电感耦合等离子体发射光谱法在地质样品分析中的应用进展

概述了电感耦合等离子体发射光谱法(ICP-AES)在测定技术方面的进展,强调该仪器测定条件对测定元素曝光强度的影响以及对测定中各元素分析谱线的选择和干扰元素的影响;介绍了ICP-AES测定技术在地质样品分析中的应用。测定土壤、岩石、水洗沉积物、矿石样品、植物样品和水样样品中的元素时,应根据样品性质的不同和测定元素的不同而采用不同的消解体系(酸溶法、碱熔法和微波消解法)。在测定土壤、岩石和水洗沉积物样品时,比较了不同消解体系各自的特点,同时也对比了采用不同消解体系时各元素的方法检出限,结果显示,酸溶法的检出限要明显优于碱熔法;在测定矿石样品时,对比了各元素在不同消解体系中的测定精密度,结果显示测定精密度均较好;总结了测定常见植物样品中无机元素的典型前处理方法以及ICP-AES测定水样中的元素全量和元素不同价态含量的方法。最后,对ICP-AES测定技术在地质行业的应用作了展望,相信ICP-AES还将在地质样品的分析中继续发挥作用。     

煤镜质体反射率测定条件与测定值分析

针对部分应用单位在煤镜质体反射率测定中存在的对测定条件把握不准、对影响测定值准确性的因素理解不深等问题,提出了煤镜质体反射率测定必须遵守的仪器状态一致性与组分定位一致性原则,据此确立了仪器校正、样品测定和结果检验的方法与要求;分析了仪器线性度、稳定性、工作曲线、单色光、温度校正、视频窗口、油浸物镜与浸油、准焦程度和测定样品磨抛质量等对测定值准确性的影响与测定误差控制措施。在此基础上,提出了测定值精密度分级的改进建议,以及用煤镜质体反射率测定结果指导企业生产可简化的仪器条件与测定过程,即:使用50倍干物镜;勿需546 nm滤光片;用有固定反射率值的镀膜玻璃替代宝石标准片;建立工作曲线数据库等。      

微波消解-磷钒钼黄光度法测定海洋沉积物中总磷

采用微波消解样品,磷钒钼黄光度法测定海洋沉积物中总磷。优化了消解用酸的种类和用量、消解时间、消解温度等微波消解条件。选择HNO3作为消解剂,消解最终温度190℃,保持时间15 min,总磷的测定快速和准确。探讨了显色酸度(微波消解液是否需要赶酸)和稀释倍数等测定条件。对两种国家一级沉积物标准物质GBW07314和GBW07311进行分析验证,测定值与标准值相符,相对标准偏差(RSD,n=6)分别为0.74%和1.66%。与常规消解方法进行比对实验,测定结果无显著性差异。与国标GB 17378.5方法相比,该法具有简单、快速、准确、空白值低、环境污染少等优点。在实际样品测定中,取得了满意的结果,适用于海洋沉积物中总磷的测定。     

EDTA-铅滴定法测定水中硫酸根条件试验

测定水中硫酸根的方法有重量法、容量法、硫酸钡比浊法和间接极谱法等。常用硫酸钡比浊法和容量法来测定。EDTA 铅滴定法测定水中硫酸根的含量是一种经典的容量法,通过对该法滴定条件———溶液酸度、沉淀放置时间、缓冲溶液的加入量等进行较详细的试验。提出了测定时应控制的实验条件,验证了该法的可行性,且测定结果更精确。进一步氯离子的干扰试验表明:此方法适用于氯离子含量小于600mg·L-1的水样测定。     

高分辨电感耦合等离子体质谱法测定地球化学样品中钪钇和稀土元素

建立了高分辨电感耦合等离子体质谱法(HR-ICP-MS)测定地球化学样品中钪、钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱和镥的分析方法。样品经氢氟酸-硝酸-硫酸-王水消解,试液直接用HR-ICP-MS测定钪、钇和14种稀土元素。用高分辨模式有效地避免了多原子离子及难熔氧化物离子对待测元素测定的干扰,为钪、钇和14种稀土元素选择了最佳的测定同位素和合适的分辨率;用地球化学标准物质制备的溶液优化仪器工作参数,确定了最佳的仪器测定条件。方法检出限(6σ)为0.003～0.013μg/g(稀释因子为1000),相对标准偏差(RSD,n=12)小于6%。方法经国家一级地球化学标准物质验证,测定值与标准值吻合。     

氯化物解聚快速测定铁矿石中二氧化硅

采用NaOH熔融、蒸馏水浸取、盐酸中和并酸化、氟化物解聚和钼酸铵显色测定铁矿石中的二氧化硅。本方法的检出限为0．10％。本实验以测定了国家一级铁矿标样来验证方法的准确度和精密度,测定结果与标准值相符,且测定12次的相对标准偏差（RSD）均小于10％。     

自动和人工测定煤镜质组反射率的对比研究

对比分析了煤镜质组反射率人工测定与自动测定的各自特点,给出了与人工测定结果高度相关的自动测定方法和条件。测定结果表明,自动测定结果的重现性好于人工测定结果。;区分能力与人工测定相当。     

氢化物发生-电感耦合等离子体发射光谱法同时测定土壤中的痕量砷铜铅锌镍钒

土壤中砷的测定方法多采用氢化物发生-原子荧光光谱法(HG-AFS);电感耦合等离子体发射光谱法(ICP-OES)在多元素同时测定方面应用普遍,但测定砷的检出限稍高。氢化物发生技术与ICP-OES两者联用也多有研究,较大幅度降低了砷的检出限,已能实现砷锑铋汞等元素的同时测定。但联用技术只能应用于测定能够发生氢化反应的元素,无法实现易氢化元素和难氢化元素的同时测定。本文通过改进ICP-OES仪器的进样装置,采用氢化反应气与ICP-OES雾化气双管路同时进样的方法,实现了一次溶样、一台设备同步测定样品中的砷和多种金属元素。土壤样品经氢氟酸、硝酸、高氯酸、盐酸溶解后,用10%盐酸提取,用硫脲-抗坏血酸溶液将砷元素预还原为+3价后双流路同时进样测定。对于溶液中共存的离子,高于1.0mg/L的La和Dy对砷测定有干扰;低于50.0mg/L的K、Na、Ca、Mg、Fe,低于20.0mg/L的Pb、Mo、Zn、Cu、Ba、Ti、Mn、Ni、Sr、V、Cr,低于10.0mg/L的Co、Ag、U、Cd、Li、Au对砷测定无影响。本方法提高了砷的测定灵敏度,又充分利用多元素同测的优势,实现了同时测定易氢化的痕量砷和难氢化的铜、铅、锌、镍、钒等元素。方法精密度高(RSD5%),经土壤标准物质验证方法可靠,适合痕量砷与其他元素的同步测定。     

容量法连续测定磷矿石中钙锶镁

改进了用EDTA络合滴定Ca、Sr和Mg的条件,建立了磷矿石中连续测定Ca、Sr和Mg的方法,用于实际样品测定,结果符合质量要求。     

稀土钙钛矿型LaMnO3+λ系列化合物的结构计算与分析

在不同氧分压下合成了LaMnO3 λ、系列化合物,用XRD法进行了结构测定与分析,用化学滴定法测定了Mn^4 含量,由测定结果计算晶胞参数,LaMnO3 λ中系数λ值和La^3 空位率。     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

Mercury,arsenic, antimony,and selenium contents of sediment from the Kuskokwim River,Bethel, Alaska,USA

The Kuskokwim River at Bethel, Alaska, drains a major mercury-antimony metallogenic province in its upper reaches and tributaries. Bethel (population 4000) is situated on the Kuskokwim floodplain and also draws its water supply from wells located in river-deposited sediment. A boring through overbank and floodplain sediment has provided material to establish a baseline datum for sediment-hosted heavy metals. Mercury (total), arsenic, antimony, and selenium contents were determined; aluminum was also determined and used as normalizing factor. The contents of the heavy metals were relatively constant with depth and do not reflect any potential enrichment from upstream contaminant sources.     

滇东南花岗岩与锡、银、铜、铅、锌多金属矿床的成因关系

滇东南锡、银、铅、锌多金属矿床主要分布在个旧、白牛厂、都龙3个矿区,而滇东南较大的3个花岗岩体又分别出露在3个矿区或附近.花岗岩体均形成于燕山晚期,岩石化学、矿物成分相似,富含锡、银、铅、锌、钨、铜等成矿元素.矿床主金属元素组合与岩体之间的距离由远而近出现由锡、钨、(铍、铌、钽)→锡、钨、(铁)、铜、铟→锡、铅、锌、银、铟、(锑)有规律的变化.花岗岩浆是成矿物质来源和成矿热源.岩浆侵入初期使上覆地层隆起产生背斜(凹陷部位成向斜);同时使地层产生一系列裂隙、压性断层或层间断裂;岩浆侵入晚期,这些断层再次活动,表现为张性,岩浆产生的含矿热液沿由其活动所造成的断裂迁移、充填、交代、沉淀而形成矿床.     

岩石密度和超高压岩石折返速率

在常温常压条件下对中国大陆科学钻CCSD主孔100-3000米岩心样品进行了密度测量,建立了密度连续剖面,并界定了不同超高压岩石的密度值。通过对比高温高压物性实验资料,岩石密度随着退变程度增强而降低,榴辉岩密度变化序列为3.52g/cm3→3.49g/cm3→3.07g/cm3→2.93g/cm3。超高压长英质岩石密度变化序列为3.00g/cm→2.80g/cm3→2.65g/cm3。上述实验资料是讨论不同折返阶段岩石所受浮力的基础,为研究折返速率大小提供了基本参数。本文通过折返板块运动平衡时,上浮力与粘滞力平衡这一关系式,定量研究了大陆俯冲板块的折返速率,认为密度差产生上浮力从而引起折返,温度对板块折返速率的影响最为显著;密度差大小、折返角度、折返板块大小对折返速率也有直接的影响。定量模拟分析表明,在温度高于850℃时,板块的折返速率可以超过100mm/a;当温度降至700℃时,折返速率则低于1.5mm/a。作者认为在折返早期,温度较高,板块快速折返至60-70km榴辉岩相深度;随着传导散热,温度降低,板块以较慢的速率折返至中下地壳。折返速率的估算表明,浮力是板块折返第一阶段(从>100km深部折返至<40km的中下地壳)的主要驱动力。     

Bellechester,Minnesota, USA,lagoon collapses

Bellechester, Minnesota, is a small community of approximately 155 residents located on the county line between Goodhue and Wabasha counties in southeast Minnesota's karst region. Bellechester is served by a 21-year-old wastewater treatment facility (WWTF) consisting of three waste-stabilization ponds. On 28 April 1992 six sinkholes were discovered to have drained cell 2 of the WWTF resulting in the loss of approximately 8.7×10⁶ 1 of partially treated effluent and about 600 m³ of soil into previously undetected subsurface voids of unknown dimensions. In the week following the collapse, approximately 200 water wells located within a 5-km radius of the WWTF were sampled in an after-the-fact, emergency sampling program. Twelve samples with elevated fecal coliform levels, 18 samples with nitrate-nitrogen greater than the 10 mg/1 standard, and no samples with elevated chlorides were found. However, the elevated levels could not be unambiguously attributed to the WWTF collapse. This is the third WWTF to fail by sinkhole collapse in southeast Minnesota since 1974. All three collapsed lagoons have been located in similar geomorphic and stratigraphic settings. However, at least two lagoons have collapsed in the adjacent area in northeast Iowa, and these lagoons are located at different stratigraphic positions. Twenty-two WWTFs constructed in southeast Minnesota's karst region in the last 25 years have been identified as subject to potential sinkhole collapse. An unknown but significant number of manure storage lagoons, flood control structures, etc., have also been constructed in the karst region and are at risk. Public agencies are beginning to develop plans to deal with the risk associated with existing and future waste lagoons in this environment. The critical hydrogeologic parameters that can be used to prioritize the risk of collapse at existing facilities include: (1) the lithology of the first bedrock beneath each lagoon, (2) the thickness of surficial materials between the lagoon and the bedrock surface, (3) the presence and construction of liners (seepage rate), and (4) the proximity to existing sinkholes.