An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H2O from 300 to 800°C

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.     

Torngat ultramafic lamprophyres and their relation to the North Atlantic Alkaline Province

Geological mapping and diamond exploration in northern Quebec and Labrador has revealed an undeformed ultramafic dyke swarm in the northern Torngat Mountains. The dyke rocks are dominated by an olivine-phlogopite mineralogy and contain varying amounts of primary carbonate. Their mineralogy, mineral compositional trends and the presence of typomorphic minerals (e.g. kimzeyitic garnet), indicate that these dykes comprise an ultramafic lamprophyre suite grading into carbonatite. Recognized rock varieties are aillikite, mela-aillikite and subordinate carbonatite. Carbonatite and aillikite have in common high carbonate content and a lack of clinopyroxene. In contrast, mela-aillikites are richer in mafic silicate minerals, in particular clinopyroxene and amphibole, and contain only small amounts of primary carbonate. The modal mineralogy and textures of the dyke varieties are gradational, indicating that they represent end-members in a compositional continuum.

The Torngat ultramafic lamprophyres are characterized by high but variable MgO (10–25 wt.%), CaO (5–20 wt.%), TiO₂ (3–10 wt.%) and K₂O (1–4 wt.%), but low SiO₂ (22–37 wt.%) and Al₂O₃ (2–6 wt.%). Higher SiO₂, Al₂O₃, Na₂O and lower CO₂ content distinguish the mela-aillikites from the aillikites. Whereas the bulk rock major and trace element concentrations of the aillikites and mela-aillikites overlap, there is no fractional crystallization relation between them. The major and trace element characteristics imply related parental magmas, with minor olivine and Cr-spinel fractionation accounting for intra-group variation.

The Torngat ultramafic lamprophyres have a Neoproterozoic age and are spatially and compositionally closely related with the Neoproterozoic ultramafic lamprophyres from central West Greenland. Ultramafic potassic-to-carbonatitic magmatism occurred in both eastern Laurentia and western Baltica during the Late Neoproterozoic. It can be inferred from the emplacement ages of the alkaline complexes and timing of Late Proterozoic processes in the North Atlantic region that this volatile-rich, deep-seated igneous activity was a distal effect of the breakup of Rodinia. This occurred during and/or after the rift-to-drift transition that led to the opening of the Iapetus Ocean.     

Geological setting and chemistry of kimberlite clan rocks in the Dharwar Craton, India

Diamond exploration in India over the past decade has led to the discovery of over 80 kimberlite-inferred and lamproite-related intrusions in three of the four major Archean cratons that dominate the subcontinent. These intrusions are Proterozoic (1.1 Ga), and are structurally controlled: locally (at the intersections of faults); regionally (in a 200 km wide, 1000 km long diamond corridor); and globally (in the reconstructed supercontinent of Rodinia). The geochemistry of 57 samples from 13 intrusions in the southern Dharwar Craton of Andhra Pradesh has been determined by XRF spectrometry. The bodies are iron-rich with mg#=50–70 and are neither archetypal kimberlites nor ideal lamproites; this may be the underlying reason that conventional exploration techniques have thus far failed to locate the primary sources of India's historically famous diamonds. The two major fields of kimberlite-clan rocks (KCR) in the Dharwar Craton, Wajrakur and Narayanpet, are separated by a NW–SE trending, transcontinental (Mumbai-Chennai) gravity lineament. About 80% of intrusions in Wajrakur are diamondiferous, but diamonds have not yet been reported in Narayanpet. The gravity anomaly may mark the boundary of an architectural modification in the keel of the sub-continental lithosphere, a suggestion that is supported by differences in kimberlite mineralogy, chemistry, mantle xenoliths, structural setting and crustal host rocks.     

Volcanic resurfacing and the early terrestrial crust: Zircon U-Pb and REE constraints from the Isua Greenstone Belt, southern West Greenland

The oldest known bona fide succession of clastic metasediments occurs in the Isua Greenstone Belt, SW Greenland and consists of a variety of mica schists and rare metaconglomerates. The metasediments are in direct contact with a felsic metavolcanic lithology that has previously been dated to 3.71 Ga. Based on trace element geochemical data for > 30 metasediments, we selected the six samples with highest Zr concentrations for zircon extraction. These samples all yielded very few or no zircon. Those extracted from mica schists yielded ion probe U/Pb ages between 3.70 and 3.71 Ga. One metaconglomerate sample yielded just a single zircon of 3.74 Ga age.The mica schist hosted zircons have U/Pb ages, Th / U ratios, REE patterns and Eu anomalies indistinguishable from zircon in the adjacent 3.71 Ga felsic metavolcanic unit. Trace element modelling requires the bulk of material in the metasediments to be derived from variably weathered mafic lithologies but some metasediments contain substantial contribution from more evolved source lithologies. The paucity of zircon in the mica schists is thus explained by incorporation of material from largely zircon-free volcanic lithologies. The absence of older zircon in the mica schists and the preponderance of mafic source material imply intense, mainly basaltic resurfacing of the early Earth. The implications of this process are discussed.Thermal considerations suggest that horizontal growth of Hadean crust by addition of mafic-ultramafic lavas must have triggered self-reorganisation of the protocrust by remelting. Reworking of Hadean crust may have been aided by burial of hydrated (weathered) metabasalt due to semi-continuous addition of new voluminous basalt outpourings. This process causes a bias towards eruption of Zr-saturated partial melts at the surface with O-isotope compositions potentially different from the mantle. The oldest zircons hosted in sediments would have been buried to substantial depth or formed in plutons that crystallised at some depth, from which it took hundreds of millions of years for them to be exhumed and incorporated into much younger sediments.     

Geomorphic and sedimentological signature of a two‐phase outburst flood from moraine‐dammed Queen Bess Lake,British Columbia,Canada

On 12 August 1997, the lower part of Diadem Glacier in the southern Coast Mountains of British Columbia fell into Queen Bess Lake and produced a train of large waves. The waves overtopped the broad end moraine at the east end of the lake and ?ooded the valley of the west fork of Nostetuko River. The displacement waves also incised the out?ow channel across the moraine. Stratigraphic and sedimentologic evidence supports the conclusion that the ?ood had two phases, one related to wave overtopping and a second to breach formation. Empirical equations were used to calculate the peak discharge of the ?ood at various points along the west fork of the Nostetuko valley and to describe the attenuation of the ?ood wave. The velocity of the ?ood was also calculated to determine the time it took for the ?ood to reach the main fork of Nostetuko River. The highest peak discharges were achieved in the upper reach of the valley during the displacement phase of the ?ood. Peak discharge declined rapidly just below the moraine dam, with little change thereafter for approximately 7 km. Empirical formulae and boulder measurements indicate a rise in peak discharge in the lower part of the west fork valley. We suggest that ?ow in the upper part of the valley records the passage of two separate ?ood peaks and that the rise in discharge in the lower part of the valley is due to amalgamation of the wave and breach peaks. Hydraulic ponding in con?ned reaches of the valley extended the duration of the ?ood. In addition, erosion of vegetation and sediment in the channel and valley sides may also have exerted an in?uence on the duration and nature of ?ooding. Sediments were deposited both upstream and downstream of channel constrictions and on a large fan extending out into the trunk Nostetuko River valley. This study extends our understanding of the variety and complexity of outburst ?oods from naturally dammed lakes. It also shows that simple empirical and other models for estimating peak discharges of outburst ?oods are likely to yield erroneous results. Copyright © 2005 John Wiley & Sons, Ltd.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Seismic velocities of granulite-facies xenoliths from Central Ireland: Implications for lower crustal composition and anisotropy

V_p and V_s values have been measured experimentally and calculated for granulite-facies lower crustal xenoliths from central Ireland close to the Caledonian Iapetus suture zone. The xenoliths are predominantly foliated and lineated metapelitic (garnet–sillimanite–K-feldspar) granulites. Their metapelitic composition is unusual compared with the mostly mafic composition of lower crustal xenoliths world-wide. Based on thermobarometry, the metapelitic xenoliths were entrained from depths of c. 20–25 ± 3.5 km and rare mafic granulites from depths of 31–33 ± 3.4 km. The xenoliths were emplaced during Lower Carboniferous volcanism and are considered to represent samples of the present day lower crust.V_p values for the metapelitic granulites range between 6.26 and 7.99 km s^{− 1} with a mean value of 7.09 ± 0.4 km s^{− 1}. Psammite and granitic orthogneiss samples have calculated V_p values of 6.51 and 6.23 km s^{− 1}, respectively. V_s values for the metapelites are between 3.86 and 4.34 km s^{− 1}, with a mean value of 4.1 ± 0.15 km s^{− 1}. The psammite and orthogneiss have calculated V_s values of 3.95 and 3.97 km s^{− 1}, respectively.The measured seismic velocities correlate with density and with modal mineralogy, especially the high content of sillimanite and garnet. V_p anisotropy is between 0.15% and 13.97%, and a clear compositional control is evident, mainly in relation to sillimanite abundance. Overall V_s anisotropy ranges from 1% to 11%. Poisson's ratio (σ) lies between 0.25 and 0.35 for the metapelitic granulites, mainly reflecting a high V_p value due to abundant sillimanite in the sample with the highest σ. Anisotropy is probably a function of deformation associated with the closure of the Iapetus ocean in the Silurian as well as later extension in the Devonian. The orientation of the bulk strain ellipsoid in the lower crust is difficult to constrain, but lineation is likely to be NE–SW, given the strike-slip nature of the late Caledonian and subsequent Acadian deformation.When corrected for present-day lower crustal temperature, the experimentally determined V_p values correspond well with velocities from the ICSSP, COOLE I and VARNET seismic refraction lines. Near the xenolith localities, the COOLE I line displays two lower crustal layers with in situ V_p values of 6.85–6.9 and 6.9–8.0 km s^{− 1}, respectively. The upper (lower velocity) layer corresponds well with the metapelitic granulite xenoliths while the lower (higher velocity) layer matches that of the basic granulite xenoliths, though their metamorphic pressures suggest derivation from depths corresponding to the present-day upper mantle.     

Comparison of Proterozoic and Phanerozoic rift-related basaltic-granitic magmatism

This paper compares the 1.67–1.47 Ga rapakivi granites of Finland and vicinity to the 1.70–1.68 Ga rapakivi granites of the Beijing area in China, the anorogenic 130 Ma granites of western Namibia, and the 20–15 Ma granites of the Colorado River extensional corridor in the Basin and Range Province of southern Nevada. In Finland and China, the tectonic setting was incipient, aborted rifting of Paleoproterozoic or Archean continental crust, in Namibia it was continental rifting and mantle plume activity that led to the opening of southern Atlantic at 130 Ma. The 20–15 Ma granites of southern Nevada were related to rifting that followed the Triassic–Paleogene subduction of the Farallon plate beneath the southwestern United States. In all cases, extension-related magmatism was bimodal and accompanied by swarms of diabase and rhyolite–quartz latite dikes. Rapakivi texture with plagioclase-mantled alkali feldspar megacrysts occurs in varying amounts in the granites, and the latest intrusive phases are commonly topaz-bearing granites or rhyolites that may host tin, tungsten, and beryllium mineralization. The granites are typically ferroan alkali-calcic metaluminous to slightly peraluminous rocks with A-type and within-plate geochemical and mineralogical characteristics. Isotope studies (Nd, Sr) suggest dominant crustal sources for the granites. The preferred genetic model is magmatic underplating involving dehydration melting of intermediate-felsic deep crust. Juvenile mafic magma was incorporated either via magma mingling and mixing, or by remelting of newly hybridized lower crust. In Namibia, partial melting of subcontinental lithospheric mantle was caused by the Tristan mantle plume, in the other cases the origin of the mantle magmatism is controversial. For the Fennoscandian suites, extensive long-time mantle upwelling associated with periodic, migrating melting of the subcontinental lithospheric mantle, governed by heat flow and deep crustal structures, is suggested.     

The dynamics of chironomid assemblages and vegetation during the Late Quaternary at Laguna Facil, Chonos Archipelago, southern Chile

We compare high-resolution pollen and chironomid records from the last 15,000 yr in Laguna Facil, southern Chile. Major vegetation and chironomid changes are recorded between ca 14,900 and 14,700 cal. yr BP. During the Lateglacial, changes in the chironomid stratigraphy lag behind changes in the pollen stratigraphy suggesting that the chironomids are responding to changes in the tree canopy or in soil chemistry brought about by vegetational development. At about 7200 cal. yr BP there is a change in the chironomid stratigraphy in advance of changes in the vegetation. This suggests that the response is to regional climatic change. The relatively close correlation of the chironomid and pollen stratigraphies with changes in charcoal concentrations also implicates the importance of fire and/or vulcanism in influencing the dynamics of forest and limnological systems. There is no clear evidence of cooling during the Younger Dryas chronozone in Laguna Facil.