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1.
Single-crystal electron paramagnetic resonance (EPR) spectra of a gem-quality jeremejevite, Al6B5O15(F, OH)3, from Cape Cross, Namibia, reveal an S = 1/2 hole center characterized by an 27Al hyperfine structure arising from interaction with two equivalent Al nuclei. Spin-Hamiltonian parameters obtained from single-crystal EPR spectra at 295 K are as follows: g 1 = 2.02899(1), g 2 = 2.02011(2), g 3 = 2.00595(1); A 1/g e β e  = −0.881(1) mT, A 2/g e β e  = −0.951(1) mT, and A 3/g e β e  = −0.972(2) mT, with the orientations of the g 3- and A 3-axes almost coaxial and perpendicular to the Al–O–Al plane; and those of the g 1- and A 1-axes approximately along the Al–Al and Al–OH directions, respectively. These results suggest that this aluminum-associated hole center represents hole trapping on a hydroxyl oxygen atom linked to two equivalent octahedral Al3+ ions, after the removal of the proton (i.e., a VIAl–O−–VIAl center). Periodic ab initio UHF and DFT calculations confirmed the experimental 27Al hyperfine coupling constants and directions, supporting the proposed structural model. The VIAl–O−–VIAl center in jeremejevite undergoes the onset of thermal decay at 300 °C and is completely bleached at 525 °C. These data obtained from the VIAl–O−–VIAl center in jeremejevite provide new insights into analogous centers that have been documented in several other minerals.  相似文献   

2.
Deep-seated landslides are complex systems. In many cases, multidisciplinary studies are necessary to unravel the key hydrological features that can influence their evolution in space and time. The deep-seated Berceto landslide, in the northern Apennines of Italy, has been investigated in order to define the origin and geochemical evolution of groundwater (GW), to identify the slope system hydrological boundary, and to highlight the GW flow paths, transit time and transfer modalities inside the landslide body. This research is based on a multidisciplinary approach that involves monitoring GW levels, obtaining analyses of water chemistry and stable and unstable isotopes (δ18O-δ2H, 3H, 87Sr/86Sr), performing soil leaching tests, geochemical modelling (PHREEQC), and principal component analysis (PCA). The results of δ18O-δ2H and 87Sr/86Sr analyses show that the source of GW recharge in the Berceto landslide is local rainwater, and external contributions from a local stream can be excluded. In the landslide body, two GW hydrotypes (Ca-HCO3 and Na-HCO3) are identified, and the results of PHREEQC and PCA confirm that the chemical features of the GW depend on water–rock interaction processes occurring inside the landslide. The 3H content suggests a recent origin for GW and appears to highlight mixing between shallow and deep GW aliquots. The 3H content and GW levels data confirm that shallow GW is mainly controlled by a mass transfer mechanism. The 3H analyses with GW levels also indicate that only deep GW is controlled by a pressure transfer mechanism, and this mechanism is likely the main influence on the landslide kinematics.  相似文献   

3.
Biotite is one of the most common minerals dated by the 40Ar–39Ar method. It frequently shows K contents below the expected stoichiometric value, suggesting the presence of low-K impurities. The most common low-K alteration product of biotite is chlorite. Therefore, it is important to understand the effects of chlorite interlayering on 40Ar–39Ar ages in order to correctly interpret 40Ar–39Ar data. This study examines the outcome of 40Ar–39Ar dating analyses on variably chloritised biotites from Ordovician intrusive rocks. The infrared (IR) laser-probe technique and different gas extraction methods were adopted. Incremental laser-heating data on bulk samples yielded hump-shaped age profiles with meaningless young and old age steps. Both the extent of anomalous old age steps and the degree of discordance of the age spectra were much more pronounced in the more chloritised biotite samples. In contrast, in situ data on rock chips and total-fusion ages on single biotite flakes yielded ages concordant with, or younger than, the inferred emplacement ages. Transmission electron microscopy (TEM) was used to texturally characterise biotite samples at the nanometre scale. It was also used to document the complex decomposition-transformation process affecting interlayered biotite–chlorite during in-vacuo IR-laser heating to temperatures ranging from ~600 to >1,000 °C. TEM results suggest that hump-shaped age profiles result from an interplay between 39ArK redistribution by recoil during sample irradiation and differential release of argon isotopes hosted in three main reservoirs. These reservoirs are (from least to most retentive): extended defects, chlorite and biotite. The final descending age segment is attributed to the progressive release of argon with increasing temperature from large biotite domains for which 39ArK recoil loss was less important. 40Ar–39Ar data support previous findings, which suggest that 40Ar–39Ar ages when recoil effects are minimised, provide minimum estimates that approach the true biotite age, when the pristine domains are analysed. The most effective approach for obtaining meaningful 40Ar–39Ar ages was using individual total-fusion analyses on carefully selected, single flakes previously split along the basal cleavage by wet-grinding and corresponding to a sample mass of a few micrograms.Editorial responsibility: I Parsons  相似文献   

4.
The uneven character of the distribution of 18O/16O and 234U/238U values was established in the vertical cross section of the productive sequence of the Dybryn uranium deposit (Vitim uranium-ore region, Buryatia). Both a deficiency and an excess of 234U in relation to the equilibrium 234U/238U ratio in the vertical sequence may provide evidence for the extremely low rate of the infiltration water flow. The behavior of oxygen isotope characteristics for different size fractions of terrigenous rocks provides evidence for active uranium redistribution and openness of the isotope system of this element during interaction of terrigenous–sedimentary rocks with infiltration waters.  相似文献   

5.
Chemistry of major and minor elements, 87Sr/86Sr, δD, δ18O and δ34S of brines were measured from Tertiary strata and Quaternary salt lakes in the western Qaidam Basin. The water chemistry data show that all oilfield brines are CaCl2 type. They were enriched in Ca2+, B3+, Li+, Sr2+, Br−, and were depleted in Mg2+, SO4 2−, which indicated that these brines had the characteristics of deeply circulated water. The relationship between δD and δ18O shows that all data of these brines decline towards the Global Meteoric Water Line (GWL) and Qaidam Meteoric Water Line (QWL), and that the intersection between oilfield brines and Meteoric Water Lines was close to the local spring and fresh water in the piedmont in the western Qaidam Basin. The results suggest that oilfield brines has initially originated from meteoric water, and then might be affected by water-rock metamorphose, because most oilfield brines distribute in the range of metamorphosing water. The 87Sr/86Sr values of most oilfield brines range from 0.71121 to 0.71194, and was less than that in salt lake water (>0.712), but close to that of halite in the study area. These imply that salt dissolution occurred in the process of migration. In addition, all oilfield brines have obviously much positive δ34S values (ranging from 26.46‰ to 54.57‰) than that of salt lake brines, which was caused by bacterial sulfate reduction resulting in positive shift of δ34S value and depleteed SO4 2− in oilfield brines. Combined with water chemical data and δD, δ18O, 87Sr/86Sr, δ34S values, we concluded that oilfield brines mainly originate from the deeply circulated meteoric waters, and then are affected by salt dissolution, water-rock metamorphose, sulfate reduction and dolomitization during the process of migration. These processes alter the chemical compositions of oilfield brines and accumulate rich elements (such as B, Li, Sr, Br, K and so on) for sustainable utilization of salt lake resources in the Qaidam Basin.  相似文献   

6.
New 87Sr/86Sr, δ13C, and δ18О chemostratigraphic data were obtained for carbonate rocks of the Lower Riphean Yusmastakh and the Vendian Starorechenskaya formations. The δ13С values in dolomites of the Yusmastakh Formation varies from–0.6 to–0.1‰ and in dolomites and dolomitic limestones of the Starorechenskaya Formation, from–1.2 to–0.4‰ PDB, and δ18О values, from 24.4 to 26.4‰ and from 25.3 to 27.6‰ SMOW, respectively. The Rb–Sr systematics of carbonate rocks was studied using the refined method of stepwise dissolution of samples in acetic acid, including chemical removal of up to one-third of the ground sample by preliminary acid leaching and subsequent partial dissolution of the rest of the sample. Owing to this procedure, secondary carbonate material is removed, which enables one to improve the quality of the Sr-chemostratigraphic data obtained. The initial 87Sr/86Sr ratios in carbonate rocks of the Yusmastakh (0.70468–0.70519) and Starorechenskaya (0.70832–0.70883) formations evidence the Riphean–Vendian boundary in the Precambrian sequence of the Anabar Uplift.  相似文献   

7.
Irradiation techniques are often applied to gem minerals for color enhancement purposes. Natural green, blue and colorless specimens of rare gemological quality euclase, BeAlSiO4(OH), from Brazil were irradiated with gamma rays in the dose range from 10 to 500 kGy. Although the colors of the different specimens were not strongly influenced, two different irradiation-induced paramagnetic defect centers were found by electron paramagnetic resonance (EPR). The first one is an O− hole center interacting with one Al neighbor and the second is a Ti3+ electron center. The EPR angular rotation patterns of both irradiation-induced defects were measured and analyzed. The results suggest that O− hole centers are formed by dissociation of the hydroxyl ions, similar as in topaz crystals. In euclase the OH− ions interconnect distorted Al octahedra and Be tetrahedra in O5 positions. During irradiation, the electrons are captured by titanium ions (Ti4+ + e−), leading to the formation of paramagnetic Ti3+ ions. From the EPR rotation patterns it is clear that these ions substitute for Al ions. The spin Hamiltonian parameters of the irradiation-induced defects are analyzed and compared to similar defect centers in other mineral specimens. Thermal annealing experiments show that the O− hole centers and Ti3+ electron centers are directly connected through the radiation process.  相似文献   

8.
This paper reports a classical molecular dynamics study of the potential of mean forces (PMFs), association constants, microstructures K+–Cl? ion pair in supercritical fluids. The constrained MD method is used to derive the PMFs of K+–Cl? ion pair from 673 to 1273 K in low-density water (0.10–0.60 g/cm3). The PMF results show that the contact ion-pair (CIP) state is the one most energetically favored for a K+–Cl? ion pair. The association constants of the K+–Cl? ion pair are calculated from the PMFs, indicating that the K+–Cl? ion pair is thermodynamically stable. It gets more stable as T increases or water density decreases. The microstructures of the K+–Cl? ion pair in the CIP and solvent-shared ion-pair states are characterized in detail. Moreover, we explore the structures and stabilities of the KCl–Au(I)/Cu(I) complexes by using quantum mechanical calculations. The results reveal that these complexes can remain stable for T up to 1273 K, which indicates that KCl may act as a ligand complexing ore-forming metals in hydrothermal fluids.  相似文献   

9.
With depleted coal resources or deteriorating mining geological conditions, some coal mines have been abandoned in the Fengfeng mining district, China. Water that accumulates in an abandoned underground mine (goaf water) may be a hazard to neighboring mines and impact the groundwater environment. Groundwater samples at three abandoned mines (Yi, Er and Quantou mines) in the Fengfeng mining district and the underlying Ordovician limestone aquifer were collected to characterize their chemical and isotopic compositions and identify the sources of the mine water. The water was HCO3·SO4-Ca·Mg type in Er mine and the auxiliary shaft of Yi mine, and HCO3·SO4-Na type in the main shaft of Quantou mine. The isotopic compositions (δD and δ18O) of water in the three abandoned mines were close to that of Ordovician limestone groundwater. Faults in the abandoned mines were developmental, possibly facilitating inflows of groundwater from the underlying Ordovician limestone aquifers into the coal mines. Although the Sr2+ concentrations differed considerably, the ratios of Sr2+/Ca2+ and 87Sr/86Sr and the 34S content of SO42? were similar for all three mine waters and Ordovician limestone groundwater, indicating that a close hydraulic connection may exist. Geochemical and isotopic indicators suggest that (1) the mine waters may originate mainly from the Ordovician limestone groundwater inflows, and (2) the upward hydraulic gradient in the limestone aquifer may prevent its contamination by the overlying abandoned mine water. The results of this study could be useful for water resources management in this area and other similar mining areas.  相似文献   

10.
Three natural Mg(Al2-yCry)O4 spinels (y 0.07–0.16), highly ordered in terms of Mg–Al, and one Mg(Al2–yFe3+y)O4 spinel (y0.08), highly ordered also in terms of Fe3+, were studied by means of X-ray single-crystal diffraction. All samples were heated in situ from 25 to 1000 °C in order to follow both thermal expansion and evolution of the structural state of spinel with temperature. Thermal expansion was monitored by means of the variation of cell edge a with temperature, and found to be well represented throughout the temperature range by a regression line a = a0 (1+T), slightly different at lower and higher temperatures. Thermal expansion coefficient 1, referring to the lower temperature range (i.e. during pure thermal expansion), was slightly lower than 2, calculated only over the highest temperatures. The trend showed different slopes for individual crystals. Structural evolution with temperature was studied by means of the variation of oxygen positional parameter u, which is strongly influenced by intersite cation exchange and thus closely correlated with inversion parameter x. In particular, in the three Cr samples, in which Cr resides only in the octahedral site, u parameter variations and hence the order–disorder process, started at about 700 °C. Instead, in the Fe3+ sample, this process was triggered at lower temperatures, starting at 550 °C with Fe3+–Mg exchange followed at higher temperatures by that of Mg–Al. Cr contents in the Cr samples affected the occupancy of Al in the tetrahedral site at the highest temperatures. In both Mg–Al–Cr and Mg–Al–Fe3+ compositions, if CrFe3+, parameter u reached the same value only when the Mg–Al exchange was dominant, i.e. at the highest temperatures, but not before. Cation distribution at each temperature was obtained by the bond-length model, applying thermal expansion to pure bond lengths. This method is applied here to complex compositions for the first time.  相似文献   

11.
In order to characterize the post-Svecofennian tectonothermal evolution of the Fennoscandian Shield, 40Ar–39Ar biotite and some 40Ar–39Ar muscovite geochronological data are reported from a total of 30 surface outcrop and 1,000 m long borehole samples at Forsmark, central Sweden. The 13 surface samples were collected across 3 branches of a major WNW to NW trending system of deformation zones, whereas the boreholes were drilled within a tectonic lens, in between two of these zones. The 40Ar–39Ar biotite ages indicate that the present erosion surface, in central Sweden, cooled below c. 300°C at 1.73–1.66 Ga, and that the rocks could have accommodated strain in a brittle manner between 1.8 and 1.7 Ga. The variation in surface ages is suggested to be due to fault along the large WNW to NW trending deformation zones, following the establishment of a sub-Cambrian peneplain. The minor variation of ages within a single crustal block may be due to disturbance along ENE to NNE trending fracture zones. Possible cooling paths, derived from 40Ar–39Ar hornblende, muscovite and biotite ages, were calculated for the time interval from 1.80 to 1.67 Ga, when the area cooled from c. 500 to 300°C. Cooling rates of 1.9–4°C/m.y. have been attained. Between 1.68 and 1.64 Ga, uplift rates of c. 22 m/m.y. were calculated from borehole 40Ar–39Ar biotite data. Tectonothermal histories, inferred from the combined cooling and uplift rates, are related to simple cooling after the Svecofennian orogeny, to crustal movement in response to far-field effects of c. 1.7 Ga orogenic activities further to the west or to a combination of these possibilities.  相似文献   

12.
We have modeled absorption lines of the 12CO and 13CO (Δυ = 2) molecular bands at λλ 2.29–2.45 µm in the spectrum of Arcturus (K2III). A grid of model atmospheres and synthetic spectra were computed for the red giant using T eff = 4300, log g = 1.5, and the elemental abundances of Peterson et al. (1993), with the exception of the abundances of carbon, log N(C), and oxygen, log N(O) and the carbon isotopic ratio, 12C/13C, which were varied in our computations. The computed spectra were compared to the observed spectrum of Arcturus from the atlas of Hinkle et al. (1976). The best fit between the synthetic and observed spectra is achieved for log N(C) = ?3.78, 12C/13C = 8 ± 0.5. We discuss the dependence of 12C/13C on log N(C) and log N(O) in the atmosphere of the red giant.  相似文献   

13.
A new 190Pt–4He method for dating isoferroplatinum has been developed at the Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences. Here we publish the first results of dating of isoferroplatinum from the main mineralogical and geochemical types of PGE mineralization in dunite. The obtained 190Pt–4He age of isoferroplatinum is 129 ± 6 Ma. The gained 190Pt–4He age of isoferroplatinum specimens of different genesis (magmatic, fluid–metamorphogenic, and metasomatic) from the Kondyor Massif indicates that the PGM mineralization took place synchronously and successively with evolution of primarily picrite, followed by subalkaline and alkaline melts of the Mesozoic tectonic–magmatic activation of the Aldan Shield.  相似文献   

14.
The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ13C values from–6.6 to 1.3‰ and δ18O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ13C from–5.2 to–2.9 and δ18O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ13C from–16.4 to–13.1 and δ18O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ13C from–13.0 to–10.4‰ and δ18O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ18O from 18.7 to 17.6‰ and δ13C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO2. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.  相似文献   

15.
The Warburton Basin of central Australia has experienced a complex tectonic and fluid-flow history, resulting in the formation of various authigenic minerals. Geochemical and geochronological analyses were undertaken on vein carbonates from core samples of clastic sediments. Results were then integrated with zircon U–Pb dating and uraninite U–Th–total Pb dating from the underlying granite. Stable and radiogenic isotopes (δ18O, Sr and εNd), as well as trace element data of carbonate veins indicate that >200 °C basinal fluids of evolved meteoric origin circulated through the Warburton Basin. Almost coincidental ages of these carbonates (Sm–Nd; 432 ± 12 Ma) with primary zircon (421 ± 3.8 Ma) and uraninite (407 ± 16 Ma) ages from the granitic intrusion point towards a substantial period of active tectonism and an elevated thermal regime during the mid Silurian. We hypothesise that such a thermal regime may have resulted from extensional tectonism and concomitant magmatic activity following regional orogenesis. This study shows that the combined application of geochemical and geochronological analyses of both primary and secondary species may constrain the timing of tectonomagmatic events and associated fluid flow in intraplate sedimentary basins. Furthermore, this work suggests that the Sm–Nd-isotopic system is surprisingly robust and can record geologically meaningful age data from hydrothermal mineral species.  相似文献   

16.
The Rb–Sr and 147Sm–143Nd age data obtained for sheeted dolerite dykes and rocks of the Platinum Belt of the Urals within the Tagil segment of the paleoceanic spreading structure (Middle Urals) are discussed. The study of the Rb–Sr isotope systematics of gabbro allowed us to reveal errochronous dependencies, which yielded ages of 415 and 345 Ma at (87Sr/86Sr)0 = 0.70385 ± 0.00068 and 0.7029 ± 0.0010, correspondingly. The 147Sm–143Nd isotope age data demonstrate a specific coincidence of the chronometric ages of the sheeted dolerite dyke complex (426 ± 54, 426 ± 34, and 424 ± 19 Ma) and gabbro from the Revda gabbro–ultramafic massif (431 ± 27 Ma) and from screens between dolerite dykes in the sheeted dyke complex (427 ± 32 Ma, 429 ± 26 Ma). The proximity of the 147Sm–143Nd ages of gabbro and dolerite can be explained by the thermal effect of the basaltic melt, which is the protolith for the dyke complex, on the hosting gabbro.  相似文献   

17.
Isotopic compositions of carbon (δ13C from −51.4 to −10.8 PDB) and oxygen (δ18O from 14.4 to 21.4 SMOW) were studied in rhodochrosite and calcite from manganese ores in the South Faizuly and Kyzyltash deposits of the southern Urals. The geological, petrographic, and isotopic data indicate that the studied carbonates are diagenetic formations. It is suggested that the main ore element (Mn) was delivered to the marine basin with hydrothermal solutions percolating in the oceanic crust. Manganese precipitated on the oceanic bottom as oxides near solution discharge zones. Manganese carbonates formed in sediments as a result of the oxidation of organic matter by manganese oxides. High biological productivity of the environment was caused by proximity to the hydrothermal vent that provided favorable biogeochemical conditions for the development of biocoenosis. Anomalously low 13C values in the South Faizuly deposit testify to the large-scale oxidation of methane in the course of manganese carbonate formation.__________Translated from Litologiya i Poleznye Iskopaemye, No. 4, 2005, pp. 416–429.Original Russian Text Copyright © 2005 by Kuleshov, Brusnitsyn.  相似文献   

18.
Reliable age estimation was obtained originally in this study for gold mineralization of the Malomyr deposit (the eastern part of the Mongolian–Okhotsk foldbelt), which is one of the most well-known deposits in the Russian Far East. The data obtained show that the age of hydrothermal process that resulted in the formation of the Malomyr deposit may be estimated as ～133–132 Ma. Data on magmatism of the same age within the considered region are absent. In the opinion of the authors, mobilization, redistribution of the ore material, and the formation of the Malomyr deposit were mostly controlled by dislocation processes accompanied by hydrothermal activity, which is supported by the results of structural studies.  相似文献   

19.
The Pampa region in Argentina includes vast unconfined–semiconfined aquifers that local economies depend upon, but detailed knowledge of the associated water resources is still lacking. The Pampeano aquifer in the Pampa plain of Argentina covers around 1.5 million km2. In order to achieve a better understanding of the hydrogeological system through the estimation of mean residence times (MRT), water samples were taken from 12 monitoring wells, drilled at different depths in four locations, and analyzed for environmental tracers. The concentrations of 3H, tritiogenic 3He and chlorofluorocarbons (CFCs) can be explained by mixtures of young waters adjusted to exponential piston flow models (EPM) or dispersion models (DM), and different proportions of tracer-free waters (dead water). The sampling site located very close to the water divide shows a dominance of young waters: 85 % of water best represented by a DM model with a MRT of 3 years. For the shallow wells at other sites, best-fitting models result in a DM with MRT between 20 and 35 years, and proportions of dead water between 40 and 60 %. These results lead to important updates in the conceptual model of the Pampeano aquifer. Large proportions of dead water at a few meters depth can be the consequence of upward flows in a multilayered aquifer or diffusive retardation in the inter-bedded clay layers.  相似文献   

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

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