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1.
Davide Lenaz Henrik Skogby Francesco Princivalle 《Geochimica et cosmochimica acta》2008,72(2):475-479
Four nearly pure MgAl2O4 spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm−1 indicate an OH content of 90 ppm H2O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for VIO-Ounsh (2.825 Å) and IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H2O. However, at appreciable Fe2+ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe2+ in the tetrahedral position. 相似文献
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3.
D.?LenazEmail author H.?Skogby F.?Princivalle U.?H?lenius 《Physics and Chemistry of Minerals》2004,31(9):633-642
The influence on the structure of Fe2+ Mg substitution was studied in synthetic single crystals belonging to the MgCr2O4–FeCr2O4 series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as IVFe2+. Only minor Fe3+ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr2+ and Cr3+ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a0, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr3+ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe2+ content (apfu) is described by the following linear relations: a0=8.3325(5) + 0.0443(8)Fe2+ (Å) and T–O=1.9645(6) + 0.033(1)Fe2+ (Å) Consequently, Fe2+ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively. 相似文献
4.
Holtstam Dan Cámara Fernando Skogby Henrik Karlsson Andreas Langhof Jörgen 《Mineralogy and Petrology》2019,113(1):7-16
Mineralogy and Petrology - Potassic-richterite, ideally AKB(NaCa)CMg5TSi8O22W(OH)2, is recognized as a valid member of the amphibole supergroup (IMA-CNMNC 2017–102). Type material is from the... 相似文献
5.
Magnus Ivarsson Stefan Bengtson Henrik Skogby Veneta Belivanova Federica Marone 《Geo-Marine Letters》2013,33(4):233-243
The deep subseafloor crust is one of the few great frontiers of unknown biology on Earth and, still today, the notion of the deep biosphere is commonly based on the fossil record. Interpretation of palaeobiological information is thus central in the exploration of this hidden biosphere and, for each new discovery, criteria used to establish biogenicity are challenged and need careful consideration. In this paper networks of fossilized filamentous structures are for the first time described in open fractures of subseafloor basalts collected at the Emperor Seamounts, Pacific Ocean. These structures have been investigated with optical microscopy, environmental scanning electron microscope, energy dispersive spectrometer, X-ray powder diffraction as well as synchrotron-radiation X-ray tomographic microscopy, and interpreted as fossilized fungal mycelia. Morphological features such as hyphae, yeast-like growth and sclerotia were observed. The fossilized fungi are mineralized by montmorillonite, a process that probably began while the fungi were alive. It seems plausible that the fungi produced mucilaginous polysaccharides and/or extracellular polymeric substances that attracted minerals or clay particles, resulting in complete fossilization by montmorillonite. The findings are in agreement with previous observations of fossilized fungi in subseafloor basalts and establish fungi as regular inhabitants of such settings. They further show that fossilized microorganisms are not restricted to pore spaces filled by secondary mineralizations but can be found in open pore spaces as well. This challenges standard protocols for establishing biogenicity and calls for extra care in data interpretation. 相似文献
6.
Davide Lenaz Henrik Skogby Alla M. Logvinova Nikolai V. Sobolev Francesco Princivalle 《Physics and Chemistry of Minerals》2013,40(9):671-679
Oxygen fugacity ( $ f_{{{\text{O}}_{ 2} }} $ f O 2 ) is a fundamental but little known intensive variable in mantle processes. It influences the P/T position of a mantle solidus and the composition of mantle-derived melts and fluids and constrains mantle-core equilibria and a number of geophysical properties of the mantle. An important source of information on oxidation states is the ferric–ferrous iron ratio in mantle spinels. Since the magnetite component is low in mantle spinels, normal analytical errors translate into considerable $ f_{{{\text{O}}_{ 2} }} $ f O 2 uncertainties. In this study, we analyzed the Fe3+–Fetot ratio of chromites present as inclusions in diamond and other mantle-related occurrences by point-source Mössbauer spectroscopy using single-crystal absorbers as well as conventional Mössbauer spectroscopy using powder absorbers. The studied spinels have been previously analyzed by single-crystal X-ray diffraction and electron microprobe. The ferric–ferrous ratios found are normally similar to the different techniques apart from some samples where a large number of grains have been used for the analyses (powder absorbers). The general agreement between the different techniques allows us to conclude that the studied chromites are stoichiometric. However, conventional Mössbauer spectroscopy on powder absorbers should be conducted with great care, since the method requires a relatively large amount of sample material. Spinel frequently occurs as small grains, and the large number of crystals required may possess different degrees of oxidation/alteration and, consequently, different ferric–ferrous ratio leading to possible errors in the interpretation of the results. 相似文献
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Nuclear reaction analyses on boron in flux-grown Me3+- and Na+-doped diopside crystals utilising the 11B(p,2α)4He reaction in conjunction with EMP analyses for major elements and optical absorption spectroscopy for determination of Me-valence
state distributions show that appreciable amounts of B may enter the diopside lattice in crystals produced in Na2B4O7 fluxes. The results indicate that the substitution [6]Me3+[4]B3+[6]Mg2+
−1
[4]Si4+
−1 operates in the present diopside samples in addition to the coupled substitution [6]Me3+[8]Na+[6]Mg2+
−1
[8]Ca2+
−1. The specific NRA technique applied allows for quantitative, high resolution (ca. 5 μm) B analyses at ppm level as well as
high-resolution and high-contrast imaging of B-concentration patterns in minerals. The estimated detection limit and relative
error of the B analyses are 10 ppm and 5–10%, respectively.
Received: 20 September 1999 / Accepted: 6 June 2000 相似文献
8.
Ferdinando Bosi Henrik Skogby Tonči Balić-Žunić 《Physics and Chemistry of Minerals》2016,43(6):395-407
A dravite from Yemen of near end-member composition was treated in air and hydrogen atmospheres at 600–900 °C to reveal changes in Mg and Al order over the octahedrally coordinated Y and Z sites, and to explore related changes in the characteristic vibrational bands in the principal (OH)-stretching frequency. Relevant information was obtained using electron microprobe analysis (EMPA), structural refinement (SREF) and polarized infrared (IR) single-crystal spectroscopy. Overall, the EMPA, SREF and IR data show that only minor changes occur during thermal treatment up to at least 800 °C, including variations in structural parameters, Mg–Al order–disorder and (OH)-stretching bands, indicating limited hydrogen loss. Untreated and treated dravite samples have very similar long-range and short-range atomic structures, which may be related to the occurrence of stable Al–Mg extended clusters around the O1 (=W) and O3 (=V) sites: W(F)–Y(MgMgMg)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(OH)–Y(MgMgAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(O2–)–Y(AlAlAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]. These extended clusters remain stable to temperatures close to the observed start of decomposition (~900 °C). 相似文献
9.
Davide Lenaz Henrik Skogby Francesco Princivalle Ulf Hålenius 《Physics and Chemistry of Minerals》2006,33(7):465-474
The influence on the spinel structure of Fe3+ → Cr substitution was studied in flux-grown synthetic single crystals of the magnesiochromite–magnesioferrite (MgCr2O4–MgFe2O4) solid solution series. Samples were analysed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption and Mössbauer spectroscopy. With the exception of iron-poor samples (3–12 mol-% MgFe2O4), optical absorption and Mössbauer spectra show that iron occurs almost exclusively as trivalent Fe in the present samples. A very intense and broad absorption band at ca 7,800 cm?1 dominates the optical absorption spectra of samples with higher Fe-contents. The appearance of this band is related to a distinct structural disorder of Fe3+ and a development of magnetic ordering as demonstrated by Mössbauer spectra. Profound composition-related changes are observed in the Mössbauer spectra, which are magnetically unsplit in the range 2–41 mol-% magnesioferrite, but become magnetically split in the range 59–100 mol-% magnesioferrite. Structural parameters a 0 and M–O increase with magnesioferrite content and inversion degree, while u and T–O decrease. Our study confirms the previously reported (Lavina et al. 2002) influence of Fe3+ at the M site on T–O bond lengths in the spinel structure. 相似文献
10.
Coordination of boron in nominally boron-free rock forming silicates: Evidence for incorporation of BO3 groups in clinopyroxene 总被引：1，自引：0，他引：1
Ulf Hålenius Henrik Skogby Sabrina Nazzareni Jeppa Resmark 《Geochimica et cosmochimica acta》2010,74(19):5672-1594
To explore mechanisms of B-incorporation in common chain silicates we have investigated synthetic diopside samples produced under boron-saturated conditions by 11B and 29Si magic-angle spinning (MAS) NMR and single-crystal NRA, FTIR, EMP and XRD/SREF techniques. Our samples contain 0.14-0.65 wt.% B2O3. NMR reveals that B is predominantly present in trigonal coordination in the clinopyroxene structure. This observation is supported by vibrational bands characteristic for B-O stretching in BO3 groups in the range 1250-1400 cm−1 in polarised single crystal FTIR-spectra. Single crystal structure refinements suggest that boron replaces Si at the T site. Combined, these results suggest that boron replacement for Si at the T-site leads to disruption of one of the T-O bonds of the nominal clinopyroxene structure resulting in replacement of SiO4 tetrahedra by BO3 groups. Our results show that high concentrations of boron can be incorporated in the nominally boron-free diopside. Elevated B-concentrations in the present calcic clinopyroxenes are accompanied by modifications of the diopside crystal structure involving the breaking of one T-O bond and simultaneous formation of vacancies at the octahedral M2 site. These structural modifications destabilize the structure and constitute thereby limiting factors for incorporating higher boron concentrations in diopside. 相似文献