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.     

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.     

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。     

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.     

NEW SET OF LOW CONCENTRATION STANDARDS FOR LA, CE, SM, YB, LU, Y, SC, V, NB AND TA IN SILICATES

We have developed a set of four synthetic standards for the rare earth and high field strength elements designed for use in the determination of those elements in silicates. The base material is a glass nominally at the eutectic of the MgO-Al₂O₃-SiO₂ ternary system. The nominal doping level was 2 wt% of the elements as oxides. To avoid problems associated with peak interference, the elements were doped in four separate glasses.     

电感耦合等离子体发射光谱法测定钼矿石中钴铬铜钼镍铅锡钨钇锌

采用盐酸-硝酸-氢氟酸-高氯酸-柠檬酸处理样品,电感耦合等离子体发射光谱法同时测定钼矿中钴、铬、铜、钼、镍、铅、锡、钨、钇、锌10个元素,筛选了不同溶矿方法和仪器参数条件。测定的相对标准偏差(RSD,n=11)均小于3.0%,经国家一级钼矿标准物质分析验证,结果与推荐值吻合。     

电感耦合等离子体发射光谱法同时测定卤水中锂钠钾钙镁硼硫氯

建立了电感耦合等离子体发射光谱法(ICP-AES)同时测定碳酸盐型、硫酸盐型、氯化物型三种类型卤水中Li、Na、K、Ca、Mg、B、S、Cl等高低含量元素的分析方法。选择仪器最佳的工作条件为射频功率1400W,炬管位置位于-3,载气流量0.60 L/min。确定了各元素测定谱线,使用ICP-AES的双向观测模式、轴向观测模式测定Li、Ca、B、S、Cl以及低含量的K、Mg,径向观测模式测定高含量的Na、K、Mg,可确保卤水中不同含量的元素同时检出。Li、Na、K、Ca、Mg、B、S的检测下限为0.07～3.00 mg/L,Cl的测定下限为165mg/L。方法精密度(RSD,n=10)均小于5%,回收率为92.4%～109.7%。其中Na、K、Mg、S、Cl测定结果与传统方法测定结果基本吻合。     

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.     

Stratigraphic status,age, and paleobathymetry of the Grey shale Member,Dalmiapuram Formation,Cauvery Basin,India

Grey shale Member of the Dalmiapuram Formation, Ariyalur Group, Cauvery Basin, India was studied for its stratigraphic position, age, and paleobathymetry with a re-look into the lithological relationship and foraminifer assemblages in the deepened limestone mine excavations at M/s Dalmia Cements, Dalmiapuram. Twenty grey shale samples from Kovandankurchchi (pit-4) and Kallakkudi mines yielded diversified calcareous, benthic, and rare index planktic foraminifera. The foraminiferal assemblages suggest a latest Albian age and middle neritic depositional conditions. The abundance of kaolinite and smectite clay minerals relate to warm/humid climate which corroborate with rising relative sea level during grey shale deposition. The grey shale occurs in patches within the marl bedded limestone member which exhibits cyclic deposition of limestone and marl. The limestone mine sections demonstrate that the grey shale forms part of basal marl bedded limestone, directly overlying the coral algal limestone. The present study demonstrates that the grey shale outcrops in Dalmiapuram Formation should be placed stratigraphically as part of marl bedded limestone. The member status for grey shale which is current usage stands discounted.     

微波消解-电感耦合等离子体发射光谱法同时测定白云石中铁铝钙镁钾钠硫

采用微波消解白云石样品，电感耦合等离子体发射光谱法测定其中铁、铝、钙、镁、钾、钠、硫的氧化物，对微波消解条件和等离子体发射光谱仪的工作条件进行了选择，克服了常规化学分析方法步骤繁琐、耗时长、工作量大的不足。利用所建立的方法快速分析了白云石中铁、铝、钙、镁、钾、钠、硫的含量，结果与标准值或化学法相符，10次测定的相对标准偏差（RSD）7种元素均小于1％，可以满足生产和科研的要求。     

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.     

Monohydrocalcite,hydromagnesite, nesquehonite,dolomite, aragonite,and calcite in speleothems of the Fränkische Schweiz,Western Germany

The formation of calcite, aragonite, dolomite, hydromagnesite, and nesquehonite in speleothems of a small cave within dolostone may be compared with the formation of these carbonate minerals in much larger environments in which evaporation exceeds precipitation (salt lakes, tropical lagoons, sebkhas etc...). In all cases the formation and diagenetic alteration is mainly governed by the Mg/Ca-ratio of the solutions, from which precipitation (or transformation) takes place.The certain occurrence of monohydrocalcite in the speleothems and in technical incrustations lead to the conclusion, that this very rare mineral precipitates from solutions which are transported as aerosols.     

Titanium,Ti, A New Mineral Species from Luobusha,Tibet, China

We describe the new mineral species titanium,ideally Ti,found in the podiform chromitites of the Luobusha ophiolite in Tibet,People’s Republic of China.The irregular crystals range from 0.1 to 0.6 mm in diameter and form an intergrowth with coesite and kyanite.Titanium is silver grey in colour,the luster is metallic,it is opaque,the streak is grayish black,and it is non-fluorescent.The mineral is malleable,has a rough to hackly fracture and has no apparent cleavage.The estimated Mohs hardness is 4,and the calculated density is 4.503 g/cm3.The composition is Ti 99.23-100.00 wt%.The mineral is hexagonal,space group P63 /mmc.Unit-cell parameters are a 2.950(2),c 4.686(1),V 35.32(5) 3,Z = 2.The five strongest powder diffraction lines [d in(hkl)(I/I0)] are: 2.569(010)(32),2.254(011)(100),1.730(012)(16),1.478(110)(21),and 0.9464(121)(8).The species and name were approved by the CNMNC(IMA 2010–044).     

Delivery of Trace Metals (Al,Fe, Mn,V, Co,Ni, Cu,Cd, Ag,Pb) from the Trinity River Watershed Towards the Ocean

The Trinity River (Texas, USA) contains in its watershed 23 different reservoir lakes, the largest one being Lake Livingston situated in the lower Trinity River watershed and two potentially polluting metroplexes, Dallas and Houston. In order to determine fluxes of nutrients and trace metals to Galveston Bay, a survey that included 24 discreet samples collected over a year and at various stages of discharge was carried out during 2000–2001. Geochemical (i.e., sorption by Fe oxyhydroxides), biological (i.e., seasonal uptake by sinking algae in Lake Livingston), and hydrological (i.e., dilution effects by increasing flow rates) controls were found to be mainly responsible for variations in dissolved trace metal concentrations rather than pollution sources. The Trinity River loads of suspended sediments and pollutant trace metals entering Galveston Bay at Anahuac were <20% of those reaching Lake Livingston, and only a few percent of the total upstream trace metal load is entering the Gulf of Mexico. Thus, during the transit through the 23 man-made lakes and an estuary, >96% of the pollutant trace metal load is lost to sediments.     

Shock-induced amorphous textures in plagioclase,Manicouagan, Quebec,Canada

The textural relationships and structural states of optically isotropic labradorite from the Manicouagan, Quebec, impact structure have been examined by light (optical) and transmission electron (TEM) microscopy. Two distinct diaplectic glasses have been recognized based on their contrasting morphology, timing and the inferred modes of formation. The earliest isotropic bands and grain-scale isotropism (maskelynite) optically exhibit a gradational,in situ transformation from crystalline plagioclase with preservation of relict textures (twins, grain boundaries). The same transformation from crystalline to amorphous structure is observed in TEM to occur heterogeneously at scales on the order of the unit cell. The progressive transformation of optical properties reflects an increase in the volume fraction and eventual coalescence of these amorphous units. This maskelynite-type diaplectic glass is interpreted to form in the solid-state directly from crystalline material during the compressional phase of the shock wave. The other isotropic material occurs in spatially discrete tensiongashes and planar deformation features (PDFs) that overprint the maskelynite-type glass. This second type of diaplectic glass (PDF-type) is developed homogeneously within a given glass band and exhibits sharp crystal-glass boundaries, in contrast to the gradational boundaries of the maskelynite-type glass. PDF-type glass is interpreted to form by melting in tensional release zones during passage of the rarefaction wave. These observations emphasize the ability of naturally shocked rocks to preserve subtle evidence of variations in the shock process from highly transient events.     

Neutron-capture elements in halo, thick-disk, and thin-disk stars. Strontium, yttrium, zirconium, cerium

We derived Sr, Y, Zr, and Ce abundances for a sample of 74 cool dwarfs and subgiants with iron abundances, [Fe/H], between 0.25 and ?2.43. These estimates were obtained using synthetic spectra, assuming local thermodynamic equilibrium (LTE) for Y, Zr, and Ce, allowing for non-LTE conditions for Sr. We used high-resolution (λ/Δλ?40 000 and 60 000) spectra with signal-to-noise ratios between 50 and 200. We find that the Zr/Y, Sr/Y, and Sr/Zr ratios for the halo stars are the same in a wide metallicity range (?2.43 ≤ [Fe/H] ≤ ?0.90), within the errors, indicating a common origin for these elements at the epoch of halo formation. The Zr/Y ratios for thick-disk stars quickly decrease with increasing Ba abundance, indicating a lower rate of production of Zr compared to Y during active thick-disk formation. The thick-disk and halo stars display an increase in the [Zr/Ba] ratio with decreasing Ba abundance and a correlation of the Zr and Eu overabundances relative to Ba. The evolutionary behavior of the abundance ratios found for the thick-disk and halo stars does not agree with current models for the Galaxy’s chemical evolution. The abundance ratios of Y and Zr to Fe and Ba for thin-disk stars, as well as the abundance ratios within each group, are, on average, solar, though we note a slight decrease of Zr/Ba and Zr/Y with increasing Ba abundance. These results provide evidence for a dominance of asymptotic-giant-branch stars in the enrichment of the interstellar medium in heavy elements during the thin-disk epoch, in agreement with the predictions of the nucleosynthesis theory for the main s-process component.     

云南德钦鲁春铜铅锌矿床硫铅氢氧同位素特征及地质意义

鲁春铜铅锌矿床位于中咱-中甸板块和昌都-思茅板块之间的金沙江构造带中部,矿体长约3 km,厚度在1.06～16.35 m之间。其赋矿围岩为火山沉积岩系,容矿构造为印支期逆断层。鲁春铜铅锌矿床矿石中硫化物的δ34S值变化于3.5‰～6.8‰之间,硫化物的206Pb/204Pb比值为18.554～18.656,207Pb/204Pb比值为15.662～15.752,208Pb/204Pb比值为38.801～39.009。石英流体包裹体的HO182δO值变化范围为2.74‰～1.25‰,δDV-SMOW变化范围为107‰～123‰。鲁春铜铅锌矿床的硫铅氢氧同位素分析结果表明,该矿床成矿物质来源于地幔,部分来源于岩浆,在成矿流体上升过程中,有壳源物质的加入。早二叠世晚期金沙江洋盆向西俯冲形成了一系列逆断层,同时导致下地壳部分熔融,引发大规模的火山岩浆作用。在晚三叠世早期,构造背景由挤压环境到伸展环境的转折期,这些逆断层具有张性的特点,为后期的成矿热液提供了有利的容矿构造。上升的岩浆为地幔楔内的成矿流体提供了通道。岩浆内的部分成矿流体进入白茫雪山花岗闪长岩体附近的逆断层富集成矿。     

X射线荧光光谱法测定生物样品中氯硫氮磷钾铜锌溴

研究了用微晶纤维素垫底镶边粉末压片制样-X射线荧光光谱测定生物样品中的Cl、S、N、P、K、Cu、Zn和Br的分析方法。重点研究了N的分析条件和校正方式,K、Cu和Zn的内标选定,测量次数对测定结果的影响。方法的检出限、精密度和准确度基本满足生物样品的分析要求。方法用于实际生物样品的测定,结果与化学法相符。     

辽宁省营口地区玉隆铅锌矿床成因探讨

玉隆铅锌矿的成因是一个颇有争议的问题，笔者通过野外地质测量及矿区、矿的详细研究，提出该矿的成因与构造有着切的联系，其成矿物质的迁移和富集，均受特定的构造运动所制约，是前寒武纪构造控矿类型的典型范倒。指出该角砾状铅锌矿的成矿过程实际上是成矿物质在压力梯度作用下活化重应位的过程。