Zircon and baddeleyite from the economic ultramafic-mafic Noril'sk-1 intrusion (Russia): Hf-isotope constraints on source composition

NASA Astrophysics Data System (ADS)

Malitch, K. N.; Belousova, E. A.; Badanina, I. Yu.; Griffin, W. L.

2012-04-01

The ultramafic-mafic Noril'sk-1 intrusion in the northwestern part of the Siberian Craton (Russia) represents one of three known Noril'sk-type, ore-bearing intrusions, which host one of the world's major economic sulphide platinum-group-element (PGE)-Cu-Ni deposits. Zircon and baddeleyite dated previously both by SHRIMP (i.e. 248.0 ± 3.7 Ma, Campbell et al. 1992) and ID-TIMS (251.1 ± 3.6 Ma, Kamo et al. 1996) have been restricted to one lithology (e.g. leucogabbro) of the Noril'sk-1 intrusion. To better constrain the age of igneous event and sources involved in its generation our multi-technique study utilized ten rock samples characteristic of unmineralized and mineralized lithologies. The rocks investigated comprise (from top to bottom) gabbro-diorite (sample N1-1), leucogabbro (N1-3), olivine-free gabbro (N1-2 and N1-4), olivine-bearing gabbro (N1-5), olivine gabbro (N1-6), plagiowehrlite and plagiodunite (N1-7), taxitic-textured rocks comprising melanotroctolite, olivine gabbro with relics of ultramafic rocks (N1-8, N1-9) and contact fine-grained gabbro (N1-10). Sulphide PGE-Cu-Ni ores occur in ultramafic (N1-7) and taxitic-textured rocks (N1-8 and N1-9), which have thickness of about 17 m, whereas the low-sulphide horizon of about 1 m thick occurs in the upper part of intrusion (N1-3). In situ U-Pb analyses of zircon from these rocks, combined with detailed study of crystal morphology and internal structure, identify four zircon populations (Malitch et al. 2012). The U-Pb ages of baddeleyite and the defined zircon populations cover a significant time span, from Late Paleozoic to Early Mesozoic (e.g., 290 ± 2.8; 261.3 ± 1.6; 245.7 ± 1.1; 236.5 ± 1.8 and 226.7 ± 0.9 Ma). The established distribution of U-Pb ages implies that crystallization of baddeleyite and zircon corresponds to several stages of protracted evolution of ultramafic-mafic magmas at deep-seated staging chambers and/or probably characterizes interaction of distinct magmas during formation of the Noril'sk-1 intrusion, which served as the favorable factor for accumulation of ores of unique scales and concentrations, To test this hypothesis, in situ Hf-isotope data were collected on the dated spots within single zircon grains. The analysis used a New Wave LUV213 laser-ablation microprobe attached to a Nu plasma MC-ICP-MS at GEMOC (Griffin et al. 2002). Hf-isotope results grouped on the basis of lithology show notable differences. Zircons from the unmineralized 'layered rock sequence' (e.g., olivine-free gabbro, olivine-bearing gabbro and olivine gabbro) are characterized by the most 'radiogenic' initial 176Hf/177Hf and some of ɛHf values close to those of the Depleted Mantle. Irrespective of zircon population most radiogenic Hf-isotope compositions are typical for olivine-free gabbro (mean ɛHf 7.3 ± 1.1 for sample N1-4), olivine-bearing gabbro (9.2 ± 3.8, sample N1-5) and olivine gabbro (8.3 ± 2.0, sample N1-6). In contrast, zircons from the leucogabbro that encloses the low-sulphide horizon (N1-3), and plagiowehrlite (N1-7) and taxitic-textured rocks (N1-8 and N1-9) with disseminated sulphide ores have less radiogenic Hf-isotope values (e.g., mean ɛHf6.2 ± 1.4, 5.9 ± 2.3, 6.4 ± 1.2 and 4.9±1.4, respectively). The least radiogenic values (ɛHffrom -2.9 to +2.3, mean ɛHf = 0.1 ± 1.9) are recorded in gabbro-diorite from the upper part of intrusion. The baddeleyite from olivine-free gabbro has the narrowest range of ɛHf values (e.g. 6.8-8.4), with a mean of ɛHfof 7.6 ± 0.8, closely matching that of zircon (mean ɛHf= 7.3 ± 1.1). Zircons from the leucogabbro that hosts the low-sulphide horizon (N1-3), and ultramafic and taxitic-textured lithologies with disseminated sulphide ores (N1-7, N1-8 and N1-9) have less radiogenic ɛHf values than those in barren lithologies. The Hf-isotope data for zircons from ore-bearing rocks thus suggest that the Noril'sk magmas represent mixing between a juvenile source equivalent to the Depleted Mantle and a subcontinental lithospheric source probably at least Neoproterozoic in age. We propose that the SCLM component is especially prominent in the mineralized portions of the intrusion. This is consistent with the suggestion of Zhang et al (2008) that ancient cratonic lithospheric mantle may have contributed significantly to the PGE and Ni budget of the "fertile" Siberian Large Igneous Province. Small population of zircons from the gabbro-diorite show the least 'radiogenic' Hf-isotope values, indicating the input of a distinctly older lithospheric, possibly crustal, component, being consistent with a hybrid nature of this lithology. Our approach for deciphering the origin of zircon and baddeleyite from mafic and ultramafic rocks provides a unique set of U-Pb and Hf-isotope constraints on temporal evolution and petrologic history of the Noril'sk-1 intrusion. The study was supported by Uralian Branch of Russian Academy of Sciences (12-U-5-1038). Refereneces: Campbell I.H., Czamanske G.K., Fedorenko V.A., Hill R.I., Stepanov V. (1992) Synchronism of the Siberian traps and the Permian-Triassic boundary. Science 255, 1760-1763. Griffin W.L., Wang X., Jackson S.E., Pearson N.J., O'Reilly S.Y., Xu X., Zhou X. (2002) Zircon chemistry and magma genesis, SE China: in-situ analysis of Hf isotopes, Pingtan and Tonglu igneous complexes. Lithos 61, 237-269. Kamo S.L., Czamanske G.K., Krogh T.E. (1996) A minimum U-Pb age for Siberian flood-basalt volcanism. Geochim. Cosmochim. Acta 60, 3505-3511. Malitch K.N., Badanina I.Yu., Belousova E.A., Tuganova E.V. (2012) Results of U-Pb dating of zircon and baddeleyite from the Noril'sk-1 ultramafic-mafic intrusion (Russia). Russian Geology and Geophysics 53(2), 123-130. Zhang M., O'Reilly S.Y., Wang K-L., Hronsky J., Griffin W.L. (2008) Flood basalts and metallogeny: The lithospheric connection. Earth-Science Reviews 86, 145-174.

New nanostructured ceramics from baddeleyite with improved mechanical properties for biomedical applications

NASA Astrophysics Data System (ADS)

Tyurin, Alexander I.; Zhigachev, Andrey O.; Umrikhin, Alexey V.; Rodaev, Vyacheslav V.; Korenkov, Viktor V.; Pirozhkova, Tatyana S.

2017-12-01

A method for the preparation of novel nanostructured zirconia ceramics from natural zirconia mineral—baddeleyite—using CaO as the stabilizer is described in the present work. Optimal synthesis conditions, including calcia content, planetary mill treatment regime, sintering time and temperature, corresponding to the highest values of hardness H, Young modulus E, and fracture toughness KC are found. The values of the mechanical properties H = 10.8 GPa, E = 200 GPa, and KC = 13.3 MPa m1/2 are comparable with or exceed the corresponding properties of commercial yttria-stabilized ceramics prepared from chemically precipitated zirconia.

Paleomagnetism and geochronological studies on a 450 km long 2216 Ma dyke from the Dharwar craton, southern India

NASA Astrophysics Data System (ADS)

Nagaraju, E.; Parashuramulu, V.; Kumar, Anil; Srinivas Sarma, D.

2018-01-01

Paleomagnetic and geochronological studies were carried out on a ∼ 450 km long (from 17 sites) N-S striking Paleoproterozoic dyke swarm exposed along a natural crustal cross section of about 10 km (increasing from North to South) in the Dharwar Craton, to study the characteristics of paleomagnetism and geochronology in vertical dimension. U-Pb/Pb-Pb dating on baddeleyite gives a crystallisation age of 2216.0 ± 0.9 Ma for long dyke AKLD. Paleomagnetic data from this well dated ∼ 2216 Ma dyke swarm in Dharwar Craton are of excellent quality. High coercivity and high blocking temperature components are carried by single domain magnetite and show dual polarity remanence directions. Combined normal and reverse polarity remanences on AKLD and other N-S dykes define the most reliable paleomagnetic pole for ∼ 2216 Ma at latitude 36°S and longitude 312°E (A95 = 7°). Though paleomagnetic data is unavailable on other N-S dykes below the Cuddapah basin, high precision geochronology suggest that they are of similar age within errors. Though there is a variation in the crustal depth of Dharwar craton from north to south, consistent Pb-Pb/U-Pb baddeleyite geochronology and paleomagnetic studies along the AKLD established its continuity and preservation along its entire strike length. The virtual geomagnetic poles of these sites confirm a stable remanence and are almost identical to the previously reported paleomagnetic pole and also supported by positive reversal test. Positive paleomagnetic reversal test on these dykes signify that the remanent magnetization is primary and formed during initial cooling of the intrusions. Updated apparent polar wander path of Dharwar craton indicates relatively low drift rate during 2.21-2.08 Ga interval. Magnetogranulometry and SEM studies show that remanent magnetization in this dyke was carried by single domain magnetite residing within silicate minerals.

Zirconium

USGS Publications Warehouse

Bedinger, G.M.

2013-01-01

Zirconium is the 20th most abundant element in the Earth’s crust. It occurs in a variety of rock types and geologic environments but most often in igneous rocks in the form of zircon (ZrSiO4). Zircon is recovered as a coproduct of the mining and processing of heavy mineral sands for the titanium minerals ilmenite and rutile. The sands are formed by the weathering and erosion of rock containing zircon and titanium heavy minerals and their subsequent concentration in sedimentary systems, particularly in coastal environments. A small quantity of zirconium, less than 10 kt/a (11,000 stpy), compared with total world production of 1.4 Mt (1.5 million st) in 2012, was derived from the mineral baddeleyite (ZrO2), produced from a single source in Kovdor, Russia.

Rare earth element carriers in the Shergotty meteorite and implications for its chronology

NASA Technical Reports Server (NTRS)

Lundberg, Laura L.; Crozaz, Ghislaine; Zinner, Ernst; Mckay, Gordon

1988-01-01

This paper reports on the results of ion-probe measurements of REE concentrations in individual grains of the Shergotty meteorite. The phases analyzed included whitlockite, apatite, baddeleyite, augite, pigeonite, maskelynite, and K-rich glass; the whitlockite and apatite phases were also analyzed for U. Results indicate that whitlockite contains the bulk of the REE in Shergotty, with no evidence for distinct light-REE patterns in texturally different whitlockites. The results on the evolution of the REE abundances in the Shergotty late-stage interstitial melt, inferred from the analysis of whitlockite, are consistent with closed system crystallization. No metasomatic alteration is required to explain the REE data. It is concluded that there is no compelling reason to attribute chronological significance to the Sm-Nd array, as was done by Jagoutz and Waenke (1986).

Partial pressures of oxygen, phosphorus and fluorine in some lunar lavas

NASA Technical Reports Server (NTRS)

Nash, W. P.; Hausel, W. D.

1973-01-01

Lunar sample 14310 is a feldspar-rich basalt which shows no evidence of shock deformation or recrystallization. Pyroxenes include Mg-rich orthopyroxene, pigeonite and augite; pyroxferroite occurs in the interstitial residuum. Plagioclase feldspars are zoned from An(96) to An(67), and variations in feldspar compositions do not necessarily indicate loss of Na during eruption of the lava. Opaque phases include ilmenite, ulvospinel, metallic iron, troilite, and schreibersite. Both whitlockite and apatite are present, and the interstitial residua contain baddeleyite, tranquillityite and barium-rich sanidine. Theoretical calculations provide estimates of partial pressures of oxygen, phosphorus, and fluorine in lunar magmas. In general, partial pressures of oxygen are restricted by the limiting assemblages of iron-wuestite and ilmenite-iron-rutile; phosphorus partial pressures are higher in lunar magmas than in terrestrial lavas. The occurrence of whitlockite indicates significantly lower fugacities of fluorine in lunar magmas than in terrestrial magmas.

Isotope Sm-Nd age of the paleoproterozoic PGE-bearing Monchetundra massif trachytoid gabbronorites (Fennoscandian shield)

NASA Astrophysics Data System (ADS)

Kunakkuzin, Evgeniy; Bayanova, Tamara; Serov, Pavel; Borisenko, Elena

2015-04-01

Monchetundra massif is located in the central part of the Kola Peninsula (Russia) and it is the south-eastern part of the Main Ridge Intrusion. Monchetundra massif together with well-known layered mafic-ultramafic PGE-bearing intrusions in the Fennoscandian shield such as the Fedorovo-Pansky complex, the mt. Generalskaya, the Monchepluton is of interest as a target for the PGE prospecting (Mitrofanov et al. 2006; Nerovich et al., 2009; Grokhovskaya et al., 2003). According to some previously researchers (Nazimova, Rayan, 2008, Nerovich et al., 2009, Layered intrusions…p.1, 2004) rocks of the Monchetundra massif is subdivided into two to five syngenetic zones. Hence the last isotope-geochronological and isotope-geochemical data revealed that the massif includes at least four groups of mafic rocks distinguished by formation ages (Bayanova et al., 2010). The aim of this work is to present Sm-Nd dating results of trachytoid gabbronorites, which are the second mafic rocks group in the Monchetundra massif. The Sm-Nd investigations for these rocks were carried out for the first time. The second group of mafic rocks comprises of medium-grained and coarse-grained mesocratic gabbronorites of trachytoid texture, with they characterized by well-preserved primary magmatic minerals and gabbro-ophitic texture. The U-Pb ages on single zircon-baddeleyite for these rocks recently obtained (2505 ± 6 Ma, 2501 ± 8 Ma, 2504.4±2.7 Ma and 2507.5±7.7 Ma (Layered intrusions…p.1., 2004, Borisenko et al., 2013)). Two samples of trachytoid gabbronorites were selected to study these rocks by Sm-Nd isotopic method. Mineral isochrons plotted from plagioclase, ortho- and clinopyroxene and whole-rock minerals gave ages of 2496±27 (MSWD = 0.9; ɛNd = -1.6±0.5) and 2492±55 Ma (MSWD = 0.5; ɛNd = -1.7±0.5). The new Sm-Nd ages obtained are close to the U-Pb data on zircons and baddeleyites for this rocks group and consider as oridin of second mafic rocks group. All investigations are devoted to memory of academician RAS, professor F. Mitrofanov (Russia), he was a leader of scientific school for geology, geochemistry and metallogeny of ore deposits. The researches are conducted with the financial support of RFBR 13-05-00493, OFI-M 13-05-12055, IGCP-SIDA 599.

U-Pb baddeleyite ages and geochemistry of dolerite dykes in the Bas Drâa Inlier of the Anti-Atlas of Morocco: Newly identified 1380 Ma event in the West African Craton

NASA Astrophysics Data System (ADS)

El Bahat, Abdelhakim; Ikenne, Moha; Söderlund, Ulf; Cousens, Brian; Youbi, Nasrrddine; Ernst, Richard; Soulaimani, Abderrahmane; El Janati, M'hamed; Hafid, Ahmid

2013-08-01

In the Bas-Drâa Inlier (Anti-Atlas, Morocco), the Paleoproterozoic basement which is cut by the Ediacaran Taourgha granite is also crosscut by numerous dykes of a variety of trends, mostly of uncertain age. Two doleritic dykes are dated by the ID-TIMS U-Pb method on baddeleyite and yield emplacement ages of 1381 ± 8 Ma (MSWD = 0.84) and 1384 ± 6 Ma (MSWD = 1.4) determined for a N135°E and a N40°E trending dyke, respectively. These dates represent the first geochronological evidence of a Mesoproterozoic magmatic event in the Anti-Atlas. This magmatic event falls in the previously considered ca 1.7-1.0 Ga (Mesoproterozoic) gap in geological activity in the Anti-Atlas. The poorly dated Taghdout and Taarotihate sequences could represent remnants of the ca. 1380 Ma magmatism and rift-related sedimentation. The Mesoproterozoic sedimentary succession of the Atar Group in the Taoudeni basin (Mauritania) could also represent a good candidate for rift-related sedimentation but it postdates the 1380 Ma magmatic event by 270 Ma. The dated 1380 Ma dykes are transitional to mildly alkaline basalts, not unlike some Hawaiian lavas. However, these dykes have a distinct negative Nb anomaly (a common features in many Large Igneous Provinces, LIPs), and this requires interaction with the lithosphere. This interaction may have occurred at the level of the lithospheric mantle or the crust. These newly dated 1380 Ma dykes may converge to the north, speculatively suggesting a magmatic center (associated with a 1380 Ma mantle plume?) along the northern margin, and possibly linked to rifting and possible breakup on that margin, and also to a regional uplift that largely removed the evidence of a 1380 Ma cover sequence. Contemporaneous 1380-1390 Ma magmatism is reported elsewhere on other crustal blocks, and that in northeastern Laurentia (northern Greenland), northern Siberia (Anabar shield), and Baltica (southern Urals) can be reconstructed with that of the Bas Drâa Inlier (Anti Atlas region of the West African Craton, WAC) into a single Large Igneous Province (LIP) extending over an area of > 1 million km2, and associated with the final fragmentation of the Columbia (Nuna) supercontinent.

Kampelite, Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O, a new very complex Ba-Sc phosphate mineral from the Kovdor phoscorite-carbonatite complex (Kola Peninsula, Russia)

NASA Astrophysics Data System (ADS)

Yakovenchuk, Victor N.; Ivanyuk, Gregory Yu.; Pakhomovsky, Yakov A.; Panikorovskii, Taras L.; Britvin, Sergei N.; Krivovichev, Sergey V.; Shilovskikh, Vladimir V.; Bocharov, Vladimir N.

2018-02-01

Kampelite, Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O, is a new Ba-Sc phosphate from the Kovdor phoscorite-carbonatite complex (Kola Peninsula, Russia). It is orthorhombic, Pnma, a = 11.256(1), b = 8.512(1), c = 27.707(4) Å, V = 2654.6(3) Å3 and Z = 4 (from powder diffraction data) or a = 11.2261(9), b = 8.5039(6), c = 27.699(2) Å, V = 2644.3(3) Å3 (from single-crystal diffraction data). The mineral was found in a void within the calcite-magnetite phoscorite (enriched in hydroxylapatite and Sc-rich baddeleyite) inside the axial zone of the Kovdor phoscorite-carbonatite pipe. Kampelite forms radiated aggregates (up to 1.5 mm in diameter) of platy crystals grown on the surfaces of crystals of quintinite-2 H in close association with pyrite, bobierrite and quintinite-3 R. Kampelite is colourless, with a pearly lustre and a white streak. The cleavage is perfect on {001}, the fracture is smooth. Mohs hardness is about 1. In transmitted light, the mineral is colourless without pleochroism or dispersion. Kampelite is biaxial + (pseudouniaxial), α ≈ β = 1.607(2), γ = 1.612(2) (589 nm), and 2 V calc = 0°. The calculated and measured densities are 3.28 and 3.07(3) g·cm-3, respectively. The mean chemical composition determined by electron microprobe is: MgO 4.79, Al2O3 0.45, P2O5 31.66, K2O 0.34, Sc2O3 16.17, Mn2O3 1.62, Fe2O3 1.38, SrO 3.44, and BaO 29.81 wt%. The H2O content estimated from the crystal-structure refinement is 7.12 wt%, giving a total of 96.51 wt%. The empirical formula calculated on the basis of P = 6 apfu (atoms per formula unit) is (Ba2.62Sr0.45K0.10Ca0.06)Σ3.23Mg1.60Mn0.28(Sc3.15Fe3+ 0.23Al0.12)Σ3.50(PO4)6(OH)2.61·4.01H2O. The simplified formula is Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O. The mineral easily dissolves in 10% cold HCl. The strongest X-ray powder-diffraction lines [listed as d in Å ( I) ( hkl)] are as follows: 15.80(100)(001), 13.86(45)(002), 3.184(18)(223), 3.129(19)(026), 2.756(16)(402), 2.688(24)(10 10). The crystal structure of kampelite was refined to R 1 = 0.092 on the basis of 2620 unique observed reflections. It is based upon complex [MgBa2Sc4(PO4)6] layers consisting of the Ba-PO4 zigzag sheet inserted between two Mg-Sc-PO4 sheets. Raman spectrum of kampelite contains characteristic bands of vibrations of the PO4, ScO6 and H2O groups. Kampelite formed as a result of low-temperature hydrothermal alteration of Sc-bearing baddeleyite, which also produces Sc-rich pyrochlore and juonniite. The structural complexity parameters for kameplite are equal to 5.272 bits/atom and 1244.304 bits/cell, which points out that the mineral is structurally very complex, in agreement with its late-stage hydrothermal origin. The mineral is named in honour of Russian mining engineer Felix Borisovich Kampel' (b. 1935) for his contribution to the development of technologies of mining and processing of complex magnetite-apatite-baddeleyite ores of the Kovdor deposit.

U–Pb geochronology documents out-of-sequence emplacement of ultramafic layers in the Bushveld Igneous Complex of South Africa

PubMed Central

Mungall, James E.; Kamo, Sandra L.; McQuade, Stewart

2016-01-01

Layered intrusions represent part of the plumbing systems that deliver vast quantities of magma through the Earth's crust during the formation of large igneous provinces, which disrupt global ecosystems and host most of the Earth's endowment of Pt, Ni and Cr deposits. The Rustenburg Layered Suite of the enormous Bushveld Igneous Complex of South Africa has been presumed to have formed by deposition of crystals at the floor of a subterranean sea of magma several km deep and hundreds of km wide called a magma chamber. Here we show, using U–Pb isotopic dating of zircon and baddeleyite, that individual chromitite layers of the Rustenburg Layered Suite formed within a stack of discrete sheet-like intrusions emplaced and solidified as separate bodies beneath older layers. Our U–Pb ages and modelling necessitate reassessment of the genesis of layered intrusions and their ore deposits, and challenge even the venerable concept of the magma chamber itself. PMID:27841347

Mineralogy, Petrology and Oxygen Fugacity of the LaPaz Icefield Lunar Basaltic Meteorites and the Origin of Evolved Lunar Basalts

NASA Technical Reports Server (NTRS)

Collins, S. J.; Righter, K.; Brandon, A. D.

2005-01-01

LAP 02205 is a 1.2 kg lunar mare basalt meteorite found in the Lap Paz ice field of Antarctica in 2002 [1]. Four similar meteorites were also found within the same region [1] and all five have a combined mass of 1.9 kg (LAP 02224, LAP 02226, LAP 02436 and LAP 03632, hereafter called the LAP meteorites). The LAP meteorites all contain a similar texture, mineral assemblage, and composition. A lunar origin for these samples comes from O isotopic data for LAP 02205 [1], Fe/Mn ratios of pyroxenes [1-5], and the presence of distinct lunar mineralogy such as Fe metal and baddeleyite. The LAP meteorites may represent an area of the Moon, which has never been sampled by Apollo missions, or by other lunar meteorites. The data from this study will be used to compare the LAP meteorites to Apollo mare basalts and lunar basaltic meteorites, and will ultimately help to constrain their origin.

U-Pb geochronology documents out-of-sequence emplacement of ultramafic layers in the Bushveld Igneous Complex of South Africa.

PubMed

Mungall, James E; Kamo, Sandra L; McQuade, Stewart

2016-11-14

Layered intrusions represent part of the plumbing systems that deliver vast quantities of magma through the Earth's crust during the formation of large igneous provinces, which disrupt global ecosystems and host most of the Earth's endowment of Pt, Ni and Cr deposits. The Rustenburg Layered Suite of the enormous Bushveld Igneous Complex of South Africa has been presumed to have formed by deposition of crystals at the floor of a subterranean sea of magma several km deep and hundreds of km wide called a magma chamber. Here we show, using U-Pb isotopic dating of zircon and baddeleyite, that individual chromitite layers of the Rustenburg Layered Suite formed within a stack of discrete sheet-like intrusions emplaced and solidified as separate bodies beneath older layers. Our U-Pb ages and modelling necessitate reassessment of the genesis of layered intrusions and their ore deposits, and challenge even the venerable concept of the magma chamber itself.

U-Pb zircon geochronology and evolution of some Adirondack meta-igneous rocks

NASA Technical Reports Server (NTRS)

Mclelland, J. M.

1988-01-01

An update was presented of the recent U-Pb isotope geochronology and models for evolution of some of the meta-igneous rocks of the Adirondacks, New York. Uranium-lead zircon data from charnockites and mangerites and on baddeleyite from anorthosite suggest that the emplacement of these rocks into a stable crust took place in the range 1160 to 1130 Ma. Granulite facies metamorphism was approximately 1050 Ma as indicated by metamorphic zircon and sphene ages of the anorthosite and by development of magmatitic alaskitic gneiss. The concentric isotherms that are observed in this area are due to later doming. However, an older contact metamorphic aureole associated with anorthosite intrusion is observed where wollastonite develops in metacarbonates. Zenoliths found in the anorthosite indicate a metamorphic event prior to anorthosite emplacement. The most probable mechanism for anorthosite genesis is thought to be ponding of gabbroic magmas at the Moho. The emplacement of the anorogenic anorthosite-mangerite-charnockite suite was apparently bracketed by compressional orogenies.

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

U, Th, Pb and REE abundances and Pb 207/Pb 206 ages of individual minerals in returned lunar material by ion microprobe mass analysis.

NASA Technical Reports Server (NTRS)

Andersen, C. A.; Hinthorne, J. R.

1972-01-01

Results of ion microprobe analyses of Apollo 11, 12 and 14 material, showing that U, Th, Pb and REE are concentrated in accessory minerals such as apatite, whitlockite, zircon, baddeleyite, zirkelite, and tranquillityite. Th/U ratios are found to vary by over a factor of 40 in these minerals. K, Ba, Rb and Sr have been localized in a K rich, U and Th poor glass phase that is commonly associated with the U and Th bearing accessory minerals. Li is observed to be fairly evenly distributed between the various accessory phases. The phosphates have been found to have REE abundance patterns (normalized to the chondrite abundances) that are fairly flat, while the Zr bearing minerals have patterns that rise steeply, by factors of ten or more, from La to Gd. All the accessory minerals have large negative Eu anomalies. Radiometric age dates (Pb 207/Pb 206) of the individual U and Th bearing minerals compare favorably with the Pb 207/Pb 206 age of the bulk rocks.

Approach of automatic 3D geological mapping: the case of the Kovdor phoscorite-carbonatite complex, NW Russia.

PubMed

Kalashnikov, A O; Ivanyuk, G Yu; Mikhailova, J A; Sokharev, V A

2017-07-31

We have developed an approach for automatic 3D geological mapping based on conversion of chemical composition of rocks to mineral composition by logical computation. It allows to calculate mineral composition based on bulk rock chemistry, interpolate the mineral composition in the same way as chemical composition, and, finally, build a 3D geological model. The approach was developed for the Kovdor phoscorite-carbonatite complex containing the Kovdor baddeleyite-apatite-magnetite deposit. We used 4 bulk rock chemistry analyses - Fe magn , P 2 O 5 , CO 2 and SiO 2 . We used four techniques for prediction of rock types - calculation of normative mineral compositions (norms), multiple regression, artificial neural network and developed by logical evaluation. The two latter became the best. As a result, we distinguished 14 types of phoscorites (forsterite-apatite-magnetite-carbonate rock), carbonatite and host rocks. The results show good convergence with our petrographical studies of the deposit, and recent manually built maps. The proposed approach can be used as a tool of a deposit genesis reconstruction and preliminary geometallurgical modelling.

U-Pb geochronology and paleomagnetism of the Neoproterozoic St Simeon dolerite dykes, Quebec: an eastern Laurentian perspective of Ediacaran Rodinia breakup

NASA Astrophysics Data System (ADS)

Pisarevsky, Sergei; Murphy, Brendan; Hamilton, Mike; Söderlund, Ulf; Hodych, Joseph

2013-04-01

The St Simeon (SS) mafic dykes (150 km NE of Quebec City) are now dated at 548 ± 1 Ma (U-Pb; baddeleyite). This age is similar to a published LA-ICPMS zircon age of 550 ± 7 Ma for the Mt. St-Anselme (MS) basalts, which supports previous inferences of (i) a genetic relationship between them, (ii) the pene-contemporaneity of OIB-type mafic magmatism in East Laurentia and (iii) the existence of two late Ediacaran plumes that attended the final breakup of Rodinia and opening of the Iapetus Ocean and Tornquist Sea. Both the SS dykes and the MS basalts were sampled for paleomagnetic study. The paleomagnetic pole for SS is similar to the previously published pole for coeval basalts (Skinner Cove, SC) from Newfoundland. Unlike SC, the St Simeon pole represents rocks which are unambiguously coherent tectonically with the Laurentian Craton. This new pole is also coeval with high quality poles from the Winter Coast (Baltica) and provides paleomagnetic constraints on the history of the final breakup of Rodinia and opening of Eastern Iapetus and Tornquist Sea.

A Sulfate Aerosol Trigger for the Sturtian Neoproterozoic Snowball Event

NASA Astrophysics Data System (ADS)

Wordsworth, R. D.; Macdonald, F. A.

2017-12-01

Despite the dominance of the carbon cycle in determining the evolution of Earth's climate in general, certain events defy easy explanation via atmospheric CO2 changes alone. Here we discuss the particular role that transient planetary albedo changes via sulfate aerosol formation can play in major climate transitions. Specifically, we propose that SO2 outgassing associated with the eruption of the Franklin Large Igneous Province (LIP) led to the first Neoproterozoic Snowball event, the Sturtian, 716 Ma. We summarize U/Pb zircon and baddeleyite dating indicating the synchronicity of the Franklin eruptions and the onset of the Sturtian, and paleomagnetic data indicating that the Franklin erupted close to the equator. We then discuss in detail the modeling we have performed of eruption rate, the plume height achieved during basaltic fissure volcanism, the chemistry and microphysics of sulfate aerosol formation, and the dependence of aerosol longwave and shortwave radiative effects on atmospheric loading, particle size and surface albedo. We discuss the critical importance of the latitude of eruption, the tropopause height, and ocean dynamics in determining the strength and sign of aerosol radiative forcing. We finish by comparing the Franklin event with other LIP emplacement events in Earth history and make suggestions for future modeling.

Multistage formation processes in the acapulcoite-lodranite parent body: Mineralogical study of anomalous lodranite, Yamato 983119

NASA Astrophysics Data System (ADS)

Yasutake, Masahiro; Yamaguchi, Akira

2017-12-01

Y 983119 is a coarse-grained rock consisting mainly of orthopyroxene (44-71 vol%, Wo3En94Fs4), olivine (4-30 vol%, Fo97), Fe, Ni metal (4-14 vol%) and interstitial plagioclase (9-14 vol%, Or2Ab67An29) and augite (2-5 vol%, Wo46En53Fs2). The modal abundance of orthopyroxene is higher than known acapulcoites and lodranites. Olivine grains show chemical zoning with higher Fe/Mn values along rims and cracks. Orthopyroxene and olivine contain melt inclusions that mainly consist of augite, feldspar and glass. Hornblende, biotite, rutile and baddeleyite were also found in melt inclusions. Based on the compositions of melt inclusions, the parent melt is felsic, and contains a significant amount of Na, K, Ti, Zr, F and OH. The major mineral and oxygen isotopic compositions indicate that Y 983119 is a lodranite. However, the high abundance of orthopyroxene and the presence of melt inclusions indicate that Y 983119 is not a residue in contrast to other lodranites. We suggest that Y 983119 formed by more complex formation processes than the other lodranites.

Metal dioxides as analogue of SiO2 under strong compression studied by synchrotron XRD and simulations

NASA Astrophysics Data System (ADS)

Liu, H.; Liu, L. L.

2017-12-01

The phase transition sequence of SiO2 inducing by high pressure was theoretically predicted as coordination number (CN=6) structures (rutile, pyrite), CN=8 (Pnma) and CN=9 (P-62m) structures, but only the phases up to pyrite structure in SiO2 were observed experimentally up to now. The CN8 phase and CN9 phases of SiO2 were predicted to be stable at least 650 GPa, which is challenging to achieve in the static DAC experiment at present. In other metal dioxide systems, such as TiO2, the ambient rutile and anatase phases first transform to pyrite (CN6), then to the baddeleyite (CN7) phase, to a Pnma (CN8) phase and P-62m(CN9) phase. In this report, under strong compression at room temperature, several metal dioxides were studied experimentally and theoretically, to verify whether this theoretical predicted trend is common transition path under strong compression. This work was supported by Natural Science Foundation of China (11374075), Heilongjiang Province Science Fund for Distinguished Young Scholars (JC201005), Longjiang Scholar, the Fundamental Research Funds for the Central Universities (HIT. BRET1.2010002, HIT. IBRSEM.A.201403).

Crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics for immobilization of simulated sulfate bearing high-level liquid waste

NASA Astrophysics Data System (ADS)

Wu, Lang; Xiao, Jizong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang; Liao, Qilong

2018-01-01

The crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics with different content (0-30 wt %) of simulated sulfate bearing high-level liquid waste (HLLW) were evaluated. The sulfate phase segregation in vitrification process was also investigated. The results show that the glass-ceramics with 0-20 wt% of HLLW possess mainly zirconolite phase along with a small amount baddeleyite phase. The amount of perovskite crystals increases while the amount of zirconolite crystals decreases when the HLLW content increases from 20 to 30 wt%. For the samples with 20-30 wt% HLLW, yellow phase was observed during the vitrification process and it disappeared after melting at 1150 °C for 2 h. The viscosity of the sample with 16 wt% HLLW (HLLW-16) is about 27 dPa·s at 1150 °C. The addition of a certain amount (≤20 wt %) of HLLW has no significant change on the aqueous stability of glass-ceramic waste forms. After 28 days, the 90 °C PCT-type normalized leaching rates of Na, B, Si, and La of the sample HLLW-16 are 7.23 × 10-3, 1.57 × 10-3, 8.06 × 10-4, and 1.23 × 10-4 g·m-2·d-1, respectively.

3D model of fault and fissures structure of the Kovdor Baddeleyite-Apatite-Magnetite Deposit (NE of the Fennoscandian Shield)

NASA Astrophysics Data System (ADS)

Zhirov, Dmitry; Klimov, Sergey

2015-04-01

The Kovdor baddeleyite-apatite-magnetite deposit (KBAMD) is represented by a large vertical ore body and is located in the southwestern part of the Kovdor ultramafic-alkaline central-type intrusion. The intrusion represents a concentrically zoned complex of rocks with an oval shape in plan, and straight zoning, which complies with the injection and displacement of each of further magma phases from the center towards the periphery. The operation of the deposit in open pits started in 1962, and nowadays, it has produced over 500,000,000 tons of ore. This is one of the largest open pits in the Kola region, which is ca. 2 km long, 1.8 km wide, and over 400 m deep. Regular structural studies has been carried out since late 1970. A unique massif of spatial data has been accumulated so far to include over 25,000 measurements of fissures and faults from the surface, ca. 20,000 measurements of fissures in the oriented drill core (over 18 km) etc. Using this data base the 3D model of fault and fissures structure was designed. The analysis of one has resulted in the identification of a series of laws and features, which are necessary to be taken into account when designing a deep open pit and mining is carried out. These are mainly aspects concerning the origin, kinematics, mechanics and ratio of spatial extension of various fault systems, variation of their parameters at deep horizons, features of a modern stress field in the country rocks, etc. The 3D model has allowed to divide the whole fracture / fissure systems of the massif rocks into 2 large groups: prototectonic system of joints, including cracks of 'liquid magmatic (carbonatite stage) contraction genesis', and newly formed faults due to the superimposed tectonic stages. With regard to the deposit scale, these are characterized as intraformational and transformational, respectively. Each group shows a set (an assemblage) of fault systems with unique features and signs, as well as regular interconnections. The prototectonic assemblage of fissures includes the following main systems: 2-3 subsystems Rd of radial with angle of dip within 65-90° (median at 78°), two subsystems S of a circular subvertical (tangential, crossing Rd) with angle of dip within 60-90° (74°), and two diagonal-conic ones: a centriclinal C dipping towards the center of the intrusion at angles of 25-55° (43°), and a periclinal P dipping from the center of the intrusion at angles of 5-35° (18°). The system of subhorizontal joints L (angle of dip within 0-12°) at deep horizons is insignificantly manifested. All the prototectonic systems are regularly interrelated, and vary asymuthal features according to the law of axial symmetry (when moving around the vertical axis of symmetry passed through the geometric center of the carbonatite intrusion). The superimposed tectonics of post-ore stages forms a few large faults and systems of rupture discontinuities. A few (up to 3) variously oriented displacements are documented in the field on kinematic features (slide furrows, oriented cleavages). They were used for reconstruction of stresses and tectonic evolution. The superimposed tectonic faulting has heterogeneous (local) distribution in the rocks of the deposit, and slight predictability of main parameters. This study was supported by the Russian Scientific Fund (project nos. 14-17-00751).

Growth of epitaxial orthorhombic YO{sub 1.5}-substituted HfO{sub 2} thin film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shimizu, Takao; Katayama, Kiliha; Kiguchi, Takanori

YO{sub 1.5}-substituted HfO{sub 2} thin films with various substitution amounts were grown on (100) YSZ substrates by the pulsed laser deposition method directly from the vapor phase. The epitaxial growth of film with different YO{sub 1.5} amounts was confirmed by the X-ray diffraction method. Wide-area reciprocal lattice mapping measurements were performed to clarify the crystal symmetry of films. The formed phases changed from low-symmetry monoclinic baddeleyite to high-symmetry tetragonal/cubic fluorite phases through an orthorhombic phase as the YO{sub 1.5} amount increased from 0 to 0.15. The additional annular bright-field scanning transmission electron microscopy indicates that the orthorhombic phase has polarmore » structure. This means that the direct growth by vapor is of polar orthorhombic HfO{sub 2}-based film. Moreover, high-temperature X-ray diffraction measurements showed that the film with a YO{sub 1.5} amount of 0.07 with orthorhombic structure at room temperature only exhibited a structural phase transition to tetragonal phase above 450 °C. This temperature is much higher than the reported maximum temperature of 200 °C to obtain ferroelectricity as well as the expected temperature for real device application. The growth of epitaxial orthorhombic HfO{sub 2}-based film helps clarify the nature of ferroelectricity in HfO{sub 2}-based films (186 words/200 words)« less

Pressure effect on the Raman and photoluminescence spectra of Eu3+-doped Na2Ti6O13 nanorods

NASA Astrophysics Data System (ADS)

Zeng, Q. G.; Yang, G. T.; Chen, F.; Luo, J. Y.; Zhang, Z. M.; Leung, C. W.; Ding, Z. J.; Sheng, Y. Q.

2013-12-01

Eu3+-doped Na2Ti6O13 (Na2Ti6O13:Eu) nanorods with diameters of 30 nm and lengths 400 nm were synthesized by hydrothermal and heat treatment methods. Raman spectra at ambient conditions indicated a pure monoclinic phase (space group C2/m) of the nanorods. The relations between structural and optical properties of Na2Ti6O13:Eu nanorods under high pressures were obtained by photoluminescence and Raman spectra. Two structural transition points at 1.39 and 15.48 GPa were observed when the samples were pressurized. The first transition point was attributed to the crystalline structural distortion. The later transition point was the result of pressure-induced amorphization, and the high-density amorphous (HDA) phase formed after 15.48 GPa was structurally related to the monoclinic baddeleyite structured TiO2 (P21/c). However, the site symmetry of the local environment around the Eu3+ ions in Na2Ti6O13 increased with the rising pressure. These above results indicate the occurrence of short-range order for the local asymmetry around the Eu3+ ions and long-range disorder for the crystalline structure of Na2Ti6O13:Eu nanorods by applying pressure. After releasing the pressure from 22.74 GPa, the HDA phase is transformed to low-density amorphous form, which is attributed to be structurally related to the α-PbO2-type TiO2.

Raman Spectroscopy for Mineral Identification and Quantification for in situ Planetary Surface Analysis: A Point Count Method

NASA Technical Reports Server (NTRS)

Haskin, Larry A.; Wang, Alian; Rockow, Kaylynn M.; Jolliff, Bradley L.; Korotev, Randy L.; Viskupic, Karen M.

1997-01-01

Quantification of mineral proportions in rocks and soils by Raman spectroscopy on a planetary surface is best done by taking many narrow-beam spectra from different locations on the rock or soil, with each spectrum yielding peaks from only one or two minerals. The proportion of each mineral in the rock or soil can then be determined from the fraction of the spectra that contain its peaks, in analogy with the standard petrographic technique of point counting. The method can also be used for nondestructive laboratory characterization of rock samples. Although Raman peaks for different minerals seldom overlap each other, it is impractical to obtain proportions of constituent minerals by Raman spectroscopy through analysis of peak intensities in a spectrum obtained by broad-beam sensing of a representative area of the target material. That is because the Raman signal strength produced by a mineral in a rock or soil is not related in a simple way through the Raman scattering cross section of that mineral to its proportion in the rock, and the signal-to-noise ratio of a Raman spectrum is poor when a sample is stimulated by a low-power laser beam of broad diameter. Results obtained by the Raman point-count method are demonstrated for a lunar thin section (14161,7062) and a rock fragment (15273,7039). Major minerals (plagioclase and pyroxene), minor minerals (cristobalite and K-feldspar), and accessory minerals (whitlockite, apatite, and baddeleyite) were easily identified. Identification of the rock types, KREEP basalt or melt rock, from the 100-location spectra was straightforward.

Development of phase analysis methods of impurity elements in alloys based on iron and nickel

NASA Astrophysics Data System (ADS)

Andreeva, N. A.; Anuchkin, S. N.; Volchenkova, V. A.; Kazenas, E. K.; Penkina, T. N.; Fomina, A. A.

2018-04-01

Using the method of AES with ICP, new methods have been developed for quantifying the content of various forms of existence of impurity elements: Al-Al2O3; Zr-ZrO2 in alloys based on iron (Fe-Sn) and nickel (Ni-Sn). Open systems were used to dissolve Al and Zr. To translate difficult-to-open aluminum oxides (corundum) and zirconium oxide (baddeleyite) into the solution, accelerated techniques were developed using the microwave system Mars 5. To confirm the completeness of the dissolution of oxides, a classical scheme of alloy fusion with alkali metal salts was used. Optimal analytical parameters for determining the elements: Al and Zr were chosen. The influence of matrix elements (iron and nickel) and methods of its elimination were studied. This made it possible to determine the elements in a wide concentration range from 1 • 10-3 to n% Al and from 1 • 10-4 to n% Zr without preliminary separation of the matrix with good metrological characteristics. The relative standard deviation (Sr) does not exceed 0,2. The separate determination of the contents of aluminum and aluminium oxide in the model melt of Fe-Sn-Al2O3 and zirconium and zirconium oxide in the Ni-Sn-ZrO2 model melt allowed us to estimate the number of nanoparticles participating in the heterophase interaction with tin and retired to the interface in the form of ensembles and the number of nanoparticles present in the melt and affecting the crystallization process and the structure of the metal.

The Žermanice sill: new insights into the mineralogy, petrology, age, and origin of the teschenite association rocks in the Western Carpathians, Czech Republic

NASA Astrophysics Data System (ADS)

Matýsek, Dalibor; Jirásek, Jakub; Skupien, Petr; Thomson, Stuart N.

2018-04-01

The Žermanice locality represents the best-exposed example of the meta-basaltoid/meta-gabbroic rock type of the teschenite association. It forms a subhorizontal volcanic body (sill) 27-30 m thick. The subvolcanic rock is inhomogeneous and slightly differentiated. The predominant rock type is a basaltoid (diabase-dolerite), medium-grained, speckled, mesocratic rock exhibiting an evident subophitic texture. Miarolitic cavities are abundant in some places. The major rock constituents are albite, microcline, chlorite, and pyroxene, as well as analcime and plagioclase in places. The accessory magmatic phases are biotite, ilmenite, fluorapatite, sulphides, Ti-rich magnetite, Nb-rich baddeleyite, and chevkinite-(Ce) or perrierite-(Ce). A large extent of alteration is evident from the presence of chloritization, albitization of plagioclases, and zeolitization (analcimization). Geochemical analyses reveal an affinity for metaluminous igneous rocks. The best fit is with the within-plate basalts or the within-plate volcanic zones. The classification of this rock is problematic because of the mixed intrusive and extrusive features; the choice is between meta-alkali basalt and metadolerite (meta-microgabbro). 207Pb common lead-corrected U-Pb apatite dating yields a weighted mean age of 120.4 ± 9.6 Ma, which corresponds to the middle Aptian. The igneous body is at most ca. 10 Ma younger than the surrounding late Hauterivian sediments and might have been emplaced into unconsolidated or partly consolidated sediments. According to our research, it is evident that at least some teschenite association rocks are in fact low-grade metamorphic rocks.

Rb-Sr and Sm-Nd isotopic and REE studies of igneous components in the bulk matrix domain of Martian breccia Northwest Africa 7034

NASA Astrophysics Data System (ADS)

Nyquist, Laurence E.; Shih, Chi-Yu; McCubbin, Francis M.; Santos, Alison R.; Shearer, Charles K.; Peng, Zhan X.; Burger, Paul V.; Agee, Carl B.

2016-03-01

The bulk matrix domain of the Martian breccia NWA 7034 was examined petrographically and isotopically to better understand the provenance and age of the source material that make up the breccia. Both 147Sm-143Nd and 146Sm-142Nd age results for mineral separates from the bulk matrix portion of breccia NWA 7034 suggest that various lithological components in the breccia probably formed contemporaneously ~4.44 Ga ago. This old age is in excellent agreement with the upper intersection ages (4.35-4.45 Ga) for U-Pb discordia and also concordia defined by zircon and baddeleyite grains in matrix and igneous-textured clasts. Consequently, we confirm an ancient age for the igneous components that make up the NWA 7034 breccia. Substantial disturbance in the Rb-Sr system was detected, and no age significance could be gleaned from our Rb-Sr data. The disturbance to the Rb-Sr system may be due to a thermal event recorded by bulk-rock K-Ar ages of 1.56 Ga and U-Pb ages of phosphates at about 1.35-1.5 Ga, which suggest partial resetting from an unknown thermal event(s), possibly accompanying breccia formation. The NWA 7034 bulk rock is LREE enriched and similar to KREEP-rich lunar rocks, which indicates that the earliest Martian crust was geochemically enriched. This enrichment supports the idea that the crust is one of the enriched geochemical reservoirs on Mars that have been detected in studies of other Martian meteorites.

An Integrated Geochronological, Petrological, Geochemical and Paleomagnetic Study of Paleoproterozoic and Mesoproterozoic Mafic Dyke Swarms in the Nain Craton, Labrador

NASA Astrophysics Data System (ADS)

Sahin, Tugce

The Nain craton comprises the western, Labrador segment of the larger North Atlantic craton (NAC) which exposes Early through Late Archean gneisses. The NAC is bounded on all sides by Paleoproterozoic collisional orogens that involved either considerable structural reworking (Torngat-Nagssugtoqidian-Lewisian) or the accretion of juvenile arc magmas (Ketilidian-Makkovik). The NAC remains poorly understood compared to other Archean crustal blocks now dispersed globally. Compounding this problem is a lack of reliable paleomagnetic poles for NAC units that predate its assembly into the supercontinent Laurentia by ca. 1800 Ma, which could be used to test neighboring relationships with other cratonic fragments. In order to understand the history of the NAC as part of a possible, larger supercontinent, the record of mafic dyke swarms affecting the craton, particularly those that postdate the Late Archean terrane assembly, were examined in this study. Diabase or gabbroic dyke swarms are invaluable in such studies because their geometries offer possible locus points, they often have a punctuated emplacement and precisely datable crystallization histories, and they have cooling histories and oxide mineralogy amenable to recovering robust paleopoles. Coastal Labrador exposes a number of mafic dykes, some of which are demonstrably Paleoproterozoic (e.g. 2235 Ma Kikkertavak dykes; 2121 Ma Tikkigatsiagak dykes) or Mesoproterozoic (e.g. 1280-1270 Ma Nain and Harp dykes) in age (U-Pb; baddeleyite or zircon). The southern half of the Nain craton (Hopedale block) in particular preserves a rich array of mafic dykes. Dyke cross-cutting relationships are numerous and relatively well exposed, permitting multiple opportunities for paleomagnetic field tests (e.g. baked contact). The results presented here allow understanding of the tectonic evolution of the NAC with implications for strengthened Labrador-Greenland correlations, and testing possible Paleoproterozoic supercontinent reconstructions.

Zirconium and hafnium

USGS Publications Warehouse

Jones, James V.; Piatak, Nadine M.; Bedinger, George M.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Zirconium and hafnium are corrosion-resistant metals that are widely used in the chemical and nuclear industries. Most zirconium is consumed in the form of the main ore mineral zircon (ZrSiO4, or as zirconium oxide or other zirconium chemicals. Zirconium and hafnium are both refractory lithophile elements that have nearly identical charge, ionic radii, and ionic potentials. As a result, their geochemical behavior is generally similar. Both elements are classified as incompatible because they have physical and crystallochemical properties that exclude them from the crystal lattices of most rock-forming minerals. Zircon and another, less common, ore mineral, baddeleyite (ZrO2), form primarily as accessory minerals in igneous rocks. The presence and abundance of these ore minerals in igneous rocks are largely controlled by the element concentrations in the magma source and by the processes of melt generation and evolution. The world’s largest primary deposits of zirconium and hafnium are associated with alkaline igneous rocks, and, in one locality on the Kola Peninsula of Murmanskaya Oblast, Russia, baddeleyite is recovered as a byproduct of apatite and magnetite mining. Otherwise, there are few primary igneous deposits of zirconium- and hafnium-bearing minerals with economic value at present. The main ore deposits worldwide are heavy-mineral sands produced by the weathering and erosion of preexisting rocks and the concentration of zircon and other economically important heavy minerals, such as ilmenite and rutile (for titanium), chromite (for chromium), and monazite (for rare-earth elements) in sedimentary systems, particularly in coastal environments. In coastal deposits, heavy-mineral enrichment occurs where sediment is repeatedly reworked by wind, waves, currents, and tidal processes. The resulting heavy-mineral-sand deposits, called placers or paleoplacers, preferentially form at relatively low latitudes on passive continental margins and supply 100 percent of the world’s zircon. Zircon makes up a relatively small percentage of the economic heavy minerals in most deposits and is produced primarily as a byproduct of heavy-mineral-sand mining for titanium minerals.From 2003 to 2012, world zirconium mineral concentrates production increased by more than 40 percent, and Australia and South Africa were the leading producers. Global consumption of zirconium mineral concentrates generally increased during the same time period, largely as a result of increased demand in developing economies in Asia and the Middle East. Global demand weakened in 2012, causing a decrease in world production of zirconium mineral concentrates and delaying the development of several new mining projects. Global consumption is expected to increase in the future, however, as demand from the ceramics, chemicals, and metals industries increases (driven by renewed growth in developing economies) and demand for zirconium and hafnium metal increases (driven by the construction and operation of new nuclear powerplants).The behaviors of zirconium and hafnium in the environment are very similar to one another in that most zirconium- and hafnium-bearing minerals have limited solubility and reactivity. Anthropogenic sources of zirconium, and likely hafnium, are from industrial zirconium-containing byproducts and emissions from the processing of sponge zirconium, and exposure to the general population from these sources is small. Zirconium and hafnium are likely not essential to human health and generally are considered to be of low toxicity to humans. The main exposure risks are associated with industrial inhalation and dermal exposure. Because of the low solubility of zirconium and hafnium, ecological health concerns in the aquatic environment and in soils are minimal. Heavy-mineral-sand mining may lead to increased erosion rates when the mining is managed improperly. In addition, surface mining requires removal of the overlying organic soil layer and produces waste material that includes tailings and slimes. The soil removal and mining activity disturbs the surrounding ecosystem and alters the character of the landscape. Dry mineral separation processes create high amounts of airborne dust, whereas wet mineral separation processes do not. In operations that restore the landscape to pre-mining conditions, the volume of waste and the impact on the landscape may be relatively temporary.

UHT overprint of HP rocks? A case study from the Adula nappe complex (Central Alps, N Italy)

NASA Astrophysics Data System (ADS)

Tumiati, Simone; Zanchetta, Stefano; Malaspina, Nadia; Poli, Stefano

2014-05-01

The Adula-Cima Lunga nappe complex is located on the eastern flank of the Lepontine Dome and represents the highest of the Lower Penninic units of the Central Alps. The Adula nappe largely consists of orthogneiss and paragneiss of pre-Mesozoic origin, variably retrogressed eclogites preserved as boudins within paragneiss, minor ultramafic bodies and metasedimentary rocks of presumed Mesozoic age. The higher metamorphic conditions have been estimated for the peridotite lenses in the southern part of the nappe at pressure over 3.0 GPa and temperature of 800-850°C. Garnet lherzolite bodies crop out at three localities, from west to east: Cima di Gagnone, Alpe Arami and Mt. Duria. After the partial subduction of the European distal margin beneath the Africa-Adria margin, the HP rocks were overprinted by an upper amphibolite facies metamorphism that postdates the main phase of nappe stacking. In the southern sector of the Lepontine Dome, adjacent to the Insubric Fault, metamorphic conditions promoted extensive migmatization of both metasedimentary and metagranitoid rocks. In one single outcrop, at Monte Duria, garnet lherzolites occur in m-sized boudins hosted within partly granulitized amphibole-bearing and k-feldspar gneisses that contain also some decimeter-sized boudins of both mafic and metapelitic eclogites. This rock association is in turn embedded within the migmatitic gneisses that form most of the southern sector of the Adula nappe. Petrographic and chemical analyses indicate that garnet peridotite is composed of olivine (XMg=0.88), orthopyroxene, clinopyroxene and garnet (Py68; Cr2O3 up to 1.45 wt%) with inclusions of Cr-rich spinel (up to Cr/(Al+Cr)=0.55) surrounded by kelyphitic symplectites of opx + cpx/amph + spl. These reaction produced double coronas, one composed of opx (former ol) and one composed of cpx + opx+ spl. In one kelyphite, we observed the uncommon occurrence of ZrO2 (baddeleyite) and ZrTi2O6 (srilankite). Tiny crystals of these two Zr-bearing phases (˜1 μm) are invariably located in the opx corona after ol. The cpx + opx + spl corona (after grt) contains, instead, zircon. Baddeleyite should have formed through a reaction of the type Mg2SiO4 + ZrSiO4 = MgSiO3 + ZrO2. ZrO2 and ZrTi2O6 display a low amount of solid solution. These compositions are consistent with T below 1200°C, but an improvement of the thermodynamic model is needed in order to better constrain the T of the granulitic overprint on the basis of these Zr-bearing phases. In mafic eclogites, the HP association consists of garnet (Py40Alm37Sp20), omphacite (preserved as inclusion, containing Jd30 and Mg# 0.87), kyanite and minor quartz. Omphacite is almost always replaced by cpx (Jd5) + plag (An55) symplectites. Garnet is surrounded by plag (An33) + opx (En70) symplectites. Kyanite is replaced by plag (An84) + spinel + sapphirine. The spinel-sapphirine Fe-Mg thermometer suggests T of about 850°C due to granulite-facies overprint. We observed sapphirine associated with cpx + opx + plag also in kelyphites after garnet in clinopyroxenites. In eclogitic metapelites, kyanite is replaced by a corundum + anorthite ± spinel assemblage. A corundum-rich layer occurs between eclogites and the host gneiss. Cm-sized emerald green zoisite in this layer is replaced by anorthitic plagioclase ± cpx ± spinel ± calcite. The observed assemblages point to a diffuse granulitization of both the peridotites and the hosting HP rocks of Mt. Duria, suggesting a nearly isothermal decompression from peak-pressure conditions. The surrounding migmatitic gneiss do not display evidence of such granulitic event, having been formed at T<700°C. The mechanism and timing of emplacement of the garnet peridotite and associated HP-HT rocks in the country migmatites, and whether or not the subduction event is related to the Alpine or to an older orogenic cycle are still a matter of debate.

Mineralogy and geochemistry of triassic carbonatites in the Matcha alkaline intrusive complex (Turkestan-Alai Ridge, Kyrgyz Southern Tien Shan), SW Central Asian orogenic belt

NASA Astrophysics Data System (ADS)

Vrublevskii, V. V.; Morova, A. A.; Bukharova, O. V.; Konovalenko, S. I.

2018-03-01

Postorogenic intrusions of essexites and alkaline and nepheline syenites in the Turkestan-Alai segment of the Kyrgyz Southern Tien Shan coexist with dikes and veins of carbonatites dated at ∼220 Ma by the Ar-Ar and Rb-Sr age methods. They are mainly composed of calcite and dolomite (60-85%), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500 °C. Alkaline silicate and salt-carbonate melts are derived from sources with mainly negative bulk εNd(t) ∼ from -11 to 0 and high initial 87Sr/86Sr ratios (∼0.7061-0.7095) which may be due to mixing of PREMA and EM-type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb = 18.38; 207Pb/204Pb = 15.64; 208Pb/204Pb = 38.41) exhibit an EM2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of δ13C (-6.5 to -1.9‰), δ18O (9.2-23‰), δD (-58 to -41‰), and δ34S (12.6-12.8‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the "last echo" of the Tarim mantle plume.

Origin of carbonatites of the Matcha alkaline pluton from Turkestan-Alai ridge, Kyrgyz Southern Tien Shan

NASA Astrophysics Data System (ADS)

Vrublevskii, V. V.

2017-12-01

Postorogenic alkaline intrusions in the Turkestan-Alai segment of the Southern Tien Shan coexist with dikes and veins of carbonatites dated at ˜220 Ma. They are primarily composed of calcite and dolomite (60-85 %), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500°C. Silicate and salt-carbonate melts are derived from sources with mainly negative bulk ɛND(t) ˜ from -11 to 0 and high initial 87Sr/86Sr ratios (˜ 0.7061-0.7095) which may be due to mixing of PREMA and EM-type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb = 18.38; 207Pb/204Pb = 15.64; 208Pb/204Pb = 38.41) exhibit an EM 2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of δ 13C (-6.5 to -1.9 ‰), δ 18O (9.2-23 %„), δD (-58 to -41 %„), and δ 34S (12.6-12.8 ‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the «last echo» of the Tarim mantle plume.

1.1 Ga K-rich alkaline plutonism in the SW Grenville Province

NASA Astrophysics Data System (ADS)

Corriveau, Louise; Heaman, Larry M.; Marcantonio, Franco; van Breemen, Otto

1990-09-01

U-Pb zircon and baddeleyite dating of six syenitic stocks establishes that the ultrapotassic, potassic alkaline and shoshonitic magmatism with island-arc affinities in the Central Metasedimentary Belt (CMB) of the southwestern Grenville Province, Canada took place between 1089 and 1076 Ma, along a 400-km-long, northeast-trending plutonic belt. These ages indicate that ultrapotassic rocks with arc affinities are not unique to the Phanerozoic. West to east emplacement ages along a northern and southern cross-section of this belt range from 1083±2 Ma (Kensington), through 1081±2 Ma (Lac Rouge) to 1076{-1/+3}Ma (Loranger) in the north, and from 1089{-3/+4}Ma (loon Lake) and 1088±2 Ma (Calabogie), to 1076±2 Ma (Westport) in the south. Although closely spaced in time, in detail these ages suggest a slight younging of this magmatic activity to the southeast. Integration of the geochronological data with the spatial extent and potassic character of the plutons shows that the K-rich alkaline suite is distinct from the nepheline-syenite belt of the Bancroft terrane and from the syenite-monzonite suite of the Frontenac terrane of the CMB, and it is considered to be a magmatic episode unique to the Elzevir terrane and its Gatineau segment. The timing and the postmetamorphic emplacement of these plutons indicate that the regional greenschist to granulite-facies metamorphism of the country rock (precise age unknown) is older than 1089 Ma throughout the entire Elzevir terrane. The potassic magmatism is interpreted as the initiation of the 1090 1050 Ma Ottawan Orogeny in the Elzevir terrane; thus, the regional metamorphism in this terrane, previously assigned to the Ottawan Orogeny, is an earlier event. The contemporaneous emplacement of this postmetamorphic plutonic belt with Keweenawan volcanism is at variance with current tectonic models which consider the Keweenawan rift to be formed at the same time as regional metamorphism in the CMB.

The P3 kimberlite and P4 lamproite, Wajrakarur kimberlite field, India: mineralogy, and major and minor element compositions of olivines as records of their phenocrystic vs xenocrystic origin

NASA Astrophysics Data System (ADS)

Shaikh, Azhar M.; Kumar, Satya P.; Patel, Suresh C.; Thakur, Satyajeet S.; Ravi, Subramanian; Behera, Duryadhan

2018-03-01

Distinctly different groundmass mineralogy characterise the hypabyssal facies, Mesoproterozoic diamondiferous P3 and P4 intrusions from the Wajrakarur Kimberlite Field, southern India. P3 is an archetypal kimberlite with macrocrysts of olivine and phlogopite set in a groundmass dominated by phlogopite and monticellite with subordinate amounts of serpentine, spinel, perovskite, apatite, calcite and rare baddeleyite. P4 contains mega- and macrocrysts of olivine set in a groundmass dominated by clinopyroxene and phlogopite with subordinate amounts of serpentine, spinel, perovskite, apatite, and occasional gittinsite, and is mineralogically interpreted as an olivine lamproite. Three distinct populations of olivine, phlogopite and clinopyroxene are recognized based on their microtextural and compositional characteristics. The first population includes glimmerite and phlogopite-clinopyroxene nodules, and Mg-rich olivine macrocrysts (Fo 90-93) which are interpreted to be derived from disaggregated mantle xenoliths. The second population comprises macrocrysts of phlogopite and Fe-rich olivine (Fo 81-89) from P3, megacrysts and macrocrysts of Fe-rich olivine (Fo 85-87) from P4 and a rare olivine-clinopyroxene nodule from P4 which are suggested to have a genetic link with the precursor melt of the respective intrusions. The third population represents clearly magmatic minerals such as euhedral phenocrysts of Fe-rich olivine (Fo 85-90) crystallised at mantle depths, and olivine overgrowth rims formed contemporaneously with groundmass minerals at crustal levels. Close spatial association and contemporaneous emplacement of P3 kimberlite and P4 lamproite is explained by a unifying petrogenetic model which involves the interaction of a silica-poor carbonatite melt with differently metasomatised wall rocks in the lithospheric mantle. It is proposed that the metasomatised wall rock for lamproite contained abundant MARID-type and phlogopite-rich metasomatic veins, while that for kimberlite was relatively refractory in nature.

Evolution of crystalline target rocks and impactites in the chesapeake bay impact structure, ICDP-USGS eyreville B core

USGS Publications Warehouse

Horton, J. Wright; Kunk, Michael J.; Belkin, Harvey E.; Aleinikoff, John N.; Jackson, John C.; Chou, I.-Ming

2009-01-01

The 1766-m-deep Eyreville B core from the late Eocene Chesapeake Bay impact structure includes, in ascending order, a lower basement-derived section of schist and pegmatitic granite with impact breccia dikes, polymict impact breccias, and cataclas tic gneiss blocks overlain by suevites and clast-rich impact melt rocks, sand with an amphibolite block and lithic boulders, and a 275-m-thick granite slab overlain by crater-fill sediments and postimpact strata. Graphite-rich cataclasite marks a detachment fault atop the lower basement-derived section. Overlying impactites consist mainly of basement-derived clasts and impact melt particles, and coastal-plain sediment clasts are underrepresented. Shocked quartz is common, and coesite and reidite are confirmed by Raman spectra. Silicate glasses have textures indicating immiscible melts at quench, and they are partly altered to smectite. Chrome spinel, baddeleyite, and corundum in silicate glass indicate high-temperature crystallization under silica undersaturation. Clast-rich impact melt rocks contain α-cristobalite and monoclinic tridymite. The impactites record an upward transition from slumped ground surge to melt-rich fallback from the ejecta plume. Basement-derived rocks include amphibolite-facies schists, greenschist(?)-facies quartz-feldspar gneiss blocks and subgreenschist-facies shale and siltstone clasts in polymict impact breccias, the amphibolite block, and the granite slab. The granite slab, underlying sand, and amphibolite block represent rock avalanches from inward collapse of unshocked bedrock around the transient crater rim. Gneissic and massive granites in the slab yield U-Pb sensitive high-resolution ion microprobe (SHRIMP) zircon dates of 615 ± 7 Ma and 254 ± 3 Ma, respectively. Postimpact heating was <~350 °C in the lower basement-derived section based on undisturbed 40Ar/39Ar plateau ages of muscovite and <~150 °C in sand above the suevite based on 40Ar/39Ar age spectra of detrital microcline.

Magmatic (silicates/saline/sulfur-rich/CO2) immiscibility and zirconium and rare-earth element enrichment from alkaline magma chamber margins : Evidence from Ponza Island, Pontine Archipelago, Italy

USGS Publications Warehouse

Belkin, H.E.; de Vivo, B.; Lima, A.; Torok, K.

1996-01-01

Fluid inclusions were measured from a feldspathoid-bearing syenite xenolith entrained in trachyte from Ponza, one of the islands of the Pontine Archipelago, located in the Gulf of Gaeta, Italy. The feldspathoid-bearing syenite consists mainly of potassium feldspar, clinopyroxene, amphibole, biotite, titanite, manganoan magnetite, apatite with minor nosean, Na-rich feldspar, pyrrhotite, and rare cheralite. Baddeleyite and zirkelite occur associated with manganoan magnetite. Detailed electron-microprobe analysis reveals enrichments in REE, Y, Nb, U, Th as well as Cl and F in appropriate phases. Fluid inclusions observed in potassium feldspar are either silicate-melt or aqueous inclusions. The aqueous inclusions can be further classified as. (1) one-phase vapor, (2) two-phase (V + L) inclusions, vapor-rich inclusions with a small amount of CO2 in most cases; homogenization of the inclusions always occurred in the vapor phase between 359 and 424??C, salinities vary from 2.9 to 8.5 wt. % NaCl equivalent; and. (3) three-phase and multiphase inclusions (hypersaline/sulfur-rich aqueous inclusions sometimes with up to 8 or more solid phases). Daughter minerals dissolve on heating before vapor/liquid homogenization. Standardless quantitative scanning electron microscope X-ray fluorescence analysis has tentatively identified the following chloride and sulfate daughter crystals; halite, sylvite, glauberite. arcanite, anhydrite, and thenardite. Melting of the daughter crystals occurs between 459 and 536??C (54 to 65 wt. % NaCI equivalent) whereas total homogenization is between 640 and 755??C. The occurrence of silicate-melt inclusions and high-temperature, solute-rich aqueous inclusions suggests that the druse or miarolitic texture of the xenolith is late-stage magmatic. The xenolith from Ponza represents a portion of the peripheral magma chamber wall that has recorded the magmatic/hydrothermal transition and the passage of high solute fluids enriched in chlorides, sulfur, and incompatible elements.

Magmatic-hydrothermal fluid interaction and mineralization in alkali-syenite nodules from the Breccia Museo pyroclastic deposit, Naples, Italy: Chapter 7 in Volcanism in the Campania Plain — Vesuvius, Campi Flegrei and Ignimbrites

USGS Publications Warehouse

Fedele, Luca; Tarzia, Maurizio; Belkin, Harvey E.; De Vivo, Benedetto; Lima, Annamaria; Lowenstern, Jacob

2007-01-01

The Breccia Museo, a pyroclastic flow that crops out in the Campi Flegrei volcanic complex (Naples, Italy), contains alkali-syenite (trachyte) nodules with enrichment in Cl and incompatible elements (e.g., U, Zr, Th, and rare-earth elements). Zircon was dated at ≈52 ka, by U-Th isotope systematics using a SHRIMP. Scanning electron microscope and electron microprobe analysis of the constituent phases have documented the mineralogical and textural evolution of the nodules of feldspar and mafic accumulations on the magma chamber margins. Detailed electron microprobe data are given for alkali and plagioclase feldspar, salite to ferrosalite clinopyroxene, pargasite, ferrogargasite, magnesio-hastingsite hornblende amphibole, biotite mica, Cl-rich scapolite, and a member (probable davyne-type) of the cancrinite group. Detailed whole rock, major and minor element data are also presented for selected nodules. A wide variety of common and uncommon accessory minerals were identified such as zircon, baddeleyite, zirconolite, pollucite, sodalite, titanite, monazite, cheralite, apatite, titanomagnetite and its alteration products, scheelite, ferberite, uraninite/thorianite, uranpyrochlore, thorite, pyrite, chalcopyrite, and galena. Scanning electron microscope analysis of opened fluid inclusions identified halite, sylvite, anhydrite, tungstates, carbonates, silicates, sulfides, and phosphates; most are probably daughter minerals. Microthermometric determinations on secondary fluid inclusions hosted by alkali feldspar define a temperature regime dominated by hypersaline aqueous fluids. Fluid-inclusion temperature data and mineral-pair geothermometers for coexisting feldspars and hornblende and plagioclase were used to construct a pressure-temperature scenario for the development and evolution of the nodules. We have compared the environment of porphyry copper formation and the petrogenetic environment constructed for the studied nodules. The suite of ore minerals observed in the nodules supports a potential for mineralization, which is similar to that observed in the alkaline volcanic systems of southern Italy (Pantelleria, Pontine Archipelago, Mt. Somma-Vesuvius).

Zircon: Free Energy of Formation by Aqueous Solubility Measurements at High T and P

NASA Astrophysics Data System (ADS)

Newton, R. C.; Manning, C. E.; Hanchar, J. M.

2002-12-01

We measured the silica solubility at 800 °C, 12 kbar, of small (~0.5 mg) limpid euhedral zircon crystals grown by a flux-melt method (Hanchar et al., Am. Min., 86, 667, 2001). Incongruent solution occurs according to ZrSiO4 = ZrO2 + SiO2,aq. Zircon lost ~0.1 mg after exposure of 1-2 mg of zircon to ~32 mg H2O in welded Pt envelopes for 90-120 hr in piston-cylinder apparatus using NaCl-graphite furnaces. The average solubility was 0.0645+/-0.007 molal (m), or a mole fraction (XS) of 0.00116. Reversibility was established by rerunning the baddeleyite-coated zircons with a fluid initially slightly SiO2-oversaturated, as determined by the forward experiments, resulting in weight gains of the composite crystals. Similar runs on sintered ZrO2 compacts yielded spontaneous surface nucleation and growth of zircons up to 1 mm. Concentrations were corrected for a small, measured solubility of ZrO2 (0.001 m). Nonideality of aqueous silica was calculated assuming that SiO2,aq consists of a mixture of monomers and dimers (Zotov and Keppler (Chem. Geol., 184, 71, 2002; Newton and Manning, GCA, in press). Our zircon solubility and that of quartz at the same conditions (XS=0.02634, Manning, GCA, 58, 4831, 1994) give activity coefficients at the two concentrations of 0.730 and 0.255, respectively. The activity coefficients and concentrations yield the free energy of formation of zircon from the oxides at 800 °C, 12 kbar of -18.46+/-0.96 kJ/mol, which translates to -11.91+/-0.96 kJ/mol at 800 °C, 1 bar. Our value is compatible with previous estimates based on experiment (Schuiling et al., Am. Min., 61, 166, 1976) and high-T oxide-melt calorimetry (Ellison and Navrotsky, J. Am. Ceram. Soc., 75, 1430, 1992), but is four times more precise than these estimates.

Increasing the Efficiency of Electron Microprobe Measurements of Minor and Trace Elements in Rutile

NASA Astrophysics Data System (ADS)

Neill, O. K.; Mattinson, C. G.; Donovan, J.; Hernández Uribe, D.; Sains, A.

2016-12-01

Minor and trace element contents of rutile, an accessory mineral found in numerous lithologic settings, has many applications for interpreting earth systems. While these applications vary widely, they share a need for precise and accurate elemental measurements. The electron microprobe can be used to measure rutile compositions, although long X-ray counting times are necessary to achieve acceptable precision. Continuum ("background") intensity can be estimated using the iterative Mean Atomic Number (MAN) method of Donovan and Tingle (1996), obviating the need for direct off-peak background measurements, and reducing counting times by half. For this study, several natural and synthetic rutiles were measured by electron microprobe. Data was collected once but reduced twice, using off-peak and an MAN background corrections, allowing direct comparison of the two methods without influence of other variables (counting time, analyte homogeneity, beam current, calibration standards, etc.). These measurements show that, if a "blank" correction (Donovan et al., 2011, 2016) is used, minor and trace elements of interest can be measured in rutile using the MAN background method in half the time of traditional off-peak measurements, without sacrificing accuracy or precision (Figure 1). This method has already been applied to Zr-in-rutile thermometry of ultra-high pressure metamorphic rocks from the North Qaidam terrane in northwest China. Finally, secondary fluorescence of adjacent phases by continuum X-rays can lead to artificially elevated concentrations. For example, when measuring Zr, care should be taken to avoid analytical spots within 100 microns of zircon or baddeleyite crystals. References: 1) J.J. Donovan and T.N Tingle (1996) J. Microscopy, 2(1), 1-7 2) J.J. Donovan, H.A. Lowers, and B.G. Rusk (2011) Am. Mineral., 96, 274­282 3) J.J. Donovan, J.W. Singer and J.T. Armstrong (2016) Am. Mineral., 101, 1839-1853 4) G.L. Lovizotto et al. (2009) Chem. Geol., 261, 346-369

Crystallisation sequence and magma evolution of the De Beers dyke (Kimberley, South Africa)

NASA Astrophysics Data System (ADS)

Soltys, Ashton; Giuliani, Andrea; Phillips, David

2018-06-01

We present petrographic and mineral chemical data for a suite of samples derived from the De Beers dyke, a contemporaneous, composite intrusion bordering the De Beers pipe (Kimberley, South Africa). Petrographic features and mineral compositions indicate the following stages in the evolution of this dyke: (1) production of antecrystic material by kimberlite-related metasomatism in the mantle (i.e., high Cr-Ti phlogopite); (2) entrainment of wall-rock material during ascent through the lithospheric mantle, including antecrysts; (3) early magmatic crystallisation of olivine (internal zones and subsequently rims), Cr-rich spinel, rutile, and magnesian ilmenite, probably on ascent to the surface; and (4) crystallisation of groundmass phases (i.e., olivine rinds, Fe-Ti-rich spinels, perovskite, apatite, monticellite, calcite micro-phenocrysts, kinoshitalite-phlogopite, barite, and baddeleyite) and the mesostasis (calcite, dolomite, and serpentine) on emplacement in the upper crust. Groundmass and mesostasis crystallisation likely forms a continuous sequence with deuteric/hydrothermal modification. The petrographic features, mineralogy, and mineral compositions of different units within the De Beers dyke are indistinguishable from one another, indicating a common petrogenesis. The compositions of antecrysts (i.e., high Cr-Ti phlogopite) and magmatic phases (e.g., olivine rims, magnesian ilmenite, and spinel) overlap those from the root zone intrusions of the main Kimberley pipes (i.e., Wesselton, De Beers, Bultfontein). However, the composition of these magmatic phases is distinct from those in `evolved' intrusions of the Kimberley cluster (e.g., Benfontein, Wesselton water tunnel sills). Although the effects of syn-emplacement flow processes are evident (e.g., alignment of phases parallel to contacts), there is no evidence that the De Beers dyke has undergone significant pre-emplacement crystal fractionation (e.g., olivine, spinel, ilmenite). This study demonstrates the requirement for detailed petrographic and mineral chemical studies to assess whether individual intrusions are in fact `evolved'; and that dykes are not necessarily produced by differentiated magmas.

Paleomagnetism of the Red Lake greenstone belt, northwestern Ontario: Possible evidence for the timing of gold mineralization

NASA Astrophysics Data System (ADS)

Constanzo-Alvarez, Vincenzo; Dunlop, David J.

1993-10-01

We report paleomagnetic results from (1) largely unaltered batholiths and (2) sheared and altered units in the Archean Red Lake greenstone belt, a major gold-producing region in the Uchi subprovince of northwestern Ontario. Group 1 includes the Hammell Lake, Killala Baird, Trout Lake and Little Vermilion Lake batholiths, which were intruded between 2730 and 2700 Ma ago (U/Pb, zircon). Group 2 includes the Howey diorite, the Dome Stock, and dikes and andesites from the Dickenson mine. These units, from the mineralized deformation zones (DZs) between the batholiths, were sheared and hydrothermally altered in the same event that caused gold mineralization in supracrustal units. The batholiths carry a stable reversed remanence (RLR), with D = 159 deg, I = -74 deg (k = 20, alpha(sub 95) = 16 deg, N = 4 units, 14 sites). RLR has high coercivities, unblocking temperatures and remanence intensities an appears to be a primary thermal remanence dating from approximately 2700 ma. The altered units from the gold-bearing Dzs carrying a different remanence (RLG), with D = 180 deg, I = -57 deg (k = 23, alpha (sub 95) = 3 deg, N = 3 units, 6 sites). RLG also has relatively high coercivities and unblocking temperatures but its magnetization intensities are 1-2 orders of magnitude lower than those of RLR. Opaque minerals and silicates observed in thin section are highly altered. RLG is therfore believed to be a chemical or thermochemical remanence acquired approximately 2580 Ma ago during the late stages of cooling and gold mineralization. Seeing as RLG characterizes the shear zone rocks but is absent from unaltered rocks outside the DZs, it could be used as a rapid prospecting tool in delineating areas of alteration and posible mineralization. The palepoles for RLR (approximately 2700 Ma) and RLG (approximately 2580 Ma) link with those of the Shelley Lake granite (2580 Ma, Ar-40/Ar-39, hornblende and biotite) and the Matachewan/Hearst dikes (2450 Ma, U/Pb, zircon and baddeleyite). The sense of motion on the late Archean-early Proterozoic apparent polar wander path for Laurentia, as defined by this sequence of pale poles, is opposite to that previously accepted.

Multiphase inclusions in plagioclase from anorthosites in the Stillwater Complex, Montana: implications for the origin of the anorthosites

USGS Publications Warehouse

Loferski, P.J.; Arculus, R.J.

1993-01-01

Multiphase inclusions, consisting of clinopyroxene+ilmenite+apatite, occur within cumulus plagioclase grains from anorthosites in the Stillwater Complex, Montana, and in other rocks from the Middle Banded series of the intrusion. The textures and constant modal mineralogy of the inclusions indicate that they were incorporated in the plagioclase as liquid droplets that later crystallized rather than as solid aggregates. Their unusual assemblage, including a distinctive manganiferous ilmenite and the presence of baddeleyite (ZrO2), indicates formation from an unusual liquid. A process involving silicater liquid immiscibility is proposed, whereby small globules of a liquid enriched in Mg, Fe, Ca, Ti, P, REE, Zr and Mn exsolved from the main liquid that gave rise to the anorthosites, became trapped in the plagioclase, and later crystallized to form the inclusions. The immiscibility could have occurred locally within compositional boundaries around crystallizing plagioclase grains or it could have occurred pervasively throughout the liquid. It is proposed that the two immiscible liquids were analogous, n terms of their melt structures, to immiscible liquid pairs reported in the literature both in experiments and in natural basalts. For the previously reported pairs, immiscibility is between a highly polymerized liquid, typically granitic in composition, and a depolymerized liquid, typically ferrobasaltic in composition. In the case of the anorthosites, the depolymerized liquid is represented by the inclusions, and the other liquid was a highly polymerized aluminosilicate melt with a high normative plagioclase content from which the bulk of the anorthosites crystallized. Crystallization of the anorthosites from this highly polymerized liquid accounts for various distinctive textural and chemical features of the anorthosites compared to other rocks in the Stillwater Complex. A lack of correlation between P contents and chondrite-normalized rare earth element (REE) ratios of plagioclase separates indicates that the amount of apatite in the inclusions is too low to affect the REE signature of the plagioclase separates. Nevertheless, workers should use caution when attempting REE modelling studies of cumulates having low REE contents, because apatite-bearing inclusions can potentially cause problems. ?? 1993 Springer-Verlag.

Coordinated U-Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

NASA Astrophysics Data System (ADS)

Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

2017-04-01

We present the results of a coordinated SIMS U-Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ∼4.33 Ga, however they differ in that only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ⩽300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb-206Pb ages of 4.33 Ga. These grains are our best constraints on impact ages within our sample population, and suggest at least one large impact is contemporaneous with the most common time of magmatic zircon formation on the Moon's crust visited by the Apollo missions.

40Ar/39Ar geochronology of terrestrial pyroxene

NASA Astrophysics Data System (ADS)

Ware, Bryant; Jourdan, Fred

2018-06-01

Geochronological techniques such as U/Pb in zircon and baddeleyite and 40Ar/39Ar on a vast range of minerals, including sanidine, plagioclase, and biotite, provide means to date an array of different geologic processes. Many of these minerals, however, are not always present in a given rock, or can be altered by secondary processes (e.g. plagioclase in mafic rocks) limiting our ability to derive an isotopic age. Pyroxene is a primary rock forming mineral for both mafic and ultramafic rocks and is resistant to alteration process but attempts to date this phase with 40Ar/39Ar has been met with little success so far. In this study, we analyzed pyroxene crystals from two different Large Igneous Provinces using a multi-collector noble gas mass spectrometer (ARGUS VI) since those machines have been shown to significantly improve analytical precision compared to the previous single-collector instruments. We obtain geologically meaningful and relatively precise 40Ar/39Ar plateau ages ranging from 184.6 ± 3.9 to 182.4 ± 0.8 Ma (2σ uncertainties of ±1.8-0.4%) and 506.3 ± 3.4 Ma for Tasmanian and Kalkarindji dolerites, respectively. Those data are indistinguishable from new and/or published U-Pb and 40Ar/39Ar plagioclase ages showing that 40Ar/39Ar dating of pyroxene is a suitable geochronological tool. Scrutinizing the analytical results of the pyroxene analyses as well as comparing them to the analytical result from plagioclase of the same samples indicate pure pyroxene was dated. Numerical models of argon diffusion in plagioclase and pyroxene support these observations. However, we found that the viability of 40Ar/39Ar dating approach of pyroxene can be affected by irradiation-induced recoil redistribution between thin pyroxene exsolution lamellae and the main pyroxene crystal, hence requiring careful petrographic observations before analysis. Finally, diffusion modeling show that 40Ar/39Ar of pyroxene can be used as a powerful tool to date the formation age of mafic rocks affected by greenschist metamorphism and will likely play an important role in high temperature thermochronology.

Geodynamic Setting of Proterozoic Dyke Swarms of the Leo-Man Craton, West Africa, Based on New U-Pb Dating and Geochemistry

NASA Astrophysics Data System (ADS)

Baratoux, L.; Jessell, M.; Söderlund, U.; Ernst, R. E.; Benoit, M.; Naba, S.; Cournede, C.; Perrouty, S.; Metelka, V.; Yatte, D.; Diallo, D. P.; Ndiaye, P. M.; Dioh, E.; Baratoux, D.

2016-12-01

Over 20 sets of dolerite dykes crosscutting Paleoproterozoic basement in West Africa were distinguished via the interpretation of regional and high-resolution airborne magnetic data available over the West African Craton. Some of the dykes reach over 300 km in length and are considered parts of much larger systems of mafic dyke swarms which form the plumbing system of Large Igneous Provinces (LIPs). Five different dyke swarms in Burkina Faso, Niger, Ghana and Senegal were investigated. In terms of petrography and composition, the mafic dykes correspond to tholeiitic basalts and are typically composed of plagioclase + clinopyroxene ± orthopyroxene ± olivine. They display a doleritic texture of variable grain size. Eleven ID-TIMS U-Pb ages obtained on baddeleyite define five generations of Proterozoic age. The N10 Libiri dyke swarm, found in western Niger, yielded an age of ca. 1790 Ma. The N40 Bassari swarm in Senegal was dated at ca. 1764 Ma, and is potentially linked to the 1790 Ma Libiri swarm, 1400 km away. The 300 by 400 km Korsimoro N100 dyke swarm transects central Burkina Faso and was dated at ca. 1575 Ma. Five ca. 1520 Ma ages were obtained for dykes of the Essakane swarm, three in Burkina Faso, one from Ghana (N130 orientation) and one from Senegal (E-W orientation), and document a large extent (600 km wide and 1500 km long) and short duration of dyke emplacement. The Manso N350 dyke swarm in southern Ghana, which is about 400 km long and about 200 km wide, yields a preliminary age of ca 870 Ma. A mantle plume origin is suggested for these swarms, especially the 1790-1765 Ma Libiri-Bassari swarm and the 1520 Ma Essakane swarms (which have lithosphere-contaminated E-MORB chemistry), whose scale is similar to largest giant radiating swarms (e.g. CAMP and Mackenzie). The 870 Ma Manso swarm has composition closer to OIB, consistent with a plume/hotspot origin. The 1575 Ma Korsimoro swarm has composition between EMORB and NMORB, which suggests a rift setting.

Paraná flood basalt volcanism primarily limited to 1 Myr beginning at 135 Ma: New 40Ar/39Ar ages for rocks from Rio Grande do Sul, and critical evaluation of published radiometric data

NASA Astrophysics Data System (ADS)

Baksi, Ajoy K.

2018-04-01

40Ar/39Ar step heating analyses were carried out on seven rocks (five basalts, an andesite and a rhyolite) from the southern Paraná Province ( 28°S-30°S); they yield plateau/isochron ages of 135-134 Ma, in good agreement with published step heating data on rocks from the same area. Critical review of laser spot isochron ages for rocks from the Province, ranging from 140 to 130 Ma, are shown to be unreliable estimates of crystallization ages, as the rocks were substantially altered; step heating results on three of these rocks thought to yield good plateau ages, are shown to be incorrect, as a result of a technicality in dating procedures followed. U-Pb ages on zircon and baddeleyite separated from a variety of rock types ( 30°S-23°S) fall in the range 135 to 134 Ma. All reliable 40Ar/39Ar and U-Pb ages indicate volcanism was sharply focused, initiated at 135 Ma, and 1 Myr in duration; no variation of age with either latitude or longitude is noted, Scrutiny of published 40Ar/39Ar ages on the Florianopolis dykes shows they cannot be used as reliable crystallization ages. U-Pb work shows that this dyke swarm was formed coevally with the main part of the Parana province. Most of the published 40Ar/39Ar ages on the Ponta Grossa dyke swarm are unreliable; a few ages appear reliable and suggest the magmatic event in this area, may have postdated the main Paraná pulse by 1-2 Myr. A single 40Ar/39Ar age from a high-Nb basalt in the southernmost part ( 34°S) of the Paraná at 135 Ma, highlights the need for further radiometric work on other areas of this flood basalt province. The Paraná Province postdates the time of the Jurassic-Cretaceous bound­ary by 10 Myr.

Silurian extension in the Upper Connecticut Valley, United States and the origin of middle Paleozoic basins in the Québec embayment

USGS Publications Warehouse

Rankin, D.W.; Coish, R.A.; Tucker, R.D.; Peng, Z.X.; Wilson, S.A.; Rouff, A.A.

2007-01-01

Pre-Silurian strata of the Bronson Hill arch (BHA) in the Upper Connecticut Valley, NH-VT are host to the latest Ludlow Comerford Intrusive Suite consisting, east to west, of a mafic dike swarm with sheeted dikes, and an intrusive complex. The rocks are mostly mafic but with compositions ranging from gabbro to leucocratic tonalite. The suite is truncated on the west by the Monroe fault, a late Acadian thrust that carries rocks of the BHA westward over Silurian-Devonian strata of the Connecticut Valley-Gaspe?? trough (CVGT). Dikes intrude folded strata with a pre-intrusion metamorphic fabric (Taconian?) but they experienced Acadian deformation. Twenty fractions of zircon and baddeleyite from three sample sites of gabbrodiorite spanning nearly 40 km yield a weighted 207Pb/206Pb age of 419 ?? 1 Ma. Greenschist-facies dikes, sampled over a strike distance of 35 km, were tholeiitic basalts formed by partial melting of asthenospheric mantle, with little or no influence from mantle or crustal lithosphere. The dike chemistry is similar to mid-ocean ridge, within-plate, and back-arc basin basalts. Parent magmas originated in the asthenosphere and were erupted through severely thinned lithosphere adjacent to the CVGT. Extensive middle Paleozoic basins in the internides of the Appalachian orogen are restricted to the Que??bec embayment of the Laurentian rifted margin, and include the CVGT and the Central Maine trough (CMT), separated from the BHA by a Silurian tectonic hinge. The NE-trending Comerford intrusions parallel the CVGT, CMT, and the tectonic hinge, and indicate NW-SE extension. During post-Taconian convergence, the irregular margins of composite Laurentia and Avalon permitted continued collision in Newfoundland (St. Lawrence promontory) and coeval extension in the Que??bec embayment. Extension may be related to hinge retreat of the northwest directed Brunswick subduction complex and rise of the asthenosphere following slab break-off. An alternative hypothesis is that the basins originated as pull-apart basins between northwest-trending, left-stepping, sinistral strike-slip faults along the southern flanks of the New York and St. Lawrence promontories.

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

USGS Publications Warehouse

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.

Mantle reservoirs (EM-1, OIB, E-MORB and N-MORB), long duration and polystages history for PGE-bearing paleoproterozoic layered intrusions in the N-E part of Fennoscandian Shield.

NASA Astrophysics Data System (ADS)

Bayanova, Tamara; Nerovich, Ludmila; Serov, Pavel; Kunakkuzin, Evgeniy; Elizarov, Dmitriy

2015-04-01

Paleoproterozoic layered PGE -bearing intrusions located in the N-E part of the Fennoscandian Shield and have a total are about 2000 km2. Long multidisciplinary studies using isotope Nd-Sr, U-Pb and 3He/4He systematics permit create a big bank of geochemistry data for different part of the intrusions: barren and main Cu-Ni-Cr-Ti-V and PGE phases, dykes complexes and host rocks. Based on U-Pb isotope data (on baddeleyite and zircon) and Sm-Nd mineral isochrones (on rock-forming and sulphides minerals) there is distinguished long magmatic duration from 2.53 to 2.40 Ga. Using precise U-Pb and Sm-Nd data for different part of the intrusions there are established four main impulses: 2.53, 2.50, 2.45, and 2.40 Ga of magmatic (LIP) activities for gabbronorite, anothosite et.set. rocks. The primary reservoir for all precious and multimetal massifs are considered as enriched mantle EM-1 using ɛNd- ISr system with negative ɛNd values and low ISr data for whole rocks of the intrusions. Dyke complexes are presented as three groups: high Ti-ferrodolerites, low Ti and low Fe-gabbronorites. Complex isotope (U-Pb, Sm-Nd) and geochemistry (REE, ɛNd, ISr) data investigations reflect OIB, E-MORB and N-MORB reservoirs for its origin (Nerovich et all., 2014). Isotope 3He/4He and 3He concentrations for accessory minerals ( ilmenite, magnetite et. set ) from the layered paleoproterozoic intrusions reflect significant lower mantle component and upper mantle contribution. According to the model of binary mixing (Jahn et all, 2000) there were calculated mantle and core component into plume magmatic reservoir connected with the origin of the PGE paleoproterozoic intrusions. The mantle contributions lie in the interval from 85 to 93% and core component are very less. All investigations are devoted to memory of academician RAS, professor F.Mitrofanov (Russia), he was a leader of scientific school for geology, geochemistry and metallogenesis of ore deposits. The studies are contribution by RFBR OFI-M 13-05-12055, 13-05-00493, Department of Earth Sciences RAS (programs 2 and 4) and IGCP-SIDA 599.

Bald Friar Metabasalt and Kennett Square Amphibolite: Two Iapetan Ocean Floor Basalts

USGS Publications Warehouse

Smith, R.C.

2006-01-01

The Bald Friar Metabasalt (BFM) and Kennett Square Amphibolite (KSA) are basaltic units found in the Piedmont of southeastern Pennsylvania. The BFM is also recognized in northern Maryland. Both are believed to represent fragments of the floor of the Iapetus Ocean, but are not known occur in direct association with one another. The BFM typically occurs as small fragments having typical stratigraphic thicknesses of 2.5 m, and composed of greenish, fine-grained chlorite-epidote-actinolite-albite metabasalt in ophiolite me??lange. One bed of pillow basalt has been found at the type locality, Bald Friar, Cecil County, Maryland. Even though outcrops of BFM are highly discontinuous, they have a remarkable chemical uniformity over a strike length of 143 km and appear to be equivalent to the Caldwell Group 1b metabasalt of the Thetford, Quebec, area. The BFM is typically associated with ultramafic fragments and may be affiliated with the Baltimore Mafic Complex (BMC), from which a baddeleyite date of 442 +/- 7 Ma (Silurian) has been obtained. The BFM is probably a back arc basin basalt (BABB). Pod and schlieren chromite compositions suggest an island arc environment for the BMC itself. The poorly defined, informal "Conowingo Creek metabasalt" of Lancaster County, Pennsylvania, occurs on the north margin of the BMC and appears to be a fore arc boninite. The BFM and associated ultramafic fragments serve as a field-mappable marker for the structural equivalent of the Baie Verte-Brompton line in southeastern Pennsylvania and northern Maryland. Steatization of the associated ultramafic fragments has produced zones of extremely low competence that facilitated and localized thrusts of presumed Silurian age and later Alleghanian folding. The KSA typically occurs as much larger bodies having lengths of 3 km and composed of dark, medium-grained hornblende-plagioclase-clinopyroxene gneiss. No ultramafic rocks or me??lange have been recognized with the KSA. In Pennsylvania, the KSA appears to be restricted to a single belt on the south side of the Brandywine massifs. The KSA is transitional from N-OFB (Normal-Ocean Floor Basalt, which can be generated in a variety of oceanic spreading center environments) on the east to P=E-OFB (Plume=Enriched Ocean Floor Basalt, also generated in spreading centers) on the west, suggesting an evolving tectonomagmatic environment. It may be affiliated with the Wilmington Complex.

Coordinated U–Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

Here, we present the results of a coordinated SIMS U–Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ~4.33 Ga, however they differ in thatmore » only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ≤300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb– 206Pb ages of 4.33 Ga. These grains are our best constraints on impact ages within our sample population, and suggest at least one large impact is contemporaneous with the most common time of magmatic zircon formation on the Moon’s crust visited by the Apollo missions.« less

Shoshonites and Associated Calc-Alkaline Rocks from the Eastern Sayan, Central Asian Orogenic Belt: Geochemistry and Tectonic Setting

NASA Astrophysics Data System (ADS)

Vernikovskaya, A. E.; Romanov, M. I.; Kadilnikov, P. I.; Matushkin, N. Y.; Romanova, I.

2017-12-01

The Central Asian Orogenic Belt (CAOB) is one of the largest accretionary orogens in the world, which formation started in the Neoproterozoic giving rise to numerous assemblages of island arcs, ophiolites, continental fragments and sedimentary basins. The Eastern Sayan, located at the southwestern margin of the Siberian craton, is the key area in understanding the initiation of orogenic processes in the CAOB. Widely distributed mafic igneous rocks (dolerites, gabbro etc.) in the Eastern Sayan were previously considered as part of the Nersa igneous complex of the Neoproterozoic age, whereas tectonic setting of these rocks remained highly debatable. New geochemical and mineralogical data from igneous mafic rocks within the Eastern Sayan show presence of rocks with shoshonitic and high- and low-K calc-alkaline affinities and allowed us to refine the tectonic context of their formation in the southwestern margin of the Siberian craton.All studied intrusive and volcanic rocks in the Eastern Sayan showing OIB-like geochemical signatures. The high-K rocks contain orthoclase, olivine, diopside, augite, anorthite, various amphiboles, including edenite, cataphorite, Mg-cataphorite, anthophyllite-gedrite, Mg-Fe hornblende, biotites of the siderophyllite-eastonite-annite series, as well as zircon, baddeleyite, apatite, magnetite, ilmenite and Cr-spinel. The high-K rock type is characterised by high K2O contents (up to 9.2 wt. %), K2O/Na2O ratios over 90, lowered TiO2 and MgO and moderate FeO contents and negative P and Sr anomalies. In contrast, low-K rocks, characterised by moderate and increased TiO2 and MgO contents, contain augite, pigeonite, olivine, andesine and accessory minerals, such as rutile, titanite, ilmenite and apatite. Both rock types vary considerably in Nb and Ta concentrations, from OIB-like to E-MORB. Such geochemical signatures of calc-alkaline and shoshonitic igneous rocks are indicative of an active continental margin setting. Presence of the active continental margin setting in the southwestern margin of the Siberian craton during the late Neoproterozoic-early Cambrian time is in agreement with the U-Pb age of 511 Ma of high-K dolerites (Gladkochub et al., 2006) and the development of the coeval island arc assemblages in the northern part of the CAOB.

The 1.33-1.30 Ga Yanliao large igneous province in the North China Craton: Implications for reconstruction of the Nuna (Columbia) supercontinent, and specifically with the North Australian Craton

NASA Astrophysics Data System (ADS)

Zhang, Shuan-Hong; Zhao, Yue; Li, Xian-Hua; Ernst, Richard E.; Yang, Zhen-Yu

2017-05-01

The Yanliao rift zone in the northern North China Craton (NCC) is the location of the standard section for late Paleoproterozoic-Mesoproterozoic stratigraphy in China and is associated with the emplacement of large volumes of diabase sills. Detailed field investigations show that the sills are distributed over a region that is >600 km long and >200 km wide, with areal extent > 1.2 ×105 km2 and cumulative thickness of the sills in any one area ranging from 50 m to >1800 m. High-resolution secondary ion mass spectrometry (SIMS) baddeleyite dating shows that emplacement of these sills occurred between about 1330 and 1305 Ma with a peak age of 1323 Ma. Emplacement of these diabase sills was accompanied by pre-magmatic uplift that started at about 1.35-1.34 Ga as indicated by the disconformity between the Changlongshan and Xiamaling formations and absence of sedimentation after the Xiamaling Formation in some areas. All the diabase sills exhibit similar geochemical features of tholeiitic compositions with intraplate characteristics. Given a relatively short duration of emplacement at 1.33-1.30 Ga, along with the large areal extent and volume, as well as intraplate character, this magmatic province constitutes a large igneous province (LIP). This Yanliao LIP and the accompanying pre-magmatic uplift were related either to a mantle plume and/or continental rifting during breakup of the NCC from the Nuna (Columbia) supercontinent. Paleomagnetic, ash bed and LIP data and other geological constraints suggest that the NCC had a close connection with Siberia, Laurentia, Baltica, North Australia and India crustal blocks. In particular, the most direct age match between the 1.33-1.30 Ga Yanliao LIP and the 1.33-1.30 Ga Derim Derim-Galiwinku LIP of the North Australian Craton (NAC), as well as the similarities between the late Paleoproterozoic-Mesoproterozoic stratigraphic units of the Yanliao rift in the NCC with the southeastern McArthur Basin in the NAC, indicate that the Yanliao and Derim Derim-Galiwinku events are fragmented parts of the same LIP, supporting the paleomagnetically plausible idea that the NCC and NAC were connected (or at least near neighbors) during the early Mesoproterozoic period.

A new grand mean palaeomagnetic pole for the 1.11 Ga Umkondo large igneous province with implications for palaeogeography and the geomagnetic field

NASA Astrophysics Data System (ADS)

Swanson-Hysell, N. L.; Kilian, T. M.; Hanson, R. E.

2015-12-01

We present a new grand mean palaeomagnetic pole (Plong: 222.1°, Plat: -64.0°, A95: 2.6°, N = 49) for the ca. 1110 Ma Umkondo large igneous province (LIP) of the Kalahari Craton. New palaeomagnetic data from 24 sills in Botswana and compiled reprocessed existing data are used to develop a palaeomagnetic pole as the Fisher mean of cooling unit virtual geomagnetic poles (VGPs). The mean and its associated uncertainty provide the best-constrained pole yet developed for the province. Comparing data from individual cooling units allows for evaluation of palaeosecular variation at this time in the Mesoproterozoic. The elongation of the population of VGPs is consistent with that predicted by the TK03.GAD model lending support to the dipolar nature of the field in the late Mesoproterozoic. In our new compilation, 4 of 59 (˜7 per cent) of the igneous units have northerly declinations while the rest are south-directed indicating that a geomagnetic reversal occurred during magmatic activity. Interpreting which of these polarities corresponds with a normal or reversed geomagnetic field relative to other continents can constrain the relative orientations between cratons with time-equivalent data. This interpretation is particularly important in comparison to Laurentia as it bears on Kalahari's involvement and position in the supercontinent Rodinia. The dominance of south-directed declinations within the Umkondo Province was previously used to suggest that these directions are the same polarity as reversed directions from the early magmatic stage of the Keweenawan Midcontinent Rift of Laurentia. Two Umkondo sills with northerly declinations have U-Pb baddeleyite ages of ca. 1109 Ma that are temporally close to dated Midcontinent Rift units having reversed directions. Based on this comparison, and palaeomagnetic data from younger units in the Kalahari Craton, we favour the option in which the sites with northerly declinations from the Umkondo Province correspond to the reversed polarity directions from the early magmatic stage in the Midcontinent Rift. This interpretation allows for the Namaqua-Natal metamorphic belt of Kalahari to be a conjugate to the Grenville margin of North America and for Kalahari to have become conjoined with Laurentia within the supercontinent Rodinia subsequent to Umkondo LIP magmatic activity.

Coordinated U–Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

DOE PAGES

Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

2016-12-28

Here, we present the results of a coordinated SIMS U–Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ~4.33 Ga, however they differ in thatmore » only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ≤300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb– 206Pb ages of 4.33 Ga. These grains are our best constraints on impact ages within our sample population, and suggest at least one large impact is contemporaneous with the most common time of magmatic zircon formation on the Moon’s crust visited by the Apollo missions.« less

Tiny twists in time; exploring angular resolution of in situ EBSD orientation microstructures in solar system zircon

NASA Astrophysics Data System (ADS)

Moser, D. E.

2012-12-01

Kikuchi discovered electron diffraction in samples of calcite in the 1920's, and orientation of lattice planes by Electron Backscatter Diffraction (EBSD) is now routinely measured by automated camera systems at a spatial resolution of tens of nanometers using Field Emission Gun SEM. The current methodology is proving particularly powerful when measuring lattice orientation microstructure in U-Pb geochronology minerals such as zircon and baddeleyite that have experienced high temperature deformation or shock metamorphism. These are among the oldest preserved mineral phases in inner solar system materials, and we have been applying EBSD to rare samples of the Early Earth and grains from extraterrestrial environments such as the Moon and Mars. In these cases the EBSD orientation data are useful for identifying high diffusivity pathways that may have afforded isotopic and trace element disturbance, microstructural proxies for shock metamorphic pressures, as well as resolving glide plane systems in ductile zircon and shear twin mechanisms. Blanket estimates of angular resolution for automated EBSD misorientation measurements are often in the range of 0.5 degrees. In some cases strain giving rise to only a few degrees of lattice misorientation has facilitated 100% Pb-loss. In some cases, however, there is a spatial correlation between trace element or cathodoluminescence zoning in zircon and what appears to be low magnitudes misorientation close to the limits of resolution. Given the proven value of performing EBSD analysis on geochronology minerals, a more thorough exploration of the precision and accuracy of EBSD lattice misorientation measurements is warranted. In this talk the relative weighting of the factors that limit EBSD angular resolution will be investigated, focusing on U-Pb dating minerals such as zircon. These factors include; sample surface preparation, phase symmetry, pseudo-symmetry effects, degree of crystallinity, Kikuchi band contrast and indexing, solid solution effects on unit cell, dimension camera calibration and camera-sample distance, beam conditions and focussing, and general microscope operating conditions (e.g. high vacuum vs. variable pressure). An assessment of potential zircon EBSD reference materials and sample preparation protocols will be presented, along with case studies of zircon orientation microstructures from meteorites and terrestrial craters representative of different strain and thermal environments in the inner solar system.BSD lattice misorientation maps of a) crystal-plastically deformed and partly recrystallized zircon, after Rayner et al. (in prep.), and b) shock-metamorphosed lunar zircon (Darling et al., in prep.).

Extreme isotopologue disequilibrium in molecular SIMS species during SHRIMP geochronology

NASA Astrophysics Data System (ADS)

Magee, Charles W., Jr.; Danišík, Martin; Mernagh, Terry

2017-12-01

The current limitation in the accuracy and precision of inter-element analysis in secondary ion mass spectrometry (SIMS) is the ability to find measurable quantities that allow relative differences in ionization and transmission efficiency of secondary ions to be normalized. In uranium-thorium-lead geochronology, the ability to make these corrections, or "calibrate" the data, results in an accuracy limit of approximately 1 %. This study looks at the ionization of uranium and thorium oxide species, which are traditionally used in U-Pb calibration, to explore the conditions under which isotopologues, or molecular species whose composition differs only in the isotopic composition of one or more atoms in the molecule, remain in or deviate from equilibrium. Isotopologue deficits of up to 0.2 (200 ‰) below ideal mixing are observed in UO2+ species during SIMS gechronological analyses using the SHRIMP IIe SIMS instrument. These are identified by bombarding natural U-bearing minerals with an 18O2- primary beam. The large anomalies are associated with repeat analyses down a single SIMS sputtering crater (Compston et al., 1984), analysis of high-uranium, radiation-damaged zircon, and analysis of baddeleyite. Analysis of zircon under routine conditions yield UO2+ isotopologue anomalies generally within a few percent of equilibrium. The conditions under which the isotopologue anomalies are observed are also conditions in which the UOx-based corrections, or calibration, for relative U vs. Pb ionization efficiencies fail. The existence of these isotopologue anomalies suggest that failure of the various UOx species to equilibrate with each other is the reason that none of them will successfully correct the U  / Pb ratio. No simple isotopologue-based correction is apparent. However, isotopologue disequilibrium appears to be a more sensitive tool for detecting high-U calibration breakdowns than Raman spectroscopy, which showed sharper peaks for ˜ 37 Ma high-uranium zircons than for reference zircons OG1 and Temora. U-Th-Sm / He ages were determined for aliquots of reference zircons OG1 (755±71 Ma) and Temora (323±43 Ma), suggesting that the broader Raman lines for the Temora reference zircons may be due to something other than accumulated radiation damage. Isotopologue abundances for UO+ and ThO+ and their energy spectra are consistent with most or all molecular species being the product of atomic recombination when the primary beam impact energy is greater than 5.7 keV. This, in addition to the large UO2+ instrumentally generated isotopologue disequilibria, suggests that any attempts to use SIMS to detect naturally occurring isotopologue deviations could be tricky.

CONCH: A Visual Basic program for interactive processing of ion-microprobe analytical data

NASA Astrophysics Data System (ADS)

Nelson, David R.

2006-11-01

A Visual Basic program for flexible, interactive processing of ion-microprobe data acquired for quantitative trace element, 26Al- 26Mg, 53Mn- 53Cr, 60Fe- 60Ni and U-Th-Pb geochronology applications is described. Default but editable run-tables enable software identification of secondary ion species analyzed and for characterization of the standard used. Counts obtained for each species may be displayed in plots against analysis time and edited interactively. Count outliers can be automatically identified via a set of editable count-rejection criteria and displayed for assessment. Standard analyses are distinguished from Unknowns by matching of the analysis label with a string specified in the Set-up dialog, and processed separately. A generalized routine writes background-corrected count rates, ratios and uncertainties, plus weighted means and uncertainties for Standards and Unknowns, to a spreadsheet that may be saved as a text-delimited file. Specialized routines process trace-element concentration, 26Al- 26Mg, 53Mn- 53Cr, 60Fe- 60Ni, and Th-U disequilibrium analysis types, and U-Th-Pb isotopic data obtained for zircon, titanite, perovskite, monazite, xenotime and baddeleyite. Correction to measured Pb-isotopic, Pb/U and Pb/Th ratios for the presence of common Pb may be made using measured 204Pb counts, or the 207Pb or 208Pb counts following subtraction from these of the radiogenic component. Common-Pb corrections may be made automatically, using a (user-specified) common-Pb isotopic composition appropriate for that on the sample surface, or for that incorporated within the mineral at the time of its crystallization, depending on whether the 204Pb count rate determined for the Unknown is substantially higher than the average 204Pb count rate for all session standards. Pb/U inter-element fractionation corrections are determined using an interactive log e-log e plot of common-Pb corrected 206Pb/ 238U ratios against any nominated fractionation-sensitive species pair (commonly 238U 16O +/ 238U +) for session standards. Also displayed with this plot are calculated Pb/U and Pb/Th calibration line regression slopes, y-intercepts, calibration uncertainties, standard 204Pb- and 208Pb-corrected 207Pb/ 206Pb dates and other parameters useful for assessment of the calibration-line data. Calibrated data for Unknowns may be automatically grouped according to calculated date and displayed in color on interactive Wetherill Concordia, Tera-Wasserburg Concordia, Linearized Gaussian ("Probability Paper") and Gaussian-summation probability density diagrams.

Structural environments of incompatible elements in silicate glass/melt systems: I. Zirconium at trace levels

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Ponader, Carl W.; Brown, Gordon E., Jr.

1991-06-01

The structural environments of trace levels (2˜000 ppm) of Zr 4+ in several silicate glasses were examined as a function of melt composition and polymerization using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Glass compositions investigated were albite (NaAlSi 3O 8: AB) and a peralkaline composition (Na 3.3AlSi 7O 17: PR)- Zirconium was added to the oxide-carbonate mix prior to melting in the form of ZrO 2 (baddeleyite). A second set of Zr-silicate glasses containing 2000 ppm Zr and 1.0 to 2.4 wt% halogens (F as NaF and Cl as NaCl) was also synthesized. These included the Zr-AB and Zr-PR base-glass compositions as well as Zr-sodium trisilicate composition (Na2Si 3O 7: TS). In all glasses studied, Zr is mainly 6-coordinated by oxygen atoms ( d[Zr-O] ˜2.07 ± 0.01 Å). In the most polymerized glass (AB), a small but significant amount of Zr was also found to occur in 8-coordinated sites ( d[Zr-O] ˜2.22 Å). No clear evidence for F or Cl complexes of Zr was observed in any of the halogen-containing glasses. The regularity of the Zr site increases in the series AB < TS ˜PR. We attribute this change to an increase in the number of non-bridging oxygens in the first-coordination sphere of Zr related to the depolymerizing effects of halogens and/or sodium. Minor but significant interactions of Zr with the tetrahedral network were observed ( d[Zr-{Si, Al}] ˜3.65-3.71 Å ± 0.03 Å), which are consistent with Zr-O-{Si, Al} angles close to 160-170°, as in catapleiite (Na 2ZrSi 3O 9 · 2H 2O). Intermediaterange order, as reflected by the presence and number of second-neighbor {Si, Al} around Zr, increases significantly with increasing melt polymerization. The local environment around Zr is more strongly influenced by bonding requirements than by the network topology of the melt. Stabilization of zirconium in 6-coordinated sites in relatively depolymerized melts should act to decrease the crystal-melt partition coefficients of Zr and may explain the normally incompatible character of Zr during magmatic differentiation. The presence of Zr in sites of higher coordination (ZrO 8) in highly polymerized melts could be a precursor to the crystallization of zircon from such melts and thus may explain why Zr becomes a more compatible element, especially in the latest stages of magmatic differentiation.

Variation in 142Nd/144Nd of Archean rocks from southwest Greenland : Implications for early Earth mantle dynamics

NASA Astrophysics Data System (ADS)

Rizo, H.; Boyet, M.; Blichert-Toft, J.; Rosing, M.; Paquette, J. L.

2012-04-01

The short-lived 146Sm-142Nd chronometer (half-life = 103 Ma) has proven successful in bringing constraints on the dynamics of the early Earth mantle. Since the parent isotope, 146Sm, was extant only during the first 300 Ma of the history of the Solar System, the positive 142Nd anomalies measured in southwest Greenland Archean rocks imply that their incompatible element-depleted mantle source formed during the Hadean. Interestingly, the magnitude of these anomalies seems to decrease over time. 3.7-3.8 Ga old rocks from the Amitsoq Complex have revealed +10 to +20 ppm 142Nd anomalies [1, 2, 3, 4, 5, 6, 7], whereas younger 3.0 Ga old samples from the Ivisaartoq greenstone belt yield smaller positive anomalies, ranging from +5.5 to +8.5 ppm [8]. Thus, the chemical heterogeneities detected in the southwest Greenland mantle were formed during the first 150 Ma of Earth's history, and seem to have resisted re-mixing by mantle convection until 3.0 Ga. In this study, we investigate the evolution of the southwest Greenland mantle during the time period of 3.3-3.4 Ga. The samples analyzed come from both the ~3.3 Ga amphibolite unit and the ~3.4 Ga Ameralik basic dyke swarm from the Amitsoq Complex. Coupled Sm-Nd and Lu-Hf bulk-rock ages obtained for seven amphibolites are in good agreement (3351 ± 210 Ma and 3302 ± 260 Ma, respectively) and consistent with the minimum age found by Nutman and Friend (2009) [9] for this formation. We further obtained coherent bulk-rock 147Sm-143Nd and zircon+baddeleyite 207Pb/206Pb ages for the Ameralik dykes (3428 ± 250 Ma and 3421 ± 34 Ma, respectively), in line with ages suggested by Nielsen at al., (2002) [10] and Nutman et al., (2004) [11]. We are currently in the process of analyzing these samples for 142Nd isotopic compositions and the results will be compared with the existing southwest Greenland data in order to shed new light on the evolution and destruction of heterogeneities in the early Earth mantle. [1] Rizo et al., (2011) Earth Planet. Sci. Lett. [2] Bennett et al., (2007b) Science. [3] Boyet et al., (2003) Earth Planet. Sci. Lett. [4] Boyet and Carlson (2006) Earth Planet. Sci. Lett. [5] Caro et al., (2003) Nature. [6] Caro et al., (2006) Geochim. Cosmochim. Acta. [7] Harper and Jacobsen (1992) Nature. [8] Bennett et al., (2010) Goldschmidt 2010. [9] Nutman and Friend (2009) Precamb. Res. [10] Nielsen et al., (2002) Precamb. Res. [11] Nutman et al., (2004) J. Geol. Soc. Lond.

Sulfide minerals as new Sm-Nd geochronometers for ore genesis dating of mafic-ultramafic layered intrusions

NASA Astrophysics Data System (ADS)

Serov, Pavel; Ekimova, Nadezhda; Bayanova, Tamara

2014-05-01

The main method of dating the ore process was the Re-Os method of sulfides (Luck, Allegre, 1983; Walker et. al., 1991). However, studies of Re-Os systematics of sulfide minerals do not always give the correct ages and showing the disturbances of the Re-Os systematics. At the same time, Sm-Nd age of sulfides in good agreement with the U-Pb dating on zircon and baddeleyite and suggests that the Sm-Nd system of sulfides is more resistant to secondary alteration processes. Our studies have shown that along with rock-forming, ore minerals (sulfides) can be used to determine the ore genesis time of industrially important geological sites, since exactly with the sulfides the industry Pt-Pd mineralization is closely connected. The Sm-Nd investigations steadily employ new minerals-geochronometers. Of these, sulfides of PGE-bearing layered intrusions are quite important in terms of dating the process of ore origin. Studying the REE distribution in the sulfides of MOR hydrothermal sources has shown possible REE presence in the sulfide lattice (Rimskaya-Korsakova et. al., 2003). These are difficult to carry out because the concentrations of Sm and Nd isotopes in sulfides are much lower than chondrites (Rimskaya-Korsakova et. al., 2003). For the first time in Russia with sulfide and rock-forming minerals and WR in Sm-Nd method have been dated impregnated and brecciform ores of the following objects: Pilguyarvi Cu-Ni deposits, Pechenga (1965±87 Ma); impregnated (2433±83 Ma) and redeposited (1903±24 Ma) ores of Ahmavaara intrusion (Finland); ore gabbronorites of Penikat PGE-bearing layered intrusion (2426±38 Ma (Ekimova et.al., 2011); Pt-Pd gabbro-pegmatite ores (2476± 41 Ma, which agrees with the U-Pb zircon age - 2470±9 Ma (Bayanova, 2004) and gabbronorites (2483±86 Ma) of PGE Kievei deposit and Fedorova Tundra metagabbroids (2494±54 Ma); Monchetundra gabbronorites - 2489±49 Ma. In (Kong et. al., 2000) sulfides from two metamorphosed chondrites studied by instrumental neutron activation analysis (INAA) and ion probe. As shown, the level of REE in the sulfide phase determined by the ion probe is quite similar to that obtained by INAA. Although the concentrations of REE in the enstatite and the Fe, Si, Cr-rich inclusions are comparable to those in sulfide, estimates based on mass balance calculations show that the silicate inclusions would not noticeably contribute to the REE budget in sulfides (Kong et. al., 2000). These studies were supported by the RFBR 13-05-00493, OFI-M 13-05-12055, State Earth Division Program #4 and IGCP-599.

Compositional variations of zirconolite from the Evate apatite deposit (Mozambique) as an indicator of magmatic-hydrothermal conditions during post-orogenic collapse of Gondwana

NASA Astrophysics Data System (ADS)

Hurai, Vratislav; Huraiová, Monika; Gajdošová, Michaela; Konečný, Patrik; Slobodník, Marek; Siegfried, Pete R.

2018-06-01

Zirconolite is documented from the Evate apatite-magnetite-carbonate deposit in the circular Monapo Klippe (eastern Mozambique)—a relic of Neoproterozoic nappe thrusted over the Mesoproterozoic basement of the Nampula block. Zirconolite enriched in rare earth elements—REE = Y + Lu+ΣLa-Yb (up to 24.11 wt% REE2O3, 0.596 apfu REE) creates thin rims around spinel and magnetite grains, whereas zirconolite enriched in U and Th (up to 18.88 wt% ThO2 + UO2, 0.293 apfu Th + U) replace the Late Ediacaran ( 590 Ma) zircon and baddeleyite along contacts with pyrrhotite and magnetite. Both types of zirconolite contain locally increased Nb and Ta concentrations (up to 7.58 wt% Nb2O5 + Ta2O5, 0.202 apfu Nb + Ta). Typical substitutions in zirconolite from Evate involve REE + U,Th → Ca, and M 2++ M 5+→Ti + M 3+ ( M 2+ = Fe2++Mg, M 3+ = Fe3+, M 5+ = Nb5++Ta5+). In addition, REE-zirconolite is typical of the REE + M 2+ → Ca + M 3+ substitution ( M 2+ = Mg, M 3+ = Fe3++Al3+). Hence, Fe3+ predominates over Fe2+ in all types of zirconolite, thus enabling the high REE content in Nb-poor zirconolites to be stored in locally dominant REEZrTiFe3+O7 component known so far only as a synthetic analogue of natural zirconolite. Other types of zirconolite from Evate are dominated by the common CaZrTi2O7 end member, but the aforementioned "synthetic" REEZrTiFe3+O7 accompanied by another `synthetic' (U,Th)ZrFe3 + 2O7 component are also abundant. The U,Pb,Th concentrations in U,Th-zirconolites plot discordantly to theoretical isochrons, thus indicating 440 ppm of non-radiogenic excess lead in earlier Nb-rich zirconolite contrasting with secondary Pb loss from later Nb-poor zirconolite. The non-radiogenic Pb-corrected age of the early zirconolite corresponded to 485 ± 9 Ma, within uncertainty limit identical with the 493 ± 10 Ma age of the associated uranothorianite. The variegated chemical composition of zirconolites reflects the complex history of the Evate deposit. Compositional and substitution trends of the REE-zirconolite overlaps that genetically linked with carbonatites, syenites and mafic igneous rocks, whereas the U,Th-zirconolite is reminiscent of hydrothermal-metasomatic deposits. The predominance of trivalent iron in zirconolite most likely reflects strongly oxidizing parental fluids that percolated during episodic Late Ordovician to Late Cambrian rifting of Gondwana.

Dating sub-20 micron zircons in granulite-facies mafic dikes from SW Montana: a new approach using automated mineralogy and SIMS U-Pb geochronology

NASA Astrophysics Data System (ADS)

Ault, A. K.; Mahan, K. H.; Flowers, R. M.; Chamberlain, K.; Appleby, S. K.; Schmitt, A. K.

2010-12-01

Geochronological data is fundamental to all tectonic studies, but a major limitation for many lithologies is a paucity of sizeable zircons suitable for conventional U-Pb techniques. In particular, mafic dike swarms provide important time markers for tectonometamorphic activity in Precambrian terranes, but commonly yield little or no zircon or baddeleyite sufficient for TIMS or standard ion-probe analysis of crystal separates. We apply a new approach involving in-situ automated mineralogy and high spatial resolution Secondary Ion Mass Spectrometry (SIMS) geochronology to a mafic dike swarm exposed in the Northern Madison Range of SW Montana. The dikes cross-cut early fabrics but are also variably deformed and metamorphosed to P-T conditions as high as 1.2 GPa and 850 C. The swarm emplacement age is inferred to be ca. 2.1 Ga based on similarities to dated dikes in the adjacent Tobacco Root Mountains. Resolving the timing of dike emplacement and high-grade metamorphism in the study area is important for understanding the extent of post-Archean modification to the northwest margin of the Wyoming craton. Identification and textural characterization of zircons were facilitated by in-situ automated mineralogical analysis, in contrast to a standard elemental X-ray mapping approach. Our technique uses an SEM-based platform coupling calibrated BSE data with X-ray data collected by multiple energy dispersive spectrometers to rapidly identify target accessory phases at high spatial resolution. Whole thin section search maps were generated in ~30 minutes at 4 µm pixel resolution. Our dike thin sections commonly contained >300 zircons in a variety of textural settings, with 80% having a short dimension <10 µm. Zircons were dated in-situ by adjusting the field aperture of the CAMECA ims1270 to preferentially collect secondary ions emitted from within the inner few microns of the ~15 µm diameter analysis pit. This allows us to analyze zircon grains with a minimum dimension as small as 8 μm at radiogenic yields typically >95% for 206Pb. SIMS data for 22 zircons from a granulite-facies mafic dike thin section define a chord with upper and lower intercepts of 1753.1 ± 9.5 Ma and 63.2 ± 7.9 Ma, respectively (2 sigma error, MSWD = 1.6). A positive correlation between U concentration and degree of discordance indicates that the more radiation-damaged zircons underwent greater Pb loss. We infer Pb loss to reflect re-heating linked to emplacement of the nearby Tobacco Roots Batholith (ca. 74-71 Ma). Metamorphic zircon growth ca. 1750 Ma indicates that the high-grade metamorphic core of the Big Sky orogeny extends into the Northern Madison Range, farther inboard into the Wyoming craton than previously recognized. Coupling automated mineralogy searching with refined SIMS methods enables acquisition and interpretation of in-situ U-Pb data from zircons of a size that would not be feasible with most other techniques.

Paleomagnetism and geochronology of an Early Proterozoic quartz diorite in the southern Wind River Range, Wyoming, USA

USGS Publications Warehouse

Harlan, S.S.; Geisman, J.W.; Premo, W.R.

2003-01-01

We present geochronologic and paleomagnetic data from a north-trending quartz diorite intrusion that cuts Archean metasedimentary and metaigneous rocks of the South Pass Greenstone Belt of the Wyoming craton. The quartz diorite was previously thought to be either Archean or Early Proterozoic (?) in age and is cut by north and northeast-trending Proterozoic diabase dikes of uncertain age, for which we also report paleomagnetic data. New U-Pb analyses of baddeleyite and zircon from the quartz diorite yield a concordia upper intercept age of 2170 ?? 8 Ma (95% confidence). An 40Ar/39Ar amphibole date from the same sample yields a similar apparent age of about 2124 ?? 30 Ma (2??), thus confirming that the intrusion is Early Proterozoic in age and that it has probably not been thermally disturbed since emplacement. A magmatic event at ca. 2.17 Ga has not previously been documented in the Wyoming craton. The quartz diorite and one of the crosscutting diabase dikes yield essentially identical, well-defined characteristic remanent magnetizations. Results from eight sites in the quartz diorite yield an in situ mean direction of north declination and moderate to steep positive inclination (Dec.=355??, Inc.=65??, k=145, ??95=5??) with a paleomagnetic pole at 84??N, 215??E (??m=6??, ??p=7??). Data from other diabase dike sites are inconsistent with the quartz diorite results, but the importance of these results is uncertain because the age of the dikes is not well known. Interpretation of the quartz diorite remanent magnetization is problematic. The in situ direction is similar to expected directions for magnetizations of Late Cretaceous/early Tertiary age. However, there is no compelling evidence to suggest that these rocks were remagnetized during the late Mesozoic or Cenozoic. Assuming this magnetization to be primary, then the in situ paleomagnetic pole is strongly discordant with poles of 2167, 2214, and 2217 Ma from the Canadian Shield, and is consistent with proposed separation of the Wyoming Craton and Laurentia prior to about 1.8 Ga. Correcting the quartz diorite pole for the possible effects of Laramide-age tilting of the Wind River Range, based on the attitude of nearby overlying Cambrian Flathead Sandstone (dip=20??, N20??E), gives a tilt corrected pole of 75??N, 58??E (??m=4??, ??p=6??), which is also discordant with respect to time-equivalent poles from the Superior Province. Reconstruction of the Superior and Wyoming Province using a rotation similar to that proposed by Roscoe and Card [Can. J. Earth Sci. 46(1993)2475] is problematic, but reconstruction of the Superior and Wyoming Provinces based on restoring them to their correct paleolatitude and orientation using a closest approach fit indicates that the two cratons could have been adjacent at about 2.17 Ga prior to rifting at about 2.15 Ga. The paleomagnetic data presented are consistent with the hypothesis that the Huronian and Snowy Pass Supergroups could have evolved as part of a single epicratonic sedimentary basin during the Early Proterozoic. ?? 2002 Elsevier Science B.V. All rights reserved.

Zirconium and hafnium in the southeastern Atlantic States

USGS Publications Warehouse

Mertie, J.B.

1958-01-01

The principal source of zirconium and hafnium is zircon, though a minor source is baddeleyite, mined only in Brazil. Zircon is an accessory mineral in igneous, metamorphic, and sedimentary rocks, but rarely occurs in hardrock in minable quantities. The principal sources of zircon are therefore alluvial deposits, which are mined in many countries of five continents. The principal commercial deposits in the United States are in Florida, though others exist elsewhere in the southeastern Coastal Plain. The evidence indicates that conditions for the accumulation of workable deposits of heavy minerals were more favorable during the interglacial stages of the Pleistocene epoch than during Recent time. Therefore detrital ores of large volume and high tenor are more likely to be found in the terrace deposits than along the present beaches. Other concentrations of heavy minerals, however, are possible at favored sites close to the Fall Line where the Tuscaloosa formation rests upon the crystalline rocks of the Piedmont province. A score of heavy and semiheavy minerals occur in the detrital deposits of Florida, but the principal salable minerals are ilmenite, leucoxene, rutile, and zircon, though monazite and staurolite are saved at some mining plants. Commercial deposits of heavy minerals are generally required to have a tenor of 4 percent, though ores with a lower tenor can be mined at a profit if the content of monazite is notably high. The percentages of zircon in the concentrates ranges from 10 to 16 percent, and in eastern Florida from 13 to 15 percent. Thus the tenor in zircon of the ore-bearing sands ranges from 0.4 to 0.6 percent. The content of hafnium in zircon is immaterial for many uses, but for some purposes very high or very low tenors in hafnium are required. Alluvial zircon cannot be separated into such varieties, which, if needed, must be obtained from sources in bedrock. It thus becomes necessary to determine the Hf : Zr ratios in zircon from many kinds of bedrock.Granitic rocks are the principal sources of zircon, though not the best sources of zircon with a high tenor in hafnium. A general study by the Geological Survey of the granitic rocks of the Southeastern Atlantic States has been in progress for 10 years, and hundreds of samples of granitic accessory minerals have been acquired. Thirty samples of zircon from these collections were selected for spectrographic and X-ray determinations of their tenors in hafnium. Nine other samples of alluvial zircon were included, of which three are from Florida and six from foreign countries. No domestic zircon was discovered with very high or very low tenors in hafnium.The volume of zircon in the southeastern Coastal Plain is enormous, but most of it is not recoverable. The minable reserves of heavy minerals, however, are very large, and from these it is estimated conservatively that 10 million short tons of zircon can be obtained. The corresponding amounts of zirconium and hafnium, using the mean Hf:Zr ratio of the deposits in Florida, are 4,868,000 and 112,000 tons, respectively. These reserves could be delivered, if needed, at the rate of 100,000 tons a year.

Ore genesis dating: implication of Sm-Nd method using sulfide minerals for mafic-ultramafic layered intrusions of Fennoscandian Shield

NASA Astrophysics Data System (ADS)

Serov, Pavel; Bayanova, Tamara; Steshenko, Ekaterina; Ekimova, Nadezhda

2015-04-01

The main method of dating the ore process was the Re-Os method of sulfides (Luck, Allegre, 1983; Walker et. al., 1991). However, studies of Re-Os systematics of sulfide minerals do not always give the correct ages and showing the disturbances of the Re-Os systematics. At the same time, Sm-Nd age of sulfides in good agreement with the U-Pb dating on zircon and baddeleyite and suggests that the Sm-Nd system of sulfides is more resistant to secondary alteration processes. Our studies have shown that along with rock-forming, ore minerals (sulfides) can be used to determine the ore genesis time of industrially important geological sites, since exactly with the sulfides the industry Pt-Pd mineralization is closely connected. In to Sm-Nd measurements steadily introduce new minerals-geochronometers (i.e. titanite, burbancite, eudialite etc.). Of these, sulfides of PGE-bearing layered intrusions are quite important in terms of dating the process of ore origin. Studying the REE distribution in the sulfides of MOR hydrothermal sources has shown possible REE presence in the sulfide lattice (Rimskaya-Korsakova et. al., 2003). These are difficult to carry out because the concentrations of Sm and Nd isotopes in sulfides are much lower than those in chondrites (Rimskaya-Korsakova et. al., 2003). In (Kong et. al., 2000) sulfides from two metamorphosed chondrites were studied by instrumental neutron activation analysis (INAA) and ion probe. As shown, the level of REE in the sulfide phase determined by the ion probe is quite similar to that obtained by INAA. Although the concentrations of REE in the enstatite and the Fe, Si, Cr-rich inclusions are comparable to those in sulfide, estimates based on mass balance calculations show that the silicate inclusions would not noticeably contribute to the REE budget in sulfides (Kong et. al., 2000). For the first time in Russian geochemistry laboratories using sulfide and rock-forming minerals and WR in Sm-Nd method have been dated impregnated and brecciform ores of the following objects - Pilguyarvi Cu-Ni deposits, Pechenga (1965±87 Ma); impregnated (2433±83 Ma) and redeposited (1903±24 Ma) ores of Ahmavaara intrusion (Finland); Kolvitsa massif metagabbro (1990±92 Ma, which reflect the age of Sm-Nd system closure in sulfide minerals); olivine orthopyroxenites of Sopcha 'Ore bed' (2442±59 Ma); ore gabbronorites of Penikat PGE-bearing layered intrusion (2426±38 Ma (Ekimova et.al., 2011); Pt-Pd gabbro-pegmatite ores (2476± 41 Ma, which agrees well with the U-Pb zircon age - 2470±9 Ma (Bayanova, 2004) and gabbronorites (2483±86 Ma) of PGE Kievey deposit and Fedorova Tundra metagabbroids (2494±54 Ma); Monchetundra gabbronorites - 2489±49 Ma. All investigations are devoted to memory of academician RAS, professor F. Mitrofanov (Russia), he was a leader of scientific school for geology, geochemistry and metallogenesis of ore deposits. The studies were supported by the RFBR 13-05-00493, OFI-M 13-05-12055, Department of Earth Sciences RAS (programs 2 and 4), IGCP-599.

Evaluating crustal contributions to enriched shergottites from the petrology, trace elements, and Rb-Sr and Sm-Nd isotope systematics of Northwest Africa 856

NASA Astrophysics Data System (ADS)

Ferdous, J.; Brandon, A. D.; Peslier, A. H.; Pirotte, Z.

2017-08-01

The origin of the incompatible trace element (ITE) characteristics of enriched shergottites has been critical for examining two contradicting scenarios to explain how these Martian meteorites form. The first scenario is that it reflects ITE enrichment in an early-formed mantle reservoir whereas the second scenario attributes it to assimilation of ancient Martian crust (∼4-4.5 Ga) by ITE-depleted magmas. Strongly differentiated shergottite magmas may yield added constraints for determining which scenario can best explain this signature in enriched shergottites. The meteorite Northwest Africa (NWA) 856 is a basaltic shergottite that, unlike many enriched shergottites, lacks olivine and has undergone extensive differentiation from more primitive parent magma. In similarity to other basaltic shergottites, NWA 856 is comprised primarily of compositionally zoned clinopyroxenes (45% pigeonite and 23% augite), maskelynite (23%) and accessory minerals such as ulvöspinel, merrillite, Cl-apatite, ilmenite, pyrrhotite, baddeleyite and silica polymorph. The CI-chondrite normalized rare earth element (REE) abundance patterns for its maskelynite, phosphates, and its whole rock are flat with corresponding light-REE depletions in clinopyroxenes. The 87Rb-87Sr and 147Sm-143Nd internal isochron ages are 162 ± 14 (all errors are ±2σ) Ma and 162.7 ± 5.5 Ma, respectively, with an initial εNdI = -6.6 ± 0.2. The Rb-Sr isotope systematics are affected by terrestrial alteration resulting in larger scatter and a less precise internal isochron age. The whole rock composition is used in MELTS simulations to model equilibrium and fractional crystallization sequences to compare with the crystallization sequence from textural observations and to the mineral compositions. These models constrain the depth of initial crystallization to a pressure range of 0.4-0.5 GPa (equivalent to 34-42 km) in anhydrous conditions at the Fayalite-Magnetite-Quartz buffer, and consistently reproduce the observed mineralogy throughout the sequence with progressive crystallization. The Ti/Al ratios in the clinopyroxenes are consistent with initial crystallization occurring at these depths followed by polybaric crystallization as the parent magma ascended to the surface. The REE abundances in the clinopyroxenes and maskelynite are consistent with progressive crystallization in a closed system. The new results for NWA 856 are combined with other shergottite data and are compared to mixing and assimilation and fractional crystallization (AFC) models using depleted shergottite magmas and ancient Martian crust as end-members. The models indicate that the range of REE abundances and ratios, when taken in isolation, can be successfully explained for all shergottites by crustal contamination. However, no successful crustal contamination model can explain the restricted εNdI of -6.8 ± 0.2 over the wide range of Mg# (0.65-0.25), and corresponding trace element variations from enriched shergottites to depleted shergottites. The findings indicate that the origin of the long-term ITE-enriched signature in enriched shergottites and the geochemical variability seen in shergottites is not a result of crustal contamination but instead reflects ancient mantle heterogeneity.

Indications for a CO2-rich fluid cap in the uppermost part of the Laacher See Magma Chamber

NASA Astrophysics Data System (ADS)

Aßbichler, Donjá; Heuss-Aßbichler, Soraya; Kunzmann, Thomas

2017-04-01

Sanidinites are rare holocrystalline to hypocrystalline magmatic cumulates and are found as volcanic ejecta of potassic explosive volcanoes. They all have trachytic to phonolitic whole rock composition. Main constituent of these rocks is sanidine forming a framework of interlocking crystals creating miarolithic cavities. In this study we were investigating sodalite bearing sanidinites from the tephra deposits of the Laacher See Volcano, Eifel, Germany with the aim to decipher the processes in the uppermost, rigid part of the magma chamber. Macroscopically three different types can be distinguished: (1) dark haüyne-sanidinites, (2) bright haüyne-sanidinites and (3) nosean-sanidinites. Both types of haüyne-sanidinites contain glass, rich in vesicles, forming a film around most of the mineral grains or sometimes filling up the miarolithic cavities. Minor mineral phases are haüyne occurring within these cavities, mainly adjacent to plagioclase as well as clinopyroxene and biotite. Accessories are apatite, magnetite and titanite. In nosean-sanidinites glass is absent or occurs occasionally as a minor phase. Major crystals within the miarolithic cavities are nosean and calcite, while clinopyroxene and biotite are rarely observed. A special feature is the formation of HFSE minerals as euhedral crystals, including zircon, baddeleyite, pyrochlore and REE-apatites. The difference in mineral assemblage is also reflected in the whole rock composition of the investigated samples. Nosean-sanidinites are compared to haüyne-sanidinites (i) enriched in Na, Ca, Mn, S, Cl, Zr, U, Th, Hf, Zn and REE (+LOI) and (ii) depleted in K, Mg, Si, Ti, P, Ba, Sr and V. From dark haüyne-sanidinite over bright haüyne-sanidinite to nosean-sanidinites the mineral composition of the major phases shows following systematic trends: Ca content of sanidine decreases indicating decreasing temperature during crystallization. The minerals of the sodalite group show an increase of Na and CO2 whereas the content of Ca and SO4 decreases. Clinopyroxene observed in the haüyne-sanidinite has diospidic to hedenbergitic composition while in the nosean-sanidinites it is enriched in Mn (ferroan johannsenite with up to 0.55 apfu Mn; 15.5 wt.-% MnO). Several features indicate the presence of an aggressive fluid phase during formation of the nosean-sanidinites: all silicates expose etching structures such as jagged or rounded mineral surfaces, and/or holes and channels within the mineral grains. To a lesser extent these structures are also observed in the silicates of the bright haüyne-sanidinites. In nosean-sanidinites the etching holes are often filled by calcite. Occasionally these fillings are bounded by a calcite filled fluid vain. All these observations indicate the presence of a CO2-rich fluid phase. The sanidinites are suggested to be formed at late magmatic conditions from a phonolitic melt. The systematics in the textures indicates, that the minerals within the miarolithic cavities of the haüyne-sanidinites crystallized from an evolved, volatile rich phonolitic melt. In contrast the crystallization within the miarolithic pore space of the nosean-sanidinites took place in the rigid zone of the uppermost part of the magma chamber where the mineral forming processes are induced by CO2-rich fluid.

Emeishan volcanism and the end-Guadalupian extinction: New U-Pb TIMS ages

NASA Astrophysics Data System (ADS)

Mundil, Roland; Denyszyn, Steve; He, Bin; Metcalfe, Ian; Yigang, Xu

2010-05-01

High-resolution geochronology with an age resolution at the permil level is instrumental in testing proposed causal links between continental-scale, short-term volcanic events and environmental crises that affect life globally. Synchroneity with large-scale volcanic events has been shown for three of the five most severe extinctions, namely the end-Permian extinction coinciding with Siberian Trapp volcanism, the end-Triassic extinction with Central Atlantic Magmatic Province) volcanism and the end-Cretaceous with Deccan Trapp volcanism. Recent studies also show that the magnitude of the extinction is not solely a function of the size (volume) of the volcanic event but more importantly of the eruption rate and also the nature of the host rock that is intruded, and the resulting reactions and release of gases that can affect climate. The end-Guadalupian (end Middle Permian, ca 260 Ma) biotic crisis has traditionally not been included in the 'big five' mass extinctions, possibly because of its close proximity in time to the end-Permian event, although its magnitude (in terms of total extinction rate) is comparable to the three most severe extinctions (end-Ordovician, end-Permian, end-Cretaceous). As a result, research of the end-Guadalupian event has so far been neglected and its timing as well as the temporal relation to the Emeishan volcanic province in western China is as yet not fully studied. Geochronological data are so far mostly based on ambiguous 40Ar/39Ar analyses of commonly altered basaltic products and U-Pb zircon analyses on felsic products using micro-beam techniques that typically result in radio-isotopic ages with percent-level uncertainty, and thus insufficient for high-resolution correlations of events. In addition, no precise and accurate radio-isotopic data exist from this time period so that evolutionary events (extinction and recovery) on land and in the ocean are notoriously difficult to correlate though biostratigraphic records are available from numerous sedimentary archives. A further complication arises from the severe tectonic (and resulting thermal) overprint, due to the closure of the Tethys and the collision of the Indian plate with Asia, of most of the area where Emeishan volcanic products are exposed. Also, currently existing paleo-environmental data are scarce and insufficient for testing this hypothesis with confidence, because studies using stable isotopes as proxies are restricted to short profiles from only a few sites. Therefore, fundamental questions remain unanswered. We present new data U-Pb IDTIMS ages with permil-level resolution that constrain the timing of Emeishan volcanism and the timing of biotic events recorded in sediments. In detail, U-Pb results are from felsic intercalations within late stage Emeishan products and biostratigaphically calibrated marine sedimentary sections in southwestern and central China as well as thick tuffs within terrestrial sections from the Bowen Basin in eastern Australia. There is also great potential for obtaining precise U-Pb age results on volcanic products with basaltic composition using the accessory mineral baddeleyite the occurrence of which we have already confirmed. Geochronological and geochemical research is complemented with paleo-enviromental studies and biostratigraphy. We expect that through integration of U-Pb and 40Ar/39Ar geochronology with chemo- and biostratigraphy, the time scale of the Middle through Late Permian will be greatly improved and will lead to a more realistic evaluation of potential causes for the biotic crisis and its aftermath.

Palaeoproterozoic Indian shield in the global continental assembly: Evidence from the palaeomagnetism of mafic dyke swarms

NASA Astrophysics Data System (ADS)

Radhakrishna, T.; Krishnendu, N. R.; Balasubramonian, G.

2013-11-01

Palaeomagnetic study of Palaeoproterozoic mafic dykes in the basement along the margins of the Cuddapah basin, the largest Precambrian sedimentary basin in south India, is presented in detail for a general discussion of Palaeoproterozoic igneous activity in India. The results are compared with all earlier published data on mafic dykes in India and are integrated with recently-published high-precision U-Pb baddeleyite ages to provide a comprehensive account of Palaeoproterozoic igneous activity in India. The analysis consolidates palaeomagnetic poles for six age divisions between 2.45 and 1.85 Ga with robust statistical criteria. Our best estimates of overall mean poles from 241 dykes are situated at (1) λ = 17.7°N; Φ = 106.0°E (A95 = 9.0°; 7N = 24) at c. 2.45 Ga, (2) λ = 7.1°N; Φ = 57.2°E (A95 = 4.5°; N = 69) at c. 2.37 Ga, (3) λ = 41.6°S; Φ = 5.5°E (A95 = 5.1°; N = 34) at c. 2.22 Ga, (4) λ = 4.7°N; Φ = 343.0°E (A95 = 4.4°; N = 31) at 2.18 Ga, (5) λ = 49.2°N; Φ = 332.9°E (A95 = 4.8°; N = 24) at 1.99-1.89 Ga and (6) λ = 73.7°N; Φ = 282.6°E (A95 = 2.9°; N = 39) at 1.86 Ga. The data permit us to construct an apparent polar wander path for the Indian shield for an ~ 600 Ma interval of the Palaeoproterozoic eon (2.45-1.85 Ga). Testing and evaluation of continental reconstructions for this interval, which are mostly based on geological correlations, reveal many inconsistencies. Between 2.45 and 2.37 Ga, the Indian shield was situated at higher latitudes similar to the Yilgarn craton of Australia. It was subsequently located near the equator at 2.22, 2.18, 1.99 and 1.86 Ga. Thus, an India-Australia connection is supported during these times, but a proposed Australia-Kaapvaal link in "Zimvaalbara" and a Dharwar (India)-Slave connection in "Sclavia" or a Superior-Zimbabwe-India connection in "Superia" are inconsistent with Indian data. In addition, the close palaeomagnetic comparison between the Palaeoproterozoic dykes of Dharwar-Bastar-Bundelkhand cratons in India indicates an age of > 2.45 Ga for orogenic activity along the central Indian tectonic zone; hence, matching this zone with the 2.0-1.8 Ga Trans-North China orogenic belt, or positioning North China adjacent to India or juxtaposition of the Indian shield along the western margin of Laurentia in the Columbia reconstructions is not supported. The Indian data appear to be in accord with the essential features of the refined Protopangaea model and the original Ur configuration. Finally, the results are interpreted in terms of four dyke emplacement events in the age range 2.45-2.18 Ga linked to short-lived (5-10 Ma) LIPs developed over mantle plumes. The dykes of ~ 1.99-1.89 Ga age probably relate to continued long lived igneous activity while the ~ 1.86 Ga dykes are relatively fewer in number and may represent waning stage of a large igneous event related to a major mantle plume.

Paleomagnetism of the Grenville diabase dyke swarm and implications for the mid Vendian paleolatitude of Laurentia

NASA Astrophysics Data System (ADS)

Buchan, K. L.; Ernst, R. E.; Kumarapeli, P. S.

2004-05-01

The Vendian-early Cambrian drift of Laurentia is important for theories of `Snowball Earth' and the continental breakup that formed the Iapetus Ocean. However, estimates of Laurentia's paleolatitude in this period differ widely. Some authors have proposed that Laurentia remained in low latitude throughout this period, whereas others have supported rapid drift of the continent from low to high and back to low latitude. To assist in evaluating these models, a paleomagnetic study was conducted on the mid Vendian Grenville dyke swarm of southeastern Laurentia. This 700 km long swarm was emplaced along the Ottawa graben, an aulacogen associated with rifting that preceded the opening of the Iapetus Ocean. The swarm was the subject of an early paleomagnetic study by Murthy (1971). More recently, U-Pb baddeleyite and zircon ages of ca. 590 Ma have been described for three Grenville dykes (Kamo et al. 1995). At one of these sites, on the `Mattawa' dyke, a positive paleomagnetic baked contact test was also reported (Hyodo and Dunlop 1993). In that detailed test thermoremanent overprinting in the zone of hybrid magnetization was shown to match that expected from heat conduction for a cooling dyke. Nevertheless, Hyodo and Dunlop suggested that the steep down remanence in the dyke, although primary, was likely acquired during a geomagnetic excursion because it did not appear to fit the then-available polar wander path. In our study, paleomagnetic sampling was carried out at 36 sites, including all three dated locations. A detailed analysis has been completed for the dated sites and preliminary analysis for the remaining sites. A stable steep down remanence was obtained for all samples in the Mattawa dyke, and in most samples from a second dated site. The third dated site is less stably magnetized and has not yielded a usable remanence direction. Ten additional sites yield stable steep down or occasionally steep up remanences. The presence of a steep remanence in two dated dykes and several others demonstrates that the remanence was not simply acquired during a short-term geomagnetic excursion. The positive baked contact test suggests that it is a primary remanence. If so, this would indicate that Laurentia was at high latitude 590 Ma ago. This would correspond to interpretations of steep magnetizations in the 577 Ma Callander Complex of the Ottawa graben (Symons and Chiasson 1991). However, other dykes in our study do not carry the steep down remanence. Six have an intermediate up WNW magnetization (or its reversal to the SE), suggesting that these dykes may not be 590 Ma in age. The WNW remanence is similar to that reported for the poorly-dated Buckingham volcanics of the Ottawa graben (Dankers and Lapointe 1981). Five additional sites carry other SE directions (both up and down) that are scattered along or near a great circle through the Mattawa and Buckingham volcanic directions, indicating that unresolved overprinting may have smeared the site directions. Therefore, caution should be exercised in interpreting the overall paleomagnetic data set until further U-Pb dating and paleomagnetic analysis have clarified whether more than one age of dyke swarm is present and whether significant overprinting has occurred. References: Dankers and Lapointe, 1981, Can. J. Earth Sci. 18: 1174; Hyodo and Dunlop, 1993, J. Geophys. Res. 98: 7997; Kamo, Krogh, and Kumarapeli, 1995, Can. J. Earth Sci. 32: 273; Murthy, 1971, Can. J. Earth Sci. 8: 802; Symons and Chiasson, 1991, Can. J. Earth Sci. 28: 355.

Bulk and Interface Thermodynamics of Calcia-, and Yttria-doped Zirconia Ceramics: Nanograined Phase Stability

NASA Astrophysics Data System (ADS)

Drazin, John Walter

Calcia-, and yttria- doped zirconia powders and samples are essential systems in academia and industry due to their observed bulk polymorphism. Pure zirconia manifests as Baddeleyite, a monoclinic structured mineral with 7-fold coordination. This bulk form of zirconia has little application due to its asymmetry. Therefore dopants are added to the grain in-order to induce phase transitions to either a tetragonal or cubic polymorph with the incorporation of oxygen vacancies due to the dopant charge mis-match with the zirconia matrix. The cubic polymorph has cubic symmetry such that these samples see applications in solid oxide fuel cells (SOFCs) due to the high oxygen vacancy concentrations and high ionic mobility at elevated temperatures. The tetragonal polymorph has slight asymmetry in the c-axis compared to the a-axis such that the tetragonal samples have increased fracture toughness due to an impact induced phase transformation to a cubic structure. These ceramic systems have been extensively studied in academia and used in various industries, but with the advent of nanotechnology one can wonder whether smaller grain samples will see improved characteristics similar to their bulk grain counterparts. However, there is a lack of data and knowledge of these systems in the nano grained region which provides us with an opportunity to advance the theory in these systems. The polymorphism seen in the bulk grains samples is also seen in the nano-grained samples, but at slightly distinct dopant concentrations. The current theory hypothesizes that a surface excess, gamma (J/m 2), can be added to the Gibbs Free energy equation to account for the additional free energy of the nano-grain atoms. However, these surface energies have been difficult to measure and therefore thermodynamic data on these nano-grained samples have been sparse. Therefore, in this work, I will use a well established water adsorption microcalorimetry apparatus to measure the water coverage isotherms while simultaneously collecting the energetic contribution of the adsorbing water vapor. With this data and apparatus, I have derived a 2nd order differential equation that relates the surface energy to the measured quantities such that I collected surfaces energies for over 35 specimens in the calcia-zirconia and yttria-zirconia systems for the first time. From the results, it was found that the monoclinic polymorph had the largest surface energy in the range of 1.9 - 2.1 ( J/m2) while the tetragonal surface energies were roughly 1.4 - 1.6 (J/m2), the cubic surface energies were roughly 0.8 - 1.0 (J/m2), and the amorphous surface energies were the smallest at roughly 0.7 - 0.8 (J/m 2). With the measured surface energy data, collected for the first time, we can create a nano-grain phase diagram similar to a bulk phase diagram that shows the stable polymorph as a function of dopant concentration and grain size using the bulk enthalpy data collected from high temperature oxide melt drop solution calorimetry. The phase diagrams show that pure zirconia will transform into tetragonal and cubic polymorphs from the monoclinic one at 7 and 5 nm respectively which confirms the experimental observations. The results are powerful predictive tools successfully applied in the nCZ and nYZ systems to a high degree of accuracy and adds a new development to conventional bulk phase diagrams. These diagrams should be the basis for nanotechnological efforts in nCZ and nYZ based systems, and suggest similar efforts are needed in other nano systems to pursue an in depth understanding and optimization of nanomaterials. After working on the theoretical aspects of phase stability, the focus of the research will shift to producing dense samples to measure observable quantities such as oxygen conduction and mechanical hardness. However, producing said samples with the nanocrystalline grain sizes has also been challenging as conventional sintering requires high temperatures which, as a consequence, induces grain growth of the samples limiting the minimum grain size of the samples. Therefore, in this work, we have developed a Pressure Assisted Rapid Sintering Technique (PARS) that uses high currents to Joule heat the samples to moderate temperatures (650-900 °C) for short durations (5-10 min) under large compressive pressures (600-2200 MPa). With this new technique, atomic level grain sizes (sub-10nm) can be easily achieved at high relative densities (>98 %). Using the PARS setup, multiple 3nYZ samples were produced with varied grain sizes down to 9 nm and as large as 5mum. The mechanical hardness of these samples were tested using a Vicker's microhardness indentation apparatus. The hardness of the "bulk" grains was roughly 12.9 GPa while the smallest grain size pellet had a hardness approaching 15 GPa. All of the 3nYZ pellets had a higher hardness with diminishing grain size, thereby extending the Hall-Petch relationship to 9 nm in the 3YZ system. This is an amazing and unprecedented result to date. After producing the extreme nano-grained samples (15nCZ and 17.5nYSZ), they were tested for inter- and intragranular oxygen ion conduction as well. The results showed that the smaller grained samples have increased levels of oxygen ion conduction from both inter- and intragranular diffusion regardless of the operating temperatures. In addition, it was seen that the activation energies for both modes of oxygen ion diffusion were lowered for the nCZ system while a plateaued effect was seen in the nYZ system. A new theoretical formulation was proposed to explain the trends such that there are two modifiable parameters to exploit; activation energy and grain size. With the lowering of the grain size, the number of interconnected grain boundaries would increase dramatically allowing for more efficient travel around and through the grains. The activation energy can be lowered by modifying the chemistry of the grain boundary by specifically choosing larger dopants with a positive enthalpy of segregation such the concentration of the dopants on the grain boundary would increase, spacing the unattached bonds further apart and reducing their number. Therefore, one can use an engineered nanograined SOFC to decrease the operating temperature of the device without altering the output power density; significantly improving safety and economics.