C10H6-Fe+ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C10H6-Fe+ systems are models for larger PAHs-Fe+ complexes, which are believed to play a key rôle in space chemistry. 相似文献
The crab Carcinus maenas (L.) and the barnacle Elminius modestus Darwin were exposed to a range of dissolved concentrations of Zn, Cu and Cd for 21 days in artificial seawater. Accumulation of Zn and Cu by crabs has been interpreted in terms of the presence of a regulation mechanism to maintain constant body concentrations (83·2 ± 19·4 μg Zn g?1 dry wt.; 39·8 ± 9·8 μg Cu g?1 dry wt.) under varying external dissolved metal levels, until a threshold dissolved metal concentration (c. 400 μg Zn l?1; c. 170 μg Cu l?1) beyond which net accumulation of metal begins. Cadium appears to be accumulated by C. maenas at all exposures with no evidence for regulation of body cadmium concentrations. Exposure of E. modestus to Zn, Cu or Cd caused net accumulation of the respective metal in the bodies of the barnacles, with no evidence for regulation of body metal concentrations. 相似文献
Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment. 相似文献
To determine if Cu mediated reactions on atmospheric particles are important to HO2 chemistry in the ambient atmosphere, Cu molalities were calculated from measured Cu aerosol particle concentrations, mass and number size distribution data from a site in central Sweden. A comparison of characteristic times indicates that at low relative humidities the reaction is limited by the mass transport of gas phase HO2 to the particle surface and not by the chemical kinetics of the aqueous reaction. Comparison of half-lives for particle reactions and the gas phase destruction of HO2 to form H2O2 indicate that heterogeneous reactions on aerosol particles may have important consequences on the chemistry of HO2 and H2O2 in the troposphere. 相似文献
Low pressure partial melting of basanitic and ankaramitic dykes gave rise to unusual, zebra-like migmatites, in the contact aureole of a layered pyroxenite–gabbro intrusion, in the root zone of an ocean island (Basal Complex, Fuerteventura, Canary Islands). These migmatites are characterised by a dense network of closely spaced, millimetre-wide leucocratic segregations. Their mineralogy consists of plagioclase (An32–36), diopside, biotite, oxides (magnetite, ilmenite), +/− amphibole, dominated by plagioclase in the leucosome and diopside in the melanosome. The melanosome is almost completely recrystallised, with the preservation of large, relict igneous diopside phenocrysts in dyke centres. Comparison of whole-rock and mineral major- and trace-element data allowed us to assess the redistribution of elements between different mineral phases and generations during contact metamorphism and partial melting.
Dykes within and outside the thermal aureole behaved like closed chemical systems. Nevertheless, Zr, Hf, Y and REEs were internally redistributed, as deduced by comparing the trace element contents of the various diopside generations. Neocrystallised diopside – in the melanosome, leucosome and as epitaxial phenocryst rims – from the migmatite zone, are all enriched in Zr, Hf, Y and REEs compared to relict phenocrysts. This has been assigned to the liberation of trace elements on the breakdown of enriched primary minerals, kaersutite and sphene, on entering the thermal aureole. Major and trace element compositions of minerals in migmatite melanosomes and leucosomes are almost identical, pointing to a syn- or post-solidus reequilibration on the cooling of the migmatite terrain i.e. mineral–melt equilibria were reset to mineral–mineral equilibria. 相似文献
Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si4+ by Al3+ and Fe3+. The induced charge imbalance is compensated chiefly by Ca2+, Mg2+, Mn2+, Ba2+, K+, and Na+. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence. 相似文献