The absorption- and luminescence spectra of Mn3+ in beryl and vesuvianite
NASA Astrophysics Data System (ADS)
Czaja, Maria; Lisiecki, Radosław; Chrobak, Artur; Sitko, Rafał; Mazurak, Zbigniew
2018-05-01
The electron absorption-, photoluminescence- and electron paramagnetic-resonance spectra of Mn3+ in red beryl from Wah Wah Mountains (Utah USA) and of pink- and purple vesuvianite from Jeffrey Mine (Asbestos, Canada) were measured at room- and low temperatures. The crystal field stabilization energies are equal to 130.9 kJ/mol for the red beryl, and 151.5-158.0 and 168.0 kJ/mol for for the pink- and the purple vesuvianite, respectively. The red photoluminescence of Mn3+ was not intensive either at room- or at low temperatures. The high Mn content in the crystals caused the emergence of an additional emission band and short photoluminescence-decay lifetimes. The latter are only 183 μs for beryl and 17 μs for vesuvianite.
The absorption- and luminescence spectra of Mn3+ in beryl and vesuvianite
NASA Astrophysics Data System (ADS)
Czaja, Maria; Lisiecki, Radosław; Chrobak, Artur; Sitko, Rafał; Mazurak, Zbigniew
2017-12-01
The electron absorption-, photoluminescence- and electron paramagnetic-resonance spectra of Mn3+ in red beryl from Wah Wah Mountains (Utah USA) and of pink- and purple vesuvianite from Jeffrey Mine (Asbestos, Canada) were measured at room- and low temperatures. The crystal field stabilization energies are equal to 130.9 kJ/mol for the red beryl, and 151.5-158.0 and 168.0 kJ/mol for for the pink- and the purple vesuvianite, respectively. The red photoluminescence of Mn3+ was not intensive either at room- or at low temperatures. The high Mn content in the crystals caused the emergence of an additional emission band and short photoluminescence-decay lifetimes. The latter are only 183 μs for beryl and 17 μs for vesuvianite.
NASA Astrophysics Data System (ADS)
Panikorovskii, Taras L.; Mazur, Anton S.; Bazai, Ayya V.; Shilovskikh, Vladimir V.; Galuskin, Evgeny V.; Chukanov, Nikita V.; Rusakov, Vyacheslav S.; Zhukov, Yurii M.; Avdontseva, Evgenia Yu.; Aksenov, Sergey M.; Krivovichev, Sergey V.
2017-09-01
Two wiluite samples from the Wiluy River, Yakutia, Russia have been investigated by means of single-crystal and powder X-ray diffraction, electron microprobe analysis, 1H, 27Al, 11B, and 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR), thermogravimetric analysis (DSC/TGA), X-ray photoelectron spectroscopy (XPS) at the Si2p, Ca2p, Al2p, Mg1s, B1s and Fe2p core levels, 57Fe Mössbauer spectroscopy, infrared (IR) spectroscopy and optical measurements. The crystal structures have been refined in the P4/ nnc space group [ a = 15.7027(3), c = 11.7008(3) Å, V = 2885.1(1) Å3 for 1 and a = 15.6950(2), c = 11.6787(4) Å, V = 2876.9(1) Å3 for 2] to R 1 = 0.022 and R 1 = 0.021, respectively. In the crystal structure of wiluite, five-coordinated Y1 site is predominantly occupied by Mg. IR spectra of wiluite substantially different from those of vesuvianite, in particular, by the presence of additional bands in the range 1080‒1415 cm-1, which correspond to symmetric B‒O stretching vibrations of the BO 3 3- and BO 4 5- groups. According to the MAS NMR data, tetrahedrally coordinated T1 site is occupied by B3+ with minor amounts of Al3+. The general formula of wiluite can be written as follows ( Z = 2): Ca19Mg(Al,Mg,Fe,Ti,Mn)12(B,Al,◻)5(Si2O7)4(SiO4)10(O,OH)9O2-3. The diversity of vesuvianite-group minerals is largely determined by the population of the Y1 sites. However, wiluite is characterized by the presence of additional T1 and T2 sites and should be considered as special among other vesuvianite-group minerals. The reasonability of subdivision of the wiluite subgroup within the vesuvianite group is discussed.
The quantitative analysis of OH in vesuvianite: a polarized FTIR and SIMS study
NASA Astrophysics Data System (ADS)
Bellatreccia, Fabio; della Ventura, Giancarlo; Ottolini, Luisa; Libowitzky, Eugen; Beran, Anton
2005-05-01
A well-characterized suite of vesuvianite samples from the volcanic ejecta (skarn or syenites) from Latium (Italy) was studied by single-crystal, polarized radiation, Fourier-transform infrared (FTIR) spectroscopy and secondary-ion mass-spectrometry (SIMS). OH-stretching FTIR spectra consist of a rather well-defined triplet of broad bands at higher-frequency (3,700 3,300 cm-1) and a very broad composite absorption below 3,300 cm-1. Measurements with E//c or E⊥c show that all bands are strongly polarized with maximum absorption for E//c. They are in agreement with previous band assignments (Groat et al. Can Mineral 33:609, 1995) to the two O(11) H(1) and O(10) H(2) groups in the structure. Pleochroic measurements with changing direction of the E vector of the incident radiation show that the orientation of the O(11) H(1) dipole is OH∧c~35°, in excellent agreement with the neutron data of Lager et al. (Can Mineral 37:763, 1999). A SIMS-based calibration curve at ~10% rel. accuracy has been worked out and used as reference for the quantitative analysis of H2O in vesuvianite by FTIR. Based on previous SIMS results for silicate minerals (Ottolini and Hawthorne in J Anal At Spectrom 16:1266, 2001; Ottolini et al. in Am Mineral 87:1477, 2002) the SiO2 and FeO content of the matrix were assumed as the major factors to be considered at a first approximation in the selection of the standards for H. The lack of vesuvianite standards for quantitative SIMS analysis of H2O has been here overcome by selecting low-silica elbaite crystals (Ottolini et al. in Am Mineral 87:1477, 2002). The resulting integrated molar absorption FTIR coefficient for vesuvianite is ɛi=100.000±2.000 l mol-1 cm-2. SIMS data for Li, B, F, Sr, Y, Be, Ba REE, U and Th are also provided in the paper.
NASA Astrophysics Data System (ADS)
Wallmach, T.; Hatton, C. J.; De Waal, S. A.; Gibson, R. L.
1995-11-01
Two calc-silicate xenoliths in the Upper Zone of the Bushveld complex contain mineral assemblages which permit delineation of the metamorphic path followed after incorporation of the xenoliths into the magma. Peak metamorphism in these xenoliths occurred at T=1100-1200°C and P <1.5 kbar. Retrograde metamorphism, probably coinciding with the late magmatic stage, is characterized by the breakdown of akermanite to monticellite and wollastonite at 700°C and the growth of vesuvianite from melilite. The latter implies that water-rich fluids (X CO 2 <0.2) were present and probably circulating through the cooling magmatic pile. In contrast, calc-silicate xenoliths within the lower zones of the Bushveld complex, namely in the Marginal and Critical Zones, also contain melilite, monticellite and additional periclase with only rare development of vesuvianite. This suggests that the Upper Zone cumulate pile was much 'wetter' in the late-magmatic stage than the earlier-formed Critical and Marginal Zone cumulate piles.
NASA Astrophysics Data System (ADS)
Smith, Varina Campbell
The role of growth steps in inducing disequilibrium is investigated in crystals of vesuvianite from the Jeffrey mine, Asbestos, Quebec, using optical microscopy, atomic force microscopy, electron microprobe analysis, and single-crystal X-ray diffraction. The selective uptake of elements Fe and Al by asymmetric growth-steps on three crystallographic forms, {100}, {110}, and {121}, is documented. The prisms {100} and {110} show hillocks that display kinetically controlled oscillatory zoning along growth steps parallel to <010> and <11¯1>, but not on vicinal faces defined by [001] steps. Sector-specific zoning of extinction angles and 2V angles indicate different degrees of optical dissymmetrization in crystals spanning a range of growth habits. Unit-cell parameters and the presence of violating reflections confirm sectoral deviations from P4/nnc symmetry in the prismatic sectors. The partial loss of three glide planes follows the pattern expected from order of the cations Al and Fe induced by tangential selectivity at the edge of non-equivalent steps during layer-by-layer growth.
NASA Astrophysics Data System (ADS)
Panikorovskii, Taras L.; Chukanov, Nikita V.; Aksenov, Sergey M.; Mazur, Anton S.; Avdontseva, Evgenia Yu; Shilovskikh, Vladimir V.; Krivovichev, Sergey V.
2017-12-01
Alumovesuvianite (IMA 2016-014), ideally Ca19Al(Al,Mg)12Si18O69(OH)9, is a new vesuvianite-group member found in the rodingite zone at the contact of a gabbroid rock with host serpentinite in the abandoned Jeffrey mine, Asbestos, Estrie Region, Québec, Canada. It occurs as prismatic tetragonal crystals up to 4 × 4 × 6 mm3 in size encrusting walls of cavities in a granular diopside. Associated minerals are diopside, grossular and prehnite. Single crystals of alumovesuvianite are transparent colorless or light pink with a vitreous lustre. The dominant crystal forms are {100}, {110}, {210}, {111}, {101} and {001}. The Mohs hardness is 6.5. The specific gravitiy is D meas = 3.31(1) g/cm3 and D calc = 3.36 g/cm3, respectively. The mineral is optically uniaxial (-), ω = 1.725(2), ɛ = 1.722(2). The chemical composition, determined by SEM-WDS (wavelength-dispersive spectroscopy on a scanning electron microscope; all oxides except H2O) and TG (thermogravimety; H2O) analysis, is: SiO2 37.1 wt%, Al2O3 18.8 wt%, CaO 36.6 wt%, MgO 2.48 wt%, Mn2O3 0.67 wt%, Fe2O3 0.22 wt%, H2O 2.61 wt%, total 98.5 wt%. The empirical formula based on 19 Ca atoms per formula unit and taking into account the MAS-NMR (magic-angle spinning nuclear magnetic resonance) data, is: Ca19.00(Al0.92Fe3+ 0.08)Σ1.00(Al9.83Mg1.80Mn3+ 0.25)Σ11.88Si17.98O69.16(OH)8.44. The most intense IR absorption bands lie in the ranges 412-609, 897-1024, and 3051-3671 cm-1. The eight strongest lines of the powder X-ray diffraction pattern are ( I-d(Å)- hkl): 22-2.96-004, 100-2.761-432, 61-2.612-224, 25-2.593-600, 20-1.7658-831, 20-1.6672-734, 21-1.6247-912, and 22-1.3443-880. Alumovesuvianite is tetragonal, space group P4/ n, unit-cell parameters refined from the powder data are a = 15.5603(5) Å, c = 11.8467(4) Å, V = 2868.3(4) Å3, Z = 2. The crystal structure has been refined to R 1 = 0.036 for 3098 unique observed reflections with | F o| ≥ 4σ F . The structure refinement provides the < Y1A-O > bond length of 1.916 Å and the scattering factor for the Y1 site of 16 e - , which is in good agreement with the total occupancy of this site as (Al0.73Mn3+ 0.20Fe3+ 0.07)Σ1.00 and is confirmed by the 27Al MAS NMR data. Alumovesuvianite is a new member of the vesuvianite group with Al3+ as a dominant cation in the Y1 site. The name alumovesuvianite is given to highlight the species-defining role of Al.
Isotope geochemistry and fluid inclusion study of skarns from Vesuvius
Gilg, H.A.; Lima, A.; Somma, R.; Belkin, H.E.; de Vivo, B.; Ayuso, R.A.
2001-01-01
We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes "fassaitic" clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (THOM = 1000-1050??C), b) CO2 ?? H2S-rich fluid inclusions (THOM = 20-31.3??C into the vapor phase), c) multiphase aqueous brine inclusions (THOM = 720-820??C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (THOM = 870-890??C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt - aqueous chloride-rich liquid - carbonate/sulfate melt?) during heating and cooling below 870??C. There is no evidence for fluid circulation below 700??C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable 206Pb/204Pb (19.047-19.202), 207Pb/204Pb (15.655-15.670), and 208Pb/204Pb (38.915-39.069) and relatively low 143Nd/144Nd (0.51211-0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (??13CV-PDB = -5.4 to -1.1???; ??18OV-SMOW = 11.7 to 16.4???) indicate formation from a 18O- and 13C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO2-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns.
2007-01-01
Fluid inclusions and geological relationships indicate that rodingite formation in the Asbestos ophiolite, Québec, occurred in two, or possibly three, separate episodes during thrusting of the ophiolite onto the Laurentian margin, and that it involved three fluids. The first episode of rodingitization, which affected diorite, occurred at temperatures of between 290 and 360°C and pressures of 2.5 to 4.5 kbar, and the second episode, which affected granite and slate, occurred at temperatures of between 325 and 400°C and pressures less than 3 kbar. The fluids responsible for these episodes of alteration were moderately to strongly saline (~1.5 to 6.3 m eq. NaCl), rich in divalent cations and contained appreciable methane. A possible third episode of alteration is suggested by primary fluid inclusions in vesuvianite-rich bodies and secondary inclusions in other types of rodingite, with significantly lower trapping temperatures, salinity and methane content. The association of the aqueous fluids with hydrocarbon-rich fluids containing CH4 and higher order alkanes, but no CO2, suggests strongly that the former originated from the serpentinites. The similarities in the composition of the fluids in all rock types indicate that the ophiolite had already been thrust onto the slates when rodingitization occurred. PMID:17961257
NASA Astrophysics Data System (ADS)
Karkalis, Christos; Magganas, Andreas; Koutsovitis, Petros
2014-05-01
The island of Skyros is located in the Sporades-Aegean region. It includes an ophiolitic mélange sequence consisting of serpentinites, gabbroic and doleritic rocks, and also lavas which mostly appear in massive form, but in rare cases as deformed pillows. The ophiolitic mélange sequence also includes rodingites, ophicalcites, as well as radiolarites. This formation belongs to the Eohellenic tectonic nappe, which encompasses marbles, sandstones and schists and was emplaced onto the Pelagonian Zone during Early Cretaceous [1, 2]. Serpentinites were most likely formed after serpentinization of harzburgitic protoliths and consist of serpentine, bastite, spinel and magnetite. The chemistry of spinels (TiO2=0.14-0.25 wt.%, Al2O3=35.1-35.21 wt.%, Cr#=37.38-38.87), shows that the harzburgitic protoliths plausibly resemble back-arc basin peridotites [3]. Gabbros and dolerites present mostly subophitic textures, between the hornblende/clinopyroxene and plagioclase grains. Based upon their petrography and on their mineral chemistry hornblendes have been distinguished into magmatic and metamorphic hornblendes, with the first occurring mostly in gabbroic rocks. Magmatic hornblendes exhibit relatively high TiO2 (1.42-1.62 wt.%), Al2O3 (5.11-5.86 wt.%) and Na2O (1.01-1.09 wt.%) contents, with their presence implying that the magma was at least to some degree hydrous. Lavas are tholeiitic basalts with relatively high FeOt≡12 wt.% and low K2O and Th contents, consisting mostly albite, altered clinopyroxene and devitrified glass. Tectonomagmatic discrimination diagrams [4, 5] illustrate that the studied gabbros and lavas of Skyros are most likely associated with SSZ processes. Gabbroic rocks, subvolcanic dolerites and lavas have been subjected to greenschist/subgreenschist metamorphic processes, as confirmed by the presence of secondary amphiboles (metamorphic hornblende, actinolite/tremolite), epidote, pumpellyite and chlorite in all of the studied samples. On the other hand, the occurrence of rodingites and ophicalcites clearly point to interaction of the gabbroic rocks and serpentinites with hydrothermal fluids, which most probably took place during the stage of exhumation and tectonic emplacement. Ophicalcites contain serpentine, calcite, magnetite, as well as rare pyroxene and spinel. Rodingites on their behalf include hydroandradite (Alm0.00Adr61.33-67.43Grs28.25-35.18Prp0.10-2.49Sps0.00-0.33Uv0.41-2.75), vesuvianite (MgO=2.78-3.33 wt.%; TiO2=0.02-0.59 wt.%) diopside neoblasts (En48.53-49.89Wo47.56-48.10Fs2.32-3.33; Mg#=93.96-96.28), chlorite and also accessory prehnite. Some small-sized Cr-bearing hydrogarnet crystals (Cr2O3=10.34 wt.%) were most likely formed at the expense of spinel. The types of hydrogarnet and vesuvianite crystals are highly indicative for the involvement of subduction-related fluids during the formation of the rodingites [6]. References: [1] Jacobshagen & Wallbrecher 1984: Geol. Soc., London, Sp. Pub. 17, 591-602, [2] Pe-Piper 1991: Ofioliti, 16, 111 - 120, [3] Kamenetsky Sobolev, Joron & Semet 2001: J Petrol 42, 655-671, [4] Agrawal, Guevara & Verma 2008: Intern. Geol. Rev. 50, 1057-1079, [5] Pearce & Cann 1973: Earth Plan. Sci. Lett. 19, 290-300, [6] Koutsovitis, Magganas, Pomonis & Ntaflos 2013. Lithos 172-173, 139-157.
Mineral identification of black-jade gemstone from Aceh Indonesia
NASA Astrophysics Data System (ADS)
Ismail; Nizar, Akmal; Mursal
2018-04-01
One of the gemstones in Aceh Indonesia is called black-jade where the name of black-jade is a local name. Unfortunately, detail information about this gemstone is still limited. No one knows whether this gemstone can be categorized as jade or not until this study is presented. We have utilized X-Ray Fluorescent (XRF) to study the black-jade gemstone from Aceh Tengah (Takengon) and Nagan Raya regions in Indonesia. Our results show that the black-jade gemstone from Aceh Tengah contains 39.6% of SiO2, 35% of Fe2O3, 17% of MgO, 3% of CaO, and 2% of NiO. While, the black-jade gemstone from Nagan Raya contains a little bit less SiO2 but more Fe2O3 than that of black-jade from Aceh Tengah: 38.4% of SiO2, 39% of Fe2O3, 17% of MgO, 0.5% of CaO, and 2.6% of NiO. By comparing the results to the available mineral data (jadeite, nephrite-actinolite, nephrite-tremolite, serpentine-clinochrysotile, serpentine-antigorite, and vesuvianite), we found that oxide compounds contained in the black-jade gemstone from Aceh are found in the serpentine-antigorite, except H2O. The total difference between the oxide compositions in black-jade and serpentine-antigorite is 43% with its average difference of 11%. This means that the oxide composition in black-jade is almost the same as in the serpentine-antigorite. Accordingly, the black-jade gemstone from Aceh Indonesia is a type of serpentine-antigorite-jade.
Townsend, G.N.; Gibson, R.L.; Horton, J. Wright; Reimold, W.U.; Schmitt, R.T.; Bartosova, K.
2009-01-01
The Eyreville B core from the Chesapeake Bay impact structure, Virginia, USA, contains a lower basement-derived section (1551.19 m to 1766.32 m deep) and two megablocks of dominantly (1) amphibolite (1376.38 m to 1389.35 m deep) and (2) granite (1095.74 m to 1371.11 m deep), which are separated by an impactite succession. Metasedimentary rocks (muscovite-quartz-plagioclase-biotite-graphite ?? fibrolite ?? garnet ?? tourmaline ?? pyrite ?? rutile ?? pyrrhotite mica schist, hornblende-plagioclase-epidote-biotite- K-feldspar-quartz-titanite-calcite amphibolite, and vesuvianite-plagioclase- quartz-epidote calc-silicate rock) are dominant in the upper part of the lower basement-derived section, and they are intruded by pegmatitic to coarse-grained granite (K-feldspar-plagioclase-quartz-muscovite ?? biotite ?? garnet) that increases in volume proportion downward. The granite megablock contains both gneissic and weakly or nonfoliated biotite granite varieties (K-feldspar-quartz-plagioclase-biotite ?? muscovite ?? pyrite), with small schist xenoliths consisting of biotite-plagioclase-quartz ?? epidote ?? amphibole. The lower basement-derived section and both megablocks exhibit similar middleto upper-amphibolite-facies metamorphic grades that suggest they might represent parts of a single terrane. However, the mica schists in the lower basement-derived sequence and in the megablock xenoliths show differences in both mineralogy and whole-rock chemistry that suggest a more mafi c source for the xenoliths. Similarly, the mineralogy of the amphibolite in the lower basement-derived section and its association with calc-silicate rock suggest a sedimentary protolith, whereas the bulk-rock and mineral chemistry of the megablock amphibolite indicate an igneous protolith. The lower basement-derived granite also shows bulk chemical and mineralogical differences from the megablock gneissic and biotite granites. ?? 2009 The Geological Society of America.
Townsend, Gabrielle N.; Gibson, Roger L.; Horton, J. Wright; Reimold, Wolf Uwe; Schmitt, Ralf T.; Bartosova, Katerina
2009-01-01
The Eyreville B core from the Chesapeake Bay impact structure, Virginia, USA, contains a lower basement-derived section (1551.19 m to 1766.32 m deep) and two megablocks of dominantly (1) amphibolite (1376.38 m to 1389.35 m deep) and (2) granite (1095.74 m to 1371.11 m deep), which are separated by an impactite succession. Metasedimentary rocks (muscovite-quartz-plagioclase-biotite-graphite ± fibrolite ± garnet ± tourmaline ± pyrite ± rutile ± pyrrhotite mica schist, hornblende-plagioclase-epidote-biotite-K-feldspar-quartz-titanite-calcite amphibolite, and vesuvianite-plagioclase-quartz-epidote calc-silicate rock) are dominant in the upper part of the lower basement-derived section, and they are intruded by pegmatitic to coarse-grained granite (K-feldspar-plagioclase-quartz-muscovite ± biotite ± garnet) that increases in volume proportion downward. The granite megablock contains both gneissic and weakly or nonfoliated biotite granite varieties (K-feldspar-quartz-plagioclase-biotite ± muscovite ± pyrite), with small schist xenoliths consisting of biotite-plagioclase-quartz ± epidote ± amphibole. The lower basement-derived section and both megablocks exhibit similar middle- to upper-amphibolite-facies metamorphic grades that suggest they might represent parts of a single terrane. However, the mica schists in the lower basement-derived sequence and in the megablock xenoliths show differences in both mineralogy and whole-rock chemistry that suggest a more mafic source for the xenoliths. Similarly, the mineralogy of the amphibolite in the lower basement-derived section and its association with calc-silicate rock suggest a sedimentary protolith, whereas the bulk-rock and mineral chemistry of the megablock amphibolite indicate an igneous protolith. The lower basement-derived granite also shows bulk chemical and mineralogical differences from the megablock gneissic and biotite granites.
Palandri, J.L.; Reed, M.H.
2004-01-01
In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300??C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25??C and w/r less than ???32, conditions are sufficiently reducing to yield H2 gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH- production by olivine and pyroxene dissolution in the absence of counterbalancing OH- consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg2+ and Ca2+ to accumulate in the aqueous phase in exchange for H+. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300??C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg??. In serpentinization by seawater at 300??C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300??C yields rodingite-type mineral assemblages, including grossular, clinozoisite, vesuvianite, prehnite, chlorite, and diopside. ?? 2004 Elsevier Ltd.
NASA Astrophysics Data System (ADS)
Zanoni, D.; Rebay, G.; Spalla, M. I.
2015-12-01
Hydration-dehydration of mantle rocks affects the viscosity of the mantle wedge and plays a prominent role in subduction zone tectonics, facilitating marble cake-type instead of large-slice dynamics. An accurate structural and petrologic investigation of serpentinites from orogenic belts, supported by their long-lived structural memory, can help to recognize pressure-sensitive mineral assemblages for deciphering their P-prograde and -retrograde tectonic trajectories. The European Alps preserve large volumes of the hydrated upper part of the oceanic lithosphere that represents the main water carrier into the Alpine subduction zone. Therefore, it is important to understand what happens during subduction when these rocks reach P-T conditions proximal to those that trigger the break-down of serpentine, formed during oceanic metamorphism, to produce olivine and clinopyroxene. Rodingites associated with serpentinites are usually derived from metasomatic ocean floor processes but rodingitization can also happen in subduction environments. Multiscale structural and petrologic analyses of serpentinites and enclosed rodingites have been combined to define the HP mineral assemblages in the Zermatt-Saas ophiolites. They record 3 syn-metamorphic stages of ductile deformation during the Alpine cycle, following the ocean floor history that is testified by structural and metamorphic relics in both rock types. D1 and D2 developed under HP to UHP conditions and D3 under lower P conditions. Syn-D2 assemblages in serpentinites and rodingites indicate conditions of 2.5 ± 0.3 GPa and 600 ± 20°C. This interdisciplinary approach shows that the dominant structural and metamorphic imprint of the Zermatt-Saas eclogitized serpentinites and rodingites developed during the Alpine subduction and that subduction-related serpentinite de-hydration occurred exclusively at Pmax conditions, during D2 deformation. In contrast, in the favourable rodingite bulk composition (Ca-rich), hydrated minerals such as vesuvianite are stable up to the estimated P-climax conditions.
NASA Astrophysics Data System (ADS)
Upton, B. G. J.; Craven, J. A.; Kirstein, L. A.
2006-11-01
Aillikites (carbonated, melilite-free ultramafic lamprophyres grading to carbonatites) are minor components of the Gardar alkaline igneous province. They occur principally as minor intrusions and as clasts in diatremes, but more voluminous aillikitic intrusions crop out near the Ilímaussaq Complex, which they predate by a few million years. These larger intrusions were emplaced at 1160 ± 5 Ma. They are essentially carbonate-free and, consisting almost wholly of ferromagnesian silicate and oxide minerals, are mela-aillikites. Typically the mela-aillikites are fine-grained rocks composed largely of olivine, clinopyroxene, phlogopite and magnetite that crystallised in open systems, permitting loss of volatile-rich residues. The petrography is highly complex, involving at least 28 mineral species. Pyroxenitic veins were emplaced while the host-rocks were still at high temperatures and represent channels through which fluorinated silico-carbonatitic residual melts escaped, with exsolving CO 2 as propellant. Precipitation of Ca-rich minerals including monticellite, perovskite, vesuvianite, wollastonite and cuspidine was a result of dissociation of the calcium carbonate in the residual melts. Late-stage crystallisation was in a highly oxidising environment in which the 'common minerals' attain extreme compositions (almost pure forsterite, ferrian-diopside, highly magnesian ilmenite, Ba-Ti-rich phlogopite and Sr-rich kaersutite). Spatially associated diatremes may be vents through which CO 2-rich gases erupted. The whole-rock compositions are considered to be well removed from those of co-existing melts: compaction and expulsion of highly mobile residual melts is inferred to have left the mela-aillikites as aberrant cumulates. The mela-aillikites are a late-Gardar manifestation of the aillikitic magmatism that occurred intermittently in the province for over 120 Ma. Repetitive formation of metasomite vein systems in the deep lithospheric mantle is postulated. These readily fusible metasomites had short residence histories, experiencing either adiabatic melting or thermal melting as a result of plume activity. The abnormally large volumes of ultramafic lamprophyre magma, from which the mela-aillikites crystallised, may denote the culmination of metasomatic processes in the closing stages of the evolution of the Gardar Province.
NASA Astrophysics Data System (ADS)
Ferrando, S.; Castelli, D.; Frezzotti, M. L.
2017-12-01
Abiogenic CH4 can be produced by interaction between carbonates and reducing fluids derived from the hydration of ultramafics (e.g., mantle peridotite or HP Ol-serpentinite). This process occurs during slab exhumation because cooling promotes serpentinization of olivine in presence of water (Fo + H2O = Atg + Brc and the linked reactions: Fa + H2O = Fe-Atg + Mag + H2 and Atg + CaCO3 + H2 = Di + Brc + CH4 + H2O) at ca. 500-375°C (P=2.0-0.2 GPa). Experiments in the CH4-H2O-NaCl system indicate that, at these conditions, fluids are immiscible even for very low salinity (ca. 3 wt%) and that the NaCl content in the aqueous part of the fluid increases with temperature whereas the CH4 content in the gaseous part shows an opposite trend (Lamb et al., 2002; Li, 2017).In HP rodingite from the Piemonte ophiolite Zone (W Alps), primary fluid inclusions consisting of a brine (6 wt% CaCl2 + 6 wt% NaCl) with H2 + CH4 ≤ 1 mol % [CH4/(H2+CH4) = 0.37-10] occur in vesuvianite veins that formed at P=0.2 GPa and T=375°C. We interpret them as the aqueous part of an immiscible reducing fluid produced during late Alpine serpentinization of the surrounding ultramafics. Interestingly, CH4-H2 gaseous fluids are never reported in rodingite, whereas early CH4-H2O-H2±graphite and CH4-H2±graphite fluid inclusions, with variable gas-water proportions, trapped in calcite at P≤1.0 GPa and T≤450°C, are recently reported from HP "graphitized" ophicarbonate from the Lanzo peridotite Massif (W Alps; Vitale Brovarone et al., 2017).Both HP ophiolites and partially-serpentinized peridotite massifs are, thus, efficient lithologies to produce CH4 during exhumation. The amount of released CH4 depends on the amount of water available during exhumation. However, when fluids immiscibility occurs, the gaseous-rich part (CH4-H2) of the immiscible fluid produced in ultramafics likely remains confined in the slab because it is less mobile with respect to the aqueous-rich part due to its high dihedral angle. If C saturation conditions are reached, graphite precipitates in the rock. Conversely, the aqueous-rich part (brine with minor CH4-H2) of the immiscible fluid is more mobile and, then, able to migrate to the surface. Lamb et al. (2002): Geochim. Cosmochi. Acta, 66, 3971-3986 Li (2017): Geochem. Persp. Let., 3, 12-21 Vitale Brovarone et al. (2017): Nat. Comm., 8, 14134
NASA Astrophysics Data System (ADS)
Koutsovitis, Petros
2017-04-01
In Central Greece, the East Thessaly region encompasses ophiolitic and metaophiolitic formations emplaced onto Mesozoic platform series rocks. Metaophiolitic thrust sheets are characterized either by the predominance of serpentinites or metabasites. Serpentinites have been distinguished into three groups, representing distinct metamorphic degrees. Group-1 serpentinites (East Othris region) are characterized by the progressive transformation of lizardite to antigorite, estimated to have been formed under greenschist facies conditions (˜320-340 ˚ C, P≈6-8 kbar) [1]. Group-2 serpentinites (NE Othris and Agia-Agiokampos region) are marked by the further prevalence of antigorite over lizardite, suggesting upper-greenschist to low-blueschist facies metamorphism (˜340-370 ˚ C, P≈9-11 kbar) [1]. Group-3 serpentinites (Agia-Agiokampos region) are characterized by the predominance of antigorite and Cr-magnetite, as well as by their relatively low LOI (10.9-12.6 wt.%), corresponding to blueschist facies metamorphism (˜360-400 ˚ C, P≈12 kbar) [1]. These metamorphic conditions are highly comparable with the P-T estimates from the Easternmost Thessaly metabasic rocks, strongly indicating that the entire metaophiolitic formation (excluding East Othris) underwent blueschist facies metamorphism. Serpentinites from East Thessaly were formed from serpentinization of highly depleted harzburgitic protoliths under extensive partial melting processes (>15%), pointing to a hydrous subduction-related environment. Group-1 serpentinites exhibit higher Mg/Si ratio values and LOI compared to serpentinite Groups-2 and -3. Differences in the trace element behavior amongst the three serpentinite groups are also consistent with increasing metamorphic conditions (e.g. Pb, La enrichments, Ti, Y, Yb depletions) [1]. The East Thessaly serpentinites reflect highly oxidizing conditions (-0.4< FMQ<1.2) [1]. These serpentinites appear to have also been subjected to deserpentinization retrograde metamorphic processes (P<8 kbar and T<350 ˚ C) [1]. Retrograde metamorphism also resulted in the occurrence of late-stage rodingitization and derodingitization processes upon the rodingite intrusions hosted within the serpentinites. Late-stage derodingitization processes (T=250-300 oC) account for the formation of metarodingites (vesuvianite and/or chlorite bearing). Chlorite-serpentinite schists represent a reaction zone between the serpentinites and the hosted metarodingites [1]. Exhumation of the high-pressure serpentinite- and metabasic-bearing metaophiolitic occurrences may have occurred from either one or even from both of the bilateral oceanic basins (Pindos and Vardar) that coexisted besides the elongated Pelagonian zone. The Middle-Late Jurassic Pindos oceanic SSZ model appears to successfully interpret not only the geochemical and structural data recorded in the western Hellenic-Dinaric ophiolitic complexes, but additionally seems to explain the formation and emplacement for many of the East Thessaly metaophiolite occurrences. In this context, the exhumed metaophiolites represent parts either of a serpentinized subduction channel or of the serpentinized wedge, located on the hanging wall side close to the slab in the forearc system of the Pindos Ocean. The Hellenic-Dinaric ophiolitic units, as well as the metaophiolitic occurrences, were likely remobilized during thrusting of the flyschic nappe at the main Alpine orogenetic phase of the Upper Cretaceous-Paleogene period. References. [1] Koutsovitis 2016: Lithos, Special Issue, in Press. DOI: 10.1016/j.lithos.2016.11.008
NASA Astrophysics Data System (ADS)
Koutsovitis, Petros
2016-04-01
The East Thessaly region, Central Greece, includes metaophiolitic mélange formations which extend from the eastern foothills of Mt. Olympus and Ossa, throughout the Agia basin, Mt. Mavrovouni (Sklithro region), South Pelion and reaching up to northeast Othris (regions of Aerino and Velestino). They appear in the form of dispersed and deformed thrust sheets having been variably emplaced onto Mesozoic platform series rocks of the Pelagonian tectonostratigraphic zone[1]. These formations consist mainly of serpentinites, as well as metasediments, metagabbros, metadolerites, rodingites, ophicalcites, talc-schists and chromitites. Based upon petrographic observations, mineral chemistry data and XRD patterns, the subduction zone-related serpentinites from the regions of Potamia, Anavra, Aetolofos and Kalochori-Chasanbali (Agia basin), as well as from the regions of Aerino and Velestino, are characterized by the progressive transformation of lizardite to antigorite and are distinguished into two groups. The first group includes serpentinites from the metaophiolitic formations of Potamia, Anavra, Aerino and Velestino, which are marked by destibillization of lizardite to antigorite, mostly along the grain boundaries of the lizardite mesh textured relics. The presence of lizardite and antigorite in almost equal amounts indicates medium-temperature blueschist facies metamorphic conditions (˜340-370 ° C; P≈10-11 kbar)[2,3,4]. The second serpentinite group appears in the regions of Aetolofos and Kalochori, characterized by the predominance of antigorite, the minor occurrence of lizardite and the complete replacement of spinel by Cr-magnetite. The absence of metamorphic olivine suggests that these serpentinites were most likely formed at slightly higher temperature and pressure conditions compared to the first serpentinite group, corresponding to medium or high temperature blueschist facies metamorphism (˜360-380 ° C; P≈12 kbar)[2,3,4]. These metamorphic conditions are highly comparable with the P-T estimates from the East Thessaly metabasic rocks (˜350 ° C; P≈10-11 kbars)[5], suggesting that the entire metaophiolitic formation underwent blueschist facies metamorphism, comparable with high-pressure metaophiolitic formations appearing in Evia, Attica and the Cyclades. The East Thessaly serpentinites exhibit significantly high PM-normalized Pb, U enrichments and rather high Cs, La, As and Sb concentrations, which are comparable with subduction-related serpentinites, formed after mantle wedge peridotite hydration, and that have interacted with sedimentary derived fluids [2,6,7,8]. These serpentinites were also partly affected by de-serpentinization retrograde metamorphism (estimated at P<8 kbar and T<350 ° C) which is noticed by the following: secondary crosscuting antigorite veins occasionally with chlorite, coronas of chlorite along Cr-magnetite crystals, appearance of secondary calcite veins and talc. In the Kalochori-Chasanbali area, intense carbonization processes formed ophicalcite breccias enveloped by imbricated serpentinites[9], whereas talc-rich serpentinites appear in the region of Sklithro. Retrograde metamorphism may have occurred during exhumation, possibly within a serpentinite channel[8]. In addition, their retrograde history can also be indirectly identified through the study of their rodingite intrusions and more specifically through the formation of late-stage vesuvianite-rich dykes at low-moderate temperature conditions (T=250-300 oC) and subsequent derodingitization processes, forming metarodingites. The latter include abundant high-Mg replacive chlorite formed by continuous serpentinization which provided Mg2+ to the infiltrating fluids, causing the partial breakdown of Ca-bearing minerals. References. [1] Pe-Piper & Piper 2002: Borntraeger, Stuttgart, 1-645; [2] Lafay et al 2013: Chem Geol 343, 38-54; [3] Schwartz et al 2013: Lithos 178, 197-210; [4] Guillot, et al 2015: Tectonophysics 646, 1-19; [5] Perraki et al 2002: Geologica Carpathica 53, 164-165; [6] Deschamps, et al 2013: Lithos 178, 96-127; [7] Hattori & Guillot, 2007: G-Cubed 8 (9); [8] Barnes et al 2014: Chemi Geol 389, 29-47; [9] Melfos et al 2009: Geoph. Res. Abst, 11.