地球化学样品中有机碳的光谱分析

有机碳已成为多目标地球化学调查、土地质量地球化学调查等项目研究的必测指标,对有机碳的准确定量是地球化学调查工作的重要内容,准确测定有机碳含量具有重要意义。然而传统的重量法、容量法流程长、速度慢,已经不能满足大批量及快速测定地球化学样品的要求。采用稀盐酸去除样品中的无机碳,应用高频红外碳硫分析仪对不同类型地球化学样品中有机碳的测定进行了研究,着重从称样量、酸的选择、最佳浓度及用量、助熔剂的选择和最佳加入量进行对比实验,优化出适合分析地球化学样品中有机碳含量的条件,并采用国家一级地球化学标准物质建立校准曲线,建立盐酸预处理-红外吸收光谱法测定地球化学样品中有机碳含量的分析方法。结果表明：陶瓷坩埚经1 200 ℃灼烧处理可以有效降低碳空白,减小对分析结果的影响;选择50.0～70.0 mg称样量,测试准确度高且样品熔融时不易喷溅;0.40～0.60 mL稀盐酸（1+7）除尽样品中的无机碳同时减少有机碳流失损失;0.40～0.50 g纯铁屑和1.50～1.70 g钨粒作为助熔剂,助熔效果稳定;采用国家一级地球化学标准物质建立校准曲线,校准曲线线性良好（R2=0.998 5）。该方法的检出限为69 μg·g-1,测定结果的相对标准偏差（RSD,n=12）均小于8%。经63个不同类型国家一级地球化学标准物质（土壤、岩石、水系沉积物）验证,测定结果与标准值相符。本方法操作简便,检出限低,灵敏度高,结果准确可靠,适用于地球化学样品中有机碳含量的测定。     

钦杭结合带南段和寮铅锌多金属矿床石英的谱学特征及其指示意义

钦杭成矿带南段和寮铅锌多金属矿地区矿化、近矿体和远离矿体等三类岩石样品中石英的粉晶X射线衍射、红外光谱及拉曼光谱研究结果表明,远离矿体和矿化岩石样品中的石英较为纯净,而近矿岩石样品中的石英含有少量杂质,但这种少量的杂质并没有引起石英晶胞参数的明显变化;远离矿体的岩石→近矿岩石→矿化岩石中石英的结晶度和有序度越来越高的,且矿化岩石样品中的α-石英有向对称性较低的石英转变趋势;石英的1 050cm-1红外吸收峰分裂为一对强双峰为含矿岩石样品所独有,可以有效地作为是否成矿的标志;造成石英微观结构变化的原因可能与后期成矿热液的活动密切相关。远离矿体的岩石中石英形成后受后期热液的影响很弱,含矿样品中的石英受多期次热液的作用易产生重结晶、结构调整作用等而纯化,而近矿岩石样品中的石英受到热液的影响但不足以达到纯化的效果。谱学研究是一种深入探讨研究区成矿过程、成矿规律的有效技术。     

Monthly sea surface temperature records reconstructed by δ18O of reef-building coral in the east of Hainan Island,South China Sea

Stable oxygen isotopic compositions of a coral colony ofPorites lutea obtained on a core allowed the reconstruction of a 56-a (1943–1998) proxy record of the sea surface temperatures. This coral δ¹⁸O data are from the east of Hainan Island water (22°20’N, 110°39’E), South China Sea. The relationship between δ¹⁸O in the skeletal aragonite carbonate and the sea surface temperature (SST) is SST = -5.36 δ¹⁸O_PDB-3.51 (r = 0.73,n = 470), dδ¹⁸O/d(SST) = -0.187‱/ °C; and the thermometer was set at monthly resolution. The 56-a (1943–1998) proxy record of the sea surface temperatures reflected the same change trend in the northern part of South China Sea as the air temperature change trend in China.

     

New evidence from stable isotope for the uplift of mountains in northern edge of the Qinghai-Tibetan Plateau

New data of oxygen and carbonate isotope in calcite cements from Cenozoic rocks in the Jianggelesayi area to reconstruct the uplift history of mountains in northern edge of the Qing-hai-Tibetan Plateau are presented. Analyses results show that rapid changes of δ¹⁸O and δ¹³C in the calcite cement occurred in both the Early Oligocene and Early Miocene. Studies on sedimentary features indicate that a rapid up-coarsing of the sediments size occurred in the Early Miocene, and sedimentary velocity increased rapidly during the Pliocene and Early Quaternary. Thus, it is suggested that the uplift of mountains in the northern edge of the Qinghai-Tibetan Plateau initiated from the Early Oligocene, and a rapid uplift occurred in the early stage of the Miocene, while the sharp difference in topography between the northern plateau and the Tarim Basin predominately formed later than the Miocene.

     

新的极谱催化体系连续测定岩溶地下水中钨和钼

钨、钼-二苯基乙醇酸-2,2′-联吡啶-钛铁试剂连测体系还未见报道。本文提出了在0.05mol/L的硫酸中,钨与二苯基乙醇酸,2,2′-联吡啶的络合物在-0.79V(vs.SEC)产生一个极其灵敏的极谱催化波,测定完钨后,加入少量钛铁试剂测定钼。钼于-0.20V(vis.SEC)处产生极灵敏的阴极化导数波,波形尖锐对称,易于测量。采用此种连测体系,钨钼的灵敏度都可满足要求,钨和钼的检出限分别为0.004、0.01μg/L。确定最佳条件和拟定了不经分离富集直接测定岩溶地下水中痕量钨和钼的方法。此外还对极谱波性质进行了探讨,讨论了阴、阳离子表面活性物质对极谱催化波的作用机理。     

Luminescence lifetimes in quartz: dependence on annealing temperature prior to beta irradiation

It is well known that the thermal history of a quartz sample influences the optically stimulated luminescence sensitivity of the quartz. It is found that the optically stimulated luminescence lifetime, determined from time resolved spectra obtained with pulsed stimulation, also depends on past thermal treatment. For samples at 20°C during stimulation, the lifetime depends on beta dose and on duration of preheating at 220°C prior to stimulation for quartz annealed at 600°C and above, but is independent of these factors for quartz annealed at 500°C and below. For stimulation at higher temperatures, the lifetime becomes shorter if the sample is held at temperatures above 125°C during stimulation, in a manner consistent with thermal quenching. A single exponential decay is all that is required to fit the time resolved spectra for un-annealed quartz regardless of the temperature during stimulation (20–175°C), or to fit the time resolved spectra from all samples held at 20°C during stimulation, regardless of annealing temperature (20–1000°C). An additional shorter lifetime is found for some combinations of annealing temperature and temperature during stimulation. The results are discussed in terms of a model previously used to explain thermal sensitisation. The luminescence lifetime data are best explained by the presence of two principal luminescence centres, their relative importance depending on the annealing temperature, with a third centre involved for limited combinations of annealing temperature and temperature during stimulation.     

X-ray diffraction and Raman spectra of merrillite at high pressures

ABSTRACT

The compressibility and effect of pressure on the vibrations of merrillite, Ca₉NaMg(PO₄)₇, were studied by using diamond anvil cell at room temperature combined with in-situ synchrotron X-ray diffraction and Raman spectroscopy up to about 18 and 15?GPa, respectively. The pressure-volume data was fitted by a third-order Birch–Murnaghan equation of state to determine the isothermal bulk modulus as K₀ ?=?87.2(32) GPa with pressure derivative K₀′?=?3.2(4). If K₀′?=?4, the isothermal bulk modulus was obtained as 81.6(10) GPa. The axial compressibility was estimated and an axial elastic anisotropy exists since a-axis is less compressible than the c-axis. The Raman frequencies of all observed modes for merrillite continuously increase with pressure, and the pressure dependences of stretching modes (v ₃ and v ₁) are larger than those of the bending modes (v ₄ and v ₂) and external modes. The isothermal mode Grüneisen parameters and intrinsic anharmonicity of merrillite were also calculated.     

In situ sulfur isotopes (δS and δS) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS

The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N₂ on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4–8 ml min⁻¹ nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N₂ = 4 ml min⁻¹). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d₉₀ values of the particles in pressed powder pellets for accurate and precise S isotope analysis should be less than 10 μm. Under the selected optimized analytical conditions, excellent agreements between the determined values and the reference values were achieved for the IAEA-S series standard reference materials and a set of six well-characterized, isotopic homogeneous sulfide standards (PPP-1, MoS₂, MASS-1, P-GBW07267, P-GBW07268, P-GBW07270), validating the capability of the developed method for providing high-quality in situ S isotope data in sulfides and elemental sulfur.     

从环境样品中分离氩气和氪气用于放射性惰性气体探测

放射性惰性气体同位素⁸⁵Kr(半衰期为10.8年)、³⁹Ar(半衰期为269年)和⁸¹Kr(半衰期为22.9万年)是理想的环境示踪剂,基于激光技术的原子阱痕量分析方法(Atom trap trace analysis, ATTA)可以实现对空气、地下水等环境样品中这几种同位素的有效探测. 在进行ATTA测量之前,需要将样品中的氪气和氩气有效分离出来. 利用低温蒸馏、海绵钛化学吸附和气相色谱分离等技术,可以从1~10 L气体样品中分别提取出90%以上的氪气和98%以上的氩气,从而满足ATTA测量的样品要求. 通过对包括两个野外地下水样品等一系列样品进行分离实验,验证了气体分离装置的可靠性能.     

A simple transformation for converting CW-OSL curves to LM-OSL curves

A simple mathematical transformation is introduced to convert from OSL decay curves obtained in the conventional way to those obtained using a linear modulation technique based on a linear increase of the stimulation light intensity during OSL measurement. The validity of the transformation was tested by the IR-stimulated luminescence curves from feldspars, recorded using both the conventional and the linear modulation techniques. The transformation was further applied to green-light-stimulated OSL from K and Na feldspars.