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1.
A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.  相似文献   

2.
Three natural hematites, α-Fe2O3, from the region of Elba have been investigated by means of 57Fe Mössbauer spectroscopy at variable temperatures between 80 and 400K. The samples were selected on the basis of their different morphology as observed from powder X-ray diffraction and transmission electron microscopy. The mean crystallite diameters (MCD) along [104] are 1000, 280 and 40 nm respectively. Energy-dispersive analyses of X-rays revealed the presence of minor amounts of Si impurities in those two hematites having the largest MCD. All three hematites show the coexistence at low temperatures of antiferromagnetic-like (AF) and weakly-ferromagnetic-like (WF) spin states. The saturation values of the AF and WF magnetic hyperfine fields and quadrupole shifts have been determined, from which conclusions are drawn concerning the spin structure in relation to the crystallinity of the samples. The variations of the hyperfine parameters in the Morin-transition region indicate a gradual reorientation of both AF and WF spins towards the basal plane. As expected, the Morin transition itself is affected by the particle size. The two hematites exhibiting the largest particle dimensions still show an AF contribution for T>270K. It is suggested, and argued that this unusual behaviour is due to the presence of Si4+, and hence Fe2+, in the lattice. The characteristic Mössbauer temperatures and the intrinsic isomer shifts were evaluated from the temperature variation of the observed isomer shifts. Both parameters are not significantly affected by the morphology and are in excellent agreement with data obtained for synthetic hematites.  相似文献   

3.
Aluminous hematites prepared in three different ways have been examined at 300K and 4.2K using the Mössbauer technique. The results indicate significant differences between the behaviour of aluminous hematites that have been subjected to high temperatures (>600° C) and those which have not. The magnitude of the room temperature quadrupole splitting of the former increases with aluminium content, approaching at ～16 mole percent substitution the value (?0.22 mm/s) exhibited by all of the low temperature specimens. This variation may be explained qualitatively in terms of a preferential c-axis contraction of the lattice upon incorporation of aluminium, which does not occur unless a c-axis defect structure is removed by subjection of the hematite to high temperatures. The solid solubility limits of high and low temperature hematites (～15 mol % and ≥19 mol % respectively) also differ, as do the room temperature decreases in hyperfine splitting (?0.82 kOe/mol % Al and ?0.86 kOe/mol % Al). At 4.2 K only low temperature hematite exhibits a decrease in hyperfine splitting with increasing Al content (?0.40 kOe/mol % Al). The absolute values of the recoil free fractions of hydrothermally prepared aluminous hematites have been determined at 4.2 K (0.70±0.02 — pure hematite, 0.82±0.02, 14±2 mol % Al substitution) and exhibit a similar increase with Al content to that previously observed for aluminous goethites. The room temperature recoil free fraction of pure hematite has been measured to be 0.64±0.02. The effects of particle size on both hyperfine splitting and recoil free fraction have been investigated.  相似文献   

4.
The new synthetic phase Mg2Al3O[BO4]2(OH) provisionally named “pseudosinhalite” is optically, chemically, and structurally similar to the mineral sinhalite, MgAl[BO4], isostructural with forsterite. It grows hydrothermally from appropriate bulk compositions in the range 4–40?kbar at temperatures that increase with pressure (～650?→?900?°C), and it breaks down at higher temperatures to sinhalite?+?corundum?+?H2O. At P?≥?20?kbar single-phase products of euhedral twinned crystals could often be obtained. Pseudosinhalite is monoclinic with a?=?7.455 (1) Å, b?=?4.330 (1) Å, c?=?9.825 (2) Å, β?=?110.68 (1)°, and space group P21/c. Crystal structure analysis reveals that pseudosinhalite is also based on hexagonal close packing (hcp) of oxygen atoms with Mg and Al in octahedral and B in tetrahedral coordination. In pseudosinhalite the winged octahedral chains in the plane of hcp are not straight as in sinhalite but have a zigzag, 3-repeat period (Dreierkette), and only 1/10 instead of 1/8 of all tetrahedral sites are filled by boron. Hydrogen is located at a split position between two oxygen atoms O5—O5, which are only 2.550 Å apart and thus generate strong hydrogen bonding. This may be responsible for the absence of an hydroxyl absorption band between 2800?cm?1 and 3500?cm?1 in the powder IR spectrum. The equilibrium breakdown curve of pseudosinhalite to form sinhalite, corundum, and water was determined by bracketing experiments to pass through 10?kbar, 745?°C and 35?kbar, 950?°C, giving a slope of about 8?°C/kbar, similar to dehydration curves of some silicates at high pressure. In nature pseudosinhalite could have been misidentified as sinhalite. A possible appearance, like sinhalite in boron-rich skarns, would require more aluminous bulk compositions than for sinhalite at relatively low temperatures. However, pseudosinhalite might also form as a hydrous alteration product of sinhalite at low temperatures, perhaps in association with szaibelyite, MgBO2(OH).  相似文献   

5.
Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe3+ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr2O3, Al2O3 and MgO and complementary increase in Fe2O3 at constant FeO. In diffusion profiles, Fe2O3–Cr2O3 crossover coincides with Al2O3 decrease to values <0.5 wt% in ferritchromite zone, with Cr2O3 continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O2): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.  相似文献   

6.
Protohematite (Fe2?x/3(OH) x O3?x 1 ≤ x < 0.5) and hydrohematite (Fe2?x/3(OH) x O3?x 0.5 ≤ x < 0) are iron-defective phases containing hydroxyl groups in their structures. These species were described in prior studies mainly with the aid of X-ray diffraction and Infrared spectroscopy. The existence of these phases in soils might have influence in redox processes, and they were considered as a possible water reservoir in Martian soils. In this study, we have used for the first time the Karl Fischer titration method to determine the amount of water released after heating several synthetic samples of goethite, hematite and natural iron ores at 105, 400, 600 and 900 °C. It was found that heating at 105 °C did not remove all moisture from the samples, and higher temperatures were necessary to completely remove all the absorbed water. The water contents determined at 400, 600 and 900 °C were found to be the same within the experimental errors, suggesting the inexistence of both protohematite and hydrohematite in the investigated samples. Therefore, the above-mentioned effects of these phases in soils might have to be reevaluated.  相似文献   

7.
Corundum (ruby-sapphire) is known to have formed in situ within Archean metamorphic rocks at several localities in the North Atlantic Craton of Greenland. Here we present two case studies for such occurrences: (1) Maniitsoq region (Kangerdluarssuk), where kyanite paragneiss hosts ruby corundum, and (2) Nuuk region (Storø), where sillimanite gneiss hosts ruby corundum. At both occurrences, ultramafic rocks (amphibole-peridotite) are in direct contact with the ruby-bearing zones, which have been transformed to mica schist by metasomatic reactions. The bulk-rock geochemistry of the ruby-bearing rocks is consistent with significant depletion of SiO2 in combination with addition of Al2O3, MgO, K2O, Th and Sr relative to an assumed aluminous precursor metapelite. Phase equilibria modelling supports ruby genesis from the breakdown of sillimanite and kyanite at elevated temperatures due to the removal of SiO2. The juxtaposition of relatively silica- and aluminum-rich metasedimentary rocks with low silica ultramafic rocks established a chemical potential gradient that leached/mobilized SiO2 allowing corundum to stabilize in the former rocks. Furthermore, addition of Al2O3 via a metasomatic reaction is required, because Al/Ti is fractionated between the aluminous precursor metapelites and the resulting corundum-bearing mica schist. We propose that Al was mobilized either by complexation with hydroxide at alkaline conditions, or that Al was transported as K-Al-Si-O polymers at deep crustal levels. The three main exploration vectors for corundum within Archean greenstone belts are: (1) amphibolite- to granulite-facies metamorphic conditions, (2) the juxtaposition of ultramafic rocks and aluminous metapelite, and (3) mica-rich reactions zones at their interface.  相似文献   

8.
A series of hematite structures containing various amounts of aluminum and hydroxyl groups was modeled using first-principles methods based on the density functional theory. Evolution of the lattice parameters was quantified as a function of Al and H concentrations. The a and c lattice parameters decrease with the aluminum content and increase with the water content. This allows explaining experimental data reported for synthetic hematites, in particular the observed deviation from the Vegard’s rule. Investigation of several hydroxyl configurations associated with cationic vacancies suggests that the speciation of water also significantly affects the hematite structure. The 57Fe and 18O reduced partition functions (β-factor) were determined. Results show a linear dependence of the iron and oxygen β-factors on the aluminum content. An incorporation of 18 mole % Al2O3 in hematite would increase the iron β-factor of about 0.6‰ and the oxygen β-factor of about 5.5‰ at 0 °C. This effect is sufficiently large to be measurable and to affect the interpretation of natural isotopic compositions. On the other hand, the effect of water is found to be negligible for the hydroxyl configuration investigated.  相似文献   

9.
Gahnite, ZnAl2O4, present as an accessory mineral in regionally metamorphosed low-grade diasporites, has reacted in adjacent higher-grade, corundum-bearing metabauxite equivalents (emeries) to form Zn-rich högbomite, (Zn,Fe2+,Mg,Ni)t-2x (Ti,Sn)xAl2O4, of the 4H polytype. Commonly, the initial högbomite crystals grew epitactically along the octahedral faces of gahnite, which was subsequently dissolved, so that högbomite now forms spectacularly intergrown sets of eight crystals in perfect crystallographic orientation to each other. This indicates a metamorphic reaction, probably involving a fluid, transporting mainly the elements Zn and Al. Reactant Ti minerals in the diasporites were rutile and titanian hematite (10–15 mol% FeTiO3). In the emeries högbomite coexists with still more Ti-rich hematites containing between 26 and 37 mol% FeTiO3. The overall reaction relations involving partial reduction may be subdivided into the intial univariant reaction, gahnite+diaspore+Ti-hematite+rutile=högbomite+H2O+O2. This was followed, in the absence of gahnite, by compositional readjustments of högbomite and Ti-hematite and the appearance of magnetite. Core to rim zoning profiles indicate that, with continued growth, the högbomite crystals became poorer in Zn and Ti, but richer in Fe2+, while the Ti-contents of coexisting hematite increased. Högbomite formation at the expense of gahnite started at temperatures as low as about 400° C for an estimated pressure of 5–6 kbar.  相似文献   

10.
The main driving force behind Al/Si ordering in tetrahedral framework aluminosilicates is nearest-neighbour Al/Al avoidance. Computer simulation is used to explore the direct consequences of such Al/Al avoidance. The main result is that the order-disorder transition temperature T c falls dramatically as the concentration x of Al in the structure is reduced, and if the only interactions are those associated with nearest-neighbour Al/Al avoidance, T c becomes zero for x less than some critical value x c , where x c =0.31 for the feldspar framework and x c =0.34 for cordierite. Also a large degree of short range order is found above T c . Both results differ radically from the standard Bragg-Williams model. Plots of entropy and enthalpy of ordering are given as functions of x and T, which may be used to interpret experimental data or for extrapolation into ranges of x and T inaccessible to experiment. Received: 14 May 1997 / Revised, accepted: 2 June 1997  相似文献   

11.
 The structural behavior of stuffed derivatives of quartz within the Li1− x Al1− x Si1+ x O4 system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD). Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5. Received: 26 June 2000 / Accepted: 1 December 2000  相似文献   

12.
Natural samples of K-feldspar representing various states of Al, Si order were characterised using X-ray methods, transmission electron microscopy, and Fourier transform infrared spectroscopy. Line profiles of infrared absorption bands were observed to show strong correlation with the degree of Al, Si order present. In particular, the absorption frequencies of the 540 cm?1 and 640 cm?1 bands were seen to vary by ca. 10 cm?1 between sanidine and microcline, with modulated samples respresenting intermediate behaviour. Linewidths of these modes also decrease by ca. 50% in this series. The experimental results are discussed within the framework of Hard Mode Infrared Spectroscopy (HMIS), and it is shown that the absorption frequencies vary with the short range order parameter τ = (4t1-1)2 and the symmetry breaking order parameter describing Al, Si order, Q od=(t1 0?t1 m)/Q od=(t1 0+t1 m), where t1 is the average Al occupancy on the T1 sites and t1 o and t1 m are the individual site occupancies of the T1 o and T1 m sites, respectively. The structural state of orthoclase is characterised by strain-induced modulations with large spatial variations of the modulation wavelength. No such modulations were observed in the degree of local Al, Si order. Sanidine shows mode hardening in excess of the extrapolated effect of symmetry breaking Al, Si order, which is presumably related to nonsymmetry breaking ordering between T1 and T2 sites and/or as yet unobserved short range order of the symmetry breaking ordering scheme. The possibility of an additional phase transition in K-feldspar at temperatures above 1300 K is discussed.  相似文献   

13.
Three (Cr1?x Al x )N (x = 0.33, 0.5, 0.66) coatings were deposited on Ni-super alloy IN718 using reactive magnetron sputtering. The oxidation behavior of all coatings at 900 °C up to 500 h in air was studied. Furthermore, the corrosion behavior of the (Cr0.33,Al0.66)N coating at 900 °C (corrosion type I) by spraying a uniform salt scale of Na2SO4 on the sample surface (1 mg/cm2) was investigated. It was found that the coated samples indicate significantly higher oxidation and corrosion resistance compared to uncoated Ni super alloy. This is mainly due to the formation of protective Cr2O3 and Al2O3 layers on the coating surface. With the increase of Al content, the coatings exhibited improved oxidation resistance. The formation of thin and adherent Al2O3 scale on the surface of Al rich coating is the reason for its better oxidation behavior. The detailed structures of the oxide scales and the interdiffusion between coating and substrate were studied using energy dispersive X-ray spectroscopy-analysis.  相似文献   

14.
A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D25°C = 3 × 10?22 and 1.5 × 10?20 cm2sec?1 at PCO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10?8 to n × 10?5 cm according to the temperature and PCO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)3](1?x)[SiO2]x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al3+] + xlog [H4SiO4] ? (3 ? 3x) log [H+] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.  相似文献   

15.
Specificity of pyrometamorphic minerals of the ellestadite group   总被引：1，自引：0，他引：1  
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16.
Fragments of aluminous enstatite from lunar meteorites of highland origin were investigated. It was found that such fragments usually occur in impact breccias of troctolitic composition. The aluminous enstatite contains up to 12 wt % Al2O3 and shows low CaO (<1 wt %) and almost constant high Mg/(Mg + Fe) ratio (89.5 ± 1.4 at %) identical to that of the Earth’s mantle. With respect to these parameters, the aluminous enstatites are distinctly different from common orthopyroxene of lunar rocks. The aluminous enstatite associates with spinel (pleonaste), olivine, anorthite (clinopyroxene was never found), and accessory minerals: rutile, Ti-Zr oxides, troilite, and Fe-Ni metal. The same assemblage was described in rare fragments of spinel cataclasites from the samples of the Apollo missions. Thermobarometry and the analysis of phase equilibria showed that the rocks hosting aluminous enstatite are of deep origin and occurred at depths from 25 km to 130–200 km at T from 800 to 1300°C, i.e., at least in the lower crust and, possibly, in the upper mantle of the Moon. These rocks could form individual plutons or dominate the composition of the lower crust. The most probable source of aluminous enstatite is troctolitic magnesian rocks and, especially, spinel troctolites with low Ca/Al and Ca/Si ratios. The decompression of such rocks must produce cordierite-bearing assemblages. The almost complete absence of such assemblages in the surficial rocks of lunar highlands implies that vertical tectonic movements were practically absent in the lunar crust. The transport of deep-seated materials to the lunar surface was probably related to impact events during the intense meteorite bombardments >3.9 Ga ago.  相似文献   

17.
Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (XFe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.  相似文献   

18.
Thirteen Cr-bearing spinels from major horizons of magma replenishment in the open-system Rum Layered Suite have been analysed by X-ray single crystal diffraction and electron microprobe analyses. On the basis of the structural parameters and the chemistry of these spinels the so-called Rum trend, in which Al-content increases at the expense of Cr and Fe3+, has been easily recognised. In addition, natural spinels with Fe3+ content similar to synthetic spinels on the MgCr2O4?CMgFe2O4 join have been analysed for the first time. Layers of chromitite, anorthosite and peridotite situated within several cm of one another have yielded different intracrystalline exchange temperatures using an intercrystalline spinel-olivine thermometer. The Rum anorthosite Cr-spinels are interpreted as having crystallised within the cumulus pile following rejuvenation of the crystal mush. Their low Al-content is a function of simultaneous plagioclase crystallisation, reducing the amount of Al3+ present for the Cr-spinel. By contrast, Cr-spinels in well-known Archean anorthosites (e.g. Ujaragssuit nunat and Fisken?sset, western Greenland) and Sittampundi (southern India) are very aluminous in composition, attributed to crystallisation of Cr-spinel from high-alumina basalts in lower crustal magma chambers and linked to the control exerted by plagioclase crystallisation on Al content of the melt, in the absence of clinopyroxene crystallisation. The compositional differences between the Rum anorthosite Cr-spinels and the Fisken?sset and Sittampundi Cr-spinels suggest that postcumulus reaction of Cr-spinel and melt to low (800?C900°C) temperatures, as invoked for the Rum crystals, may not have been as important a process in the Archean anorthosites.  相似文献   

19.
Mössbauer measurements at 300 K, 77 K and 4.2 K and X-ray data are presented for synthetic aluminous goethites (α Fe1?x Al x OOH) in two series containing up to 15 mole percent aluminium (hydrothermal preparation) and 19 mole percent aluminium (low-temperature preparation). The Mössbauer spectra for specimens at 300 K and 77 K display broadened and relaxed line-shapes with the relaxation rate increasing with aluminium substitution, whereas all the 4.2 K spectra can be described by a single magnetically split spectrum. At 4.2 K the magnitude of this splitting is 505 kOe for pure goethite and it decreases by 0.52 kOe per mole percent aluminium substitution. The absolute value of the recoil-free fraction f at 4.2 K has been measured for pure goethite and for aluminous goethites containing 7, 15 and 19 mole percent aluminium; it increases from f=0.69±0.02 to f=0.89±0.02 in this range. The increase is attributed to a stiffening of the goethite lattice as it contracts to accommodate the smaller aluminium ion. At 300 K f is found to decrease from f=0.65±0.05 for pure goethite to f=0.50±0.03 for goethite with 19 mole percent aluminium.  相似文献   

20.
Nitrogen oxides (NO x ) are involved in acid rain and ozone formation, as well as destruction. NO x are climate-relevant trace gases in the atmosphere. Atmospheric NO x originate from anthropogenic emissions (mainly combustion processes). NO from natural processes derives from thunderstorms and soil microbial processes. They may play a crucial role in soil?Catmosphere feedback processes. This study aims to investigate NO x -emissions from soils under different land use, geographical and meteorological conditions. NO x -emissions were quantified in both field and laboratory experiments with a closed static chamber. Disturbed soil samples have been used for laboratory experiments. A climate chamber was used to regulate soil temperature of the samples. Field experiments showed that NO-soil emissions strongly depend on soil temperature. NO-emissions from a soil under meadow showed significant daily variations, unlike soil below spruce forest. Peak emission values were 18???g NO?CN?m?2?h?1 above meadow and 1.3???g NO?CN?m?2?h?1 under forest canopy. In addition, NO-emissions of meadow and forest soil were studied in a climate chamber, enhanced by an additional experiment with agricultural soil. These experiments revealed strong exponential correlations of NO-emissions and soil temperature. Maximum values reached above 400???g NO?CN?m?2?h?1 from agricultural soils at soil temperatures above 50°C. This study shows that soil NO-emissions strongly depend on temperature, vegetation type and geographical position. Consequently, NO-emissions may have a positive feedback effect on climate change.  相似文献   

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