手持式X射线荧光光谱仪在富钴结壳资源勘查中的应用

便携式X射线荧光光谱仪具有快速、无损分析的特点,本文重点研究了手持式X射线荧光光谱仪在富钴结壳碎块和浅钻岩心野外现场原位分析中的应用能力。采用压片法制样,以富钴结壳国家标准物质(GBW 07337~GBW 07339)和多金属结核国家标准物质(GBW 07249、GBW 07295和GBW 07296)作为校准样品,建立了手持式X射线荧光光谱仪测定富钴结壳样品的校准曲线。方法经国家标准物质GBW 07339验证,元素Mn、Fe、Co、Ni和Cu的精密度(RSD)在0.3%~3.0%之间,满足富钴结壳样品现场分析的要求。在海上资源勘查现场,应用手持式X射线荧光光谱仪对富钴结壳碎块和浅钻岩心原样进行了现场原位分析。富钴结壳碎块原样烘干后直接测试分析数据与实验室压片制样XRF分析数据对比表明,Mn、Fe、Co、Ni和Cu元素的测定值一致性良好;浅钻岩心的原位分析数据与实验室人工分层分析数据对比表明,各层位Mn、Fe、Co、Ni和Cu元素直接测试数据与实验室压片制样XRF分析数据分布趋势基本一致。实际应用研究表明,手持式X射线荧光光谱仪适合于现场原位分析,满足野外富钴结壳资源快速评价的要求,同时原位分析能更真实地反映原始富钴结壳岩心不同层位中各元素的变化特征,为进一步研究富钴结壳成矿机制提供更丰富的数据资料。     

安徽庐江泥河铁矿床蚀变-矿化作用及元素迁移规律

传统方法不能明确揭示泥河铁矿床多阶段热液叠加蚀变过程中元素迁移的继承性特征.运用等浓度图法(the isocon diagram),根据该区晚阶段蚀变都是叠加在稍早阶段蚀变之上的实际情况,采用早期蚀变岩石为原岩与稍晚期蚀变岩石的不活动元素拟合最佳等浓度方程,定量揭示主量元素在热液蚀变过程的迁移规律.研究表明,泥河铁矿床阳离子的沉淀顺序大致为:Na→Ca、Mg、Fe、P→Ca、Fe→Al、Si.从早到晚,元素的带入和带出是连续互补的,蚀变矿化作用是一个连续的过程.钠长石的大量出现是Na质沉淀的标志,代表铁矿化的开始;膏辉岩化是Ca、Mg、Fe质沉淀的表现形式,为磁铁矿体的近矿和容矿蚀变;次生石英岩化、高岭石化是早期迁移出的Al、Si质沉淀的结果,是磁铁矿化远程指示性蚀变.      

便携式X荧光元素分析法在浅覆盖区萤石矿勘查中的应用与分析——以内蒙古乌力吉敖包萤石矿为例

随着现场X荧光元素分析技术的发展,便携式X荧光元素分析仪在野外矿产勘查工作中崭露头角。以内蒙古乌力吉敖包浅覆盖区的萤石矿为基础,开展现场X荧光勘查验证工作,通过元素异常分析和矿区实际情况对比得出以下结论:(1)便携式X荧光元素分析仪在浅层覆盖区勘查中具有较高的效率与精度;(2)连续的Ca元素异常对萤石矿脉具有良好的指示作用;(3)化探方法存在一定多解现象,但根据矿床类型并结合其他勘查方法可排除多解区域。     

云南普朗铜矿首采区构造(蚀变岩)地球化学特征及找矿预测

普朗铜矿床是格咱岛弧内最大的斑岩型Cu-Au-Mo矿床,主矿体的展布与复式斑岩体、岩体裂隙发育程度、钾化与青磐岩化蚀变带分布密切相关,为构造(蚀变岩)地球化学勘查技术应用奠定了基础。本次在对首采区8线剖面进行构造-蚀变-矿化编录的基础上,开展构造(蚀变岩)地球化学研究,通过R型聚类分析和因子分析得到3组矿化元素组合,结合矿床地质特征, F₁(Ag、Cu、Au、In、Se、S、Co、Fe、Zn、K、Ba、LREE、HREE)为Cu-Au矿化元素组合, F₃(Rb、Be、Nb、Ta、Th、U、Mo、Re、LREE)为Mo-Re矿化元素组合, F₄(Cu、Au、Se、Mo、-Ca、-Sr)为Cu-Au-Mo矿化元素组合。构造(蚀变岩)地球化学异常特征表明:(1)F₁、F₃、F₄因子在浅部的异常与已知矿体位置基本一致,深部未封闭异常指示剖面深部东侧具有较好找矿潜力,可圈定有利找矿靶区;(2)同时出现了两组Cu-Au矿化和两组Mo矿化组合异常叠加,指示具叠加成矿作用...     

基于pXRF的荞麦山铜多金属矿床元素富集规律研究

大数据技术在地学领域的应用越来越广泛,大数据思维为地学研究开辟了新的思路。从数据出发,以数据驱动模式去分析地质问题,在元素分布特征分析、矿床地化异常识别等方面较传统地学分析方法有着明显的优势。文章基于便携式X荧光分析仪（pXRF）测试的原位、无损、快捷、多元素分析等优点,对宣城矿集区内的荞麦山铜多金属矿床岩芯进行高密度的全数据原位采集,使用主成分分析（PCA）、多元逐步线性回归等方法进行量化分析。2种方法均表明,荞麦山铜多金属矿床中元素Mg、Ca、Mn、Co、As、Se、Ag、Hg、U和成矿元素Cu、Fe、S、W存在正相关关系;钻孔矿化和蚀变特征、铜硫矿石、钨矿石、石英砂岩均表现出不同的元素组合,特别是主成分综合得分（PCA）和第一主成分（PC1）元素对钻孔成矿区具有较好的指示效果;逐步多元线性回归分析进一步量化了元素富集规律,对成矿元素的拟合能够较好地与钻孔信息形成对应。因此,pXRF高密度的原位测量能够快速获取全面、准确的元素数据,分析结果能够直观反映荞麦山铜多金属矿床各元素的深度空间分布情况及量化相关关系,对深部地球化学特征的恢复和找矿提供帮助。     

Application of Borehole Core Magnetic Susceptibility and PXRF Measurement to the Moon Mountain Copper-Iron Mining Area in Chile and Prospecting Prediction

以智利月亮山铁氧化物铜金型矿床为例,利用磁化率K对铁磁性矿物及蚀变岩的现场识别能力和X射线荧光分析仪（PXRF）快速分析元素含量功能,结合矿床地质以闪长岩（5．5×10-3SI〈K〈17．9×10-3SI）、角砾岩（0．35×10-3SI〈K〈0．7×10-3SI）、磁铁矿（K〉753．4×10-3SI）、磁赤铁矿（313．3×10-3SI〈K〈753．4×10-3SI）、赤铁矿（0．78×10-3SI〈K〈1．62×10-3S1）、镜铁矿（0．67×10-3SI〈K〈0．78×10-3SI）等划分闪长岩亚相、角砾岩亚相、磁铁矿微相、磁赤铁矿微相、赤铁矿微相、镜铁矿微相;以PXRF现场测量铁含量〉30％,铜含量〉0．5％为含矿（化）界限,确定磁化率-铁铜含量对应关系：高磁化率-高铁含量-磁铁矿型、低磁化率-高铁含量-赤铁矿型（镜铁矿）、低磁化率-低铁含量-蚀变岩型,及岩相学找矿标志-矿物标志、构造标志、闪长岩标志、蚀变分带标志和矿物蚀变标志等,对月亮山矿区进行深部找矿预测。     

山东龙口大磨曲家金矿床地质特征及地球化学勘查模型

山东龙口市大磨曲家金矿区位于沂沭断裂带东侧,招平成矿带北端。矿床矿化类型为含金蚀变岩型,矿床经历了热液和表生 2 个成矿期及 5 个成矿阶段,围岩蚀变主要为硅化、绢云母化、钾化等。通过对 302 号脉坑道及钻孔岩心原生岩石地球化学特征研究,提出矿体前缘指示元素组合为 Hg-- As--Sb,近矿或矿体指示元素组合为 Au--Ag--Cu--Pb--Zn,矿体尾晕指示元素组合为 Bi--Co--Ni; 据此,建立了地球化学勘查模型。     

手持式X射线荧光光谱仪在富钴结壳资源勘查中的应用

便携式X射线荧光光谱仪具有快速、无损分析的特点,本文重点研究了手持式X射线荧光光谱仪在富钴结壳碎块和浅钻岩心野外现场原位分析中的应用能力。采用压片法制样,以富钴结壳国家标准物质（GBW 07337~GBW 07339）和多金属结核国家标准物质（GBW 07249、GBW 07295和GBW 07296）作为校准样品,建立了手持式X射线荧光光谱仪测定富钴结壳样品的校准曲线。方法经国家标准物质GBW 07339验证,元素Mn、Fe、Co、Ni和Cu的精密度（RSD）在0.3%~3.0%之间,满足富钴结壳样品现场分析的要求。在海上资源勘查现场,应用手持式X射线荧光光谱仪对富钴结壳碎块和浅钻岩心原样进行了现场原位分析。富钴结壳碎块原样烘干后直接测试分析数据与实验室压片制样XRF分析数据对比表明,Mn、Fe、Co、Ni和Cu元素的测定值一致性良好;浅钻岩心的原位分析数据与实验室人工分层分析数据对比表明,各层位Mn、Fe、Co、Ni和Cu元素直接测试数据与实验室压片制样XRF分析数据分布趋势基本一致。实际应用研究表明,手持式X射线荧光光谱仪适合于现场原位分析,满足野外富钴结壳资源快速评价的要求,同时原位分析能更真实地反映原始富钴结壳岩心不同层位中各元素的变化特征,为进一步研究富钴结壳成矿机制提供更丰富的数据资料。     

山东蒙阴金伯利岩中蛇纹石化橄榄石的微组构特征及其地质意义

为探究山东蒙阴金伯利岩中蛇纹石化橄榄石的微组构特征、蚀变环境、元素迁移规律及其对金伯利岩表生演化的指示意义,对该区金伯利岩中部分蛇纹石化的橄榄石和完全蚀变的橄榄石进行了XRD、EPMA和LA-ICP-MS分析测试。结果表明,蛇纹石中少部分Mg被Fe、Al、Ca、Ni、Mn取代,其中Fe含量仅次于Mg;从蚀变橄榄石的中心到边缘,Li与Zn、Ba与Sc、Co与Y含量分别呈3组变化趋势;部分蚀变的橄榄石为负Eu异常、低氧逸度,推测其形成于封闭的还原环境;完全蚀变的橄榄石无Eu异常,氧逸度相对较高,推测其形成于更开放的偏氧化环境;未完全蚀变的橄榄石大部分微量元素含量都高于完全蚀变橄榄石;稀土元素在蛇纹石化过程中可能存在迁移活动。     

内蒙古野狼沟锌多金属矿床地球化学异常特征及找矿意义

运用1∶5万水系沉积物测量方法,在野狼沟圈出Ag、Mo、Zn、W、As、Sb、Bi、Au、Cu等组合异常,其中Ag、Mo、Zn、W、As、Sb异常峰值较高,吻合程度较好,有一定连续性。该组合异常受断裂、褶皱构造复合控制明显,尤以断裂构造蚀变带的发育为特征,在构造蚀变带部位,成矿元素异常峰值较高。指示元素岩石地球化学异常面积不大,但成矿元素强度高。在野狼沟地区,主成矿元素Zn的Zn11原生晕面积约0.11 km2,Zn含量几何平均值为1 368.51×10-6,有3个连续样品中w(Zn)>3 000×10-6,为矿致异常。Zn、Ag、As指示元素在矿带上形成较大规模和连续性较好的原生地球化学异常,对成矿成晕研究和主成矿金属元素远景预测很有意义。     

便携式X射线荧光光谱仪在岩石样品分析中的应用研究

便携式X射线荧光光谱仪(PXRF)因具有快速、无损检测元素含量的能力,通常被用于野外或实验室地质样品的元素含量检测工作中,对于大多数地质样品,在2 min内就能够获得几十种元素的半定量-定量分析结果。但在实际应用中,被测样品的表面平整度、样品中物质的均一性和施测时间等因素都会影响元素分析结果。为了进一步了解样品类型和分析测试方法等因素对元素分析的具体影响,本文对比了PXRF与实验室分析结果、岩石和粉末样品PXRF分析结果、不同检测时间所得PXRF分析结果的关系,在不损失过多分析精度的前提下提出了通过PXRF降低勘查成本、提高工作效率的方案。结果表明:用PXRF直接分析岩石样品时,大多数元素的分析结果可靠性较差,尤其是成矿预测工作中常用的Cu、Pb、Zn、As和Ni等元素;粉末样品的PXRF分析结果与实验室分析结果具有较好的相关性,表明对岩石样品进行粉碎处理能够明显改善PXRF分析质量;元素种类不同,岩石和粉末样品PXRF测量结果的相关性也不同。因此,在实际工作中可以根据感兴趣的目标元素确定是否需要对岩石样品进行粉碎制样处理;检测时间对元素含量分析结果没有明显影响,对于特定元素,如果能够在较短时间内获得其含量信息,则无需增加检测时间。     

Using Field-Portable XRF to Assess Geochemical Variations Within and Between Dolerite Outcrops of Preseli, South Wales

Eight dolerite outcrops in Preseli, south Wales were measured in situ using field-portable XRF analysis, in order to compare two different analysis ("sampling") strategies, and to investigate geochemical variability within and between outcrops. A sampling strategy of two (neighbouring but independent) measurements at each of a maximal number of locations dispersed over an outcrop was the more effective in indicating the overall chemical variance of that outcrop. Analysis of variance indicated that much of the observed variance within individual outcrops stems from real geochemical variability rather than from sampling and analytical factors. Standard ANOVA F tests showed that several of the studied outcrops are heterogeneous at the 5% significance level for one or more elements. Geochemical distinctions between some outcrops were demonstrated using discriminant analysis. PXRF analysis offers an alternative approach to conventional characterisation of outcrops, which is often based on laboratory analysis of small numbers of samples. However, PXRF data are affected by rock weathering and may require correction for this if they are to be compared with analyses of fresh rock.     

Quantifying Heterogeneity of Small Test Portion Masses of Geological Reference Materials by Portable XRF Spectrometry: Implications for Uncertainty of Reference Values

There is an increasing use of analytical macro‐beam techniques (such as portable XRF, PXRF) for geochemical measurements, as a result of their convenience and relatively low cost per measurement. Reference materials (RMs) are essential for validation, and sometimes calibration, of beam measurements, just as they are for the traditional analytical techniques that use bulk powders. RMs are typically supplied with data sheets that tabulate uncertainties in the reference values by element, for which purpose they also specify a minimum recommended mass of material to be used in the chemical analysis. This minimum mass may not be achievable using analytical beam techniques. In this study, the mass of the test portion interrogated by a handheld PXRF within pellets made from three silicate RMs (SdAR L2, M2 and H1) was estimated using a theoretical approach. It was found to vary from 0.001 to 0.3 g for an 8 mm beam size and 0.0001 to 0.045 g for a 3 mm beam. These test portion masses are mainly well below the recommended minimum mass for these particular RMs (0.2 g), but were found to increase as a function of atomic number (as might be expected). The uncertainties caused by heterogeneity (U_HET) in PXRF measurements of the three RMs were experimentally estimated using two different beam diameters for eighteen elements. The elements showing the highest levels of heterogeneity (U_HET > 5%) seem generally to be those usually associated with either an accessory mineral (e.g., Zr in zircon, As in pyrite) or low test portion mass (associated with low atomic number). When the beam size was changed from nominally 8 to 3 mm, the uncertainty caused by heterogeneity was seen to increase for most elements by an average ratio of 2.2. These values of U_HET were used to calculate revised uncertainties of the reference values that would be appropriate for measurements made using a PXRF with these beam sizes. The methods used here to estimate U_HET in PXRF measurements have a potential application to other analytical beam techniques.     

钻孔岩心磁化率及PXRF 测量在智利 月亮山铁铜矿区应用与找矿预测

[摘 要]以智利月亮山铁氧化物铜金型矿床为例,利用磁化率K 对铁磁性矿物及蚀变岩的现场识别能力和X 射线荧光分析仪(PXRF)快速分析元素含量功能,结合矿床地质以闪长岩(5.5×10^-3SI< K <17.9×10-3 SI)、角砾岩(0.35×10^-3SI< K <0.7×10^-3SI)、磁铁矿(K>753. 4×10^-3SI)、磁赤铁矿(313.3×10^-3SI < K <753.4×10^-3SI)、赤铁矿(0.78×10^-3SI< K <1.62×10^-3SI)、镜铁矿(0.67×10^-3SI< K <0.78×10^-3SI)等划分闪长岩亚相、角砾岩亚相、磁铁矿微相、磁赤铁矿微相、赤铁矿微相、镜铁矿微相;以PXRF现场测量铁含量>30%,铜含量>0.5%为含矿(化)界限,确定磁化率-铁铜含量对应关系:高磁化率-高铁含量-磁铁矿型、低磁化率-高铁含量-赤铁矿型(镜铁矿)、低磁化率-低铁含量-蚀变岩型,及岩相学找矿标志-矿物标志、构造标志、闪长岩标志、蚀变分带标志和矿物蚀变标志等,对月亮山矿区进行深部找矿预测。     

我国古代两种珍稀宝玉石文物分析

为了科学辨别易混淆文物的材质,以蓝绿色和蓝紫色宝玉石文物为例,利用外束质子激发X射线荧光、便携式能量色散X射线荧光、激光拉曼光谱和X射线衍射分析等现代无损科技手段,从安徽蚌埠双墩一号春秋墓、河南洛阳烧沟东汉墓和新疆和田皮山古城唐代墓葬中甄别与鉴定出被误认为是绿松石和琉璃（玻璃）器的天河石串珠和青金石耳？及青金石管饰。简要阐述了这两种彩色宝玉石的矿物学特征及应用历史。这三件彩色宝玉石文物的发现,丰富了中国宝玉石史的研究内容,拓宽了对我国古代先民开采、引进及应用宝玉石的认识。     

Mine tailings dams: Characteristics,failure, environmental impacts,and remediation

On a global scale demand for the products of the extractive industries is ever increasing. Extraction of the targeted resource results in the concurrent production of a significant volume of waste material, including tailings, which are mixtures of crushed rock and processing fluids from mills, washeries or concentrators that remain after the extraction of economic metals, minerals, mineral fuels or coal. The volume of tailings is normally far in excess of the liberated resource, and the tailings often contain potentially hazardous contaminants. A priority for a reasonable and responsible mining organization must be to proactively isolate the tailings so as to forestall them from entering groundwaters, rivers, lakes and the wind. There is ample evidence that, should such tailings enter these environments they may contaminate food chains and drinking water. Furthermore, the tailings undergo physical and chemical change after they have been deposited. The chemical changes are most often a function of exposure to atmospheric oxidation and tends to make previously, perhaps safely held contaminants mobile and available. If the tailings are stored under water, contact with the atmosphere is substantially reduced, thereby forestalling oxygen-mediated chemical change. It is therefore accepted practice for tailings to be stored in isolated impoundments under water and behind dams. However, these dams frequently fail, releasing enormous quantities of tailings into river catchments. These accidents pose a serious threat to animal and human health and are of concern for extractive industries and the wider community. It is therefore of importance to understand the nature of the material held within these dams, what best safety practice is for these structures and, should the worst happen, what adverse effects such accidents might have on the wider environment and how these might be mitigated. This paper reviews these factors, covering the characteristics, types and magnitudes, environmental impacts, and remediation of mine tailings dam failures.     

Precambrian phosphorites in the Bijawar rocks of Hirapur-Bassia areas,sagar district,madhya pradesh,India

The Precambrian phosphorites of Bijawar Group of rocks show characteristics of a epicontinental sea with restricted and very shallow marine environment of formation along some shoals, which existed during the iron-rich Precambrian times. These phosphorite deposits located in the Hirapur-Bassia areas show extensive leaching of carbonate and phosphate minerals during episodes of weathering. X-ray diffraction studies indicated that carbonate-flourapatite is the major apatitic phase in these phosphorites while crandallite developed on the surface outcrops. There is a general tendency for the depletion of CO₂ in these apatites leading to formation of flourapatite. This CO₂ is an indicator of hidden weathering in the rocks. Major and trace element determinations of phosphorite have been used to indicate various correlation factors responsible for the concentration of elements in these Precambrian leached phosphorites.The paper is a contribution to the aims and objectives of IGCP Project 156The paper is dedicated to Prof. Dr. R. C. Misra, who as a teacher and guide had been a source of inspiration to the senior author for the last two decades     

Clinopyroxene-matrix partitioning of K,Rb, Cs,Sr and Ba

Extremely pure samples of clinopyroxene phenocrysts from two volcanic rocks have been analyzed for K, Rb, Cs, Sr and Ba. In conjunction with matrix concentrations, partition coefficients are obtained which are in the range 0.001–0.004 for K, Rb, Cs and Ba. These values are lower than those in the literature by factors of 6–100 but are in good agreement with values determined experimentally at pressures of 15–30 kb by Shimizu (Geochim. Cosmochim. Acta38, 1974). Values for partition coefficients measured on separates of impure or cloudy pyroxenes from these same rocks were higher and similar to those in the literature. We suggest this effect is related to ‘trapping,’ during crystal growth, of liquid which is enriched in the larger ions (such as Rb and Cs) due to lack of diffusion equilibrium in the liquid. Partition coefficient values for olivine and plagioclase from one of these same rocks were also determined.     

Diffusion control of garnet growth,Harpswell Neck,Maine, USA

A detailed analysis of chemical zoning in two garnet crystals from Harpswell Neck, Maine, forms the basis of an interpretation of garnet nucleation and growth mechanisms. Garnet apparently nucleates initially on crenulations of mica and chlorite and quickly overgrows the entire crenulation, giving rise to complex two‐dimensional zoning patterns depending on the orientation of the thin section cut. Contours of Ca zoning cross those of Mn, Fe and Mg, indicating a lack of equilibrium among these major garnet constituents. Zoning of Fe, Mg and Mn is interpreted to reflect equilibrium with the rock matrix, whereas Ca zoning is interpreted to be controlled by diffusive transport between the matrix and the growing crystal. Image analysis reveals that the growth of garnet is more rapid along triple‐grain intersections than along double‐grain boundaries. Moreover, different minerals are replaced by garnet at different rates. The relative rate of replacement by garnet along double‐grain boundaries is ordered as muscovite > chlorite > plagioclase > quartz. Flux calculations reveal that replacement is limited by diffusion of Si along double‐grain boundaries to or from the local reaction site. It is concluded that multiple diffusive pathways control the bulk replacement of the rock matrix by garnet, with Si and Al transport being rate limiting in these samples.     

Diffusion of Au, Pd, Re, and P in FeNi alloys at High Pressure

Multi-anvil and piston cylinder experiments were performed to determine the effect of both pressure and temperature on the diffusivities of several siderophile elements in a Fe₉₀Ni₁₀ core-analog alloy. Activation energies were calculated to be between 244 and 257 kJ/mol for Re, Pd, and Au at 10 GPa, and 264 kJ/mol for P at 1 GPa. It was found that pressure has a marked negative effect on the diffusivities of Au, Re, and Pd, and activation volumes for these elements were calculated to be between 3 and 6 cm³/mol at 10 GPa. The effect of both temperature and pressure on P diffusion is noticeably less, and the absolute diffusivity of phosphorus is consistently higher than that of the other elements. It is inferred that the reason for this difference is because P is diffusing via an interstitial mechanism as opposed to Re, Pd, and Au which occupy regular lattice sites in the crystal. The effect of pressure and temperature together with depth in the Earth suggests that these elements may continue to exhibit different behavior at more extreme conditions. The significance of these new results lies in the ability to place constraints on many time-dependent processes that pertain to the formation and evolution of planetary cores, as well as the formation and cooling histories of other metal-rich bodies in the solar system, such as meteorites.