Application of Laser‐Induced Breakdown Spectroscopy and Hyperspectral Images for Direct Evaluation of Chemical Elemental Profiles of Coprolites

This study demonstrates the application of laser‐induced breakdown spectroscopy (LIBS) and hyperspectral imaging to the investigation of coprolite and fossil samples. Solid samples from the Permian (seven coprolites and one fossil), Cretaceous (one coprolite) and Oligo‐Miocene (two coprolites) periods were directly analysed, and emission spectra from 186 to 1042 nm were obtained in several areas covering coprolite/fossil and rock material. Initial exploratory analyses were performed using principal component analysis with the data set normalised by the norm (Euclidean norm = 1). After identification and selection of emission lines of eleven elements (Al, Ca, Cr, Fe, K, Mg, Mn, Na, Ni, P and Si), the signals were normalised again by the relative intensity of the selected element. Phosphorus was identified mainly in the coprolites, while K and Na were primarily found in the rock material. In several cases, there was a positive correlation between Ca and P. A sample from the Oligo‐Miocene series was also analysed using inductively coupled plasma‐optical emission spectrometry (ICP‐OES) (rock and coprolites were analysed separately). Based on the quantitative results from ICP‐OES, it was confirmed that the tendency was the same as that observed with the results obtained from LIBS directly in the solid sample.     

Determination of Platinum‐Group Elements and Gold in Ferromanganese Nodule Reference Samples

A measurement procedure for determining of Ru, Pd, Ir, Pt and Au mass fractions in ferromanganese deposits by inductively coupled plasma‐mass spectrometry after acid digestion and anion exchange preconcentration is presented. To eliminate incomplete recovery after sorption preconcentration of the platinum‐group elements (PGE) and Au, a standard addition method was used. Detection limits ranged from 0.02 ng (Pd, Ir) to 0.19 ng (Ru). The measurement results for ferromanganese nodule reference material NOD‐A‐1 and NOD‐P‐1 agree with earlier reported values. Intermediate precision of PGE concentration data for nodule reference materials in this work was 5–24% (1s) and could reflect sample heterogeneity.     

A New LA‐ICP‐MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti‐in‐quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining ⁴⁸Ti mass fractions in quartz by LA‐ICP‐MS at the 1 μg g^?1 level, relevant to quartz in HP‐LT terranes. We suggest that natural quartz such as the low‐CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g^?1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of ⁴⁸Ti as a normalising mass. Average titanium mass fraction from thirty‐three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g^?1 (2s) using ⁴⁸Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of ⁴⁸Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using ⁴⁹Ti as an analyte.     

Suitability of AuRM2 as a Reference Material for Trace Element Microanalysis of Native Gold

Microanalysis of native gold specimens has been hampered by the lack of a suitable reference material (RM) known to be sufficiently homogeneous at the scale of microanalytical sampling. The suitability of gold reference material AuRM2 for microanalysis was assessed. This RM was created for bulk analysis of refined gold and was only certified for homogeneity at the bulk scale. However, it contains trace elements in appropriate mass fraction ranges for analysis of native gold. This study was not intended to provide alternative mass fractions from the original certified values, only to assess its suitability for microanalytical methods. Micro‐scale (~ 3.4 μg sample mass) heterogeneity was calculated from measurement repeatability of LA‐ICP‐MS analyses of AuRM2 by factoring in signal (represented by counting statistics) and instrument set‐up‐specific variability (determined using measurement variability of a reference material known to be homogeneous). Elements determined to be homogeneous or to have minor heterogeneity (< 10% calculated heterogeneity RSD) are Mg, Al, Ti, Fe, Ni, Cu, Zn, Se, Rh, Sn, Sb, Pt and Pb. Elements with moderate heterogeneity (10–20% heterogeneity RSD) are: Mn, As, Pd, Te and Bi. Correlation of element mass fractions indicates that micro‐scale inclusions of chalcophile‐rich phases along grain boundaries may be responsible for some of the chemical heterogeneity. However, the level of heterogeneity is statistically negligible compared with the ranges of chemical signatures observed in sample populations of native gold. Therefore, AuRM2 is shown to be sufficiently homogenous at a micro‐scale for use as a RM for microanalysis of native gold.     

东昆仑洪水川地区科科鄂阿龙岩体锆石U Pb年代学、地球化学及其地质意义

东昆仑地区出露大量呈带状分布的中生代花岗岩,是我国一条巨型花岗质岩浆岩带,它的发育与该地区岩石圈动力学演化有着密切联系.对东昆仑造山带东段南缘洪水川地区的科科鄂阿龙石英闪长岩体的岩相学、岩石地球化学和LA-ICP-MS锆石U-Pb同位素年代学研究结果显示,岩石具有3组谐和锆石年龄:第一组年龄大于402Ma,为捕获围岩的锆石年龄;第二组年龄为243.9±3.0Ma(MSWD=0.94),代表该区玄武质岩浆底侵事件;第三组年龄为218.3±1.4Ma(MSWD=0.52),代表岩体的结晶年龄.地球化学分析表明该岩体具有高Sr,低Y、Yb,高Sr/Y比值,轻重稀土分异明显,Eu异常不明显,其微量元素显示出埃达克质岩石特征.其较低的Nb、Ta和较高的Mg=、Cr、Ni含量,高Nb/Ta比值,说明了在金红石稳定域内部分熔融形成的熔体交代了岩石圈地幔.岩体的年代学及地球化学特征表明,东昆仑地区在218Ma的晚三叠世时期发生了岩石圈地壳拆沉作用,它是早期俯冲形成的玄武质岩浆底侵而形成的加厚下地壳,在高压缺水的条件下相变为榴辉岩相并拆沉进入软流圈,部分熔融的熔体在上升过程中先与岩石圈地幔反应,然后与地壳围岩发生同化混染作用,最终形成了科科鄂阿龙石英闪长岩.     

辽宁四道沟热液金矿床中石英的稀土元素的特征及意义

本文用ＩＣＰ－ＭＳ测定了辽宁四道沟金矿矿脉中石英及其中流体包裹体中的稀土元素含量,发现石英的稀土元素配分模式类似于其中流体包裹体的稀土元素配分模式,推断石英中的稀土元素主要赋存于注流体包裹体中,流体包裹体中的稀土元素了石英的稀土元素配分模式,原生包裹中的流体是和石英同源的,其稀土元素指示的是石英形成过程中流体的信息。而次生包裹体中的流体是石英形成后的流体活动产物,其稀土元素指示的是后期流体活动的信     

New ICP‐MS Results for Trace Elements in Five Iron‐Formation Reference Materials

Iron formations (IFs) typically contain low mass fractions of most trace elements, including the rare earth elements (REE), and few publications describe analytical methods dedicated to this matrix. In this study, we used bomb and table‐top acid dissolution procedures and ICP‐MS to determine the mass fractions of trace elements in IF reference materials FER‐1, FER‐2, FER‐3, FER‐4 and IF‐G. The full digestion of the IF samples with the bomb procedure required the addition of a small amount of water together with the acids. The results obtained by this method mostly agreed statistically with published values. The most remarkable exception was the higher values obtained for the heavy REE in FER‐3. The recoveries of the REE obtained with the table‐top procedure were slightly higher than those of the bomb digestion, except for the values of the heavy REE in FER‐3 and FER‐4, which were up to 30% lower than published values. Sintering of the samples with sodium peroxide was performed to determine the REE, but the results tended to be lower than those derived following acid digestion. On the whole, the recoveries showed dependence on the conditions of digestion, but subtle differences in trace mineral composition between samples also exerted influence on the analytical results for trace elements.     

西昆仑慕士塔格-公格尔印支期侵入岩岩石与锆石地球化学特征及研究意义

西昆仑造山带南侧的麻扎-康西瓦缝合带,是古特提斯洋闭合的位置。慕士塔格-公格尔作为昆仑山的主峰,紧邻该缝合带的东北侧分布,主要岩性为花岗闪长岩和黑云母二长花岗岩。作者系统研究了两种岩性的地球化学及年代学特征,探讨了岩石成因,反演了古特提斯洋的构造演化历史。岩体岩浆锆石LA-ICP-MS U-Pb测年结果显示,花岗闪长岩和黑云母二长花岗岩的成岩年龄分别为(213.0±0.5)~(215.4±0.9)Ma和(220.6±0.5)~(222.1±0.4)Ma,是晚三叠世岩浆活动的产物。两种岩性均为高硅(w(SiO2)65%)、富碱(w(K2O+Na2O)6%)、钙碱性-高钾钙碱性、准铝质(A/CNK1),富集大离子亲石元素(LILE)和轻稀土元素(LREE),亏损高场强元素(HFSE)和重稀土(HREE)。微量元素组成特征、低锆石饱和温度及高分异指数显示慕士塔格-公格尔花岗岩体为高分异I型花岗岩。岩体锆石的εHf(t)值变化范围较小,为-4.46~-0.17,指示岩浆以壳源为主。综合研究表明,慕士塔格-公格尔花岗岩体可能是同碰撞造山环境下,老的下地壳受地幔热源影响部分熔融,形成的长英质壳源岩浆侵入地壳内部而冷却结晶形成。     

川西呷村黑矿型多金属矿床热液体系稀土元素组成特征

本文首次测定了呷村黑矿矿石中流体包裹体的ＲＥＥ组成,计算了与含矿流纹岩系熔体平衡的岩浆热液ＲＥＥ含量。主成矿期流体具有轻稀土富集、Ｅｕ明显正异常的特点,但岩浆热液却具有明显的Ｅｕ负异常特征,结合热液体系氧同位素及稀土元素交换反应模拟,表明岩浆热液不是直接的成矿热液。蚀变围岩具显著的Ｅｕ正异常,其它稀土元素出现亏损。蚀变反应水／岩比值较大,蚀变岩中的ＲＥＥ组成反映了成矿热液ＲＥＥ的特点,且ＲＥＥ亏损     

大兴安岭中段柴河地区玛尼吐组火山岩年代学、地球化学及岩石成因

对大兴安岭中段柴河地区玛尼吐组火山岩进行了锆石LA-ICP-MS U-Pb年代学和岩石地球化学研究,以了解其形成时代、岩石成因及其所揭示的区域构造背景。玛尼吐组火山岩岩相学鉴定结果为安山岩、英安岩,化学成分显示其为粗面英安岩、粗面岩和英安岩。玛尼吐组火山岩锆石多呈自形半自形晶,振荡环带发育,Th/U=0.33~2.08,指示其岩浆成因。定年结果显示,玛尼吐组火山岩形成于139~148 Ma的晚侏罗世。岩石地球化学研究表明,玛尼吐组火山岩的w(SiO₂)为64.87%~68.65%,w(Al₂O₃)为15.53%~16.72%,全碱w(Na₂O+K₂O)为6.75%~9.22%,K₂O/Na₂O=0.63~1.57,属于高钾钙碱性系列。所有样品的稀土配分曲线具有相似的特征,稀土丰度总量w(∑REE)为(124.95~208.57)×10^-6,轻重稀土分馏明显,(La/Yb)_N=11.50~14.88, Eu负异常(0.45~1.17),微量元素以富集Rb、Ba、K,亏损Nb、P、Ti为特征。玛尼吐组火山岩原始岩浆来源于地壳岩石的部分熔融,形成于蒙古-鄂霍茨克缝合带闭合后的岩石圈伸展构造环境。