Internal characteristics, chemical compounds and spectroscopy of sapphire as single crystals

In this study more than 450 natural sapphire samples (most of basaltic type) collected from 19 different areas were examined. They are from Dak Nong, Dak Lak, Quy Chau, two unknown sources from the north (Vietnam); Bo Ploi, Khao Ploi Waen (Thailand); Ban Huay Sai (Laos); Australia; Shandong (China); Andapa, Antsirabe, Nosibe (Madagascar); Ballapana (Sri Lanka); Brazil; Russia; Colombia; Tansania and Malawi. rnThe samples were studied on internal characteristics, chemical compositions, Raman-, luminescence-, Fourier transform infrared (FTIR)-, and ultraviolet-visible-near infrared (UV-Vis-NIR)- spectroscopy. The internal features of these sapphire samples were observed and identified by gemological microscope, con focal micro Raman and FTIR spectroscopy. The major and minor elements of the samples were determined by electron probe microanalysis (EPMA) and the trace elements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). rnThe structural spectra of sapphire were investigated by con focal Raman spectroscopy. The FTIR spectroscopy was used to study the vibration modes of OH-groups and also to determine hydrous mineral inclusions in sapphire. The UV-Vis-NIR absorption spectroscopy was used to analyze the cause of sapphire color. rnNatural sapphires contain many types of mineral inclusions. Typically, they are iron-containing inclusions like goethite, ilmenite, hematite, magnetite or silicate minerals commonly feldspar, and often observed in sapphires from Asia countries, like Dak Nong, Dak Lak in the south of Vietnam, Ban Huay Sai (Laos), Khao Ploi Waen and Bo Ploi (Thailand) or Shandong (China). Meanwhile, CO2-diaspore inclusions are normally found in sapphires from Tansania, Colombia, or the north of Vietnam like Quy Chau. rnIron is the most dominant element in sapphire, up to 1.95 wt.% Fe2O3 measured by EPMA and it affects spectral characteristics of sapphire.rnThe Raman spectra of sapphire contain seven peaks (2A1g + 5Eg). Two peaks at about 418.3 cm-1 and 577.7 cm-1 are influenced by high iron content. These two peaks shift towards smaller wavenumbers corresponding to increasing iron content. This shift is showed by two equations y(418.3)=418.29-0.53x andy(577.7)=577.96-0.75x, in which y is peak position (cm-1) and x is Fe2O3 content (wt.%). By exploiting two these equations one can estimate the Fe2O3 contents of sapphire or corundum by identifying the respective Raman peak positions. Determining the Fe2O3 content in sapphire can help to distinguish sapphires from different origins, e.g. magmatic and metamorphic sapphire. rnThe luminescence of sapphire is characterized by two R-lines: R1 at about 694 nm and R2 at about 692 nm. This characteristic is also influenced by high iron content. The peak positions of two R-lines shift towards to smaller wavelengths corresponding to increasing of iron content. This correlation is showed by two equations y(R_2 )=692.86-0.049x and y(R_1 )=694.29-0.047x, in which y is peak position (nm) of respective R-lines and x is Fe2O3 content (wt.%). Two these equations can be applied to estimate the Fe2O3 content of sapphire and help to separate sapphires from different origins. The luminescence is also applied for determination of the remnant pressure or stress around inclusions in Cr3+-containing corundum by calibrating a 0-pressure position in experimental techniques.rnThe infrared spectra show the presence of vibrations originating from OH-groups and hydrous mineral inclusions in the range of 2500-4000 cm-1. Iron has also an effect upon the main and strongest peak at about 3310 cm-1. The 3310 cm-1 peak is shifted to higher wavenumber when iron content increases. This relationship is expressed by the equation y(3310)=0.92x+3309.17, in which y is peak position of the 3310 cm-1 and x is Fe2O3 content (wt.%). Similar to the obtained results in Raman and luminescence spectra, this expression can be used to estimate the Fe2O3 content and separate sapphires from different origins. rnThe UV-Vis-NIR absorption spectra point out the strong and sharp peaks at about 377, 387, and 450 nm related to dispersed Fe3+, a broad band around 557 and 600 nm related to intervalence charge transfer (IVCT) Fe2+/Ti4+, and a broader band around 863 nm related to IVCT of Fe2+/Fe3+. rnGenerally, sapphires from different localities were completely investigated on internal features, chemical compounds, and solid spectral characteristics. The results in each part contribute for identifying the iron content and separate sapphires from different localities order origins. rn

Miocene basin development and volcanism along a strike-slip to flat-slab subduction transition: Stratigraphy, geochemistry, and geochronology of the central Wrangell volcanic belt, Yakutat-North America collision zone

New geochronologic, geochemical, sedimentologic, and compositional data from the central Wrangell volcanic belt (WVB) document basin development and volcanism linked to subduction of overthickened oceanic crust to the northern Pacific plate margin. The Frederika Formation and overlying Wrangell Lavas comprise >3 km of sedimentary and volcanic strata exposed in the Wrangell Mountains of south-central Alaska (United States). Measured stratigraphic sections and lithofacies analyses document lithofacies associations that reflect deposition in alluvial-fluvial-lacustrine environments routinely influenced by volcanic eruptions. Expansion of intrabasinal volcanic centers prompted progradation of vent-proximal volcanic aprons across basinal environments. Coal deposits, lacustrine strata, and vertical juxtaposition of basinal to proximal lithofacies indicate active basin subsidence that is attributable to heat flow associated with intrabasinal volcanic centers and extension along intrabasinal normal faults. The orientation of intrabasinal normal faults is consistent with transtensional deformation along the Totschunda-Fairweather fault system. Paleocurrents, compositional provenance, and detrital geochronologic ages link sediment accumulation to erosion of active intrabasinal volcanoes and to a lesser extent Mesozoic igneous sources. Geochemical compositions of interbedded lavas are dominantly calc-alkaline, range from basaltic andesite to rhyolite in composition, and share geochemical characteristics with Pliocene-Quaternary phases of the western WVB linked to subduction-related magmatism. The U/Pb ages of tuffs and Ar-40/Ar-39 ages of lavas indicate that basin development and volcanism commenced by 12.5-11.0 Ma and persisted until at least ca. 5.3 Ma. Eastern sections yield older ages (12.5-9.3 Ma) than western sections (9.6-8.3 Ma). Samples from two western sections yield even younger ages of 5.3 Ma. Integration of new and published stratigraphic, geochronologic, and geochemical data from the entire WVB permits a comprehensive interpretation of basin development and volcanism within a regional tectonic context. We propose a model in which diachronous volcanism and transtensional basin development reflect progressive insertion of a thickened oceanic crustal slab of the Yakutat microplate into the arcuate continental margin of southern Alaska coeval with reported changes in plate motions. Oblique northwestward subduction of a thickened oceanic crustal slab during Oligocene to Middle Miocene time produced transtensional basins and volcanism along the eastern edge of the slab along the Duke River fault in Canada and subduction-related volcanism along the northern edge of the slab near the Yukon-Alaska border. Volcanism and basin development migrated progressively northwestward into eastern Alaska during Middle Miocene through Holocene time, concomitant with a northwestward shift in plate convergence direction and subduction collision of progressively thicker crust against the syntaxial plate margin.

Comparison of magnetic properties and petrography between dykes and lava flows from La Cienega, New Mexico and Thunder Bay area, Canada

Data on the evolution of geomagnetic paleointensity are crucial for understanding the geodynamo and Earth’s thermal history. Although basaltic flows are preferred for paleointensity experiments, quickly cooled mafic dykes have also been used. However, the paleointensity values obtained from the dykes are systematically lower than those from lava flows. This bias may originate from the difference in cooling histories and resultant magnetic mineralogies of extrusive and intrusive rocks. To explore this hypothesis, the magnetic mineralogy of two feeder dyke-lave flow systems, from Thunder Bay (Canada) and La Cienega (New-Mexico), has been studied using magnetic and microscopy methods. Within each system, the flow and dyke show different stages of deuteric oxidation of titanomagnetite, but the oxidation stages also differ between the two systems. It is concluded that the tested hypothesis is viable, but the relationships between the magnetic and mineralogical properties of flows and dykes are complex and need a further investigation.

Investigations into the degassing and eruption mechanisms of Nyamuragira volcano, Democratic Republic of the Congo (Africa)

One of two active volcanoes in the western branch of the East African Rift, Nyamuragira (1.408ºS, 29.20ºE; 3058 m) is located in the D.R. Congo. Nyamuragira emits large amounts of SO2 (up to ~1 Mt/day) and erupts low-silica, alkalic lavas, which achieve flow rates of up to ~20 km/hr. The source of the large SO2 emissions and pre-eruptive magma conditions were unknown prior to this study, and 1994-2010 lava volumes were only recently mapped via satellite imagery, mainly due to the region’s political instability. In this study, new olivine-hosted melt inclusion volatile (H2O, CO2, S, Cl, F) and major element data from five historic Nyamuragira eruptions (1912, 1938, 1948, 1986, 2006) are presented. Melt compositions derived from the 1986 and 2006 tephra samples best represent pre-eruptive volatile compositions because these samples contain naturally glassy inclusions that underwent less post-entrapment modification than crystallized inclusions. The total amount of SO2 released from the 1986 (0.04 Mt) and 2006 (0.06 Mt) eruptions are derived using the petrologic method, whereby S contents in melt inclusions are scaled to erupted lava volumes. These amounts are significantly less than satellite-based SO2 emissions for the same eruptions (1986 = ~1 Mt; 2006 = ~2 Mt). Potential explanations for this observation are: 1) accumulation of a vapor phase within the magmatic system that is only released during eruptions, and/or 2) syn-eruptive gas release from unerupted magma. Post-1994 Nyamuragira lava volumes were not available at the beginning of this study. These flows (along with others since 1967) are mapped with Landsat MSS, TM, and ETM+, Hyperion, and ALI satellite data and combined with published flow thicknesses to derive volumes. Satellite remote sensing data was also used to evaluate Nyamuragira SO2 emissions. These results show that the most recent Nyamuragira eruptions injected SO2 into the atmosphere between 15 km (2006 eruption) and 5 km (2010 eruption). This suggests that past effusive basaltic eruptions (e.g., Laki 1783) are capable of similar plume heights that reached the upper troposphere or tropopause, allowing SO2 and resultant aerosols to remain longer in the atmosphere, travel farther around the globe, and affect global climates.

Paleomagnetic Study of the Portage Lake Volcanics exposed in the Quincy Mine

A detailed paleomagnetic and rock-magnetic investigation was conducted on thirty six basaltic flows of the ~1095 Ma Portage Lake Volcanics. The flows were sampled along the East Adit of the Quincy Mine (Hancock, MI). Thirty two flows yielded well-defined primary magnetization directions carried by magnetite. A secondary magnetization component carried by hematite was also found in twenty nine flows. After correction for serial correlation between the flows, nineteen independent mean directions were calculated. The corresponding paleomagnetic pole is located at 25.5 °N, 182.1 °W (A95 = 3.5°). The new pole overlaps with the pole from the ~1087 Ma Lake Shore Traps suggesting a standstill of the North American plate during that time period. The low angular dispersion of virtual geomagnetic poles (S = 7.9°) suggests that the flows were erupted within a short time period, or that the strength of geomagnetic secular variation was lower than that of the recent field.

GROUND-BASED AND SATELLITE REMOTE SENSING OF PAROXYSMAL ERUPTIONS AT ETNA VOLCANO, 2011-2012.

Mt Etna's activity has increased during the last decade with a tendency towards more explosive eruptions that produce paroxysmal lava fountains. From January 2011 to April 2012, 25 lava fountaining episodes took place at Etna's New South-East Crater (NSEC). Improved understanding of the mechanism driving these explosive basaltic eruptions is needed to reduce volcanic hazards. This type of activity produces high sulfur dioxide (SO2) emissions, associated with lava flows and ash fall-out, but to date the SO2 emissions associated with Etna's lava fountains have been poorly constrained. The Ultraviolet (UV) Ozone Monitoring Instrument (OMI) on NASA's Aura satellite and the Atmospheric Infrared Sounder (AIRS) on Aqua were used to measure the SO2 loadings. Ground-based data from the Observatoire de Physique du Globe de Clermont-Ferrand (OPGC) L-band Doppler radar, VOLDORAD 2B, used in collaboration with the Italian National Institute of Geophysics and Volcanology in Catania (INGV-CT), also detected the associated ash plumes, giving precise timing and duration for the lava fountains. This study resulted in the first detailed analysis of the OMI and AIRS SO2 data for Etna's lava fountains during the 2011-2012 eruptive cycle. The HYSPLIT trajectory model is used to constrain the altitude of the observed SO2 clouds, and results show that the SO2 emission usually coincided with the lava fountain peak intensity as detected by VOLDORAD. The UV OMI and IR AIRS SO2 retrievals permit quantification of the SO2 loss rate in the volcanic SO2 clouds, many of which were tracked for several days after emission. A first attempt to quantitatively validate AIRS SO2 retrievals with OMI data revealed a good correlation for high altitude SO2 clouds. Using estimates of the emitted SO2 at the time each paroxysm, we observe a correlation with the inter-paroxysm repose time. We therefore suggest that our data set supports the collapsing foam (CF) model [1] as driving mechanism for the paroxysmal events at the NSEC. Using VOLDORAD-based estimates of the erupted magma mass, we observe a large excess of SO2 in the eruption clouds. Satellite measurements indicate that SO2 emissions from Etnean lava fountains can reach the lower stratosphere and hence could pose a hazard to aviation. [1] Parfitt E.A (2004). A discussion of the mechanisms of explosive basaltic eruptions. J. Volcanol. Geotherm. Res. 134, 77-107.

Photometric properties of Mars soils analogs

We have measured the bidirectional reflectance of analogs of dry, wet, and frozen Martian soils over a wide range of phase angles in the visible spectral range. All samples were produced from two geologic samples: the standard JSC Mars-1 soil simulant and Hawaiian basaltic sand. In a first step, experiments were conducted with the dry samples to investigate the effects of surface texture. Comparisons with results independently obtained by different teams with similar samples showed a satisfying reproducibility of the photometric measurements as well as a noticeable influence of surface textures resulting from different sample preparation procedures. In a second step, water was introduced to produce wet and frozen samples and their photometry investigated. Optical microscope images of the samples provided information about their microtexture. Liquid water, even in relatively low amount, resulted in the disappearance of the backscattering peak and the appearance of a forward-scattering peak whose intensity increases with the amount of water. Specular reflections only appeared when water was present in an amount large enough to allow water to form a film at the surface of the sample. Icy samples showed a wide variability of photometric properties depending on the physical properties of the water ice. We discuss the implications of these measurements in terms of the expected photometric behavior of the Martian surface, from equatorial to circum-polar regions. In particular, we propose some simple photometric criteria to improve the identification of wet and/or icy soils from multiple observations under different geometries.

Petrogenesis of rift-related tephrites, phonolites and trachytes (Central European Volcanic Province, Rhon, FRG): Constraints from Sr, Nd, Pb and O isotopes

The volcanic rocks of the Rhön area (Central European Volcanic Province, Germany) belong to a moderately alkali basaltic suite that is associated with minor tephriphonolites, phonotephrites, tephrites, phonolites and trachytes. Based on isotope sytematics (87Sr/86Sr: 0.7033–0.7042; 143Nd/144Nd: 0.51279–0.51287; 206Pb/204Pb: 19.1–19.5), the inferred parental magmas formed by variable degrees of partial melting of a common asthenospheric mantle source (EAR: European Asthenospheric Reservoir of Cebriá and Wilson, 1995). Tephrites, tephriphonolites, phonotephrites, phonolites and trachytes show depletions and enrichments in some trace elements (Sr, Ba, Nb, Zr, Y) indicating that they were generated by broadly similar differentiation processes that were dominated by fractionation of olivine, clinopyroxene, amphibole, apatite and titaniferous magnetite ± plagioclase ± alkalifeldspar. The fractionated samples seem to have evolved by two distinct processes. One is characterized by pure fractional crystallization indicated by increasing Nb (and other incompatible trace element) concentrations at virtually constant 143Nd/144Nd ~ 0.51280 and 87Sr/86Sr ~ 0.7035. The other process involved an assimilation–fractional crystallization (AFC) process where moderate assimilation to crystallization rates produced evolved magmas characterized by higher Nb concentrations at slightly lower 143Nd/144Nd down to 0.51275. Literature data for some of the evolved rocks show more variable 87Sr/86Sr ranging from 0.7037 to 0.7089 at constant 143Nd/144Nd ~ 0.51280. These features may result from assimilation of upper crustal rocks by highly differentiated low-Sr (< 100 ppm Sr) lavas. However, based on the displacement of the differentiated rocks from this study towards lower 143Nd/144Nd ratios and modeled AFC processes in 143Nd/144Nd vs. 87Sr/86Sr and 207Pb/204Pb vs. 143Nd/144Nd space assimilation of lower crustal rocks seems more likely. The view that assimilation of lower crustal rocks played a role is confirmed by high-precision double-spike Pb isotope data that reveal higher 207Pb/204Pb ratios (15.62–15.63) in the differentiated rocks than in the primitive basanites (15.58–15.61). This is compatible with incorporation of radiogenic Pb from lower crustal xenoliths (207Pb/204Pb: 15.63–15.69) into the melt. However, 206Pb/204Pb ratios are similar for the differentiated rocks (19.13–19.35) and the primitive basanites (19.12–19.55) implying that assimilation involved an ancient crustal end member with a higher U/Pb ratio than the mantle source of the basanites. In addition, alteration-corrected δ18O values of the differentiated rocks range from c. 5 to 7‰ which is the same range as observed in the primitive alkaline rocks. This study confirms previous interpretations that highlighted the role of AFC processes in the evolution of alkaline volcanic rocks in the Rhön area of the Central European Volcanic Province.

The structure of the asteroid 4 Vesta as revealed by models of planet-scale collisions

Asteroid 4Vesta seems to be a major intact protoplanet, with a surface composition similar to that of the HED (howardite-eucrite-diogenite) meteorites. The southern hemisphere is dominated by a giant impact scar, but previous impact models have failed to reproduce the observed topography. The recent discovery that Vesta's southern hemisphere is dominated by two overlapping basins provides an opportunity to model Vesta's topography more accurately. Here we report three-dimensional simulations of Vesta's global evolution under two overlapping planet-scale collisions. We closely reproduce its observed shape, and provide maps of impact excavation and ejecta deposition. Spiral patterns observed in the younger basin Rheasilvia, about one billion years old, are attributed to Coriolis forces during crater collapse. Surface materials exposed in the north come from a depth of about 20kilometres, according to our models, whereas materials exposed inside the southern double-excavation come from depths of about 60-100kilometres. If Vesta began as a layered, completely differentiated protoplanet, then our model predicts large areas of pure diogenites and olivine-rich rocks. These are not seen, possibly implying that the outer 100kilometres or so of Vesta is composed mainly of a basaltic crust (eucrites) with ultramafic intrusions (diogenites).

High exchangeable calcium concentrations in soils on Barro Colorado Island, Panama

The soils on four lithologies (basaltic conglomerates, Bohio; Andesite; volcanoclastic sediments with basaltic agglomerates, Caimito volcanic; foraminiferal limestone, Caimito marine) on Barro Colorado Island (BCI) have high exchangeable Ca concentrations and cation-exchange capacities (CEC) compared to other tropical soils on similar parent material. In the 0–10 cm layer of 24 mineral soils, pH values ranged from 5.7 (Caimito volcanic and Andesite) to 6.5 (Caimito marine), concentrations of exchangeable Ca from 134 mmolc kg− 1 (Caimito volcanic) to 585 mmolc kg− 1 (Caimito marine), and cation exchange capacities from 317 mmolc kg− 1 (Caimito volcanic) to 933 mmolc kg− 1 (Caimito marine). X-ray diffractometry of the fraction < 2 μm revealed that smectites dominated the clay mineral assemblage in soil except on Caimito volcanic, where kaolinite was the dominant clay mineral. Exchangeable Ca concentrations decreased with increasing soil depth except on Caimito marine. The weathering indices Chemical Index of Alteration (CIA), Plagioclase Index of Alteration (PIA) and Weathering Index of Parker (WIP) determined for five soils on all geological formations, suggested that in contrast to expectation the topsoil (0–10 cm) appeared to be the least and the subsoil (50–70 cm) and saprolite (isomorphically weathered rock in the soil matrix) the most weathered. Additionally, the weathering indices indicated depletion of base cations and enrichment of Al-(hydr)oxides throughout the soil profile. Tree species did not have an effect on soil properties. Impeded leaching and the related occurrence of overland flow seem to be important in determining clay mineralogy. Our results suggest that (i) edaphic conditions favor the formation of smectites on most lithologies resulting in high CEC and thus high retention capacity for Ca and (ii) that there is an external source such as dust or sea spray deposition supplying Ca to the soils.

Magma Extraction from the Mantle Wedge at Convergent Margins Through Dikes: A Parametric Sensitivity Analysis

We address under what conditions a magma generated by partial melting at 100 km depth in the mantle wedge above a subduction zone can reach the crust in dikes before stalling. We also address under what conditions primitive basaltic magma (Mg # >60) can be delivered from this depth to the crust. We employ linear elastic fracture mechanics with magma solidification theory and perform a parametric sensitivity analysis. All dikes are initiated at a depth of 100 km in the thermal core of the wedge, and the Moho is fixed at 35 km depth. We consider a range of melt solidus temperatures (800-1100 degrees C), viscosities (10-100 Pa s), and densities (2400-2700 kg m(-3)). We also consider a range of host rock fracture toughness values (50-300 MPa m(1/2)) and dike lengths (2-5 km) and two thermal structures for the mantle wedge (1260 and 1400 degrees C at 100 km depth and 760 and 900 degrees C at 35 km depth). For the given parameter space, many dikes can reach the Moho in less than a few hundred hours, well within the time constraints provided by U series isotope disequilibria studies. Increasing the temperature in the mantle wedge, or increasing the dike length, allows additional dikes to propagate to the Moho. We conclude that some dikes with vertical lengths near their critical lengths and relatively high solidus temperatures will stall in the mantle before reaching the Moho, and these may be returned by corner flow to depths where they can melt under hydrous conditions. Thus, a chemical signature in arc lavas suggesting partial melting of slab basalts may be partly influenced by these recycled dikes. Alternatively, dikes with lengths well above their critical lengths can easily deliver primitive magmas to the crust, particularly if the mantle wedge is relatively hot. Dike transport remains a viable primary mechanism of magma ascent in convergent tectonic settings, but the potential for less rapid mechanisms making an important contribution increases as the mantle temperature at the Moho approaches the solidus temperature of the magma.

A tephra lattice for Greenland and a reconstruction of volcanic events spanning 25–45 ka b2k

Tephra layers preserved within the Greenland ice-cores are crucial for the independent synchronisation of these high-resolution records to other palaeoclimatic archives. Here we present a new and detailed tephrochronological framework for the time period 25,000 e 45,000 a b2k that brings together results from 4 deep Greenland ice-cores. In total, 99 tephra deposits, the majority of which are preserved as cryptotephra, are described from the NGRIP, NEEM, GRIP and DYE-3 records. The major element signatures of single glass shards within these deposits indicate that 93 are basaltic in composition all originating from Iceland. Specifically, 43 originate from Grimsv € otn, 20 are thought to be sourced from the Katla volcanic system and 17 show affinity to the Kverkfj € oll system. Robust geochemical characterisations, independent ages derived from the GICC05 ice-core chronology, and the stratigraphic positions of these deposits relative to the Dansgaard-Oeschger climate events represent a key framework that provides new information on the frequency and nature of volcanic events in the North Atlantic region between GS-3 and GI-12. Of particular importance are 19 tephra deposits that lie on the rapid climatic transitions that punctuate the last glacial period. This framework of well-constrained, time-synchronous tie-lines represents an important step towards the independent synchronisation of marine, terrestrial and ice-core records from the North Atlantic region, in order to assess the phasing of rapid climatic changes during the last glacial period.

Volcanostratigraphic Controls on the Occurrence of Massive Sulfide (VMS) Deposits in the Semail Ophiolite, Oman

The Semail ophiolite in Oman is capped by up to 2 km of basaltic-andesitic lavas that host copper-dominant, Cyprus-type, volcanogenic massive sulfide (VMS) deposits. This study identifies multiple volcanostratigraphic horizons on which the deposits are situated, based on characterization of footwall and hanging-wall lavas from 16 deposits or deposit clusters. Comparison of field and petrographic features, compositions of igneous clinopyroxenes, and whole-rock geochemical signatures permits classification of the lavas within a modified version of the established regional volcanostratigraphy. Four extrusive units host deposits: Geotimes (earliest), Lasail, Alley, and Boninitic Alley (latest). The latter was previously known only at few localities, but this study reveals its regional extent and significance as a host for VMS deposits. The Geotimes and Lasail units represent Late Cretaceous, ocean spreading ridge and related off-axis volcanic environments, respectively. The Alley and Boninitic Alley units represent younger, subduction-related volcanism prior to Coniacian-Santonian obduction of the ophiolite. Our results show that VMS deposits occur on or near the Geotimes/Lasail and Geotimes/Alley contacts as well as entirely within the Geotimes, Lasail, Alley, and Boninitic Alley units. Highest Cu grades tend to occur in deposits lying on or within the Geotimes, whereas highest Au grades occur in deposits within the Boninitic Alley. In contrast to earlier studies, we conclude that essentially every horizon marking a hiatus in lava deposition in the Semail ophiolite, i.e., contacts between the four major eruptive units, and umbers and sedimentary chert layers within the units, has exploration potential for Cu-Au VMS deposits.

Eclogitic diamonds from variable crustal protoliths in the northeastern Siberian craton: trace elements and coupled δ13C – δ18O signatures in diamonds and garnet inclusions

Diamonds of eclogitic assemblages are dominant in the placer diamond deposits of the northeastern Siberian platform. In this study we present new trace elements and stable isotopes (δ13C and δ18O) data for alluvial diamonds and their garnet inclusions from this locality. Cr-rich garnets of peridotitic affinity in the studied diamonds have a narrow range of δ18O values from 5.7‰ to 6.2‰, which is largely overlapping with the accepted mantle range. This narrow range suggests that the garnet inclusions showing different REE patterns and little variations in oxygen isotopes may have formed by different processes involving fluid/melts that, however, were in oxygen isotopic equilibrium with the mantle. The trace element composition of the eclogitic garnet inclusions supports a crustal origin for at least the high-Ca garnets, which show flat HREE patterns and in some cases a positive Eu-anomaly. High-Ca eclogitic garnets generally show heavier oxygen isotope compositions (δ18O 6.5–9.6‰) than what is observed in low-Ca garnets (δ18O 5.7–7.4‰). The variability in oxygen isotopes and trace elements is suggested to be inherited from contrasting crustal protoliths. The relationship between the high δ18O values of inclusions and the low δ13C values of the host diamonds implies that the high-Ca garnet inclusions were derived from intensely hydrated (e.g., δ18O > 7‰) and typically oxidised basaltic rock close to the seawater interface, and that the carbon for diamonds was closely associated with this protolith.

A systematic evaluation of the Zr-in-rutile thermometer in ultra-high temperature (UHT) rocks

The Zr-in-rutile geothermometer is potentially a widely applicable tool to estimate peak metamorphic temperatures in rocks from diverse geological settings. In order to evaluate its usefulness and reliability to record and preserve high temperatures in granulite facies rocks, rutile from UHT rocks was investigated to assess different mechanisms of Zr (re-)distribution following cooling from high temperature. Granulite facies paragneisses from the lowermost part of the Ivrea Zone, Italy, incorporated as thin sheets into the extensive basaltic body of the Mafic Complex were selected for this study. The results show that Zr-in-rutile thermometry, if properly applied, is well suited to identify and study UHT terranes as it preserves a record of temperatures up to 1190 °C, although the thermometer is susceptible to partial post-peak metamorphic resetting by Zr diffusion. Texturally homogeneous rutile grains preserve Zr concentrations corresponding to temperatures of prograde rutile growth. Diverse rutile textures and relationships between some rutile host grains and included or adjacent Zr-bearing phases bear testimony to varying mechanisms of partial redistribution and resetting of Zr in rutile during cooling and link Zr-in-rutile temperatures to different steps of the metamorphic evolution. Rutile grains that equilibrated their Zr concentrations at temperatures above 1070 °C (i.e. 1.1 wt% Zr) could not retain all Zr in the rutile structure during cooling and exsolved baddeleyite (ZrO2). By subsequent reaction of baddeleyite exsolution lamellae with SiO2, zircon needles formed before the system finally closed at 650–700 °C without significant net loss of Zr from the whole host rutile grain. By reintegration of zircon exsolution needles, peak metamorphic temperatures of up to 1190 °C are derived for the studied rocks, which demonstrates the suitability of this solution thermometer to record UHT conditions and also confirms the extraordinary geological setting of the lowermost part of the Ivrea Zone.