X-ray photoelectron spectroscopic study on the goethites with variations in crystallinity and morphology: their effects on surface hydroxyl concentration

We examined the effects of crystallinity and crystal morphology on surface hydroxyl concentration of goethite using four kinds of goethite samples prepared by aging a hydrous ferric oxide (ferrihydrite) at different temperatures ranging from 4 to 70?°C. These samples were analyzed with the following methods: powder X-ray diffraction, Brunauer–Emmett–Teller surface area analyzer, atomic force microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and high-resolution X-ray photoelectron spectroscopy (XPS). The first three analyses showed that the goethite aged at lower temperature has lower crystallinity, smaller particle size and lower aspect ratio. The ATR-FTIR analysis revealed that the OH-stretching band of goethite aged at 4?°C moves to slightly higher wavenumber than those of the samples aged at higher temperatures. Their XPS analyses demonstrated that variation in the concentration of surface hydroxyl group ranges from 6.6 (nm^?2) for the sample aged at 4?°C to 7.7 (nm^?2) for the sample aged at 70?°C. Considering the analytical depth of the XPS (~5?nm), photoelectrons are emitted from the uppermost layers of the analyte. Hence, XPS results are interpreted to reflect variations in the morphology of fine crystals (<100?nm thick). The morphology of the present goethites can be characterized by their aspect ratio, in other words, the degree of development of (110)–(110) intersection edges at which protons preferentially accumulate. This variation in the concentration of surface hydroxyl group revealed by XPS analysis offers experimental evidence for the effects of crystallinity and morphology on the surface chemical properties of goethite.     

Decrease in anthropogenic nutrients and its effect on the C/N/P molar ratio of suspended particulate matter in hypertrophic Dokai Bay (Japan) in summer

Biologically important nutrient concentrations in Dokai Bay have declined as a result of reductions in anthropogenic inputs of total nitrogen and total phosphorus. A decrease in nutrient concentrations affects phytoplankton growth, thereby changing the biochemical characteristics of autochthonous particulate matter. We therefore investigated changes in the C/N/P molar ratio of suspended particulate matter (SPM) in the summer, when phytoplankton growth is vigorous, before environmental quality standards (EQSs) were attained (1995–1998) and afterward (2006–2009). We found that the ratio of particulate organic nitrogen (PON) to particulate phosphorus (PP) changed in conjunction with changes in the ratio of dissolved inorganic nitrogen to dissolved inorganic phosphorus (DIP) that resulted from reductions in nutrient loading. Furthermore, we suggest that because the DIP concentration in seawater was high before EQSs were attained, inorganic phosphorus was possibly adsorbed onto SPM. After the attainment of EQSs, however, the DIP concentration fell, and PON/PP was high. Phosphorus limitation of phytoplankton growth in the mouth of the bay may explain the high PON/PP ratios after EQS attainment.     

The influence of environmental variability on silicate exchange rates between sediment and water in a shallow-water coastal ecosystem,the Seto Inland Sea,Japan

Silicate regeneration was determined in a shallow-water coastal ecosystem (Shido Bay, the Seto Inland Sea, Japan) during 1999-2000. The present study was carried out directly by core incubation and by determining gradients of dissolved silicate (DSi) in the pore water. Incubated fluxes ranged from 25.5 to 132.6 mgSim(-2)d(-1), and were 1.6-21.6 times greater than diffusive fluxes (5.4-43.3 mgSim(-2)d(-1)). The disparity between fluxes measured by core incubation and modeling pore water indicated that other physical, chemical or biological processes, in addition to diffusion of DSi from below, contribute to DSi fluxes measured during the incubation of undisturbed cores. A regression analysis revealed that water temperature and salinity explained 24% and 23%, respectively, of season to season variability in incubated fluxes. Microphytobenthos was responsible for 37% of the variability in measured rate of DSi fluxes, with greatly reducing DSi release rates due to their own DSi demand. Moreover, the inverse relationship between the DSi fluxes and biogenic silica (Bio-Si) concentrations in the surface sediment, suggested that about 41% of the variability in the DSi fluxes were explained by Bio-Si concentrations in the surface sediment. As a result, Shido Bay showed silicate regeneration of incubated cores to be a consequence of Bio-Si dissolution depending on microphytobenthos, temperature and salinity, while diffusive fluxes appeared to be limited by DSi in the pore water. An annual average of DSi flux (68.7+/-32.9 mgSim(-2)d(-1)) from the sediments to the water column corresponds to 38% of DSi, required for primary production by phytoplankton in Shido Bay.     

DATABASE ON INTERNET FOR GEOLOGICAL SURVEY OF JAPAN GEOCHEMICAL REFERENCE SAMPLES

A database on thirty-one Geological Survey of Japan (GSJ) geochemical reference samples has been set up on Internet which allows the retrieval of recommended or preferable values, compiled data, location, sample preparation and other relevant information. The URL location on WWW server is: http://www.aist.go.jp./RIODB/geostand/welcome.html     

Determination of Indium and Tellurium in Fifty Nine Geological Reference Materials by Solvent Extraction and Graphite Furnace Atomic Absorption Spectrometry

The indium (In) and tellurium (Te) contents of fifty nine geological reference materials, issued by several reference material producers (USGS, CRPG, ANRT, GIT-IWG and GSJ) have been determined by graphite furnace atomic absorption spectrometry, after aqua regia and HF digestion, and extraction of iodide complexes with trioctylmethylammonium (TOMA) - metyl isobutyl ketone (MIBK). Although the interferences from most elements can be minimised by the addition of palladium solution as the matrix modifier, large concentrations of Bi, Cu, Pb or Sn suppress the absorbance of In and/or Te. Samples for analysis were therefore restricted to those in which the concentrations of these interfering elements did not cause a significant interference. The limit of detection was 0.2 ng g⁻¹ In and Te for 1 g test portions. The agreement between the reported results and published data is satisfactory.     

GOLD IN TWENTY-SIX JAPANESE GEOCHEMICAL REFERENCE SAMPLES

Gold has been determined in 26 geochemical reference samples with graphite furnace AAS after digesting the samples with aqua regia and hydrofluoric acid and extracting gold by methyl isobutyl ketone (MIBK). This method yields clearly higher values than those by the partial attack using aqua regia digestion.     

Fluorite Deposits at Voznesenka in the Khanka Massif, Russia: Geology and Age of Mineralization

Abstract. A huge fluorite deposit at Voznesenka in the Khanka massif, Far East Russia is concluded to have formed at ca. 450 Ma in Late Ordovician time based on the K‐Ar ages for Li‐micas in the fluorite ore and greisenized leucogranite within the deposit. This conclusion is inconsistent with the current view of Devonian mineralization that stemmed from widely scattered whole‐rock Rb‐Sr isotope data for the heterogeneous leucogranite stocks influenced by strong alteration. The Voznesenka and neighboring fluorite deposits may have formed in Cambrian limestone in relation to the intrusion of the Li‐F‐rich felsic magma which has a similar chemistry to representative Li‐F‐rich felsic rocks including topaz granite and ongonite or topaz rhyolite; these rocks may be classified as a specific group of highly fractionated felsic magmas. Biotite granite plutons exposed in the Voznesenka district are divided in age into two groups based on the CHIME age data for zircon, monazite and xenotime: Ordovician and Permian. The Ordovician plutons seem to be coeval to the fluorite deposits and are characterized by F‐rich chemistry, reduced nature and association of tin mineralization with the deposition of fluorite and tourmaline. The biotite granite magmas of initially enhanced F contents could have been highly fractionated to form Li‐F‐rich leucogranite cupolas that provided fluorite deposits within the host limestone. Future prospecting for similar fluorite deposits is to be focused on areas of intersection between Ordovician Li‐F‐rich granite and Cambrian carbonate sequences. The Permian granite of southeastern margin of the Grodekovo batholith is characterized by lesser F content, oxidized nature and the lack of tin and fluorite mineralization in contrast to the Ordovician granite. The result of Permian age does not support the current view of Silurian age for the batholith and requires overall chronological reinvestigation in connection with the tectonic history of the Khanka massif because the Grodekovo is a representative of Paleozoic batholiths in Primorie.