Synthesis of crystallographically oriented olivine aggregates using colloidal processing in a strong magnetic field

This study develops a fabrication technique to obtain Fe-free and Fe-bearing (Fe:Mg = 1:9) olivine aggregates not only with high density and fine grain size but with crystallographic preferred orientation (CPO). A magnetic field (≤12 T) is applied to synthetic, fine-grained (~120 nm), olivine particles dispersed in solvent. The alignment of certain crystallographic axes of the particles with respect to a magnetic direction is anticipated due to magnetic anisotropy of olivine. The dispersed particles are gradually consolidated on a porous alumina mold covered with a solid–liquid separation filter during drainage of the solvent. The resultant aligned consolidated aggregate is then isostatically pressed and vacuum sintered. We find that (1) preparation of fully reacted olivine particles, with less propensity to coalesce; (2) preparation of a suspension with highly dispersed particles; and (3) application of a certain strength of the magnetic field are essential to obtain well-sintered and well-aligned aggregates. High density (i.e., <1 vol% porosity) and fine grain size (~1 μm) Fe-free and Fe-bearing olivine aggregates were successfully synthesized with uniaxially aligned a- and c-axes, respectively. Attempts to uniaxially align the magnetization hard axis and to triaxially align Fe-bearing olivine by rotating the suspension in the magnetic field succeeded in obtaining weakly developed CPO aggregates.     

Direct observation of Cm(III)-fulvate species on fulvic acid-montmorillonite hybrid by laser-induced fluorescence spectroscopy

Particulate matter plays an important role in the removal of metal ions from water in natural aquifers. Some of the most important of these materials consist of associations of inorganic particles (clay minerals, oxides) with humic substances, associations that can form readily in such an environment due to the strong affinity between inorganic particles and humic substances. These associations are referred to in this paper as organic-inorganic hybrids. However, it is not clear whether the sorbed species of metal ions in such organic-inorganic hybrids are organic or inorganic species because of the complexity of such hybrids and the lack of appropriate methods for characterizing the trace metal ions incorporated in them. In this study, laser-induced fluorescence spectroscopy (LIF) was used successfully to characterize the Cm(III) species on an FA(fulvic acid)-montmorillonite hybrid, an example of such organic-inorganic hybrids. The LIF clearly showed that Cm(III) can be sorbed as Cm(III)-fulvate complex in the FA-montmorillonite hybrid. These results were consistent with those of experiments of solid-water partitioning of Cm(III) (or Eu(III) used as an analogue) and speciation calculations based on the stability constants of Cm(III)-fulvate complexes determined in this study. The results of LIF and the partitioning experiments showed that the solid-water distribution of humic substances governed that of Cm(III) under our experimental conditions. The Cm(III) preference for forming Cm(III)-fulvate complexes was also evident under a condition that would be found in a natural aquifer with a fairly low concentration of organic matter in freshwater (dissolved organic carbon: 2 mg/dm³), as determined by our speciation calculations. These findings on the importance of humic substances in the migration of Cm(III) indicate that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Cm(III), or actinide(III) and lanthanide(III) ions, in natural aquifers.     

Evaluation of intrinsic vulnerability to nitrate contamination of groundwater: appropriate fertilizer application management

In agricultural areas, fertilizer application is the main source of nitrate contamination of groundwater. To develop fertilizer management strategies to combat this problem, arable land in Hokkaido, Japan was evaluated using geographic information system techniques for intrinsic groundwater vulnerability to nitrate contamination. The DRASTIC method was modified to adapt it to the Hokkaido environment and used for the evaluation. Of the seven original DRASTIC factors, the depth to water (D), net recharge (R), soil media (S), topography (T), and impact of vadose zone media (I) were selected and used to explain the vertical movement of contaminants to the aquifer. The rating for the net recharge factor was also modified to a dilution factor for contaminants, rather than as a transporter. The frequency of wells with nitrate concentrations exceeding the Japanese environmental standard (10 mg/L) was reasonably explained by vulnerability evaluation results (GLM: logit-link, quasi-binomial distribution, Y = [1 + exp(6.873765 − 0.045988 × X)]⁻¹, p < 0.001). However, in the paddy fields and pastures, vulnerability did not exhibit a clear relationship with the frequency of wells exceeding the standard. This suggests that the modified DRASTIC method is applicable for fertilizer application management in upland fields. In addition, under the ongoing policy for acreage allotment for rice production, this method will be useful for deciding the arrangement of arable land and crop rotation taking into consideration the potential risk of fertilizer-induced nitrate contamination of groundwater.     

Indigenous Knowledge on Soil Classification of Ethnic Groups in Luang Prabang Province of the Lao PDR

Introduction Traditional agriculture based on indigenous knowledge (IK) has been practiced in many areas for centuries. Such practices are often the basis of very sustainable technologies, which are potentially suitable for developmental programs. Polthanee (2001) reported that such farmer practices have been repeatedly found to be valid, rational and usually suited to the local environmental conditions. Moreover, with increased under- standing of agro-ecosystems, professionals in agricultura…     

Open boundary value problems in ocean dynamics by finite elements

This paper presents recent results of application of the finite element models to wave overtopping and wave run-up problems in ocean dynamics. Open boundaries are prescribed as natural boundary condition obtained from the continuity equation of the Galerkin finite element formulation. The numerical results are, in general, reasonably good agreements with the histrical field data.     

EXAFS study on the cause of enrichment of heavy REEs on bacterial cell surfaces

Rare earth element (REE) pattern is a unique geochemical tracer and has been measured for various natural materials. Among these, the REE distribution pattern between bacteria and water exhibits anomalous enrichment in the heavy REE (HREE) part, which can act as a signature of bacteria-related materials in natural samples. In this study, the REE binding site on the cell surface of a Gram-positive bacterium (Bacillus subtilis) responsible for HREE enrichment has been identified using extended X-ray absorption fine structure (EXAFS) coupled with a study of the variation in REE distribution patterns. The EXAFS data showed that the HREEs form complexes with multiple phosphate site (including phosphoester site) with a larger coordination number (CN) at lower REE-bacteria ratios ([REE]/[bac]), while light and middle REEs form complexes to the phosphate site with a lower CN. The fraction coordinated to carboxylate increased for all REEs with increasing [REE]/[bac] ratio. On the other hand, the enrichment of HREE in the REE distribution patterns of the bacteria was less marked with increasing [REE]/[bac] ratio. This result is consistent with the EXAFS data, because the REE pattern of surface complex with multiple phosphate in a reference material exhibits a monotonous increase for heavier REE, while phosphate surface complex with a low CN and a carboxylate site reach a maximum around Sm and Eu. Based on these results, it is clear that the REE are primarily bound to the phosphate site and subsequently to the carboxylate site on the bacterial cell surface.Regarding the pH dependence in the range (3 < pH < 7), both the EXAFS and REE pattern data indicate that the fraction of REE-carboxylate increased as the pH increases. The results above obtained for B. subtilis were also valid for Escherichia coli, a Gram-negative bacterium, showing that similar phosphate and carboxylate sites are also available in the cell walls of E. coli, or other Gram negative bacteria. In all our results, the variation in REE patterns correlated with the binding site indicated by EXAFS, showing that the REE pattern itself reflects the binding site of the REE at the bacterial surface for various parameters (pH and [REE]/[bac] ratio). Thus, the REE patterns can be used to estimate the binding sites for lower [REE]/[bac] ratios where spectroscopic techniques cannot be applied.The average bond length between the REE and oxygen was compared for various REE sorbed on bacteria, showing that the bond length for HREE (Er to Lu) was much shorter than those extrapolated from the trend between La and Dy, because of the selective binding of the HREE as the multiple phosphate surface complexes. Our results are consistent with the selective enrichment of the HREE at the bacterial cell surfaces, considering that chemical species with a shorter bond length are more stable. Thus, it is clear that the HREE enrichment at the bacterial cell surfaces is caused by the formation of the multiple phosphate surface complexes. Based on these results, it is suggested that materials having such phosphate sites such as bacteria and bacteria-related materials can induce anomalous HREE enrichment in natural systems.     

Occurrence of arsenic (V) in forearc mantle serpentinites based on X-ray absorption spectroscopy study

We examined As concentration, mineralogical site, and oxidation state in the serpentinites associated with the Tso Morari eclogitic rocks in the Indus suture zone, northwest Himalaya, to examine how highly fluid-soluble elements like As are transferred from slabs to arc magmas in subduction zones. The serpentinite samples represent hydrated peridotites at the base of the mantle wedge beneath Eurasia, and were exhumed from a depth of ∼100 km during subduction of the Indian continental margin. The bulk serpentinite samples contain total As concentrations ranging from 6 to 275 ppm. Arsenic in the samples is most likely present with magnetite and antigorite, since electron probe analysis yielded up to 90 ppm As in these minerals. X-ray absorption near-edge structure spectra indicate that As in serpentinites is mostly As(V) and that the neighboring atoms of As are O, although there are minute grains of sulfides and arsenides. The ratio of As(V) to total As is greater in samples with higher As contents, suggesting that the major source of As was oxidized As(V), introduced to the mantle wedge. Arsenic(V), originally adsorbed on Fe-oxides in slabs and overlying sediments, was most likely liberated during their subduction and incorporated subsequently in the overlying mantle wedge. Our data constrain the introduction of As into the mantle wedge at relatively shallow levels, much shallower than 25 km. Arsenic incorporated in the serpentinites was transported to deeper levels by mantle flow downward along the subduction zone, to be subsequently exhumed together with eclogitic rocks.     

An atomic level study of rhenium and radiogenic osmium in molybdenite

Local atomic structures of Re and radiogenic Os in molybdenite from the Onganja mine, Namibia, were examined using X-ray absorption fine structure (XAFS). Rhenium L_III-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) show that the oxidation state of Re, the interatomic distances between Re and the neighboring atoms, and the coordination number of Re to S are very similar to those of Mo in molybdenite. The results confirm that Re is present as Re(IV) in the Mo site in molybdenite.Measurement of L_III-edge XANES and EXAFS of a minor concentration (8.55 ppm) of radiogenic Os was accomplished in fluorescence mode by removing the interfering X-rays from Re and other elements using a crystal analyzer system. The data indicate that the oxidation state of radiogenic Os is Os(III) and Os(IV) and clearly different from Os(II) in natural sulfide minerals, such as OsS₂ (erlichmanite). XANES data also suggest that radiogenic Os does not form a secondary Os phase, such as OsS₂ or Os metal, in molybdenite.EXAFS of radiogenic Os was successfully simulated assuming that Os is present in the Mo site in molybdenite. The data are consistent with the XANES data; Os does not form Os phases in molybdenite. The EXAFS simulation showed that the interatomic distance between Os and S is 2.27 Å, which is 0.12 Å smaller than the distances of Re-S and Mo-S (2.39 Å) in molybdenite. Similar valences and ionic sizes of Re and Mo in molybdenite support the fact that large amounts of Re can be incorporated into the Mo site as has been observed in previous studies, whereas the different properties of Os compared to Mo and Re suggested here support much lower abundance of common Os in molybdenite. This makes molybdenite an ideal mineral for the Re-Os geochronometer as shown in many studies. However, the shorter distance between radiogenic Os and S compared to those of Re-S and Mo-S in molybdenite suggests that the radiogenic Os has a smaller ionic size than Re(IV) and Mo(IV). Furthermore, Os may be partly present as Os(III). Smaller and lower charge Os can diffuse faster than larger and higher charge Re in molybdenite at a given set of conditions. Hence, our study provides an atomic-level explanation for the high mobility of Os compared to Re, which has been suggested by earlier workers using laser ablation ICP-MS.