同位素稀释—感耦等离子体质谱法测定钐铕钆的研究

文章研究了地质样品中稀土元素Ｓｍ，Ｅｕ，Ｇｄ的同位素稀释－感耦等离子体质谱的测定方法。验证了同位素稀释法不受基体的影响，实验了利用Ｐ５０７树脂分离干扰元素Ｂａ，Ｌａ和Ｐｒ的条件。Ｓｍ，Ｅｕ，Ｇｄ的检出限（ｎｇ／ｇ）分别为１５、２．７１、１２；对样样ＧＳＤ－１０平行测定１０次，各元素的相对标准偏差均＜２．５％；标样测定结果与推荐值相符。     

色层分离－端视电感耦合等离子体发射光谱法测定高纯氧化铕中稀土杂质元素

对Ｐ５０７萃淋树脂分离稀土元素的条件进行了实验，拟定了以Ｐ５０７萃淋树脂为固定相，ＨＣｌ为流动相分离４Ｎ级荧光材料Ｅｕ＿２Ｏ＿３中１４种稀土杂质元素的流程，使被测杂质与基体Ｅｕ＿２Ｏ＿３达到了较好的分离；再用阳离子交换树脂分离被测液中非稀土杂质元素。选择了端视ＩＣＰ－ＡＥＳ测量稀土杂质元素的最佳条件。称样量５０ｍｇ时各杂质组分的测定下限（ｕｇ／ｇ）为：ＣｅＯ＿２、Ｐｒ＿６Ｏ＿（１１）、Ｎｄ＿２Ｏ＿３、Ｓｍ＿２Ｏ＿３、Ｔｂ＿４Ｏ＿７、Ｈｏ＿２Ｏ＿３、Ｅｒ＿２Ｏ＿３，Ｔｍ＿２Ｏ＿３、Ｌｕ＿２Ｏ＿３０．４，Ｌａ＿２Ｏ＿３、Ｇｄ＿２Ｏ＿３、０．２，Ｄｙ＿２Ｏ＿３、Ｙ＿２Ｏ＿３０．０４，Ｙｂ＿２Ｏ＿３０．０２。６次取样分析，各杂质组分加入量为１０ｕｇ／ｇ（ＣｅＯ＿２为２ｕｇ／ｇ），加入回收率在８４％～１１２％；ＲＳＤ＜１３％。方法可用于纯度在９９．９９％～９９．９９９５％Ｅｕ＿２Ｏ＿３中１４种稀土杂质元素的测定。     

未经分离和预富集条件下用ICP—AES测定硅酸盐岩中的10种稀土元素和钇

未经离子交换分离和预富集,采用电感耦合等离子体原子发射光谱法（ＩＣＰ－ＡＥＳ）测定了８种国际岩矿标样中的镧,铈,钕,钐,铕,钆,镝,铒,镱,镥和钇。Ｌａ,Ｃｅ,Ｎｄ,Ｅｕ,Ｙｂ和Ｙ与报道值得一致,而Ｓｍ,Ｇｄ,Ｅｒ和Ｌｕ的结果准确性较差,但是,Ｓｍ,Ｇｄ,Ｅｒ和Ｌｕ的结果也可用于研究岩石成因。     

P507萃取色层分离ICP—AES法测定高纯氧化镱中14种稀土杂质元素

本文采用Ｐ５０７萃取树脂－盐酸体系色谱法对高纯氧化镱中１４种稀土杂质元素进行分离、富集,用ＩＣＰ－ＡＥＳ法测定其稀土元素含量。当上柱量为２００ｍｇＹｂ２Ｏ３时,所能达到的测定下限：Ｅｕ２Ｏ３为１μｇｇ－１;Ｙ２Ｏ３,Ｇｄ２Ｏ３,Ｄｙ２Ｏ３,Ｈｏ２Ｏ３,Ｔｍ２Ｏ３,Ｌｕ２Ｏ３为２μｇｇ－１;Ｌａ２Ｏ３,Ｅｒ２Ｏ３为４μｇｇ－１;Ｐｒ６Ｏ１１,Ｎｄ２Ｏ３,Ｓｍ２Ｏ３,Ｔｂ４Ｏ７为８μｇｇ－１;ＣｅＯ２为１６μｇｇ－１。５次取样分离,加入试验回收率在８８％—１１２％之间,相对标准偏差＜１０％。本方法可适用于纯度为９９．９５％—９９．９９％的氧化镱中１４种稀土杂质元素的测定。     

硅同位素标准物质的研制

本文所研制的硅同位素标准物质为：ＧＴＢ１，选用震旦亚界长城系常州沟组石英砂岩中的石英；ＧＴＢ２，选用上海试剂一厂生产的高纯二氧化硅试剂。２个标准物质均按国家计量技术规范统一标准物质〈ＪＪＧ１００６８６〉的规定，用ＳｉＦ４法进行了均匀性检验及定值分析工作。结果表明其硅同位素组成均匀，定值准确，并获得了ＧＴＢ１标准物质的δ３０ＳｉＮＢＳ２８（‰）为－０．０２±０．１０，ＧＴＢ２标准物质的δ３０ＳｉＮＢＳ２８（‰）为－２．６８±０．１０。经两年多的稳定性检查，硅同位素值无变化。     

氢化物发生原子荧光法和无火焰原子荧光法连续测定地球化学样品中…

建立了一种连续测定Ａｓ、Ｓｂ、Ｂｉ、Ｈｇ四元素的方法，对测汞用还原剂及几种测量体系进行了比较，采用对原子化器适当加温的无火焰原子荧光法测汞，以ＫＭｎＯ４消除Ｔｅ、Ｓｅ对汞测定的干扰。本方法Ａｓ、Ｓｂ、Ｂｉ、Ｈｇ四元素的检出限分别为２．０１×１０＾－１０ｇ／ｍｌ１．５６×１０＾－１０ｇ／ｍｌ、２．９８×１０６－１０ｇ／ｍｌ；４．２×１０＾－１１ｇ／ｍｌ；对ＧＳＳＩ平行测定１１欠，Ｈｇ的标准偏差为２．     

蚀变超基性岩金（镍）矿床中的贵金属元素──以云南墨江金矿和陕西煎茶岭金矿为例

云南墨江金矿和陕西煎茶岭金矿中Ａｇ、Ａｕ和ＰＧＥ（铂族元素）的丰度和共生状况如下：（１）两矿床中的Ａｇ－Ａｕ关系呈三种情况：硅质岩型矿石和其他类型低品位金矿石中Ａｇ－Ａｕ基本上不具相关关系；石英脉型矿石中Ａｇ－Ａｕ呈明显的正相关关系；氧化矿石中Ａｇ－Ａｕ呈负相关关系。（２）所有样品中的ＰＧＥ均低于７１×１０（－６），其ＰＧＥ的特征是Ｐｔ≥Ｐｄ和Ｒｕ＞Ｏｓ、Ｉｒ、Ｒｈ。（３）这些样品的地幔标准化ＰＧＥ分布模式是以Ｒｈ为峰的上凸曲线，而墨江样品又具Ｉｒ的负异常。与一般超基性岩的情况不同，这些样品的模式曲线中Ｐｄ－Ａｕ部分呈陡弯折，它表明矿化元素金可能主要由区域成矿流体提供。     

华北地台前寒武纪变质基底的Sm－Nd同位素地质信息

华北前寒武纪变质基底的Ｓｍ－Ｎｄ同位素资料，主要来自冀东、辽东、内蒙古中部，五台－太行、河南和鲁西等地早前寒武纪以基性岩为主的表壳岩和深成酸性侵入体，也有少量副变质岩的分析结果。已搜集的华北地台前寒武纪变质基底的３０４个Ｓｍ－Ｎｄ分析资料表明，除同位素年龄信息外，作为壳－幔演化示踪剂，给出了岩石圈早期演化的重要信息：除已由Ｕ－ｐｂ法证实的冀东曹庄、辽东鞍山有≥３．８Ｇａ的地壳残留外，Ｓｍ－Ｎｄ资料还暗示吕粱和登封一带存在＞３．５Ｇａ的古老地壳。在华北地台上，除＞３．５Ｇａ的早期壳－幔分离事件外，３．２～３．６Ｇａ，２．６～３．０Ｇａ和２．０～２．２Ｇａ分别为三次造壳的高峰时间。来自华北不同地区的Ｓｍ－Ｎｄ资料还表明，在３．０Ｇａ以前即存在一个规模较大的古老地壳，加之晚太古的造壳规模，太古宙地壳规模之宏大已与现代地壳相近似。除壳－幔分离的造壳事件外，华北地台早前寒武纪地壳活化再造十分强烈。活化再造形成的酸性侵入体的Ｓｍ－Ｎｄ同位素资料显示Ｔ＿（ＤＭ）＝２．６～２．８Ｇａ是活化再造的最高峰时期。     

横岭关铜矿床地球化学研究

对横岭关铜矿床中稀土元素、同位素和矿物包裹体地球化学研究表明，矿床形成温度为３５０℃±３０℃；压力为３８×１０~５Ｐａ～２４０×１０~５Ｐａ；盐度为３０ｗｔ％～４２ｗｔ％；ｌｏｇｆｏ_２为－３０．４１～－３１．４７；ｌｏｇｆｓ_２为－５．４～－８；ｐＨ值为７．３；ｌｏｇｆｃｏ_２为－２．４９；铜的溶解度（ｌｏｇｍ_（Ｃｕ））为－５．８７～－２．２１。围岩的铅－铅同位素年龄为１７７５×１０~６ａ，矿石的铅－铅同位素年龄为１８４５×１０~６ａ；矿石硫同位素组成，δ~（３４）Ｓ为－８．１‰～３６．９‰，显示出硫同位素为非平衡特征；碳酸盐岩的碳同位素组成，δ~（１３）Ｃ为－７．１‰～－２．６‰，δ~（１３）Ｃ_（∑Ｃ）为－５．３‰；成矿流体的氢氧同位素组成具有变质热卤水的特点，认为该矿床属于变质热卤水成矿。     

4l0哌啶树脂分离富集－原子吸收测定化探样品中痕量镉

研究了４１０哌啶树脂对Ｃｄ的吸附行为，在２％～２０％ＨＣＩ介质中［ＣｄＣｌ＿３］￣－被树脂吸附，采用４％～３０／ＨＮＯ＿３溶液可以解脱Ｃｄ，回收率在９６％以上。测定了Ｃｄ在该树脂上的分配系数为５４９０，对含Ｃｄ０．０６７μｇ／ｇ的标样ＧＳＲ－３平行测定６次，相对标准偏差为９．５％。方法用于化探样品中０．０Ｘ×１０￣－６级Ｃｄ的测定，结果满意。     

Pressure-Dependence of Rare Earth Element Distribution in Amphibolite- and Granulite- Grade Garnets. A LA-ICP-MS Study

Using an excimer (KrF) laser ablation ICP-MS system, we studied the distribution of REE in garnets from metapelites and metabasites from Ivrea-Verbano (Western Alps, Italy) and from the Peña Negra Anatectic Complex (Central Iberia), finding systematic variations that correlate well with the metamorphic grade. Chondrite-normalized REE patterns of garnets from amphibolite-grade metapelites have lower-than-chondrite levels from La to Sm, a very small or no Eu anomaly, and a steep rise in the abundance of heavy REE as the atomic number increases. Metapelitic garnets from the amphibolite-granulite transition have a marked Eu negative anomaly and are enriched in MREE such that Sm is 10-15 times chondrite and the pattern is almost flat from Dy to Yb-Lu. In garnets from granulite-grade metapelites, the intensity of the Eu anomaly and the relative concentration of Nd, Sm, Gd and Tb increase, with almost flat chondrite-normalized patterns from Sm to Lu. Garnets from mafic granulites are remarkably similar to those of metapelitic garnets equilibrated at the same pressure, except for the Eu anomaly. The apparent paradox of enhanced uptake of larger REE ions with increasing pressure is attributed to the 3M²⁺ 2REE³⁺+ vacancy substitution, which produces a net decrease in the dimensions of the unit-cell of garnet. Variations in REE patterns depend essentially on the pressure and have little dependence on either temperature, bulk-composition of garnet, or REE whole-rock composition, so they could represent a new approach for geobarometric studies. The best numerical parameter to express pressure-related variations of REE distribution in garnets is the Gd/Dy ratio which does not seem perceptibly affected by disequilibrium partitioning. The regression equation between GASP pressure and the average Gd/Dy^garnet is P = 3.6 + 5.6 Gd/Dy. This equation seems to be reliable for garnets: (1)equilibrated within a pressure range of 4-9 kbar, (2) coexisting with modal monazite; and (3) with unit-cell dimensions under 11.46 Å.     

高分辨电感耦合等离子体质谱法测定地质样品中稀土元素的氧化物干扰研究

电感耦合等离子体质谱(ICP-MS)用于测定稀土元素经常会引起M+、MO+、MOH+离子的质谱重叠干扰,其中制约分析准确度和精密度的主要因素是多原子离子干扰,尤其是轻稀土元素的氧化物和氢氧化物对重稀土元素的干扰,以及钡的7个天然同位素形成的氧化物和氢氧化物对轻稀土元素的干扰.本文采用高温高压密闭消解地质样品,高分辨电感耦合等离子体质谱法(ICP-MS)测定其中的痕量稀土元素,研究了低、中、高三种分辨率模式下氧化物的干扰情况,确定了最佳的测定同位素和合适的分辨率.分析结果表明,在低、中分辨率模式下,轻稀土元素Ce、Pr、Nd、Sm的氧化物和Ba的氧化物干扰明显,Gd元素的测定值严重偏离;在高分辨模式下,Ba氧化物对Eu的干扰以及大部分轻稀土元素氧化物对重稀土元素的干扰基本可以消除,无需进行校正,而只有157Gd受到141pr16O的干扰突出,当样品中Pr/Gd的浓度比值大于100时,Gd的测量值必须进行数学校正.     

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。     

Determination of rare-earth elements in USGS standard rocks by mixed-solvent ion exchange and mass-spectrometric isotope dilution

The development is described of a mixed-solvent ion-exchange technique for separating trace amounts of rare-earth elements from silicate rocks and minerals. A two-column method is used, bulk separation of rare earths from other elements being accomplished on the first, and separation into three groups for mass-spectrometric analysis on the second. This has been applied to the determination of nine REE (La, Ce, Nd, Sm, Eu, Gd, Dy, Er and Yb) in standard rock samples. Smooth variation of the chondrite-normalized abundance distributions and comparison with other published results indicate that the accuracy of the method, with the exception of La, is generally ± 2%.     

电感耦合等离子体质谱法测定地质样品中铜锌铕钆铽的干扰及校正

由于电感耦合等离子体质谱(ICP-MS)分析不是在封闭的真空系统中进行,在测定过程中,气体、水和酸产生的一些离子都可能进入检测系统,产生干扰,严重影响痕量元素的准确分析。文章采用氢氟酸-硝酸封闭压力酸溶分解样品,ICP-MS法同时测定地质样品中Cu、Zn、Eu、Gd、Tb,研究了Ti、Ba、Ce、Pr、Nd对Cu、Zn、Eu、Gd、Tb的干扰情况。实验选择质量数65Cu、66Zn、153Eu、157Gd、159Tb作为测定同位素,用干扰系数脱机校正法校正分别来自Ti、Ba、Ce、Pr、Nd的氧化物重叠干扰,有效地解决了被干扰元素在测定时数值准确度低的问题。方法检出限(稀释因子1000)为:Cu 0.47μg/g、Zn 0.82μg/g、Eu 0.002μg/g、Gd 0.004μg/g、Tb 0.002μg/g,方法精密度(RSD,n=12)<5%,准确度(RE)<5%。方法用岩石、土壤、水系沉积物国家一级标准物质进行验证,测定值与标准值相符,适用于地质样品中Cu、Zn、Eu、Gd、Tb的测定。     

云南会泽金红铅锌矿区赋矿地层及断裂构造岩稀土元素组成特征

在研究区域地质背景基础上,分析了金红铅锌矿区赋矿地层及控矿断裂构造岩的稀土元素组成特征.按其特征和配分模式得知：赋矿白云岩属于LREE富集-HREE平坦型,轻重稀土分馏程度都较高,Eu异常差异明显,Ce异常差异较大,（La/Yb）_N、（La/Sm）_N和（Gd/Yb）_N值具有一定的差异;断裂构造岩属于LREE富集-HREE平坦型,轻重稀土分馏程度都较高,Eu异常差异微弱,Ce异常差异明显,（La/Yb）_N、（La/Sm）_N和（Gd/Yb）_N值比较相似.以上特征可作为成矿预测的微观标志.     

Sm and Gd isotopic shifts of Apollo 16 and 17 drill stem samples and their implications for regolith history

The isotopic compositions of Sm and Gd in lunar regolith samples from the Apollo 16 and 17 deep drill stems showed clear isotopic shifts in ¹⁵⁰Sm /¹⁴⁹Sm (ε = +124 to +191 for A-16, and +37 to +111 for A-17) and ¹⁵⁸Gd/¹⁵⁷Gd (ε = +107 to +169 for A-16, and +31 to +84 for A-17) corresponding to neutron fluences of (5.68-9.03) × 10¹⁶ n cm⁻² for A-16 and (1.85-5.04) × 10¹⁶ n cm⁻² for A-17. The depth profiles of neutron fluences suggest that the regoliths at both sites were due to incomplete mixing of three different slabs which experienced individual two-stage irradiation before and after deposition of the upper slabs. The variations in REE compositions provide chemical evidence for incompletely vertical mixing of regoliths especially at upper layers of the two sites. The thermal neutron energy index estimated from the combination of Sm and Gd isotopic shifts, defined as ε_Sm/ε_Gd, shows a small variation (0.61-0.64) in the A-16 core except for the surface layer. On the other hand, a large variation in ε_Sm/ε_Gd = 0.67 to 0.83 in the A-17 core may result from complicated history such as two-stage irradiation and incomplete mixing during the gardening processes. Isotopic enrichments of ¹⁵²Gd and ¹⁵⁴Gd correlated with Eu/Gd elemental abundances and neutron fluences were also observed in almost all of 15 samples, showing evidence of neutron-capture from ¹⁵¹Eu and ¹⁵³Eu, respectively.     

Fractionation of REE in the xenotime and florencite paragenetic association from Au-REE mineral occurrences of the Nether-Polar Urals

A detailed survey of REE distribution in the xenotime and florencite paragenetic association from quartz veins of Au-REE mineral occurrences of the Nether-Polar Urals revealed maximum contents of Ce, Nd, Sm, Gd, Dy, and Y. Four of these elements form their own minerals: florencite-(Ce), -(Nd), and -(Sm) and xenotime-(Y) containing up to 25% Gd₂O₃. The compositions of the minerals are isomorphous mixtures of two different groups: Yb_pg (Y, Ho, Er, Yb, Lu, Nd, and As) and Gd_pg (Gd, Tb, Dy, Eu, and Sm) in xenotime and La_pg (La, Ce, Pr, Eu, and As) and Sm_pg (Nd, Sm, Gd, Sr, Ca, and S) in florencite. Both minerals display strong heterogeneities in the distribution of isomorphous components and two types of zoning, oscillatory and trend. The crystal cores are enriched in HREE. Variations in the composition of isomorphous mixtures are accompanied by a change in the dominant crystal forms of florencite. Redeposited varieties are distinguished by homogeneous composition, the absence of impurities, and weak correlations between elements. The REE fractionation is interpreted in terms of quantum mechanics.     

Off-Line and On-Line Determination of Eleven Rare Earth Elements in Silicate Rocks by ICP-AES Using Dowex Minicolumns for Separation of Interfering Elements in Continuous Flow Systems

The methodologies developed in this work comprise ion-exchange separation of interfering elements from rare earth elements (Fe, Al and Ca), by using resin minicolumns (Dowex-50W-X8 200-400 mesh) for the determination of La, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb and Lu by inductively coupled plasma-atomic emission spectrometry, using both off-line and on-line continuous flow systems. These methods can be used to determine rare earth elements in common silicate rocks, such as granite, basalt, rhyolite and andesite. Thirteen geochemical reference materials were used to evaluate the accuracy and precision of the off-line and on-line methods. Chondrite-normalized diagrams were obtained and compared to values reported in the literature. When compared to conventional procedures, the proposed methods provide fast and low cost rare earth elements determinations in the analysis of silicate rocks. Eighteen samples per hour could be analysed by the proposed method using the automated procedure for the determination of the eleven rare earth elements.     

贵州镇宁重晶石矿中硅质岩稀土元素地球化学研究

通过对镇宁泥盆系重晶石矿中硅质岩稀土元素地球化学特征研究,发现硅质岩稀土总量较低,轻稀土富集,δCe呈弱的负异常,δEu呈负异常到正异常,{La/Sm}N和{Gd/Yb}N值表明轻稀土分异强;通过∑REE、Ce/Ce＊、Eu/Eu＊、{La/Ce}N和{La/Lu}N参数综合分析,硅质岩沉积成岩过程中有明显的热水参与,...