Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

<Superscript>226</Superscript>Ra, <Superscript>232</Superscript>Th and <Superscript>40</Superscript>K activities in soils of Cuihua Mountain National Geological Park,China

Gamma activity from the naturally occurring radionuclides namely, ²²⁶Ra, ²³²Th, the primordial radionuclide ⁴⁰K was measured in the soil of Cuihua Mountain National Geological Park, China using γ-ray spectrometry technique. The mean activity of ²²⁶Ra, ²³²Th and ⁴⁰K were found to be 27.2 ± 6.5, 43.9 ± 6.2 and 653.1 ± 127.6 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil. The radium equivalent activity, the air absorbed dose rate, the annual effective dose rate, and the external hazard index were evaluated and compared with the internationally approved values. All the soil samples have Ra_eq lower than the limit of 370 Bq kg⁻¹ and H _ex less than unity. The overall mean outdoor terrestrial gamma dose rate is 66.3 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.081 mSv.     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.     

Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

Room-temperature equation of state of Li<Subscript>2</Subscript>VOSiO<Subscript>4</Subscript> up to 8.5 GPa

High-pressure single-crystal X-ray diffraction measurements of lattice parameters of the compound Li₂VOSiO₄, which crystallises with a natisite-type structure, has been carried out to a pressure of 8.54(5) GPa at room temperature. Unit-cell volume data were fitted with a second-order Birch-Murnaghan EoS (BM-EoS), simultaneously refining V ₀ and K ₀ using the data weighted by the uncertainties in V. The bulk modulus is K ₀ = 99(1) GPa, with K′ fixed to 4. Refinements of third order equations-of-state yielded values of K′ that did not differ significantly from 4. The compressibility of the unit-cell is strongly anisotropic with the c axis (K ₀(c) = 49.7 ± 0.5 GPa) approximately four times more compressible than the a axis (K ₀(a) = 195 ± 3 GPa).     

In situ strength measurements on natural upper-mantle minerals

Using in situ strength measurements at pressures up to 10 GPa and at room temperature, 400, 600, and 700°C, we examined rheological properties of olivine, orthopyroxene, and chromian-spinel contained in a mantle-derived xenolith. Mineral strengths were estimated using widths of X-ray diffraction peaks as a function of pressure, temperature, and time. Differential stresses of all minerals increase with increasing pressure, but they decrease with increasing temperature because of elastic strain on compression and stress relaxation during heating. During compression at room temperature, all minerals deform plastically at differential stress of 4–6 GPa. During subsequent heating, thermally induced yielding is observed in olivine at 600°C. Neither orthopyroxene nor spinel shows complete stress relaxation, but both retain some stress even at 700°C. The strength of the minerals decreases in the order of chromian-spinel ≈ orthopyroxene > olivine for these conditions. This order of strength is consistent with the residual pressure of fluid inclusions in mantle xenoliths.     

Optical spectrum based measurement of flotation slurry contents

Monitoring and control of a flotation circuit is mainly based on the information gained by assaying the process slurry lines. In flotation plants, usually an X-ray fluorescence analyzer is used to obtain the on-line assays. This article introduces the visual and near-infrared reflectance spectroscopic analysis of the process slurries as a supplementary method which complements the on-line assay information available from an X-ray fluorescence analyzer. It is shown that the spectral information can be used to accurately predict the element contents in the slurry in between successive XRF analyses. Since the spectral measurements can be taken with high frequency as opposed to the sparse X-ray fluorescence analysis, a practically continuous on-line estimate of the slurry contents is reached. These estimates can be used in the plant control to improve the overall performance of the circuits and to yield also economical savings. Additionally, the frequent monitoring of the grades can provide means to eliminate rapid disturbances in the circuits, thus improving the stability of the process.     

UV-B辐射对海洋微藻抗氧化系统的影响

研究了UV－B辐射对两种海洋微藻－小新月菱形藻（Ntzschia closterlum)和亚心形扁藻（Platymonas subcordiforming)的抗氧化系统的影响。结果表明：在本实验的辐射剂量范围内，随着UV－B辐射剂量的增强，两种藻的抗氧化防御系统的非酶性组分还原型谷胱甘肽（GSH）和类胡萝卜素（CAR）的含量随之下降；抗氧化防御系统的酶性组分超氧化歧化酶（SOD）和过氧化氢酶（CAT）的活性逐渐降低。加入外源性抗氧化剂GSH可减轻UV－B辐射对藻的伤害。分析表明海洋微藻的UV－B伤害是由于抗氧化防御系统遭到破坏而导致活性氧积累的结果。     

15N示踪-离子质谱法测定新生产力的研究

本文提出了~(15)N示踪-离子质谱法实测新生产力的方法,并于1991年11月—1992年5月结合胶州湾现场调查的实际样品,对示踪剂量、培养时间、样品贮存、消解剂量和时间、铵离子的扩散吸收,以及方法的空白值、检出限、精密度和准确度等进行了实验研究。结果表明,该法具有较高的精密度和良好的准确度,与经典的气体质谱法相比,还具有进样量少以及可同时分析~(15)N丰度、总氮浓度和水中铵离子浓度等特点,对于含氮量极低、铵氮再生迅速的海洋环境中新生产力的研究,具有特殊的意义。     

海洋光合有效辐射分布的计算模式

针对一类海水，采用美国标准大气模型和一类水体海洋生物-光学特性的半分析方法，建立了海洋光合有效辐射计算模式。模式比较全面地考虑了大气、海-气界面和水体的光辐射传输过程，能较好地用于分析叶绿素浓度以及光辐射场的角分布对光俣有效辐射分布的影响。对模拟结果的分析以及与实测结果的比较表明，该模式能较好地应用于计算衰减系数、光谱辐照度随深度的分布、光合有效辐射随深度的分布和真光层深度，在海洋生态系统的光动力学研究和水色遥感方面有效好的应用前景。