Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

APPLICATION OF THE ICP-MS TECHNIQUE TO TRACE ELEMENT ANALYSIS OF PERIDOTITES AND THEIR MINERALS

Inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of Rb, Sr, Ba, Zr, Hf, Nb, Ta, Th, U, Pb, Sc and 14 REE in peridotites and their constituent minerals: garnet, clinopyroxene, orthopyroxene and olivine. Determination limits for most elements are 1–10 ppb (in the solid sample), with accuracy and precision comparable to those of thermal ionisation and spark-source mass spectrometry. New data on international standards PCC-1, DTS-1, UB-N and JP-1 are reported.     

Major and trace element variation in ilmenite in the Skaergaard Intrusion: petrologic implications

Ilmenite separates from the floor (LS), roof (UBS), and wall (MBS) sequences of the Skaergaard Intrusion were analyzed for major and trace elements using DCP-AES and ICP-MS techniques. In all three sequences, FeO progressively increases, and MgO and Al₂O₃ progressively decrease with differentiation. Although trace element abundances are, in general, higher in UBS ilmenite than in MBS and LS ilmenite, all three sequences have similar trends for trace element abundance vs. crystallization. Ba, Cs, Rb, Sr, Th, U, Y, and the REEs are excluded elements in ilmenite, and remained at low abundances during differentiation. Cr, Ni, Sc, and V are included elements in ilmenite and other mafic phases, and decreased during differentiation. V contents in ilmenite, however, do not decrease significantly until the upper part of the middle zone, suggesting that magnetite did not begin to affect the magma differentiation trend until much later than when it first appears in the intrusion. Hf, Nb, Ta, and Zr, which are strongly excluded elements in silicates, are included elements in ilmenite. The element ratios Zr/Hf, Y/Ho, Nb/Ta, and U/Th are relatively constant in Skaergaard ilmenite from different parts of the intrusion, suggesting that fluid transport did not significantly effect these elements during differentiation or post-solidification cooling. Calculated partition coefficients for ilmenite in the Skaergaard Intrusion are similar to those reported from previous studies of lunar and terrestrial basalts and kimberlites, and for most elements are significantly lower than those reported for ilmenite in rhyolitic magma. Similar D_i's for Zr, Hf, Nb, and Ta suggest that ilmenite crystallization did not significantly affect Zr/Nb or Hf/Ta in the Skaergaard magma, but the ratios of Zr, Hf, Nb, or Ta to other high field strength elements, such as Th, U, Y, or the REEs, may have been altered by ilmenite fractionation.     

Analysis of Standard Reference Materials for Zr,Nb, Hf and Ta by ICP-MS after Lithium Metaborate Fusion and Cupferron Separation*

Results are presented of the determination of Zr, Nb, Hf and Ta in 74 standard reference materials by inductively coupled plasma mass spectrometry (ICP-MS). Samples are decomposed by fusion with lithium metaborate and the analytes are separated prior to analysis by precipitation of their cupferrates. Calibration is made using synthetic solutions and internal standardization with Ru (for Zr and Nb) and Re (for Hf and Ta). Accuracy is assessed by comparison with recommended values and precision is evaluated by replicate analyses of five SRMs.     

Determination of REE, Y, Nb, Zr, Hf, Ta, Th and U in Geological Reference Materials LSHC-1 and Amf-1 by Solution and Laser Ablation ICP-MS

This paper presents data on REE and Y, Nb, Zr, Hf, Ta, Th and U abundances for two candidate reference materials (RMs), spinel lherzolite LSHC-1 and amphibole Amf-1, being currently developed at the Institute of Geochemistry SB RAS, Irkutsk. To determine the contents of these elements inductively coupled plasma-mass spectrometry was applied with: (i) solution nebulisation (solution ICP-MS) and (ii) laser ablation (LA-ICP-MS) of fused glass disks. The precision of results obtained by both techniques was better than 6% RSD for most elements. Accuracy was assessed by using the geochemical RMs JB-2, JGb-1 (GSJ) and MAG-1 (USGS). The trace element results by solution ICP-MS for JGb-1 and JB-2 agree with reference values presented by Imai et al. (1995, this Journal) within 1–10%. Significant differences were found for Nb and Ta determinations. The accuracy of LA-ICP-MS results evaluated by RM MAG-1 was within 4%, except for Eu (about 10%). The analytical results obtained for LSHC-1 and Amf-1 by solution ICP-MS and LA-ICP-MS were in good agreement with each other and with INAA and XRF data presented for the certification of these RMs. They can be considered as the indicative values for assigning certified values to the above-mentioned RMs.     

Pedo-geochemical baseline content levels and soil quality reference values of trace elements in soils from the Mediterranean (Castilla La Mancha, Spain)

To evaluate trace element soil contamination, geochemical baseline contents and reference values need to be established. Pedo-geochemical baseline levels of trace elements in 72 soil samples of 24 soil profiles from the Mediterranean, Castilla La Mancha, are assessed and soil quality reference values are calculated. Reference value contents (in mg kg^?1) were: Sc 50.8; V 123.2; Cr 113.4; Co 20.8; Ni 42.6; Cu 27.0; Zn 86.5; Ga 26.7; Ge 1.3; As 16.7; Se 1.4; Br 20.1; Rb 234.7; Sr 1868.4; Y 38.3; Zr 413.1; Nb 18.7; Mo 2.0; Ag 7.8; Cd 4.4; Sn 8.7; Sb 5.7; I 25.4; Cs 14.2; Ba 1049.3; La 348.4; Ce 97.9; Nd 40.1; Sm 10.7; Yb 4.2; Hf 10.0; Ta 4.0; W 5.5; Tl 2.3; Pb 44.2; Bi 2.2; Th 21.6; U 10.3. The contents obtained for some elements are below or close to the detection limit: Co, Ge, Se, Mo, Ag, Cd, Sb, Yb, Hf, Ta, W, Tl and Bi. The element content ranges (the maximum value minus the minimum value) are: Sc 55.0, V 196.0, Cr 346.0, Co 64.4, Ni 188.7, Cu 49.5, Zn 102.3, Ga 28.7, Ge 1.5, As 26.4, Se 0.9, Br 33.0 Rb 432.7, Sr 3372.6, Y 39.8, Zr 523.2, Nb 59.7, Mo 3.9, Ag 10.1, Cd 1.8, Sn 75.2, Sb 9.9, I 68.0, Cs 17.6, Ba 1394.9, La 51.3, Ce 93.5, Nd 52.5, Sm 11.2, Yb 4.2, Hf 11.3, Ta 6.3, W 5.2, Tl 2.1, Pb 96.4, Bi 3.0, Th 24.4, U 16.4 (in mg kg^?1). The spatial distribution of the elements was affected mainly by the nature of the bedrock and by pedological processes. The upper limit of expected background variation for each trace element in the soil is documented, as is its range as a criterion for evaluating which sites may require decontamination.     

Trace elements and their behaviour during the combustion of marine oil shale from Changliang Mountain, northern Tibet, China

The Shengli River–Changshe Mountain oil shale zone represents a potentially large marine oil shale resource in China. With the aim of better understanding the geochemistry of trace elements in marine oil shale and its combustion residues, 40 raw samples, 27 oil shale combustion residues and 29 selected minerals from Changliang Mountain oil shale are studied for geochemical analyses. The contents of Se, Cd, Mo, As, Cs, Pb, Sr and U in the oil shale samples are enriched from 1.47 to 33.91 times as compared with the Clarke values, whereas the concentrations of other elements are slightly higher/lower than the respective worldwide means. The most enriched elements in oil shale combustion residues are Se, Cd, Mo, As and U with enrichment values from 4.78 to 50.92. Trace elements with high volatile behaviour such as As, Co, Ni, Sc, Sn and V occur predominantly in organic matter and/or sulphides. Other non-volatile or slightly volatile trace elements (e.g., Be, Bi, Cs, Cu, Ga, Hf, Li, Nb, Rb, Ta, Th, W, Zr and REEs) may occur mainly in original and relatively refractory minerals in raw oil shale. The potentially hazardous trace elements in Changliang Mountain oil shale include As, Cd, Mo and Se. Arsenic and Se are controlled mainly by Fe-bearing minerals (probably pyrite) in Changliang Mountain oil shale. Cadmium is present mainly in dolomite, while Mo occurs mainly in organic matter.     

Concentration and distribution of elements in Late Permian coals from western Guizhou Province,China

With the aim of better understanding geochemistry of coal, 71 Late Permian whole-seam coal channel samples from western Guizhou Province, Southwest China were studied and 57 elements in them were determined. The contents of Al, Ca, Co, Cr, Cu, Fe, Ga, Hf, K, Li, Mn, Mo, Nb, Ni, Sn, Ta, Ti, Th, U, V, Zr, and REEs in the Late Permian coals from western Guizhou Province are higher than the arithmetic means for the corresponding elements in the US coals, whereas As, Ba, Br, F, Hg, P, Se, and Tl are lower. Compared to common Chinese coals, the contents of Co, Cr, Cu, Ga, Hf, Li, Mn, Mo, Ni, Sc, Sn, Ti, U, V, Zn, and Zr in western Guizhou coals are higher, and As, F, Hg, Rb, Sb, Tl, and W are lower. Five groups of elements may be classified according to their mode of occurrence in coal: The first two, Group A, Tm–Yb–Lu–Y–Er–Ho–Dy–Tb–Ce–La–Nd–Pr–Gd–Sm, and Group B, As–Sr–K–Rb–Ba–F–Ash–Si–Sn–Ga–Hf–Al–Ta–Zr–Be–Th–Na, have high positive correlation coefficients with ash yield and they show mainly inorganic affinity. Some elements from Group B, such as Ba, Be, Ga, Hf, and Th, are also characterized by significant aluminosilicate affinity. In addition, arsenic also exhibits high sulfide affinity (r_S–Fe>0.5). The elements, which have negative or lower positive correlation coefficients with ash yield (with exceptions of Bi, Cs, Nb, Mn, Se, and Ti), are grouped in other four associations: Group C, Cr–V–Mo–U–Cd–Tl; Group D, Hg–Li–Sc–Ti–Eu–Nb–Cs–W; Group E, Bi–Sb; and Group F, Co–Ni–Cu–Pb–Zn–Mg–Se–Ca–Mn–S–Fe. The correlation coefficients of some elements, including Co, Cr, Cu, Fe, Hg, Li, Mo, Ni, P, S, Sc, U, V, and Zn, with ash yield are below the statistically significant value. Only Cr and Cu are negatively correlated to ash yield (−0.07 and −0.01, respectively), showing intermediate (organic and inorganic) affinity. Manganese and Fe are characterized by carbonate affinity probably due to high content of epigenetic veined ankerite in some coals. Phosphorus has low correlation coefficients with any other elements and is not included in these six associations. There are five possible genetic types of enrichment of elements in coal from western Guizhou Province: source rock, volcanic ash, low-temperature hydrothermal fluid, groundwater, and magmatic hydrothermal inputs.     

Rutile R632 – A New Natural Reference Material for U‐Pb and Zr Determination

A new natural rutile reference material is presented, suitable for U‐Pb dating and Zr‐in‐rutile thermometry by microbeam methods. U‐Pb dating of rutile R632 using laser ablation ICP‐MS with both magnetic sector field and quadrupole instruments as well as isotope dilution‐thermal ionisation mass spectrometry yielded a concordia age of 496 ± 2 Ma. The high U content (> 300 μg g^?1) enabled measurement of high‐precision U‐Pb ages despite its young age. The sample was found to have a Zr content of 4294 ± 196 μg g^?1, which makes it an excellent complementary reference material for Zr‐in‐rutile thermometry. Individual rutile grains have homogeneous compositions of a number of other trace elements including V, Cr, Fe, Nb, Mo, Sn, Sb, Hf, Ta and W. This newly characterised material significantly expands the range of available rutile reference materials relevant for age and temperature determinations.     

Extreme enrichment of Sb, Tl and other trace elements in altered MORB

We have analyzed 25 trace elements (e.g., Sb, Tl, Sn, rare earth elements (REE), Th, U, Nb, Pb, Zr, Hf, and Y) in altered mid-ocean ridge basalts (MORB) from locations near the mouth of the Gulf of California. Our results imply that the heavy REE and Y are not seriously affected by seawater alteration, in agreement with previous studies. The elements Zr, Hf, Nb, light REE and Sr are enriched up to a factor of 2 in some extremely altered samples. However, element ratios between Zr, Hf, and Nb (e.g., Zr/Hf, and Zr/Nb) are not greatly affected, presumably due to the chemical similarity of these elements during any exchange process. The enrichment of Th and Sn is even higher. Antimony, Tl, Cs, Rb, Rb, and Ba are most easily altered by water-rock interaction and are therefore the best indicators for seawater alteration. The enrichment factor of the most mobile element Sb is up to 2000.

There is a weak correlation between the concentration in seawater and the enrichment factors. On the other hand, the worldwide pelagic clay pattern matches the enrichment pattern much more closely, and the limited data available for local oceanic sediments give an even better correlation. A plausible model to explain the enrichment pattern may be an elemental exchange between basalt and seawater that had interacted earlier with overlying sediments.     

岩石中多元素的X射线荧光光谱测定——经验系数法

采用经验和数法校正基体效应,X荧光光谱测定样品中的主、次痕量元素是一种简便而快速的方法,但由于经验系数的求取很大程度上取决于标准样品的类型、含量范围和计算方法,往往使用范围有一定的局限性,本文提出的标准分类法计算经验系数,     

流域上游基岩与下游冲积平原土壤化学组成的对比

对海河水系流域、鄱阳湖水系流域上游的基岩与下游的冲积平原土壤之间化学组成的对比研究显示,下游冲积物土壤的化学组成明显地受源岩成分、形成过程和形成环境的影响。流域上游基岩的一些特征元素在冲积物土壤中被明显地继承,如海河流域基岩和土壤中的CO2、CaO、MgO、FeO、Sr,鄱阳湖流域基岩和土壤中的W、Sn、Bi、U、Th、Pb、Rb、Tl、As、Sb、Se、Hg、Nb、Ta、Hf、B、Be、Ge、Pt、Pd、Y。受形成过程和形成环境的影响,处于暖温带半湿润季风气候下的海河流域冲积平原土壤以极富集CO2、CaO、Na2O、Cl,显著富集MgO、FeO、Sr,富集P、S为特征;而处于亚热带湿润季风气候下的鄱阳湖流域冲积平原土壤则以显著富集Hg、Se和富集Al2O3、Fe2O3H2O^＋、W、Sn、Bi、Mo、U、Th、Pb、Rb、Cs、Tl、Li、Be、B、Ga、Ge、Nb、Ta、Zr、Hf、As、Sb、Co、Cr、Ti、V、Zn、Pt、Pd、REE、Y为特征。无论是海河流域还是鄱阳湖流域的冲积平原土壤,均富集As、Sb、Hg、B、Cl、W、Sn、Bi、Pb、Se、Ge、Li、Cs、Cu、Au、Fe2O3、V、Cr、Ni、Zr、Hf、Y。     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO₄ high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml⁻¹ in solution (equivalent to 0.08 to 16.2 ng g⁻¹ in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g⁻¹) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g⁻¹). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.     

The Direct Determination of Rare Earth Elements in Basaltic and Related Rocks using ICP-MS: Testing the Efficiency of Microwave Oven Sample Decomposition Procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelândia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO₃, 100 mg of sample), and that for the Niquelândia samples also by Parr bomb treatment (5 days at 200°C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelândia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.     

广西苍梧社洞钨钼矿床花岗岩类岩石的地球化学特征及其与成矿关系

广西苍梧社洞钨钼矿是与花岗岩类有关的矿床。矿区主要花岗岩类包括加里东期花岗闪长岩、花岗闪长斑岩和燕山晚期花岗斑岩。加里东期花岗闪长岩、花岗闪长斑岩具有低Si、K,富Na、Al和基性组分特征,属于强过铝质的正常钙碱性系列岩石;稀土总量低,轻重稀土分馏明显,弱负Eu异常(δEu=0.62~0.70);Ti、Nb、Ta亏损,Th、U、Pb、Zr、Hf富集,Rb/Sr平均值为0.78,明显富集W、Cu、Mo,属于I型花岗岩,为陆内造山带碰撞早期挤压背景下岩浆活动的产物,表现为对钨、钼、铜的成矿专属性。燕山晚期花岗斑岩具有高Si、K,贫Na、Ca和基性组分,属于强过铝质的高钾-中钾钙碱性系列岩石;稀土总量高,轻重稀土分馏不明显,强负Eu异常(δEu=0.03~0.06);Ti、Ba、K、Eu亏损,Th、U、Sm、Dy、Y、Ho、Yb、Lu富集程度更高,Rb/Sr平均值为7.56,明显富集Sn、Bi,属于燕山晚期岩浆演化程度较高的S型花岗岩,为碰撞后伸展环境的板内花岗岩,表现为对锡、金的成矿专属性。     

电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中的铌钽锆铪

建立电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中铌、钽、锆、铪四种元素的分析方法。将样品与氢氧化钠、过氧化钠混合物放入高温炉中,熔融分解完全,用热水提取,过滤后弃去滤液,将滤纸及沉淀用酒石酸-盐酸溶液溶解,稀释至刻度测定。方法检出限(3s)为:LD(Nb)=0.08μg/g,LD(Ta)=0.04μg/g,LD(Zr)=0.5μg/g,LD(Hf)=0.04μg/g,精密度(RSD%,n=6)为:0.84%~4.21%。该测定方法具有灵敏度高、精密度好、分析速度快、线性范围宽、操作性强等优势。采用该方法对国家一级标准物质进行测定表明,其结果与标准值吻合。此方法已在实际地质调查样品分析中得到应用。     

Synthesis and Preliminary Characterisation of New Silicate, Phosphate and Titanite Reference Glasses

Eleven synthetic silicate and phosphate glasses were prepared to serve as reference materials for in situ microanalysis of clinopyroxenes, apatite and titanite, and other phosphate and titanite phases. Analytical results using different micro-analytical techniques showed that the glass fragments were homogeneous in major and trace elements down to the micrometre scale. Trace element determinations using inductively coupled plasma-mass spectrometry (ICP-MS), multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ionisation mass spectrometry (SIMS) showed good agreement for most elements (Li, Be, B, Cs, Rb, Ba, Sr, Ga, Pb, U, Th, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, Zr, Hf, Ta, Nb) studied and provide provisional recommended values.     

桂西田阳堆积型铝土矿矿物学及地球化学

[摘 要]桂西田阳堆积型铝土矿产于第四纪红土层中。本文通过对桂西田阳第四系堆积型铝土矿进行一系列矿物学与地球化学研究,探索铝土矿的物质来源。矿物学分析显示铝土矿石中主要矿物为硬水铝石、赤铁矿和锐钛矿,含有少量高岭石、鲕绿泥石、三水铝石、针铁矿、金红石、伊利石、蒙脱石和石英等。地球化学分析显示,组成铝土矿石的主要化学组分有Al₂O₃、Fe₂O₃、SiO₂、TiO₂、FeO 和H₂O⁺;微量元素分析显示,铝土矿石相对地壳和原始地幔富集B、Li、Ga、Zr、Hf、Nb、Ta、W、Th、U 等元素,而亏损Ni、Cr 等元素。矿石中明显富集稀土元素,稀土总量变化大,轻重稀土分异明显,轻稀土元素富集明显;矿石具有明显的铈异常和铕异常,且铕异常相对稳定,为一致的负异常。元素相关性分析显示常量元素间相关性较差;部分微量元素如Zr、Hf、Nb 和Ta 间呈现出较高的正相关性。通过Zr/ Hf、Nb/ Ta 图解、Eu/ Eu* - TiO₂/ Al₂O₃图解和Zr-Cr-Ga 图解综合分析显示铝土矿物质来源复杂,底板碳酸盐岩和周围火成岩都为铝土矿提供物源。     

Compositional Heterogeneity in NIST SRM 610-617 Glasses

Extensive compositional heterogeneity is shown to affect at least twenty four of the doped trace elements in the NIST SRM 610-617 glasses.
Compositional profiling and mapping using laser ablation ICP-MS reveals that all NIST SRM 610-617 wafers examined here contain domains that are significantly depleted in Ag, As, Au, B, Bi, Cd, Cr, Cs, Mo, Pb, Re, (Rh), Sb, Se, Te, Tl and W, and antithetically enriched in Cu (and Pt), with large enrichments in Cd, Fe and Mn also being encountered in some cases. These domains are visible in doubly polished wafers by unaided visual inspection and by transmitted light and schlieren microscopy. They occur in close proximity to the wafer perimeters and also as stretched and complexly folded forms within wafer interiors. The chemical and optical properties of these heterogeneous domains are consistent with those of compositional cords, a phenomenon of glass manufacture where glass bulk composition and physical properties are modified by loss of volatile components from the molten glass surface. The NIST SRM 610-617 glasses may be considered reliable reference materials for microanalysis of only between one half and two thirds of the trace elements with which they were doped, including Be, Mg, Sr, Ba, Sc, Y, REE, V, Zr, Hf, Nb, Ta, Th, U, Ga, In, Sn, Co, Ni and Zn. These elements show no evidence of significant heterogeneity, indicating that the original glass constituents and possible residues remaining in the furnace from preceding glass batch fusions were well homogenised during manufacture.     

THE GEOCHEMISTRY OF TANTALUM AND NIOBIUM

Ta and Nb are associated in nature. Both are oxyphile and are related geochemically to Fe, Mn, Ti, rare earths U, Th, Zr, W, Sn, Bi, and Sb. Both accompany the alkali metals,especially Na and Li. Their close relationship explains their isomorphism in mineral-forming processes. Zr, W, and Sn entrain Ta and Nb in the crystal lattices of their minerals in limited amounts. The concentration of Ta and Nb increases in the course of magma evolution from ultrabasic to alkalic. Nb predominates over Ta in the main kinds of rocks by from 5:1 to 17:1. Only in granite pegmatites is Ta dominant. In granitic rocks Ta and Nb are associated with Fe, Mn, Bi, Sb, W, and Sn. In granosyenitic complexes they form complex minerals with Ti, rare earths of the Y subgroup, U, and Th. Concentrations of Ta and Nb in granitic and granosyenitic complexes increase toward the end of the magmatic and pegmatitic processes, and afterward diminish toward the end of the pneumatolytic-hydrothermal processes. In alkalic complexes Ta and Nb are associated with Ti, rare earths of the Ce group, and Th. Concentrations of Ta and Ni in alkalic massifs are caused by magmatic differentiation. In alkalic ultrabasic complexes, in magmatic and pegmatitic processes, Ta and Nb do not form independent minerals but enter into minerals of Ti and Fe, i. e. perovskite, titanomagnitite, and pyroxenes. --M. Russell.