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1.
Vaterite is shown to be unstable with respect to calcite at 25°C by measurements of the enthalpies of solution in 0·1 N HCl under 0·97 atm CO2 and the solubilities in water under 0·97 atm CO2 of the two polymorphs. For a pure, synthetic vaterite ΔH (tr) = ?1036 ±16 cal mol?1 and ΔG(tr) = ?790 ± 25 cal mol?1 for the transition to calcite. For other vaterites aged longer during preparation ΔH(tr) is smaller and shows a linear relationship with the X-ray line broadening which extrapolates to ΔH(tr) = ?545 ± 30 cal mo?1 for zero broadening. The use of X-ray line broadening as a measure of crystal imperfection and stability is discussed for various synthetic and natural vaterites.  相似文献   

2.
In this paper, we have developed a least-squares minimization method to estimate the depth of a buried conducting sphere using electromagnetic induction (EMI) data. This approach is basically based on the solving a set of algebraic linear equations to estimate the depth of sphere embedded in an insulating media. In electromagnetic induction method, the transmitter coil produces the incident magnetic and electric fields that obey the Maxwell’s equations. In the receiver coil, the received response is created in two modes—eddy-current mode (V ec) derived from the perfectly conductor placed in the shallow depth and another mode called current-channeling response (V cc) which depends on the conductivity of the medium. As expected, these responses differ depending on the direction of the incident field related to the receiver coil’s axis. In our case, the transmitter coil’s axis is parallel to the ground surface, and only the eddy-current response is measured in the receiver coil. The validity of this new method is demonstrated through studying and analyzing synthetic EMI anomalies, using simulated data generated from a known model with different random error components and a known statistical distribution.  相似文献   

3.
The effect the metal casing of a vertical borehole may exert on transient electromagnetic (TEM) responses has been studied in a field experiment. Eddy currents in the casing affect transients only slightly at early times, but the casing effect predominates at late times. Therefore, early-time TEM response measured near a borehole can provide information on shallow subsurface. The late-time TEM signals induced by the eddy currents in the casing show exponential behavior b⋅ exp(–t/τ). The time constant τ refers to the rate of eddy current decay in the casing; the amplitude b is M12⋅ M23⋅ L–1⋅ τ–1, where L is the casing self-inductance, and M12 and M23 are the mutual inductances between the transmitter loop and the borehole and between the borehole and the receiver, respectively. Both M12 and M23 are controllable, while M23 is especially important for survey applications: by reducing it, one can reduce the casing effect on the TEM data.© 2014, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.  相似文献   

4.
The integration of geophysical data with direct hydrogeological measurements can provide a minimally invasive approach to characterize the subsurface at a variety of resolutions and over many spatial scales. The field of hydrogeophysics has attracted much attention during the last two decades. In this domain, the geophysical data inverted to geophysical models are interpreted in terms of the hydrogeology to serve as a basis for the definition of hydraulic models in the areas of interest. The hydraulic conductivity (K) value measured in a reference borehole has been combined with the electrical conductivity obtained from nearby geo-electromagnetic sounding data in the Cenomanian (Upper Cretaceous) aquifer, central Sinai, Egypt. The resulting relation was interpreted with Dar Zarrouk parameters to infer the transmissivity variations at other vertical electrical sounding locations, where K values are unknown. Coincident transient electromagnetic data have been adopted to increase accuracy while interpreting the aquifer geoelectrical properties. The results indicate that the transmissivity values in the aquifer of interest vary from 2,446 to 9,694 m2/day, and K varies from 12.9 to 57.0 m/day throughout the studied area.  相似文献   

5.
The spatial structure of the metal-poor globular cluster M15 is studied as a function of magnitude interval ΔB and the limiting B magnitude of star counts. Astrometric and photometric measurements of two plates obtained with the 2-m reflector of the National Academy of Sciences of Bulgaria were used. Analysis of the differential and integrated apparent (ΔF(r) and F(r)) and spatial (Δf(r) and f(r)) stellar density distributions in different ΔB intervals and to different limiting magnitudes reaching B=21.5m indicates that the cluster structure changes systematically as we consider fainter stars, beginning with the transition region between the subgiant branch and the main-sequence turnoff in the (V, B-V) diagram. This variation is manifest in two ways: a homological growth in the radii of spatial zones of the cluster and of the cluster radius in accordance with a single law, and variations in the stellar density, with the rate of increase in the number of faint stars growing toward the outer zones of the cluster. Empirical relations describing these variations and parameters determining the cluster structure are obtained.  相似文献   

6.
《Applied Geochemistry》1998,13(5):543-552
The accumulation chamber methodology allows one to obtain reliable values of the soil CO2 flux, ϕsoil CO2, in the range 0.2 to over 10 000 g m−2 d−1, as proven by both laboratory tests and field surveys in geothermal and volcanic areas. A strong negative correlation is observed between Δϕsoil CO2/Δt and ΔPatm/Δt. Maps of classes of log ϕsoil CO2 for the northern sector of Vulcano Island, Solfatara of Pozzuoli, Nea Kameni Islet and Yanbajain geothermal field evidence that active faults and fractures act as uprising channels of deep, CO2-rich geothermal or magmatic gases. The total diffuse CO2 output was evaluated for each surveyed area.  相似文献   

7.
Owing to the rapid increase in available data on the natural variations of the 238U/235U ratio, new isotopic geochemical mark of redox processes are beginning to emerge. In this connection, numerical estimates of the 238U and 235U fractionation factor (α(UIV?UVI)) accompanying the reduction UVI → UIV are needed. Such an estimate has been obtained for hydrothermal pitchblende formation based on results of high-precision (±0.06‰) measurements of the 238U/235U ratio in local microsamples of coarse spherulitic pitchblende from carbonate-pitchblende veins at the Oktyabr’sky deposit (Strel’tsovsky uranium ore field, eastern Transbaikal region). For this purpose, we used the formation temperature of hydrothermal pitchblende and a maximum estimate of the fractionation factor for 238U and 235U isotopes in the solution-solid phase system under normal (25°C) conditions (Murphy et al., 2014). The most probable isotopic fractionation factor accompanying pitchblende crystallization from hydrothermal solution at T = 320?250°C falls into the interval α(UIV?UVI) = 1.00020?1.00023.  相似文献   

8.
The potential for photo-induced dissociation of ferri- and ferro-cyanide was investigated. The overall reactions followed first order kinetics, judged by the free cyanide analyzed in aqueous solution. The dissociation rates for ferri- and ferro-cyanide were mathematically described by the equations: C (CN,t) = C (CN,O)e1.3t and C (CN,t) = C (CN,O)e0.39t , respectively. In addition, photo-induced dissociation of both iron cyanides was enhanced under an alkaline environment than a neutral condition. Results from the temperature-dependent tests indicated that the dissociation rate of ferri- cyanide was significantly higher than that of ferro-cyanide at all treatment temperatures. The kinetic parameter, activation energy (E a ) was also experimentally determined to be 12.02 and 12.32 kJ/mol for ferri- and ferro-cyanide, respectively. The results obtained suggest that both iron cyanides are susceptible to photo-dissociation and the rates are positively correlated to the change of temperatures. The information collectively also has important implications for waste management of iron cyanides as well as for risk assessment in a field trial.  相似文献   

9.
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 ΔHro = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔSro = ?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 ΔHro = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔSr0 = ?47.4 ± 1.0 cal/deg mol at 25°C.  相似文献   

10.
The field of mechanical energy transfer from the atmosphere to the ocean is computed for the first time. The numerical simulation of waves within the Indian Ocean (IO) water area for the period of 1998?C2009 is used. Mechanical energy transfer is described by two integrated parameters calculated per area unit: the speed of complete energy flux from wind to waves, I E (x, t), and the speed of complete losses in the energy of wind waves, D E (x, t). In order to solve this problem, the wind field W(x, t) (the NCEP/NOAA data) is used; the I E (x, t) and D E (x, t) fields are calculated on the basis of the WAM numerical model containing a modified source function. The results obtained allow us, first, to assess the characteristic spatial distribution of zones ??pumped?? by the wind with mechanical energy for both the wave field and the upper layer of the ocean by seasons, years, and the whole period discussed, second, to determine the extreme and average zonal values of I E (x, t) and D E (x, t), the degree of their shift spacing and balance B E = (I E + D E ); and third, to define the characteristic time scales of variations in the wind field and wave field energies, caused by energy transfer from the wind to waves in the zones and within the Indian ocean as a whole. These results significantly specify the climatic estimates obtained earlier.  相似文献   

11.
The paper deals with the relationship between the sea surface wind speed (U) and the backscattering coefficient (σ0) for microwave frequencies and quasi specular range of angles. Valenzuela’s effective reflection coefficient based on the theory of scattering of electromagnetic waves from rought dielectric surfaces has been introduced in the expression of backscattering coefficient and the final result compared with the σ0-U relationship derived fromSEASAT scatterometer and concurrent sea truth data.  相似文献   

12.
We present geochemical and geochronological data of host granodiorites and mafic microgranular enclaves (MMEs) from the Heping pluton, which is situated in the central part of the Wuyi-Yunkai Orogen (WYO) in the South China Block (SCB), and reveal syn-convergent extension and asthenosphere upwelling during the early Paleozoic intracontinental orogeny. Two host and two MME samples from the Heping pluton yield LA-ICP-MS zircon UPb ages of ca. 445 Ma, coincident with the peak magmatism-metamorphism of the WYO. The host granodioritic samples are metaluminous (A/CNK = 0.68–0.91) and have abundant amphibole and low-moderate SiO2 (59.1 to 67.3 wt%), belonging to high-K calc-alkaline I-type granite, whereas the MMEs are more basic with SiO2 of 56.3 to 59.6 wt%. Both the host and MME samples display weakly negative Eu anomalies and distinctly relative depletions of Ta, Nb, and Ti, and most of them share similar initial 87Sr/86Sr ratios of 0.7089–0.7112 and εNd(t) values of −6.52 to −7.12, except one MME sample with a lower initial 87Sr/86Sr of 0.70758 and a higher εNd(t) of −4.33. The zircon εHf(t) values exhibit a wide range from −13.68 to −0.87. Petrological, geochemical, and chronological data suggest that the Heping pluton were generated by mingling of mafic and felsic magmas. The mafic endmember magma was originated mainly from the enriched subcontinental lithosphere mantle at the spinel–garnet transitional zone (~70 km), subsequently underplated/intraplated into the lower-middle crust resulting in the melting of the intermediate rock at pressure < 8 kbar to produce the felsic endmember magma. We proposed a new tectonic model “syn-convergent extension and asthenosphere upwelling during the intracontinental orogeny”. The syn-convergent extension zones, which include a series of NW-trending transverse faults and the NE-trending reactivated pre-exsiting suture and rift zone (i.e. Shaoxing-Jiangshan -Pingxiang- Chenzhou fault) within the WYO, are in favor of asthenosphere upwelling leading to intensive crust-mantle interaction.  相似文献   

13.
Ground-based (Big Bear Solar Observatory) and extra-atmospheric (SOHO/MDI) measurements of the photospheric line-of-sight magnetic field of one active and two quiet regions are used to calculate power spectra of the field, taking into account the characteristic function for the diffraction limit of the telescope resolution. At high frequencies, the physically meaningful linear interval in the spectrum extends to a wave number of k=4.6 Mm?1 (spatial scale l=1.4 Mm) for the quiet regions and k=3.35 Mm?1 (l=1.9 Mm) for the active region. A high-frequency spectral break at k≥3 Mm?1 is associated with the characteristic telescope function; the position of the break and the spectral slope beyond the break do not reflect the turbulent state of the field. As the field recording improves, the break shifts toward higher frequencies. The spectral indices in the physically meaningful linear interval are substantially different for the active and quiet regions: in the active region (NOAA 8375), the spectrum behaves as E(k)≈k ?1.7 (very close to the Kolmogorov index, ?5/3) in the interval 0.78≤k≤3.35 Mm?1, while in the quiet regions E(k)≈k ?1.3 for 0.77≤k≤4.57 Mm?1. This difference can be explained by the additional effect of a small-scale turbulent dynamo in the unperturbed photosphere. In this case, this mechanism can generate at least 6% of the magnetic energy of the photospheric line-of-sight field in quiet regions.  相似文献   

14.
The effect of presure on the solubility of minerals in water and seawater can be estimated from In
(KPspK0sp) + (?ΔVP + 0.5ΔKP2)RT
where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by
ΔV = V?(M+, X?) ? V?[MX(s)]ΔK = K?(M+, X?) ? K?[MX(s)]
Values of the partial molal volume (V?) and compressibilty (K?) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10?3 cm3 bar?1 mol?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In Ksp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of KPspKosp for the solubility of CaCO3, SrSO4 and CaF2 in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.  相似文献   

15.
Pyrite dissolution and interaction with Fe(II), Co(II), Eu(III) and U(VI) have been studied under anoxic conditions by solution chemistry and spectroscopic techniques. Aqueous data show a maximal cation uptake above pH 5.5. Iron (II) uptake can explain the non-stoichiometric [S]aq/[Fe]aq ratios often observed during dissolution experiments. Protonation data corrected for pyrite dissolution resulted in a proton site density of 9 ± 3 sites nm−2. Concentration isotherms for Eu(III) and U(VI) sorption on pyrite indicate two different behaviours which can be related to the contrasted redox properties of these elements. For Eu(III), sorption can be explained by the existence of a unique site with a saturation concentration of 1.25 × 10−6 mol g−1. In the U(VI) case, sorption seems to occur on two different sites with a total saturation concentration of 4.5 × 10−8 mol g−1. At lower concentration, uranium reduction occurs, limiting the concentration of dissolved uranium to the solubility of UO2(s).Scanning electron microscopy and micro-Raman spectrometry of U(VI)-sorbed pyrite indicate a heterogeneous distribution of U at the pyrite surface and a close association with oxidized S. X-ray photoelectron spectroscopy confirms the partial reduction of U and the formation of a hyperstoichiometric UO2+x(s). Our results are consistent with a chemistry of the pyrite surface governed not by Fe(II)-bound hydroxyl groups, but by S groups which can either sorb cations and protons, or sorb and reduce redox-sensitive elements such as U(VI).  相似文献   

16.
Bima Formation volcanic rocks, which record the history of Neo-Tethyan subduction, are found within the central and eastern segments of the southern Lhasa subterrane, Tibetan Plateau. Zircon UPb dating, whole-rock major and trace element analysis, and Sr–Nd–Pb–Hf isotopic compositions of Bima Formation volcanic rocks from the central segment of the southern Lhasa subterrane were used to constrain the magmatic and tectonic evolution of the Lhasa terrane during the early Mesozoic. Zircon UPb dating of five samples yielded consistent ages of 184.3 ± 2.4 to 176.8 ± 3.5 Ma. The dominant volcanic rock types within the Bima Formation are basalts, basaltic andesites, andesites, and dacites, which are enriched in the large-ion lithophile elements (e.g., Rb, Sr, and Ba) and depleted in high-field-strength elements (e.g., Nb, Ta, and Ti). (87Sr/86Sr)t ratios are low (0.702900–0.704146), εNd(t) and εHf(t) values are high and positive (+4.4 to +6.9 and + 9.6 to +15.7, respectively), and Pb isotope ratios are homogeneous (initial 206Pb/204Pb = 18.28–18.40; 207Pb/204Pb = 15.53–15.56; 208Pb/204Pb = 38.21–38.38). Combining the new data with those from a previous study of Bima Formation volcanic rocks from the eastern segment of the southern Lhasa subterrane indicates that the Bima Formation formed between the Middle Triassic and Early Jurassic. It suggests that more widespread early Mesozoic volcanic rocks in the southern margin of the Lhasa terrane. The basaltic rocks of the Bima Formation were generated by partial melting of a depleted mantle wedge metasomatized by slab-derived fluids, and subsequently experienced fractional crystallization without significant crustal contamination. The andesitic and dacitic rocks were formed by fractional crystallization of the basaltic magma. Our study indicates that the Bima Formation volcanic rocks were generated within a continental island arc setting related to northward subduction of the Neo-Tethyan oceanic slab during the early Mesozoic.  相似文献   

17.
Electron spin resonance of allowed (Δm=0) and forbidden (Δm=±1) hyperfine transitions of Mn2+ in sodalite, Na8(Al6Si6O24)Cl2, is reported. No fine structure other than the central M=∣+1/2>?∣?1/2> transition is observed. From intensity ratios of forbidden to allowed transitions and doubling of allowed lines in powder spectra the crystal field parameter |D| was estimated as equal to (8±5) 10?3 cm?1. The g-value for the spectrum was obtained as equal to 2.0033±0.0005. The hyperfine structure constant |A| was 83±1 gauss, equal to (77±1) 10?4 cm?1.  相似文献   

18.
Transient electromagnetic responses measured in the field or in the laboratory may bear effects of viscous remanent magnetization (VRM) associated with magnetic relaxation of ultrafine grains of ferrimagnetic minerals or superparamagnetism. The behavior of VRM can be studied in time or frequency domain, TDEM measurements being advantageous because they are done in the absence of primary field and owing to broad time range providing high accuracy of VRM parameters. Another advantage is that the rate of viscous decay measured as voltage decay does not need to be corrected for stable and/or slowly decaying viscous component of total remanence. Time-dependent transient responses of viscous decay follow the power law a ⋅ t–b, where a is the initial emf signal (varying in a broad range) and b is the exponent approaching 1. Laboratory tests with a pulse induction coil system reveal a strong linear correlation of the parameter a with frequency-dependent magnetic susceptibility Δκ used commonly for constraining the relative abundances of superparamagnetic particles. Such systems are thus suitable for quick measurements of the large number of samples for detection of superparamagnetic (SP) particles and quantifying their contribution. The difference of b from 1, though being minor, exceeds markedly its error in estimates from measured data. Simulated TDEM responses of a superparamagnetic ground show both parameters (a and b) to depend on particle volume distribution, which is prerequisite for inversion of time-domain transients to magnetic properties of rocks and soils.  相似文献   

19.
Latest Permian to Triassic plutons are widespread in the northern North China Craton(NCC); most of them show calc-alkaline, high-K calc-alkaline, or alkaline geochemical features. The Shadegai pluton in the Wulashan area has shoshonitic affinity and I-type character, and is composed of syenogranites containing abundant mafic microgranular enclaves(MMEs). LA-MC-ICP-MS U-Pb data yield weighted mean 206 Pb/238 U ages of 222 ± 1 Ma and 221 ± 1 Ma for the syenogranites and MMEs, respectively, suggesting their coeval formation during the Late Triassic. The syenogranites have high SiO_2(70.42-72.30 wt%),K_2O(4.58-5.22 wt.%) and Na_2O(4.19-4.43 wt.%) contents but lower concentrations of P_2O_5(0.073-0.096 wt.%) and TiO_2(0.27-0.37 wt.%), and are categorized as I-type granites, rather than A-type granites, as previously thought. These syenogranites exhibit lower(~(87)Sr/~(86)Sr)i ratios(0.70532-0.70547) and strongly negative whole-rock εNd(t) values(-12.54 to-11.86) and zircon εHf(t) values(-17.81 to-10.77),as well as old Nd(1962-2017 Ma) and Hf(2023-2092 Ma) model ages, indicating that they were derived from the lower crust.Field and petrological observations reveal that the MMEs within the pluton probably represent magmatic globules commingled with their host magmas. Geochemically, these MMEs have low SiO_2(53.46-55.91 wt.%)but high FeOt(7.27-8.79 wt.%) contents. They are enriched in light rare earth elements(LREEs) and large ion lithophile elements(LILEs), and are depleted in heavy rare earth elements(HREEs) and high field strength elements(HFSEs). They have whole-rock(~(87)Sr/~(86)Sr)i ratios varying from 0.70551 to 0.70564, εNd(t) values of -10.63 to -9.82, and zircon εHf(t) values of -9.89 to 0.19. Their geochemical and isotopic features indicate that they were derived from the subcontinental lithospheric mantle mainly metasomatized by slab-derived fluids, with minor involvement of melts generated from the ascending asthenospheric mantle. Petrology integrated with elemental and isotopic geochemistry suggest that the Shadegai pluton was produced by crust-mantle interactions, i.e., partial melting of the lower continental crust induced by underplating of mantle-derived mafic magmas(including the subcontinental lithospheric mantle and asthenospheric mantle), and subsequent mixing of the mantle-and crust-derived magmas. In combination with existing geological data, it is inferred that the Shadegai pluton formed in a post-collisional extensional regime related to lithospheric delamination following the collision between the NCC and Mongolia arc terranes.  相似文献   

20.
The speciation of CO2 in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO2 into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO2 re-appeared. Infrared extinction coefficients of both carbonate and molecular CO2 decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO2 + O2? = CO3 2? in the melt shifts toward CO2 with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 103 T ?1 for dacite melt (ΔH = ?42 kJ mol?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 103 T ?1 for phonolite melt (ΔH = ?65 kJ mol?1), where K is the molar ratio of carbonate over molecular CO2 and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO2 speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO2, and therefore, the diffusion coefficient of CO2 is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO2 solubility and speciation on melt composition, in accordance with available solubility data.  相似文献   

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