Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

江苏常州4.2级地震前的重力变化

利用江苏地区2019~2021年流动重力观测资料,分析江苏省常州市4.2级地震前不同时间尺度下的重力场变化。结果表明：1）0.5 a尺度重力场变化图像较好地反映了此次地震下降-转折上升-持续上升-反向变化及零值线附近发震的演化过程;2）常州4.2级地震前0.5 a和1 a尺度下的重力场均显示,地震发生在重力变化零值线附近。     

M4–18: the planetary nebula and its WC10 central star

We present a detailed analysis of the planetary nebula M4–18 (G146.7+07.6) and its WC10-type Wolf–Rayet (WR) central star, based on high‐quality optical spectroscopy (WHT/UES, INT/IDS, WIYN/DensPak) and imaging ( HST /WFPC2). From a non-LTE model atmosphere analysis of the stellar spectrum, we derive T _eff=31 kK,     v _∞=160 km s⁻¹ and abundance number ratios of H/He<0.5, C/He=0.60 and O/He=0.10. These parameters are remarkably similar to those of He 2–113 ([WC10]). Assuming an identical stellar mass to that determined by De Marco et al. for He 2–113, we obtain a distance of 6.8 kpc to M4–18 [ E ( B−V )=0.55 mag from nebular and stellar techniques]. This implies that the planetary nebula of M4–18 has a dynamical age of ∼3100 yr, in contrast to ≥270 yr for He 2–113. This is supported by the much higher electron density of the latter. These observations may be reconciled with evolutionary predictions only if [WC]-type stars exhibit a range in stellar masses.
Photoionization modelling of M4–18 is carried out using our stellar WR flux distribution, together with blackbody and Kurucz energy distributions obtained from Zanstra analyses. We conclude that the ionizing energy distribution from the WR model provides the best consistency with the observed nebular properties, although discrepancies remain.     

Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2 · 4H2O, and of its oxidation products

Mössbauer spectra (MS) of anapaite (Ca₂ Fe²⁺(PO₄)₂?·?4H₂O) and of a sample after being immersed in a 4% H₂O₂ solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe²⁺ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V _zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE _Q(T), cannot be interpreted on the basis of the thermal population of the ⁵ D electronic levels resulting from the tetragonal compression of the O₆ co-ordination. The low-temperature linear behaviour of ΔE _Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H₂O₂ concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe²⁺ (～6.5%) is converted into Fe³⁺.     

57Fe Mössbauer spectroscopy of tektites

Tektite glasses are investigated using ⁵⁷Fe Mössbauer spectroscopy. Room temperature spectra analysis is performed using two complementary analytical methods based on two-dimensional distributions of both isomer shift and quadrupole splitting. No a priori correlation between the two hyperfine parameters is considered. The first method, based on a shape independent distribution, provides the justification for the Gaussian distribution shape used in the second method. No ferric iron contribution is evidenced by Mössbauer spectra analysis in these samples, although several criteria are used. Ferrous iron sites are shown to be continuously distributed between four- and five-fold co-ordinated sites.     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998     

吉林松原5.8级震群震相特征

选取2013年松原5.8级震群23个M_S≥3.0地震事件,通过地震波的振动持续时间、速度、周期、振幅等,进行震相识别,综合分析发现：该区域土层较厚,且震源相对较浅,面波较发育,波列的振动持续时间较长;地震震相主要以Pn、Sn、Pg、Sg、PmP、SmS为主：其中PmP、SmS震相在震中距70—110 km范围内较易识别;Pn、Sn震相在震中距150 km以上可较清晰的识别,随着震中距增大,Sn震相在震中距350 km以上将不易识别。     

A NEW FINDING OF SURFACE RUPTURE ZONES ASSOCIATED WITH THE 1936 LINGSHAN M6(3/4) EARTHQUAKE,GUANGXI, CHINA

On April 1, 1936, an M6(3/4) earthquake occurred on the Fangcheng-lingshan Fault. This event is the biggest historical earthquake on the coastal seismic zone, South China ever. But so far, no any findings about the surface rupture of this event have been reported. This paper is the first to find several intact surface rupture zones associated with the 1936 Lingshan seismic event, in the areas of Gaotang, Jiaogengping etc. on the northeast segment of the Fangcheng-Lingshan Fault. According to the field work, the surface rupture stretches to 10km and distributes along NE direction in front of Luoyang Mountain, represented by earthquake scarp, extensional fracture, dextrally faulted gully and river system etc. The characteristics of surface ruptures and faulted landforms indicate that the surface rupture is of normal-dextral strike slip faulting. The trenching on this fault exposed that at least three seismic events have been recorded, including two historical earthquake events and the latest one is the 1936 Lingshan M6(3/4) earthquake. These surface rupture zones are the key to the detection of seismogenic structure and the re-estimate of magnitude of this event. The new finding of these surface rupture zones would be particularly significant for the detection of the seismogenic structure of Lingshan M6(3/4) earthquake.