Influence of biopolymers on the rheological properties of seafloor sediments and the runout behavior of submarine debris flows.

Submarine debris flows are mass movement processes on the seafloor, and are geohazards for seafloor infrastructure such as pipelines, communication cables, and submarine structures. Understanding the generation and run-out behavior of submarine debris flows is thus critical for assessing the risk of such geohazards. The rheological properties of seafloor sediments are governed by factors including sediment composition, grain size, water content, and physico-chemical conditions. In addition, extracellular polymeric substances (EPS) generated by microorganisms can affect rheological properties in natural systems. Here we show that a small quantity of EPS (~ 0.1 wt%) can potentially increase slope stability and decrease the mobility of submarine debris flows by increasing the internal cohesion of seafloor sediment. Our experiments demonstrated that the flow behavior of sediment suspensions mixed with an analogue material of EPS (xanthan gum) can be described by a Herschel-Bulkley model, with the rheological parameters being modified progressively, but not monotonously, with increasing EPS content. Numerical modeling of debris flows demonstrated that the run-out distance markedly decreases if even 0.1 wt% of EPS is added. The addition of EPS can also enhance the resistivity of sediment to fluidization triggered by cyclic loading, by means of formation of an EPS network that binds sediment particles. These findings suggest that the presence of EPS in natural environments reduces the likelihood of submarine geohazards.

Fluidized landslides triggered by the liquefaction of subsurface volcanic deposits during the 2018 Iburi-Tobu earthquake, Hokkaido.

The 6.6 Mw Iburi-Tobu earthquake struck southern Hokkaido, Japan on 6 September 2018. The earthquake triggered widespread slope collapses in the hills near the epicenter, resulting in destructive landslides that killed 36 people. Volcanic deposits covering the region slid downhill in a flow-like manner suggestive of fluidized landslides. Here, we report a distinctive example of liquefaction in the field, which could be a prerequisite for the generation of fluidized landslides triggered by large earthquakes. In the scarp of a typical landslide, an altered halloysite-bearing volcanic layer is observed at a level almost coincident with the sliding surface. The layer is intensely undulating and can be divided into an upper clay-rich layer and a lower pumice-rich layer, suggesting that the altered layer had liquefied as a result of the strong coseismic ground motion. The layer had been soaked by heavy rainfall just one day before the earthquake and could have liquefied, producing a weak and slippery plane, resulting in the catastrophic landslides in this area.

Structure and composition of the plate-boundary slip zone for the 2011 Tohoku-Oki earthquake.

The mechanics of great subduction earthquakes are influenced by the frictional properties, structure, and composition of the plate-boundary fault. We present observations of the structure and composition of the shallow source fault of the 2011 Tohoku-Oki earthquake and tsunami from boreholes drilled by the Integrated Ocean Drilling Program Expedition 343 and 343T. Logging-while-drilling and core-sample observations show a single major plate-boundary fault accommodated the large slip of the Tohoku-Oki earthquake rupture, as well as nearly all the cumulative interplate motion at the drill site. The localization of deformation onto a limited thickness (less than 5 meters) of pelagic clay is the defining characteristic of the shallow earthquake fault, suggesting that the pelagic clay may be a regionally important control on tsunamigenic earthquakes.

Low coseismic shear stress on the Tohoku-Oki megathrust determined from laboratory experiments.

Large coseismic slip was thought to be unlikely to occur on the shallow portions of plate-boundary thrusts, but the 11 March 2011 Tohoku-Oki earthquake [moment magnitude (Mw) = 9.0] produced huge displacements of ~50 meters near the Japan Trench with a resultant devastating tsunami. To investigate the mechanisms of the very large fault movements, we conducted high-velocity (1.3 meters per second) friction experiments on samples retrieved from the plate-boundary thrust associated with the earthquake. The results show a small stress drop with very low peak and steady-state shear stress. The very low shear stress can be attributed to the abundance of weak clay (smectite) and thermal pressurization effects, which can facilitate fault slip. This behavior provides an explanation for the huge shallow slip that occurred during the earthquake.

Characterization of the multilayered shell of a limpet, Lottia kogamogai (Mollusca: Patellogastropoda), using SEM-EBSD and FIB-TEM techniques.

The microstructure and its crystallographic aspect of the shell of a limpet, Lottiakogamogai, have been investigated, as the first step to clarify the mechanism of shell formation in limpet. The shell consists of five distinct layers stacked along the shell thickness direction. Transmission electron microscopy (TEM) with the focused ion beam (FIB) sample preparation technique was primarily adopted, as well as scanning electron microscopy (SEM) with electron back-scattered diffraction (EBSD). The five layers were termed as M+3, M+2, M+1, M, M-1 from the outside to the inside in previous works, where M means myostracum. The outmost M+3 layer consists of calcite with a "mosaic" structure; granular submicron sub-grains with small-angle grain boundaries often accompanying dislocation arrays. M+2 layer consists of flat prismatic aragonite crystals with a leaf-like cross section, stacked obliquely to the shell surface. It looks that the prismatic crystals are surrounded by organic sheets, forming a compartment structure. M+1 and M-1 layers adopt a crossed lamellar structure consisting of aragonite flat prisms with rectangular cross section. M layer has a prismatic structure of aragonite perpendicular to the shell surface and with irregular shaped cross sections. Distinct organic sheets were not observed between the crystals in M+1, M and M-1 layers. The {110} twins are common in all aragonite M+2, M+1, M and M-1 layers, with the twin boundaries parallel to the prisms. These results for the microstructure of each layer should be considered in the discussion of the formation mechanism of the limpet shell structure.

Microtexture of larval shell of oyster, Crassostrea nippona: a FIB-TEM study.

The initial formation and subsequent development of larval shells in marine bivalve, Crassostrea nippona were investigated using the FIB-TEM technique. Fourteen hours after fertilization (the trochophore stage), larvae form an incipient shell of 100-150nm thick with a columnar contrast. Selected-area electron diffraction analysis showed a single-crystal aragonite pattern with the c-axis perpendicular to the shell surface. Plan-view TEM analysis suggested that the shell contains high density of {110} twins, which are the origin of the columnar contrast in the cross-sectional images. 72h after fertilization (the veliger stage), the shell grows up to 1.2-1.4mum thick accompanying an additional granular layer between the preexisting layer and embryo to form a distinctive two-layer structure. The granular layer is also composed of aragonite crystals sharing their c-axes perpendicular to the shell surface, but the crystals are arranged with a flexible rotation around the c-axes and not restricted solely to the {110} twin relation. No evidence to suggest the existence of amorphous calcium carbonate (ACC) was found through the observation. The well-regulated crystallographic properties found in the present sample imply initial shell formation probably via a direct deposition of crystalline aragonite.

Morphological analyses of minute crystals by using stereo-photogrammetric scanning electron microscopy and electron back-scattered diffraction.

We present a new method for the morphological analyses of minute faceted crystals by combining stereo-photogrammetric analysis of scanning electron microscope images and electron back-scattered diffraction. Two scanning electron microscope images of the same crystal, recorded at different tilt angles of the specimen stage, are used to determine the orientations of crystal edges in a specimen-fixed coordinate system. The edge orientations are converted to the indices [uvw] in the crystal system using the crystal orientation determined by electron back-scattered diffraction analysis. The Miller indices of crystal facets are derived from the indices of the edges surrounding the facets. The method is applicable to very small crystal facets. The angular error, as derived from tests using a calcite crystal of known morphology, is a few degrees. To demonstrate the applicability of the method, the morphology of boehmite (gamma-AlOOH) precipitated from solution during the dissolution of anorthite was analyzed. The micrometre-sized boehmite crystals are surrounded by two {010} basal facets and eight equivalent side facets that can be indexed equally well as {323}, {434} or {545}. We suggest that these side facets are in fact {111}, the morphology having been modified slightly (by a few degrees) by a small extension associated with opening along (010) microcleavage planes. Tiny {140} facets are also commonly observed.

Electron transfer through clay monolayer films fabricated by the Langmuir-Blodgett technique.

Hybrid films composed of amphiphilic molecules and clay particles were constructed by the modified Langmuir-Blodgett (LB) method. Clays used were sodium montmorillonite (denoted as mont) and synthetic smectite containing Co(II) ions in the octahedral sites (denoted as Co). Two kinds of amphiphilic molecules were used-[Ru(dC(18)bpy)(phen)2](ClO4)2 (dC(18)bpy = 4,4'-dioctadecyl-2,2'-bipyridyl and phen = 1,10-phenanthroline) (denoted as Ru) and octadecylammonium choloride (ODAH+Cl- or denoted as ODAH). Three kinds of hybrid films (denoted as Ru-mont, Ru-Co, and ODAH-Co films) were prepared by spreading an amphiphilic molecule onto an aqueous suspension of a clay. Atomic force microscopy (AFM) analyses of the films deposited on silicon wafers indicated that closely packed films were obtained at 20 ppm for all the above three cases. Cyclic voltammetry (CV) was measured on an ITO electrode modified with a hybrid film or a monolayer film of pure Ru(II) complex salt (denoted as Ru film). The Ru(II) complexes incorporated in the Ru-mont film lost their redox activity, indicating that montmorillonite layers acted as a barrier against electron transfer. In contrast, the same complexes in the Ru-Co film were electrochemically active with the simultaneous appearance of the redox peaks due to the Co(II)/Co(III) (or Co(II)/Co(IV)) couple. The results implied that electron transfer through cobalt clay layers was possible via mediation by Co(II) ions in a clay sheet. For an aqueous solution containing nitrite ions (NO2-) at pH 3.0, a large catalytic oxidation current was observed for both the electrodes modified with the Ru-mont and Ru-Co films. The results were interpreted in terms of the mechanisms that the charge separation of an incorporated Ru(II) complex took place to produce a pair of a Ru(III) complex and an electron and that the generated Ru(III) complex was reduced by a nitrite ion before it recombined with the electron.

Evidence for the role of organic layers in photoconductivity of organic/inorganic hybrid nanosheets as prepared by Langmuir-Blodgett methods.

By measuring the photoconductivity of hybrid LB films of exfoliative layered niobate and octadecylamine, it was evidenced that the film underwent a transition from an insulator to a photosemiconductor during photo-modification treatment by UV light, which was rationalized in terms of the direct contact of inorganic nanosheets achieved by the elimination of organic layers.

Photoconductive properties of organic-inorganic hybrid films of layered perovskite-type niobate.

A hybrid film of layered niobate and an organic amphiphile was prepared by the Langmuir-Blodgett (LB) method. Trimethylammonium-exchanged perovskite-type niobates ((CH(3))(3)NHSr(2)Nb(3)O(10)) were exfoliative to form an aqueous suspension. A monolayer of octadecylamine was produced on such an aqueous dispersion as a template for a hybrid film. A hybrid film was transferred as a Y-type LB film onto a hydrophilic glass plate or an ITO substrate. The structure of a deposited film was investigated with X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and atomic force microscopy (AFM) measurements, indicating a layer-by-layer structure with a single or double sheet of niobate as an inorganic composite. From the cyclic voltammogram on an ITO electrode modified with the Y-type 10 layered film, the lower edge of the conduction band of a niobate layer was determined to be - 0.6 V (vs Ag/AgCl). ac impedance and dc measurements were carried out on 1, 5, and 10-layered LB films (2 mm (electrode spacing) x 8 mm (width)) with aluminum electrodes. The freshly deposited samples behaved as an insulator under the illumination of 280 nm light (2.04 x 10(16) quanta s(-1)). Photoconductivities appeared, however, when they were preirradiated with a 150 W Xe lamp (ca. 2 x 10(18) quanta s(-1)) for 0.5-8.5 h. The process was denoted as photomodification. From the FT-IR and XRD results, it was deduced that the photomodification of LB films caused the decomposition of organic templates (octadecylammonium) accompanied by the collapse of layer-by-layer structures. dc analyses on the 5- and 10-layered films after photomodification also showed that they behaved as a photosemiconductor under UV light illumination.

H2 generation during dry grinding of kaolinite.

H2 generation during mechanochemical treatment of kaolinite by dry grinding was examined by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and BET surface area measurement. The H2 concentration in the mill pot, measured by gas chromatography, increased with grinding time up to a maximum concentration of 156 ppm (0.35 micromol) after 600 min. This H2 generation is considered to occur as a result of three processes: (1) structural destruction characterized by the delamination and loss of hydroxyl groups as a result of dry grinding, (2) transformation of liberated hydroxyls into water molecules by mechanochemical effects such as prototropy, and (3) H2 generation through reaction between surface water molecules and mechanoradicals created by the rupture of Si-O or Al-O-Si bonds. Although the surface area plateaued after 240 min grinding, the H2 concentration continued to increase, indicating that surface mechanoradicals are created during this later grinding stage. Thus, H2 generation can be used as an indicator of mechanoradical formation during mechanochemical treatment.