The structure and transformation of the nanomineral schwertmannite: a synthetic analog representative of field samples

The phase transformation of schwertmannite, an iron oxyhydroxide sulfate nanomineral synthesized at room temperature and at 75 °C using H₂O₂ to drive the precipitation of schwertmannite from ferrous sulfate (Regenspurg et al. in Geochim Cosmochim Acta 68:1185–1197, 2004), was studied using high-resolution transmission electron microscopy. The results of this study suggest that schwertmannite synthesized using this method should not be described as a single phase with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers in diameter, within a characteristic ‘pin-cushion’-like amorphous matrix. The difference in synthesis temperature affected the density of the needles on the schwertmannite surface. The needles on the higher-temperature schwertmannite displayed a dendritic morphology, whereas the needles on the room-temperature schwertmannite were more closely packed. Visible lattice fringes in the schwertmannite samples are consistent with the powder X-ray diffraction (XRD) pattern taken on the bulk schwertmannite and also matched d-spacings for goethite, indicating a close structural relationship between schwertmannite and goethite. The incomplete transformation from schwertmannite to goethite over 24 h at 75 °C was tracked using XRD and TEM. TEM images suggest that the sample collected after 24 h consists of aggregates of goethite nanocrystals. Comparing the synthetic schwertmannite in this study to a study on schwertmannite produced at 85 °C, which used ferric sulfate, reveals that synthesis conditions can result in significant differences in needle crystal structure. The bulk powder XRD patterns for the schwertmannite produced using these two samples were indistinguishable from one another. Future studies using synthetic schwertmannite should account for these differences when determining schwertmannite’s structure, reactivity, and capacity to take up elements like arsenic. The schwertmannite synthesized by the Regenspurg et al. method produces a mineral that is consistent with the structure and morphology of natural schwertmannite observed in our previous study using XRD and TEM, making this an ideal synthetic method for laboratory-based mineralogical and geochemical studies that intend to be environmentally relevant.     

Relation between dislocation density and subgrain size of naturally deformed olivine in peridotites

The subgrain size and the dislocation density of subgrain interiors were measured by the oxidation-decoration method under the optical microscope on naturally deformed olivine from peridotite xenoliths and alpine-type peridotites. Relation of the subgrain size, d and the dislocation density, , within subgrains is represented by the equation, d=15/. Combining with relations of the differential stress and the dislocation density proposed by Kohlstedt and Goetze (1974), relation between the stress () and the subgrain size becomes d=45 Gb/, where G and b are the rigidity and the magnitude of the Burgers vector of olivine. This relation is in good agreement with those in a simple oxide (MgO), and alkali halides (NaCl, LiF) given by Hüther and Reppich (1973), Poirier (1972), and Streb and Reppich (1973), respectively.     

Physics-Based 3-D Simulation for Earthquake Generation Cycles at Plate Interfaces in Subduction Zones

The generation of interplate earthquakes can be regarded as a process of tectonic stress accumulation and release, driven by relative plate motion. We completed a physics-based simulation system for earthquake generation cycles at plate interfaces in the Japan region, where the Pacific plate is descending beneath the North American and Philippine Sea plates, and the Philippine Sea plate is descending beneath the North American and Eurasian plates. The system is composed of a quasi-static tectonic loading model and a dynamic rupture propagation model, developed on a realistic 3-D plate interface model. The driving force of the system is relative plate motion. In the quasi-static tectonic loading model, mechanical interaction at plate interfaces is rationally represented by the increase of tangential displacement discontinuity (fault slip) across them on the basis of dislocation theory for an elastic surface layer overlying Maxwell-type viscoelastic half-space. In the dynamic rupture propagation model, stress changes due to fault slip motion on non-planar plate interfaces are evaluated with the boundary integral equation method. The progress of seismic (dynamic) or aseismic (quasi-static) fault slip on plate interfaces is governed by a slip- and time-dependent fault constitutive law. As an example, we numerically simulated earthquake generation cycles at the source region of the 1968 Tokachi-oki earthquake on the North American-Pacific plate interface. From the numerical simulation, we can see that postseismic stress relaxation in the asthenosphere accelerates stress accumulation in the source region. When the stress state of the source region is close to a critical level, dynamic rupture is rapidly accelerated and develops over the whole source region. When the stress state is much lower than the critical level, the rupture is not accelerated. This means that the stress state realized by interseismic tectonic loading essentially controls the subsequent dynamic rupture process.     

Sill dynamics and fjord deep water renewal: Idealized modeling study

Fjord exchange circulation and its response to abrupt changes in forcing is examined by means of an idealized modeling experiment. Puget Sound, a fjord-type estuary in western North America (State of Washington), is the main context for this study. Parameters of the idealized model are representative of the entrance sill at Admiralty Inlet and the Main Basin of Puget Sound. Sensitivity to some of the model parameters relevant to a 3D realistic model is discussed. An idealized tidal forcing with fortnightly modulation drives a qualitatively realistic cycle of exchange circulation while the other boundary conditions are kept fixed in time. The cycle is characterized by fortnightly pulses of deep water intrusions with a sharp front at the leading edge and reversed circulation cells below the sill depth developing between the intrusions. This basic state is then perturbed and response of the circulation to abrupt changes in oceanic salinity and river discharge is examined.     

Continuing observation of disturbed reproductive cycle and ovarian spermatogenesis in the giant abalone, Haliotis madaka from an organotin-contaminated site of Japan

Histological examination of gonads as well as chemical analysis of organotin compounds in tissues of the giant abalone, Haliotis madaka, was conducted to evaluate continuing endocrine disruption in abalone populations in Japan. Abalone specimens were collected from two different areas, Tsushima as a reference site and Jogashima as a site representative of declining abalone populations where serious organotin contamination had been observed, each month from January 1998 to March 1999. Scores were given to the development stages of reproductive cells in the ovary and testis. The degree of sexual maturation was evaluated by calculating the mean value of a histogram of these scores for the reproductive cells of each abalone. The temporal variations in degree of sexual maturation showed that female and male abalone from Tsushima matured synchronously, while those from Jogashima did not, which were similar to results of the previous study during September 1995–November 1996. Approximately 19% of the female abalone from Jogashima were masculinized with an ovo-testis, which was also similar to the result of the previous study. The masculinization of female abalone is reported to be induced by tributyltin (TBT) and triphenyltin (TPhT) from antifouling paints. Concentrations of the sum of butyltins (TBT, dibutyltin (DBT) and monobutyltin (MBT): ΣBTs) and the sum of phenyltins (TPhT, diphenyltin (DPhT) and monophenyltin (MPhT): ΣPhTs) in the muscle of abalone from Jogashima (n = 73) of 7.8 ± 9.0 ng/g wet wt. and 4.5 ± 6.8 ng/g wet wt., respectively, were significantly higher than those from Tsushima (n = 87) of 4.7 ± 4.9 ng/g wet wt. and 0.8 ± 1.7 ng/g wet wt., respectively (p < 0.05 for ΣBTs; p < 0.001 for ΣPhTs), although concentrations of TBT and TPhT in the muscle of abalone from Jogashima (n = 73) of 2.2 ± 2.5 ng/g wet wt. and 5.8 ± 5.1 ng/g wet wt., respectively, were insignificantly and significantly higher than those from Tsushima (n = 87) of 0.4 ± 0.6 ng/g wet wt. and 0.5 ± 0.9 ng/g wet wt., respectively, (p > 0.05 for TBT; p < 0.001 for TPhT). Thus, endocrine disruption as well as contamination by organotins in the giant abalone from Jogashima is still persisting.     

Heavy oil exposure increases viral production in natural marine bacterial populations

This study examined whether heavy oil (HO) increases viral production and how that change may affect the marine bacterial community. The addition of a relatively low concentration (10 μg/mL) of HO to seawater resulted in the highest degree of viral lysis. Although the composition of the bacterial community did not change upon the viral lysis in terms of the taxa present, the relative abundance of the γ-Proteobacteria family Alteromonadaceae decreased (by 10 %) after the HO exposure, implying that the selective lysis by viruses and induced prophages may be responsible for changes in the composition of the bacterial community.     

K–Ar age–chemistry–fabric relations of phengite from the Sanbagawa high-pressure schists, Japan

The Sanbagawa high-pressure schists from central Shikoku in Southwest Japan have experienced high-strain ductile deformation during exhumation and cooling. This study examines the effects of high-strain ductile deformation on K–Ar ages of phengites on the basis of fabric, chemistry and K–Ar ages of phengites from the pelitic, psammitic and quartzose (or albitic) schists collected from the same outcrop in the albite–biotite zone. Phengites in the pelitic and psammitic schists generally occur forming aggregates consisting of fine-grained phengite crystals and are extremely fine-grained in domains close to relatively rigid garnet and albite porphyroblasts, indicating that deformation-induced grain-size reduction had taken place in phengite during the ductile deformation accompanying the exhumation of host schists. We suggest that the grain-size reduction of phengite is due to strain-induced recrystallization or dynamic recrystallization. The matrix phengites in schists are chemically heterogeneous on the thin-section scale but the phengites from pelitic and psammitic schists from the same outcrop have similar chemical range. Phengite included in garnet has a high Si value and its Na/(Na + K) and Mg/(Mg + Fe) ratios are significantly low in comparison with those in matrix. The phengite included in garnet records the chemistry in equilibrium with other major silicate phases during the higher pressure stage of the P–T–t history of the schists. In contrast, the matrix phengites having low Si values are likely to have been formed during retrograde metamorphism in extremely restricted equilibrium domains. The two or three different types of schists from the same outcrop, which have a similar grain size of phengite, have similar K–Ar ages, suggesting that the closure temperature does not depend on chemistry. However, the hematite-rich quartzose schist with strong grain-size reduction of both phengite and quartz has a significantly younger K–Ar phengite age than the pelitic and quartzose schists in the same outcrop that do not show grain-size reduction. We suggest that the exhumation tectonics of the schists, which have experienced strong ductile deformation at temperatures less than ~350°C, played an important role resulting in the observed variation in age.     

Atmospheric correction scheme for GLI with absorptive aerosol correction

The present study proposes an atmospheric correction scheme for Advanced Earth Observation Satellite II (ADEOS-II)/Global Imager (GLI) ocean color retrieval that corrects for the atmospheric absorptive aerosol effect. Radiative transfer simulations were conducted assuming a non-absorptive model aerosol with a soot-type aerosol at various mixture ratios. The results indicate that while the spectral dependency of aerosol reflectance does not change in the longer (>550 nm) wavelength region, the reflectance at shorter wavelengths is highly variable and depends on the mixture ratio. The influence of aerosol absorption was also investigated using GLI data from ocean areas adjacent to Japan in the presence of absorptive Siberian fire smoke aerosol in the spring of 2003. The spectral curvature of the aerosol was estimated from the data obtained. An empirical, iterative scheme that detects and evaluates the influence of absorptive aerosols was developed by comparing 380 nm GLI-observed aerosol reflectance with predicted reflectances derived using an in-water optical model. To evaluate the performance of this scheme, satellite-derived normalized water-leaving radiances were compared with those measured from a ferry servicing Nagasaki and Fukue. The results of data acquired on March 20, 2003, indicate that this absorption correction scheme improved root mean square estimation error for normalized water-leaving radiance by approximately 40% in the 380, 400, and 412 nm bands. This atmospheric correction algorithm was used as a part of the second version of the GLI standard ocean color data process system at Japan Aerospace Exploration Agency (JAXA).