电感耦合等离子体质谱法测定地质样品中稀散元素铬镓铟碲铊

采用电感耦合等离子体质谱技术,研究了地质样品中稀散元素铬、镓、铟、碲、铊含量的质谱分析方法。研究确定了最佳测定酸度、干扰元素的校正方法,结果令人满意。方法检出限为0.001 3~0.063μg/g,精密度(RSD,n=11)为2.00%~4.87%,优于其他方法,具有较好的灵敏度。方法快速、简便,结果准确,可用于地质样品中稀散元素铬、镓、铟、碲、铊含量的分析,适用于批量样品的快速测定。     

基于一维变分算法的地基微波辐射计遥感大气温湿廓线研究

为研究地基微波辐射计遥感温、湿度廓线的一维变分算法的反演能力,用北京地区2010—2011年00和12时(世界时)的多通道地基微波辐射计亮温资料进行试验。首先,利用同时次的地面观测资料、红外亮温(由地基微波辐射计自带红外传感器测得)及探空观测数据,给出提取无云样本的方案,得到432个无云样本;再以辐射传输模式计算得到的模拟亮温为参考,对无云条件下的观测亮温进行质量控制;然后利用探空数据进行模拟试验,结果发现,一维变分算法对3 km以下的温度廓线有较大调整。使反演结果更加接近探空,而对湿度廓线在0—10 km都有不同程度的优化;最后利用一维变分算法对地基微波辐射计观测亮温进行大气温湿廓线反演,将结果与探空对比可以看出,温度廓线的均方根误差小于2.9 K,绝对湿度的均方根误差小于0.47 g/m~3;进一步与地基微波辐射计自带神经网络的反演结果比较表明,一维变分的反演结果更接近实际大气。     

田口方法用于地质样品中痕量超痕量金三种分析方法的对比

目前测定地质样品痕量、超痕量金常用的三种方法是活性炭吸附富集-发射光谱法、泡塑吸附富集-石墨炉原子吸收光谱法、活性炭吸附富集-电感耦合等离子体质谱法,这三种方法的检出限在0.1~0.3ng/g之间,由于矿石矿物的组成非常复杂,因此在有效富集和分离的基础上,采用合适的分析手段,能够对地质样品提供满意的分析结果。为保证试样要求的灵敏度和准确性,分析方法的选择需求应根据具体试样情况和实验室条件而定。根据田口玄一博士在测量工程学中提出的信噪比(S/N)能测量系统抗干扰能力,评价测量系统的稳健性和可靠性这一观点,本文利用田口测量质量控制理论,评价地质样品中痕量、超痕量金常用的上述三种分析测试方法,对这三种分析方法三个金标准物质的测试数据进行分类处理,计算S/N值和相对标准不确定度,通过比较三者的S/N值和相对标准不确定度值,确定更为可靠的测试体系。分析结果表明,对于地质样品中痕量金(含量大于1 ng/g)的测试,三种分析方法均能够满足要求;对于超痕量金(含量小于1 ng/g)的测试,活性炭吸附富集-电感耦合等离子体质谱法是较好的测试方案。     

环境植物样品中铜铅锌铁锰的测定

将环境植物样品在４００─５００℃灰化，用硝酸、氢氟酸和高氯酸分解，用盐酸（１＋１）提取，控制２％─３％的盐酸介质，用火焰原子吸收分光光度法测定环境植物样品中的微量铜、铅、锌、铁、锰。该方法简单、快速、可靠。对环境植物标准样品的测定结果理想。     

东北黑土区侵蚀沟遥感影像特征提取与识别

东北黑土区是中国重要的粮食生产区,而长期的开垦造成了严重的水土流失现象,坡耕地表面出现大量的侵蚀沟。侵蚀沟的识别是土壤侵蚀监测的重要手段之一,目前遥感技术在侵蚀沟的识别中应用广泛,但自动化程度不高。针对特定地物影像的识别,如何选取最能够有效描述该地物的特征是解决问题的关键。本文构建了耕地和侵蚀沟遥感影像的训练样本集,基于样本集分别提取了由光谱特征和纹理特征组成的浅层特征、SIFT特征经编码后得到的中层特征,以及利用卷积神经网络提取的深层特征;再基于不同层次的特征选用合适的分类器对遥感影像进行分类,识别出含有侵蚀沟的遥感影像,形成了一套针对侵蚀沟的特征提取与识别方法,为东北黑土区的耕地保护提供有力支持。测试结果表明:基于中层特征的识别精度最高,为98.5%,但该特征需要人工设计,自动化程度有限;而利用卷积神经网络可自动提取深层特征,其识别精度达到了95.5%,同时大大提高了自动化程度,满足侵蚀沟影像的识别的需求。     

Evaluation of the Residual Mass Fractionation in High-Precision Cr Isotopic Analysis with TIMS

The Cr isotope ratios of terrestrial and extra-terrestrial materials are emerging as one of the most important tracers in geosciences. Previous studies on Cr isotopic measurements using TIMS have found that there is residual Cr isotopic fractionation between the mass-fractionation-corrected ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios, which may cause an offset of obtained ratios from the reference values. The residual fractionation was thought to be caused by the evaporation of Cr-oxide species during thermal ionisation, but the mechanism by which this residual fractionation could be reduced remained unclear. Here we revisit the issue of residual fractionation and propose that this problem can be alleviated by utilising W filaments instead of conventionally used Re filaments for Cr ionisation. Using W filaments, the formation of CrO⁺ was suppressed during heating as the filament temperature was ~ 100 °C lower than when Re filaments were used. In repeated measurement of a carbonaceous chondrite, the intermediate precisions of ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios in the W filament runs were two to three times better than those of the Re filament runs. Therefore, the new finding of this study will be of key importance for future studies of Cr isotopes for terrestrial and extra-terrestrial materials.     

Rapid screening of Zr-containing particles from Chang’e-5 lunar soil samples for isotope geochronology: Technical roadmap for future study

New samples returned by China Chang’e-5 (CE-5) mission offer an opportunity for studying the lunar geologic longevity, space weathering, and regolith evolution. The age determination of the CE-5 samples was among the first scientific questions to be answered. However, the precious samples, most in the micrometer size range, challenge many traditional analyses on large single crystals of zircon developed for massive bulk samples. Here, we developed a non-destructive rapid screening of individual zirconium-containing particle for isotope geochronology based on a Micro X-ray fluorescence analysis (µXRF). The selected particles were verified via scanning electron microscopy (SEM), 3D X-ray microscopy (XRM), and focused ion beam scanning electron microscopy (FIB-SEM) techniques, which showed that zirconium-bearing minerals with several microns were precisely positioned and readily suitable for site-specific isotopic dating by second ion mass spectrometry (SIMS). Such protocol could be also applicable in non-destructively screening other types of particles for different scientific purposes. We therefore proposed a correlative workflow for comprehensively studying the CE-5 lunar samples from single particles on nanometer to atomic scales. Linking various microscopic and spectromicroscopic instruments together, this workflow consists of six steps: (1) single-particle selection with non-destructive µXRF technique, (2) 2D/3D morphological and structural characterization with a correlative submicron 3D XRM and nanoscale resolution FIB-SEM imaging methods, (3) SEM analysis of the surface morphology and chemistry of the selected particle, (4) a series of microscopic and microbeam analyses (e.g., SEM, electron probe microanalysis, and SIMS) on the cross-section of the selected particle to obtain structural, mineralogical, chemical, and isotopic features from the micron to nanometer scale, (5) advanced 2D/3D characterization and site-specific sample preparation of thin foil/tip specimens on a microregion of interest in the selected particle with FIB-SEM technique, and (6) comprehensive analyses on the FIB-milled specimens at nanometer to atomic scale with synchrotron-based scanning transmission X-ray microscopy, analytic transmission electron microscopy, and atom probe tomography. Following this technical roadmap, one can integrate multiple modalities into a uniform frame of multimodal and multiscale correlated datasets to acquire high-throughput information on the limited or precious terrestrial and extraterrestrial samples.     

真三轴单面临空下煤岩组合体冲击破坏特征试验研究

煤岩复合承载结构所处的应力边界条件不同,冲击地压在巷道中的显现特征和前兆规律亦不相同。采用高频振动采集及孔内成像三轴动静载试验系统,开展了高静载和动静载耦合作用下煤岩组合体真三轴单面临空试验,分析了煤岩组合体界面处力学特征和强度条件,探究了不同应力边界下煤岩组合体的破坏形态、动力显现特征和声发射信号的演变规律。研究结果表明:(1)受煤岩变形相互制约的影响,交界面处砂岩强度被"弱化"。当界面处煤体裂隙尖端的应力大于"弱化"后砂岩强度时,裂隙将穿过煤岩界面发育至砂岩中,砂岩呈现出屈曲层裂、劈裂成板的破坏形态。(2)高静载作用下,煤岩组合体变形破坏特征和声发射信号具有明显的前兆规律,组合体发生承载失效前煤体局部颗粒弹射动能增大、弹射颗粒块度降低,声发射信号由"高频低能"向"高频高能"转变,组合体的破坏形态以剪切-张拉复合破坏为主。(3)受冲击动载影响,顶底板砂岩夹持作用减弱,煤体裂纹尖端应力得不到有效积聚,裂纹扩展到煤岩交界面时被阻隔,组合体以煤样的张拉破坏为主,声发射信号呈现出"高频高能"的特点,但大多集中在冲击破坏之后,导致组合体动力破坏难以预测。(4)与纯静载作用相比,虽然动静载耦合作...     

电感耦合等离子体质谱法测定灌木枝叶中微量元素的样品预处理方法研究

利用电感耦合等离子体质谱法(ICP-MS)测定植物样品中微量元素的关键技术是消除植物样品的有机基体效应,本文通过预处理方法中的酸消解体系、称样量和消解方式消除其影响。以国家标准物质灌木枝叶组合样(GBW07603)为材料进行研究,对比分析了硝酸-过氧化氢、硝酸-氢氟酸、硝酸-氢氟酸-过氧化氢3种酸溶体系的消解效果,以确定最佳酸溶体系,进而定量研究2种称样量(50 mg和100 mg)和3种消解方式(密封高压二次消解、密封高压一次消解、微波消解)的消解效果,并以In作为内标采用ICP-MS测定微量元素含量。结果表明:硝酸-氢氟酸-过氧化氢酸溶体系的消解效果最好;50 mg的测定值更接近于参考值;微波消解法的测定值明显偏低,而密封高压二次消解法是灌木枝叶样品预处理的有效方法。     

巯基棉富集-分光光度法测定地球化学样品中铂钯的野外快速分析方法研究

对于地球化学样品中铂钯的测定,传统和现代分析方法均是建立在试金或树脂及活性炭富集后用分光光度法或电感耦合等离子体质谱法测定,而在野外满足不了这些条件。本文基于样品的性质及分光光度法的适应性强等特点,开发了一种适合于野外简单条件下快速测定地质样品中铂和钯的分析方法。样品用盐酸-氯酸钾-氯化钠-氟化氢铵常温常压密闭分解,巯基棉分别富集铂和钯,灰化处理后采用三氯甲烷-石油醚(1∶3)为萃取剂,DDO为显色剂萃取比色测定铂、钯的含量。巯基棉对钯的吸附率可达98%;加入氯化亚锡-水合肼(还原剂)使铂的吸附率提高到99%。方法检出限为Pt 0.05μg/g,Pd 0.02μg/g,标准物质的测定值与推荐值基本一致,野外地质样品的测定值与实验室分析结果吻合。