The isotopic composition of zircon and garnet: A record of the metamorphic history of Naxos, Greece

Growth of zircon with respect to that of garnet has been studied using a combination of petrography, U–Pb dating and oxygen isotope analysis. The aim is to document the mechanism and pressure–temperature conditions of zircon growth during metamorphism in order to better constrain the Tertiary metamorphic history of Naxos, Greece. Two metamorphisms are recognised: (1) an Eocene Franciscan metamorphism (M1) and (2) a widespread Miocene Barrovian metamorphism (M2) that increases from greenschist facies up to partial melting. An amphibolite sample contains zircon crystals characterised by a magmatic core and two metamorphic rims, denoted as A and B, dated at 200–270, 42–69, and 14–19 Ma, respectively. The first metamorphic rim A (δ¹⁸O = 7 ± 1‰) preserves the δ¹⁸O value of the magmatic core (6.2 ± 0.8‰), whereas rim B is characterised by higher δ¹⁸O values (7.8 ± 1.8‰). These observations indicate the formation of A rims by solid-state recrystallisation in a closed system with regard to oxygen and those of B in an open system. Compositional zoning in garnet is interpreted as the result of decompressional heating. Zircon B rims and garnet rims display similar δ¹⁸O values which indicates a contemporaneous growth of garnet and zircon rims during the Miocene Barrovian event (M2). Calcic gneiss and metapelite samples contain zircon crystals with single metamorphic overgrowths aged 41–57 Ma. δ¹⁸O values measured in zircon overgrowths (11.8 ± 1.4‰) from the calcic gneiss are similar to those measured in garnet rims (11.4 ± 1.1‰) from the same rock. This suggests that garnet rims and zircon overgrowths grew during the high pressure–low temperature event in equilibrium with prograde fluids. In the metapelite sample, δ¹⁸O values are similar in garnet cores (14.8 ± 0.2‰) and in zircon metamorphic overgrowths (14.2 ± 0.5‰). As zircon overgrowths have been dated at ca. 50 Ma by U–Pb, garnet cores and zircon overgrowths are interpreted to have grown during the high pressure event.

As demonstrated here for the island of Naxos, correlating the crystallisation of zircon with that of metamorphic index minerals such as garnet using stable isotope composition and U–Pb determination is a powerful tool for deciphering the mechanism of zircon growth and pin-pointing zircon crystallisation within the metamorphic history of a terrain. This approach is potentially hampered by an inability to verify the degree of textural equilibrium of zircon with other mineral phases, and the possible preservation (in metamorphic rims) of isotopic signatures from pre-existing zircon when they form by recrystallisation. Nevertheless, this study illustrates the application of this approach in providing key constraints on the timing and mechanism of growth of minerals important to understanding metamorphic petrogenesis.     

大别山碰撞后火山岩的锆石U-Pb年龄和氧同位素组成

利用阴极发光技术 (CL)观察了大别山碰撞后玄武岩和安山岩的锆石内部结构 ,并通过离子探针技术 (SIMS)测定了其U Pb年龄和氧同位素组成。玄武岩中锆石都是直接从玄武质岩浆中结晶的岩浆锆石 ,其年龄为 130± 2Ma(1σ) ;安山岩中有两种锆石 ,绝大多数是直接从安山质岩浆中结晶出来的岩浆锆石 ,年龄为 133± 3Ma(1σ) ,少数是残留的原岩锆石 ,其年龄有两组 :76 8～80 5Ma和 182 7～ 1873Ma。玄武岩和安山岩的岩浆锆石年龄表明 ,大别山碰撞后火山岩的主体应形成于 130Ma左右 ,属早白垩世。结合文献资料来看 ,大别山碰撞后火山岩和侵入岩无论是化学组成、微量元素配分、Sr Nd同位素比值还是年龄 ,都是基本一致的 ,说明火山岩和侵入岩的源区以及成因可能是相同的。玄武岩和安山岩的岩浆结晶年龄一致 ,暗示着它们之间的可能的成因联系。玄武岩锆石相对于正常地幔亏损18O(δ18O =(4 .1± 0 .6 )‰ ) ,说明其岩浆源区可能含有一定数量的俯冲板块断离后进入该区地幔的大别山榴辉岩原岩组分。安山岩中残留的原岩锆石既有扬子板块的年龄信息 ,又有华北板块的年龄信息 ,这表明华北和扬子的深部界线可能就在北淮阳     

Iron isotope fractionation between pyrite (FeS2), hematite (Fe2O3) and siderite (FeCO3): A first-principles density functional theory study

In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α⁵⁷Fe/⁵⁴Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III)_aq-hematite and Fe(II)_aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions (β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived β-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined.     

Uraniferous bitumen nodules in the Talvivaara Ni–Zn–Cu–Co deposit (Finland): influence of metamorphism on uranium mineralization in black shales

In the central part of the Fennoscandian Shield, the Talvivaara Ni–Zn–Cu–Co deposit, hosted by Palaeoproterozoic metamorphosed black schists, contains low uranium concentrations ranging from 10 to 30 ppm. The Talvivaara black schists were deposited 2.0–1.9 Ga ago and underwent subsequent metamorphism during the 1.9–1.79 Ga Svecofennian orogeny. Anhedral uraninite crystals rimmed by bitumen constitute the main host of uranium. U–Pb secondary ion mass spectrometry dating indicates that uraninite crystals were formed between 1,878?±?17 and 1,871?±?43 Ma, during peak metamorphism. Rare earth element patterns and high Th content (average 6.38 wt%) in disseminated uraninite crystals indicate that U was concentrated during high temperature metamorphism (>400 °C). The formation of bitumen rims around uraninite may be explained by two distinct scenarios: (a) a transport of U coincident with the migration of hydrocarbons or (b) post-metamorphic formation of bitumen rims, through radiolytic polymerization of gaseous hydrocarbons at the contact with uraninite.     

Late Wisconsinan deglaciation and proglacial lakes development in the Charlevoix region,southeastern Québec,Canada

The Charlevoix region, in southeastern Québec, is characterized by a dramatic landscape formed by the junction of the Laurentian Highlands, the Charlevoix Astrobleme and the St Lawrence Estuary. At the Last Glacial Maximum (LGM), the region was completely covered by the Laurentide Ice Sheet (LIS). The complex topography of the region was the stage of many of the major deglacial events of southern Quebec (e.g. Goldthwait Sea Invasion, St Lawrence Ice‐Stream, Saint‐Narcisse Episode). We present a detailed reconstruction of the pattern of retreat of the LIS in the Charlevoix region based on the interpretation of ice‐marginal features (e.g. moraines, fans) and glaciolacustrine landforms and deposits, two extensive field campaigns, and the interpretation of high‐resolution 3D digital aerial photographs and LiDAR data. Our results indicate five moraine complexes in the region: the Rochette, the Brûlée, the Sainte‐Anne, the Saint‐Narcisse and the Mars‐Batiscan complexes. Deltas, fans, fine‐grained sediments, littoral deposits, drainage breaches and deposits were used to identify 91 palaeo‐proglacial lakes. The identification of these lakes and their relation to moraine complexes enabled the reconstruction of six stages of lake development during the Charlevoix deglaciation. The development of proglacial lakes occurred in all types of terrain (highlands, lowlands, transitory levels above marine limit). We conclude that local topography had a decisive effect on promoting both moraine deposition and lake development. We suggest that similar topographical regions (hilly‐mountainous) that were affected by major ice‐margin stabilizations during glacial retreat should have experience small lakes dominating valleys and topographical lows.     

Frozen orbits for satellites close to an Earth-like planet

We say that a planet is Earth-like if the coefficient of the second order zonal harmonic dominates all other coefficients in the gravity field. This paper concerns the zonal problem for satellites around an Earth-like planet, all other perturbations excluded. The potential contains all zonal coefficientsJ ₂ throughJ ₉. The model problem is averaged over the mean anomaly by a Lie transformation to the second order; we produce the resulting Hamiltonian as a Fourier series in the argument of perigee whose coefficients are algebraic functions of the eccentricity — not truncated power series. We then proceed to a global exploration of the equilibria in the averaged problem. These singularities which aerospace engineers know by the name of frozen orbits are located by solving the equilibria equations in two ways, (1) analytically in the neighborhood of either the zero eccentricity or the critical inclination, and (2) numerically by a Newton-Raphson iteration applied to an approximate position read from the color map of the phase flow. The analytical solutions we supply in full to assist space engineers in designing survey missions. We pay special attention to the manner in which additional zonal coefficients affect the evolution of bifurcations we had traced earlier in the main problem (J ₂ only). In particular, we examine the manner in which the odd zonalJ ₃ breaks the discrete symmetry inherent to the even zonal problem. In the even case, we find that Vinti's problem (J ₄+J ₂ ² =0) presents a degeneracy in the form of non-isolated equilibria; we surmise that the degeneracy is a reflection of the fact that Vinti's problem is separable. By numerical continuation we have discovered three families of frozen orbits in the full zonal problem under consideration; (1) a family of stable equilibria starting from the equatorial plane and tending to the critical inclination; (2) an unstable family arising from the bifurcation at the critical inclination; (3) a stable family also arising from that bifurcation and terminating with a polar orbit. Except in the neighborhood of the critical inclination, orbits in the stable families have very small eccentricities, and are thus well suited for survey missions.     

Active oceanic spreading in the northern North Fiji Basin: Results of the NOFI cruise of R/V L'Atalante (newstarmer project)

The South Pandora and the Tripartite Ridges are active spreading centers located in the northern part of the North Fiji Basin. These spreading centers were surveyed over a distance of 750 km during the NOFI cruise of R/V L'Atalante (August–September 1994) which was conducted in the frame of the french-japanese Newstarmer cooperation project. SIMRAD EM12-dual full coverage swath bathymetric and imagery data as well as airgun 6-channel seismic, magnetics and gravity profiles were recorded along and offaxis from 170°40 E to 178° E. Dredging and piston coring were also performed along and off-axis. The axial domain of the South Pandora Ridge is divided into 5 first-order segments characterized by contrasted morphologies. The average width of the active domain is 20 km and corresponds either to bathymetric highs or to deep elongated grabens. The bathymetric highs are volcanic constructions, locally faulted and rifted, which can obstruct totally the axial valley. The grabens show the typical morphology of slow spreading axes, with two steep walls flanking a deep axial valley. Elongated lateral ridges may be present on both sides of the grabens. Numerous volcanoes, up to several kilometers in diameter, occur on both flanks of the South Pandora Ridge. The Tripartite Ridge consists of three main segments showing a sigmoid shape. Major changes in the direction of the active zones are observed at the segment discontinuities. These discontinuities show various geometrical patterns which suggest complex transform relay zones. Preliminary analysis of seismic reflection profiles suggest that the Tripartite Ridge is a very young feature which propagates into an older oceanic domain characterized by a significant sedimentary cover. By contrast, a very thin to absent sedimentary cover is observed about 100 km on both flanks of the South Pandora Ridge active axis. The magnetic anomaly profiles give evidence of long and continuous lineations, parallel to the South Pandora Ridge spreading axis. According to our preliminary interpretation, the spreading rate would have been very low (8 km/m.y. half rate) during the last 7 Ma. The South Pandora and Tripartite Ridges exhibit characteristics typical of active oceanic ridges: (1) a segmented pattern, with segments ranging from 80 to 100 km in length; (2) an axial tectonic and volcanic zone, 10 to 20 km wide; (3) well-organized magnetic lineations, parallel to the active axis; (4) clear signature on the free-air gravity anomaly map. However, no typical transform fault is observed; instead, complex relay zones are separating first-order segments.     

Experimental melting of phlogopite-peridotite in the garnet stability field

Melting experiments have been performed at 3 GPa, between 1150 and 1450 °C, on a phlogopite-peridotite source in the garnet stability field. We succeeded to extract and determine the melt compositions of both phlogopite-bearing lherzolite and harzburgite from low to high degrees of melting (? = 0.008–0.256). Accounting for the presence of small amounts of F in the mantle, we determined that phlogopite coexists with melt >150 °C above the solidus position (1150–1200 °C). Fluorine content of phlogopite continuously increases during partial melting from 0.2 to 0.9 wt% between 1000 and 1150 °C and 0.5 to 0.6 wt% between 1150 and 1300 °C at 1 and 3 GPa, respectively. The phlogopite continuous breakdown in the lherzolite follows the reaction: 0.59 phlogopite + 0.52 clinopyroxene + 0.18 garnet = 0.06 olivine + 0.23 orthopyroxene + 1.00 melt. In the phlogopite-harzburgite, the reaction is: 0.93 phlogopite + 0.46 garnet = 0.25 olivine + 0.14 orthopyroxene + 1.00 melt. Melts from phlogopite-peridotite sources at 3 GPa are silica-undersaturated and are foiditic to trachybasaltic in composition from very low (0.8 wt%) to high (25.6 wt%) degrees of melting. As observed at 1 GPa, the potassium content of primary mantle melts is buffered by the presence of phlogopite, but the buffering values are higher, from 6.0 to 8.0 wt% depending on the source fertility. We finally show that phlogopite garnet-peridotite melts are very close to the composition of the most primitive post-collisional lavas described worldwide.     

Hydromagmatic amphibole in komatiitic, tholeiitic and ferropicritic units, Abitibi greenstone belt, Ontario and Québec: evidence for Archaean wet basic and ultrabasic melts

Summary ?Detailed petrographic, electron microprobe and ion probe studies of Archaean hydromagmatic amphiboles from the Abitibi greenstone belt, Canada, yield new insights into the origin of Al-undepleted komatiitic and Al-depleted tholeiitic and ferropicritic melts. The amphiboles are present in peridotite layers and basal chill zones of thick differentiated basic and ultrabasic sills and flows, and are titanian pargasite–hastingsite in composition. They can be grouped into two petrographic types: (1) amphibole in the groundmass; and (2) amphibole-bearing melt inclusions. The groundmass amphiboles are oikocrysts, rims and interstitial grains, present in minor to major amounts. The oikocrysts host cumulus olivines (Fo_83–84) that are rounded in shape, embayed, and smaller in size. The amphibole-bearing melt inclusions are hosted in cumulus olivines (Fo_83–84 in komatiitic rocks and Fo₇₉ in tholeiitic rocks), spherical to ovoid in shape, 50–500 μm in size, and dominated modally by amphibole. The melt inclusions also contain euhedral chromite and aluminous spinel and micrometric clinopyroxene and glass, and sub-micrometric iron–nickel sulphide, chloro-apatite and ilmenite. In-situ ion probe analyses indicate the amphibole is: (1) enriched in Nb, LREE and Zr and depleted in Sr and HREE relative to primitive mantle; (2) contains up to 1–3 wt% H₂O; and (3) overall displays δD values from 50‰ to −140‰, including many values in the accepted magmatic range of −60‰ to −90‰. The petrographic relationships and geochemical compositions, and comparisons to experimental systems, indicate amphibole formation by subsolidus reaction of residual hydrous silicate melt with olivine and clinopyroxene. Some of the hydrous melt intruded and was entrapped as secondary melt inclusions within relict olivine. Rapid crystallization of the hydrous melt inclusions formed amphibole+clinopyroxene±glass±spinel or solely glass. Bulk compositions of the melt inclusions, comparisons to experimental phase equilibria, and presence of magmatic water suggest amphibole crystallisation from olivine → pyroxene residual melts with at least 2–3 wt% H₂O during rapid solidification of the host units. Adjustment for anhydrous phase crystallization (mainly olivine) suggests the initial melts contained 1–2 wt% H₂O. Such high H₂O contents and the magmatic δD compositions are consistent with the participation of H₂O in melt petrogenesis. However, most Abitibi komatiites and tholeiites lack hydromagmatic minerals, making it difficult to attribute all basic and ultrabasic melts to melting in hydrous Archaean mantle. The favoured model is that some Abitibi basic and ultrabasic melts were wet and some were dry, as well as Al-depleted or Al-undepleted. Received July 24, 2001; revised version accepted January 9, 2002