Mobilization and speciation of arsenic from hydrothermally altered rock containing calcite and pyrite under anoxic conditions

The effects of water residence time and anoxic conditions on the mobilization and speciation of As in a calcite- and pyrite-bearing altered rock excavated during a road-tunnel project has been evaluated using batch and column laboratory experiments. Higher infiltration rates (i.e., shorter water residence times) enhanced the leaching of As due to the higher pH values of the effluents and more rapid transport of dissolved As through the columns. The concentration of As in the effluent also increased under anoxic conditions regardless of the water residence time. This enhanced leaching of As under anoxic conditions could be attributed to a significant pH increase and decreased Fe oxyhydroxide/oxide precipitation compared to similar experiments done under ambient conditions. Processes that controlled the evolution of pH and the temporal release mechanisms of As under anoxic conditions were identical to those previously observed under ambient conditions: the dissolution of soluble phases, pyrite oxidation, co-precipitation and/or adsorption/desorption reactions. Speciation of As in the column experiments could partly be attributed to the pH-dependent adsorption of As species onto Fe oxyhydroxide/oxide precipitates. Moreover, apparent equilibrium of the total As and As[III] concentrations was delayed under anoxic conditions in both batch and column experiments.     

Sequential Chemical Separation of Cr and Ti from a Single Digest for High‐Precision Isotope Measurements of Planetary Materials

Combined determination of Cr and Ti isotopes of planetary materials offers a means with which to investigate their genetic relationship and the evolution of the protoplanetary disk. Here, we report the new sequential chemical separation procedure for combined Cr and Ti isotope ratio measurements. It comprises three steps: (a) Fe removal using AG1‐X8 anion exchange resin, (b) Ti separation using TODGA resin and (c) Cr separation using AG50W‐X8 cation exchange resin (with one additional step of Ti purification using AG1‐X8 anion exchange resin for samples having high Cr/Ti and Ca/Ti ratios). We applied the proposed procedure to terrestrial and meteorite samples with various compositions. Typical recovery rates of 90–100% were achieved with total procedural Cr and Ti blanks of 3–5 and 2–3 ng, respectively. We measured the Cr and Ti isotope compositions of the separated samples using thermal ionisation mass spectrometry and multiple collector‐inductively coupled plasma‐mass spectrometry, respectively. Our Cr and Ti isotope data were found to be consistent with those of previous studies of individual Cr and Ti isotopic compositions of the meteorites. These results demonstrate the capability of our separation method when applied to combined high‐precision Cr and Ti isotope analyses for single digests of planetary materials.     

Anisotropic thermal properties of talc under high temperature and pressure

The anisotropic thermal conductivity and diffusivity of talc were simultaneously measured up to 5.3 GPa and 900 K using the pulse transient method. Although significant anisotropy was observed in the thermal conductivity of talc, the average thermal conductivity is comparable to that of olivine and roughly three times greater than that of antigorite. From the ratio of the thermal conductivity to the thermal diffusivity, the heat capacity of talc was evaluated. The pressure derivative of heat capacity was found to be positive, which is related to the anomaly of thermal expansivity of talc above 50 °C at atmospheric pressure.     

Regolith history of the aubritic meteorite parent body revealed by neutron capture effects on Sm and Gd isotopes

Enstatite achondrites (aubrites) when compared to other stone meteorites have unusually long cosmic-ray exposure (CRE) ages. We report here the ¹⁵⁰Sm/¹⁴⁹Sm and ¹⁵⁸Gd/¹⁵⁷Gd ratios in six different structural phases, i.e., light and dark (shocked) grains and in matrix materials of Pesyanoe, in three different fragments from Pena Blanca Spring, and in one from Norton County, Shallowater, and Khor Temiki, to investigate the regolith history on the aubrite parent body. The results from phases components of Pesyanoe confirm earlier reported evidence for regolith irradiation of several aubrites. The inferred neutron fluences for six Pesyanoe separates vary between (2.13 and 2.82) × 10¹⁶ n cm⁻². The fluences also significantly exceed those expected from cosmic-ray irradiation during transit to Earth and approach those observed in the lunar regolith. These observations confirm that the brecciated Pesyanoe meteorite, which contains solar wind (SW) gases only in dark phases, was processed in a regolith and that structural phases were differentially irradiated before compaction. On the other hand, in some aubrites (Mt. Egerton, Shallowater, Pena Blanca Spring, Norton County) neutron capture effects may entirely be due to space irradiation.     

Temporal changes in the phytoplankton community of the southern basin of Lake Baikal over the last 24,000 years recorded by photosynthetic pigments in a sediment core

Photosynthetic pigments and other indicators of phytoplankton were analyzed in a dated undisturbed sediment core obtained from the southern basin of Lake Baikal to reveal temporal changes in the phytoplankton community in the lake through the last glacial/post-glacial transition. The sedimentation age of the core spans the last 24 ¹⁴C ka. Chlorophyll a, its derivatives, carotenoids and total organic carbon (TOC) started to increase after 15 ¹⁴C ka, and the onset of biogenic silica occurred at 10 ¹⁴C ka. This indicated that the post-glacial growth of diatoms was preceded by that of other phytoplankton groups. In the record of the pigments and TOC, a temporary decrease was observed in the period 11.5–10.5 ¹⁴C ka, corresponding to the Younger Dryas cold period. The similarity found between the depth profiles of pyropheophytin a and steryl chlorin esters formed through predation of phytoplankton by zooplankton and that of TOC suggested the important contribution of fecal pellets to sedimentary organic matter in the lake.     

Effect of topography and subsurface inhomogeneities on seismic SV waves

The effect of topography and subsurface inhomogeneity on surface motion is investigated in the case of incident SV waves. Several types of topography, such as a cliff, a cliff with a soft layer and filled land, are considered. Computations are made using a new method combining a particle model with a finite element method. The accuracy of this method is discussed through comparisons with Wong's solutions, which are in good agreement. It is found that the surface displacement is very much influenced by surface irregularities when the incident wavelengths are comparable to the size of the topographic features. Rayleigh waves are strongly produced in the neighbourhoods of the slopes of a cliff and a cliff with a soft layer, the latter being a cliff adjacent to and covered at its foot by a soft layer. Thus, a zone of large amplification takes place near a slope, combining incident SV waves and Rayleigh waves. A large displacement also occurs at the upper corner of the slope. In filled land, vertical and horizontal displacements are produced, which are 3 times larger than those at a distance. The present results are considered to be significant from the viewpoint of engineering seismology.     

Diverse nucleosynthetic components in barium isotopes of carbonaceous chondrites: Incomplete mixing of s- and r-process isotopes and extinct Cs in the early solar system

Barium isotopic compositions of chemical leachates from six carbonaceous chondrites, Orgueil (CI), Mighei (CM2), Murray (CM2), Efremovka (CV3), Kainsaz (CO3), and Karoonda (CK4), were determined using thermal ionization mass spectrometry in order to assess the chemical evolution in the early solar system.The Ba isotopic data from most of the leachates show variable ¹³⁵Ba excesses correlated with ¹³⁷Ba excesses, suggesting the presence and heterogeneity of additional nucleosynthetic components for s- and r-processes in the solar system. The isotopic deviations observed in this study were generally small (−1 < ε < +1) except in the case of the acid residues of CI and CM meteorites. Large deviations of ¹³⁵Ba (ε = −13.5 to −5.0) and ¹³⁷Ba (ε = −6.2∼−1.2) observed in the acid residues from one CI and two CM meteorites show significant evidence for the enrichment of s-process isotopes derived from presolar grains. Two models were proposed to estimate the ¹³⁵Cs isotopic abundances by subtraction of the s- and r-isotopic components from the total Ba isotopic abundances in the three CM meteorites, Mighei, Murchison (measured in a previous study), and Murray. The data points show individual linear trends between ¹³⁵Cs/¹³⁶Ba ratios and ¹³⁵Ba isotopic deviations for the three samples. Considering the different trends observed in the three CM meteorites, the Ba isotopic composition of the CM meteorite parent body was heterogeneous at its formation. Chronological information is unclear in the data for Murchison and Murray because of large analytical uncertainties imposed by error propagation. Only the Mighei meteorite data indicate the possible existence of presently extinct ¹³⁵Cs (¹³⁵Cs/¹³³Cs = (2.7 ± 1.6) × 10⁻⁴) in the early solar system. Another explanation of the data for the three CM meteorite is mixing of at least three components with different Ba isotopic compositions, although this is model-dependent.     

Sm and Gd isotopic shifts of Apollo 16 and 17 drill stem samples and their implications for regolith history

The isotopic compositions of Sm and Gd in lunar regolith samples from the Apollo 16 and 17 deep drill stems showed clear isotopic shifts in ¹⁵⁰Sm /¹⁴⁹Sm (ε = +124 to +191 for A-16, and +37 to +111 for A-17) and ¹⁵⁸Gd/¹⁵⁷Gd (ε = +107 to +169 for A-16, and +31 to +84 for A-17) corresponding to neutron fluences of (5.68-9.03) × 10¹⁶ n cm⁻² for A-16 and (1.85-5.04) × 10¹⁶ n cm⁻² for A-17. The depth profiles of neutron fluences suggest that the regoliths at both sites were due to incomplete mixing of three different slabs which experienced individual two-stage irradiation before and after deposition of the upper slabs. The variations in REE compositions provide chemical evidence for incompletely vertical mixing of regoliths especially at upper layers of the two sites. The thermal neutron energy index estimated from the combination of Sm and Gd isotopic shifts, defined as ε_Sm/ε_Gd, shows a small variation (0.61-0.64) in the A-16 core except for the surface layer. On the other hand, a large variation in ε_Sm/ε_Gd = 0.67 to 0.83 in the A-17 core may result from complicated history such as two-stage irradiation and incomplete mixing during the gardening processes. Isotopic enrichments of ¹⁵²Gd and ¹⁵⁴Gd correlated with Eu/Gd elemental abundances and neutron fluences were also observed in almost all of 15 samples, showing evidence of neutron-capture from ¹⁵¹Eu and ¹⁵³Eu, respectively.     

Gravity measurements with a portable absolute gravimeter A10 in Syowa Station and Langhovde,East Antarctica

Absolute gravity values were measured with a portable absolute gravimeter A10 in East Antarctica, for the first time by the Japanese Antarctic Research Expedition. This study aims to investigate regional spatiotemporal variations of ice mass distributions and associated crustal deformations around Syowa Station by means of repeated absolute gravity measurements, and we obtained the first absolute gravity value in Southern Langhovde on the Antarctic Continent. The average absolute gravity value at the newly installed benchmark AGS01 in Langhovde (obtained on 3 February 2012) was 982535584.2 ± 0.7 μgal (1 [μgal] = 1 × 10^?8 [m/s²]), which was in agreement with the gravity values obtained by the past relative gravity measurements within 1 mgal. In addition, the average absolute gravity value obtained at AGSaux in Syowa Station was consistent with both previous absolute gravity values and those obtained by simultaneous measurements using an FG5 gravimeter, owing to adequate data corrections associated with tidal effects and time variations in atomic clock frequencies. In order to detect the gravity changes associated with the ice mass changes and other tectonic phenomena, we plan to conduct absolute gravity measurements at AGS01 again and at other campaign sites around Syowa Station as well in the near future, with careful attention paid to the impacts of severe environmental conditions in Antarctica on gravity data collection.