1994 COMPILATION OF ANALYTICAL DATA FOR MINOR AND TRACE ELEMENTS IN SEVENTEEN GSJ GEOCHEMICAL REFERENCE SAMPLES, "IGNEOUS ROCK SERIES"

Analytical data for minor and trace elements published or communicated to us, on seventeen GSJ (Geological Survey of Japan) reference samples, "Igneous rock series" received up to April 1994 are compiled. The data were evaluated statistically in consideration of analytical methods. Based on the selected available data, 1994 recommended and proposed values for 65 minor and trace elements are presented.     

Sulfate-coated dust particles in the free troposphere over Japan

Airborne aerosol collections were performed over Wakasa bay (36°00′N, 135°30′E) in March and Kumano open sea (34°00′N, 136°50′E) and Seto (35°10′N, 137°10′E) in July 2001 at altitudes between 1.0 and 5.8 km. The particles were individually analyzed using transmission electron microscopy (TEM). Relatively large mineral-dust (mostly clay) particles were abundant in the March samples. They also dominated in July in the mid-troposphere higher than 4 km altitude, whereas sea salt and ammonium sulfate were more abundant at lower altitudes. Ca-coated grid samples show many traces of aqueous sulfate droplets. The proportions of former sulfate droplets to the total collected particles apparently increased with increasing relative humidity at the time of sampling. TEM analysis revealed that a significant fraction of these former droplets enclose mineral-dust particles as well as sea salt, soot, and fly ash. Some enclose mixtures of mineral-dust, sea-salt, soot, and fly ash particles. The results provide evidence that mineral dust from the Asian continent could acquire coatings of sulfate while being transported in the free troposphere. The mineral-dust particles probably acquired the sulfate coatings either through heterogeneous uptake of gaseous SO₂ and subsequent oxidation or through coagulation with cloud or fog droplets. The presence of the mixed particles in sulfate droplets also indicates that aggregation of particles of different origins occurred through cloud processing. Such sulfate-coated dust particles would affect cloud formation, precipitation, and chemistry of the free troposphere.     

Crystallization of microlites and degassing during magma ascent: Constraints on the fluid mechanical behavior of magma during the Tenjo Eruption on Kozu Island, Japan

Bubble and crystal textures provide information with regard to the kinetics of the vesiculation and crystallization processes. They also provide insights into the fluid mechanical behavior of magma in a conduit. We performed textural (bubble and crystal) and compositional analyses of pyroclasts that were obtained from the Tenjo pyroclastic flow, which resulted on account of the eruption in 838 A.D. on Kozu Island, about 200 km south of Tokyo, Japan. Pyroclasts in one flow unit (300∼2,060 kg/m³; average density 1330 kg/m³) can be classified into three types on the basis of vesicle textures. Type I pyroclasts have small isolated spherical bubbles with higher vesicularities (67–77 vol.%) and number density (10.8–11.7 log m⁻³). Type II pyroclasts have vesicularities similar to type I (61–69 vol.%), but most bubbles exhibit evidences of bubble coalescence, and lower number densities than type I (8.9–9.5 log m⁻³). Type III pyroclasts contain highly deformed bubbles with lower vesicularities (16–34 vol.%) and number densities (8.2–9.0 log m⁻³). The microlite volume fraction (DRE converted) also changes consistently across type I, type II, and type III as 0.06, 0.08, and 0.10–0.15, respectively. However, the number density of the microlites remains nearly invariant in all the pyroclast types. These facts indicate that the variation in the microlite volume fraction is controlled not by the number density (i.e., nucleation process), but by the size (i.e., growth process); the growth history of each type of microlite was different. Water content determinations show that the three types of pumices have similar H₂O contents (2.6±0.2 wt%). This fact implies that all three types were quenched at nearly the same depth (35±5 MPa, assuming that the magma was water-saturated) in the conduit. If the crystal sizes are limited only by growth time, a variation in this parameter can be related to the residence time, which is attributed to the flow heterogeneity in the conduit. By assuming a laminar Poiseuille-type flow, these textural observations can be explained by the difference in ascent velocity and shearing motion across the conduit, which in turn results in the differences in growth times of crystals, degrees of deformation, and bubble coalescence. Consequently, for crystals in the inner part of the conduit, the crystal growth time from nucleation to quenching is shorter than that near the conduit wall. The vesicle texture variation of bubbles in types I, II, and III results from the difference in the deformation history, implying that the effect of degassing occurred primarily towards the conduit wall.     

Spatial representativeness of single tower measurements and the imbalance problem with eddy-covariance fluxes: results of a large-eddy simulation study

A large-eddy simulation (LES) study is presented that investigates the spatial variability of temporal eddy covariance fluxes and the systematic underestimation of representative fluxes linked to them. It extends a prior numerical study by performing high resolution simulations that allow for virtual measurements down to 20 m in a convective boundary layer, so that conditions for small tower measurement sites can be analysed. It accounts for different convective regimes as the wind speed and the near-surface heat flux are varied. Moreover, it is the first LES imbalance study that extends to the stable boundary layer. It reveals shortcomings of single site measurements and the necessity of using horizontally-distributed observation networks. The imbalances in the convective case are attributed to a locally non-vanishing mean vertical advection due to turbulent organised structures (TOS). The strength of the TOS and thus the imbalance magnitude depends on height, the horizontal mean wind and the convection type. Contrary to the results of a prior study, TOS cannot generally be responsible for large energy imbalances: at low observation heights (corresponding to small towers and near-surface energy balance stations) the TOS related imbalances are generally about one order of magnitude smaller than those in field experiments. However, TOS may cause large imbalances at large towers not only in the case of cellular convection and low wind speeds, as found in the previous study, but also in the case of roll convection at large wind speeds. In the stably stratified boundary layer for all observation heights neither TOS nor significant imbalances are observed. Attempting to reduce imbalances in convective situations by applying the conventional linear detrending method increases the systematic flux underestimation. Thus, a new filter method is proposed.     

Potential Influence of Ocean Acidification on Deep-Sea Fe–Mn Nodules and Pelagic Clays: An Improved Assessment by Using Artificial Seawater

In order to assess the potential risk of metal release from deep-sea sediments in response to pH decrease in seawater, the mobility of elements from ferromanganese (Fe–Mn) nodules and pelagic clays was examined. Two geochemical reference samples (JMn-1 and JMS-2) were reacted with the pH-controlled artificial seawater (ASW) using a CO₂-induced pH regulation system. Our experiments demonstrated that deep-sea sediments have weak buffer capacities by acid–base dissociation of surface hydroxyl groups on metal oxides/oxyhydroxides and silicate minerals. Element concentrations in the ASW were mainly controlled by elemental speciation in the solid phase and sorption–desorption reaction between the charged solid surface and ion species in the ASW. These results indicated that the release of heavy metals such as Mn, Cu, Zn and Cd should be taken into consideration when assessing the influence of ocean acidification on deep-sea environment.     

Persistent Differences in Horizontal Gradients in Phytoplankton Concentration Maintained by Surf Zone Hydrodynamics

Surf zones, regions of breaking waves, are at the interface between the shore and coastal ocean. Surf zone hydrodynamics may affect delivery of phytoplankton subsidies to the intertidal zone. Over a month of daily sampling at an intermediate surf zone with bathymetric rip currents and a reflective surf zone, we measured surf zone hydrodynamics and compared concentrations of coastal phytoplankton taxa in the surf zones to concentrations offshore. At the intermediate surf zone, ~80% of the variability in the concentration of coastal phytoplankton taxa within the surf zone was explained by their variation offshore; however, concentrations were much higher and lower than those offshore in samples from a bathymetric rip current and over the adjacent shoal, respectively. Hydrodynamics at this intermediate surf zone did not hinder the delivery of coastal phytoplankton to the surf zone, but the bathymetric rip current system appeared to redistribute phytoplankton concentrating them within eddies. At the reflective shore, we sampled surf zones at a beach and two adjacent rocky intertidal sites. Concentrations of typical coastal phytoplankton taxa were usually an order of magnitude or more lower than those offshore, even when offshore samples were collected just 20 m beyond the breakers. The phytoplankton assemblages inside and outside the surf zone often appeared to be disconnected. Surf zone hydrodynamics at the steep, reflective shore coupled with low phytoplankton concentrations in near-surface water appeared to limit delivery of phytoplankton subsidies to the surf zone. Surf zone hydrodynamics may be a key factor in the alongshore variation in phytoplankton subsidies to coastal communities.     

Characterization of serpentinization in olivine-orthopyroxene-H2O system revealed by thermogravimetric and multivariate statistical analyses

Thermogravimetric (TG) analyses were used to characterize the products and quantify the extent of serpentinization as a stepwise weight loss during heating (TG loss) or its derivative (DTG). Multivariate analyses are powerful tools for extracting information from complicated spectrum data; however, no studies have applied them to characterize serpentinites. In this study, hydrothermal experiments of olivine-H₂O, olivine–orthopyroxene-H₂O and orthopyroxene-H₂O were conducted at 250–400°C and under vapor-saturated pressure. The product minerals observed were serpentine+brucite+magnetite in the olivine-H₂O experiments and serpentine±talc in the orthoyroxene-H₂O and olivine-orthopyroxene-H₂O experiments. These results are consistent with those of previous studies; however, the positions and width of DTG peaks for individual minerals were varied depending on the experimental conditions. To extract systematics from the TG spectra, non-negative matrix factorization (NMF), an unsupervised machine learning technique, was applied to the DTG spectra of the experimental products. NMF revealed that the DTG profiles were explained by a linear combination of six basis spectra, which corresponded to the characteristic products, including three types of serpentine minerals (low-, medium-, and high-T), two types of brucite (low-and high-T), two type of talc (talc+serpentine mixture, well-crystallized talc) with different crystallinity, and noise during the TG measurement. Systematic changes in the factor loading revealed that, in the olivine-H₂O systems, the products changed from medium-T serpentine+low-T brucite to high-T serpentine+high-T brucite as serpentinization progressed. In the olivine-orthopyroxene system, low-T serpentine or poorly crystallized talc+serpentine mixture was initially formed, followed by the formation of well-crystallized talc, resulting in dehydration. Applying NMF to DTG showed the mineralogical differences between olivine and orthopyroxene systems and increases of the crystallinity during the progress of serpentinization, suggesting its potential for characterizing various serpentinites within oceanic lithospheres that suffer from several stages of alteration and weathering at different temperatures.     

Reconstructing the evolution of fault zone architecture: Field‐based study of the core region of the Atera Fault,Central Japan

In order to reconstruct the architectural evolution of a fault zone with heterogeneous structures, we studied the Atera Fault in Central Japan, and described the detailed mesoscopic and microscopic features of the zone. The fault zone studied consists of a 1.2‐m wide fault core of fault breccia mixed with fragments derived from welded tuff, granite, and mafic volcanic rocks. The 1.2‐m wide fault core is bordered by a western damage zone characterized by a welded tuff fault breccia and an eastern damage zone characterized by a granite cataclasite. A secondary fault core, a 30‐cm wide granite‐derived fault gouge, cross‐cuts the granite cataclasite. Although welded tuff fault breccia and granite cataclasite are also pervasively fractured and fragmented, the fault cores are significantly affected by fragment size reduction due to intense abrasive wear and comminution. The 1.2‐m wide fault core includes fragments and a sharp dark layer composed of mafic volcanic rocks, which can be correlated with neighboring 1.6 Ma volcanic rocks. This observation places a younger constraint on the age of the fault core formation. Carbonate coating on basalt fragments in the 1.2‐m wide fault core has also been fractured indicating the repetition of intense fragmentation. Bifurcated, black and gray veins near the 1.2‐m wide fault core are likely injection veins, formed by the rapid injection of fine material within fault zones during seismic events. The granite‐derived fault gouge, characterized by hard granite fragments without intense brecciation and microfracturing, in a kaolinite‐rich clay matrix, is interpreted as the most recent slip zone within the exposed fault zone. A preview of published geological and hydrological studies of several fault zones shows that clay‐rich fault cores can exhibit much lower permeability than the adjacent damage zones represented in this present case by the welded tuff fault breccia and granite cataclasite.