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1.
High-resolution 27Al MAS NMR spectra of natural leucite recorded at H 0=11.7T contain three resolvable resonances at 27Al δ i = 69.2, 64.7, and 61.0±0.5 ppm. These three resonances are assigned to the three inequivalent framework positions of leucite: T3, T2, and T1, respectively. Fitting the observed spectra yields a Si,Al distribution for leucite in which approximately one-half of the Al is in T1 and one-quarter in each of T2 and T3. This Si,Al distribution differs substantially from those obtained by previous workers using 29Si NMR spectroscopy and X-ray diffraction. New 29Si NMR spectra and revision of previously reported 29Si NMR peak assignments, however, make the 27Al and 29Si NMR results consistent. The 27Al δ i correlate linearly with the mean T-O-T′ bond angles of the average structure, which allows the peak assignments to be made. However, this correlation lies distinctly toward higher frequency and larger bond angles than correlations for Si,Al ordered aluminosilicates, suggesting that the mean T(Al)-O-T′(Si) bond angle for each site in leucite is smaller than the mean bond angle of the average structure, which is averaged over T(Al)-O-T′(Si) and T(Si)-OT′(Si,Al) angles.  相似文献   

2.
We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An65)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t 1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t 1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 105 years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 103 years; a mean grain size of 3 mm is reached in 105 years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.  相似文献   

3.
We report petrological, chemical and Os–Nd–Sr isotopic data for the Gaositai ultramafic complex from northern North China craton (NCC) to reveal its petrogenesis. The complex shows features of Alaskan-type intrusions, including (1) the concentric zoning from dunite core, to clinopyroxenite and hornblendite in the rim, and the common cumulative textures; (2) the abundance of olivine, clinopyroxene and hornblende, and the scarcity of orthopyroxene and plagioclase, and (3) the systematic decrease in Mg# of ferromagnesian phases from core to rim, accompanied by the Fe-enrichment trend of accessory spinel. The different rock types show highly varied, radiogenic Os isotopic ratios (0.129–5.2), and unradiogenic Nd isotopic composition (εNd(t) = −8 to −15), but are homogeneous in ISr ratios (0.7054–0.7066). The (187Os/188Os)i ratios are found to be anti-correlated with εNd(t) values and whole-rock Mg# as well. These data suggest significant crustal contamination during magma evolution. The crustal contaminants are dominantly Archean mafic rocks in the lower crust, and subordinate TTG gneisses at shallower crustal levels. The parental magma was hydrous picritic in composition, derived from an enriched lithospheric mantle source above a subduction zone. The zoned pattern of the complex formed probably through “flow differentiation” of a rapidly rising crystal mush along a fracture zone that was developed as a result of lithospheric extension in a back-arc setting in the northern margin of the NCC at ca. 280 Ma.  相似文献   

4.
Study of micro-area chemical compositions indicates that phengite in albite gneiss from hole ZK2304 of the Donghai region has evident compositional zoning. SiO2 and tetrahedrally coordinated Si contents decrease, and Al2O3, AlIV and AlVI contents increase gradually from core to rim. However, K2O, MgO and FeO contents basically remain unchanged from core to rim. According to P-T estimates obtained from geothermometers and barometers, combined with previous experimental data, the core belt (micro-area I) of phengite was formed at T=637-672℃ and P=1.55-1.73 GPa, and the transitional belt (micro-area II) of the phengite were formed at r=594-654℃ and P=1.35-1.45 GPa. Towards the rim belt (micro-area III), the temperature decreased slightly, but the pressure decreased rapidly with r=542-630℃ and P=1.12-1.19 GPa. The P-T evolution path recorded by the compositional zoning of phengite is characterized by significant near-isothermal decompression, revealing that the gneiss has. undergone high-pressure-ultrahi  相似文献   

5.
High-spatial resolution carbon isotope analyses of natural graphite using secondary ion mass spectrometry (SIMS), together with conventional mass spectrometry techniques, demonstrate isotopic heterogeneity within single graphite crystals precipitated from a partially melted metamorphic rock. SIMS 13C/12C measurements were calibrated using an internal graphite standard previously analyzed by conventional isotope ratio mass spectrometry, which gave a reproducibility of 0.3‰ (1σ) at a spatial resolution of 2–3 μm. This resolution helped to identify an unusual carbon isotope distribution in a single graphite crystal from a metapelitic leucosome, showing remarkable core to rim variations with sharp δ13C steps up to 10‰. The results suggest that the graphite crystal grew from one edge to other forming layers perpendicular to the c-axis. The sharp isotopic steps indicate the presence of disequilibrium carbon isotope zoning in graphite and points to the possible existence of carbon isotope sector zoning. Intra-crystalline carbon isotope disequilibrium in graphite is believed to have resulted from the difference in diffusivity between 12C and 13C in the growth medium to the interface of graphite precipitation in different growth sectors.  相似文献   

6.
Progressive leaching of plagioclase for Sr isotopes and microdrilling for Sr and Pb isotopes from grains of plagioclase and orthopyroxene from the Critical Zone and the Lower Zone indicates that these minerals are not in isotopic equilibrium. Leaching suggests Critical Zone plagioclase either lost Rb or had a more radiogenic Sri rim relative to the core, whereas plagioclase from an Upper Zone sample is isotopically homogeneous for Sri. Microdrilling analyses of plagioclase from the Lower and Critical Zones consistently have a higher initial 87Sr/86Sr (Sri) and a less radiogenic modeled 238U/204Pb composition (μ2) than coexisting orthopyroxene. The range of calculated Sri for plagioclase and orthopyroxene is 0.70506–0.70662(34) and 0.70290–0.70654(36), respectively. The average difference in Sri between mineral pairs was 0.00095. The range of calculated μ2 for plagioclase and orthopyroxene is 9.42–10.30 (average 9.7) and 9.83–15.75 (average 10.1), respectively. The range of measured 208Pb/206Pb for plagioclase and orthopyroxene is 34.757–36.439(33) and 36.669–41.845(85), respectively. One orthopyroxenite without evidence for more than one population of crystal size distribution, nonetheless had Sri = 0.70654 (36) with calculated μ2 of 10.32 for larger grains as compared with Sri = 0.70290 (32) and calculated μ2 of 9.97 for smaller grain-size fractions. Isotopic results from this study demonstrate that whole-rock isotopic data may not provide the appropriate level of detail necessary to address some processes in the Bushveld Complex. However, systematic changes have the potential to elucidate the timing of contamination with regard to other processes (crystal aging, compaction-driven recrystallization, and mineral exsolution) occurring within a slowly cooled crystal–liquid–vapor mush system.  相似文献   

7.
Observations by transmission electron microscopy (TEM) of the submicrometer phases present in calcium aluminate cements have shown that Ca-Al-Fe oxides coexist in two forms with brownmillerite (b) and perovskite (p) structures, respectively. Homogeneous single crystals of both brownmillerite and perovskite have been observed but exsolved lamellae also occur on the scale of tens of nanometers. Perovskite lamellae in brownmillerite exhibit coherent interfaces with an almost perfect [1 0 1]b = {1 0 0}p topotactic relationship. Energy-dispersive X-ray spectroscopy (EDXS) measurements show that perovskite lamellae are enriched in Ti and Si relative to the brownmillerite lamellae. The perovskite phase may accommodate up to 0.17 Si atoms per formula unit, but the exsolution process seems mainly to concern the Ti content. It is estimated that the solvus width ranges between concentrations of 0.06 < Ti < 0.13 atoms per formula unit. O K and Fe L 2,3 edges collected by electron energy loss spectrometry (EELS) confirm that both phases are mainly composed of Fe3+, requiring that the perovskite is highly oxygen-deficient. Al K and Si K EELS spectra have features comparable with those of fourfold-co-ordinated Al and Si sites, suggesting that they are probably located close to oxygen-vacant sites. Received: 23 June 1999 / Accepted: 18 February 2000  相似文献   

8.
OH in zoned amphiboles of eclogite from the western Tianshan,NW-China   总被引：1，自引：0，他引：1  
Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member ( B Na2 C M2+ 3 M3+ 2 T Si8(OH)2) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition ( A 0.5 B Ca1.5Na0.5 C M 2+ 4.5 M 0.53+ T Si7.5Al0.5(OH)2) (A = Na and/or K; M 2+ = Mg and Fe2+; M 3+ = Fe3+ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm−1) which can be attributed to a local O(3)-H dipole surrounded by M(1) M(3)Mg3, M(1) M(3)Mg2Fe2+ and M(1) M(3) Fe2+ 3, respectively, an empty A site and T Si8 environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm−1) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism.  相似文献   

9.
南秦岭镇安地区发现了以白钨矿-绿柱石为矿石矿物组合的矿床新类型。为查明该矿床中首次发现的翠绿色祖母绿级绿柱石的致色机理并进一步揭示其成矿机制,本文在野外地质调查的基础上,对绿柱石开展了电子探针与微区X射线衍射等矿物学研究。结果表明:矿区中首次发现的祖母绿级绿柱石,呈自形晶产于石英(方解石)脉中并与白钨矿共(伴)生。祖母绿级绿柱石从核部至边缘V2O3含量较高,分别为0.64%~0.98%和1.04%~1.42%,且有增高趋势。X射线衍射数据表明区内祖母绿为"正常"绿柱石,同时存在Al■Me2+和Be■Li两种类质同象替换机制。V为本区祖母绿主要致色元素,来自于区内碳质板岩、金云母片岩及白云质大理岩等地层,Be、Si、Al等主要元素则来自于深部酸性岩浆岩。本次发现为该矿床中钨、铍矿产资源的综合开发利用提供了基础地质资料,并为南秦岭在区域及深部继续寻找稀有金属矿指出新的找矿方向。  相似文献   

10.
Al-containing MgSiO3 perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg0.975Si0.975Al0.05O3 and Mg0.95Si0.95Al0.10O3 considering only coupled substitution Mg2+ + Si4+ = 2Al3+, and nonstoichiometric compositions of Mg0.99Si0.96Al0.05O2.985 and Mg0.97Si0.93Al0.10O2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si4+ = 2Al3+ + VO¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X Al range of 0–0.05, where X Al is Al number on the basis of total cation of two (X Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X Al of 0.10, though they are the same as each other at X Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O6 octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.  相似文献   

11.
 Selenomethionine (SeM) is an organic toxicant that is present in seleniferous environments. No kinetic data is yet available regarding SeM reactions in coal mine environments, where selenium (Se) toxicity is a potential concern. A kinetic study was conducted on two reclaimed coal mine soils (Typic Torriorthents) from Wyoming having sandy and clayey textures. Four levels of SeM treatments (0, 50, 100 μM, and plant amendment from the mine vegetation) were reacted with the soils for 4, 7, 14, 28, 42, 56, and 84 days to characterize the kinetic behavior of overall SeM disappearance from soil solutions. Detection of SeM in soil solutions at the control level (0 μM SeM) indicated occurrence of indigenous SeM in the soils. In the plant-amended soil solutions, much greater concentrations of SeM were observed as compared with the soil-only systems. This indicated the plant material was a more potential source of SeM than the mine soils. A time-dependent loss in solution SeM concentrations was observed for both soils under 0, 50, 100 μM SeM treatments. For the soil-plant mixtures, the solution SeM concentration increased initially, reached a maximum after 14 days, and then decreased thereafter. In the plant-amended soil solutions, SeM concentrations at all time intervals were higher for the sandy as compared to the clayey soil. At 50 and 100 μM SeM treatments, the solution pH was linearly related to the percentages of SeM disappeared from the solutions; greater percentage of SeM was removed from solutions at comparatively lower pH levels, which was ≥90% at pH 7.7 for both soils. Solution SeM concentrations decreased exponentially with time following first-order kinetic reactions. Under all applications (except for the control), C 0 (SeM concentration at t=0) values for the sandy soil were greater than those determined for the clayey soil, indicating higher solution SeM availability for the former and more SeM retention by the latter at t=0. Comparison of C 0 in controls (0 μM SeM addition) suggested greater indigenous SeM in the clayey soil. For both soils, C 0 values under different treatments followed the order, (soil+100 μM)>(soil+50 μM)>(soil+0 μM). The specific reaction rate constants (K r) of SeM for both soils were similar (0.031 and 0.029 day–1 for sandy and clayey soils, respectively); low K r values indicated that SeM loss from our reclaimed coal mine soil solutions would follow rather slow kinetics. The half-life (t 0.5) of SeM varied from 15 to 55 days depending on treatment level. The knowledge obtained from this study should contribute in developing time-based Se reclamation strategies in coal mine environments. Received: 18 September 1995 · Accepted: 28 December 1995  相似文献   

12.
The rate of static dislocation recovery in Fo90 olivine has been studied under conditions of high temperature and controlled atmosphere in compressively deformed polycrystals hot-pressed from synthetic (sol–gel) and natural (San Carlos) precursor powders. The sol–gel olivine, containing a small fraction of orthopyroxene, was deformed to a final strain of 19% with a maximum differential stress of 266 MPa whereas the San Carlos specimen was deformed to 15% strain and 260 MPa differential stress. Small samples cut from these deformed materials were annealed under high-temperature, controlled atmosphere conditions, for different durations to allow partial recovery of the dislocation sub-structures. Oxidative-decoration of the microstructural features, followed by backscattered electron imaging at 5 kV and image analysis, was used to determine dislocation density. The variation of dislocation density ρ with time t at absolute temperature T was fitted to a second-order rate equation, in integral form, 1/ρ(t) − 1/ρ(0) = kt with k = k 0 exp(−E a/RT). The activation energy E a of the recovery process is 240 ± 43 and 355 ± 81 kJ mol−1 for sol–gel and San Carlos olivine polycrystals, respectively. The measured rates are one to two orders of magnitude lower than those reported in previous studies on natural single crystal olivine. The difference may be explained by several factors such as high dislocation densities measurable from large areas at high magnification for the SEM and the technique used to estimate dislocation densities. Comparison between fine-grained sol–gel olivine and the coarser-grained San Carlos olivine aggregate did not indicate that grain boundaries play an important role in dislocation recovery, but the absence of grain boundaries might also have contributed to the high dislocation recovery rates previously measured for single crystals.  相似文献   

13.
Within the KUSTOS program (Coastal Mass and Energy Fluxes-the Land-Sea Transition in the Southeastern North Sea) 28 to 36 German Bight stations were seasonally surveyed (summer 1994, spring 1995, winter 1995–1996) for light conditions, dissolved inorganic nutrient concentrations, chlorophylla (chla), and photosynthesis versus light intensity (P:E) parameters. Combining P:E curve characteristics with irradiance, attenuation, and chlorophyll data resulted in seasonal estimates of the spatial distribution of total primary production. These data were used for an annual estimate of the total primary production in the Bight. In winter 1996 the water throughout the German Bight was well mixed. Dissolved inorganic nutrient concentrations were relatively high (nitrogen [DIN], soluble reactive phosphorus [SRP], and silicate [Si]: 23, 1, and 10 μM, respectively). Chla levels generally were low (< 2 μg l−1) with higher concentrations (4–16 μg l−1) in North Frisian coastal waters. Phytoplankton was limited by light. Total primary production averaged 0.2 g C m−2 d−1. Two surveys in April and May 1995 captured the buildup of a strong seasonal thermo-cline accompained by the development of a typical spring diatom bloom. High nutrient levels in the mixed layer during the first survey (DIN, SRP, and Si: 46, 0.45, and 11 μM, respectively) decreased towards the second survey (DIN, SRP, and Si: 30.5, 0.12, and 1.5 μM, respectively) and average nutrient ratios shifted further towards highly imbalanced values (DIN:SRP: 136 in survey 1, 580 in survey 2; DIN:Si: 13.5 in survey 1, 96 in survey 2). Chla ranged from 2 to 16 μg l−1 for the first survey and rose to 12–50 μg l−1 in the second survey. Phytoplankton in nearshore areas continued to be light limited during the second survey, while data from the stratified regions in the open German Bight indicates SRP and Si limitation. Total primary production ranged from 4.0 to 6.3 g C m−2 d−1. During summer 1994 a strong thermal stratification was present in the German Bight proper and shallow coastal areas showed unusually warm (up to 22°C), mixed waters. Chla concentrations ranged from 2 to 18 μg l−1. P:E characteristics were relatively high despite the low nutrient regime (DIN, SRP, and Si: 2, 0.2, and 1.5 μM, respectively), resulting in overall high total primary production values with an average of 7.7 g C m−2 d−1. Based on the seasonal primary production estimates of the described surveys a budget calculation yielded a total annual production of 430 g C m−2 yr−1 for the German Bight.  相似文献   

14.
In situ analysis of a garnet porphyroblast from a granulite facies gneiss from Sør Rondane Mountains, East Antarctica, reveals discontinuous step‐wise zoning in phosphorus and large δ18O variations from the phosphorus‐rich core to the phosphorus‐poor rim. The gradually decreasing profile of oxygen isotope from the core (δ18O = ~15‰) to the rim (δ18O = ~11‰) suggests that the 18O/16O zoning was originally step‐wise, and modified by diffusion after the garnet rim formation at ~800°C and 0.8 GPa. Fitting of the 18O/16O data to the diffusion equation constrains a duration of the high‐T event (~800°C) to c. 0.5–40 Ma after the garnet rim formation. The low δ18O value of the garnet rim, together with the previously reported low δ18O values in metacarbonates, indicates regional infiltration, probably along a detachment fault, of low δ18O fluid/melt possibly derived from meta‐mafic to ultramafic rocks.  相似文献   

15.
Low‐T eclogites in the North Qilian orogen, NW China share a common assemblage of garnet, omphacite, glaucophane, epidote, phengite, quartz and rutile with or without paragonite. Phase relations for the low‐T eclogites can be modelled well in the system NCKFMASHO with the updated solid‐solution models for amphibole and clinopyroxene. Garnet in the eclogite typically exhibits growth zonations in which pyrope increases while grossular somewhat decreases from core to rim, which is modelled as having formed mainly in the P–T conditions of lawsonite‐eclogite facies at the pre‐peak stage. Omphacite shows an increase in jadeite component as aegirine and also total FeO decrease in going from the inclusions in garnet to grains in the matrix, and from core to rim of zoned crystals, reflecting an increase in metamorphic P–T conditions. Glaucophane exhibits a compositional variation in X(gl) (= Fe2+/(Fe2+ + Mg)) and F(gl) (= Fe3+/(Fe3+ + Al) in M2 site), which decrease from the inclusions in garnet to crystals in the matrix, consistent with an increase in P–T conditions. However, for zoned matrix crystals, the X(gl) and F(gl) increase from core to rim, is interpreted to reflect a late‐stage decompression. Using composition isopleths for garnet rim and phengite in P–T pseudosections, peak P–T conditions for three samples Q5–45, Q5–01 and Q7–28 were estimated as 530–540 °C at 2.10–2.25 GPa, 580–590 °C at 2.30–2.45 GPa and 575–590 °C at 2.50–2.65 GPa, respectively, for the same assemblage garnet + omphacite + glaucophane + lawsonite (+ phengite + quartz + rutile) at the peak stage. The eclogites suggest similar P–T ranges to their surrounding felsic–pelitic schists. During post‐peak decompression of the eclogites, the most distinctive change involves the transformation of lawsonite to epidote, releasing large amount of water in the rock. The released fluid promoted further growth of glaucophane at the expense of omphacite and, in appropriate bulk‐rock compositions, paragonite formed. The decompression of eclogite did not lead to pronounced changes in garnet and phengite compositions. Peak P–T conditions of the North Qilian eclogite are well constrained using both the average P–T and pseudosection approaches in Thermocalc. Generally, the conventional garnet–clinopyroxene geothermometer is too sensitive to be used for constraining the temperature of low‐T eclogite because of the uncertainty in Fe3+ determination in omphacite and slight variations in mineral compositions because of incomplete equilibration.  相似文献   

16.
Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l−1, As 1–125 μg l−1, Br 6–60 μg l−1, Cl 500–25,000 μg l−1, Cr 1–6 μg l−1, Cu 1–15 μg l−1, Fe 10–352 μg l−1, Mg 2,940–40,100 μg l−1, Mn 0–8 μg l−1, Na 3,650–13,740 μg l−1, P 20–48 μg l−1, Pb 0–7 μg l−1, Sb 0–21 μg l−1, Si 3,310–13,240 μg l−1 and Zn 7–994 μg l−1. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.  相似文献   

17.
Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl2O4 spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D Cr–Al = D 0 exp {−(Q′ + PV*)/RT}, where D 0 = exp{(10.3 ± 0.08) × Cr#0.54±0.02} + (1170 ± 31.2) cm2/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm3/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.  相似文献   

18.
To evaluate the applicability of P2O5 concentration in potassic alkali feldspar as a monitor of P2O5 in melt for undercooled systems, crystal–melt partitioning for P was evaluated via feldspar growth experiments in P-bearing ((3 wt% P2O5), water-saturated haplogranitic liquids at 200 MPa, with liquidus undercoolings (ΔT) of 25, 50, 100, 200, and 300°C. Increasing undercooling in the range ΔT=25–200°C shows an evolution of crystal morphologies, from euhedral and well-filled individuals at ΔT=25–50°C to radial clusters with increasingly skeletal habit at greater undercooling. Experiments at ΔT=100–200°C also document the development of P- (up to (9 wt% P2O5) and Si-enriched, more alkaline boundary layers adjacent to crystals. Experiments at ΔT=300°C show an additional change in crystallization fabric in which spherulites of skeletal crystals form in open (vapor) space created by the dissolution of bulk silicate, and compositional boundary layers are not observed. We interpret the changes in reaction products at ΔT=300°C to indicate conditions below a glass transition; hence, partition coefficients were not determined for this undercooling. Values of K d(P)Kfs/melt from experiments at ΔT=25–200°C, calculated from pairs of crystal and immediately adjacent liquid compositions (including boundary layers at higher undercooling), are mostly in the range of 0.25–0.55 and show no effective change with increased undercooling. Essentially no change in K d(P)Kfs/melt with undercooling apparently stems from an interplay between boundary layer composition and a change in the substitution mechanism for P in feldspar from AlPSi−2, common in peraluminous to metaluminous liquids near equilibrium, to increasing proportions of ([ ],P)(M+,Si)−1 with increased undercooling. Bulk glass and liquid beyond boundary layers in experiments with significant percentages of crystallization are homogeneous, and show pronounced fractionation primarily due to the removal of an orthoclase component. Because crystallization was still in progress in experiments with ΔT≤200°C, compositional homogeneity in the bulk liquid requires extremely rapid diffusion of most haplogranite components (Na, K, and Al), apparently resulting from chemical potential gradients stemming from the removal of components from the liquid by crystal growth. Similar homogeneity and bulk fractionation in experiments with ΔT=300°C requires rapid diffusive equilibration for the alkalis even at temperatures below an apparent glass transition. Unlike the haplogranite components, P is only concentrated in liquid boundary layers (ΔT≤200°C) or low-density aqueous vapor (ΔT=300°C) adjacent to crystals. Hence, the P2O5 contents of melt inclusions likely are not representative of bulk melt concentrations in significantly undercooled systems (ΔT≤50–100°C).  相似文献   

19.
Euhedral dissakisites from Trimouns dolomite mine, France, is compositionally zoned. Back-scattered electron (BSE) images reveal that each of the described dissakisite crystals has three distinct compositional zones: normal zoned core (Mg-rich), oscillatory zoned middle (Ca–Al-rich) and homogeneous rim (Fe–ΣREE-rich). The latter zone with Fe2+ > Mg corresponds to allanite-(Ce). Dissakisite-(Ce) also displays pronounced zoning in Fe/Mg which may suggest that the temperature of crystallization continuously decreased from core to rim. Despite a systematic increase in Fe/Mg of the dissakisite with an allanite rim, there is no monotonic decrease in the REE zoning: the normal zoned core and homogeneous rim are rich in La, Ce and Pr, but the relatively REE-poor oscillatory zoned middle is relatively abundant in Y, Sm and Gd. Discontinuous variation in REE content of the dissakisite, with the allanite rim may indicate a localized change in either the relative concentration of various ligands or pH of the crystallizing fluid. Observations under the polarizing microscope confirm that the different zones have simultaneous extinction. These chemical and optical observations suggest that epitaxial crystallization of dissakisite, from Trimouns, passes through three formation stages. The ternary Fe2+–Mg2+–(Al + Fe)3+ diagram illustrates that in general dissakisite can be classified into two groups, (Al + Fe)3+-rich and an Mg-rich; dissakisite from Trimouns belongs to the former group. Chondrite-normalized REE patterns of dissakisites from Trimouns are similar to those of allanites formed by hydrothermal fluids. In conclusion, it is clear from the above two geochemical characteristics that dissakisites from Trimouns are of (Al + Fe)3+-type, and were derived from hydrothermal fluids.  相似文献   

20.
The mechanism of re-equilibration of albite in a hydrothermal fluid has been investigated experimentally using natural albite crystals in an aqueous KCl solution enriched in 18O at 600°C and 2 kbars pressure. The reaction is pseudomorphic and produces a rim of K-feldspar with a sharp interface on a nanoscale which moves into the parent albite with increasing reaction time. Transmission electron microscopy (TEM) diffraction contrast and X-ray powder diffraction (XRD) show that the K-feldspar has a very high defect concentration and a disordered Al, Si distribution, compared to the parent albite. Raman spectroscopy shows a frequency shift of the Si-O-Si bending vibration from ~476 cm−1 in K-feldspar formed in normal 16O aqueous solution to ~457 cm−1 in the K-feldspar formed in 18O-enriched solution, reflecting a mass-related frequency shift due to a high enrichment of 18O in the K-feldspar silicate framework. Raman mapping of the spatial distribution of the frequency shift, and hence 18O content, compared with major element distribution maps, show a 1:1 correspondence between the reaction rim formed by the replacement of albite by K-feldspar, and the oxygen isotope re-equilibration. The textural and chemical characteristics as well as the kinetics of the replacement of albite by K-feldspar are consistent with an interface-coupled dissolution-reprecipitation mechanism.  相似文献   

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