A Simplified, Accurate and Fast Method for Lithium Isotope Analysis of Rocks and Fluids, and δ7Li Values of Seawater and Rock Reference Materials

We report a new approach to conduct fast and accurate lithium isotope ratio measurements by MC-ICP mass spectrometry after wet chemical sample preparation. In contrast to most previously published methods our MC-ICP-MS set-up did not use a desolvating system to achieve appropriate ion beam intensities and, therefore, was less affected by matrix-induced shifts of the instrumental mass bias. As the total lithium background and build-up in the sample introduction system was low, previous sample residues could be washed out by an extended uptake of the new sample. Elimination of a nitric acid rinse step increased the sample throughput by a factor of two and allowed the instrumental mass bias drift to be tracked more precisely. δ⁷Li values of powdered silicate rock reference materials and seawater obtained in this study revealed good accuracy and an overall analytical uncertainty of typically 0.5‰ (2s). On the basis of a comparison between our lithium isotope data and compiled literature data, we recommend preliminary average δ⁷Li values for seawater (+30.8‰) and several silicate rock reference materials (BHVO-1: +5.0‰; JA-1: +5.6‰; JB-2: +4.8‰). The compilation of published δ⁷Li values for seawater suggests that the observed large lithium isotope differences are due to inter-method and/or interlaboratory bias. Most recently published δ⁷Li values for seawater show little variation and confirm a constant lithium isotope composition (at the sub ‰ level) of seawater in well mixed ocean basins.     

High-pressure transitions and thermochemistry of MGeO3 (M=Mg, Zn and Sr) and Sr-silicates: systematics in enthalpies of formation of A2+B4+O3 perovskites

Phase transitions in MgGeO₃ and ZnGeO₃ were examined up to 26 GPa and 2,073 K to determine ilmenite–perovskite transition boundaries. In both systems, the perovskite phases were converted to lithium niobate structure on release of pressure. The ilmenite–perovskite boundaries have negative slopes and are expressed as P(GPa)=38.4–0.0082T(K) and P(GPa)=27.4−0.0032T(K), respectively, for MgGeO₃ and ZnGeO₃. Enthalpies of SrGeO₃ polymorphs were measured by high-temperature calorimetry. The enthalpies of SrGeO₃ pseudowollasonite–walstromite and walstromite–perovskite transitions at 298 K were determined to be 6.0±8.6 and 48.9±5.8 kJ/mol, respectively. The calculated transition boundaries of SrGeO₃, using the measured enthalpy data, were consistent with the boundaries determined by previous high-pressure experiments. Enthalpy of formation (ΔH _f°) of SrGeO₃ perovskite from the constituent oxides at 298 K was determined to be −73.6±5.6 kJ/mol by calorimetric measurements. Thermodynamic analysis of the ilmenite–perovskite transition boundaries in MgGeO₃ and ZnGeO₃ and the boundary of formation of SrSiO₃ perovskite provided transition enthalpies that were used to estimate enthalpies of formation of the perovskites. The ΔH _f° of MgGeO₃, ZnGeO₃ and SrSiO₃ perovskites from constituent oxides were 10.2±4.5, 33.8±7.2 and −3.0±2.2 kJ/mol, respectively. The present data on enthalpies of formation of the above high-pressure perovskites were combined with published data for A²⁺B⁴⁺O₃ perovskites stable at both atmospheric and high pressures to explore the relationship between ΔH _f° and ionic radii of eightfold coordinated A²⁺ (R _A) and sixfold coordinated B⁴⁺ (R _B) cations. The results show that enthalpy of formation of A²⁺B⁴⁺O₃ perovskite increases with decreasing R _A and R _B. The relationship between the enthalpy of formation and tolerance factor ( R _o: O²⁻ radius) is not straightforward; however, a linear relationship was found between the enthalpy of formation and the sum of squares of deviations of A²⁺ and B⁴⁺ radii from ideal sizes in the perovskite structure. A diagram showing enthalpy of formation of perovskite as a function of A²⁺ and B⁴⁺ radii indicates a systematic change with equienthalpy curves. These relationships of ΔH _f° with R _A and R _B can be used to estimate enthalpies of formation of perovskites, which have not yet been synthesized.     

Ion Probe Study of Silicate Inclusions from Colomera （IIE） Iron Meteorite： the Rare Earth Element Perspective

Coupled with a petrographical study, I carried out an ion probe study of rare earth element microdistributions in mineral phases of silicate inclusions from the Colomera IIE iron meteorite. Most mineral grains have homogeneous REEs, but show considerable inter-grain variations by a factor of 2 to 100. The whole rock REE abundances for Colomera,estimated by combining REE data with modal abundances, are relatively LREE-enriched with REEs of～10’CI, which suggest that Colomera silicates were highly differentiated and might represent a low degree partial melt (-10%) of a chondritic source. REE geochemistry of Colomera silicate inclusions points to an origin that involves differentiation,dynamic mixing, remelting, reduction, recrystallization, and subsequent rapid cooling near the surface of a planetary body.     

A Mssbauer effect study of Fe3+ bearing

Three synthetic Fe3+ bearing γ-Fe2SiO4 were analyzed usingelectron probe method, and the Mssbauer spectra of the samples at 298 K, 150 K, and 95 K were measured. Each spectrum at three temperatures is composed of two doublets. These two doublets are assigned to Fe2+ in the octahedral sites and Fe3+ in the tetrahedral sites, respectively. Site occupancies were determined. The results show that Fe3+ and a small amount of Si4+ are in the tetrahedral and octahedral sites, respectively. The average bond lengths of the octahedral and tetrahedral sites were calculated according to the equations primarily given by Hill et al., O’Neill and Navrotsky and modified by the authors. Furthermore, the octahedral and tetrahedral bond lengths were used to calculate cell parameters and oxygen parameters. In addition, Fe3+ line broadening in the M?ssbauer spectra of Fe3+ bearing γ-Fe2SiO4 were interpreted by using the next nearest neighbor effects.     

中酸性硅酸盐熔体-水体系氢同位素分馏的压力效应

对0．2－2000MPa条件下钠长石熔体，钾长石熔体以及0．2－150MPa条件下流纹岩熔体－－水体系的氢同位素分馏实验数据进行了筹压拟合，发现硅酸盐熔体与水之间的氢同位素分馏存在显著的压力效应，在800，1000和1200度条件下对钠长石熔体，水体系和流夺熔体－－水体系氢同位素分馏压力方程进行的等温拟合表明，只有在特定的压力条件下才可以用钠长石熔体－水体系来近似流纹岩熔体－－水体系的氢同位素分馏行为，当压力超过临界值时，硅酸盐熔体－水体系氢同位素分馏会发生变化，本文拟合的硅酸盐熔体－水体系氢同位素分馏等值线在P－T空间的形态变化特征与矿物－水体系存在较大差异，依据流纹岩熔体与水之间氢同位素分馏的压力效应，成功地模拟了美国西部Glass Creek流纹岩δD值和水含量变化规律与岩浆去气之间的关系。     

Compaction in a mantle with a very small melt concentration: Implications for the generation of carbonatitic and carbonate-bearing high alkaline mafic melt impregnations

Xenoliths entrained in alkaline basalts and kimberlites give strong evidence that mantle carbonatitic and carbonated high alkaline mafic silicate melts, which are initially produced at very low degrees of partial melting (?1%), percolate and accumulate to form impregnations with a melt concentration of up to 10%. At present no compaction model has explained such huge local amplification of melt concentration. Recently, Bercovici et al. [1] have shown that the commonly used equations of compaction are not sufficiently general to describe all melt percolation processes in the mantle. In particular, they show that, when the melt concentration in the mantle is very low, the pressure jump ΔP between the solid and liquid fractions of the mantle mush is very important and plays a driving role during compaction. 1-D compaction waves generated with two different systems of equations are computed. Three types of wave-trains are observed, i.e. (1) sinusoidal waves; (2) periodic waves with flat minima and very acute maxima (‘witch hat waves’); (3) periodic solitary waves with flat maxima and extremely narrow minima (‘bowler hat waves’). When the initial melt distribution in the mantle is quite homogeneous, the compaction waves have sinusoidal shapes and can locally amplify the melt concentration by a factor less than two. When there is a drastic obstruction at the top of the wetted domain, the pressure jump ΔP between solid and liquid controls the shape of the waves. If the computation assumes the equality of pressure between the two phases (ΔP=0), the compaction wave has a ‘bowler hat shape’, and locally amplifies the melt concentration by a factor less than 5. Alternatively, simulations taking into account the pressure jump between phases ΔP predict compaction waves with ‘witch hat shape’. These waves collect a large quantity of melt promoting the development of magmons with local melt concentration exceeding 100× the background melt concentration. It is inferred that in a mantle with very low concentrations of carbonatitic or high alkaline mafic silicate melt the magmons are about 1 km thick and reach, in less than 1 Ma, a melt concentration of about 10%. The magmons are likely generated below the lithosphere at some distance away from the center of hot spots. This can explain the development of mantle carbonatitic eruptions in the African rift and the carbonatite and high alkaline mafic silicate volcanic activity in oceanic islands.     

硅酸盐岩石分析50年

评述了硅酸盐岩石分析在过去的50年中的主要进展。其中包括化学快速分析、仪器分析、痕量元素分析、微区分析和硅酸盐标准物质研制。     

Comparison of UV and IR Laser Ablation ICP-MS on Silicate Reference Materials and Implementation of Normalisation Factors for Quantitative Measurements

Direct analysis of geological reference materials was performed by LA-ICP-MS using two Nd:YAG laser systems operating at 266 nm and 1064 nm. The aim of this work was to compare UV and IR laser ablation and to assess the potential of the technique for the quantitative bulk analysis of rocks, sediments and soils. The laser sampling process was investigated and the analytical performance of both systems was compared. The influence of the laser operating conditions and the nature of the matrix on ICP-MS response factors calculated for major, minor and trace elements was evaluated. Under consistent laser settings, the response factors appeared to be matrix dependent. For a given matrix, the response factors were also significantly different for the two lasers. Normalisation with a single matrix element was effective only for matrices with similar mineralogy. When operating at 266 nm instead of 1064 nm, matrix effects could be reduced but not overcome. However, variations of the response factors between the different matrices appeared to be similar within distinct groups of elements, reflecting geochemical associations. When using multiple internal standards, matrix effects but also effects of the laser wavelength, could be fully compensated.     

Characterization of NH4-phlogopite (NH4) (Mg3) [AlSi3O10] (OH)2 and ND4-phlogopite (ND4) (Mg3) [AlSi3O10] (OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

 A synthesis technique is described which results in >99% pure NH₄-phlogopite (NH₄) (Mg₃) [AlSi₃O₁₀] (OH)₂ and its deuterium analogue ND₄-phlogopite (ND₄) (Mg₃) [AlSi₃O₁₀] (OD)₂. Both phases are characterised using both IR spectroscopy at 298 and 77 K as well as Rietveld refinement of their X-ray powder diffraction pattern. Both NH₄ ⁺ and ND₄ ⁺ are found to occupy the interlayer site in the phlogopite structure. Absorption bands in the IR caused by either NH₄ ⁺ or ND₄ ⁺ can be explained to a good approximation using T_d symmetry as a basis. Rietveld refinement indicates that either phlogopite synthesis contains several mica polytypes. The principle polytype is the one-layer monoclinic polytype (1M), which possesses the space group symmetry C2/m. The next most common polytype is the two-layer polytype (2M ₁ ) with space group symmetry C2/c. Minor amounts of the trigonal polytype 3T with the space group symmetry P3₁12 were found only in the synthesis run for the ND₄-phlogopite. Electron microprobe analyses indicate that NH₄-phlogopite deviates from the ideal phlogopite composition with respect to variable Si/Al and Mg/Al on both the tetrahedral and octahedral sites, respectively, due to the Tschermaks substitution ^VIMg²⁺+^IVSi⁴⁺↔^VIAl³⁺+^IVAl³⁺ and with respect to vacancies on the interlayer site due to the exchange vector ^XII(NH₄)⁺+^IVAl³⁺↔^XII□+^IVSi⁴⁺. Received: 30 August 1999 / Accepted: 2 October 2000     

新疆库车地区放射虫新资料及其意义

在新疆库车地区硅质岩地层中发现了丰富的保存良好的放射虫化石，共计１７属３７种，包括一新种。并在此基础上，建立了５个放射虫组合带。该放射虫动物群的多数分子曾见于德国的Ｆｌａｎｄｋｅｎｗａｌｄ地区和美国Ａｌａｓｋａ和Ｏｈｉｏ页岩中以及我国广酉。通过大量资料的分析对比，确定该套放射虫组合时代为晚泥盆世—早石炭世，进而阐述了这套放射虫硅质岩的大地构造意义。