月岩的穆斯堡尔谱学研究

The results of Moessbauer study of Apollo-17 Mare basalt are reported in this paper.It has been revealed that Fe in iron.bearing minerals in the basalt is almost present in the form of Fe^3 , with Fe^3 less than 3% of total iron. The site occupancy of Fe^3 ions at M1 and M2 is approximately 0.3 and the corresponding equilibrium constant K (T) is about 0.06, thus indicating that the mare basalt is formed through crystallization under high-temperature reducing and rather slow cooling conditions.     

新疆铁陨石穆斯堡尔效应的研究

本文利用穆斯堡尔谱仪，X射线衍射等方法研究了新疆铁陨石。新疆铁陨石主要由体心立方的铁纹石及立方面心的镍纹石组成，此外还有极少量的其他矿物。新疆铁陨石中镍含量分布不均匀，并且铁限石中的铁都是零价的。     

碱性玄武岩中的某些巨晶单斜辉石Ⅱ：穆斯堡尔谱——兼论单斜辉石的异…

本文对辽宁宽甸碱性玄武岩中巨晶单斜辉石进行穆斯堡尔谱研究，应用晶体结构研究结果较合理地解释了单斜辉石的异常穆斯堡尔谱，结合ＸＲＤ讨论了单斜辉石中Ｆｅ结构态的测定以及穆斯堡尔谱的可应用性，巨晶应结晶于相当氧化的环境。     

铁尖晶橄榄石的穆斯堡尔谱研究

本文使用穆斯堡尔效应研究了在高温高压下合成的铁橄榄石和铁尖晶橄榄石。２９８Ｋ温度下铁橄榄石的穆斯堡尔谱由一组双峰组成，它被指派给Ｆｅ＾２＋（Ｍ１，Ｍ２）离子。２９８Ｋ温度下铁尖晶橄榄石的穆斯堡尔谱由三组双峰组成，其中两组双峰指派给八面体位置Ｂ上的Ｆｅ＾２＋，另一组双峰归为四面体位置Ａ上的Ｆｅ＾３＋，两组Ｆｅ＾２＋双峰的同质异能迁移近似相等而四极分裂不同，Ｓｉ原子在八面体位置上的占有率为６％～１０％     

碱性玄武岩中的某些巨晶单斜辉石──Ⅱ:穆斯堡尔谱──兼论单斜辉石的异常穆斯堡尔谱和铁结构态的测定

本文对辽宁宽甸碱性玄武岩中巨晶单斜辉石进行穆斯堡尔谱研究。应用晶体结构研究结果较合理地解释了单斜辉石的异常穆斯堡尔谱。结合XRD讨论了单斜辉石中Fe结构态的测定以及穆斯堡尔谱的可应用性。巨晶应结晶于相当氧化的环境。     

冀东水厂麻粒岩中辉石的穆斯堡尔谱研究

水厂麻粒岩中辉石的穆斯堡尔效应研究表明，斜方辉石的谱图为两组四极双峰，分别由Ｍ＿１和Ｍ＿２位上的高自旋态Ｆｅ￣（２＋）产生，而单斜辉石则为三组四极双峰，其中两组较强的双峰分别由Ｍ＿１和Ｍ＿２位上的Ｆｅ￣（２＋）产生，第二组弱双峰是由四面体和八面体位置上的Ｆｅ￣（３＋）共同产生的。水厂麻粒岩中辉石的有序程度高，并且斜方辉石有序度大大高于单斜辉石，而单斜辉石Ｍ＿１、Ｍ＿２位置的畸变程度高于斜方辉石。在压力相同的条件下，Ｆｅ￣（２＋）的有序度具有明显地温度效应，高温有利于Ｆｅ￣（２＋）做有序分布。     

海绿石演化系列的穆斯堡尔谱特征

通过穆斯堡尔方法研究了黄海和东海沉积物中的海绿石化过程,区分了Fe的价态和晶位,并且将初始基质向海绿石的发展过程与穆斯堡尔参数联系了起来。     

赤柏松含镍基性岩体中主要金属矿物的穆斯堡尔效应研究

赤柏松含镍基性岩体,是一个产于华北地台北缘东段太古宙地体中的早元古宙阜平期侵位的复式岩体。由变质辉长辉绿岩、中色橄榄辉长苏长岩、暗色橄榄辉长苏长岩、细粒辉长苏长岩与辉长玢岩等侵入岩相构成,赋存有大型硫化铜镍矿床。为了深入探讨岩体的成矿专属性,总结成岩成矿规律等,本文着重对岩体中主要金属矿物进行了穆斯堡尔效应研究。     

冀东水厂麻粒岩中辉石的穆斯堡尔谱研究

水厂麻粒岩中辉石的穆斯堡尔效应研究表明，斜方辉石的谱图为两组四极双峰，分别由Ｍ１和Ｍ２位上的高自旋态Ｆｅ＾２＋产生，而单斜辉石则为三组四极双峰，其中两组较强的双峰分别由Ｍ１和Ｍ２位上的Ｆｅ＾２＋产生，第二组弱双峰是由四面体和八面体位置上的Ｆｅ＾３＋共同产生的。水厂麻粒岩中辉石的有序程度高，并且斜方辉石有序度大大高于单斜辉石，而单斜辉石Ｍ１、Ｍ２位置的畸变程度高于斜方辉石。在压力相同的条件下，Ｆｅ＾     

57Fe Mössbauer spectroscopic analysis of chlorite

Five chlorite samples have been studied by ⁵⁷Fe Mössbauer spectroscopy at different temperatures. The spectra are consistently described by a superposition of one ferric and three ferrous quadrupole doublets. All hyperfine data exhibit only minor variations from sample to sample, meaning that the structural and electronic properties of chlorite are rather insensitive to compositional changes and local cation disorder. Two of the ferrous doublets are ascribed to cis and trans co-ordinations in the T-O-T layers. The third ferrous doublet is interpreted as being due to ferrous ions in the hydroxide sheets. Its hyperfine parameters are close to those of the former doublets and the observed deviations from the parameter values found for pure brucite are discussed. Approximately 20 to 25 percent of the total iron is situated in the hydroxide sheets. All five chlorites contain about 10 percent Fe³⁺ which is most probably located on octahedral sites. The temperature dependence of the ferrous quadrupole splittings for two chlorites has been interpreted on the basis of the thermal populations of the two lowest electronic states of the Fe²⁺ ions. From this, the deformations of the different octahedral co-ordinations could be estimated.     

Iron in silicate glasses of granitic composition: a Mössbauer spectroscopic study

⁵⁷Fe Mössbauer spectra of natural glasses (pumices and obsidians) and of synthetic glasses of granitic composition have been analyzed. — Ferric iron is found in tetrahedral coordination if enough M⁺-cations are available to balance the charge of both M⁺Fe³⁺O₂ and M⁺AlO₂ complexes. In other compositions the ratio of tetrahedrally to octahedrally coordinated Fe³⁺ depends on the ratio of mono-to divalent cations. — Ferrous iron occurs in two distinctly different octahedral sites. The existence of these sites can be attributed to different anionic units adjacent to Fe²⁺. The degree of polymerization of these units is reflected in the quadrupole splitting. The anionic units adjacent to Fe²⁺ are depolymerized for increasing mean Z/r ² of the network modifiers, which do not stabilize M³⁺ in the tetrahedra by local charge balance. — Increasing pressure diminishes the geometric differences between these types of ferrous iron-oxygen-octahedra, which gives rise to a more even distribution of Fe²⁺ among these sites and thereby to an ordering in the network of melts.     

Mössbauer and infrared spectroscopic studies of Belgian chloritoids

Three chloritoid samples from the Stavelot massif (Belgium) and one sample from the Serpont massif (Belgium) have been characterized by chemical analyses and differential X-ray diffraction. A classification of chloritoid is proposed. Mössbauer spectra at temperatures between 78 and 360 K and in external magnetic fields were obtained for a triclinic and for a monoclinic specimen. The spectra show a superposition of a weak Fe³⁺ doublet (less than 10%) and an intense Fe²⁺ doublet. It is found that a decomposition of the ferrous absorption into two distinct quadrupole doublets leads to smaller deviations between experimental and calculated line shapes, especially at low temperatures. This suggests that Fe²⁺ is present in both cis and trans O₂(OH)₄ octahedral positions in the trioctahedral layer. However, the structural data derived from the temperature dependence of isomer shifts and quadrupole splittings, are found to be inconsistent with known crystallographic data. It is therefore concluded that Fe²⁺ is present in only one type of lattice site and that the numerically imposed decomposition into two ferrous doublets is merely an artifact due to thickness saturation effects and to the distributive character of the hyperfine parameters. The negative sign of the electric field gradient further confirms the assignment of the Fe²⁺ doublet to a cis octahedral configuration. Finally, only minor differences between the Mössbauer results for triclinic and monoclinic chloritoid are observed. The infrared absorption spectra of the four samples are almost identical except in the region around 600 cm^?1 at which the monoclinic phase exhibits two absorption bands instead of one band for the triclinic samples. All absorption bands can be well assigned to the different vibrations. Inter-layer hydrogen bonding is evidenced by the occurrence of two v _O-H absorption bands. Furthermore, the specific nature of the infrared spectra enables a fast identification of chloritoid samples.     

Mössbauer spectroscopic studies on the iron forms of deep-sea sediments

Mössbauer spectroscopy was applied to characterize the valence states Fe(II) and Fe(III) in sedimentary minerals from a core of the Peru Basin. The procedure in unraveling this information includes temperature-dependent measurements from 275?K to very low temperature (300?mK) in zero–field and also at 4.2?K in an applied field (up to 6.2?T) and by mathematical procedures (least-squares fits and spectral simulations) in order to resolve individual spectral components. The depth distribution of the amount of Fe(II) is about 11% of the total Fe to a depth of 19?cm with a subsequent steep increase (within 3?cm) to about 37%, after which it remains constant to the lower end of the sediment core (at about 40?cm). The steep increase of the amount of Fe(II) defines a redox boundary which coincides with the position where the tan/green color transition of the sediment occurs. The isomer shifts and quadrupole splittings of Fe(II) and Fe(III) in the sediment are consistent with hexacoordination by oxygen or hydroxide ligands as in oxide and silicate minerals. Goethite and traces of hematite are observed only above the redox boundary, with a linear gradient extending from about 20% of the total Fe close to the sediment surface to about zero at the redox boundary. The superparamagnetic relaxation behavior allows to estimate the order of magnitude for the size of the largest goethite and hematite particles within the particle-site distribution, e.g. ～170?Å and ～50?Å, respectively. The composition of the sediment spectra recorded at 300?mK in zero-field, apart from the contributions due to goethite and hematite, resembles that of the sheet silicates smectite, illite and chlorite, which have been identified as major constituents of the sediment in the <2?μm fraction by X-ray diffraction. The specific “ferromagnetic” type of magnetic ordering in the sediment, as detected at 4.2?K in an applied field, also resembles that observed in sheet silicates and indicates that both Fe(II) and Fe(III) are involved in magnetic ordering. This “ferromagnetic” behavior is probably due to the double-exchange mechanism known from other mixed-valence Fe(II)–Fe(III) systems. A significant part of the clay-mineral iron is redox sensitive. It is proposed that the color change of the sediment at the redox boundary from tan to green is related to the increase of Fe(II)–Fe(III) pairs in the layer silicates, because of the intervalence electron transfer bands which are caused by such pairs.     

基于穆斯堡尔谱技术的铁化学种及其在相关表生地球科学研究中的应用

由于铁元素分布的广泛性和化学反应的活泼性,它在地球科学研究中具有极为重要的应用意义。与其他多种方法相比较,穆斯堡尔技术是铁元素化学种检测最为有效的方法之一,许多研究结果显示铁元素化学种在相关表生坩球科学研究中的应用前景广阔,例如滑坡带地球化学、湖泊沉积环境、岩石光谱特征、重金属污染沉积物及其环境修复技术等。     

Mössbauer study of natural wolframites

The first Mössbauer results obtained with powdered samples of natural wolframites Fe _x Mn_1?x WO₄ from some famous Portuguese and Peruvian mines are reported here. The Mössbauer experiments have been carried out at 300, 77 and 4.2 K with four natural and one synthetic powdered samples of different compositions. The Mössbauer parameter values can be attributed to a high spin ferrous ion in a quite distorted octahedral symmetry. From the 4.2 K spectra, one deduces a weak value for the hyperfine magnetic field (H _hf?45 kOe), a negative sign for the quadrupole interaction, and an approximate value for the asymmetry parameter (η?0.7). X-ray diffractometry experiments developed to determine the lattice constants have shown a linear behaviour of the most sensitive parameter a as a function of the iron content x. In parallel, a linear behaviour of the Néel temperature T _N with x observed between x=0.5 and x=1.     

The elastic constants of monoclinic single-crystal chrome-diopside to 1,300 K

Values of the complete adiabatic elastic tensor for single-crystal chrome-diopside (a monoclinic pyroxene mineral) are presented from 298 to 1,300 K. The data were obtained using resonant ultrasound spectroscopy (RUS). They are the first published results for the temperature T dependences of the 13 individual elastic constants C _ij of any clinopyroxene mineral. Each C _ij is appropriately described by a linear function in T throughout the range of T. Values for each (∂C _ij /∂T) _P in GPa K⁻¹ are as follows: C ₁₁, −0.0291; C ₂₂, −0.0248; C ₃₃, −0.0179; C ₄₄, −0.0103; C ₅₅, −0.0077; C ₆₆, −0.0152; C ₁₂, −0.0119; C ₁₃, −0.0064; C ₂₃, 0.0000; C ₁₅, 0.0025; C ₂₅, 0.0022; C ₃₅, −0.0046; and C ₄₆, 0.0026. Values of (∂M/∂T) _P in GPa K⁻¹, where M represents an isotropic bulk property calculated from the C _ij data, are as follows: adiabatic bulk modulus K _S , −0.0123; isothermal bulk modulus K _T , −0.0178; and shear modulus G, −0.00998. Some diopside derivatives, notably (∂K _S /∂T) _P , (∂K _T /∂T) _P , and (∂V _P /∂T) _P , where V _P is the compressional wave velocity, have smaller magnitudes than all other minerals of importance in Earth’s mantle, thus, confirming predictions from systematics studies. We find several dimensionless quantities for this monoclinic mineral have normal values compared to other mantle minerals. Further, αK _T (α is the volume coefficient of thermal expansion) for diopside is approximately independent of both T and volume V at elevated temperature, so its equation of state is accurately expressed in simplified form.     

Characterization of beryl (aquamarine variety) by Mössbauer spectroscopy

The Mössbauer spectra of several blue beryls have been obtained in the temperature range of 4.2–500 K. A common feature observed in all room-temperature spectra is the presence of an asymmetric Fe²⁺ doublet (ΔE _Q ?～?2.7?mm?s^?1, δ?～?1.1?mm?s^?1), with a very broad low-velocity peak. This asymmetry seems to be related to a relaxation process involving ferrous ions and water molecules in the structural channels, as suggested by Price et?al. (1976). Surprisingly, the spectrum at 500?K also shows a broad, but symmetrical, doublet, with a clear splitting of the lines indicating the presence of at least two Fe²⁺ components. The room-temperature spectrum obtained after the 500?K run shows the same features as prior to the heating. At 4.2?K the spectrum of a deep blue beryl was well fitted with four symmetrical doublets, one of which could be related to Fe²⁺ in the structural channels. Ferrous ion was also found to occupy the octahedral and tetrahedral sites, whereas ferric ion is most probably located in the octahedral site. A meaningful fit of the room-temperature spectrum, as well as an explanation for the temperature dependence of the Mössbauer spectra, are discussed. Finally, it is believed that the color in beryl will be dictated by the relative proportions of Fe³⁺ in the octahedral sites and of Fe²⁺ in the channels.     

Mössbauer spectra of Fe x O (x>0.95)

The Mössbauer spectra of five samples of Fe _x O with compositions in the range 1.00>x>0.95 have been recorded at 298 K and 4.2 K. The spectrum of Fe _x O at 298 K consists of an asymmetric doublet which was fitted to one Fe²⁺ singlet, two Fe²⁺ doublets and 1 Fe³⁺ singlet. The Mössbauer parameters vary consistently with the increasing density of defects as x decreases. The Mössbauer spectrum of Fe _x O at 4.2 K consists of a large number of unresolved lines. The data were fitted to a series of singlets to enable the rough calculation of quantities relating to the mean Fe²⁺ and Fe³⁺ environments. The results of the fits to the 298 K spectra are briefly discussed in terms of a physical model for the defect structure of Fe _x O.