A rapid method for the determination of fluoride in silicate rocks

A rapid method for the analysis of fluoride in silicate rocks is described. The sample is heated in a stream of oxygen and superheated steam (pyrohydrolysis), and fluoride determined spectrophotometrically as the purple-blue double complex with the cerium chelate of alizarin fluorine blue (3-maminomethylalizarin-NN-diacetic acid). 5 p.p.m. F⁻ can readily be determined using 1 g of sample.     

Precise determination of ferrous iron in silicate rocks

We have developed a highly precise method for the determination of ferrous iron (Fe²⁺) in silicate rocks. Our new method is based on Wilson’s procedure (1955) in which surplus V⁵⁺ is used to oxidize Fe²⁺ into Fe³⁺ while equivalently reducing V⁵⁺ into V⁴⁺. Because V⁴⁺ is more resistant to atmospheric oxidation than Fe²⁺, Fe²⁺ in the sample can be determined by measuring unreacted V⁵⁺ by adding excess Fe²⁺ after sample decomposition and then titrating the unreacted Fe²⁺ with Cr⁶⁺. With our method, which involves conditioning the sample solution with 5 M H₂SO₄ in a relatively small beaker (7 mL), the oxidation of Fe²⁺ or V⁴⁺ that leads to erroneous results can be completely avoided, even in 100-h sample decompositions at 100°C. We have measured the concentration of FeO in 15 standard silicate rock powders provided by the Geological Survey of Japan (GSJ). Analytical reproducibility was better than 0.5% (1σ) for all but those samples that had small amounts of Fe²⁺ (<1.5 wt.% of FeO). Fourteen of these samples gave FeO contents significantly higher than the GSJ reference values. This likely indicates that the GSJ reference values, obtained by compiling previously published data, contain a large number of poor-quality data obtained by methods with lower recovery of Fe²⁺ caused by oxidation or insufficient sample decomposition during analyses. To achieve accurate determinations of Fe²⁺ in our method, several factors besides the oxidation must be considered, including: (1) long-term variations in the concentration of Fe²⁺ solution must be corrected; (2) excess use of the indicator must be avoided; and (3) the formation of inert FeF⁺ complex must be avoided during titration when using boric acid as a masking agent.     

Some reconnaissance observations on the combined use of ion-exchange enrichment and spectrochemical analysis for the determination of trace constituents in silicate rocks

A reconnaissance investigation has been made of the possible combined use of ion-exchange enrichment (cation and anion) and spectrochemical analysis for the determination of several rare elements, notably Ag, Be, Bi, Cd, Cs, In, La, Mo, Nb, Sn, Pb, Tl, Y and Zn, in silicate rocks and allied materials. Observations which have been carried out on granite G-1, a specimen of Cape granite, and diabase W-1, indicate that many of these elements should be easily detected in a wide variety of rocks and soils. The scope of the combined procedure seems to be immense and it is evidently possible to determine several elements in a single operation; the combined procedure should be particularly useful for investigating the general geochemistry of Bi.     

Spectrophotometric determination of micro quantities of zinc in rocks

A chemical method is presented for the determination of microgram amounts of zinc in rocks. Zinc is absorbed on anion-exchange resin from 1.2 M hydrochloric acid and eluted with 0.01 M hydrochloric acid. A diethyldithiocarbamate separation removes traces of interfering elements from the eluate. The zinc-diethyldithiocarbamate complex is extracted into chloroform at pH 8.5 and reextracted from other elements in the chloroform solution with 0.16 M hydrochloric acid and finally determined spectrophotometrically as the zincon complex at 621 mμ.The coefficient of variation of the method determined from replicate determinations of zinc on 75 selected samples of basalt, ranging in zinc content from 0.004 to 0.018 per cent, was found to be 6.3 per cent and essentially constant in the range of zinc content studied. This method of analysis has been used extensively for a study of zinc in basalts reported by Rader, Swadley, Huffman and Lipp (companion paper, 1963).     

硅酸盐岩石化学组成的ICPAES和ICPMS准确测定:酸溶与碱熔分解样品方法的对比

报道了采用酸溶和碱熔分解硅酸盐岩石样品,用ICP-AES和ICP-MS联合测定岩石的主元素和微量元素的分析方法,酸溶方法检出限低,能准确分析除SiO2以外的其他主元素和40余种微量元素;碱熔方法一次分解样品可以直接测定所有的主元素和30多种微量元素,但方法检出限增高,不能准确分析一些检出限高而含量低的元素,因此,根据不同的岩石类型,所需分析的元素种类以及研究目的,采用适当的样品分解方法,用ICP-AES和ICP-MS分析可以获得准确的主元素和微量元素数据。     

The use of an oxygen jet in the spectrochemical determination of trace amounts of Pb,Tl, Ga,Cu and Sn in some silicate rocks and minerals

A modified speotrochemical technique of determining low concentrations of the volatile elements, Pb, Tl, Ga, Cu and Sn is described. A comparatively large amount of sample is arced in a constant stream of oxygen delivered through a Stallwood jet. Detection limits of Tl and Sn are lowered sufficiently to determine these elements in most intermediate and acid igneous rocks. Ranges of values observed for all five elements in granitic rocks from Australia and South Africa and their co-existing minerals are presented.     

The systematics of lithium abundances in young volcanic rocks

Lithium is a moderately incompatible trace element in magmatic systems. High precision analyses for lithium conducted on well characterized suites of MORB and ocean island basalts suggest a bulk distribution coefficient of 0.25−0.35 and behavior which is similar to Yb during low pressure fractionation and V during melting, as long as garnet is not an important residual phase. Data for peridotites and basalts suggest a mantle lithium content of about 1.9 ppm and show that significant concentrations of lithium reside in olivine and orthopyroxene, resulting in unusual inter-mineral partitioning of Li and complex relationships between lithium and other incompatible trace elements.The lithium abundances of arc basalts are similar to those of MORB, but their Li/Yb ratios are considerably higher. The high Li/Yb suggests the addition of a Li-rich component to arc sources; relatively low Yb abundances are consistent with the derivation of some arc magmas by larger extents of melting or from a more depleted source than MORB. Although Li is enriched at arcs, K is enriched more, leading to elevated K/Li ratios in arc volcanics. The high K/Li and relatively low La/Yb of primitive arc basalts requires either incorporation of altered ocean crust into arc magma sources, or selective removal of K and Li from subducted sediments. Bulk incorporation of sediments alone does not explain the Li systematics.Data from primitive MORB indicate a relatively low (3–4 ppm) Li content for new oceanic crust. Thus, the Li flux from the ocean crust is probably <1 × 10¹¹ g/yr, and the oceanic crust may not be an important net source in the oceanic budget of lithium.     

A spectrophotometric method for the determination of rhenium in geologic materials

Existing methods for the chemical determination of rhenium have been modified and adapted for the analysis of rock, sediment, water, brine, and mineral concentrates.Little restriction is placed on sample size, but usually between 0.1 g and 100 g of solid sample is used which contains between 1 and 200 μg of rhenium giving a detection limit of 10 p.p.b. in the sample. Several liters of water sample may be used giving a detection limit of less than 1 p.p.b.The spectrophotometric method concentrates and isolates the rhenium from the sample by using carbon adsorption and solvent extraction.     

江南造山带基底变质沉积岩中锂元素分布和富集机制及对锂成矿的制约

内容提要:江南造山带是我国重要的稀有金属成矿带,已发现多处与锂相关的花岗伟晶岩型稀有金属矿床。锂等稀有金属元素在源区基底岩石中的富集是花岗伟晶岩型锂稀有金属矿床成矿的物质基础,但是江南造山带基底岩石中锂的分布及其富集机制仍不清楚。本文详细调查研究了江南造山带东段新元古代冷家溪群、双桥山群、溪口岩群和板溪群变质沉积岩和星子杂岩。这些基底变质岩的岩石类型包括变质砂岩、泥质板岩、千枚岩和云母片岩以及少量片麻岩。地球化学分析结果显示,冷家溪群、双桥山群和溪口岩群变质沉积岩具有相似的成分,变质砂岩和云母片岩-片麻岩整体上比泥质板岩和千枚岩具有较高的Si O₂含量,较低的Ti O₂、Al₂O₃、K₂O、Mg O和TFe₂O₃含量。泥质板岩和千枚岩含有更高的稀有金属元素含量,其中锂含量达到61.8×10^-6,而变质砂岩的锂丰度为44.9×10^-6。板溪群具有最低的稀有金属元素含量(Li=30.8×10     

The geochemistry of tungsten,with special reference to the rocks of the Uganda protectorate

In recent years the quality of the abundance data for many elements has improved considerably. One exception to this is the data for tungsten, which is still very sparse and contradictory in character. In this paper the use of a new photometric procedure for the determination of tungsten is described, and new abundance data presented. The sampling is restricted to a small area, but in spite of this limitation, the survey is considered to be of general interest to geochemists.The distribution of tungsten in silicate rocks is shown to be positively skewed, and where sufficient numbers of determinations have been made, is shown to approximate to lognormal. A value of 1.4 p.p.m. is recommended for the terrestial abundance of tungsten in granitic rocks: further work is required before the abundance values given for carbonate and other silicate rocks can be considered to be of general application. Regional bias of the distribution of this element in granitic rocks, and variation of tungsten content with age in the sedimentary rock systems have been recorded. These observations are considered in relation to the general geochemistry of tungsten and the distribution of this element in rock-forming minerals.     

The muscovite granites: Parental rocks to the Nanling Range tungsten mineralization in South China

Muscovite granites (MGs) in the Nanling Range (South China) occur as satellite intrusions within or surrounding batholitic biotite monzogranites (BMs). The MGs are massive and fine-grained with a porphyritic texture, and contain quartz, K-feldspar and albite in nearly equal portions. The accessory minerals in the MGs include alumina-rich minerals (e.g., Mn- and Fe-rich garnet, andalusite, topaz, and tourmaline), anatase, rutile, wolframite, cassiterite, xenotime, chalcopyrite, molybdenite, and volatile-rich minerals (e.g., microlite, topaz, tourmaline, fluorite, and calcite). Compared with the BMs, the MGs are geochemically enriched in major elements of Si, K, and Na, and incompatible trace elements of Rb, Cs, Y, U, Nb, Ta, W, Sn, Pb, Bi, Li, and Be, and depleted in major elements of Fe, Mg, Ca, Ti, and P, and compatible trace elements of Ba, Sr, Co, Ni, Cr, Cd, V as well as Zr and Hf. The chondrite-normalized REE patterns of the MGs are flat with large negative Eu anomalies. The mineralogical and geochemical features of the MGs indicate that they crystallized from highly fractionated granitic magmas. Zircons separated from the MG samples, which were collected from six different tungsten deposits, show characters of hydrothermal origin according to their morphologies, chemical compositions and inclusions. In-situ U–Pb dating of the zircons yields a weighted mean ²⁰⁶Pb/²³⁸U age of 133.4 ± 1.0 Ma. This age is similar to the mean age of the zircons from wolframite-bearing quartz veins (WQVs) in the Nanling Range (133.7 ± 1.3 Ma) reported from our previous study. Zircon Hf isotopes also reveal that the MGs and the WQVs are homologous. These mineralogical, geochemical and zirconological features indicate that the MGs are the parental rocks of the tungsten deposits in the Nanling Range. This study provides a new guidance for the exploration of magmatic-hydrothermal tungsten deposits.     

Experimental determination of the solubility of Au in silicate melts

Summary We report here new data on the solubility of Au in silicate melts of anorthite-diopside eutectic composition at a wide range of oxygen fugacities, from pure oxygen to 10^–8 atm, and at a temperature range of 1300 °C to 1480 °C. Because experiments were done with metal loops at temperatures above the Au-melting temperature, PdAu-metal-alloys had to be used. Pd-solubility data derived from the same set of experiments agree with earlier data obtained from experiments with pure Pd-metal (Borisov et al., 1994a). The results of the present experiments show that Pd-solubilities are by a factor of 2 to 6 higher than Au-solubilities. Both, Au and Pd solubilities decrease with decreasing oxygen fugacity. At oxygen fugacities below the iron-wiistite buffer (IW) Au solubility increases with decreasing fO₂ probably reflecting formation of Au-silicides at such reducing conditions. Compared to Pd, Au has higher activity coefficients in Fe-metal and lower solubility in silicate melts. This leads to similar metal-silicate partition coefficients for both elements. At a temperature of 1350 °C and an oxygen fugacity corresponding to IW-2 D^Au (met/sil) is about 2.5 · 10⁷ and D^Pd (met/sil) about 1.6 · 10⁷. Thus similar behavior is expected during metal separation in planetary bodies including core formation in the Earth. The metal/silicate partition coefficient of Ir is, however, by several orders of magnitudes higher (Borisov and Palme, 1995a). Equilibration with chondritic metal will therefore lead to grossly non-chondritic Pd/Ir or Au/Ir ratios in coexisting silicate phases. Chondritic ratios are thus indicative of the presence of unfractionated meteoritic components. Samples from the upper mantle of the Earth, for example, reflect the admixture of a late unfractionated (chondritic) veneer (e.g.,Kimura et al., 1974;Jagoutz et al., 1979).Solubilities of Pd and Au in silicate melts are much higher than the contents in terrestrial basalts implying that the abundances of these two elements are not buffered by residual PGE- and Au-containing alloys. The most likely process for fractionating PGEs in terrestrial magmas are mineral-melt (e.g., olivine/melt) equilibria.

---

Experimentelle Bestimmung der Löslichkeit von Au in Silikatschmelzen

Zusammenfassung In der vorliegenden Arbeit wird über die Ergebnisse der Bestimmung der Löslichkeit von Au in Silikatschmelzen mit der Zusammensetzung des Anorthit-Diopsid Eutektikums berichtet. Die Versuche wurden mittels Metallschlaufe über einen weiten Sauerstoffpartialdruckbereich, von reinem Sauerstoff bis zu 10^–8 atm und in einem Temperaturbereich von 1300 °C bis 1480 °C, durchgeführt. Da diese Temperaturen jedoch den Au-Schmelzpunkt überschreiten, wurde mit AuPd-Legierungen gearbeitet. Die Ergebnisse der dadurch zusätzlich erhaltenen Pd-Versuche stimmen mit früher bestimmten, mit reinen Pd-Schlaufen durchgeführten Pd-Löslichkkeiten überein (Borisov et al., 1994a). Die auf reine Metalle zurückgerechneten Löslichkeiten von Pd sind um einen Faktor 2 bis 6 mal höher als die entsprechenden Au-Löslichkeiten. Die Löslichkeiten beider Metalle nehmen mit abnehmendem Sauerstoffpartialdruck ab. Unter noch stärker reduzierenden Bedingungen (Eisen-Wüstit Gleichgewicht) nimmt die Löslichkeit von Au jedoch zu. Dies könnte auf die Bildung von Au-Siliziden zurückzuführen sein.Im Vergleich zu Pd sind die Aktivitätskoeffizienten von Au in metallischem Eisen höher, die Löslichkeiten in Silikatschmelzen jedoch niedriger. Das führt zu ähnlichen Metall/Silikat Verteilungskoeffizienten von Au und Pd. Bei einer Temperatur von 1350 °C und einer Sauerstoffugazität von IW-2 ergeben sich für D^Au (met/sil) 2.5 · 10⁷ und für D^Pd (met/sil) 1.6* 10⁷. Der Metall/Silikat-Verteilungskoeffizient von Ir ist jedoch unter den gleichen Bedingungen um mehrere Größenordnungen höher (Borisov andPalme, 1995a). Ein chondritisches Pd/Ir- oder Au/Ir-Verhältnis kann also auf die Anwesenheit einer unfraktionierten chondritischen Komponente zurückgeführt werden. Dies gilt beispielsweise für Proben aus dem oberen Erdmantel. Hier handelt es sich vermutlich um Zumischung einer späten chondritischen Akkretionskomponente, die sich nicht mehr mit einer metallischen Phase (Kern) ins Gleichgewicht gesetzt hat (z.B.Kimura et al., 1974,Jagoutz et al., 1979).Die Löslichkeiten von Pd und Au in Silikatschmelzen sind wesentlich höher als ihre Gehalte in basaltischen und komatiitischen Laven. Dies bedeutet, daß Au und Pd in Schmelzen aus dem Erdmantel nicht durch residuale Au- und/oder Pd-haltige Metall phasen bestimmt sind. Gleichgewichte zwischen Schmelze und Mineralen (z.B. Olivin) sind die wahrscheinlichsten Fraktionierungsmechanismen für Platingruppenelemente in terrestrischen Magmen.

---

---

With 5 Figures     

珠江流域碳酸盐岩与硅酸盐岩风化对大气CO2汇的效应

对珠江流域11个测站的河水1个水文年4次取样进行水化学和同位素测试分析,揭示无论是碳酸盐岩区还是硅酸盐岩区,岩石风化均使河流的离子成分以HCO3-、Ca2+、Mg2+为主,碳酸盐岩风化溶蚀速率和由碳酸盐岩风化溶蚀引起的大气CO2消耗量分别为27.60 mm/ka和540.21x103mol/(km2?a-1),是硅酸盐岩风化速率和由硅酸盐岩风化引起的大气CO2消耗量的10.8倍和6.7倍,说明碳酸盐岩风化是流域碳汇过程及效应的主体。由于有利的水热条件和高的碳酸盐岩面积比例,珠江流域平均岩石风化速率和由岩石风化作用引起的大气CO2消耗量分别为30.15mm/ka和620.36×103mol/(km2?a-1),为全球60条河流平均值的2.6倍。     

珠江流域碳酸盐岩与硅酸盐岩风化对大气CO_2汇的效应

对珠江流域11个测站的河水1个水文年4次取样进行水化学和同位素测试分析,揭示无论是碳酸盐岩区还是硅酸盐岩区,岩石风化均使河流的离子成分以HCO3-、Ca2+、Mg2+为主,碳酸盐岩风化溶蚀速率和由碳酸盐岩风化溶蚀引起的大气CO2消耗量分别为27.60 mm/ka和540.21x103mol/(km2·a-1),是硅酸盐岩风化速率和由硅酸盐岩风化引起的大气CO2消耗量的10.8倍和6.7倍,说明碳酸盐岩风化是流域碳汇过程及效应的主体。由于有利的水热条件和高的碳酸盐岩面积比例,珠江流域平均岩石风化速率和由岩石风化作用引起的大气CO2消耗量分别为30.15mm/ka和620.36×103mol/(km2·a-1),为全球60条河流平均值的2.6倍。     

The use of inclined hemisphere projections for analyzing failure mechanisms in discontinuous rocks

This paper demonstrates the advantages of using inclined stereographic projections in kinematic analysis of rock blocks in discontinuous rock masses. Some examples of limiting cases are presented. The application of inclined projections is illustrated by its use in a mine slope in Brazil. It is clear from the discussion of these examples that inclined hemisphere projections provide better results than horizontal projections. It is also demonstrated that horizontal projections can lead to incorrect results in limiting cases.     

The determination of chlorine in rocks and minerals by pyrohydrolytic method

In this paper a porcedute of pyrohydrolysis spectrophotometric determination has been established for chlorine in rocks and minerals. The selection of accelerator and its required quantity, the time and temperature of sample decomposition and the influence of interferring elements and other factors are also discussed in detail. Because samples are usually fused with alkalis, higher blank is an insurmountable problem. However, with our procedure, the above-mentioned drawback can be effectively overcome, and the determination of trace chlorine either in large or in minor quantities of samples also is rather ideal. The determined results indicate that the relative standard deviations are 8.7% in the former and 4.5% in the latter case. This procedure is simple, rapid and well reproduceable. The detection limit of the method is 10 ppm. The results obtained by our procedure are in good agreement with the proposed values from two reference samples in China (DZΣ-1 and DZΣ-2) and one international geochemical reference sample (RGM-1). This method has proved itself to be reliable.     

花岗-伟晶岩型锂矿床围岩变质沉积岩中锂富集的关键因素: 以松潘-甘孜构造带东部可尔因地区为例

变质沉积岩中稀有金属元素的富集通常被认为是形成花岗-伟晶岩型稀有金属矿床的物质基础,但是对于其富集的原因及关键因素却仍不清楚。松潘-甘孜构造带作为我国重要的稀有金属富集区,区内已发现多处锂矿床,是研究花岗-伟晶岩体与变质沉积岩（围岩）成因联系的理想地区。本文详细调查了松潘-甘孜构造带东部可尔因地区距花岗-伟晶岩体不同距离、不同类型的三叠系变质沉积岩。可尔因地区的三叠系变质沉积岩以块状变质砂岩（角岩）和石英/云母片岩为主,其中常夹有泥质千枚岩或云母片岩薄层。显微镜下观察表明不同类型的变质沉积岩中的主要矿物为石英、黑云母和白云母。全岩地球化学分析结果显示,变质砂岩和石英片岩比云母片岩和泥质千枚岩整体具有较高的SiO₂含量,较低的Al₂O₃、K₂O、TiO₂、MgO和Fe₂O₃^T含量,反映了石英和黑云母含量对全岩成分的控制。这些样品整体具有与平均大陆上地壳相似的微量元素含量,同时表现出不同程度地亏损Sr和Ni-Co等相容元素,以及富集Li（3×10^-6~997×10^-6）和Cs等不相容元素。值得注意的是,个别样品具有异常高的锂含量（>300×10^-6）,这些样品同时也具有较高的Cs和Sn等元素含量。黑云母成分分析结果显示这些变质沉积岩中的黑云母为富镁黑云母和富铁黑云母,Li、Rb、Cs、Sn、F等稀有金属元素和挥发分元素在这些黑云母中变化较大,而且它们之间具有一定的正相关关系。根据全岩分析结果,该地区变质沉积岩的锂含量中位数为50.4×10^-6,与周缘造山带内岩浆岩的锂含量相似。结合前人碎屑锆石的研究结果,这反映了物源对沉积岩中锂含量的控制作用。若以此作为花岗质岩浆的源岩,不可能直接通过部分熔融形成含矿熔体,而需要岩浆的高分异演化。变质沉积岩全岩和黑云母中锂的含量与Cs、Sn、F等稀有金属成矿相关元素有正相关性,表明富锂熔-流体对围岩沉积岩的改造是导致围岩变质沉积岩中锂富集的原因。富锂熔体在上升侵位过程中,对围岩中锂的萃取可以忽略不计,与之相反,这些富锂岩浆是导致区域围岩富锂的主要原因。空间上,富锂变质沉积岩与已发现的锂矿点关系密切,或许可以利用这一关系,定位区域内的含锂矿伟晶岩,特别是对于高海拔和高差较大的地区。