白云鄂博矿区土壤和植物中稀土元素的分布特征

白云鄂博矿区是稀土的主要产出地,在矿山开采和选炼等过程中,稀土元素通过迁移、富集等作用进入植物体,研究稀土元素的分布特征和迁移规律,可为白云鄂博矿体闭坑后的生物修复提供数据支持。本文设置了7个土壤采样点,采集铁花、沙蒿、沙打旺、沙朋、青蒿、小叶杨、猪毛菜七种植物,用电感耦合等离子体质谱法测定土壤和植物的根、茎、叶及整株的稀土含量,研究稀土元素在土壤和植物中的分布特征和迁移规律。统计分析结果表明:随着采样区与主矿区的距离增加,土壤样品中的稀土含量逐渐减少;在七种植物中,铁花的稀土含量最高,青蒿最低;对不同植物的整株稀土含量和各部位(根、茎、叶)稀土含量进行多元线性回归分析,叶(或花)的稀土含量在整珠植物中的占比最大。此外在不同季节,植物中的稀土含量基本保持不变,含量较高的稀土元素为Ce(0.0035%～0.020%)、La(0.0012%～0.011%)、Nd(0.0010%～0.0094%)和Pr(0.00036%～0.0046%),其中Ce最高。本研究提出:根据土壤样品中的稀土含量逐渐减少的特征,矿区周围土壤的稀土来源可能是矿石在采、选过程中的扩散造成的;根据植物富集稀土的能力,在矿山闭坑后,可种植富集稀土能力强的植物——铁花,进行矿山生物修复。     

动能歧视模式ICP-MS测定地球化学样品中14种痕量元素

应用传统ICP-MS法测定勘查地球化学样品中Ag、Cd等痕量元素,基体效应和多原子离子干扰严重,准确测定的难度较大。本文基于当前ICP-MS消除干扰技术,分析了ICP-MS标准模式(STD)及动能歧视模式(KED)测定地球化学样品中Ag、Cd等14种痕量元素的有效性,通过比较这两种模式的测定效果,在此基础上确定了各元素的有效测定模式。结果表明:在KED模式下,基体元素如Zr、Nb氧化物的产率降低,基本上消除了Zr、Nb氧化物对痕量元素Ag、Cd的多原子离子干扰。KED模式提高了信噪比,降低了方法检出限,如Ag、Cd的检出限分别为0. 004mg/kg、0. 005mg/kg,其他12种元素的检出限也低于多目标地球化学调查76种元素分析方案中的检出限。测定痕量元素的准确度显著优于STD模式。实验中采用简单的硝酸-氢氟酸-高氯酸消解样品,残渣用王水复溶,结合KED模式下优选出干扰较小的同位素作为测定同位素,以Rh作为内标校正仪器产生的信号漂移,将样品溶液稀释至1000倍,基体效应降低至最小。本方法经国家一级标准物质的验证,测定结果与认定值相符,可为勘查地球化学提供高质量数据。     

X荧光光谱分析技术在测定安徽月山矿床铁铜矿石中Fe、Cu的应用研究

为建立符合安徽月山矿区的X荧光光谱(XRF)分析方法,针对矿区铁矿、铜矿的特点,用铁、铜矿石的国家标准物质制作系列校准样片,通过粉末压片和玻璃熔融两种制样方法,波长色散X荧光光谱法测定主矿体样品中的Fe、Cu等主量元素,并将测定结果与传统化学方法分析结果进行比较。结果显示,熔片法-XRF的测定结果与化学容量法测定结果一致,试样在850℃灼烧,按40∶1大稀释比熔融制样,解决了样品在高温熔融过程中对铂黄坩埚的腐蚀,适用于月山矿区铁铜矿样品中Fe、Cu的测定。粉末压片法不能克服矿物效应和粒度效应的影响,测定结果与化学容量法结果比对偏差较大,不适用于月山地区铁铜矿中Fe、Cu的测定。     

‘Box‐Profile’ Ion Implants as Geochemical Reference Materials for Electron Probe Microanalysis and Secondary Ion Mass Spectrometry

Although electron probe microanalysis and secondary ion mass spectrometry are widely used analytical techniques for geochemical and mineralogical applications, metrologically rigorous quantification remains a major challenge for these methods. Secondary ion mass spectrometry (SIMS) in particular is a matrix‐sensitive method, and the use of matrix‐matched reference materials (RMs) is essential to avoid significant analytical bias. A major problem is that the number of available RMs for SIMS is extremely small compared with the needs of analysts. One approach for the production of matrix‐specific RMs is the use of high‐energy ion implantation that introduces a known amount of a selected isotope into a material. We chose the more elaborate way of implanting a so‐called ‘box‐profile’ to generate a quasi‐homogeneous concentration of the implanted isotope in three dimensions, which allows RMs not only to be used for ion beam analysis but also makes them suitable for EPMA. For proof of concept, we used the thoroughly studied mineralogically and chemically ‘simple’ SiO₂ system. We implanted either ⁴⁷Ti or ⁴⁸Ti into synthetic, ultra‐high‐purity silica glass. Several ‘box‐profiles’ with mass fractions between 10 and 1000 μg g^?1 Ti and maximum depths of homogeneous Ti distribution between 200 nm and 3 μm were produced at the Institute of Ion Beam Physics and Materials Research of Helmholtz‐Zentrum Dresden‐Rossendorf. Multiple implantation steps using varying ion energies and ion doses were simulated with Stopping and Range of Ions in Matter (SRIM) software, optimising for the target concentrations, implantation depths and technical limits of the implanter. We characterised several implant test samples having different concentrations and maximum implantation depths by means of SIMS and other analytical techniques. The results show that the implant samples are suitable for use as reference materials for SIMS measurements. The multi‐energy ion implantation technique also appears to be a promising procedure for the production of EPMA‐suitable reference materials.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

有机显微组分X射线衍射分析方法在油气评价中的应用

Ｘ射线衍射分析法适宜于分析有机显微组分的芳环层的层状结构。有机质的芳环层结构与其类型和演化程度有关。表征有机质芳环层的层状结构的主要参数：高度Ｌｃ、宽度Ｌａ、网面间距ｄｈｋ１和芳环层层数可作为油气勘探中判断源岩性质、类型、演化程度与生烃潜力的依据。文章还对参数的变化与意义进行了初步讨论。     

兰州第四纪黄土/古土壤序列物源演变: 来自于碳酸盐矿物的证据*

黄土/古土壤的物源研究对于揭示第四纪气候变化和青藏高原隆升历史具有重要意义。本研究以位于黄土高原西部1.4 Ma以来的兰州黄土/古土壤沉积序列为研究对象,基于X射线衍射技术分析了黄土/古土壤中的主要矿物组成,侧重于碳酸盐矿物含量,追溯了兰州黄土/古土壤的直接物源。结果显示: (1)1.4 Ma以来兰州地区黄土/古土壤沉积物的主要直接源区为柴达木盆地沙漠区和阿拉善干旱区。(2)基于二元混合模型计算的潜在原始源区对兰州黄土白云石和总碳酸盐矿物的相对贡献率以及长石与石英比值结果一致支持1.4 Ma以来兰州黄土原始物源发生了多次变化。1.4~1.1 Ma和0.9~0.3 Ma青藏高原东北缘造山带(昆仑山、祁连山)和中亚造山带对兰州黄土的贡献相当,而1.1~0.9 Ma和0.3 Ma以来,中亚造山带对兰州黄土的物源贡献增加,这可能分别是对中更新世气候转型和0.3 Ma以来青藏高原及邻近地区干冷气候增强的响应。1.15 Ma和0.8 Ma兰州黄土/古土壤中高的白云石含量、碳酸盐矿物总含量以及0.8 Ma长石与石英比值的快速升高可能是对“昆黄运动”的响应,进而造成了昆仑山、祁连山对黄土高原物源贡献的增加。     

原子荧光光谱法直接连续测定化探样品中的As Sb Bi Hg

研究了还原性介质中原子荧光光谱法直接连续测定化探样品中Ａｓ、Ｓｂ、Ｂｉ、Ｈｇ的方法。按拟定的条件进行测定,各元素的检出限分别为Ａｓ２．９×１０－９、Ｓｂ１．３×１０－１０、Ｂｉ１．８×１０－１０、Ｈｇ５×１０－１１。应用于区域化探扫面工作中,效果良好。     

Intercalation of kaolinite with acetamide

Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH₂ groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm^–1. Secondly, the appearance of additional bands at ∼3600 cm^–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm^–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH₂ deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm^–1 become a single band at 1680 cm^–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm^–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group. Received: 4 February 1998/ Revised, accepted: 30 June 1998     

CT引导下肺部穿刺活检的应用分析

本文的目的是分析和评价ＣＴ引民下肺部穿刺活检中体位的选择,穿刺点定位,穿刺针及穿刺方式等因素对本项检查结果的影响。所用材料与方法：回顾性分析分析３６例完整的病例,分别统计了切割法和抽吸法的阳笥率,假阳性率,假阴性率,气胸率及局部出血发生率组织诊断率。得到结论为切割法较抽吸法能获得更高的阳性率和组织学诊断率,但局部少量出血发生率略高