氮气、氧气和空气水合物的合成及其拉曼光谱特征

在-20℃和不同的压力下,在实验室内分别合成了氮气水合物(16MPa)、氧气水合物(13MPa)和空气水合物(15MPa),并对其N—N和O—O键伸缩振动的拉曼光谱特征进行了研究。结果表明,人工合成的水合物中的N—N和O—O键的拉曼位移与天然的空气水合物中的数据十分接近。在氮气水合物和空气水合物中,N—N键的拉曼峰值均为2322.4cm-1;O—O键的拉曼峰值在氧气水合物和空气水合物保持一致,均为1547.8cm-1。空气水合物分解的拉曼谱图表明,它不是氮气水合物和氧气水合物组成的混合物,而是由氮分子和氧分子共同生成的单一水合物,氮分子和氧分子同时进入水合物的大笼和小笼中。与空气中的氮、氧比例相比,水合物中氧分子明显富集,氮分子和氧分子的比例为2.4∶1。     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

The Late Silurian Age of the Reference Aralaul Granosyenites–Granite Massif (Northern Kazakhstan)

This work presents the results of U–Pb geochronological studies of alkaline granites of the Aralaul complex of Northern Kazakhstan, which allow one to substantiate their Late Silurian (420 ± 4 Ma) age. Taking into consideration the previously obtained data, we propose a new development scheme of Paleozoic granitoid magmatism in Northern Kazakhstan, which includes Late Ordovician granite–granodiorite (Zerenda and Krykkuduk), Early Silurian granite–leucogranite (Borovoe and Karabulak), Late Silurian granosyenites–granite (Aralaul), and Early Devonian (Balkashino and Orlinogorsk) complexes.     

Chloritöid-pyrophyllite-rectorite facies rocks from Brittany,France

Electron microprobe analyses of minerals in low grade metamorphic sandy black shales of middle Paleozoic age indicate that chemical equilibrium was closely approached in authigenic ferro-magnesian or alkali-bearing phases while aluminum silicate minerals appear to have reacted at a slower rate. The K for Mg-Fe in chlorite-chloritöid pairs is 0.19, the latter phase being iron-rich. The pseudomorphism of detrital white micas produces kaolinite, pyrophyllite and intimate mixtures of muscoviteparagonite. New phases forming in other sites include chlorite, chloritöid and rectorite which is an ordered paragonitebeidellite mixed layered phase. These minerals were formed at temperatures below 280° C. This is just above the stability of the illite-smectite mixed layered minerals which have an ISII ordering sequence (85 to 95% illite). It was noted that ferromagnesian minerals attain chemical equilibrium on a thin-section scale while the aluminous phases often seem to respond to chemical potentials operative on a submillimetric scale.     

Genesis of massive sulfide deposits in the Verkhneural’sk ore district, the South Urals, Russia: Evidence for magmatic contribution of metals and fluids

Melt inclusions and aqueous fluid inclusions in quartz phenocrysts from host felsic volcanics, as well as fluid inclusions in minerals of ores and wall rocks were studied at the Cu-Zn massive sulfide deposits in the Verkhneural’sk ore district, the South Urals. The high-temperature (850–1210°C) magmatic melts of volcanic rocks are normal in alkalinity and correspond to rhyolites of the tholeiitic series. The groups of predominant K-Na-type (K₂O/Na₂O = 0.3–1.0), less abundant Na-type (K₂O/Na₂O = 0.15–0.3), and K-type (K₂O/Na₂O = 1.9–9.3) rhyolites are distinguished. The average concentrations (wt %) of volatile components in the melts are as follows: 2.9 H₂O (up to 6.5), 0.13 Cl (up to 0.28), and 0.09 F (up to 0.42). When quartz was crystallizing, the melt was heterogeneous, contained magnetite crystals and sulfide globules (pyrrhotite, pentlandite, chalcopyrite, bornite). High-density aqueous fluid inclusions, which were identified for the first time in quartz phenocrysts from felsic volcanics of the South Urals, provide evidence for real participation of magmatic water in hydrothermal ore formation. The fluids were homogenized at 124–245°C in the liquid phase; the salinity of the aqueous solution is 1.2–6.2 wt % NaCl equiv. The calculated fluid pressure is very high: 7.0–8.7 kbar at 850°C and 5.1–6.8 kbar at 700°C. The LA-ICP-MS analysis of melt and aqueous fluid inclusions in quartz phenocrysts shows a high saturation of primary magmatic fluid and melt with metals. This indicates ore potential of island-arc volcanic complexes spatially associated with massive sulfide deposits. The systematic study of fluid inclusions in minerals of ores and wall rocks at five massive sulfide deposits of the Verkhneural’sk district furnished evidence that ore-forming fluids had temperature of 375–115°C, pressure up to 1.0–0.5 kbar, chloride composition, and salinity of 0.8–11.2 (occasionally up to 22.8) wt % NaCl equiv. The H and O isotopic compositions of sericite from host metasomatic rocks suggest a substantial contribution of seawater to the composition of mineral-forming fluids. The role of magmatic water increases in the central zones of the feeding conduit and with depth. The dual nature of fluids with the prevalence of their magmatic source is supported by S, C, O, and Sr isotopic compositions. The TC parameters of the formation of massive sulfide deposits are consistent with the data on fluid inclusions from contemporary sulfide mounds on the oceanic bottom.     

The Zhuravlinyi Log eluvial kaolin deposit,Chelyabinsk District,Russia

The Zhuravlinyi Log deposit is located 12 km southeast of Plast City. The deposit was initially prospected in 1951 and 1952 under the supervision of V.G. Lyulicheva. The prospecting revealed the presence of kaolin of quality surpassing the raw material in the Eleninsk and Kyshtym deposits. Although a positive assessment was given, new prospecting and appraisal works were carried out under the supervision of V.I. Kakorin in the vicinity of the previously discovered deposit in 1985 taking into consideration recommendations given by the VNIIgeolnerud (renamed TsNIIgeolnerud) Federal State Unitary Enterprise. The results revealed several separate white and pale kaolin deposits. Exploitation of the deposit was started even before its exploration. Construction of the Plast-Rifey dressing plant was completed during the exploitation of the central ore body. Follow-up exploration of the deposit completed in 2006 confirmed that the dry kaolin equivalent reserves of categories B + C₁ according to the Russian classification (approximately corresponding to the measured + indicated reserve in the western classification) and category C₂ (approximately corresponding to the inferred reserve) are estimated at 11.05 and 5.55 Mt, respectively. The Zhuravlinyi Log deposit is a major supplier of kaolin products fitting the standards of paper, fine ceramics, fiberglass, chemical reagents, and others. The present paper based on the exploration data attempts to show specific features of the geological setting of this deposit, as well as the mineral composition and properties of kaolin therein.     

Removal of chromium (VI) from aqueous solutions using Lewatit FO36 nano ion exchange resin

The removal of the chromium (VI) ion from aqueous solutions with the Lewatit FO36 ion-exchange resin is described at different conditions. The effects of adsorbent dose, initial metal concentration, contact time and pH on the removal of chromium (VI) were investigated. The batch ion exchange process was relatively fast and it reached equilibrium after about 90 min of contact. The ion exchange process, which is pH dependent showed maximum removal of chromium (VI) in the pH range 5.0–8.0 for an initial chromium (VI) concentration of 0.5 mg/dm³. The equilibrium related to Lewatit FO36 ion- exchange capacity and the amounts of the ion exchange were obtained using the plots of the Langmuir adsorption isotherm. It was observed that the maximum ion exchange capacity of 0.29 mmol of chromium (VLVg for Lewatit FO36 was achieved at optimum pH value of 6.0. The ion exchange of chromium (VI) on this cation-exchange resin followed first-order reversible kinetics.     

Occurrence of zinc in granitic biotites

37 granitic plutons in Great Britain and the United States were sampled and biotite separates prepared. These biotites were analysed for zinc and iron and a modal (point-count) analysis was conducted on the granitic samples. The results of these analyses were examined for differences that would characterise mineralised and non-mineralised granites, and for differences between biotites coexisting with muscovite and those coexisting with hornblende. The possibility of differentiating between mineralised and non-mineralised granites on the basis of the zinc content of biotites is rejected, but significant differences in composition are found between biotites from muscovite-biotite-granites and those from hornblende-biotite-granites. Muscovite-bearing granites have low biotite contents, these biotites having high iron and low zinc concentrations; hornblende-bearing granites have high biotite contents but these biotites, in contrast, have comparitively low iron and high zinc concentrations.

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Zusammenfassung Biotitkonzentrate aus 37 granitischen Plutonen aus Großbritannien und den U.S.A. wurden auf ihre Zn- und Fe-Gehalte analysiert. Granite, mit denen Zn-Vererzungen zusammenhängen, können nach diesen Untersuchungen nicht aufgrund der Zn-Gehalte ihrer Biotite von Graniten ohne Zn-Vererzungen unterschieden werden. Die Biotite aus muskovit- und aus hornblendeführenden Graniten unterscheiden sich hingegen: Erstere haben hohe Fe- und niedrige Zn-Konzentrationen bei geringem Biotitanteil am Gestein; bei letzteren ist es umgekehrt.

     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

The ammonite faunas of the Osmington Oolite Formation (Jurassic, Middle Oxfordian) of the Dorset coast

A detailed study of the lithologies of each of the beds present in the Osmington Oolite Formation of south Dorset is used to allocate numerous loose-collected ammonites to their correct stratigraphic horizons. Much new material has been collected by the author in addition to the limited amount of material available in museum collections. The age of the faunas of the three constituent members of the Osmington Oolite Formation is each assessed and placed into the context of Middle Oxfordian ammonite sequences elsewhere in England and in Europe.