Impact of Changes in Redox Conditions on Leaching of Some Elements from MSW Fly Ash

Abstract. Oxidation and reduction processes can influence extent of leaching of elements from solid waste. Three samples of municipal solid waste combustion fly ash were subjected to oxidizing and reducing conditions in order to evaluate leaching of elements in the Milli-Q water and fly ash (liquid to solid ratio, 100) mixtures. Although the oxidizing and reducing conditions were applied for 6 hours only, elements like Cs, Li, Mg, Sb, Tl and V leached more under oxidizing condition than under reducing condition in the case of all three ash samples. Cadmium, Pb and Zn leached more from all samples under reducing condition than under oxidizing condition. Leaching of other elements like Al, Ba, Cr, Cu, Ni and Rb was inconsistent with oxidizing or reducing conditions and varied from sample to sample, suggesting that factors other than redox may be more important in controlling leaching of these elements. Strong acid neutralization capacity of the fly ash samples let the pH vary within a narrow range, and thus severely limited the extent of leaching during the course of the experiment. Lead and Zn were the most sensitive while K and Na were the least sensitive to changes in redox conditions.     

Effects of ulvoid (Ulva spp.) accumulation on the structure and function of eelgrass (Zostera marina L.) bed

The objective of this study is to clarify the effect of ulvoid (Ulva spp.) accumulation on the structure and function of an eelgrass bed by the coast of Iwakuni, Seto Inland Sea, Japan. We monitored eelgrass shoot density and volume of ulvoid accumulation in the study site and evaluated effects of the accumulated ulvoid canopy on the percent survival, seedling density, growth rates, photosynthetic photon flux density (PPFD) and carbon contents of eelgrass. Eelgrass shoot density decreased by the accumulation of ulvoid. Also, seedling density decreased by the increase in the ulvoid volumes. Shoot density, seedling density and leaf elongation were negatively correlated with ulvoid volume. Carbon contents in eelgrass decreased by the accumulation of ulvoid (canopy height: 25cm). These results suggest that accumulation of ulvoid bloom has significant negative impacts on the structure and function of eelgrass bed, i.e. decreases in vegetative shoot density, seedling density, shoot height and growth rate.     

Factors controlling regional spatial distribution of 53 elements in coastal sea sediments in northern Japan: Comparison of geochemical data derived from stream and marine sediments

In all, 53 elements were analyzed in 1406 coastal sea sediment samples collected from an area off Hokkaido and the Tohoku region of Japan during a nationwide marine geochemical mapping project. The spatial distribution patterns of the elemental concentrations in coastal seas along with the existing geochemical maps in terrestrial areas were used to define natural geochemical background variation and mass transport processes. The terrestrial area is covered by mafic volcanic rocks and accretionary complexes associated with ophiolite, which has small amounts of felsic volcanic rocks and granite. The spatial distribution patterns of elements enriched in mafic lithologies such as Fe (Total Fe₂O₃) and Sc in marine environments are influenced by adjoining terrestrial materials. The spatial distribution patterns of Cr and Ni concentrations, which are highly abundant in ultramafic rocks on land, are used to evaluate the mass transport from land to the sea and the dispersive processes caused by oceanic currents. The scale of mass transport by oceanic currents occurs up to a distance of 100–200 km from the coast along the coastal areas. The regional differences of elements rich in felsic lithologies such as K (K₂O), Nb and La in marine sediments are determined mainly by the relative proportion of minerals and lithic fragments enriching felsic materials to those associated with mafic materials. The spatial distribution of elemental concentration is not always continuous between the land areas and coastal sea areas. That difference is interpreted as resulting from (1) transportation of marine sediments by oceanic currents and storm waves, (2) contribution of volcanic materials such as tephra, (3) occurrence of shell fragments and foraminifera tests and (4) distribution of relict sediments of the last glacial age and early transgression age. Contamination with Cu, Zn, Cd, As, Mo, Sn, Sb, Hg, Pb and Bi was not observed in marine environments because the study area has little anthropogenic activity. Terrestrial materials are the dominant source for these metals. The Mo, Cd, Sn, Sb, Hg, Pb and Bi are abundant in silty and clayey sediments locally because of early diagenetic processes, authigenic precipitation and organic substances associated with these elements. The spatial distribution of As concentration shows exceptions: it is concentrated in some coarse and fine sands on the shelf. The enrichment is explained by adsorption of As, sourced from a coal field, to Fe hydroxide.     

The pre-Cretaceous deep-seated tectonics of the Abukuma massif and its place in the structural framework of Japan

The structures and microstructures of the Takanuki and Hitachi areas in the Abukuma massif, Northeast Japan are described. In the Takanuki area, the basic Gosaisho series thrusts the pelitic Takanuki ones in a HP metamorphic context. The nappe structure is afterwards refolded by a migmatitic dome: the Samegawa dome, in a HT metamorphic context. Microtectonic analysis shows that the nappe was transported from south to north along the stretching lineation. Geometric features suggest that the Samegawa dome was emplaced by diapirism. The role of the thrust surface as an instable interface promoting the doming is emphasized. The Hitachi metamorphic rocks composed of basic schist, limestone and sandstone shist thrust the pelitic rocks of the western Hitachi gneisses. As for the Takanuki area, the thrusting occurred in ductile synmetamorphic conditions with a north or northeastward displacement. Owing to lithologic, petrologic, structural similitudes, the nappe of the Hitachi metamorphic rocks and that of the Gosaisho series are unified into a unique nappe with a northward motion. The emplacement occurred between late Permian and late Cretaceous likely in late Jurassic. The allochthonous units of the Abukuma massif are correlated with the Green Schist nappe described in Southwest Japan, since they are surrounded by the same zones, namely the Tanba zone and the Kurosegawa-Kitakami one. Moreover both in Southwest and Northeast Japan, the emplacement of the Green Schist nappes is due to a shear deformation inducing rotational structures along the stretching lineation indicating the same sense of transport, that is eastward in Southwest Japan and northward in Northeast Japan, owing to the late bending of the Japanese Islands. The late Jurassic nappe structure is obliquely overprinted by a HT metamorphism, Ryoke in Southwest Japan, Abukuma in Northeast Japan, and afterwards cut by late faults as the Median Tectonic Line or the Tanakura fault, giving rise to the present complexity.     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

Modelling Freshwater Resources at the Global Scale: Challenges and Prospects

Quantification of spatially and temporally resolved water flows and water storage variations for all land areas of the globe is required to assess water resources, water scarcity and flood hazards, and to understand the Earth system. This quantification is done with the help of global hydrological models (GHMs). What are the challenges and prospects in the development and application of GHMs? Seven important challenges are presented. (1) Data scarcity makes quantification of human water use difficult even though significant progress has been achieved in the last decade. (2) Uncertainty of meteorological input data strongly affects model outputs. (3) The reaction of vegetation to changing climate and CO₂ concentrations is uncertain and not taken into account in most GHMs that serve to estimate climate change impacts. (4) Reasons for discrepant responses of GHMs to changing climate have yet to be identified. (5) More accurate estimates of monthly time series of water availability and use are needed to provide good indicators of water scarcity. (6) Integration of gradient-based groundwater modelling into GHMs is necessary for a better simulation of groundwater–surface water interactions and capillary rise. (7) Detection and attribution of human interference with freshwater systems by using GHMs are constrained by data of insufficient quality but also GHM uncertainty itself. Regarding prospects for progress, we propose to decrease the uncertainty of GHM output by making better use of in situ and remotely sensed observations of output variables such as river discharge or total water storage variations by multi-criteria validation, calibration or data assimilation. Finally, we present an initiative that works towards the vision of hyperresolution global hydrological modelling where GHM outputs would be provided at a 1-km resolution with reasonable accuracy.     

Satellite theory

In this paper dynamical characteristics of satellites are outlined by classifying the satellites into three categories according to the values of the solar tidal factor (n/n)² which is the disturbing factor due to the sun and the oblateness factor of the primary planetJ ₂/a ². For inner satellites (n/n)² is much smaller thanJ ₂/a ² and there are several pairs among them, for which the mean motions are commensurable to each other, and for some of them secular accelerations in the mean longitudes have been detected. For outer satellites (n/n)² is much larger and the solar perturbations are dominant. For intermediary satellites the motion of the pole of the orbital plane is not so simple as those of the satellites of the other categories.     

Skarns and Genesis of the Huanggang Fe-Sn Deposit, Inner Mongolia, China

Abstract: The skarns and genesis were studied of the Huanggang Fe‐Sn deposit and the nearby Sumugou Zn‐Pb deposit in Inner Mongolia, China. In the Huanggang mine, Nos. 1 to 4 Fe ore bodies are arranged along a calcareous horizon from proximal to distal in this order to a granite intrusion named Luotuochangliang, while Sn ore body is situated near another granite intrusion named 204. According to the distance from the granitic intrusions, mineral assemblages in skarns are systematically changed. Garnet is the most predominant skarn mineral throughout the deposit. Hastingsitic amphiboles, however, predominate in the proximal skarns. Fluorite is common in the proximal skarns, while instead calcite is common in the distal skarns. Chlorite is characteristically present only in No. 3 ore body, and chlorite geothermometry gives near 300C for the mineralization of later stage. When garnet crystal shows zonal structure, isotropic andraditic garnet occupies the core, and is surrounded with anisotropic less‐andraditic garnet. The presence of white skarn along the boundary between main skarns and host sedimentary rocks confirms relatively reducing environment prevailing as a whole in the studied area. However, the compositional relation between coexisting garnet and clinopyroxene demonstrates that relatively oxidizing condition was achieved for garnet skarn and magnetite ore in the distal, Nos. 2 to 4 Fe ore bodies and Sumugou deposit, compared to that for garnet skarn in the proximal, No. 1 and Sn ore bodies. Preliminary study on the tin content of garnets in the studied area revealed a certain degree of contribution brought from granitic intrusives since the early stage of skarn formation, irrespective of proximal or distal. Oxygen isotope study on garnet, magnetite, quartz and skarn calcite, as well as hydrogen isotope study on hastingsitic amphibole, demonstrates mainly meteoric water origin for the skarn– and ore‐forming solutions. The occurrence of Sn, W, Mo and F minerals indicates that those elements were mainly supplied to the deposit later than the formation of skarns and iron ores, overlapping to them. These constraints allow to delineate the formation model of the deposit as follows (Fig. 10): At the time of late Jurassic to early Cretaceous, felsic activity occurred in this region as a part of Yanshanian magmatism, and formed granitic intrusions as well as thick volcanic piles on the surface. The circulation of meteoric water was provoked by the heat brought by the intrusions. By this circulation, much amount of iron was extracted from andesites of the Dashizhai Formation, and precipitated as skarns and magnetite ores along calcareous horizons near the bottom of the Huanggangliang Formation. Subsequently, volatile‐rich fluids with Sn, W and Mo were expelled from the solidifying granitic magmas, and precipitated these metals in the pre‐existing skarns and ores.     

Empirical shear wave velocity equations in terms of characteristic soil indexes

An investigation to systematize empirical equations for the shear wave velocity of soils was made in terms of four characteristic indexes. The adopted indexes are the N-value of the Standard Penetration Test, depth where the soil is situated, geological epoch and soil type. As some of these indexes are variates belonging to interval scales while others belong to nominal or ordinal scales, the technique known as a multivariate analysis cannot be employed. A new approach to the theory of quantification, after C. Hayashi, was introduced and developed for solving this difficulty. Fifteen sets of empirical equations to estimate low strain shear wave velocity theoretically may be obtained by combining the above four indexes. All of these sets were derived by use of about 300 data, and their accuracies were evaluated by means of correlation coefficients between the measured and estimated shear wave velocities. The best equation was found to be the one which included all the indexes, and its correlation coefficient was 0.86. The empirical equation relating the standard penetration N-value to the shear wave velocity provided a correlation of only 0.72, and is one of the lowest ranking among the 15 sets of equations.