应用波长色散X荧光仪和多晶X射线衍射仪联用技术 鉴定进口铜矿和含铜物料

本文首次研究进口可利用含铜物料与进口铜矿属性的不同特性并建立鉴定方法,采用X荧光光谱法和X射线衍射光谱法联用技术建立铜矿和含铜物料属性的鉴别方法。通过X荧光光谱法对铜矿和含铜物料中元素进行定性半定量分析,再用X射线衍射光谱法对铜矿和含铜物料的特征谱峰进行扫描,与X衍射仪中标准卡片比对分析,能够确定铜矿和含铜物料的物相组成。结果显示：X荧光光谱法铜矿和含铜物料的共同特点铜的含量较高,达到冶炼铜对原料的要求,硅、铁、钠、钙和镁元素都能够检出。差异性在铅和锌元素在含铜物料中较高,在铜矿石中基本未检出;在X荧光光谱法检测出的金属元素,通过X衍射仪扫描后与标准图片比对,各元素以不同的形式存在于含铜物料中,且有规律可循。     

基于多技术联用鉴别含镍物料固体废物属性

采用超景深显微镜、X射线荧光光谱、X射线衍射等技术,对含镍物料样品进行微观形貌、化学成分和物相组成分析,并结合镍矿及镍矿渣的特征分析,实现固体废物属性鉴别。结果表明:物料1微观呈现蓬松碎絮形态,pH值为4.30,酸性特征显著,主要物相为SiO_(2)、FeO(OH)、PbO_(2)等,样品中S含量残留达到14.7%,Pb和As含量远超有害物质限量;物料2表面有空隙,呈现明显黑色焦烧痕迹,主要物相为Mg_(2)SiO_(4)、Fe_(3)O_(4)等,样品中MgO折算含量远超镍精矿标准限量。综合分析两种物料的外观、物理性状、微观形貌、物相组成、化学成分,发现两种物料不具有天然矿物特征,推断物料1可能来自红土镍矿在硫酸酸浸工艺中产生的湿法冶炼渣,物料2可能为含镍矿物经火法冶炼中熔炼过程产生的熔炼渣或转炉渣,均属于固体废物。     

波长色散X射线荧光光谱仪和多晶X射线衍射仪联用技术鉴定进口铜矿和含铜物料

首次研究进口可利用含铜物料与进口铜矿属性的不同特性并建立了鉴定方法,采用X射线荧光光谱法和X射线衍射光谱法联用技术建立铜矿和含铜物料属性的鉴别方法。通过X射线荧光光谱法对铜矿和含铜物料中元素进行定性半定量分析,再用X射线衍射光谱法对铜矿和含铜物料的特征谱峰进行扫描,与X射线衍射仪中标准卡片比对分析,能够确定铜矿和含铜物料的物相组成。结果显示,X射线荧光光谱法测定的铜矿和含铜物料的共同特点是铜的含量较高,达到冶炼铜对原料的要求;硅、铁、钠、钙和镁元素都能够检出;差异性在铅和锌元素在含铜物料中较高,在铜矿石中基本未检出;用X射线荧光光谱法检测出的金属元素,通过X射线衍射仪扫描后与标准图片比对,各元素以不同的形式存在于含铜物料中,且有规律可循。     

火试金重量法直接测定铅精矿及其它含铅物料中的银

系统研究了火试金重量法直接测定铅精矿、铅矿石、铅合金和含铅物料中银含量的条件,将测定结果与国家标准、行业标准方法的测定结果进行比较,并采用铅精矿国家标准物质进行验证。结果表明:测定5~71 200g/t的银含量,相对标准偏差(RSD)和银标准加标回收率分别为0.10%~7.4%和99.10%~99.94%。分析结果与国家标准、行业标准方法测定结果吻合,验证结果与铅精矿国家标准物质认定值一致。     

火试金重量法直接测定铅精矿及其它含铅物料中的银

系统研究了火试金重量法直接测定铅精矿、铅矿石、铅合金和含铅物料中银含量的条件,将测定结果与国家标准、行业标准方法的测定结果进行比较,并采用铅精矿国家标准物质进行验证。结果表明:测定5~71 200g/t的银含量,相对标准偏差(RSD)和银标准加标回收率分别为0.10%~7.4%和99.10%~99.94%。分析结果与国家标准、行业标准方法测定结果吻合,验证结果与铅精矿国家标准物质认定值一致。     

FAB质谱图在中药品种鉴定上的应用

中药鉴定方法包括来源鉴定、性状鉴定、显微鉴定和理化鉴定.原有的中药理化鉴定方法或者专属性不高[1],或者需要提取、分离中药的有效成分[2],样品前处理工作繁琐,分析周期长.质谱直接进样方式对样品前处理的要求简单、分析速度快、样品用量少,特别是FAB电离方式引起的裂解少,图谱中特征峰清晰、稳定、重现性好,使FAB质谱图可能成为中药的指纹图谱,这在中药的真伪鉴别上具有实际应用意义.因此,我们对51种常用中药的乙醇提取液进行了FAB质谱测试,发现其中46种的FAB图有指纹特征,由此建立了46种中药的FAB指纹图谱库.     

Cu(In,Ga)Se_2薄膜组成表面分析准确测量国际关键比对

中国计量科学研究院参加了国际关键比对K129,采用X射线光电子能谱仪(XPS)建立了测量薄膜太阳能电池材料铜铟镓硒(CIGS)薄膜组成和深度成分分布的有效方法。采用合适的条件,对CIGS薄膜进行深度剖析,提出并完善了一套XPS深度剖析数据处理方法(全计数法和相对灵敏度因子法),对薄膜组成进行了准确测量。结果表明,该方法的测量重复性良好,5次测量的相对标准偏差(RSD)均小于2%,测量扩展不确定度优于4%,与其他国家计量院的结果取得等效一致。对比研究了不同灵敏度因子来源(由参考样品获得、仪器数据库的3种来源)对CIGS薄膜组成测量结果的影响,结果表明,仪器厂商数据库自修正的灵敏度因子最接近于参考样品,可较好地对CIGS薄膜进行原子含量测量。该方法可推广用于表面分析设备深度剖析薄膜样品时定量计算薄膜成分,提高测量薄膜成分的准确度,为薄膜太阳能电池材料研发和产业化提供参考依据。     

2002年中国机械工程学会年会理化检验分会场暨中国机械工程学会理化检验分会成立40年学术会议征文通知

20 0 2年度中国机械工程学会年会定于 2 0 0 2年11月 1～ 5日在北京国际会议中心召开 ,中国机械工程学会理化检验分会 (分会场 )主持的“中国机械工程学会理化检验分会成立 4 0年学术会议”是构成2 0 0 2年度中国机械工程学会年会活动主体的重要内容之一。热诚邀请广大会员和从事理化检验工作的科技与管理工作者踊跃参加、积极赐稿。一、征文内容(1)理化检测技术及方法的发展方向、理化检测方法标准化动态的综述报告 ;(2 )理化检测的新技术、新方法和新仪器介绍 ;(3)废品分析与失效分析技术 ;(4)测量不确定度的估算及应用 ;(5 )理化检测技术…     

高分辨率分光系统-连续光源原子吸收光谱法测定铀铌铅矿重选流程样品中铅的含量北大核心CSCD

采用盐酸(15mL)-硝酸(5mL)-氢氟酸(10mL)-高氯酸(2mL)体系溶解铀铌铅矿样品(0.030 0～0.200 0g),盐酸(1+9)溶液作为分散介质,选择Pb 283.306nm作为分析谱线,提出了高分辨率分光系统-连续光源原子吸收光谱法(HR-CS AAS)测定铀铌铅矿重选流程样品中铅的方法。结果表明:检出限(3s)为0.021mg·L-1。按标准加入法对铀铌铅矿样品中的铅进行回收试验,回收率为97.8%～103%,测定值的相对标准偏差(n=9)均小于5.0%,满足国家地质矿产行业标准DZ/T 0130-2006的要求。     

光电直读光谱法测定铸造铝合金中微量钙和钠北大核心CSCD

采用光电直读光谱法测定铸造铝合金中微量钙和钠,并对其最佳条件进行试验。做到以下几点可获得满意的分析结果:(1)用积分描迹调整光谱仪器的狭缝位置,保证了最大强度的光通过;(2)严格按照GB/T 17432-2012的规定取样,确保样品的分析面无夹杂、裂纹、气孔、油污、粉尘及氧化物等;(3)样品表面必须光滑、无污染;(4)所用氩气应保证其纯度和流量;(5)采用与被分析样品中钙、钠含量非常接近的铝合金标准物质做类型校准。钙、钠的检出限(3s)依次为0.000 01%和0.000 02%。方法分析了5块铝合金标准物质,测得钙、钠的含量与其认定值一致;另取3块已知样品各重复测定11次,测定值的相对标准偏差为1.6%～3.9%。     

Precise and accurate determination of lead isotope ratios in mining wastes by ICP-QMS as a tool to identify their source

A methodology for a precise and accurate determination of lead isotope ratios in mining wastes by inductively coupled plasma quadrupole-based mass spectrometry (ICP-QMS) has been developed. The study of instrumental bias factors led to the conclusion that internal correction to compensate mass discrimination is required as well as an interference equation correction when Hg is present. The proposed method has been applied to determine lead isotope ratios in several mining wastes, soils and sediments collected at three mining areas in Spain (Aran Valley, Cartagena and Osor).Statistical analysis highlights that ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb lead isotope ratios can be used as a fingerprint of mining waste origin which is related to the geological age of the lead ore.On the other hand, no statistically significant isotopic differences between original ore samples (galena) and processing wastes within a mining district were found, corroborating a unique lead source. Moreover, the lead isotopic composition of soil and sediment samples collected at the studied mining areas is close to that determined in the mining tailings from the same areas, suggesting that the unusual high content of lead in these samples is derived from mining activities rather than from other lead sources.     

一例进口“铜精矿”的属性分析研究

采用X射线荧光光谱、X射线衍射等技术,结合超景深显微镜、扫描电镜、化学分析等手段,对一例申报为“铜精矿”的样品进行外观形貌、元素组成、物相组成、微观等进行分析。结果表明：样品含有黄铁矿、石英、孔雀石、硅锌矿、滑石等天然矿物,还含有大量的微米级球状氧化锌、玻璃态的钠钙硅铝酸盐、疏松的胶态硅酸盐以及条状、片状的金属铜屑等。样品的特征与天然铜矿浮选得到的铜精矿有显著差别,呈现出天然矿物和多种冶炼加工产物的混合物特征。     

Elemental composition and microstructure of Early Bronze Age and medieval tin slags

The elemental composition and the internal structure of two slag samples have been analyzed and compared using scanning electron microscopy-wavelength dispersive spectrometry and secondary ion mass spectrometry. The first sample studied is a vitreous accretion found on a ceramic crucible sherd, which originates from an Early Bronze Age site in the Kestel/Göltepe area of Anatolia. The intention for examining this glassy-looking material was to verify whether it corresponds in composition to a tin slag. The results of these measurements form part of a research project involving the search for ancient tin production in Turkey and have a direct relevance on the study of tin sources in the near East. Kestel/Göltepe is presumably the first local tin source found in the Anatolian area and in view of this, the vitreous accretion is compared with a medieval tin slag from a more distant source: the Crift Farm in Cornwall, UK. Results of the present study show that both samples are composed of silicates, each with different admixtures of oxides and metals and confirm that the Anatolian crucible accretion corresponds in composition to a typical metallic tin slag.     

Quantitative Analysis of Lead Ores Using Sepharose for Sample Preparation by X-Ray Fluorescence Spectrometry

A method for the quantitative analysis of lead ores by wavelength-dispersive x-ray fluorescence spectrometry (WD-XRF) using sepharose was proposed. The sample was decomposed with aqua regia and then the solution was mixed with sepharose. The mixture was heated to boiling and became a quasi-solid gel at ambient temperature. The quasi-solid gel was detected by WD-XRF. This method was adapted in detecting high content ores, because it avoided the risk of using platinum crucible. In addition, cobalt was used as an internal standard to reduce the matrix effects caused by the loss of water in dissolving samples. Analytical characteristics of the methods used were compared, and their reliability tested against several certified geological reference materials. The results showed high precision and accuracy. This method has been applied to the determination of lead in lead concentrates successfully.     

Adsorptive Cathodic Stripping Voltammetric Method for Determination of Gallium Using an In Situ Plated Lead Film Electrode

The in situ plated lead film electrode was proposed for the first time for adsorptive stripping voltammetric determination of gallium in water samples. The method was based on simultaneous lead film formation and Ga(III)‐cupferron complex preconcentration at ?0.7 V and its cathodic stripping during the potential scan. The composition of the supporting electrolyte, cupferron concentration, conditions of lead film formation, potential and time of accumulation were studied in detail. Under optimum conditions the limit of detection was 3.8×10^?9 mol L^?1. The proposed procedure was validated in the course of Ga(III) determination in waste water certified reference materials.     

On-line liquid phase micro-extraction based on drop-in-plug sequential injection lab-at-valve platform for metal determination

A novel automatic on-line liquid phase micro-extraction method based on drop-in-plug sequential injection lab-at-valve (LAV) platform was proposed for metal preconcentration and determination. A flow-through micro-extraction chamber mounted at the selection valve was adopted without the need of sophisticated lab-on-valve components. Coupled to flame atomic absorption spectrometry (FAAS), the potential of this lab-at-valve scheme is demonstrated for trace lead determination in environmental and biological water samples. A hydrophobic complex of lead with ammonium pyrrolidine dithiocarbamate (APDC) was formed on-line and subsequently extracted into an 80 μL plug of chloroform. The extraction procedure was performed by forming micro-droplets of aqueous phase into the plug of the extractant. All critical parameters that affect the efficiency of the system were studied and optimized. The proposed method offered good performance characteristics and high preconcentration ratios. For 10 mL sample consumption an enhancement factor of 125 was obtained. The detection limit was 1.8 μg L⁻¹ and the precision expressed as relative standard deviation (RSD) at 50.0 μg L⁻¹ of lead was 2.9%. The proposed method was evaluated by analyzing certified reference materials and applied for lead determination in natural waters and urine samples.     

Characterization of lead and arsenic contamination at Barber Orchard, Haywood County, NC

Barber Orchard is a residential community in Western North Carolina that was declared a U.S. EPA Superfund Site in September 2001 because of elevated levels of arsenic, lead, and organochlorine compounds in the soil. The contamination was introduced by pesticides (e.g., lead arsenate, DDT) when the land was employed as an apple orchard. Concentration levels of lead and arsenic in soil were measured throughout two plots by inductively coupled plasma optical emission spectrometry. A linear relationship was observed between the moles of lead and arsenic. Sequential extraction procedures were employed to characterize the mobility and bioavailability of the metals. The major forms of both elements were bound to iron-manganese oxides. In general, the relative composition of the metal species did not statistically vary with depth, although higher concentration levels were observed near the surface. Brake ferns (Pteris vittata) were employed in greenhouse phytoremediation experiments employing soil which had been homogenized to a uniform concentration level. Considerable variation was observed in the amount of arsenic absorbed by the ferns.     

石墨炉原子吸收光谱法测定磷矿石中微量铅

研究了石墨炉原子吸收光谱法测定磷矿石中微量铅，探讨了熔样过程，基体效应，共存元素及载气流速等干扰，并进行了干扰抑制试验，提出了最优方式对磷矿石中微量铅进行测定，回收率为90．5％～107．0％。     

Progress in direct solid sampling analysis using line source and high-resolution continuum source electrothermal atomic absorption spectrometry

The literature about direct solid sample analysis of the past 10–15 years using electrothermal atomic absorption spectrometry has been reviewed. It was found that in the vast majority of publications aqueous standards were reported as having been used for calibration after careful program optimization. This means the frequently expressed claim that certified reference materials with a matrix composition and analyte content close to that of the sample have to be used for calibration in solid sample analysis is not confirmed in the more recent literature. There are obviously limitations, and there are examples in the literature where even calibration with certified reference materials did not lead to accurate results. In these cases the problem is typically associated with spectral interferences that cannot be corrected properly by the systems available for conventional line source atomic absorption spectrometry, including Zeeman-effect background correction. Using high-resolution continuum source atomic absorption spectrometry, spectral interferences become visible owing to the display of the spectral environment at both sides of the analytical line at high resolution, which makes program optimization straightforward. Any spectrally continuous background absorption is eliminated automatically, and even rapidly changing background absorption does not cause any artifacts, as measurement and correction of background absorption are truly simultaneous. Any kind of fine-structured background can be eliminated by “subtracting” reference spectra using a least-squares algorithm. Aqueous standards are used for calibration in all published applications of high-resolution continuum source atomic absorption spectrometry to direct solid sample analysis. This contribution is based on a presentation given at the Colloquium for Analytical Atomic Spectroscopy (CANAS ‘07) held March 18–21, 2007 in Constance, Germany.