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71.
We investigated a natural Brazilian Fe–Ti-containing andalusite and its thermal behavior by polarized infrared and optical spectroscopy. Polarized infrared spectra of the Brazilian andalusite and their evolution at thermal annealing in air clearly evidence that there are several types of OH-groups in the structure. Optical spectra and their evolution with temperature indicate that the incorporated iron (about 0.43 wt% calculated as FeO) is in the ferrous and ferric state. Incorporation of ferrous iron in the Al-sites of andalusite is discussed as a possible incorporation mechanism for hydrogen. The weakening and disappearance of the Fe2+/Ti4+ IVCT band in the andalusite spectra under annealing in air is caused by oxidization of Fe2+ to Fe3+ in Fe2+/Ti4+ IVCT pairs. The process of oxidation is accompanied by a rearrangement of the hydroxyl groups and dehydration of the sample, especially vivid at the final stage of the thermal annealing at 1,200 °C. During thermal annealing, structural hydroxyls of different types apparently transform into each other: the most distinct are the hydroxyls causing the doublet at 3,516 and 3,527 cm?1 (i.e., H bonded to O1) which seem to transform into the hydroxyls causing the line at 3,461 cm?1 (i.e., H bonded to O2). The infrared spectra scanned across differently colored zones of the crystal clearly show that some amount of hydroxyls is related to Fe2+/Ti4+ IVCT pairs which are the cause of the red-to-black coloration of the sample in E||c-polarized illumination: it is evident that in a part of the hydroxyl groups, OH-vector changes orientation aligning directly along crystallographic a-axis due to some kind of interaction with Fe2+/Ti4+ IVCT pairs.  相似文献   
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73.
We present isotope, cladoceran and diatom results from investigations of Eemian sediments of the palaeolake at Ruszkówek, central Poland. Our analyses of the 15-m-thick sediments indicate that sandy silts occur on the bottom, followed by calcareous gyttja, interbedded with lake marl. The upper part of the sequence contains peat and peaty sands. Values of δ18O change from −9.4‰ to −3.3‰ and δ13C values oscillate between −3.2‰ and +7.0‰. Nine isotope zones (Is) were defined and characterized using stable isotope analysis of carbonates. Fifteen species of subfossil Cladocera were found and six faunal zones were distinguished (Cladocera zones). One hundred and twenty-three diatom taxa, representing 31 genera were identified, enabling us to discern six Diatom Assemblage Zones. The isotope, cladoceran, and diatom data correlate well with pollen data that define seven phases of evolution of the palaeolake at Ruszkówek. The palaeolake began during the final phase of the Wartanian (Late Saalian Glaciation). During the early Eemian, the palaeolake reached its maximum depth. During the Early Vistulian glaciation, the palaeolake declined. Changes in the cladoceran and diatom communities indicate initial oligotrophic conditions in the lake, then an increase to mesotrophy, and finally eutrophic conditions.  相似文献   
74.
Synthetic ringwoodite γ-(Mg1?x Fe x )2SiO4 of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by VIFe2+ and VIFe3+, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe3+/Fetotal ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed 5 T 2g → 5 E g transitions of VIFe2+ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm?1 weakly depend on temperature, whilst the Fe2+/Fe3+ IVCT band at ~16,400 cm?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe3+ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of VIFe2+ (the bands at ~8,600 and ~12,700 cm?1) and Fe2+/Fe3+ IVCT transition (~18,100 cm?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)2SiO4-spinels and that the single band is caused by the split spin-allowed 5 E → 5 T 2 transition of IVFe2+. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).  相似文献   
75.
Anorogenic granite xenoliths occur in alkali basalts coeval with the Pliocene–Pleistocene continental rifting of the Pannonian Basin. Observed granite varieties include peraluminous, calcic to peralkalic, magnesian to ferroan types. Quartz and feldspars are dominant rock-forming minerals, accompanied by minor early ilmenite and late magnetite–ulvöspinel. Zircon and Nb–U–REE minerals (oxycalciopyrochlore, fergusonite, columbite) are locally abundant accessory phases in calc-alkalic types. Absence of OH-bearing Fe, Mg-silicates and presence of single homogeneous feldspars (plagioclase in calcic types, anorthoclase in calc-alkalic types, ferrian Na-sanidine to anorthoclase in alkalic types) indicate water-deficient, hypersolvus crystallization conditions. Variable volumes of interstitial glass, absence of exsolutions, and lacking deuteric hydrothermal alteration and/or metamorphic/metasomatic overprint are diagnostic of rapid quenching from hypersolidus temperatures. U–Pb zircon ages determined in calcic and calc-alkalic granite xenoliths correspond to a time interval between 5.7 and 5.2 Ma. Positive εHf values (14.2 ± 3.9) in zircons from a 5.2-Ma-old calc-alkalic granite xenolith indicate mantle-derived magmas largely unaffected by the assimilation of crustal material. This is in accordance with abundances of diagnostic trace elements (Rb, Y, Nb, Ta), indicating A1-type, OIB-like source magmas. Increased accumulations of Nb–U–REE minerals in these granites indicate higher degree of the magmatic differentiation reflected in Rb-enrichment, contrasting with Ba-enrichment in barren xenoliths. Incipient charnockitization, i.e. orthopyroxene and ilmenite crystallization from interstitial silicate melt, was observed in many granite xenoliths. Thermodynamic modeling using pseudosections showed that the orthopyroxene growth may have been triggered by water exsolution from the melt during ascent of xenoliths in basaltic magma. Euhedral-to-skeletal orthopyroxene growth probably reflects contrasting ascent rates of basaltic magma with xenoliths, intermitted by the stagnation in various crustal levels at a <3 kbar pressure. The Tertiary suite of intra-plate, mantle-derived A1-type granites and syenites is geochemically distinct from pre-Tertiary, post-orogenic A2-type granites of the Carpatho–Pannonian region, which exhibit geochemical features diagnostic of crustal melting along continental margins.  相似文献   
76.
77.
78.
Solid‐contacted Potentiometric Electrodes for Measurements of Sulfate Ions in Aqueous Solutions A solid‐contact electrode for potentiometric measurement of sulfate ions in aqueous solutions was developed and examined. The electrode is based on a PVC membrane which contains the ionophore 3‐decyl‐1,5,8‐triazacyclodecan‐2,4‐dione (DTADD). Instead of the usual inner fluid junction, a polypyrrole layer applied on the inner side of the PVC membrane was employed as inner solid contact. The performance of this electrode was compared to solid‐state sulfate‐selective electrodes with the ionophore α,α′‐bis(N′‐phenylthioureylene)‐m‐xylene (BTH) and to electrodes in the coated‐wire configuration. For the parameters sensitivity, selectivity, and long‐term stability, electrodes with the DTADD ionophore show improved properties. In the sulfate concentration range of 5·10–5...10–2 mol L–1 the slope of the response is –(26.8 ± 0.5) mV/decade. The new solid contact sulfate electrodes showed a very low drift of the electrode potential within a period of 150 days when the electrode was stored in 10–2 M Na2SO4. In Na2SO4 solutions of the pH range of 4...9 the electrode potentials were constant. The 95% response time was about 10 s when the sulfate concentration was changed from 10–4 mol L–1 to 10–3 mol L–1. The selectivity with DTADD ionophore relating to the nitrate ions is higher than the selectivity with BTH. Improvements are also made in comparison with sulfate‐selective electrodes described in the literature which contain other ionophores with fluid inner reference electrolytes.  相似文献   
79.
Methane fermentation is widely used to dispose of sewage sludge at wastewater treatment plants (WWTPs), due to production of renewable energy in the form of biogas. Antibiotics present in wastewater may accumulate in a sewage sludge. The aim of the present study is to investigate the impact of three antibiotics from different classes in three different doses on methane production from sewage sludge. For this purpose, metronidazole (MET), amoxicillin (AMO), and ciprofloxacin (CIP) are individually added to anaerobic reactors with sewage sludge collected from municipal WWTP. The antibiotics’ highest concentration (1024 mg kg?1 of AMO; 512 mg kg?1 of MET and CIP) lowers methane production and methane content in biogas. MET exerts the most marked effect and lowers methane production to 36.8 ± 3.7 mL CH4 kg?1 volatile solids. Tested antibiotics probably inhibit methanogenic archaea, which results in volatile fatty acids (VFAs) accumulation. Addition of MET results in accumulation of many kinds of VFAs with the highest concentration of acetic acid (17.52 ± 1.85 g L?1). The addition of of AMO results in accumulation of butyric acid only (253.00 ± 15.89 g L?1). However, addition of CIP results in accumulation of mainly acetic acid (7.58 ± 0.82 g L?1) and isovaleric acid (2.01 ± 0.41 g L?1). Next, synergistic effect of these antibiotics in a low concentration of 16 mg kg?1 of AMO, 8 mg kg?1 of MET, and 2 mg kg?1 of CIP is measured in semi‐continuous conditions and causes inbibition of methane production and accumulation of VFAs.  相似文献   
80.
Spectral decomposition is a powerful tool that can provide geological details dependent upon discrete frequencies. Complex spectral decomposition using inversion strategies differs from conventional spectral decomposition methods in that it produces not only frequency information but also wavelet phase information. This method was applied to a time‐lapse three‐dimensional seismic dataset in order to test the feasibility of using wavelet phase changes to detect and map injected carbon dioxide within the reservoir at the Ketzin carbon dioxide storage site, Germany. Simplified zero‐offset forward modelling was used to help verify the effectiveness of this technique and to better understand the wavelet phase response from the highly heterogeneous storage reservoir and carbon dioxide plume. Ambient noise and signal‐to‐noise ratios were calculated from the raw data to determine the extracted wavelet phase. Strong noise caused by rainfall and the assumed spatial distribution of sandstone channels in the reservoir could be correlated with phase anomalies. Qualitative and quantitative results indicate that the wavelet phase extracted by the complex spectral decomposition technique has great potential as a practical and feasible tool for carbon dioxide detection at the Ketzin pilot site.  相似文献   
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