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1.
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2.
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   

3.
利用激光诱导离解光谱检测铍铝元素区分透闪石白玉产地   总被引：2，自引：1，他引：1  
涂彩  袁心强  周钊 《岩矿测试》2012,31(2):301-305
利用自行搭建的激光诱导离解光谱仪分析54块新疆、青海、俄罗斯产地的透闪石白玉样品,提出通过检测Be、Al元素来区分白玉产地的方法。使用波长1064 nm的激光器激发样品,4CCD光谱仪采集光谱,为避免外界条件干扰,以透闪石白玉中含量比较固定的Si元素作为内标元素测量原子谱线强度比值IBe/ISi、IAl/ISi,分别代表Be、Al元素的含量变化,重复测量10次的相对标准偏差(RSD)<3%。结果表明,新疆白玉的IBe/ISi为0.3～0.6,IAl/ISi为0.1～0.4;青海白玉IBe/ISi<0.1,IAl/ISi<0.2,显示出低Be低Al的明显特征;俄罗斯白玉的IBe/ISi分为高值和低值两个区域,部分样品的IBe/ISi>0.7,指示Be的含量较高,另一部分样品的IBe/ISi为0.1～0.5,略低于新疆白玉。研究显示Be、Al元素特别是Be元素具有较好的产地指示意义,激光诱导离解光谱技术用于鉴别白玉产地有着较好的推广前景。  相似文献   

4.
Synthetic clinopyroxenes of compositions between CaFe3+AlSiO6 and CaFe 0.85 3+ Ti0.15Al1.15Si0.85O6 have been studied by 57Fe Mössbauer spectroscopy. The spectra consist of two doublets assigned to Fe3+ in M1 and T sites. From the area ratios of the doublets the site occupancies of Fe3+ and Al were determined. Si decreases from 1.00 to 0.85 and Al+Fe3+ increases from 1.00 to 1.15 per formula unit with increasing CaTiAl2O6 component of the clinopyroxene. The atomic ratio of Fe3+(T)/Fe3+(total) is 0.11–0.16; 4.5–7.5 percent of the T sites are occupied by Fe3+. Thus the presence of Si-O-Fe3+, Al-O-Fe3+, and Fe3+-O-Fe3+ bonds is expected in addition to Si-O-Si, Si-O-Al and Al-O-Al bonds. However, the possibility of the former bonds being present would be small, because the amount of Fe3+(T) is far less than that of Si and Al. The isomer shift of Fe3+(T) is one of the largest in the values found previously for Fe3+(T) in silicates. It increases with increasing CaTiAl2O6 component and seems to be correlated to the ionic character of the cation — anion bonds calculated from electronegativity. The quadrupole splittings of Fe3+(M1) and Fe3+(T) decrease with the substitution of Fe3+?Ti4+ in the M1 and of Si?Al in the T sites.  相似文献   

5.
Jinshanjiangite (acicular crystals up to 2 mm in length) and bafertisite (lamellar crystals up to 3 × 4 mm in size) have been found in alkali granite pegmatite of the Gremyakha-Vyrmes Complex, Kola Peninsula. Albite, microcline, quartz, arfvedsonite, zircon, and apatite are associated minerals. The dimensions of a monoclinic unit cell of jinshanjiangite and bafertisite are: a = 10.72(2), b=13.80(2), c = 20.94(6) Å, β = 97.0(5)° and a = 10.654(6), b = 13.724(6), c = 10.863(8) Å, β = 94.47(8)°, respectively. The typical compositions (electron microprobe data) of jinshanjiangite and bafertisite are: (Na0.57Ca0.44)Σ1.01(Ba0.57K0.44)Σ1.01 (Fe3.53Mn0.30Mg0.04Zn0.01)Σ3.88(Ti1.97Nb0.06Zr0.01)Σ2.04(Si3.97Al0.03O14)O2.00(OH2.25F0.73O0.02)Σ3.00 and (Ba1.98Na0.04K0.03)Σ2.05(Fe3.43Mn0.37Mg0.03)Σ3.83(Ti2.02Nb0.03)Σ2.05 (Si3.92Al0.08O14)(O1.84OH0.16)Σ2.00(OH2.39F1.61)Σ3.00, respectively. The minerals studied are the Fe-richest members of the bafertisite structural family.  相似文献   

6.
A new mineral depmeierite, the first cancrinite-group member with the species-forming extraframework anion PO 4 3? , has been found at Mt. Karnasurt in the Lovozero alkaline pluton on the Kola Peninsula in Russia. Natrolite and depmeierite are the major components of a hydrothermal peralkaline veinlet 1.5 cm thick, which cross cuts the foyaite-urtite-lujavrite complex. The associated minerals are steenstrupine-(Ce), vuonnemite, epistolite, sodalite, aegirine, serandite, natisite, and vitusite-(Ce). Depmeierite occurs as colorless transparent isometric grains up to 1 cm in size. Its luster is vitreous. The mineral is brittle, and its cleavage (100) is perfect. Its Mohs hardness is 5, and D(meas) = 2.321(1) and D(calc) = 2.313 g/cm3. Depmeierite is optically biaxial positive, ω = 1.493(2), and ? = 1.497(2). The IR spectrum is given. The chemical composition is as follows (wt %, the average of 10 microprobe analyses with the H2O and CO2 determined by selective sorption): 23.04 Na2O, 0.54 K2O, 0.03 Fe2O3, 29.07 Al2O3, 36.48 SiO2, 3.30 P2O5, 0.08 SO3, 0.97 CO2, and 5.93 H2O; the total is 99.44. The empirical formula based on (Si,Al)12O24 is (Na758K0.12)Σ7.70(Si6.19Al5.81O24)[(PO4)0.47(CO3)0.22(OH)0.02(SO4)0.01]Σ0.72 · 3.345H2O. The simplified formula is Na8[Al6Si6O24](CO3)1 ? x · 3H2O (x < 0.05). Depmeierite is hexagonal with space group P63, and the unit-cell dimensions are a = 12.7345(2), c = 5.1798(1), V = 727.46(2) Å3, and Z = 1. The strongest reflections of the X-ray powder pattern (d, Å (I, %) [hkl]) are as follows: 6.380(30) [110], 4.695(91) [101], 3.681(37) [300], 3.250(100) [211], 2.758 (33) [400], 2.596(31) [002], and 2.121(24) [330, 302]. The crystal structure was studied using a single crystal, and R hkl = 0.0362. Depmeierite differs from cancrinite in the development of wide channels containing Na cations, H2O molecules, prevailing PO 4 3? -anionic groups, and CO 3 2? . The mineral is named in honor of the German crystallographer Wulf Depmeier (born in 1944). The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences in Moscow. The cancrinite sensu stricto subgroup separated within the cancrinite group comprises six minerals with AB frameworks, the smallest unit cell is (a ≈ 12.55–12.75, c ≈ 5.1–5.4 Å), and the chain […Na…H2O…]∞ exists in narrow channels: cancrinite, vishnevite, cancrisilite, hydroxycancrinite, kyanoxalite, and depmeierite. The P-bearing varieties of the cancrinite-group minerals are discussed, as well as the formation conditions of the noncarbonate members of the group related to intrusive alkaline complexes.  相似文献   

7.
A new mineral of the neptunite group, magnesioneptunite KNa2Li(Mg,Fe)2Ti2Si8O24, a Mg-dominant analogue of neptunite and manganoneptunite, has been found in the Upper Chegem caldera near Mount Lakargi, Kabardino-Balkaria, the North Caucasus, Russia in a xenolith of altered sandstone located between skarnified carbonate xenoliths and ignimbrite. Magnesioneptunite occurs as nearly isometric grains and aggregates up to 0.1 mm in size in the cores of some grains of a Mg-rich variety of neptunite with Mg/(Fe + Mn) = 0.7?1.0. The chemical composition of magnesioneptunite with a maximum Mg content is as follows, wt %: 3.63 K2O, 8.21 Na2O, 1.73 Li2O, 6.47 MgO, 0.04 MnO, 5.87 FeO, 0.07 Al2O3, 18.73 TiO2, 56.88 SiO2, 99.62 in total. The empirical formula is (K0.67Na0.32Ca0.01)Σ1.00Na2.06Li1.00 · (Mg1.39Fe 0.71 2+ )Σ2.10(Si7.90Al0.01)Σ7.91O24. Grains of magnesioneptunite are dark brown to red-brown, translucent, with vitreous luster. D calc = 3.15 g/cm3, and the Mohs hardness is 5–6. Cleavage parallel to the (110) is perfect. The new mineral is optically biaxial, positive, α = 1.697(2), β = 1.708 (3), γ = 1.725(3), 2V meas = 45(15)°. The mineral is associated with quartz, alkali feldspar, rutile, aegirine, and neptunite. Magnesioneptunite and the Mg-rich variety of neptunite were formed as products of ilmenite alteration. Magnesioneptunite is monoclinic, C2/c; unit-cell parameters: a = 16.327(7), b = 12.4788(4), c = 9.9666(4) Å, β = 115.6519(5)°, V = 1830.5(1) Å3, Z = 4. The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.  相似文献   

8.
Dumortierite, generally simplified as Al7BSi3O18, was synthesized in the pure system Al2O3–B2O3–SiO2–H2O (ABSH) using gels with variable Al/Si ratios mixed with H3BO3 and H2O in known proportions as starting materials. Synthesis conditions ranged from 3 to 5 and 15 to 20 kbar fluid pressure at 650° to 880°C. On the basis of analyses, synthetic dumortierite shows relatively narrow homogeneity ranges with regard to Al/Si which, however, vary as a function of pressure: at low pressures (3–5 kbar) Al/Si is 2.77–2.94 versus 2.33–2.55 at high pressures (15–20 kbar). Outside of these homogeneity limits, dumortierite was found to coexist with quartz or corundum, depending on the starting composition. Whereas synthetic dumortierite invaribly contains 1.0 boron atom per formula unit (p.f.u.) based on 18 oxygens, the water contents vary drastically as a function of pressure and temperature (1.32–2.30 wt.% H2O or 0.85–1.47 H p.f.u.). H2O is an essential component in dumortierite. Structural formulae based on complete chemical analyses of the dumortierites synthesized reveal that there is invariably an Si-deficiency against the ideal number of 3.0 p.f.u. In the calculation procedure used here, this deficiency is balanced by assuming tetrahedral Al. The remaining Al, taken to occupy the octahedral sites, is always below the ideal number of 7.0 p.f.u. Charge-balancing the structure with the hydrogen found analytically leads to two different mechanisms of H incorporation: (1) 3H+ + octahedral vacancy for Al[6]; (2) H+ + tetrahedral Al for Si[4]. Dumortierite synthesized at high fluid pressure contains little Al[4] and, thus, little H+ of type 2; its hydrogen is predominantly present as type 1. Conversely, dumortierite formed at low fluid pressures is high in Al[4] and hydrogen type 2. The amounts of hydrogen type 1 in low-pressure dumortierites decrease with rising temperatures of synthesis. Typical structural formulae are: (Al6.670.33)[Al0.49Si2.51–O13.53(OH)1.47](BO3) for a low-pressure product, and (Al6.680.32)[Al0.09Si2.91O13.94(OH)1.06](BO3) for a high-pressure product. Independently of the synthesis conditions, dumortierite was found always to be orthorhombic, with b0/a0 deviating slightly, but significantly from the valid for hexagonal lattice geometry. As a function of increasing Al/Si in the synthetic crystals, their a0, c0, and V0 rise, whereas b0 decreases. Thus b0/a0 decreases most sensitively with rising Al/Si and also with growing Al[4]. More experimentation is required before the compositional variations of dumortierite found here can be applied successfully to geothermobarometry of natural rocks.  相似文献   

9.
The substituted topaz Al2GeO4(OH,F)2, Al2(SixGe1-x)O4(OH,F)2 and Ga2GeO4(OH,F)2, as well as the substituted zunyite Al13Ge5O20(OH,F)16F2Cl have been synthetised. The unit-cell parameters of these artificial minerals, isomorphs of natural compounds, have been determined; the corresponding lists of dhkl are given. The study by I.R. spectroscopy of these compounds with a total or a partial replacement of Si by Ge in the same way as Ga-Ge topaz suggests the assignment of certain absorption bands to characteristic structural groups. The thermal decomposition of AlSi and AlGe topaz into mullite has been studied.  相似文献   

10.
The Fe-rich Li-bearing magnesionigerite-6N6S occurs in the Xianghualing tin-polymetallic ore field, Linwu County, Hunan Province, Peoples Republic of China. It was found near the outer contact zone of the Laizhiling granite body and in the Middle-Upper Devonian carbonate rocks of Qiziqiao Formation. The mineral formed during the skarn stage. Its empirical formula is Sn1.81Li0.67(Fe1.43Zn1.19 Mn0.41)Σ3.03(Al14.89Mg1.46 Ti0.11Si0.01)Σ16.47O30(OH)2. The structure for magnesionigerite-6N6S was solved and refined in space group R-3?m, with a?=?5.7144(8), c?=?55.446(11) Å, V?=?1568.0(4) Å3, to R1?=?0.0528. Based on the structural refinement of single crystal diffraction data the formula of magnesionigerite-6N6S is Sn1.80Li0.97(Fe1.89Zn0.91) Σ2.80 (Al14.60Mg1.63 Ti0.20)Σ16.43O30(OH)2 with Z?=?3. Fe-rich Li-bearing magnesionigerite-6N6S contains 0.74 wt.% Li2O. The idealized charge-balanced composition of magnesionigerite-6N6S may be expressed by bivalent and trivalent cations: (Mg2+)4(Al3+)18O30(OH)2. The simplified general formula for the 6N6S polysomes in the nigerite and högbomite groups can be given as A x B18-x O30(OH)2, x?=?~4, where A?=?Mg2+, Fe2+, Zn2+; B?=?Al3+, Sn4+, Ti4+, Li+, □.  相似文献   

11.
The paper presents the results of a thermochemical and thermal study of cancrinite, (Na6.93Ca0.545K0.01)Σ7.485[(Si6.47Al5.48Fe0.05)Σ12O24](CO3)1.25 · 2.30 H2O, and cancrisilite, (Na7.17 Ca0.01)Σ7.18[(Si7.26Al4.70Fe0.04)Σ12O24][(CO3)1.05(OH)0.21(PO4)0.04(SO4)0.01] · 2.635 H2O, from the Khibina-Lovozero Complex, Kola Peninsula, Russia. Stages of the thermal decomposition of these minerals were studied using IR spectroscopy. The enthalpies of formation of the minerals from elements were determined by melt drop solution calorimetry: Δ f H el 0 (298.15 K) = ?14 490 ± 16 kJ/mol for cancrinite and ?14302 ± 17 kJ/mol for cancrisilite. The values of Δ f H el 0 (298.15 K), S o(298.15 K), and Δ f H el 0 (298.15 K) are determined for cancrinite and cancrisilite of theoretical composition.  相似文献   

12.
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13.
After its initial synthesis as the new compound Mg2Al3B2O9(OH) (Daniels et al. 1997) pseudosinhalite has now been discovered as a new mineral. It occurs, together with hydrotalcite, as a replacement product of sinhalite, MgAlBO4, in an impure marble of the contact metasomatic iron boron deposit of Tayozhnoye in the Aldan Shield of Siberia. Its chemical composition determined by electron microprobe is (wt%): Al2O3 46.88; MgO 25.12; FeO 1.99; B2O3 (calculated) 21.75; H2O (calculated) 2.81 giving a total of 98.55 and leading to the empirical formula (Mg2.00 Fe2+ 0.09)Σ=2.09 Al2.94 B2O9(OH). The small deviation from the ideal stoichiometry with (Mg?+?Fe2+):Al?≠?2:3 may be caused by either solid solution towards, or submicroscopic interlayering with lamellae of, the structurally similar mineral sinhalite. The underlying substitution involving also B and H would be (Mg?+?Fe)+?B=Al+2H. Pseudosinhalite is monoclinic, space group P21/c, with a=7.49(1), b=4.33(1), c=9.85(2) Å; β=110.7(1)°; V?=?299(1) Å3; Z?=?2. Calculated density is 3.508?g/cm3. Pseudosinhalite is colourless with white streak and has a vitreous lustre. It is transparent; no fluorescence was detected. There is no cleavage and parting; fractures are concoidal. Optical constants could not be measured properly due to polysynthetic microtwinning, but α<1.72<γ. For synthetic pseudosinhalite α=1.691(1); β=1.713(1); γ=1.730(1); Δ=0.039; 2?V=80°. The temperature of pseudosinhalite formation was below about 400?°C at low pressures and with a hydrous, CO2-bearing fluid participating in the reaction.  相似文献   

14.
Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO2, 8 wt.% Cr2O3 and 4 wt.% ZrO2, representing a solid solution of andradite (Ca3Fe3+ 2Si3O12 ≈46 mol%), uvarovite (Ca3Cr2Si3O12 ≈23 mol%), grossular (Ca3Al2Si3O12 ≈10 mol%), schorlomite (Ca3Ti2[Si,(Fe3+,Al3+)2]O12 ≈15 mol%), and kimzeyite (Ca3Zr2[Si,Al2]3O12 ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al3+, Fe3+ and Ti4+. Cr3+ and Zr4+ are found at the octahedral site along with Fe3+, Al3+ and Ti4+. The measured H2O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca2.99Mg0.03)Σ=3.02(Fe3+ 0.67Cr0.54Al0.33Ti0.29Zr0.15)Σ=1.98(Si2.42Ti0.24Fe0.18Al0.14)Σ=2.98O12OH0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.  相似文献   

15.
Friedrichbeckeite is a new milarite-type mineral. It was found in a single silicate-rich xenolith from a quarry at the Bellerberg volcano near Ettringen, eastern Eifel volcanic area, Germany. It forms thin tabular crystals flattened on {0001}, with a maximum diameter of 0.6 mm and a maximum thickness of 0.1 mm. It is associated with quartz, tridymite, augite, sanidine, magnesiohornblende, enstatite, pyrope, fluorapatite, hematite, braunite and roedderite. Friedrichbeckeite is light yellow, with white to light cream streak and vitreous lustre. It is brittle with irregular fracture and no cleavage, Mohs hardness of 6, calculated density is 2.686 gcm?3. Optically, it is uniaxial positive with nω = 1.552(2) and nε = 1.561(2) at 589.3 nm and a distinct pleochroism from yellow (//ω) to light blue (//ε). Electron microprobe analyses yielded (wt.%): Na2O 2.73, K2O 4.16, BeO 4.67, MgO 11.24, MnO 2.05, FeO 1.76, Al2O3 0.15, SiO2 73.51, (Σ CaO, TiO2 = 0.06) sum 100.33 (BeO determined by LA-ICP-MS). The empirical formula based on Si = 12 is K0.87 Na0.86 (Mg1.57Mn0.28Fe0.24)Σ2.09 (Be1.83?Mg1.17)Σ3.00 [Si12O30], and the simplified formula can be given as K (□0.5Na0.5)2 (Mg0.8Mn0.1Fe0.1)2 (Be0.6?Mg0.4)3 [Si12O30]. Friedrichbeckeite is hexagonal, space-group P6/mcc, with a = 9.970(1), c = 14.130(3) Å, V = 1216.4(3) Å3, and Z = 2. The strongest lines in the X-ray powder diffraction pattern are (d in Å / I obs / hkl): 3.180 / 100 / 121, 2.885 / 70 / 114, 4.993 / 30 / 110, 4.081 / 30 / 112, 3.690 / 30 / 022. A single-crystal structure refinement (R1 = 3.62 %) confirmed that the structure is isotypic with milarite and related [12] C [9] B 2 [6] A 2 [4] T23 [[4] T112O30] compounds. The C-site is dominated by potassium, the B-site is almost half occupied by sodium, and the A-site is dominated by Mg. The site-scattering at the T2-site can be refined to a Be/(Be?+?Mg) value close to 0.61; the T1-site is occupied by Si. Micro-Raman spectroscopy reveals an increasing splitting of scattering bands around 550 cm?1 for friedrichbeckeite. The mineral can be classified as an unbranched ring silicate or as a beryllo-magnesiosilicate. With respect to the end-member formula K (□0.5Na0.5)2 Mg2 Be3 [Si12O30] friedrichbeckeite represents the Mg-dominant analogue of almarudite, milarite or oftedalite. The mineral and its paragenesis were formed during pyrometamorphic modifications of the silicate-rich xenoliths enclosed in Quaternary leucite-tephritic lava of the Bellerberg volcano. Holotype material of friedrichbeckeite has been deposited at the mineral collection of the Naturhistorisches Museum Wien, Austria. The mineral is named friedrichbeckeite in honour of the Austrian mineralogist and petrographer Friedrich Johann Karl Becke (1855–1931).  相似文献   

16.
A new Cu-rich variety of lyonsite has been found from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia). The empirical formula is Cu4.33Fe 2.37 3+ Ti0.26Al0.26Zn0.07(V5.85As0.07Mo0.07P0.01S0.01)O24. The crystal structure was studied on single crystal using synchrotron radiation, R = 0.0514. The mineral is orthorhombic, Pnma, a = 5.1736(7), b =10.8929(12), c = 18.220(2) Å, V = 1026.8(2) Å3, and Z = 2. The structural formula is (Cu0.6Ti0.3Al0.3Fe 0.2 3+ □0.6)Σ2Cu2(Fe 2.2 3+ Cu1.8)Σ4(V5.8As0.1Mo0.1)Σ6O24. It is proposed to recast the simplified formula of lyonsite as Cu3+x (Fe 4?2x 3+ Cu2x )(VO4)6, where 0 ≤ x ≤ 1.  相似文献   

17.
Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K0.729)C (Na0.029)B (Si10.498 Al1.502)T1 (Al2.706 Fe 0.294 2+ )T2 (Mg0.735 Mn0.091 Fe 1.184 2+ )AO30. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe2+ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si2p, Al2p, Mg1s and Fe2p core levels, suggests that Fe presents Fe2+ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si4+ and Si1+ components, respectively, both in tetrahedral coordination. The binding energy of Al2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site.  相似文献   

18.
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19.
(Mg,Fe)(Si,Al)O3 perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe3+/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe3+/ΣFe with Al composition of (Mg,Fe)(Si,Al)O3 perovskite. The Fe3+/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O3 perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe3+/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe3+/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O3 perovskite.  相似文献   

20.
Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)8(Al6Si6O24)Cl2 solid solution series, 3 members of the (Na,K)8(Al6Si6O24)Br2 solid solution series and Na8(Al6Si6O24)I2. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10?6 °C?1 below and 7.7×10?6 °C?1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I? or SO 4 2? ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.  相似文献   

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