Molybdenum isotopic composition as a tracer for low-medium temperature hydrothermal ore-forming systems: A case study on the Dajiangping pyrite deposit,western Guangdong Province,China

Little is known about the range or controls on the molybdenum isotopic composition of low-medium temperature hydrothermal ore-forming systems. We present molybdenum isotope data from 12 hydrothermal syndepositional silicalite and carbonaceous slate samples from the Dajiangping pyrite deposit in western Guangdong Province, South China. The δ ^97/95 Mo values from Orebody III range from −0.02‰ to 0.29‰, with an average of 0.18‰. In contrast, the composition values from Orebody IV display a larger variation from −0.70‰ to 0.62‰. However, the five samples from the main ore bed all show strong negative values. This indicates that the significant variation in molybdenum isotopic composition supports different hydrothermal ore-forming metallogenesis and a metallogenic environment between the two orebodies. Orebody III is likely to have been deposited from submarine exhalative hydrothermal fluids under a relatively strong reducing environment and Orebody IV may have also been influenced by hydrothermal superimposition in a more oxidized disequilibrium condition. In addition, the δ ^97/95 Mo values of Orebody IV are clearly negative, together with the values increasing stratigraphically upward in the ore beds, suggesting that the metallogenic environment of Orebody IV is different from the open oceanic systems. There might be dynamic fractionation in this restricted environment. Therefore, the molybdenum isotope can be used as an effective tracer for the ore-forming fluid and metallogenic environment.     

油田用新型同位素示踪剂的研究

研究了一种油田用新型同位素示踪剂,并与以活性炭为载体的同位素示踪剂进行了对比研究,应用表明使用效果良好.     

血清中葡萄糖含量CCQM-K11.1国际比对

研究利用同位素稀释质谱法测定血清中的葡萄糖含量,并利用该方法参加国际物质量咨询委员会（CCQM）2005年组织的关键比对CCQM—K11．1,我国国家标准物质研究中心（NRCCRM）的测定结果与韩国（KRISS）和墨西哥（CENAM）的测定结果非常接近,日本（NMIJ）的测定结果离群偏高。     

银川平原地下水同位素特征分析

地下水同位素特征表明银川平原地下水具有不同的补给模式。贺兰山洪积扇单一潜水主要接受山区侧向径流及大气降水补给;青铜峡洪积扇单一潜水及冲湖积平原上覆潜水,主要接受黄河灌溉水的入渗补给。天然状态下,承压水为古地质时期补给形成的“古水”,地下水交替缓慢;开采状况下,平原东部承压水受到了现代补给水的影响,潜水越流量占补给量的50%左右。针对平原区不同的水文地质条件及循环特征,建议采取相应的措施,合理开发利用水资源。     

湖泊水体年龄与水体中放射性同位素浓度关系浅析

为了研究湖泊水体年龄与水体中放射性同位素浓度之间的定量关系,运用数学物理方法给出了湖泊水体年龄展开为湖泊水体中放射性同位素浓度的函数表达式.在介绍年龄输运方程概念及其意义的基础上,以微分方程为分析工具,根据质量守恒原理和放射性衰变原理,利用微元法分别推导了湖泊水体的年龄输运方程和湖泊水体中放射性同位素浓度的变化规律,并给出了各自的解析解;在此两者的基础上给出了湖泊水体年龄与水体中放射性同位素浓度之间的函数关系.     

Rate Coefficients and Kinetic Isotope Effects of Cl+XCl→XCl+Cl (X=H,D, Mu) Reactions from Ring Polymer Molecular Dynamics

The ring-polymer molecular dynamics (RPMD) was used to calculate the thermal rate coefficients and kinetic isotope effects of the heavy-light-heavy abstract reaction Cl+XCl\begin{document}$ \rightarrow $\end{document}XCl+Cl (X = H, D, Mu). For the Cl+HCl reaction, the excellent agreement between the RPMD and experimental values provides a strong proof for the accuracy of the RPMD theory. And the RPMD results are also consistent with results from other theoretical methods including improved-canonical-variational-theory and quantum dynamics. The most novel finding is that there is a double peak in Cl+MuCl reaction near the transition state, leaving a free energy well. It comes from the mode softening of the reaction system at the peak of the potential energy surface. Such an explicit free energy well suggests strongly there is an observable resonance. And for the Cl+DCl reaction, the RPMD rate coefficient again gives very accurate results compared with experimental values. The only exception is at the temperature of 312.5 K, results from RPMD and all other theoretical methods are close to each other but slightly lower than the experimental value, which indicates experimental or potential energy surface deficiency.     

液相色谱/串联质谱线性组合法测定动物组织中硝基呋喃代谢产物

研究了对动物组织中4种硝基呋喃类代谢产物AMOZ、AHD、SEM、AOZ的同位素稀释HPLC—MS／MS线性组合分析方法,以2-基苯甲醛作为衍生化试剂,AMOZ—d5、AOZ-4作内标,用乙酸乙脂提取,用自制的净化试剂净化,以乙腈-0．1％甲酸为流动相,采用梯度洗脱,可适应不同种类的动物组织样品前处理,15min可将4种代谢产物完全分离并测定。提出了HPLC—MS／MS多重反应监测线性组合法的原理并进行了验证,回收率为85％-118％;定量限（LOQ）为0．1μg／kg;检出限（LOD）为0．03μg／kg。     

Application of double-spike isotope dilution for the accurate determination of Cr(III), Cr(VI) and total Cr in yeast

A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate at 95±2 °C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na₂CO₃ for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO₃ and H₂O₂ was used for the determination of total Cr. Concentrations of 2,014±16, 1,952±103 and 76±48 mg kg⁻¹ (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III) to Cr(VI) (24.2±7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6±6.5% Cr(VI) reduced, n=3 ) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition, mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3, 2 and 30 mg kg⁻¹ were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample.     

Vibrational isotope effect by the low rank perturbation method

Mathematical formalism of the Low Rank Perturbation method (LRP) is applied to the vibrational isotope effect in the harmonic approximation with a standard assumption that force field does not change under isotopic substitutions. A pair of two n-atom isotopic molecules A and B which are identical except for isotopic substitutions at ρ atomic sites is considered. In the LRP approach vibrational frequencies ω _k and normal modes of the isotopomer B are expressed in terms of the vibrational frequencies ν _i and normal modes of the parent molecule A. In those relations complete specification of the normal modes is not required. Only amplitudes at sites τ affected by the isotopic substitutions and in the coordinate direction s (s = x, y, z) are needed. Out-of-plane vibrations of the (H,D)-benzene isotopomers are considered. Standard error of the LRP frequencies with respect to the DFT frequencies is on average . This error is due to the uncertainty of the input data (± 0.5 cm⁻¹) and in the absence of those uncertainties and in the harmonic approximation it should disappear. In comparing with experiment, one finds that LRP frequencies reproduces experimental frequencies of (H,D)-benzene isotopomers better () than scaled DFT frequencies () which are designed to minimize (by frequency scaling technique) this error. In addition, LRP is conceptually and numerically simple and it also provides a new insight in the vibrational isotope effect in the harmonic approximation.     

Fragmentation studies of pentacoordinated bisaminoacylspirophosphoranes by negative electrospray ionization mass spectrometry

Fragmentation pathways of a series of pentacoordinated bisaminoacylspirophosphoranes were elucidated by electrospray ionization multistage mass spectrometry (ESI-MS(n)) in negative mode. The deprotonated ions of pentacoordinated bisaminoacylspirophosphoranes tend to eliminate a corresponding amino acid to form base peak. The hydrogen/deuterium exchange experiment, the high-resolution mass spectrometry, (13)C stable isotope labeling experiment and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The results indicate that the negative molecular ions of pentacoordinated bisaminoacylspirophosphoranes dissociate through its open-chain tricoordinated tautomers. The relative Gibbs free energies (ΔG) of the product ions and proposed fragmentation pathways were estimated using the B3LYP/6-31 + + G(d, p) model. The results have some potential applications in the identification structures of similar spirophosphorane compounds by ESI-MS(n).