Determination of Chromium, Nickel, Copper and Zinc in Milligram Samples of Geological Materials Using Isotope Dilution High Resolution Inductively Coupled Plasma-Mass Spectrometry

A simple and accurate method for the determination of Cr, Ni, Cu and Zn at μg g^?1 levels in milligram‐sized bulk silicate materials is reported using isotope dilution high‐resolution inductively coupled plasma‐mass spectrometry (HR‐ICP‐MS) with a flow injection system. Silicate samples with Cr, Ni, Cu and Zn spikes were digested with HF‐HBr and Br₂, and subsequently decomposed at 518 K in a Teflon bomb. In this procedure, all sulfides and chromite, major hosts of these elements, were completely decomposed, thus allowing for isotope equilibration between the sample and spike. Magnesium and Al fluorides formed after the digestion of the sample were removed by centrifugation, and the supernatant was directly aspirated into a HR‐ICP‐MS at a mass resolution of 7500, where interfering oxide ions, ArO⁺, CaO⁺, TiO⁺, CrO⁺ and VO⁺, were separated from Cr⁺, Ni⁺, Cu⁺ and Zn⁺. No matrix effects were observed down to a dilution factor of 50. Detection limits for these elements in silicate samples were < 0.04 μg g^?1. The effectiveness of the technique was demonstrated by the analysis of 13 to 40 mg test portions of USGS and GSJ silicate reference materials with a major element composition ranging from andesite to peridotite, in addition to 8‐23 mg of the Smithsonian reference Allende. Both the reproducibility and the deviation from the reference value for most reference materials of various rock types were < 9%, and thus confirm that the method gives accurate analytical results for small sample sizes over a wide range of Cr, Ni, Cu and Zn contents. This method is, therefore, suitable for analysing small and/or precious bulk samples, such as meteorites, mantle peridotites and mineral separates, and for the characterisation of silicate and sulfide minerals for use as calibration samples in secondary ion mass spectrometry or laser ablation ICP‐MS.     

Energy determination of gamma-ray induced air showers observed by an extensive air shower array

ASTRI SST-2M is one of the prototypes of the small size class of telescopes proposed for the Cherenkov Telescope Array. Its optical design is based on a dual-mirror Schwarzschild-Couder configuration, and the camera is composed by a matrix of monolithic multipixel silicon photomultipliers managed by ad-hoc tailored front-end electronics. This paper describes the procedures for the gain calibration on the ASTRI SST-2M. Since the SiPM gain depends on the operative voltage and the temperature, we adjust the operative voltages for all sensors to have equal gains at a reference temperature. We then correct gain variations caused by temperature changes by adjusting the operating voltage of each sensor. For that purpose the SiPM gain dependence on operating voltage and on temperature have been measured. In addition, we present the calibration procedures and the results of the experimental measurements to evaluate, for each pixel, the parameters necessary to make the trigger uniform over the whole focal plane.     

Groundmass pargasite in the 1991–1995 dacite of Unzen volcano: phase stability experiments and volcanological implications

Pargasite commonly occurs in the dacitic groundmass of the 1991–1995 eruption products of Unzen volcano. We described the occurrence and chemical compositions of amphibole in the dacite, and also carried out melting experiments to determine the low-pressure stability limit of amphibole in the dacite. The 1991–1995 ejecta of the Unzen volcano show petrographic evidence of magma mixing, such as reverse compositional zoning of plagioclase and amphibole phenocrysts, and we used a groundmass separate as a starting material for the experiments. Reversed experiments show that the maximum temperature for the crystallization of amphibole is 930°C at 196 MPa, 900°C at 98 MPa, and 820°C at 49 MPa. Compared with the experimental results on the Mount St. Helens dacite, present experiments on the Unzen dacitic groundmass show that amphibole is stable to pressures ca. 50 MPa lower at 850°C. Available Fe–Ti oxide thermometry indicates the crystallization temperature of the groundmass of the Unzen dacite to be 880±30°C, suggesting that the groundmass pargasite crystallized at >70 MPa, corresponding to a depth of more than 3 km in the conduit. The chlorine content of the groundmass pargasite is much lower than that of phenocrystic magnesiohornblende in the 1991–1995 dacite of Unzen volcano, indicating that vesiculation/degassing of magma took place before the crystallization of the groundmass pargasite. The present study shows that the magma was water oversaturated and that the degassing of magma along with magma mixing caused crystallization of the groundmass amphibole at depths of more than 3 km in the conduit.     

Dynamics and local boundary properties of the dawn-side magnetopause under conditions observed by Equator-S

Magnetic field measurements, taken by the magnetometer experiment (MAM) on board the German Equator-S spacecraft, have been used to identify and categorise 131 crossings of the dawn-side magnetopause at low latitude, providing unusual, long duration coverage of the adjacent magnetospheric regions and near magnetosheath. The crossings occurred on 31 orbits, providing unbiased coverage over the full range of local magnetic shear from 06:00 to 10:40 LT. Apogee extent places the spacecraft in conditions associated with intermediate, rather than low, solar wind dynamic pressure, as it processes into the flank region. The apogee of the spacecraft remains close to the magnetopause for mean solar wind pressure. The occurrence of the magnetopause encounters are summarised and are found to compare well with predicted boundary location, where solar wind conditions are known. Most scale with solar wind pressure. Magnetopause shape is also documented and we find that the magnetopause orientation is consistently sunward of a model boundary and is not accounted for by IMF or local magnetic shear conditions. A number of well-established crossings, particularly those at high magnetic shear, or exhibiting unusually high-pressure states, were observed and have been analysed for their boundary characteristics and some details of their boundary and near magnetosheath properties are discussed. Of particular note are the occurrence of mirror-like signatures in the adjacent magnetosheath during a significant fraction of the encounters and a high number of multiple crossings over a long time period. The latter is facilitated by the spacecraft orbit which is designed to remain in the near magnetosheath for average solar wind pressure. For most encounters, a well-ordered, tangential (draped) magnetosheath field is observed and there is little evidence of large deviations in local boundary orientations. Two passes corresponding to close conjunctions of the Geotail spacecraft are analysed to confirm boundary orientation and motion. These further show evidence of an anti-sunward moving depression on the magnetopause (which is much smaller at Equator-S). The Tsyganenko model field is used routinely to assist in categorising the crossings and some comparison of models is carried out. We note that typically the T87 model fits the data better than the T89 model during conditions of low to intermediate K_p index near the magnetopause and also near the dawn-side tail current sheet in the dawnside region.     

Detrital zircon multi‐chronology,provenance, and low‐grade metamorphism of the Cretaceous Shimanto accretionary complex,eastern Shikoku,Southwest Japan: Tectonic evolution in response to igneous activity within a subduction zone

Detrital zircon multi‐chronology combined with provenance and low‐grade metamorphism analyses enables the reinterpretation of the tectonic evolution of the Cretaceous Shimanto accretionary complex in Southwest Japan. Detrital zircon U–Pb ages and provenance analysis defines the depositional age of trench‐fill turbidites associated with igneous activity in provenance. Periods of low igneous activity are recorded by youngest single grain zircon U–Pb ages (YSG) that approximate or are older than the depositional ages obtained from radiolarian fossil‐bearing mudstone. Periods of intensive igneous activity recorded by youngest cluster U–Pb ages (YC1σ) that correspond to the younger limits of radiolarian ages. The YC1σ U–Pb ages obtained from sandstones within mélange units provide more accurate younger depositional ages than radiolarian ages derived from mudstone. Determining true depositional ages requires a combination of fossil data, detrital zircon ages, and provenance information. Fission‐track ages using zircons estimated YC1σ U–Pb ages are useful for assessing depositional and annealing ages for the low‐grade metamorphosed accretionary complex. These new dating presented here indicates the following tectonic history of the accretionary wedge. Evolution of the Shimanto accretionary complex from the Albian to the Turonian was caused by the subduction of the Izanagi plate, a process that supplied sediments via the erosion of Permian and Triassic to Early Jurassic granitic rocks and the eruption of minor amounts of Early Cretaceous intermediate volcanic rocks. The complex subsequently underwent intensive igneous activity from the Coniacian to the early Paleocene as a result of the subduction of a hot and young oceanic slab, such as the Kula–Pacific plate. Finally, the major out‐of‐sequence thrusts of the Fukase Fault and the Aki Tectonic Line formed after the middle Eocene, and this reactivation of the Shimanto accretionary complex as a result of the subduction of the Pacific plate.     

Depositional environments and maturity evaluated by biomarker analyses of sediments deposited across the Cenomanian–Turonian boundary in the Yezo Group,Tomamae area,Hokkaido, Japan

Biomarker analyses for evaluating maturity of organic matter and depositional environments such as redox conditions, were performed in sediments across the Cenomanian–Turonian boundary (CTB) in the Saku Formation of the Yezo Group distributed along the Shumarinai‐gawa River and the Omagari‐zawa River, both in the Tomamae area, Hokkaido, Japan. Maturity indicators using steranes and hopanes, show that organic matter in sediments from the Shumarinai‐gawa and Omagari‐zawa sections are of lower maturity than those from the Hakkin‐gawa section (Oyubari area). Moreover, the ββ hopane ratios clearly show that the maturity of the Shumarinai‐gawa samples is lower than that of the Omagari‐zawa samples. These variations in the maturity of organic matter presumably reflect the difference in their burial histories. The results for the pristane/phytane (Pr/Ph) ratios suggest that the Shumarinai‐gawa samples were deposited under dysoxic to anoxic environments across the CTB, while the depositional environments of the Omagari‐zawa samples were relatively oxic. By another paleoredox indicator using C₃₅ homohopanoids including a homohopene index (HHenI), higher values are observed in the Shumarinai‐gawa section, particularly in the horizons of the preceding period and an early stage of the first negative shift phase and the latest oceanic anoxic event 2 (OAE2) interval. These results suggest that the Shumarinai‐gawa samples record dysoxic to anoxic environments across the CTB. In contrast, the signals for the C₃₅ homohopanoid index values show a relatively oxic condition in the Omagari‐zawa section. The trends of stratigraphic variations in redox conditions are different from those in the OAE2 interval in the proto‐Atlantic and Tethys regions as reported previously. Hence, the redox variations in the Tomamae area were basically related to a local environmental setting rather than global anoxia. However, the prominent anoxic emphasis observed in the HHenI profile of the Shumarinai‐gawa section can be a distinctive, and possibly global, event in the North‐West Pacific just before the OAE2.     

Combining IR and X‐ray microtomography data sets: Application to Itokawa particles and to Paris meteorite

In the near future, a new generation of sample return missions (Hayabusa2, OSIRIS‐REx, MMX, etc.) will collect samples from small solar system bodies. To maximize the scientific outcome of laboratory studies and minimize the loss of precious extraterrestrial samples, an analytical sequence from less destructive to more destructive techniques needs to be established. In this work, we present a combined X‐ray and IR microtomography applied to five Itokawa particles and one fragment of the primitive carbonaceous chondrite Paris. We show that this analytical approach is able to provide a 3‐D physical and chemical characterization of individual extraterrestrial particles, using the measurement of their 3‐D structure and porosity, and the detection of mineral and organic phases, and their spatial co‐localization in 3‐D. We propose these techniques as an efficient first step in a multitechnique analytical sequence on microscopic samples collected by space missions.     

Observation of Sea-Ice Thickness Using ENVISAT Data From LÜtzow-Holm Bay, East Antarctica

To investigate the suitability of synthetic aperture radar (SAR) polarization data to estimate the sea-ice thickness in early summer in Lutzow-Holm Bay, Antarctica, we compared in situ ice thicknesses with the corresponding backscattering co-efficient for each polarization and the VV-to-HH backscattering ratio. The VV-to-HH backscattering ratio was derived from data acquired by ENVISAT Advanced SAR (ASAR). This ratio is related to the near-surface dielectric constant of the sea ice, which is, in turn, related to the developing process of ice and, thus, its thickness via changes in the near-surface sea-ice salinity. The sea ice encountered in the study area is close first-year pack ice and fast ice. For these old and relatively rough sea-ice types, the VV-to-HH backscattering ratio can be expected to depend on salinity-driven changes in the near-surface dielectric constant rather than changes of the surface roughness. We applied the empirical relationships between the ice thickness and the VV-to-HH backscattering ratio with the linear and logarithm fits to ASAR data. The linear fit gave the reliable result, with an rms error being 0.08 m and a correlation coefficient being 0.91, when compared to in situ fast-ice thickness.