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1.
A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO2. The isoelectronic CO2 radical is found in the irradiated Maxixe-type beryl. The NO2 radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO2 radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO2 radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li+, Na+, and another counter-ion, which probably is Cs+. The related NO3 and CO3 radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO3 is created in Maxixe beryl by a natural process, while CO3 in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.  相似文献   

2.
The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H2O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al2O3 in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.  相似文献   

3.
Summary ?The low-pressure eutectic for the coprecipitation of calcite, portlandite, and periclase/brucite (with H2O-rich vapor) has served as a model for the existence and crystallization of carbonatite magmas. Attempts to determine conditions for the appearance of dolomite at this eutectic have been unsuccessful. We have discovered a second low-temperature eutectic for more magnesian liquids which excludes portlandite and includes dolomite (all results are vapor-saturated). Addition of Ca(OH)2-Mg(OH)2 to CaCO3-MgCO3 at 0.2 GPa depresses the liquidus to temperatures below the crest of the calcite-dolomite solvus; the vapor-saturated liquidus surface falls steeply, and the field boundary for liquids coexisting with calcite and periclase reaches a peritectic at 880 °C, where a narrow field for liquidus dolomite begins, extending down to the eutectic at 659 °C for the coprecipitation of calcite, dolomite and periclase (brucite should replace periclase at slightly higher pressures). The calcite liquidus is very large. The field boundary for coexistence of calcite and dolomite extends approximately in the direction from CaMg(CO3)2 towards Mg(OH)2. The results illustrate conditions for the formation of mineral-specific cumulates from variable magma compositions. Hydrous (or sodic) carbonate-rich liquids with compositions from CaCO3 to CaMg(CO3)2 will precipitate calcite-carbonatites first, followed by calcite-dolomite-carbonatites, with the prospect of precipitating dolomite-carbonatite alone through a limited temperature interval, and with periclase joining the assemblage in the closing stages. Periclase in the Fe-free system may represent the ubiquitous occurrence of magnetite in natural carbonatites. The restricted range for the precipitation of dolomite-carbonatites adds credibility to the evidence for primary magnesiocarbonatite (near-dolomite composition) magmas. Magnesiocarbonatite magmas can precipitate much calcite-carbonatite rock.
Zusammenfassung ?Calciokarbonatitische und magnesiokarbonatitische Gesteine und Magmen im System CaO-MgO-CO 2 -H 2 O bei 0.2 GPa Das Niedrigdruck-Eutektikum der gemeinsamen Ausscheidung von Calcit, Portlandit und Periklas/Brucit (mit H2O-reicher Fluidphase) diente als Modell um die Existenz und Kristallisation karbonatitischer Magmen zu erkl?ren. Versuche die Bedingungen des Auftretens von Dolomit an diesem Eutektikum zu bestimmen blieben bisher ergebnislos. Wir entdeckten ein zweites Niedrigtemperatur-Eutektikum für magnesiumreichere Schmelzen, das Portlandit ausschlie?t, aber Dolomit inkludiert (alle Ergebnisse bei Fluids?ttigung). Die Zugabe von Ca(OH)2-Mg(OH)2 zu CaCO3-MgCO3 bei 0.2 GPa senkt den Liquidus auf Temperaturen unter die Solvus-Schwelle von Calcit-Dolomit. Die fluidges?ttigte Liquidusfl?che verl?uft steil und die Grenzfl?che von Schmelze, die mit Calcit und Periklas koexistiert erreicht ein Peritektikum bei 880 °C. Dort ?ffnet sich ein schmales Feld für Liquidus-Dolomit, das bis zum Eutektikum bei 659 °C reicht, an dem Calcit, Dolomit und Periklas (Brucit sollte Periklas bei geringfügig h?heren Drucken ersetzen) gemeinsam ausgeschieden werden. Der Calcit- Liquidus ist sehr gro?. Die Linie an der Calcit und Dolomit koexistieren erstreckt sich ungef?hr von CaMg(CO3)2 zu Mg(OH)2. Die Ergebnisse zeigen die Bildungsbedingungen für die Bildung mineralspezifischer Kumulate aus unterschiedlichen Magmenzusammensetzungen. Aus w?ssrigen (oder Na-reichen) karbonatreichen Schmelzen mit Zusammensetzungen zwischen CaCO3 und CaMg(CO3)2 werden sich zuerst Calcitkarbonatite und dann Calcit-Dolomitkarbonatite ausscheiden, mit der M?glichkeit Dolomitkarbonatite über ein sehr eingeschr?nktes Temperaturintervall zu bilden und mit Periklas, der zu dieser Vergesellschaftung im Endstadium hinzukommt. Periklas im Fe-freien System k?nnte das weitverbreitete Analog zu Magnetit in natürlichen Karbonatiten sein. Der enge Bereich für die Ausscheidung von Dolomitkarbonatiten untermauert die Existenz prim?rer magnesiokarbonatitischer Magmen (nahe der Zusammensetzung von Dolomit). Magnesiokarbonatitische Magmen k?nnen daher entsprechende Mengen an calcitkarbonatitischen Gesteinen ausscheiden.


Received July 20, 1998;/revised version accepted August 18, 1999  相似文献   

4.
In order to determine the mechanisms of formation and properties of natural hydrosilicate liquids (HSLs), which are formed during the transition from magmatic to hydrothermal mineral formation in granitic pegmatites and rare-metal granites, the formation of HSLs was experimentally studied in the Na2O-SiO2-H2O, Na2O-Al2O3-SiO2-H2O, and Na2O-K2O-Li2O-Al2O3-SiO2-H2O systems at 600°C and 1.5 kbar. It was shown that the sequential extension of composition does not suppress HSL formation in the systems and expands the stability field of this phase. However, HSLs formed in extended chemical systems have different structure and properties: the addition of alumina induces some compression of the structure of the silicate framework of HSLs, which results in a decrease in water content in this phase and probably hinders the reversibility of its dehydration. It was demonstrated that HSL can be formed by the coagulation of silica present in a silica-oversaturated alkaline aqueous fluid. It was supposed that the HSL formed during this process has a finely dispersed structure. It was argued that anomalous enrichment in some elements in natural HSLs can be due to their sorption by the extensively developed surface of HSL at the moment of its formation.  相似文献   

5.
6.
Experimental uniaxial compression loading tests were conducted on molded gypsum and Carrara marble prismatic specimens to study the cracking and coalescence processes between pre-existing artificial flaws. The study showed that material had an influence on the cracking and coalescence processes (see the companion paper in this issue). As reported in the companion paper, one of the pronounced features as observed in the high-speed video recordings was the development of macroscopic white patches prior to the development of observable cracks in marble, but not in gypsum. This paper (part 2) deals with the microscopic aspects of the study. Specifically, the scanning electron microscope (SEM) and the environmental scanning electron microscope (ESEM) imaging techniques were used to study the microscopic development of white patches and their evolution into macroscopic tensile cracks and shear cracks in marble, and the microscopic initiation of hair-line tensile cracks and their evolution into macroscopic tensile cracks in gypsum. The microscopic imaging study in marble showed that the white patches were associated with extensive microcracking zones (process zones), while the extent of process zone development in gypsum was limited. The comparison of the macroscopic and microscopic results indicates that the different extent of microcracking zone development, related to the material textural properties, is a key factor leading to different macroscopic cracking behavior in gypsum and marble.
H. H. EinsteinEmail:
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7.
Detailed phase relations have been determined within the systems Fe2O3-MgO-TiO2 and FeO-MgO-TiO2. Experiments were performed over the temperature interval 1173–1473 K by equilibrating pelletized, fine-grained oxide mixtures in either inert calcia-stabilized zirconia pots (Fe2O3-MgO-TiO2 system) or evacuated silica tubes (FeO-MgO-TiO2 system). Equilibrium phase assemblages were determined by combined optical microscope, X-ray diffraction and EMP examination. Phase relations in the Fe2O3-MgO-TiO2 ternary are dominated by the instability of the M2O3 solid solution relative to the phase assemblage M3O4 + M3O5. A miscibility gap along the M2O3 binary also gives rise to two, 3-phase fields (α-M2O3 + M3O5 + M3O4 and α′-M2O3 + M3O5 + M3O4) separated by the M3O4 + M3O5 phase field. Phase relations in the FeO-MgO-TiO2 ternary were divided into two sub-systems. For the FeTiO3-MgTiO3-TiO2 sub-ternary, there is complete solid solution along the M2O3 and M3O5 binary joins at high temperature. At low temperatures (T < 1373 K) the M3O5 pseudobrookite solid solution decomposes to M2O3 + TiO2. Increasing the concentration of MgO in M3O5 phase results in a decrease in the temperature at which M3O5 becomes unstable and compositional tie lines linking M2O3 and TiO2 fan out, before the appearance of a three-phase region where M2O3, M3O5, and TiO2 coexist. Within the expanded FeO-MgO-TiO2 system, at temperatures above ∼1273 K there is a continuous solid solution along the M3O4 binary. At low temperatures (T < 1273 K) the Mg2TiO4 end-member breaks down to MgO and MgTiO3. The M3O4 phase shows significant non-stoichiometry, down to at least 1173 K. Fe2+-Mg partitioning data were obtained for coexisting M2O3-M3O5 and M2O3-M3O4 pairs in the FeO-MgO-TiO2 ternary. Assuming a regular solution mixing model for all phases, the M2O3 and M3O4 solid solutions were both found to exhibit moderate positive deviations from ideality (∼2600 J/mol), whereas the data for the M3O5 binary suggest close to ideal behaviour. Received: 22 May 1998 / Accepted: 3 November 1998  相似文献   

8.
The municipal solid waste (MSW) landfills are the significant sources of atmospheric contamination, due to biogas production by anaerobic decomposition of organic matter via bacterial activity. Biogas released from landfills is commonly composed of a mixture of methane (55%-60%) and carbon dioxide (40%-45%), with minor contents of N2, H2, CO and traces of toxic and bad smelling inorganic and organic compounds. Particular attention has to be paid to CH4 and CO2 because of their liability for the greenhouse effect. Presently, the U.S. methane emission from landfills is considered to be about 25% of the total methane released to the atmosphere. Accordingly, field measurements should be planned in order to verify and, eventually, optimize the amount of gases released from waste disposals to the atmosphere. Simultaneous measurements of methane and carbon dioxide fluxes are an effective tool to better evaluate: (1) the amount of biogas released, (2) the real efficiency of the impervious cover, and (3) the presence of anomalous degassing zones or of newly formed fractures. Static closed-chamber methods for CH4 and CO2 flux measurements have been developed and used in both natural and artificial systems. Furthermore, portable gas-chromatographers equipped with flame ionization detector (FID) and accumulation chamber connected to infrared detectors (IR) .have been utilized for measuring CH4 and CO2 fluxes, respectively. This paper deals with a detailed investigation that combines (1) CH4 and CO2 flux measurements from solid waste disposal and surrounding areas (determined by an accumulation chamber equipped with two IR detectors, respectively), (2) chemical composition of soil and piezometer gases (collected in pre-evacuated glass tubes and analyzed by gas-chromatography), and (3) CO2 linear concentration measurements on optical air paths with IR laser devices. This multi-methodological approach was successfully applied to an active MSW in Tuscany (Central Italy). The analytical results have shown that the CO2/CH4 ratios of the piezometer gases have large variations, likely related to the different stage of decomposition processes affecting the heterogeneous solid material of the waste landfill. Significant contents of light hydrocarbons and BTX were also detected.  相似文献   

9.
The municipal solid waste (MSW) landfills are the significant sources of atmospheric contamination, due to biogas production by anaerobic decomposition of organic matter via bacterial activity. Biogas released from landfills is commonly composed of a mixt…  相似文献   

10.
11.
Water samples were collected from the Truckee River-Pyramid Lake system, the Walker River-Walker Lake system, and the Carson River, all located in eastern California and western Nevada, U.S.A., at three different times (i.e., summer 1991, spring 1992, and autumn 1992) over a two year period. The concentrations of As, Na, Cl, PO4, and pH were measured in these river samples and the associated terminal lakes. Arsenic values ranged from below 13 nmol/kg near Truckee, California to 160 nmol/kg at Nixon, Nevada in the Truckee River, from 40 nmol/kg in the headwaters of both West and East Walker Rivers to 270 nmol/kg below Weber Reservoir on the main branch of the Walker River, and from <27 nmol/kg to 234 nmol/kg for the lower Carson River system. Arsenic concentrations in Steamboat Creek (0.91 mol/kg–1.80 mol/kg) in the Truckee River catchment are above the U.S. EPA drinking water maximum contaminant level of 0.67 mol/kg, as are the As concentrations in both Pyramid Lake (1.33 mol/kg–1.57 mol/kg ) and Walker Lake (13.7 mol/kg–18.7 mol/kg). Sources of As for all three rivers include weathering of As-rich rocks and/or regolith and input of high-As geothermal spring waters, both processes primarily, although not exclusively, adding As to the headwater regions of these rivers. Steamboat Hot Springs (29 mol/kg As 54.5 mol/kg), for example, is identified as a source of As to the Truckee River via Steamboat Creek. The high As concentrations in Pyramid and Walker Lakes are likely due to (1) desorption of arsenate from aquatic particulate matter in these high pH waters (9.0 pH 9.5), (2) limited biologic uptake of arsenate, and (3) evaporative concentration of the lake waters. Evaluation of molar PO4}/As ratios of river waters and geothermal spring waters (e.g., Steamboat Hot Springs), indicates that phosphate is substantially enriched in Steamboat Creek as well as the mid to lower reaches of the Walker and Carson Rivers. These regions of each river are dominated by agricultural interests and, additionally, in the case of Steamboat Creek, residential areas and golf courses. Our data strongly imply that phosphate-rich agricultural return flow has likely added P to these streams and, consequently, increased their respective P:As ratios.  相似文献   

12.
Activity-composition relations in the olivine solid solutions Ni2SiO4 -Mg2SiO4 and Co2SiO4-Mg2SiO4 have been determined at 1200 K and 0.1 MPa and at 1573 K and 0.5 GPa by equilibration with the corresponding oxide solutions. Both olivine solutions show small positive deviations from ideal (two site) mixing, which, within the limits of accuracy of the method, may be described by the simple regular solution model with parameters WNi+Mgol= 0.35 ± 1.0 kJ/g-atom and WCo-Mgol = 1.37 ± 0.9 kJ/g-atom. The requirements of internal consistency between the two systems also show that the recent determination by Brousse et al. (1984) of the enthalpy of formation of Mg2SiO4is to be preferred over earlier work, and that their value is also probably more accurate than the uncertainty in their own measurements indicates; activities in the NiO-MgO system are close to ideal.  相似文献   

13.
Oxygen isotope fractionation in TiO2 polymorphs has been calculated by the modi-fied increment method .The results that rutile is enriched in ^18O relative to brookite but depleted in ^18O relative to anatase.Due to the same crystal structure ,oxygen isotope partitioning in the TiO2 polymorphs is determined by the cation-oxygen inter-atomic distances.The theoretical calibrations involving rutile are in fair agreement with known experimental measurements and empirical estimates.Application of the theoretic-cal quartz-rutile calibration to geothermometry of natural eclogite assemblages indicates the preservation of isotopic equilibrium at high temperatures.The isotopic temperatures calculated are only slightly lower than the non-isotopic temperatures,indicating the slow rates of exchange for oxygen diffusion in rutile.The kinetics of exchange for oxygen diffu-sion in rutile is accordingly estimated by reconciling the differences between the isotopic and the non-isotopic temperatures.The rates of exchange for oxygen diffusion in rutile should be smaller than those for hornblende,but may be equal to or greater than those for diopside.  相似文献   

14.
During the last century, several lead mines and a metal smelter were in production in the Upper Ribeira Valley, southeastern Brazil. After fifty years of activity, the refinery was shut down in November 1995 and, thereafter the last mines in production were closed. Since 1998, a multidisciplinary research group has carried out an ambitious investigation among the population of five municipalities in the Ribeira Valley (sampled population of 472 children and 523 adults) to assess the human exposure to lead. The highest blood lead levels were found among the population of two villages in the vicinity of the smelter where soil and indoor-dust are highly contaminated. During the present study, the lead contents of several food species that are part of local population diet were investigated. Greens, vegetables, corn, chicken eggs and cow milk, were sampled in two occasions, July 2004 and February 2005. The analytical procedures included burning of organic matter, pre-concentration of lead and, finally, determination by AAS using background correction. The quantification limit was 0.05 μg/g Pb. Soil samples were also collected and analyzed by X-ray fluorescence spectroscopy with a quantification limit of 2 μg/g Pb. The results are very impressing since 100% of greens, vegetables and eggs yielded lead concentrations exceeding the upper limits established by Brazilian regulations whereas milk and maize samples presented lead contents below the regulated limit of 0.05 μg/g Pb. Lead concentrations in soil varied between 156 and 1292 μg/g Pb, resembling the results of previous studies and far exceeding the threshold of 200 μg/g Pb indicated as the intervention value. Lead contents in some species vary consistently with lead concentrations in soils, however, other factors may account for the bioavailability of lead and its intake by plants, like the soil pH, its cationic exchange capacity, clay and organic matter contents, characteristics of the plant species itself, climate, among others.  相似文献   

15.
正It is significant for recognizing the origin of chromitites to research the primary mineral inclusions in chromitites.A large number of primary mineral inclusions including CPXs,OPXs,olivines,aspidolites,Na-Cr pargasites,CPX  相似文献   

16.
In steady state the stable isotopic composition of nitrogen and oxygen in tropospheric N2O is balanced by isotopically light N2O emitted from soils and oceans and isotopically heavy N2O as a return flux from the stratosphere.However,no such balance was reached in calculations given by Kim and Caig(1993).Modifications have been made on their calculations based on the most recent reports on annual global emission of N2O.It is considered that the nitrogen and oxygen isotope budget in tropospheric N2O are approximately in balance if isotopic fractionation effects during the production of N2O in soils and furthermore this paper puts forward further evidence for validating the above results.  相似文献   

17.
The major element composition of sound-producing sand is reported together with rare-earth elements (REE) and other selected elements for the first time. Rare-earth element concentrations in beach sands from Miyagi and Tottori in Japan were determined by induction-coupled, argon-plasma spectrometry (ICP-MS) to characterize the REE of sound-producing and silent sands relative to the parental rocks. Sound-producing sand beaches are very common and all over in Japan: five beaches in Miyagi and 2 in Tottori are selected with other silent sand beaches in the areas. Both sound-producing sand and silent sand samples from Miyagi and Tottori contain more than 60wt% of SiO2 and are composed mainly of quartz and feldspar. Miyagi sand samples are characterized by light REE enrichment and flat chondrite-normalized patterns that are similar to those of local source sandstone. However, all sand samples from Miyatojima in Miyagi show positive Eu anomalies, a characteristic feature not shown in other sand samples from Miyagi. Tottori sand samples also are characterized by high REE contents and remarkable positive Eu anomalies. The sands containing lower REE contents are due to high quartz and feldspar contents. Miyatojima sand samples and Tottori sand samples have high REE contents and show remarkable positive Eu anomalies due to the presence of feldspar. The best results are obtained using all of the geological methods and the Principal Component Analysis (PCA) as a measure of the similarity between sound-producing sand and silent sand. The difference between sound-producing sand and silent sand is obtained from the PCA results.  相似文献   

18.
Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.  相似文献   

19.
This is a 4-year longitudinal study to evaluate changes to the environment and exposure of young children associated with the introduction of methylcyclopentadienyl manganese tricarbonyl (MMT) into Australia in 2000. The cohort includes 57 females and 56 males; age range of 0.29 to 3.9 years. Samples are collected every 6 months from children in residences located at varying distances from major traffic thoroughfares in Sydney. Environmental samples: air, house and day care dustfall, soil, dust sweepings and gasoline. Samples from children: blood, urine, handwipes prior to and after playing outdoors, and a 6-day duplicate diet. All samples are analyzed for a suite of 20 elements using ICP-MS. Results are presented for the first three 6-month sampling periods for Pb and Mn. For dustfall accumulation, there was no significant change over the 3 sampling periods (time) for Pb or Mn, and a positive relationship between ‘traffic exposure' (traffic volume and proximity to the road) and Pb but not Mn. For handwipes, Pb and Mn in wipes taken from children after playing outdoors were usually significantly greater than for wipes taken prior to playing. There was no significant association between Pb or Mn in handwipes with traffic exposure. Dustfall accumulation was a significant predictor for Pb in the handwipes, and dust sweepings were a significant predictor of Mn in handwipes.  相似文献   

20.
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