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1.
The thermoelastic behaviour of anthophyllite has been determined for a natural crystal with crystal-chemical formula ANa0.01 B(Mg1.30Mn0.57Ca0.09Na0.04) C(Mg4.95Fe0.02Al0.03) T(Si8.00)O22 W(OH)2 using single-crystal X-ray diffraction to 973 K. The best model for fitting the thermal expansion data is that of Berman (J Petrol 29:445–522, 1988) in which the coefficient of volume thermal expansion varies linearly with T as α V,T  = a 1 + 2a 2 (T − T 0): α298 = a 1 = 3.40(6) × 10−5 K−1, a 2 = 5.1(1.0) × 10−9 K−2. The corresponding axial thermal expansion coefficients for this linear model are: α a ,298 = 1.21(2) × 10−5 K−1, a 2,a  = 5.2(4) × 10−9 K−2; α b ,298 = 9.2(1) × 10−6 K−1, a 2,b  = 7(2) × 10−10 K−2. α c ,298 = 1.26(3) × 10−5 K−1, a 2,c  = 1.3(6) × 10−9 K−2. The thermoelastic behaviour of anthophyllite differs from that of most monoclinic (C2/m) amphiboles: (a) the ε 1 − ε 2 plane of the unit-strain ellipsoid, which is normal to b in anthophyllite but usually at a high angle to c in monoclinic amphiboles; (b) the strain components are ε 1 ≫ ε 2 > ε 3 in anthophyllite, but ε 1 ~ ε 2 ≫ ε 3 in monoclinic amphiboles. The strain behaviour of anthophyllite is similar to that of synthetic C2/m ANa B(LiMg) CMg5 TSi8 O22 W(OH)2, suggesting that high contents of small cations at the B-site may be primarily responsible for the much higher thermal expansion ⊥(100). Refined values for site-scattering at M4 decrease from 31.64 epfu at 298 K to 30.81 epfu at 973 K, which couples with similar increases of those of M1 and M2 sites. These changes in site scattering are interpreted in terms of Mn ↔ Mg exchange involving M1,2 ↔ M4, which was first detected at 673 K.  相似文献   

2.
An in situ synchrotron X-ray diffraction study was carried out on ε-FeOOH at room temperature up to a pressure of 8.6 GPa using the energy-dispersive method. The linear compressibility was determined to be β a  = 1.69(3) × 10−3 GPa−1, β b  = 2.86(6) × 10−3 GPa−1, and β c  = 1.73(5) × 10−3 GPa−1. The b-axis of the unit cell is more compressible than the a and c axes. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state. The best fit was found using a room temperature isothermal bulk modulus of K 0 = 126(3) GPa and its pressure derivative K′ = 10(1).  相似文献   

3.
The high-pressure elastic behaviour of a synthetic zeolite mordenite, Na6Al6.02Si42.02O96·19H2O [a=18.131(2), b=20.507(2), c=7.5221(5) Å, space group Cmc21], has been investigated by means of in situ synchrotron X-ray powder diffraction up to 5.68 GPa. No phase transition has been observed within the pressure range investigated. Axial and volume bulk moduli have been calculated using a truncated second-order Birch–Murnaghan equation-of-state (II-BM-EoS). The refined elastic parameters are: V 0=2801(11) Å3, K T0= 41(2) GPa for the unit-cell volume; a 0=18.138(32) Å, K T0(a)=70(8) GPa for the a-axis; b 0=20.517(35) Å, K T0(b)=29(2) GPa for the b-axis and c 0=7.531(5) Å, K T0(c)=38(1) GPa for the c-axis [K T0(a): K T0(b): K T0(c)=2.41:1.00:1.31]. Axial and volume Eulerian finite strain versus “normalized stress” plots (fe–Fe plot) show an almost linear trend and the weighted linear regression through the data points yields the following intercept values: Fe(0)=39(4) GPa for V; Fe a (0)=65(18) GPa for a; Fe b (0)=28(3) GPa for b; Fe c (0)=38(2) GPa for c. The magnitudes of the principal Lagrangian unit-strain coefficients, between 0.47 GPa (the lowest HP-data point) and each measured P>0.47 GPa, were calculated. The unit-strain ellipsoid is oriented with ε1 || b, ε2 || c, ε3 || a and |ε1|> |ε2|> |ε3|. Between 0.47 and 5.68 GPa the relationship between the unit-strain coefficient is ε1: ε2: ε3=2.16:1.81:1.00. The reasons of the elastic anisotropy are discussed.An erratum to this article can be found at  相似文献   

4.
The thermo-elastic behavior of a natural epidote [Ca1.925 Fe0.745Al2.265Ti0.004Si3.037O12(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 458.8(1)Å3, K T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a 0 = 8.8877(7) Å, K T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b 0 = 5.6271(7) Å, K T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c 0 = 10.1527(7) Å, K T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K T0(a):K T0(b):K T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, βP(°) = βP0 −0.0286(9)P +0.00134(9)P 2 (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α0 + α1 T −1/2. The refined parameters for epidote are: α0 = 5.1(2) × 10−5 K−1 and α1 = −5.1(6) × 10−4 K1/2 for the unit-cell volume, α0(a) = 1.21(7) × 10−5 K−1 and α1(a) = −1.2(2) × 10−4 K1/2 for the a-axis, α0(b) = 1.88(7) × 10−5 K−1 and α1(b) = −1.7(2) × 10−4 K1/2 for the b-axis, and α0(c) = 2.14(9) × 10−5 K−1 and α1(c) = −2.0(2) × 10−4 K1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α0(a): α0(b): α0(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with βT(°) = βT0 + 2.5(1) × 10−4 T + 1.3(7) × 10−8 T 2. A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.  相似文献   

5.
The high-pressure X-ray diffraction study of a natural arsenopyrite was investigated up to 28.2 GPa using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at National Synchrotron Light Source, Brookhaven National Laboratory. The 16:3:1 methanol–ethanol–water mixture was used as a pressure-transmitting medium. Pressures were measured using the ruby-fluorescence method. No phase change has been observed up to 28.2 GPa. The isothermal equation of state (EOS) was determined. The values of K 0, and K′ 0 refined with a third-order Birch–Murnaghan EOS are K 0 = 123(9) GPa, and K′ 0 = 5.2(8). Furthermore, we confirm that the linear compressibilities (β) along a, b and c directions of arsenopyrite is elastically isotropic (β a  = 6.82 × 10−4, β b  = 6.17 × 10−4 and β c  = 6.57 × 10−4 GPa−1).  相似文献   

6.
The behavior of selenium at the Earth’s surface and nearby at low temperatures and pressures is controlled by variations of the redox potential and the acidity of solutions. These parameters determine the migration of selenium and its precipitation as various solid phases. Understanding the mechanism of selenium’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with selenium (a ΣSe = 10−9, a ΣFe = 10−5, a ΣCu = 10−7, a ΣZn = 5 × 10−7, a ΣCo = 10−8, a ΣNi = 6 × 10−8, a ΣPb = 10−8) and in waters formed in the oxidation zone (a ΣSe = 10−5–10−4, a ΣFe = 10−2, a ΣCu = 10−2, a ΣZn = 5 × 10−2, a ΣCo = 10−3, a ΣNi = 10−2, a ΣPb = 10−4) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-Se-H2O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in underground water and for their contents in oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb selenites and selenates at the surface is discussed.  相似文献   

7.
The thermoelastic behavior of a natural clintonite-1M [with composition: Ca1.01(Mg2.29Al0.59Fe0.12)Σ3.00(Si1.20Al2.80)Σ4.00O10(OH)2] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 457.1(2) ?3, K T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K T0(a) = 0.0023(1) GPa−1; β(b) = 1/3K T0(b) = 0.0018(1) GPa−1; β(c) = 1/K T0(c) = 0.0072(3) GPa−1]. The β-angle increases in response to the applied P, with: βP = β0 + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α0 + α1 T −1/2. The refined parameters for clintonite are as follows: α0 = 2.78(4) 10−5°C−1 and α1 = −4.4(6) 10−5°C1/2 for the unit-cell volume; α0(a) = 1.01(2) 10−5°C−1 and α1(a) = −1.8(3) 10−5°C1/2 for the a-axis; α0(b) = 1.07(1) 10−5°C−1 and α1(b) = −2.3(2) 10−5°C1/2 for the b-axis; and α0(c) = 0.64(2) 10−5°C−1 and α1(c) = −7.3(30) 10−6°C1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.  相似文献   

8.
The behavior of arsenic at the Earth’s surface and nearby at low temperatures and pressures depends mainly on the redox potential and the acidity-alkalinity of the crystallization media. These parameters determine the migration of arsenic compounds and their precipitation as various solid phases. Understanding the mechanism of arsenic’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of the components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with arsenic (a ΣAs = 3 × 10−8, a ΣFe = 10−5, a ΣCu = 10−7, a ΣZn = 5 × 10−7, a ΣCo = 10−8, a ΣNi = 6 × 10−8, a ΣPb = 10−8) and in waters formed in the oxidation zone (a ΣSe = 10−3, a ΣFe = 10−2, a ΣCu = 10−2, a ΣZn = 5 × 10−2, a ΣCo = 10−3, a ΣNi = 10−2, a ΣPb = 10−4) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-As-H2O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in the underground water and for their higher contents in the oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb arsenates at the surface is discussed.  相似文献   

9.
The elastic behaviour and the high-pressure structural evolution of a natural topaz, Al2.00Si1.05O4.00(OH0.26F1.75), have been investigated by means of in situ single-crystal X-ray diffraction up to 10.55(5) GPa. No phase transition has been observed within the pressure range investigated. Unit-cell volume data were fitted with a third-order Birch-Murnaghan Equation of State (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are: V 0=345.57(7) Å3, K T0=164(2) GPa and K′=2.9(4). The axial-EoS parameters are: a 0=4.6634(3) Å, K T0(a)=152(2) GPa, K′(a)=2.8(4) for the a-axis; b 0=8.8349(5) Å, K T0(b)=224(3) GPa, K′(b)=2.6(6) for the b-axis; c 0=8.3875(7) Å, K T0(c)=137(2) GPa, K′(c)=2.9(4) for the c-axis. The magnitude and the orientation of the principal Lagrangian unit-strain ellipsoid were determined. At P−P 0=10.55 GPa, the ratios ε1:ε2:ε3 are 1.00:1.42:1.56 (with ε1||b, ε2||a, ε3||c and |ε3| > |ε2| > |ε1|). Four structural refinements, performed at 0.0001, 3.14(5), 5.79(5) and 8.39(5) GPa describe the structural evolution in terms of polyhedral distortions.  相似文献   

10.
Salt spray is one of many abiotic factors that can influence plant productivity and species composition in coastal ecosystems. However, little is known about how marsh plants respond physiologically to the accumulation of sea aerosols on foliar tissues. In this study, experimental microcosms maintained in controlled greenhouse conditions were used to evaluate how low- (1.7 mg dm−2 day−1, weekly averages) and high- (8.6 mg dm−2 day−1) salt-spray loads would influence plant–water relations in Spartina alterniflora (Loisel.). While no differences in plant performance (e.g., changes in biomass and leaf area) were observed between the treatments and control plants, a number of physiological modifications attributed to salt spray were observed. In general, salt-treated plants underwent significant decreases in water potential (Ψ) and osmotic potential (Ψ π) and increases in leaf conductance (g) and bulk modulus of elasticity (ε). It is likely that these physiological responses were used to generate lower Ψ while maintaining osmotic and water homeostasis. That is, by decreasing Ψ π and increasing g and ε, more efficient water flow through the soil–plant–atmosphere continuum can be achieved, thus generating lower Ψ without promoting loss of turgor.  相似文献   

11.
Recent zircon dating identified several late Carboniferous to early Permian hornblende gabbro–diorite–quartz diorite–granodiorite–tonalite–granite plutons in lithological assemblages at the northern margin of the North China Block (NCB) that were previously regarded as Archaean to Palaeoproterozoic. Our geochronological results indicate that emplacement of these plutons was a continuous process during the late Carboniferous to early Permian, from 324 ± 6 to 274 ± 6 Ma, and lasted for at least 50 Ma. In this paper, the early Permian components with compositions from gabbro to granite within the intrusive complex were studied. The early Permian plutons exhibit calc-alkaline or high-K calc-alkaline, metaluminous geochemical features and highly variable SiO2 contents. They have no significant Eu anomaly in their REE patterns, and in primitive-mantle-normalized spidergrams they display depletion in Th, U, Nb, Ta, P and Ti, and enrichment in Ba, K, Pb and Sr. The granitoid bodies within these plutons display I-type and adakitic geochemical signatures. The early Permian rocks exhibit low whole-rock initial 87Sr/86Sr ratios from 0.70520 to 0.70615 and have negative whole-rock ε Nd(t) values ranging from −17.4 to −9.3 and zircon ε Hf(t) values of −23.2 to −10.5. The gabbros exhibit higher ε Nd(t) values from −11.1 to −9.3 and ε Hf(t) values from −16.5 to −10.5, and one granodiorite exhibits an even lower ε Nd(t) value of −17.4 and zircon ε Hf(t) values of −23.2 to −15.1. Geochemical, Sr–Nd and in situ zircon Hf isotopic compositions suggest that the hornblende gabbros were derived from a metasomatized lithospheric mantle, and the diorite and quartz diorite were generated from a gabbroic magma by fractional crystallization, coupled with differential assimilation of ancient lower crustal material. The granodiorite was likely derived from partial melting of ancient lower crust with involvement of some mantle components. Involvement of both lithospheric mantle and ancient lower crust in the generation of the early Permian plutons indicates strong crust–mantle interaction in the northern NCB. Petrological associations as well as geochemical and Sr–Nd–Hf isotopic results show that the early Permian plutons were emplaced along an Andean-type active continental margin during southward subduction of the Palaeo-Asian oceanic plate beneath the NCB. Integration of our results with previously published data for late Carboniferous and late Permian to middle Triassic intrusions suggests that the continental arc on the northern margin of the NCB existed for at least 50 Ma during the late Palaeozoic, and final amalgamation of the Mongolian arc terranes with the northern NCB likely occurred during a period from ~270 to ~250 Ma, i.e, in the late Permian to earliest Triassic.  相似文献   

12.
Using a conventional high-T furnace, the solid solutions between magnesiochromite and manganochromite, (Mg1−x Mn x )Cr2O4 with x = 0.00, 0.19, 0.44, 0.61, 0.77 and 1.00, were synthesized at 1,473 K for 48 h in open air. The ambient powder X-ray diffraction data suggest that the V–x relationship of the spinels does not show significant deviation from the Vegard’s law. In situ high-T powder X-ray diffraction measurements were taken up to 1,273 K at ambient pressure. For the investigated temperature range, the unit-cell parameters of the spinels increase smoothly with temperature increment, indicating no sign of cation redistribution between the tetrahedral and octahedral sites. The V–T data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (aT = a0 + a1 T + a2 T - 2 \alpha_{T} = a_{0} + a_{1} T + a_{2} T^{ - 2} ), which yielded insignificant a 2 values. The effect of the composition on a 0 is adequately described by the equation a 0 = [17.7(8) − 2.4(1) × x] 10−6 K−1, whereas that on a 1 by the equation a 1 = [8.6(9) + 2.1(11) × x] 10−9 K−2.  相似文献   

13.
Petrogenesis of high Mg# adakitic rocks in intracontinental settings is still a matter of debate. This paper reports major and trace element, whole-rock Sr–Nd isotope, zircon U–Pb and Hf isotope data for a suite of adakitic monzogranite and its mafic microgranular enclaves (MMEs) at Yangba in the northwestern margin of the South China Block. These geochemical data suggest that magma mixing between felsic adakitic magma derived from thickened lower continental crust and mafic magma derived from subcontinental lithospheric mantle (SCLM) may account for the origin of high Mg# adakitic rocks in the intracontinental setting. The host monzogranite and MMEs from the Yangba pluton have zircon U–Pb ages of 207 ± 2 and 208 ± 2 Ma, respectively. The MMEs show igneous textures and contain abundant acicular apatite that suggests quenching process. Their trace element and evolved Sr–Nd isotopic compositions [(87Sr/86Sr)i = 0.707069–0.707138, and εNd(t) = −6.5] indicate an origin from SCLM. Some zircon grains from the MMEs have positive εHf(t) values of 2.3–8.2 with single-stage Hf model ages of 531–764 Ma. Thus, the MMEs would be derived from partial melts of the Neoproterozoic SCLM that formed during rift magmatism in response to breakup of supercontinent Rodinia, and experience subsequent fractional crystallization and magma mixing process. The host monzogranite exhibits typical geochemical characteristics of adakite, i.e., high La/Yb and Sr/Y ratios, low contents of Y (9.5–14.5 ppm) and Yb, no significant Eu anomalies (Eu/Eu* = 0.81–0.90), suggesting that garnet was stable in their source during partial melting. Its evolved Sr–Nd isotopic compositions [(87Sr/86Sr)i = 0.7041–0.7061, and εNd(t) = −3.1 to −4.3] and high contents of K2O (3.22–3.84%) and Th (13.7–19.0 ppm) clearly indicate an origin from the continental crust. In addition, its high Mg# (51–55), Cr and Ni contents may result from mixing with the SCLM-derived mafic magma. Most of the zircon grains from the adakitic monzogranite show negative εHf(t) values of −9.4 to −0.1 with two-stage Hf model ages of 1,043–1,517 Ma; some zircon grains display positive εHf(t) of 0.1–3.9 with single-stage Hf ages of 704–856 Ma. These indicate that the source region of adakitic monzogranite contains the Neoproterozoic juvenile crust that has the positive εHf(t) values in the Triassic. Thus, the high-Mg adakitic granites in the intracontinental setting would form by mixing between the crustal-derived adakitic magma and the SCLM-derived mafic magma. The mafic and adakitic magmas were generated coevally at Late Triassic, temporally consistent with the exhumation of deeply subducted continental crust in the northern margin of the South China Block. This bimodal magmatism postdates slab breakoff at mantle depths and therefore is suggested as a geodynamic response to lithospheric extension subsequent to the continental collision between the South China and North China Blocks.  相似文献   

14.
The natural norbergite, Mg2.98Fe0.01Ti0.02Si0.99O4(OH0.31F1.69) is examined by synchrotron X-ray diffraction analysis at pressures up to 8.2 GPa. The measured linear compressibilities of the crystallographic axes are β a  = 2.18(4) × 10−3, β b  = 2.93(7) × 10−3, and β c  = 2.77(7) × 10−3 (GPa−1), respectively and the calculated isothermal bulk modulus of the norbergite is K T = 113(2) GPa based on the Birch–Murnaghan equation of state assuming a pressure derivative of K′ = 4. The crystal structures of norbergite are refined at room temperature and pressures of 4.7, 6.3, and 8.2 GPa, yielding R values for the structure refinements of 4.6, 5.3, and 5.3%, respectively. The bulk moduli of the polyhedral sites are 293(15) GPa for the tetrahedron, 106(5) GPa for the M2 octahedron, 113(2) GPa for the M3 octahedron, and 113(3) GPa for the total void space. The bulk modulus exhibits a good linear correlation with the filling factor for polyhedral sites in structures of the humite minerals and forsterite, reflecting the Si4+ + 4O2− ⇔ □ + 4(OH, F)− substitution in the humite minerals. Moreover, two simply linear trends were observed in the relationship between bulk modulus and packing index for natural minerals and dense hydrous magnesium silicate minerals. This relationship would reflect that the differences in compression mechanism were involved with hydrogen bonding in these minerals. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

15.
Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe   总被引：6，自引：1，他引：5  
The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm−1. Bands at high energies (3,730–3,670 cm−1) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm−1 E || a, 3,597 E || a, 3,571 cm−1 E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H2O cm−2 is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H2O cm−2). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm−1). Olivine samples with a mean wavenumber of about 3,548 cm−1 should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm−1) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).
Monika Koch-MüllerEmail: Phone: +49-331-2881492
  相似文献   

16.
A new mineral species has been discovered at the calc-skarnoid occurrence near the mouth of the Tashelga River, Kuznetsky Alatau, Gorny Shoria, Russia, and named after the locality of its discovery. Associated minerals are calcite, hibonite, grossular, vesuvianite, hercynite, magnetite, corundum, perovskite, scapolite, diopside, and apatite. The new mineral occurs as prismatic or finely fibrous crystals up to 1.5–2.0 mm in length, their parallel intergrowths, and felty aggregates as large as 10 mm across. Tashelgite is bluish green, translucent to transparent, with vitreous luster; D calc = 3.67 g/cm3. The IR spectrum does not contain bands of OH groups. Tashelgite is biaxial (−), with α = 1.736(2), β = 1.746(2), γ = 1.750(2); 2V meas = −20(2)°. Dispersion is strong, r < ν. Pleochroism is distinct: X (blue-green) > Y (yellowish green) > Z (almost colorless). Chemical composition (electron microprobe, average of five-point analyses, Fe2O3 is estimated from the ratio of intensities I(FeKb5 )/I(FeKb1 )I(Fe_{K\beta _5 } )/I(Fe_{K\beta _1 } ) in the X-ray spectrum, H2O was determined as a weight loss on heating in vacuum up to 1000°C), wt %: 7.98 CaO, 6.75 MgO, 0.45 MnO, 11.32 FeO, 1.40 Fe2O3, 70.70 Al2O3, 1.8(2) H2O, 100.40 in total. The empirical formula calculated on the basis of 17 oxygen atoms is H1.27Ca0.90Mg1.06Mn0.04 Fe1.002+Fe0.113+Al8.80O17.00. The idealized formula is CaMgFe2+Al9O16(OH). According to single-crystal X-ray structural data, tashelgite is monoclinic, pseudoorthorhombic, space group Pc; unit cell parameters are: a = 5.6973(1), b = 17.1823(4), c = 23.5718(5)?; β = 90.046(3)°; V = 2307.5(1)?3, Z = 8. The crystal structure of tashelgite is unique and characterized by ordering of all cations; Al occupies sites with octahedral and tetrahedral coordination. The cation ordering has also been confirmed by IR spectroscopy. The strongest lines of the X-ray powder diffraction pattern (d, ?]-I[hkl] are: 11.79–48 [002], 2.845–43 [061], 2.616–100 [108], 2.584–81 [146], 2.437–44 [163], 2.406–61 [057], 2.202–72 [244]. The type specimen of tashlegite has been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia.  相似文献   

17.
The crystal structure of Bi2Al4−x Fe x O9 compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe3+ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi2M4O9 compounds (M = Al, Fe3+) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm−1 region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm−1 band group, which is assigned to Al(Fe3+)–O stretching vibrations of the corner-sharing MO4 tetrahedra. The Bi2Al4O9 and Bi2Fe4O9 endmembers display single bands with maxima centred at 922 and 812 cm−1, respectively. Intermediate Bi2Al4−x Fe x O9 compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm−1 range are assigned to low-energy stretching vibrations of the MO4 tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm−1 range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.  相似文献   

18.
The compressibility at room temperature and the thermal expansion at room pressure of two disordered crystals (space group C2/c) obtained by annealing a natural omphacite sample (space group P2/n) of composition close to Jd56Di44 and Jd55Di45, respectively, have been studied by single-crystal X-ray diffraction. Using a Birch–Murnaghan equation of state truncated at the third order [BM3-EoS], we have obtained the following coefficients: V 0 = 421.04(7) Å3, K T0 = 119(2) GPa, K′ = 5.7(6). A parameterized form of the BM3 EoS was used to determine the axial moduli of a, b and c. The anisotropy scheme is β c  ≤ β a  ≤ β b , with an anisotropy ratio 1.05:1.00:1.07. A fitting of the lattice variation as a function of temperature, allowing for linear dependency of the thermal expansion coefficient on the temperature, yielded αV(1bar,303K) = 2.64(2) × 10−5 K−1 and an axial thermal expansion anisotropy of α b  ≫ α a  > α c . Comparison of our results with available data on compressibility and thermal expansion shows that while a reasonable ideal behaviour can be proposed for the compressibility of clinopyroxenes in the jadeite–diopside binary join [K T0 as a function of Jd molar %: K T0 = 106(1) GPa + 0.28(2) × Jd(mol%)], the available data have not sufficient quality to extract the behaviour of thermal expansion for the same binary join in terms of composition.  相似文献   

19.
The oxidation of dihydroxyaromatics to benzoquinones by FeIII (hydr)oxides is important in respiratory electron shuttling by microorganisms and has been extensively studied. Prior publications have noted that the Gibbs Free Energy (ΔG) for the forward reaction is sensitive to dihydroxyaromatic structure, pH, and concentrations of reactants and products. Here, we address the back reaction, benzoquinone reduction by FeII. Rates markedly increase with increasing pH, in accord with increases in ΔG. Ring substituents that raise the potential of the p-benzoquinone/hydroquinone half reaction raise reaction rates: –OCH3 < –CH3 < –C6H5 < –H < –Cl. p-Naphthoquinone, with a reduction potential lower than the five substituted p-benzoquinones just listed, yields the lowest reaction rates. The complexity of the reaction is reflected in lag periods and less-pronounced S-shaped time course curves. Benzoquinone reduction by FeII may be an important link in networks of electron transport taking place in suboxic and anoxic environments.  相似文献   

20.
Single-crystal and powder electron paramagnetic resonance (EPR) spectroscopic studies of natural amethyst quartz, before and after isochronal annealing between 573 and 1,173 K, have been made from 90 to 294 K. Single-crystal EPR spectra confirm the presence of two substitutional Fe3+ centers. Powder EPR spectra are characterized by two broad resonance signals at g = ~10.8 and 4.0 and a sharp signal at g = 2.002. The sharp signal is readily attributed to the well-established oxygen vacancy electron center E 1′. However, the two broad signals do not correspond to any known Fe3+ centers in the quartz lattice, but are most likely attributable to Fe3+ clusters on surfaces. The absolute numbers of spins of the Fe3+ species at g = ~10.8 have been calculated from powder EPR spectra measured at temperatures from 90 to 294 K. These results have been used to extract thermodynamic potentials, including Gibbs energy of activation ΔG, activation energy E a, entropy of activation ΔS and enthalpy of activation ΔH for the Fe3+ species in amethyst. In addition, magnetic susceptibilities (χ) have been calculated from EPR data at different temperatures. A linear relationship between magnetic susceptibility and temperature is consistent with the Curie–Weiss law. Knowledge about the stability and properties of Fe3+ species on the surfaces of quartz is important to better understanding of the reactivity, bioavailability and heath effects of iron in silica particles.  相似文献   

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