Weathering, dust, and biocycling effects on soil silicon isotope ratios

Silicon isotope ratios (δ³⁰Si) of bulk mineral materials in soil integrate effects from both silicon sources and processing. Here we report δ³⁰Si values from a climate gradient of Hawaiian soils developed on 170 ka basalt and relate them to patterns of soil chemistry and mineralogy. The results demonstrate informative relationships between the mass fraction of soil Si depletion and δ³⁰Si. In upper (<1 m deep) soil horizons along the climate gradient, Si depletion correlates with decreases of residual δ³⁰Si values in low rainfall soils and increases in high rainfall soils. Strong positive correlation between soil δ³⁰Si and dust-derived quartz and mica content show that both trends are largely controlled by the abundance of these weathering-resistant minerals. The data also lend support to the idea that fractionation of Si isotopes in secondary phases is controlled by partitioning of silicon between dissolved and precipitated products during the initial weathering of primary basalt. Secondary mineral δ³⁰Si values from lower (>1 m deep) soil horizons generally correlate with the isotope fractionation predicted by a study of dissolved Si in basalt-watershed rivers and driven by preferential ²⁸Si removal from the dissolved phase during precipitation. In contrast, after correcting for the influence of dust, secondary mineral Si depletion and δ³⁰Si values in shallow (<1 m deep) soil horizons showed evidence of biocycling induced Si redistribution and substantially lower δ³⁰Si values than predicted. Low δ³⁰Si values in shallow soil horizons compared to predictions can be attributed to repeated fractionation as secondary minerals undergo additional cycles of dissolution and precipitation. Primary mineral weathering, secondary mineral weathering, dust accumulation, and biocycling are major processes in terrestrial Si cycling and these results demonstrate that each can be traced by δ³⁰Si values interpreted in conjunction with mineralogy and measures of Si depletion.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Internal control of fluid compositions in amphibolite-facies scapolitic calc-silicates,Mary Kathleen,Australia

Unaltered metasediments of the Mary Kathleen Fold Belt are composed predominantly of layered amphibolite-facies scapolitic calc-silicate rocks in which minimal infiltration of externally derived fluids occurred during regional metamorphism. There were substantial differences in volatile activities between different layers in the layered sequences, in particular: a _CO2/a _{H 2 O} inferred from reaction progress estimates and analysis of biotite-clinopyroxene-fluid phase relations; a _NaCl/a _{H 2 O} inferred from scapolite compositions; and a _HCl/a _{H 2 O} inferred from biotite compositions. In one outcrop in which a clinopyroxene-producing reaction dominated, differences in approximate X _{CO 2}of up to 0.25 occurred between several samples collected over 50 metres. Variations in a _{H 2 O}/a _HCl of up to one order of magnitude are inferred at 1 to 50 m scales from biotite-Cl contents, and variations in NaCl contents of scapolite from 0.0 to up to 0.6 Cl atoms in the Cl–CO₃–SO₄ site reflect a large variation of a _NaCl in the coexisting fluid at similar scales. Most calcsilicate layers internally buffered fluid compositions in the H₂O–CO₂–NaCl–HCl system. Local occurrences of NaCl-rich scapolite suggest that some layers may have been in equilibrium with halite during early prograde metamorphism. At peak metamorphic temperatures, disolution of halite was complete but layers containing high-NaCl scapolite continued to buffer fluid at high values of a _NaCl. Fluid immiscibility does not appear to have affected the progress of the devolatilization reactions. Although fluid was predominantly internally buffered, moderate quantities of fluid were released by prograde mineral reactions in many layers, up to 30 cm³ fluid per 100 cm³ rock. Numerous episodes of fluid escape were required, probably via microfractures, such that the released fluid did not obviously influence reaction progress in the layers through which it passed. The anomaly of beautifully preserved internal buffering signatures and the requirement for produced fluid locally to pass across layers in a deforming rock sequence suggest that the escaping fluid did not leave any readily observable tracks. This is explained by rapid rates of fracture propogation and fluid migration therein. This internally buffered system contrasts strongly with adjacent calc-silicate rocks that show evidence for infiltration of externally derived fluids at high fluid/rock ratios, and highlights the broad range of fluid behaviour that can be expected in deforming, heterogeneous rock sequences.     

Short-term analysis of GNSS clocks

A characterization of the short-term stability of the atomic frequency standards onboard GNSS satellites is presented. Clock performance is evaluated using two different methods. The first method derives the temporal variation of the satellite’s clock from a polynomial fit through 1-way carrier-phase measurements from a receiver directly connected to a high-precision atomic frequency standard. Alternatively, three-way measurements using inter-station single differences of a second satellite from a neighboring station are used if the receiver’s clock stability at the station tracking the satellite of interest is not sufficient. The second method is a Kalman-filter-based clock estimation based on dual-frequency pseudorange and carrier-phase measurements from a small global or regional tracking network. Both methods are introduced and their respective advantages and disadvantages are discussed. The analysis section presents a characterization of GPS, GLONASS, GIOVE, Galileo IOV, QZSS, and COMPASS clocks based on these two methods. Special focus has been set on the frequency standards of new generation satellites like GPS Block IIF, QZSS, and IOV as well as the Chinese COMPASS/BeiDou-2 system. The analysis shows results for the Allan deviation covering averaging intervals from 1 to 1,000 s, which is of special interest for real-time PPP and other high-rate applications like processing of radio-occultation measurements. The clock interpolation errors for different sampling rates are evaluated for different types of clocks and their effect on PPP is discussed.     

Do S-type granites commonly sample infracrustal sources? New results from an integrated O, U–Pb and Hf isotope study of zircon

In contrast to I-type granites, which commonly comprise infracrustal and supracrustal sources, S-type granites typically incorporate predominantly supracrustal sources. The initial aim of this study was to identify the sources of three Scottish Caledonian (~460 Ma) S-type granites (Kemnay, Cove and Nigg Bay) by conducting oxygen, U–Pb and Hf isotope analyses in zircon in order to characterise one potential end-member magma involved in the genesis of the voluminous late Caledonian (~430–400 Ma) I-type granites. Field, whole-rock geochemical and isotopic data are consistent with the generation of the S-type granites by melting their Dalradian Supergroup country rocks. While Hf isotope compositions of magmatic zircon, U–Pb data of inherited zircons, and high mean zircon δ¹⁸O values of 9.0 ± 2.7‰ (2SD) and 9.8 ± 2.0‰ for the Kemnay and Cove granites support this model, the Nigg Bay Granite contains zircons with much lower δ¹⁸O values (6.8 ± 2.1‰), similar to those found in Scottish I-type granites. This suggests that the Nigg Bay Granite contains low-δ¹⁸O material representing either altered supracrustal material, or more likely, an infracrustal source component with mantle-like δ¹⁸O. Mixing trends in plots of δ¹⁸O vs. εHf for S-type granite zircons indicate involvement of at least two sources in all three granites. This pilot study of Scottish Caledonian S-type granites demonstrates that, while field and whole-rock geochemical data are consistent with local melting of only supracrustal sources, the oxygen isotopic record stored in zircon reveals a much more complex petrogenetic evolution involving two or more magma sources.     

Relativistic reflection X-ray spectra of accretion disks

We have calculated the relativistic reflection component of the X-ray spectra of accretion disks in active galactic nuclei (AGN). Our calculations have shown that the spectra can be significantly modified by the motion of the accretion flow, and the gravity and rotation of the central black hole. The absorption edges in the spectra suffer severe en- ergy shifts and smearing, and the degree of distortion depends on the system parameters, in particular, the inner radius of the accretion disk and the disk viewing inclination angles. The effects are significant. Fluorescent X-ray emission lines from the inner accretion disk could be a powerful diagnostic of space-time distortion and dynamical relativistic effects near the event horizons of accreting black holes. However, improper treatment of the re- flection component in fitting the X-ray continuum could give rise to spurious line-like features. These features mimic the true fluorescent emission lines and may mask their relativistic signatures. Fully relativistic models for reflection continua together with the emission lines are needed in order to extract black-hole parameters from the AGN X-ray spectra.     

Simulation of moisture content in alpine rockwalls during freeze–thaw events

Rock moisture during freeze–thaw events is a key factor for frost weathering. Data on moisture levels of natural rockwalls are scarce and difficult to obtain. To close this gap, we can benefit from the extensive knowledge of moisture‐related phenomena in building materials, which is incorporated into simulation software, for example the WUFI® package of the Fraunhofer Institute of Building Physics. In this paper we applied and adapted this type of simulation to natural rockwalls to gain new insights on which moisture‐related weathering mechanisms may be important under which conditions. We collected the required input data on physical rock properties and local climate for two study areas in the eastern European Alps with different elevation [Sonnblick, 3106 m above sea level (a.s.l.) and Johnsbach, 700 m a.s.l.] and different lithologies (gneiss and dolomite, respectively). From this data, moisture profiles with depth and fluctuations in the course of a typical year were calculated. The results were cross‐checked with different thermal conditions for frost weathering reported in the literature (volumetric expansion and ice segregation theories). The analyses show that in both study areas the thresholds for frost cracking by volumetric expansion of ice (90% pore saturation, temperature < ?1 °C) are hardly ever reached (in one year only 0.07% of the time in Johnsbach and 0.4% at Sonnblick, mostly in north‐exposed walls). The preconditions for weathering by ice segregation (?3 to ?8 °C, > 60% saturation) prevail over much longer periods; the time spent within this ‘frost cracking window‘ is also higher for north‐facing sites. The influence of current climate warming will reduce effective frost events towards 2100; however the increase of liquid precipitation and rock moisture will promote weathering processes like ice segregation at least at the Sonnblick site. Copyright © 2016 John Wiley & Sons, Ltd.