( {\mathrm{CO}}_3^{2-}>{\mathrm{F}}^{-} \) in both seasons. Based on the Piper classification, most of the groundwater samples are identified as of sodium bicarbonate (\( {\mathrm{Na}}^{+}-{\mathrm{HCO}}_3^{-}\Big) \) type. According to the results of the principal component analysis (PCA), three factors and two factors were identified pre and post monsoon, respectively. The present study indicates that the groundwater chemistry is mostly controlled by geogenic processes (weathering, dissolution, and ion exchange) and some extent of anthropogenic activities.     

Majoritic garnet grains within shock-induced melt veins in amphibolites from the Ries impact crater suggest ultrahigh crystallization pressures between 18 and 9 GPa

Shock-induced melt veins in amphibolites from the Nördlinger Ries often have chemical compositions that are similar to bulk rock (i.e., basaltic), but there are other veins that are confined to chlorite-rich cracks that formed before the impact and these are poor in Ca and Na. Majoritic garnets within the shock veins show a broad chemical variation between three endmembers: (1) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}{\text{Al}}_{2} ({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (normal garnet, Grt), (2) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}[{\text{M}}^{2 + } ({\text{Si,Ti}})]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\)  (majorite, Maj), and (3) \({}^{\text{VIII}}({{\text {Na} {\text M}^{2+}}_2}) {}^{\text{VI}}[ ({\text{Si,Ti}}){\text {Al}}]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (Na-majorite₅₀Grt₅₀), whereby M²⁺ = Mg²⁺, Fe²⁺, Mn²⁺, Ca²⁺. In particular, we observed a broad variation in ^VI(Si,Ti) which ranges from 0.12 to 0.58 cations per formula unit (cpfu). All these majoritic garnets crystallized during shock pressure release at different ultrahigh pressures. Those with high ^VI(Si,Ti) (0.36–0.58 cpfu) formed at high pressures and temperatures from amphibole-rich melts, while majoritic garnets with lower ^VI(Si,Ti) of 0.12–0.27 cpfu formed at lower pressures and temperatures from chlorite-rich melts. Furthermore, majoritic garnets with intermediate values of ^VI(Si,Ti) (0.24–0.39) crystallized from melts with intermediate contents of Ca and Na. To the best of our knowledge the ‘MORB-type’ Ca–Na-rich majoritic garnets with maximum contents of 2.99 wt% Na₂O and calculated crystallisation pressures of 16–18 GPa are the most extreme representatives ever found in terrestrial shocked materials. At the Ries, the duration of the initial contact and compression stage at the central location of impact is estimated to only ~ 0.1 s. We used a ~ 200-µm-thick shock-induced vein in a moderately shocked amphibolite to model its pressure–temperature–time (P–T–t) path. The graphic model manifests a peak temperature of ~ 2600 °C for the vein, continuum pressure lasting for ~ 0.02 s, a quench duration of ~ 0.02 s and a shock pulse of ~ 0.038 s. The small difference between the continuum pressure and the pressure of majoritic garnet crystallization underlines the usefulness of applying crystallisation pressures of majoritic garnets from metabasites for calculation of dynamic shock pressures of host rocks. Majoritic garnets of chlorite provenance, however, are not suitable for the determination of continuum pressure since they crystallized relatively late during shock release. An extraordinary glass- and majorite-bearing amphibole fragment in a shock-vein of one amphibolite documents the whole unloading path.     

Si and O self-diffusion in hydrous forsterite and iron-bearing olivine from the perspective of defect chemistry

We discuss the experimental results of silicon and oxygen self-diffusion coefficients in forsterite and iron-bearing olivine from the perspective of defect chemistry. Silicon diffusion is dominated by V_O ^··-associated V_Si″″, whereas oxygen diffusion is dominated by hopping of V_O ^·· under anhydrous conditions, and by (OH)_O ^· under hydrous conditions. By considering the charge neutrality condition of [(OH)_O ^·] = 2[V_Me″] in hydrous forsterite and iron-bearing olivine, we get D _Si ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))^1/3 and D _O ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))⁰, which explains the experimental results of water effects on oxygen and silicon self-diffusion rates (Fei et al. in Nature 498:213–215, 2013; J Geophys Res 119:7598–7606, 2014). The \(C_{{{\text{H}}_{2} {\text{O}}}}\) dependence of creep rate in the Earth’s mantle should be close to that given by Si and O self-diffusion coefficients obtained under water unsaturated conditions.     

Heat capacity of hydrous trachybasalt from Mt Etna: comparison with CaAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript> (An)–CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript> (Di) as basaltic proxy compositions

The specific heat capacity (C _p) of six variably hydrated (~3.5 wt% H₂O) iron-bearing Etna trachybasaltic glasses and liquids has been measured using differential scanning calorimetry from room temperature across the glass transition region. These data are compared to heat capacity measurements on thirteen melt compositions in the iron-free anorthite (An)–diopside (Di) system over a similar range of H₂O contents. These data extend considerably the published C _p measurements for hydrous melts and glasses. The results for the Etna trachybasalts show nonlinear variations in, both, the heat capacity of the glass at the onset of the glass transition (i.e., C _p ^g ) and the fully relaxed liquid (i.e., C _p ^l ) with increasing H₂O content. Similarly, the “configurational heat capacity” (i.e., C _p ^c  = C _p ^l  ? C _p ^g ) varies nonlinearly with H₂O content. The An–Di hydrous compositions investigated show similar trends, with C _p values varying as a function of melt composition and H₂O content. The results show that values in hydrous C _p ^g , C _p ^l and C _p ^c in the depolymerized glasses and liquids are substantially different from those observed for more polymerized hydrous albitic, leucogranitic, trachytic and phonolitic multicomponent compositions previously investigated. Polymerized melts have lower C _p ^l and C _p ^c and higher C _p ^g with respect to more depolymerized compositions. The covariation between C _p values and the degree of polymerization in glasses and melts is well described in terms of SM_hydrous and NBO/T _hydrous. Values of C _p ^c increase sharply with increasing depolymerization up to SM_hydrous ~ 30–35 mol% (NBO/T _hydrous ~ 0.5) and then stabilize to an almost constant value. The partial molar heat capacity of H₂O for both glasses (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{g}} \)) and liquids (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \)) appears to be independent of composition and, assuming ideal mixing, we obtain a value for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) of 79 J mol^?1 K^?1. However, we note that a range of values for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) (i.e., ~78–87 J mol^?1 K^?1) proposed by previous workers will reproduce the extended data to within experimental uncertainty. Our analysis suggests that more data are required in order to ascribe a compositional dependence (i.e., nonideal mixing) to \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \).     

Assessment of spatial distribution of contaminants and their levels in soil and water resources of Calabar,Nigeria using geophysical and geological data

The contamination levels of soils and water resources in Calabar, Nigeria have been investigated using resistivity (vertical electrical sounding and electrical resistivity tomography), geochemical analyses of soil and water resources and textural analysis. Sixty randomly sited VES sites were investigated in two seasons while ERT investigations were performed along four profiles. The geochemical investigations were spread across seasons in order to track seasonal changes in physico-chemical parameters: hydrogen ion concentration (pH), electrical conductivity, total dissolved solids, chloride ion (Cl^?), nitrate ion (\( {\text{NO}}_{ 3}^{ - } \)), bicarbonate (\( {\text{HCO}}_{ 3}^{ - } \)), sulphate ion (\( {\text{SO}}_{ 4}^{2 - } \)), calcium ion (Ca²⁺), sodium ion (Na⁺), potassium ion (K⁺) and magnesium ion (Mg²⁺). Additionally, concentrations of ammonium, aluminium and nitrite ions in soils were determined. Results show that ionic concentrations in the sand-dominated soils and water are within permissible limits and baseline standards. The resistivities follow known trends in the area. However, at the central waste disposal site, a localised thin (< 5 m), low resistivity (< 15 Ωm) anomaly suspected to be due to contamination by leachates was observed. Comparatively, the contaminated area is also characterised by marginal increase in ionic concentrations. Strong attenuation capacities of overlying and adjoining clay/lateritic sediments and optimal design of the waste dump site probably reduced the spread of contaminants. The contaminated zone need to be closely monitored so that it does not extend to the aquifers. Hence, all strategies presently being used in managing wastes in Calabar should be sustained.     

Djerfisherite: nebular source of refractory potassium

Djerfisherite is an important carrier of potassium in highly reduced enstatite chondrites, where it occurs in sub-round metal-sulfide nodules. These nodules were once free-floating objects in the protoplanetary nebula. Here, we analyze existing and new data to derive an equation of state (EOS) for djerfisherites of $ {\text{K}}_{ 6} ({\text{Cu}},{\text{Fe}},{\text{Ni}})^{B} ({\text{Fe}},{\text{Ni}},{\text{Cu}})_{24}^{C} {\text{S}}_{ 2 6} {\text{Cl}} $ K 6 ( Cu , Fe , Ni ) B ( Fe , Ni , Cu ) 24 C S 2 6 Cl structural formula. We use this EOS to calculate the thermal stability of djerfisherite coexisting in equilibrium with a cooling vapor of solar composition enriched in a dust analogous to anhydrous, chondritic interplanetary dust (C-IDP). We find that condensed mineral assemblages closely match those found in enstatite chondrites, with djerfisherite condensing above 1,000 K in C-IDP dust-enriched systems. Results may have implications for the volatile budgets of terrestrial planets and the incorporation of K into early formed, highly reduced, planetary cores. Previous work links enstatite chondrites to the planet Mercury, where the surface has a terrestrial K/Th ratio, high S/Si ratio, and very low FeO content. Mercury’s accretion history may yield insights into Earth’s.     

Providing optimum models for predicting the water loss after harvesting and extracting trees aboveground biomass from the Hyrcanian mixed-beech forests

The ecological and biological attributes of trees stand as well as the water cycle in forests are substantially related to variations of water storage capacity in forest ecosystems. This study aimed to figure out a protocol for monitoring the water storage capacity variations in the Hyrcanian mixed-beech stands after harvesting and extracting trees form the forest. A total of 174 trees were felled and weighed, and destructive sampling following lines of exploitation was carried out for measuring the water content in aboveground biomass of trees. Curve estimation regression analyses including the tree biophysical variables (breast height diameter DBH, total height H, basic wood density \(\rho\)) were used for examining the prediction accuracy. Nonlinear models were log-transformed, and systematic bias was corrected by correction factor depending on standard error of estimate when back-transforming to the originally dependent value. The findings showed that the power-law models were the best functional form for predicting the dependent variables. Using only DBH in the simple power model explained 76% of total variance (Adj.R ² = 0.76) with a low Akaike information criterion (AIC) and normalized root-mean-square error RMSE%, indicating a high accuracy of prediction (\({\text{AIC}} \approx - 238\); RMSE% = 11.7). Adding H and \(\rho\) in the linear log-transformed power models with different interaction terms increased the certainty of prediction with the highest accuracy (\({\text{Adj}}.R^{2} = 0.86,\;{\text{AIC}} = - 329,\;{\text{RMSE}}\% = 9\)). Considering diverse conditions for natural forest sites, the optimum models including the biophysical variables may have associated parameters in the other forests having different stand types and compositions.     

Effect of solar flare on the equatorial electrojet in eastern Brazil region

The effect of solar flare, sudden commencement of magnetic storm and of the disturbances ring current on the equatorial electrojet in the Eastern Brazil region, where the ground magnetic declination is as large as \(20^{^{\circ }}\hbox {W}\) is studied based on geomagnetic data with one minute resolution from Bacabal during November–December 1990. It is shown that the mean diurnal vector of the horizontal field was aligned along \(2{^{\circ }}\hbox {E}\) of north at Huancayo and \(30{^{\circ }}\hbox {W}\) of north at Bacabal during the month of December 1990. Number of solar flares that occurred on 30 December 1990 indicated the direction of solar flare related \(\Delta H\) vector to be aligned along \(5{^{\circ }}\hbox {E}\) of north at Huancayo and \(28{^{\circ }}\hbox {W}\) of north at Bacabal. This is expected as the solar flare effects are due to the enhanced conductivity in the ionosphere. The SC at 2230 UT on 26 November 1990 produced a positive impulse in \(\Delta X\) and negative impulse in \(\Delta Y\) at Bacabal with \(\Delta H\) vector aligned along \(27{^{\circ }}\hbox {W}\) of north. At Huancayo the \(\Delta H\) vector associated with SC is aligned along \(8{^{\circ }}\hbox {E}\) of north, few degrees east to the alignment of the diurnal vector of H. The magnetic storm that followed the SC had a minimum Dst index of –150 nT. The corresponding storm time disturbance in \(\Delta X\) at Huancayo as well as at Bacabal were about –250 nT but \(\Delta Y\) at Bacabal was about +70 nT and very small at Huancayo, that give the alignment of the H vector due to ring current about \(16{^{\circ }}\hbox {W}\) of north at Bacabal and almost along N–S at Huancayo. Thus alignment of the \(\Delta H\) vector due to ring current at Bacabal is \(14{^{\circ }}\hbox {E}\) of the mean direction of \(\Delta H\) vector during December 1990. This is consistent with the direction of ring current dependent on the dipole declination at the ring current altitude which is about \(5{^{\circ }}\hbox {W}\) of north over Bacabal and the deviation of declination due to the ring current during disturbed period given by the angle (\(\psi \)-D).