Mineralogical Associations of Arsenic and Antimony in Thirty Five Geochemical Reference Materials by Sequential Extraction with Hydride Generation and Atomic Absorption Spectrometry

A method is described to estimate the chemical forms of arsenic (As) and antimony (Sb) in a variety of geochemical reference materials, combining a sequential extraction scheme with hydride generation and atomic absorption spectrometry (HG-AAS). The fractions dissolved by sequential extraction are empirically defined as the exchangeable, EDTA soluble, oxide, sulfide and residual fractions. The amount of As and Sb in the EDTA soluble fraction have been derived mainly from oxide phases, and partly from carbonate minerals. Most sulfide minerals in common geological samples were considered to be dissolved with the digestion of 0.7 mol l⁻¹ NaOCl, but only small fraction of arsenopyrite and loellingite in ores could be dissolved in this way. Satisfactory agreement was observed between the sum of the As or Sb values from exchangeable to residual fractions and the reported total As or Sb values, with a few exceptions. Analytical results of As and Sb for thirty five geochemical reference materials are tabulated, and geochemical and mineralogical features are discussed.     

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     

A high‐T metamorphic complex derived from the high‐P Suo metamorphic complex in the Omuta district,northern Kyushu,southwest Japan

New U–Pb ages of zircons from migmatitic pelitic gneisses in the Omuta district, northern Kyushu, southwest Japan are presented. Metamorphic zonation from the Suo metamorphic complex to the gneisses suggests that the protolith of the gneisses was the Suo metamorphic complex. The zircon ages reveal the following: (i) a transformation took place from the high‐P Suo metamorphic complex to a high‐T metamorphic complex that includes the migmatitic pelitic gneisses; (ii) the detrital zircon cores in the Suo pelitic rocks have two main age components (ca 1900–1800 Ma and 250 Ma), with some of the detrital zircon cores being supplied (being reworked) from a high‐grade metamorphic source; and (iii) one metamorphic zircon rim yields 105.1 ±5.3 Ma concordant age that represents the age of the high‐T metamorphism. The high‐P to high‐T transformation of metamorphic complexes implies the seaward shift of a volcanic arc or a landward shift of the metamorphic complex from a trench to the sides of a volcanic arc in an arc–trench system during the Early Cretaceous. The Omuta district is located on the same geographical trend as the Ryoke plutono‐metamorphic complex, and our estimated age of the high‐T metamorphism is similar to that of the Ryoke plutono‐metamorphism in the Yanai district of western Chugoku. Therefore, the high‐T metamorphic complex possibly represents the western extension of the Ryoke plutono‐metamorphic complex. The protolith of the metamorphic rocks of the Ryoke plutono‐metamorphic complex was the Jurassic accretionary complex of the inner zone of southwest Japan. The high‐P to high‐T transformation in the Omuta district also suggests that the geographic trend of the Jurassic accretionary complex was oblique to that of the mid‐Cretaceous high‐T metamorphic field.     

A crystal chemical study of protoanthophyllite: orthoamphiboles with the protoamphibole structure

Two new protoamphibole-type amphiboles with space group type Pnmn, have been found in nature: protoferro-anthophyllite (Fe_0.80Mn_0.20)₂ (Fe_0.98Mg_0.02)₅ (Si₄O₁₁)₂(OH)₂, and protomangano-ferro-anthophyllite, (Mn_0.70Fe_0.30)₂ (Fe_0.82Mg_0.18)₅ (Si₄O₁₁)₂(OH)₂. Protoferro-anthophyllite (PFA) occurs in pegmatites at both Gifu Prefecture, Japan and at Cheyenne Mountain, El Paso County, Colorado, USA. Protomangano-ferro-anthophyllite, (PMFA) occurs in pegmatites at Fukushima Prefecture and in a Mn mine at Tochigi Prefecture, Japan. Structure determinations of the two amphiboles show that both are isostructural with the synthetic fluorian-amphibole, protoamphibole (= protofluorian-lithian-anthophyllite). A calculation of the procrystal electron density distributions, the bond paths and the bond critical point properties of PFA, PMFA, grunerite and protoamphibole indicates that the M4 cation in these amphiboles is 4-coordinated. A calculation of the electron density distributions at the Becke3LYP/6-311G(2d,p) level for model silicate tetrahedra for these amphiboles and anthophyllite reveals that the value of the electron density at the bond critical points, ρ(r _c ), for the SiO(nbr) bonds is larger, on average (0.93 e/ų), than that for the SiO(br) bonds (0.90 e/ų). The observed SiO bond lengths decrease linearly with increasing ρ(r _c ) while the magnitudes of the curvatures of ρ(r _c ) both perpendicular and parallel to the bonds and the Laplacian of ρ(r _c ) each increases. These trends are associated with an increase in the electronegativity of the Si cation, a possible increase in the covalent character of the SiO bond and a tendency for SiO(nbr) bonds to be involved in wider OSiO angles than SiO(br) bonds. It is possible, if not likely, that protoanthophyllite has often been misidentified as anthophyllite.     

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.     

Elasticity and anharmonicity of potassium chloride at high temperature

High temperature elasticity of single crystal potassium chloride has been studied by the Rectangular Parallelepiped Resonance (RPR) method up to 870 K (? 3.8 times the Debye temperature, ?). The elastic stiffness moduli, C ₁₁ and C ₄₄, decrease linearly with temperature while C ₁₂ increases slightly with temperature. The RPR method is particularly suited to measurements of elasticity at high temperatures, since no glues (which decompose at high temperature) are used to connect the transducers to a specimen. As a consequence, the measured spectrum closely approximates the theoretical spectrum of a specimen freely suspended in space with no external contact. The present elasticity data permits the investigation of the thermodynamic properties of potassium chloride far above the Debye temperature when used together with the previous zero-pressure data on thermal expansivity and heat capacity. The equation of state of potassium chloride is virtually unaffected by anharmonicity, even at T/?=3.8. One result is that the thermal pressure for KCl above the Debye temperature linearly increases with temperature. There is also small dependence on volume, in contrast to NaCl where there is no dependence on volume.     

Effects of irradiance on excystment of tintinnids from marine sediments

The effects of irradiance on the excystment of tintinids from marine sediments were examined by incubating sediment samples in filtered seawater under various light levels. The total incidence of tintinnid excystment over five days was significantly less at low irradiance at and less than 2.5 E m^–2sec^–1 comparing to that at higher irradiance, at and more than 6.9 E m^–2sec^–1 (p<0.01), indicating that excystment of tintinnids is inhibited under low irradiance conditions. These results imply that water depth, disturbance of surface sediments and vertical mixing of water influence the excystment of tintinnids in coastal areas because these factors determine the light levels to which the tintinnid cysts are exposed.     

1996 COMPILATION OF ANALYTICAL DATA ON NINE GSJ GEOCHEMICAL REFERENCE SAMPLES, "SEDIMENTARY ROCK SERIES"

Analytical data compiled on nine Geological Survey of Japan (GSJ) reference samples, "Sedimentary rock series" received by February 1996 are reported. After excluding outliers and examining critically the analytical procedures employed, the data were evaluated statistically. Recommended or preferable values for fifteen major and sixty minor and trace elements are proposed.     

Elemental Concentrations in Nine New GSJ Rock Reference Samples "Sedimentary Rock Series"

Nine new rock reference samples of the "Sedimentary rock series", Chert JCh-1, Dolomite JDo-1, Lake sediment JLk-1, Limestone JLs-1, Stream sediments JSd-1 to JSd-3, and Slates JS1-1 and JSl-2 have been prepared by the Geological Survey of Japan(GSJ). Thirty major, minor and trace elements were determined using atomic absorption spectrometry, flame emission spectrometry, infrared absorption spectrometry and wet chemical techniques. The results of homogeneity tests showed that almost all elements, with a few exceptions, are considered to be distributed homogeneously in each reference sample.