GGR Biennial Review: Atomic Absorption,Inductively Coupled Plasma-Atomic Emission Spectrometry,Neutron Activation Analysis and X-Ray Fluorescence Spectrometry Review for 2008–2009

This review describes developments major and in trace element determination using atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), instrumental neutron activation analysis (INAA), and X-ray fluorescence (XRF) spectrometry that were reported in 2008 and 2009. Publication levels were comparable to those of previous years, except for XRF which showed an increase in the number of articles published in the past 2 years. In terms of number of publications and impact, the most active field was AAS, while INAA was the least active. As expected for well-established and mature methods, novel developments for all four analytical techniques were relatively sparse. For AAS, the most notable publications concerned developments in sample introduction, particularly focussing on solid samples, increasing analyte sensitivity, and higher sample throughput. For ICP-AES, publication of developments in sample introduction, remediation of matrix effects and calibration continues. Compared with past years, there was a clear focus on sample preconcentration methods, but very few publications reporting new hyphenated speciation methods. For INAA, there were several publications exploring the accuracy and robustness of the method, as well as the requirements for INAA to meet criteria for a primary method of measurement. Two other related techniques, delayed neutron activation analysis, and prompt gamma activation analysis, were also described. Hyphenated XRF techniques showed interesting developments in enabling XRF and XRD analysis on the same spot, and further work characterising and calibrating three-dimensional micro-XRF shows promising results for investigating sample heterogeneity.     

中国雨季的一种客观定量划分

从客观分析角度出发,利用有序样本最优分割法对中国610个台站的气候平均（1961—2010年）候降水序列进行有序分割,给出中国不同区域的雨季定量划分。根据中国13个区域候降水量的气候平均值分布特征,并基于有序样本最优分割法的划分结果需同时满足分割段内波动小、段间差异大的要求,确定了各区域的合理分割数,通过制定3种雨季划分方案,对中国区域雨季进行了细致的定量划分。第1种方案将全年降水划分为雨季和旱季,结果表明,雨、旱两季差异明显的地区出现在华南西部沿海和新疆邻近区域;第2种方案将全年降水划分为雨季相对干期、雨季相对湿期和旱季3个降水阶段,这种特征出现的区域为华南大部分地区、江南地区、长江中下游地区、西南地区东部和南部,以及西北地区中东部;第3种方案将全年降水划分为春雨季、主雨季、秋雨季和旱季,出现这种特征的区域为长三角及淮河流域、黄淮和华北地区、东北地区、西北地区中部、内蒙古地区西部、青藏高原中东部及其以东地区。与已有的中国不同区域降水特征研究结果的比较表明,有序样本最优分割法不仅对中国雨季的划分客观有效,且其划分结果合理并具有明确的气象意义。     

Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

熔融制样波长色散X射线荧光光谱法测定白云石中钙镁硅铁铝

白云石属碳酸盐矿物,应用熔融制样X射线荧光光谱法测定其中主次量组分钙、镁、硅、铁、铝时,由于白云石灼烧减量大,在试料片制备过程中,如果以干基试料制备试料片,除灼烧减量外还有少量其他组分被分解出的大量CO₂带走,导致试料损失,测定结果偏低;如果以灼烧基试料制备试料片,由于灼烧后的试料极易吸收空气中的水分和CO₂,同样使测定结果偏低。基于质量守恒原理,本文直接以灼烧减量测量后的灼烧基试料质量作为试料量(即灼烧减量测定所称量的干基试料量扣除灼烧减量的量),以四硼酸锂为熔剂,5%碘化铵溶液为脱模剂,试料与熔剂的稀释比为1:10,于1050℃熔融15 min以上制备的试料片透彻、玻璃化程度高。以白云石标准物质和标准样品作为标准试料,制作各组分的标准曲线的相关系数在0.9940~0.9994之间;方法检出限为0.011%~0.48%;标准物质和标准样品的测定值与认定值基本一致,各组分的相对标准偏差(RSD,n=11)在0.5%~1.7%之间,方法具有较好的重现性。本方法以1050℃灼烧后的试样作为试料制备XRF分析样片,最大限度地降低了灼烧减量因素(空气中的水分和CO₂)对测定结果的影响,适用于白云石及其煅烧物中钙、镁、硅、铁、铝等组分的同时测定。     

微波消解—冷原子荧光光谱法测定植物样品中的汞

为了简化测量植物中汞含量的方法,提高灵敏度及结果的可信度,实验采用微波消解植物样品的办法,使样品经氯化亚锡还原,再用冷原子荧光测定出植物样品中汞的含量。确定了消解样品的方法和微波消解样品的条件,优化了仪器的最佳工作参数。方法检出限0.30×10-9(稀释因子100倍),精密度(n=12)在2.09%~6.05%,加标回收率94.1%~105.5%,方法经生物国家一级标准物质验证方法准确可靠。     

基于VBA实现设计点位编号和坐标提取

针对实际生产需要,探讨利用计算机实现化探设计点位坐标提取和填写样品编号,重点介绍用VBA编程填写样品编号。这里还介绍了VBA语言及主要函数功能、程序流程及主要程序编码。通过实际应用表明,该程序流程合理、过程简单、运行速度快,有效改善了野外生产的精度及效率。     

Preparing For Hyperseed MAC: An Observing Campaign To Monitor The Entry Of The Genesis Sample Return Capsule

The imminent return of the Genesis Sample Return Capsule (SRC) from the Earth’s L1 point on September 8, 2004, represents the first opportunity since the Apollo era to study the atmospheric entry of a meter-sized body at or above the Earth’s escape speed. Until now, reentry heating models are based on only one successful reentry with an instrumented vehicle at higher than escape speed, the 22 May 1965 NASA “FIRE 2” experiment. In preparation of an instrumented airborne and ground-based observing campaign, we examined the expected bolide radiation for the reentry of the Genesis SRC. We find that the expected emission spectrum consists mostly of blackbody emission from the SRC surface (T∼ ∼2630 K@peak heating), slightly skewed in shape because of a range of surface temperatures. At high enough spectral resolution, shock emission from nitrogen and oxygen atoms, as well as the first positive and first negative bands of N₂⁺, will stand out above this continuum. Carbon atom lines and the 389-nm CN band emission may also be detected, as well as the mid-IR 4.6-μm CO band. The ablation rate can be studied from the signature of trace sodium in the heat shield material, calibrated by the total amount of matter lost from the recovered shield. A pristine collection of the heat shield would also permit the sampling of products of ablation.     

关联指数误差和样本容量

根据关联指数的定义，推导了ＧＰ法计算关联指数时的观测数据误差与关联指数误差的关系，导出了任意两个嵌入空间维上关联指数之差的表达式，并提出了一种确定样本容量限的方法。     

砂样图像岩屑自动分割提取方法

通过将砂样图像进行单颗粒分割,识别砂样成分,可显著提高砂样岩性分析的准确性和效率。现有的砂样图像分割方法主要以传统分水岭算法和卷积神经网络为主,但由于对单颗粒岩屑轮廓细节提取不足,误分割率高。本文提出一种以图像融合算法为桥梁,将卷积神经网络和分水岭算法相结合的单颗粒图像分割提取方法。首先利用改进的Mask R-CNN网络快速分割砂样原图,获得其初分割图像;然后,将初分割图像与砂样原图进行融合,再使用改进的分水岭算法对融合结果进行分割;最后,利用砂样原图坐标点匹配方法,将分水岭分割得到的结果图像进行修正,完成单颗粒岩屑图像提取。实验结果表明,本文的单颗粒自动分割提取方法准确率高达96.77%,且模型更轻量和精准,为岩屑图像分割提供了一种可行且有效的方法,可满足有效测算油藏层构造变化、查找潜在沉积物源及储层动态变化的需求。     

E5000型全谱直读型电弧发射光谱仪研制及其在地球化学样品分析中应用

在地球化学样品检测工作中,Ag、B、Sn等难分析元素通常采用传统的交流电弧发射光谱法(摄谱仪),随着地球化学样品数量的增加以及对检测结果质量要求的提高,该方法操作复杂、分析过程繁琐的问题与日常大量样品分析的矛盾日益突出,多道式电弧直读发射光谱也开始在行业内应用。本文基于先进的数字光源技术和CCD全谱型光谱仪技术,改进了电弧发生系统、分光系统和检测系统,将电弧激发光源与Paschen-Runge型全谱CCD光谱仪结合,研制了一款新型的台式全谱直读型电弧发射光谱仪E5000。E5000型电弧发射光谱仪通过激光定位结合程控电极技术,自动调整电极位置,提高了采谱过程的精度控制;利用CCD全谱技术获得了激发样品的全谱信息,可轻易实现光谱信号的背景扣除和干扰校正;且无需再次测定黑度,直接获得分析结果;同时结合内标法和标准加入法,可以进一步提高复杂基体样品的分析精准度。应用研制的光谱仪对水系沉积物和土壤样品进行检测,Ag、B、Sn元素的检出限分别达到了0.01μg/g、0.65μg/g、0.16μg/g,在分析水系沉积物、土壤时检测精密度基本小于10%,优于当前的摄谱法和多道电弧直读光谱法,满足了地球化学样品检测质量要求。