Gaseous transport and deposition of gold in magmatic fluid: evidence from the active Kudryavy volcano, Kurile Islands

The distribution of gold in high-temperature fumarole gases of the Kudryavy volcano (Kurile Islands) was measured for gas, gas condensate, natural fumarolic sublimates, and precipitates in silica tubes from vents with outlet temperatures ranging from 380 to 870°C. Gold abundance in condensates ranges from 0.3 to 2.4 ppb, which is significantly lower than the abundances of transition metals. Gold contents in zoned precipitates from silica tubes increase gradually with a decrease in temperature to a maximum of 8 ppm in the oxychloride zone at a temperature of approximately 300°C. Total Au content in moderate-temperature sulfide and oxychloride zones is mainly a result of Au inclusions in the abundant Fe–Cu and Zn sulfide minerals as determined by instrumental neutron activation analysis. Most Au occurs as a Cu–Au–Ag triple alloy. Single grains of native gold and binary Au–Ag alloys were also identified among sublimates, but aggregates and crystals of Cu–Au–Ag alloy were found in all fumarolic fields, both in silica tube precipitates and in natural fumarolic crusts. Although the Au triple alloy is homogeneous on the scale of microns and has a composition close to (Cu,Ni,Zn)₃(Au,Ag)₂, transmission electron microscopy (TEM) shows that these alloy solid solutions consist of monocrystal domains of Au–Ag, Au–Cu, and possibly Cu₂O. Gold occurs in oxide assemblages due to the decomposition of its halogenide complexes under high-temperature conditions (650–870°C). In lower temperature zones (<650°C), Au behavior is related to sulfur compounds whose evolution is strongly controlled by redox state. Other minerals that formed from gas transport and precipitation at Kudryavy volcano include garnet, aegirine, diopside, magnetite, anhydrite, molybdenite, multivalent molybdenum oxides (molybdite, tugarinovite, and ilsemannite), powellite, scheelite, wolframite, Na–K chlorides, pyrrhotite, wurtzite, greenockite, pyrite, galena, cubanite, rare native metals (including Fe, Cr, Mo, Sn, Ag, and Al), Cu–Zn–Fe–In sulfides, In-bearing Pb–Bi sulfosalts, cannizzarite, rheniite, cadmoindite, and kudriavite. Although most of these minerals are fine-grained, they are strongly idiomorphic with textures such as gas channels and lamellar, banded, skeletal, and dendrite-like crystals, characteristic of precipitation from a gas phase. The identified textures and mineral assemblages at Kudryavy volcano can be used to interpret geochemical origins of both ancient and modern ore deposits, particularly gold-rich porphyry and related epithermal systems.     

Immiscible silicate liquid partition coefficients: implications for crystal-melt element partitioning and basalt petrogenesis

This study investigates partitioning of elements between immiscible aluminosilicate and borosilicate liquids using three synthetic mixtures doped with 32 trace elements. In order to get a good spatial separation of immiscible liquids, we employed a high-temperature centrifuge. Experiments were performed at 1,050–1,150°C, 1 atm, in sealed Fe and Pt containers. Quenched products were analysed by electron microprobe and LA ICP-MS. Nernst partition coefficients (D’s) between the Fe-rich and Si-rich aluminosilicate immiscible liquids are the highest for Zn (3.3) and Fe (2.6) and the lowest for Rb and K (0.4–0.5). The plots of D values against ionic potential Z/r in all the compositions show a convex upward trend, which is typical also for element partitioning between immiscible silicate and salt melts. The results bear upon the speciation and structural position of elements in multicomponent silicate liquids. The ferrobasalt–rhyolite liquid immiscibility is observed in evolved basaltic magmas, and may play an important role in large gabbroic intrusions, such as Skaergaard, and during the generation of unusual lavas, such as ferropicrites.     

U–Pb zircon geochronology of silicic tuffs from the Timber Mountain/Oasis Valley caldera complex, Nevada: rapid generation of large volume magmas by shallow-level remelting

Large volumes of silicic magma were produced on a very short timescale in the nested caldera complex of the SW Nevada volcanic field (SWNVF). Voluminous ash flows erupted in two paired events: Topopah Spring (TS, >1,200 km³, 12.8 Ma)–Tiva Canyon (TC, 1,000 km³, 12.7 Ma) and Rainier Mesa (RM, 1,200 km³, 11.6 Ma)–Ammonia Tanks (AT, 900 km³, 11.45 Ma; all cited ages are previously published ⁴⁰Ar/³⁹Ar sanidine ages). Within each pair, eruptions are separated by only 0.1–0.15 My and produced tuffs with contrasting isotopic values. These events represent nearly complete evacuation of sheet-like magma chambers formed in the extensional Basin and Range environment. We present ion microprobe ages from zircons in the zoned ash-flow sheets of TS, TC, RM, and AT in conjunction with δ¹⁸O values of zircons and other phenocrysts, which differ dramatically among subsequently erupted units. Bulk zircons in the low-δ¹⁸O AT cycle were earlier determined to exhibit ∼1.5‰ core-to-rim oxygen isotope zoning; and high-spatial resolution zircon analyses by ion microprobe reveal the presence of older grains that are zoned by 0.5–2.5‰. The following U–Pb isochron ages were calculated after correcting for the initial U–Pb disequilibria: AT (zircon rims: 11.7 ± 0.2 Ma; cores: 12.0 ± 0.1 Ma); pre-AT rhyolite lava: (12.0 ± 0.3 Ma); RM: 12.4 ± 0.3); TC: (13.2 ± 0.15 Ma); TS: (13.5 ± 0.2). Average zircon crystallization ages calculated from weighted regression or cumulative averaging are older than the Ar–Ar stratigraphy, but preserve the comparably short time gaps within each of two major eruption cycles (TS/TC, RM/AT). Notably, every sample yields average zircon ages that are 0.70–0.35 Ma older than the respective Ar–Ar eruption ages. The Th/U ratio of SWNVF zircons are 0.4–4.7, higher than typically found in igneous zircons, which correlates with elevated Th/U of the whole rocks (5–16). High Th/U could be explained if uranium was preferentially removed by hydrothermal solutions or is retained in the protolith during partial melting. For low-δ¹⁸O AT-cycle magmas, rim ages from unpolished zircons overlap within analytical uncertainties with the ⁴⁰Ar/³⁹Ar eruption age compared to core ages that are on average ∼0.2–0.3 My older than even the age of the preceding caldera forming eruption of RM tuff. This age difference, the core-to-rim oxygen isotope zoning in AT zircons, and disequilibrium quartz–zircon and melt-zircon isotopic fractionations suggest that AT magma recycled older zircons derived from the RM and older eruptive cycles. These results suggest that the low-δ¹⁸O AT magmas were generated by melting a hydrothermally-altered protolith from the same nested complex that erupted high-δ¹⁸O magmas of the RM cycle only 0.15 My prior to the eruption of the AT, the largest volume low-δ¹⁸O magma presently known.Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Radar facies of paraglacial barrier systems: coastal New England, USA

Analysis of a large data base of ground-penetrating-radar (GPR) profiles from both natural and developed paraglacial barriers along the coast of New England has allowed identification of eight reflection configurations that characterize this type of mid- to high-latitude coastal environment. Bedrock anchor points yield primarily hyperbolic configurations, whereas glacial anchor points and sediment-source areas are characterized by chaotic, parallel, and tangential-oblique configurations. Beaches and dunes produce predominantly sigmoidal oblique, hummocky, reflection-free, and bounding-surface configurations. Back-barrier sediments may yield basin-fill configurations, but generally include abundant signal-attenuating units.
The GPR data, calibrated with information from cores, were collected across swash-aligned and drift-aligned barriers in a variety of wave- and tidal-energy settings. Application of a 120-MHz antenna, as used in this study, enables portrayal of a range of sedimentary units, from individual bedforms (on single records) to entire barrier elements (using large numbers of intersecting GPR sections), at maximum vertical resolutions that vary between 0·2 m and 0·7 m.
The most important drawback of GPR in the coastal environment is attenuation of the electromagnetic (EM) signal by layers of salt-marsh peat or by brackish or salty groundwater, primarily along barrier edges. This disadvantage is offset by many benefits. Data can be collected at rates of several km per day, making GPR an excellent reconnaissance tool. A core that is used in the calibration of GPR data can be matched with great accuracy to its position on the complementary GPR record, allowing detailed correlation between lithostratigraphy and reflection configuration.     

Liquid immiscibility and its role at the magmatic–hydrothermal transition: a summary of experimental studies

Several types of fluid immiscibility may affect the evolution of volatile-rich magmatic systems at the magmatic–hydrothermal transition. The topology of silicate–salt–H₂O systems implies that three-fluid immiscibility (silicate melt+hydrosaline melt+vapour) should be stable in a broad range of compositions and P–T conditions. The most important factor controlling the immiscibility appears to be the Coulombic properties (electric charges Z and ionic radii r) of the main network-modifying cations and the capacity for immiscibility appears to decrease in the following sequence: Mg>Ca>Sr>Ba>Li>Na>K. Liquid immiscibility is enhanced in peralkaline compositions and in the presence of nonsilicate anions such as F⁻, Cl⁻, CO₃²⁻ and BO₃³⁻. In volatile-rich magmatic systems, the H₂O is likely to react with the chloride, fluoride, borate and carbonate species and the chemical effects of high-temperature hydrolysis may be greatly enhanced by phase separation in systems with multiple immiscible fluid phases. Natural granitic magmas can thus exsolve a range of chemically and physically diverse hydrosaline liquids and the role of these fluid phases is likely to be especially significant in pegmatites and Li–F rare-metal granites.     

Seismic characterization of vertical fractures described as general linear-slip interfaces

Fluid flow in many hydrocarbon reservoirs is controlled by aligned fractures which make the medium anisotropic on the scale of seismic wavelength. Applying the linear‐slip theory, we investigate seismic signatures of the effective medium produced by a single set of ‘general’ vertical fractures embedded in a purely isotropic host rock. The generality of our fracture model means the allowance for coupling between the normal (to the fracture plane) stress and the tangential jump in displacement (and vice versa). Despite its low (triclinic) symmetry, the medium is described by just nine independent effective parameters and possesses several distinct features which help to identify the physical model and estimate the fracture compliances and background velocities. For example, the polarization vector of the vertically propagating fast shear wave S₁ and the semi‐major axis of the S₁‐wave normal‐moveout (NMO) ellipse from a horizontal reflector always point in the direction of the fracture strike. Moreover, for the S₁‐wave both the vertical velocity and the NMO velocity along the fractures are equal to the shear‐wave velocity in the host rock. Analysis of seismic signatures in the limit of small fracture weaknesses allows us to select the input data needed for unambiguous fracture characterization. The fracture and background parameters can be estimated using the NMO ellipses from horizontal reflectors and vertical velocities of P‐waves and two split S‐waves, combined with a portion of the P‐wave slowness surface reconstructed from multi‐azimuth walkaway vertical seismic profiling (VSP) data. The stability of the parameter‐estimation procedure is verified by performing non‐linear inversion based on the exact equations.     

Is natrocarbonatite a cognate fluid condensate?

Natrocarbonatite flows in the crater of the volcano Oldoinyo Lengai (Tanzania) are the only carbonatite magmas observed to erupt and have provided strong arguments in favor of a magmatic origin for carbonatite. The currently favored explanation for the genesis of these carbonatites by liquid immiscibility between a silicate and a carbonatite melt is questioned based on the extremely low eruption temperatures of 544-593 °C and compositional and mineralogical characteristics not in agreement with experimental constraints. Experimental investigations of the relationship between Oldoinyo Lengai natrocarbonatite and related silicate rock compositions do indicate that alkali-bearing peralkaline carbonatite with liquidus calcite can form by liquid immiscibility. At the same time, these experiments result in evidence which speaks against a liquid immiscibility origin for the highly alkaline and peralkaline Oldoinyo Lengai natrocarbonatite. On the carbonatite side of the miscibility gap, fractional crystallization cannot account for a liquid evolution from alkali-bearing peralkaline carbonatite to highly alkaline natrocarbonatite. Such an evolution does not seem to be compatible with the liquidus mineral assemblages and the chemistry of Oldoinyo Lengai natrocarbonatite. No natural silicate magma is known to produce natrocarbonatite compositions by liquid immiscibility. The best interpretation of the Oldoinyo Lengai natrocarbonatite flows involves expulsion of a cognate, mobile, alkaline, and CO₂-rich fluid condensate. This conclusion is supported by recent studies of silicate and carbonatite melt inclusions in minerals of ultramafic alkaline complexes, trace element partitioning, isotopic constraints, and by experimental data on major element partitioning between coexisting H₂O-CO₂-rich fluid and carbonatitic melt. In contrast to all other suggested modes of formation, an origin of Oldoinyo Lengai natrocarbonatite from cognate fluid appears best to be in agreement with the field observations, the petrography, mineralogy, and geochemistry of Oldoinyo Lengai natrocarbonatite and the dynamics of the Oldoinyo Lengai natrocarbonatite extrusion.     

3D waveform inversion of downhole microseismic data for transversely isotropic media

3D anisotropic waveform inversion could provide high-resolution velocity models and improved event locations for microseismic surveys. Here we extend our previously developed 2D inversion methodology for microseismic borehole data to 3D transversely isotropic media with a vertical symmetry axis. This extension allows us to invert multicomponent data recorded in multiple boreholes and properly account for vertical and lateral heterogeneity. Synthetic examples illustrate the performance of the algorithm for layer-cake and ‘hydraulically fractured’ (i.e. containing anomalies that simulate hydraulic fractures) models. In both cases, waveform inversion is able to reconstruct the areas which are sufficiently illuminated for the employed source-receiver geometry. In addition, we evaluate the sensitivity of the algorithm to errors in the source locations and to band-limited noise in the input displacements. We also present initial inversion results for a microseismic data set acquired during hydraulic fracturing in a shale reservoir.     

Image-domain wavefield tomography for tilted transversely isotropic media

Transversely isotropic models with a tilted symmetry axis have become standard for imaging beneath dipping shale formations and in active tectonic areas. Here, we develop a methodology of wave-equation-based image-domain tomography for acoustic tilted transversely isotropic media. We obtain the gradients of the objective function using an integral wave-equation operator based on a separable dispersion relation that takes the symmetry-axis tilt into account. In contrast to the more conventional differential solutions, the integral operator produces only the P-wavefield without shear-wave artefacts, which facilitates both imaging and velocity analysis. The model is parameterized by the P-wave zero-dip normal-moveout velocity, the Thomsen parameter δ, anellipticity coefficient η and the symmetry-axis tilt θ. Assuming that the symmetry axis is orthogonal to reflectors, we study the influence of parameter errors on energy focusing in extended (space-lag) common-image gathers. Distortions in the anellipticity coefficient η introduce weak linear defocusing regardless of reflector dip, whereas δ influences both the energy focusing and depth scale of the migrated section. These results, which are consistent with the properties of the P-wave time-domain reflection moveout in tilted transversely isotropic media, provide important insights for implementation of velocity model-building in the image-domain. Then the algorithm is tested on a modified anticline section of the BP 2007 benchmark model.     

Effective Rigidity of a Polar Neutron Monitor for Recording Ground-Level Enhancements

The “effective” rigidity of a neutron monitor for a ground-level enhancement (GLE) event is defined so that the event-integrated fluence of solar energetic protons with rigidity above it is directly proportional to the integral intensity of the GLE as recorded by a polar neutron monitor, within a wide range of solar energetic-proton spectra. This provides a direct way to assess the integral fluence of a GLE event based solely on neutron-monitor data. The effective rigidity/energy was found to be 1.13?–?1.42 GV (550?–?800 MeV). A small model-dependent, systematic uncertainty in the value of the effective rigidity is caused by uncertainties in the low-energy range of the neutron-monitor yield function, which requires more detailed computations of the latter.