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。     

敞开酸溶-电感耦合等离子体质谱法同时测定钨矿石和锡矿石中14种微量元素

钨矿石和锡矿石成分复杂,具有丰富的共生或伴生元素。在国家标准方法中,对其中的微量共生或伴生元素含量多采用单元素测定,分析强度大,效率低。本文采用混合酸在敞开体系中消解样品,以50%盐酸提取盐类,电感耦合等离子体质谱仪(ICP-MS)同时测定钨矿石和锡矿石中的锂钪铬钴镍铜铅锌铷钼铯锑铋钍等14种微量元素。通过比较碱熔法、盐酸+氢氟酸+硝酸+高氯酸四酸溶矿法、氢氟酸+硝酸+高氯酸三酸溶矿法这三种样品前处理方法,确定选择使用氢氟酸+硝酸+高氯酸三酸溶矿法溶解样品。ICPMS测定过程中,选择铑和铼作为内标元素,有效监控分析信号的漂移。测定结果表明,各元素的检出限为0.003~1.64μg/g,相对标准偏差在0.1%~3.1%,方法回收率在93.1%~104.3%。方法应用于实际钨矿石和锡矿石分析,测定结果与各元素标准测定值吻合较好。相对于传统处理方法,本法一次溶样,多元素同时测定,使分析效率得到了有效提高,更适合大批量多元素钨矿石和锡矿石样品的分析。     

应用能谱扫描电镜与X射线衍射等分析技术研究西藏扎西康铅锌矿中伴生元素锰的赋存状态

西藏扎西康铅锌多金属矿床是我国首次发现的喷流沉积-热泉水改造型锰铁锑铅锌银矿床,已有研究表明矿床中除了铅锌矿还伴生有银、锑、铜、硫、锰、砷等多种元素。本文在化学多元素分析和光学显微镜镜下鉴定的基础上,结合能谱扫描电子显微镜和X射线衍射分析等手段对扎西康铅锌矿中伴生组分Mn的含量、矿物种类、嵌布和包裹等特性进行了研究。分析结果表明,原生矿石的主要成矿元素Pb和Zn的含量分别为6.00%和4.00%,伴生元素Mn的含量平均达到4.36%;原生矿石中的主要矿物为方铅矿、闪锌矿,其次为黄铁矿、毒砂和菱锰矿等。原生矿石中伴生元素Mn主要以独立的菱锰矿和铁菱锰矿形式存在,与闪锌矿和方铅矿密切共生,是成矿早期重要的载矿矿物,嵌布在石英、黄铁矿、闪锌矿和毒砂的粒间、边部及空隙间,其次以类质同象形式赋存于菱铁矿和菱锌矿中。进一步对扎西康铅锌矿选冶产物中的伴生元素Mn的含量和赋存状态进行研究,研究表明Mn具有较高的综合利用价值,在原生矿石、铅精矿、锌精矿和尾矿中的质量分数分别为4.36%、0.51%、0.95%和5.36%,显示Mn很少一部分进入铅精矿和锌精矿,而绝大部分进入尾矿;Mn在尾矿中仍主要以菱锰矿形式存在,存在形式与原生矿石相比未发生改变,可通过强磁选工艺从铅锌尾矿中综合回收利用Mn。     

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。     

iCAP 6300电感耦合等离子体发射光谱仪的常规维护方法

电感耦合等离子体发射光谱仪在使用过程中,由于控制气体流量的电磁阀出现机械性移位,致使工作气流量过于偏大或偏小,对进样系统及分析数据产生不利影响;长期频繁使用条件下,由于控制光学系统的机械定位装置的磨损,致使谱峰坐标偏离而影响仪器灵敏度;很长时间不能"引燃"等离子体,检查进样系统和氩气纯度并没有发现异常,需要验证RF发生器有无功率输出时有一定的困难;在等离子体工作时产生的高温尾气的长期作用下,难免造成点火头末端铜丝的锈蚀,致使点火头放电微弱,不能"引燃"等离子体。因此,为保证仪器的正常运行,提高工作效率,确保检测数据的准确度,实验室应建立健全电感耦合等离子体发射光谱仪维护保养方案,解决上述问题。本文结合实际工作经验,以iCAP 6300电感耦合等离子体发射光谱仪为例,提出可以借助"Manufacturing and Service.exe"程序校正工作气流量,验证RF发生器是否输出功率;利用C 193.091 nm谱线为基准校正谱线修正CID检测器的谱峰坐标系统;另外,对点火头、分析软件数据库及主机灰尘的清理也进行了详细的维护说明,这些措施有益于保障仪器的性能及提高设备的利用率。     

阿尔泰南缘麦兹盆地萨吾斯铅锌矿床控矿铁闪石矽卡岩的40Ar/39Ar年代学研究

萨吾斯矿床位于麦兹盆地东部,是一个新近发现和勘探的铅锌矿床。萨吾斯铅锌矿床赋存于下泥盆统康布铁堡组上亚组凝灰岩、流纹岩及其沉积碳酸盐夹层,矿（化）体直接受石榴黑云矽卡岩和铁闪石矽卡岩控制,表现出火山喷流-沉积成矿和矽卡岩矿床的双重特征。这两类矿床的重要区别之一是同生和后生成矿。对主要矽卡岩矿物铁闪石进行精确的Ar-Ar年龄测定,将其与康布铁堡组流纹岩的年龄对比,有助于确定萨吾斯铅锌矿床的成因。高精度、高灵敏度激光⁴⁰Ar-³⁹Ar测年方法,为解决闪石类低K矿物的定年提供了新的手段。岩芯样品SW85中,铁闪石晶粒较大、晶形发育,与闪锌矿、碳酸盐矿物和石榴子石都具有平直的边界,而不是复杂交生,不含矿物和流体包裹体,代表了相对简单均一的系统。对SW85的铁闪石做了激光⁴⁰Ar-³⁹Ar测年,其结果为412±15Ma,与康布铁堡组流纹岩的SIMS锆石U-Pb年龄（401±2.7Ma）和别斯萨拉玢岩的SIMS锆石U-Pb年龄（401±3.1Ma）在误差范围内一致,表明矽卡岩和铅锌矿的形成与康布铁堡组流纹质火山岩的喷发及其碎屑岩的沉积是同时的,成因上密切相关。其次,矽卡岩呈层状产出,局限于康布铁堡组凝灰岩及其铁锰钙质碳酸盐夹层的范围内;石榴子石为铁铝榴石、锰铝榴石,闪石为铁闪石,缺失透辉石、钙铁辉石。上述特征与接触交代矽卡岩不同,后者以钙铝榴石、钙铁榴石、透辉石/钙铁辉石为特征,闪石为角闪石。接触交代矽卡岩矿床是后成矿床,它晚于岩浆侵入体的围岩。综上所述,萨吾斯铅锌矿是一个与康布铁堡组火山喷发和浅成侵入有关的喷流-沉积矿床。麦兹盆地的控盆断裂巴寨断裂从北西端向南东发展而成。阿巴宫-库尔提断裂和琼库尔断裂是克兰盆地的控盆断裂,它们在北西撒开、向南东收敛,具有羽状张剪性断裂的特征。因此,阿尔泰南缘在早泥盆世具有活动陆缘的局部拉张性质。西伯利亚板块与哈萨克斯坦-准噶尔板块的推错,在阿尔泰南缘产生局部张剪性应力场,从而形成了上述断裂以及早泥盆世火山-沉积盆地。     

Preindustrial, historical, and fertilization simulations using a global ocean carbon model with new parameterizations of iron limitation, calcification, and N2 fixation

The Canadian Model of Ocean Carbon (CMOC) has been developed as part of a global coupled climate carbon model. In a stand-alone integration to preindustrial equilibrium, the model ecosystem and global ocean carbon cycle are in general agreement with estimates based on observations. CMOC reproduces global mean estimates and spatial distributions of various indicators of the strength of the biological pump; the spatial distribution of the air-sea exchange of CO₂ is consistent with present-day estimates. Agreement with the observed distribution of alkalinity is good, consistent with recent estimates of the mean rain ratio that are lower than historic estimates, and with calcification occurring primarily in the lower latitudes. With anthropogenic emissions and climate forcing from a 1850-2000 climate model simulation, anthropogenic CO₂ accumulates at a similar rate and with a similar spatial distribution as estimated from observations. A hypothetical scenario for complete elimination of iron limitation generates maximal rates of uptake of atmospheric CO₂ of less than 1 PgC y⁻¹, or about 11% of 2004 industrial emissions. Even a ‘perfect’ future of sustained fertilization would have a minor impact on atmospheric CO₂ growth. In the long term, the onset of fertilization causes the ocean to take up an additional 77 PgC after several thousand years, compared with about 84 PgC thought to have occurred during the transition into the last glacial maximum due to iron fertilization associated with increased dust deposition.     

Meteoroid ablation models

The fate of entering meteoroids in atmosphere is determined by their size, velocity and substance properties. Material from ablation of small-sized meteors (roughly R≤0.01–1 cm) is mostly deposited between 120 and 80 km altitudes. Larger bodies (up to meter sizes) penetrate deeper into the atmosphere (down to 20 km altitude). Meteoroids of cometary origin typically have higher termination altitude due to substance properties and higher entry velocity. Fast meteoroids (V>30–40 km/s) may lose a part of their material at higher altitudes due to sputtering. Local flow regime realized around the falling body determines the heat transfer and mass loss processes. Classic approach to meteor interaction with atmosphere allows describing two limiting cases: – large meteoroid at relatively low altitude, where shock wave is formed (hydrodynamical models); – small meteoroid/or high altitudes – free molecule regime of interaction, which assumes no collisions between evaporated meteoroid particles. These evaporated particles form initial train, which then spreads into an ambient air due to diffusion. Ablation models should make it possible to describe physical conditions that occur around meteor body. Several self-consistent hydrodynamical models are developed, but similar models for transition and free molecule regimes are still under study. This paper reviews existing ablation models and discusses model boundaries.     

纳米计量学的基础技术组件

为了满足ASTROD激光宇航动力学任务慨念计划的高精度要求 ,以及实现新质量标准 ,我们开始进行次纳米激光测长与纳米定位控制的研究。本文将回顾我们在清华大学与工研院测量中心的研究成果 ,介绍如何利用外差式激光干涉仪、挠性微动台与压电陶瓷 ,进行次纳米激光测长与纳米定位控制。此研究成果将做为ASTROD计划中 ,无拖曳航天技术的研发基础。之后讨论如何将纳米定位控制系统与扫描穿隧显微镜进行整合 ,完成计量型扫描穿隧显微镜 ,进一步将微结构的测量尺寸直接追溯至长度标准。     

Coupling winds to ocean surface currents over the global ocean

A Wind stress–Current Coupled System (WCCS) consisting of the HYbrid Coordinate Ocean Model (HYCOM) and an improved wind stress algorithm based on Donelan et al. [Donelan, W.M., Drennan, Katsaros, K.B., 1997. The air–sea momentum flux in mixed wind sea and swell conditions. J. Phys. Oceanogr. 27, 2087–2099] is developed by using the Earth System Modeling Framework (ESMF). The WCCS is applied to the global ocean to study the interactions between the wind stress and the ocean surface currents. In this study, the ocean surface current velocity is taken into consideration in the wind stress calculation and air–sea heat flux calculation. The wind stress that contains the effect of ocean surface current velocity will be used to force the HYCOM. The results indicate that the ocean surface velocity exerts an important influence on the wind stress, which, in turn, significantly affects the global ocean surface currents, air–sea heat fluxes, and the thickness of ocean surface boundary layer. Comparison with the TOGA TAO buoy data, the sea surface temperature from the wind–current coupled simulation showed noticeable improvement over the stand-alone HYCOM simulation.