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1.
The nicotinamide (pyridine-3-carboxamide, nia) complexes of silver(I), [Ag(nia)2(NO3)]·H2O (1), [Ag(nia)2(NO3)] (2), and {K[Ag(nia)2](NO3)2} n (3), were prepared and characterised by IR spectroscopy and TG/DTA thermal methods. The solid state structures of 2 and 3 were determined by single-crystal X-ray diffraction analysis. In both complexes two nicotinamide ligands are coordinated to silver(I) through the nitrogen atom of the pyridine ring in a near-linear fashion. In 2, additional coordination by two oxygen atoms of one nitrate group leads to the distorted tetrahedral coordination environment of silver(I). In 3, nitrate ions bridge potassium cations giving rise to a 2D coordination network which is further stabilised by cross-bridging of each two potassium atoms in [1 0 0] direction by complex cations, [Ag(nia)2]+. Despite different aggregation of 2 and 3 in the solid state, both complexes demonstrate quite similar thermal stability. The amide self-complementary hydrogen bonds appear to be the main driving force for establishing the crystal structures of both 2 and 3. 相似文献
2.
The orthopyroxene crystal structure can be viewed as the stacking of alternating tetrahedral and octahedral layers parallel to the (100) plane. Easy glide occurs in the (100) plane at the level of the octahedral layer to prevent breakage of the strong Si-O bonds. Dislocations with c and b Burgers vectors have been activated in (100) by room temperature indentation in an orthoenstatite gem quality single crystal. Investigations in transmission electron microscopy show that the b dislocations (b?9 Å) are not dissociated while the c's (c=5.24 Å) are dissociated into four partials. This result is interpreted by considering the oxygen sublattice as a distorted FCC one. The four c partials are thus Shockley partials bounding three stacking faults. For the two outer ones, synchroshear of the cations is necessary to keep unchanged their sixfold coordination; the oxygen sublattice is locally transformed into a HCP lattice. This accounts for the observed low splitting (?100 Å) of these faults as compared to the median one (?500 Å) which does not affect the oxygen sublattice and does not require cation synchroshear. In a Fe rich orthopyroxene (eulite), semi coherent exsolution lamellae have been studied. Either only c edge dislocations or both b and c edge dislocations occur in the phase boundaries depending upon the thickness of the lamellae. Only the c dislocations are dissociated. From the observed spacing between these mismatch dislocations a crude estimate of the exsolution temperature is proposed T ex ? 700° C. 相似文献
3.
Antigorite equation of state and anomalous softening at 6 GPa: an in situ single-crystal X-ray diffraction study 总被引：1，自引：0，他引：1
Fabrizio Nestola Ross J. Angel Jing Zhao Carlos J. Garrido Vicente López Sánchez-Vizcaíno Giancarlo Capitani Marcello Mellini 《Contributions to Mineralogy and Petrology》2010,160(1):33-43
The compressibility of antigorite has been determined up to 8.826(8) GPa, for the first time by single crystal X-ray diffraction in a diamond anvil cell, on a specimen from Cerro del Almirez. Fifteen pressure–volume data, up to 5.910(6) GPa, have been fit by a third-order Birch–Murnaghan equation of state, yielding V 0 = 2,914.07(23) Å3, K T0 = 62.9(4) GPa, with K′ = 6.1(2). The compression of antigorite is very anisotropic with axial compressibilities in the ratio 1.11:1.00:3.22 along a, b and c, respectively. The new equation of state leads to an estimation of the upper stability limit of antigorite that is intermediate with respect to existing values, and in better agreement with experiments. At pressures in excess of 6 GPa antigorite displays a significant volume softening that may be relevant for very cold subducting slabs. 相似文献
4.
Metamorphic biotites examined by transmission electron microscopy contain planar defects on the (001) plane, superlattices, twins and a microstructure causing streaking of k≠3n rows. Analysis of the fringe contrast shows that the fault vectors associated with the planar defects are either R 1=±1/3 [010], R 2=±1/6 [310] or R 3=±1/6 [3 \(\bar 1\) 0]. Structural considerations indicate that a stacking fault R 1, R 2 or R 3 is most likely to exist in the octahedral layer rather than the potassium layer. The result of such a fault on a unit layer of mica is effectively to rotate it through ±120° about c* (equivalent to the common mica twin law). These stacking faults can provide the mechanism for producing the ±120° rotations associated with the common mica polytypes. Furthermore, many of the observed microstructures can be generated by these stacking faults. 相似文献
5.
Annamaria Fornelli Antonio Langone Francesca Micheletti Giuseppe Piccarreta 《Mineralogy and Petrology》2011,103(1-4):101-122
The lower crust of the Serre massif (Calabria, southern Italy) provides a window into the mid- to lower crust of the south European Variscan orogenic belt. Previously, zircon U-Pb ages were employed to date high-temperature processes affecting this portion of the Variscan crust. The present paper reports new LA-ICP-MS U-Pb data on the zircon of a deformed quartz-monzodiorite dike and of three mafic granulites sampled at the base of the lower crust section. Determination of trace elements on zircon, including rare earth elements (REE), has been also performed. The end of the Variscan exhumation, dated by anatectic zircon from migmatitic metapelites, and the growth-modification of zircon with respect to the growth of Variscan metamorphic garnet have been assumed as ??time markers??. The concordant zircon ages of the metamorphic basic rocks cover a range from 744?±?20 Ma to 231?±?10 Ma with high age density from 357?±?11?Ma to 279?±?10 Ma, a few ages comprised between 418?±?14 Ma and 483?±?12 Ma and between 505?±?11 Ma and 593?±?14 Ma. Zircon from the deformed quartz-monzodiorite dike evidences a minimum age of emplacement of 323?±?5 Ma. Most of the analysed zircon domains dated between 357?±?11 Ma to 279?±?10 Ma from garnet-bearing metabasic rocks show flat patterns of heavy rare earth elements (HREE), as expected in the case of their simultaneous growth with garnet. This allows to consider (1) zircon domains giving Variscan ages as ??metamorphic?? with specific geological significance, and (2) zircon domains with ages ranging from 564?±?17 Ma to 593?±?14 Ma as dating the emplacement of the magmatic protoliths as shown by internal microtextures, fractionated patterns of HREE and Th/U ratios (0.16?C0.19). The Variscan zircon ages (357?C279?Ma) reflect effects of crustal thickening, peak metamorphism and subsequent multistage Variscan decompression documented by the statistically significant clusters of ages around 347?C340?Ma, 323?C318?Ma, 300?C294?Ma and 279?Ma. The U-Pb zircon ages of the metabasic rocks suggest a period of about 60?C70?Ma for granulite facies metamorphism and anatectic conditions. Literature data indicate that the migmatitic metapelites of the upper part of the Serre crust section also underwent a long period, about 40?Ma, of granulite facies metamorphism and anatectic conditions. A diachronism emerges through the time comparison of the Variscan evolution between the upper and the lower portions of the Serre deep crust. The duration of the Variscan processes defined in Calabria is comparable to that of other south European Variscan blocks. 相似文献
6.
For ABO 4 type ternary oxides, high pressure phase transformations known up to the present are reviewed, and an attempt is made to explain and predict crystal structures of their high pressure phases. When ABO 4 type compounds are plotted based on the two variables, k=r A /r B and t=(r A +r B )/2r O, where r A , r B , and r O are the ionic radii of A and B cations and divalent oxygen, they can be classified into the major structure types. It is found empirically that a compound basically transforms to the structure type isostructural with a compound lying in a classified area with the same k and larger t values in the diagram. 相似文献
7.
Fine textures of exsolution lamellae and interface boundaries between augite and pigeonite in augite crystals from Skaergaard ferrogabbro 4430 have been studied by high resolution electron microscopy and X-ray methods. Thick pigeonite lamellae have higher densities of (100) stacking faults than thin lamellae. The displacement vector of the faults has been determined as 5/6c from the measured density of faults and the relative rotation of the augite and pigeonite lattices. The augite and pigeonite lattices are apparently coherent, and no growth ledges were observed at the interfaces. The stacking faults are often combined with the antiphase boundary of pigeonite resulting in a total displacement vector of 1/2(a+b)+5/6c. The observation of thick and thin pigeonite lamellae indicated that the thickening of (001) pigeonite lamellae was controlled by coherency strains accumulated at the interfaces between augite and pigeonite. 相似文献
8.
Gutenberg and Richter developed an empirical relation, \(\log_{10} N(M) = a - bM\), to quantify the seismicity rate of various magnitudes in a given region and time period. They found the equation fit observed data well both globally and for particular regions. In conventional G–R relation, N(M) represents an arithmetic mean. As a result, the arithmetic standard deviation cannot be explicitly incorporated in the log-linear G–R relation. Moreover, this representation is susceptible to influence of spuriously large numbers of aftershocks of major earthquake sequences. To overcome these shortcomings, we propose an alternative representation of the G–R relation in terms of the logarithmic mean annual seismicity rate and its standard deviation. We select the crustal earthquake data from 1973 to 2011, as listed in the National Earthquake Information Center (NEIC) global catalog and the Central Weather Bureau (CWB) Taiwan regional catalog, to illustrate our methodology. We first show that by using the logarithmic annual seismicity rates we can significantly suppress the influences of spuriously large numbers of aftershocks following major earthquake sequences contained in the Taiwan regional catalog. More significantly, both the logarithmic mean annual seismicity rate and its standard deviation can be explicitly represented in the Gutenberg–Richter relation as follows: where log10 N represents the logarithmic annual seismicity rate. Above analytical equations are very well constrained by observed global seismicity data with \(5.0 \le M \le 7.0\) and by Taiwan seismicity data with \(3.0 \le M \le 5.0\). Both equations can be extrapolated with confidence to simultaneously estimate not only the median annual seismicity rates but also their uncertainties for large earthquakes for the first time since inception of the G–R relation. These equations can be used to improve the conventional probabilistic seismic hazard assessment by including the dispersion of the annual seismicity rate. Finally, the corresponding numerical median annual seismicity rate with its upper and lower bounds obtained from above equations for \(5.0 \le M \le 9.0\) is listed in Table 1.
相似文献
$${\text{For}}\,{\text{global}}\,{\text{crustal}}\,{\text{seismicity}}{:}\;\log_{10} N = 8.14 - 1.03M \pm (0.04M - 0.13);$$
$${\text{For}}\,{\text{Taiwan}}\;{\text{crustal}}\,{\text{seismicity}}{:}\;\log_{10} N = 5.62 - 0.90M \pm (0.02M + 0.17)$$
Table 1 Observed and estimated median annual seismicity rate and return period with their dispersions for Taiwan and global crustal earthquakes
| Magnitude | Catalog | |||
|---|---|---|---|---|
| Taiwan catalog (CWB) | Taiwan catalog (CWB) | Global catalog (NEIC) | Global catalog (NEIC) | |
| Annual rate (event/year) | Return period (year) | Annual rate (event/year) | Return period (year) | |
| M ≥ 5.0 | 24.55 13.18 7.08 | 0.041 0.076 0.14 | 1148.16 977.24 831.76 | 0.0009 0.001 0.0012 |
| M ≥ 5.5 | 8.91 4.68 2.45 | 0.11 0.21 0.41 | 367.28 298.54 242.66 | 0.0027 0.0033 0.0041 |
| M ≥ 6.0 | 3.24 1.66 0.85 | 0.31 0.60 1.18 | 117.49 91.20 70.79 | 0.0085 0.011 0.014 |
| M ≥ 6.5 | 1.17 0.59 0.30 | 0.85 1.69 3.33 | 37.58 27.86 20.65 | 0.027 0.036 0.048 |
| M ≥ 7.0 | 0.43 0.21 0.10 | 2.33 4.76 10.0 | 12.02 8.51 6.03 | 0.083 0.12 0.17 |
| M ≥ 7.5 | 0.15 0.074 0.036 | 6.67 13.51 27.78 | 3.85 2.60 1.76 | 0.26 0.38 0.57 |
| M ≥ 8.0 | 0.056 0.026 0.012 | 17.86 38.46 83.33 | 1.23 0.79 0.51 | 0.81 1.27 1.96 |
| M ≥ 8.5 | 0.020 0.009 0.004 | 50.00 111.11 250.0 | 0.39 0.24 0.15 | 2.56 4.17 6.67 |
| M ≥ 9.0 | 0.0074 0.0033 0.0015 | 135.14 303.03 666.67 | 0.13 0.074 0.04 | 7.69 13.51 25.00 |
9.
E. Baum W. Treutmann W. Lottermoser G. Amthauer 《Physics and Chemistry of Minerals》1997,24(4):294-300
Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T N =7.5(5)?K, Θ P =?19(1)?K for AEG, and T N =31(1)?K, Θ P =+21(1)?K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described. 相似文献
10.
Giancarlo Della Ventura G. Diego Gatta Gunter J. Redhammer Fabio Bellatreccia Anja Loose Gian Carlo Parodi 《Physics and Chemistry of Minerals》2009,36(4):193-206
We relate a single-crystal FTIR (Fourier transform infrared) and neutron diffraction study of two natural cancrinites. The structural refinements show that the oxygen site of the H2O molecule lies off the triad axis. The water molecule is almost symmetric and slightly tilted from the (0001) plane. It is involved in bifurcated hydrogen bridges, with Ow···O donor–acceptor distances >2.7 Å. The FTIR spectra show two main absorptions. The first at 3,602 cm?1 is polarized for E ⊥ c and is assigned to the ν3 mode. The second, at 3,531 cm?1, is also polarized for E ⊥ c and is assigned to ν1 mode. A weak component at 4,108 cm?1 could possibly indicate the presence of additional OH groups in the structure of cancrinite. Several overlapping bands in the 1,300–1,500 cm?1 range are strongly polarized for E ⊥ c, and are assigned to the vibrations of the CO3 group. 相似文献
11.
Mohsen Jalali 《Environmental Earth Sciences》2013,68(7):2041-2049
The chemistry of soil solutions can be altered by human activities, due to the intense agricultural and husbandry, leading to leaching of nutrients and subsequently elevating ground water levels. Multivariate statistical and inverse geochemical modeling techniques were used to determine the main factors controlling soil solution chemistry of calcareous soils. In this research, a total of 21 calcareous soils was characterized and assessed for soil solution using soil column. The major cations in the studied soil solutions were in the decreasing order as Ca2+ > Mg2+ > Na+ > K+. The anions were also arranged in decreasing order as HCO $ _{3}^{ - } $ > Cl $ ^{ - } $ > SO $ _{4}^{2 - } $ > NO $ _{3}^{ - } $ . Concentrations of NO $ _{3}^{ - } $ , P, and K+ in soil solutions were in the range of 6.8–307.5 mg l?1 (mean 63.2 mg l?1), 5.0–10.4 mg l?1 (mean 5.9 mg l?1), and 2.8–54.6 mg l?1 (mean 11.3 mg l?1), respectively. Results suggest that the concentration of P in the soil solutions could be primarily controlled by the solubility of dicalcium phosphate dihydrate and dicalcium phosphate. Interactions between soil properties and observed solubility of nutrients were described, and put into empirical multivariate formulations. Obtained equations contained electrical conductivity (EC) as a key factor in determining nutrients solubility. Inverse geochemical modeling of soil solution using PHREEQC indicates the dissolution of calcite, anhydrite, halite, CO2 (g), N2 (g), and hydroxyapatite, and precipitation of sulfur. Cation exchange between Ca2+, Mg2+, K+ and Na+ occurred with Mg2+ and K+ into the solution, and Ca2+ and Na+ out of the solution. Determination of soil solution will improve soil management in the area, and preventing groundwater deterioration. 相似文献
12.
Two crystals of natural chalcopyrite, CuFeS2, experimentally deformed at 200° C have been studied by means of transmission electron microscopy (TEM). The activated glide planes are (001) and {112}. The dislocations in (001) have the Burgers vector [110] and a predominating edge character. They are split into two colinear partials b=1/2[110] and can cross split into {112}. The dislocations in {112} consist of straight segments along low index lattice lines. They are often arranged in dipoles generating trails of loops. Few dislocations with b=1/2[ \(\overline {11} \) 1] and [1 \(\bar 1\) 0] are present and dislocations with b=[0 \(\bar 2\) 1] occur in low angle subgrain boundaries. From weak beam contrasts it is presumed that most of the dislocations gliding in {112} have b=1/2〈3 \(\overline {11} \) 〉. They are dissociated into up to four partials. Microtwins and different types of stacking faults in {112} also occur. Models of the dissociation of dislocations are discussed. 相似文献
13.
G. V. Gibbs N. L. Ross D. F. Cox K. M. Rosso B. B. Iversen M. A. Spackman 《Physics and Chemistry of Minerals》2014,41(1):17-25
The power law regression equation, <R(M–O)> = 1.46(<ρ(r c)>/r)?0.19, relating the average experimental bond lengths, <R(M–O)>, to the average accumulation of the electron density at the bond critical point, <ρ(r c)>, between bonded pairs of metal and oxygen atoms (r is the row number of the M atom), determined at ambient conditions for oxide crystals, is similar to the regression equation R(M–O) = 1.41(ρ(r c)/r)?0.21 determined for three perovskite crystals at pressures as high as 80 GPa. The pair are also comparable with the equation <R(M–O)> = 1.43(<s>/r)?0.21 determined for oxide crystals at ambient conditions and <R(M–O)> = 1.39(<s>/r)?0.22 determined for geometry-optimized hydroxyacid molecules that relate the geometry-optimized bond lengths to the average Pauling bond strength, <s>, for the M–O bonded interactions. On the basis of the correspondence between the equations relating <ρ(r c)> and <s> with bond length, it seems plausible that the Pauling bond strength might serve a rough estimate of the accumulation of the electron density between M–O bonded pairs of atoms. Similar expressions, relating bond length and bond strength hold for fluoride, nitride and sulfide molecules and crystals. The similarity of the expressions for the crystals and molecules is compelling evidence that molecular and crystalline M–O bonded interactions are intrinsically related. The value of <ρ(r c)> = r[(1.41)/<R(M–O)>]4.76 determined for the average bond length for a given coordination polyhedron closely matches the Pauling’s electrostatic bond strength reaching each the coordinating anions of the coordinated polyhedron. Despite the relative simplicity of the expression, it appears to be more general in its application in that it holds for the bulk of the M–O bonded pairs of atoms of the periodic table. 相似文献
14.
Suzanne B. Bricker Fred T. Mackenzie Jill S. Baron Jason R. Price 《Aquatic Geochemistry》2014,20(2-3):81-86
This special volume of aquatic geochemistry is dedicated to the memory of Owen Peterson Bricker III (1936–2011) and serves as a tribute to his life and career. Owen had a distinguished and productive research career in both academics at Johns Hopkins University (Fig. 1) and as a public servant with the Maryland Geological Survey, the US Environmental Protection Agency, and the US Geological Survey. He was a pioneer and leader in aqueous geochemistry, who applied a study approach that quantified mineral weathering reactions and equilibrium thermodynamic relations to better understand the chemical evolution of stream water in small watersheds. He will be especially remembered for his efforts to establish rigorous field studies in small catchments around the United States as a means of quantifying the sources of acid-neutralizing capacity that affect the chemical status and biological health of natural waters. Fig. 1
Owen in a Johns Hopkins University laboratory in the early years (~1965, note the tie!) 相似文献
15.
Sytle M. Antao Ishmael Hassan Willem H. Mulder Peter L. Lee 《Physics and Chemistry of Minerals》2008,35(10):545-557
The temperature dependences of the crystal structure and superstructure intensities in sodium nitrate, mineral name nitratine, NaNO3, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction. Nitratine transforms from $R{\overline{3}} c\;\hbox{to}\;R{\overline{3}} m$ at T c = 552(1) K. A NO3 group occupies, statistically, two positions with equal frequency in the disordered $R{\overline{3}} m$ phase, but with unequal frequency in the partially ordered $R{\overline{3}} c$ phase. One position for the NO3 group is rotated by 60° or 180° with respect to the other. The occupancy of the two orientations in the $R{\overline{3}} c$ phase is obtained from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x ? 1, where S is 0 at T c and 1 at 0 K. The NO3 groups rotate in a rapid process from about 541 to T c, where the a axis contracts. Using a modified Bragg–Williams model, a good fit was obtained for the normalized intensities (that is, normalized, NI1/2) for the (113) and (211) reflections in $R{\overline{3}} c\hbox {\,NaNO}_{3},$ and indicates a second-order transition. Using the same model, a reasonable fit was obtained for the order parameter, S, and also supports a second-order transition. 相似文献
16.
Troilite close to FeS, with 0.17 weight percent Cr as main impurity, was obtained from the Agpalilik meteorite. Powder Mössbauer spectroscopy was made in the temperature range 77–645 K. The full Hamiltonian was applied in the fittings. Assuming the asymmetry parameter η to be constant on passing from the high-temperature NiAs-type structure to the medium-temperature MnP-type structure yields a quadrupole splitting (dq=0.5e2 qQ(1+(η2)/3)1/2) value of ?0.25(2) mm/s for these phases. In low-temperature troilite |dq|=0.85 mm/s at room temperature. The combinations of (η, θ, φ) in troilite giving identical spectra range from (0, 49°, -) to (1, 45°, 50°) for negative V zz or from (0.3, 57°, 78°) to (1, 58°, 54°) for positive V zz . Assuming a negative V zz and B‖c gives a θ value in agreement with the shortest Fe-S join being the V zz orientation. The magnetic spin flip of 90° is proposed to occur in the MnP-phase only. The MnP phase-troilite transition occurs at lower temperatures and is more sluggish than in pure FeS. 相似文献
17.
Lutz Kübler 《Physics and Chemistry of Minerals》1985,12(6):353-362
Single crystals of hexagonal and monoclinic pyrrhotite, Fe1?xS, have been experimentally deformed by uniaxial compression at 300 MPa confining pressure, and at a strain rate of 1 × 10?5 s?1 in the temperature range from 200° C to 400° C. Very high anisotropy characterizes the mechanical behaviour of the crystal structure. During compression parallel to thec-axis, when no slip system may be activated, the maximum strength is observed. One or two degrees of non-parallelism between [c] and σ1 results in slip on the basal plane, illustrating the very low resistance of the lattice against shear in this plane. At σ1 Λ(0001)=45°, i.e. when maximum resolved shear stress is attained on the basal plane, the strength reaches a minimum. Thecritical resolved shear stress (CRSS) increases from less than 4.7 MPa at 400° C to 52 MPa at 200° C. A new slip system, \((10\overline 1 0)\parallel \left\langle {1\overline 2 10} \right\rangle \) prism slip, is described. It is activated only at high angles (>70°) between σ1 and [c]. The CRSS of the prism slip ranges from 7 MPa (400° C) to 115 MPa (200° C). Twinning on \((10\overline 1 2)[(10\overline 1 2):(1\overline 2 10)]\) , earlier reported by several authors, has been produced only at the highest temperature either as secondary feature during pressure release (compression ‖[c]) or in heterogeneously strained areas (compression ⊥[c]). As twinning and prism slip attain their maximum values of the Schmidt factor under nearly equal stress conditions it is postulated that the former of the two deformation modes has the higher shear resistance. 相似文献
18.
Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm–1 were obtained for the orthorhombic thenardite-type phase Cr2SiO4, unique in its Cr2+-allocation suggesting some metal-metal bonding in Cr2+Cr2+ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr2SiO4, synthesized at 35?kbar, above 1440?°C from high purity Cr2O3, Cr (10% excess) and SiO2 in chromium capsules. The Cr2SiO4-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm–1, in the absorption spectra of Cr2SiO4 single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr2+ in a distorted square planar coordination of point symmetry C2. The crystal field parameter of Cr2+ is estimated to be 10?Dq?10700?cm–1. A relatively intense, sharp band at 18400?cm–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr2+. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr2 4+, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr2+ as well as δ-δ* transitions of Cr2 4+ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Crloc 2+?Cr2, cpl 4+ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions. 相似文献
19.
Biosorption of heavy metals by organic carbon from spent mushroom substrates and their raw materials
I. Frutos C. García-Delgado A. Gárate E. Eymar 《International Journal of Environmental Science and Technology》2016,13(11):2713-2720
The use of agricultural wastes as biosorbents is gaining importance in bioremediation of heavy metal-polluted water and soils, due to their effectiveness and low cost. This work assesses the Cd, Pb and Cu adsorption capacity of the raw materials used in the production of substrates for mushroom production (Agaricus bisporus and Pleurotus ostreatus) and the spent mushroom composted (SMC), based on the functional groups of their organic carbon. The raw materials studied included agricultural wastes (wheat straw, wheat and rice poultry litter, grape pomace) and inorganic substances (gypsum and calcareous sand). Organic carbon from wastes and their composting products were characterized by CP-MAS 13C NMR. Langmuir adsorption isotherms of metals were plotted for each raw material, composting step, spent A. bisporus and P. ostreatus substrates and the final SMC. The maximum adsorption capacities of SMC were 40.43, 15.16 and 36.2 mg g?1 for Cd, Pb and Cu, respectively. The composting process modified the adsorption properties of raw materials because of the enhanced adsorption of Cd and Cu and decreased adsorption capacity of Pb. CP-MAS 13C NMR and potentiometric titration were used to identify the functional groups of the organic carbon responsible for the metal adsorption. The content of cellulose was correlated with Pb adsorption (p < 0.001), alkyl and carboxyl carbon with Cd adsorption (p < 0.001), and N-alkyl (p < 0.001) and carboxyl (p < 0.010) groups with Cu adsorption. These results are valuable to develop new biosorbents based on agricultural wastes and demonstrate the high potential of SMC to adsorb heavy metals from polluted environments. 相似文献
20.
The electron paramagnetic resonance (EPR) spectra of Fe3+ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B 2 0 = 0.112 cm?1, B 2 2 = 0.0688 cm?1 for one and B 2 0 = 0.116 cm?1, B 2 2 = 0.0766 cm?1 for the second. These two spectra arise from Fe3+ substituted for Al3+ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites. 相似文献