The degree of Cl-loss for the particulate matter (PM) and fog water sampled at the same air mass at the Hachimantai mountain range in northern Japan

It is well known that sea-salt aerosols in particulate matter (PM) react with acids such as H₂SO₄ and HNO₃ during transportation and thereby lose chloride ions (Cl-loss). The PM and fog were sampled concurrently at different altitudes in the Hachimantai mountain range, northern Japan. The PM and fog sampled at different altitudes had nearly identical properties for the ion components. However, the PM was in a Cl-depleted state (more than 80% of all samples), but the fog water was not in so Cl-depleted state (less than 29%). As a result, it could be explained that this phenomenon caused because the fog droplets took up the gaseous state HCl other than sea-salt PM. After all Cl^- in the fog water recovered and was rather rich compared with the sea-salt or the PM by the uptake of the gaseous state HCl. Moreover, it was found that for PM_coarse(2.5 < D < 10), 86% of the acid (H₂SO₄ and HNO₃) was consumed for Cl-loss reactions and/or for dissolution of Ca and Mg in soil particles.     

Determination of Ti, K, Sm and Gd Values in Geological Survey of Japan Reference Materials by Prompt Gamma Neutron Activation Analysis

Prompt gamma neutron activation analysis was applied to the determination of the titanium, potassium, samarium and gadolinium contents of nine Geological Survey of Japan (GSJ) reference materials (JB-1, 1a, 2, 3; JA-1, 2, 3; JR-1, 2). Firstly, the values in JB-1 were determined by the standard addition method: pressed powder disks of JB-1 were used for neutron irradiation and gamma-ray measurements, after known quantities of standard reagents had been added. Secondly, the contents of eight other reference materials were determined by comparison methods using JB-1 as the comparative standard. The precision of analyses were obtained by replicate determinations on these samples. The relative standard deviation was generally less than 5%. For most samples, analysed values agreed well (< 5%) with the recommended values.     

Phase boundary between ilmenite and perovskite structures in MnGeO3 determined by in situ X-ray diffraction measurements

In situ X-ray observations of the phase transition from ilmenite to perovskite structure in MnGeO₃ were carried out in a Kawai-type high-pressure apparatus interfaced with synchrotron radiation. The phase boundary between the ilmenite and perovskite structures in the temperature range of 700–1,400°C was determined to be P (GPa) = 16.5(±0.6) − 0.0034(±0.0006)T (°C) based on Anderson’s gold pressure scale. The Clapeyron slope, dP/dT, determined in this study is consistent with that for the transition boundary between the ilmenite and the perovskite structure in MgSiO₃.     

Petrogenesis of the Kaikomagatake granitoid pluton in the Izu Collision Zone, central Japan: implications for transformation of juvenile oceanic arc into mature continental crust

The Miocene Kaikomagatake pluton is one of the Neogene granitoid plutons exposed in the Izu Collision Zone, which is where the juvenile Izu-Bonin oceanic arc is colliding against the mature Honshu arc. The pluton intrudes into the Cretaceous to Paleogene Shimanto accretionary complex of the Honshu arc along the Itoigawa-Shizuoka Tectonic Line, which is the collisional boundary between the two arcs. The pluton consists of hornblende–biotite granodiorite and biotite monzogranite, and has SiO₂ contents of 68–75 wt%. It has high-K series compositions, and its incompatible element abundances are comparable to the average upper continental crust. Major and trace element compositions of the pluton show well-defined chemical trends. The trends can be interpreted with a crystal fractionation model involving the removal of plagioclase, biotite, hornblende, quartz, apatite, and zircon from a potential parent magma with a composition of ~68 wt% SiO₂. The Sr isotopic compositions, together with the partial melting modeling results, suggest that the parent magma is derived by ~53% melting of a hybrid lower crustal source comprising ~30% Shimanto metasedimentary rocks of the Honshu arc and ~70% K-enriched basaltic rocks of the Izu-Bonin rear-arc region. Together with previous studies on the Izu Collision Zone granitoid plutons, the results of this study suggest that the chemical diversity within the parental magmas of the granitoid plutons reflects the chemical variation of basaltic sources (i.e., across-arc chemical variation in the Izu-Bonin arc), as well as a variable contribution of the metasedimentary component in the lower crustal source regions. In addition, the petrogenetic models of the Izu Collision Zone granitoid plutons collectively suggest that the contribution of the metasedimentary component is required to produce granitoid magma with compositions comparable to the average upper continental crust. The Izu Collision Zone plutons provide an exceptional example of the transformation of a juvenile oceanic arc into mature continental crust.     

Iron oxidation state of a 2.45-Byr-old paleosol developed on mafic volcanics

The 2.45-Byr-old weathering profile developed on early Proterozoic mafic volcanics located near Cooper Lake, Ontario, Canada, was examined geochemically and mineralogically for a better understanding of the atmospheric oxygen evolution. Ferrous to ferric ion, Fe(II) and Fe(III), respectively, ratios of the bulk rock samples were analyzed by Mössbauer spectrometry. The total Fe (Fe(T)) and Fe(II) concentrations decrease from 12.0 and 11.2 wt.% to 1.85 and 0.89 wt.%, respectively, from the bottom to the top of the weathering profile. The Fe(T) and Fe(II) concentrations normalized to Ti and Zr, as well as the Fe(II)/Fe(III) ratio of raw data, linearly decrease with depth toward the top, while the Fe(III) concentration remains nearly constant throughout the profile. The linear decrease of Fe(II), accompanied by the nearly constant distribution of Fe(III), is difficult to be explained by the scenario of oxidizing weathering and subsequent reducing hydrothermal alteration. The behaviors of Fe(II) and Fe(III) can be simply explained by anoxic weathering. The anoxic weathering suggests that the 2.45-Ga atmosphere was anoxic. The slight increase of Fe/(Fe+Mg) in the octahedral sites of chlorite toward the top and no Ce anomaly in the REE patterns are also consistent with anoxic weathering.     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

Determination of Chlorine Contents in Geological Survey of Japan Reference Materials by Prompt Gamma Neutron Activation Analysis

We determined chlorine contents in nine GSJ (Geological Survey of Japan) reference materials (JB-1, 1a, 2, 3; JA-1, 2, 3; JR-1, 2) by prompt gamma neutron activation analysis, employing the standard addition method. Pressed powder disks of each reference material were used for neutron irradiation and gammaray measurement, after known quantities (25-200 μl) of sodium chloride solution were added. The influence of the nearby sodium peak overlap was checked, and fluctuations in the chlorine count rate were corrected using silicon as an internal standard. The slopes of calibration lines for seven reference materials (JB-1, 2, 3; JA-1, 2, 3; JR-2) and SiO₂ powders fall within 5% error, and their chlorine values were obtained from the intercepts. Chlorine contents in JB-1 a and JR-1 were also determined by using the calibration lines. Our chlorine values ranged from 26.1 to 934 μg g-¹, which agrees well with the previously reported values.     

Determination of the oxidation state of radiogenic Pb in natural zircon using X-ray absorption near-edge structure

We examined the L_III-edge Pb X-ray absorption near-edge structure (XANES) of three natural zircon samples with different amounts of radiation doses (1.9 × 10¹⁵ to 6.8 × 10¹⁵ α-decay events/mg). The results suggest that the oxidation state of radiogenic Pb in the zircon sample with the highest radiation dose is divalent. The XANES spectra of the two other samples with lower radiation doses suggest that radiogenic Pb(II) is present, and further that some Pb may be tetravalent. This is the first work on the determination of the oxidation state of radiogenic Pb in natural zircon using XANES.     

Tracing depositional consequences of environmental radionuclides (137Cs and 210Pb) in Slovenian forest soils

Depth distribution profiles of environmental radionuclides (¹³⁷Cs and ²¹⁰Pb) have been investigated in soil to elucidate the underlying environment of semi-natural temperate deciduous and/or coniferous forest soils in Slovenia (?irovski vrh, Idrija, Ko?evski Rog, Pohorie, Gori?nica and Rakitna). Surface enrichment of both nuclides was observed at all the sites investigated in this study, suggesting that the soils had undergone little natural or anthropogenic disturbance for at least the last several decades. Apparent annual burial rates of ¹³⁷Cs (0.1–0.2 cm y^??1) were estimated to be about 1.3 times higher than those of ²¹⁰Pb at individual sites of different lithology, which suggests strong affinity of ²¹⁰Pb to soil organic matter. Variability of the vertical distribution profiles of these nuclides depends not only on “in situ” pedology but also on geographical and meteorological conditions, especially precipitation and wind direction.     

Phase equilibria in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2 and the stability limit of stilpnomelane in metamorphosed Precambrian iron-formations

The phase relations of Al- and Fe-bearing silicates in the system K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O-CO₂, in the presence of quartz and magnetite, are discussed on the basis of mineralogic and petrologic data from Precambrian iron-formations and blueschist facies meta-ironstone from the Franciscan Formation, California. These relations allow an estimation of the physiochemical conditions during low-grade metamorphism of iron-formations. Petrologic data together with available experimental and predicted thermodynamic data on the associated minerals place the upper stability limit of stilpnomelane in iron-formations at about 430–470° C and 5–6 kilobars. Fe-end member stilpnomelane can persist to a maximum temperature of 500° C and pressures up to 6–7 kilobars, although it is unlikely to occur in metamorphosed iron-formations. In iron-formation occurrences the stilpnomelane stability field is bordered by four equilibrium reactions with the assemblages stilpnomelane-zussmanite-chlorite-minnesotaite, stilpnomelane-zussmanite-chlorite-grunerite, stilpnomelane-biotite-chlorite-grunerite, and stilpnomelane-biotite-almandine-grunerite. The stability field is reduced by increasing X(CO₂) and X _Mg ^Stil , and is also a function of a(K ⁺)/ a(H ⁺) in the metamorphic fluid. If the value of a(K ⁺)/ a(H ⁺) is smaller than that defined by the above assemblages, stilpnomelane decomposes to chlorite, but if larger, it is replaced by biotite. At pressures less than 4 kilobars, the zussmanite field is restricted to a very high value of a(K ⁺)/a(H ⁺) (> 5.0 in log units at 1.0 kilobar) where iron-formation assemblages are not stable.