Helium and argon isotopes in rocks and minerals of the Lovozero Alkaline Massif

The contents and ratios of helium and argon isotopes were studied in rocks of the Lovozero Massif and related rare-metal (loparite) deposits. The gases were extracted by melting (from whole-rock and mineral samples) and crushing (mainly from fluid inclusions) methods. The wide variations in the He and Ar isotopic compositions can be explained by the fact that the trapped fluid represents a mixture of variable proportions of mantle, crustal, and atmogenic components and radiogenic in situ produced gas. The obtained gas-geochemical data reflect the complex evolution of the considered ore-magmatic system and the similar trends of melt evolution and complementary fluid phase in the magmatic chamber, in general, in three-rock (urtite-foyaite-lujavrite) units and, in each individual layers, the relative closeness of the system during magmatic crystallization and initial epimagmatic processes. It was also found that the earliest magmatic mineral was loparite and that ore units and mineralization could be partially transformed during a comparatively late postmagmatic stage. An important role of paleometeoric waters in the low-temperature mineral formation was shown.     

Chemical evolution and petrogenetic implications of loparite in the layered,agpaitic Lovozero complex,Kola Peninsula,Russia

Summary Lovozero, the largest of the world’s layered peralkaline intrusions, includes gigantic deposits of Nb + REE-loparite ore. Loparite, (Na,Ce,Ca)₂(Ti,Nb)₂O₆, became a cumulus phase after crystallisation of about 35% of the ‘Differentiated Complex’, and its compositional evolution has been investigated through a 2.35 km section of the intrusion. The composition of the cumulus loparite changes systematically upwards through the intrusion with an increase in Na, Sr, Nb and Th and decrease in REE and Ti. This main trend of loparite evolution records differentiation of the peralkaline magma through crystallisation of 1600 m of the intrusion. The formation of the loparite ores was the result of several factors including the chemical evolution of the highly alkaline magma and mechanical accumulation of loparite at the base of a convecting unit. At later stages of evolution, when concentrations of alkalis and volatiles reached very high levels, loparite reacted with the residual melt to form a variety of minerals including barytolamprophyllite, lomonosovite, steenstrupine-(Ce), vuonnemite, nordite, nenadkevichite, REE, Sr-rich apatite, vitusite-(Ce), mosandrite, monazite-(Ce), cerite and Ba, Si-rich belovite. The absence of loparite ore in the “Eudialyte complex” is likely to be a result of the wide crystallisation field of lamprophyllite, which here became a cumulus phase. Received November 6, 2000; revised version accepted January 18, 2001     

Source rocks of gem minerals

Field and laboratory studies on the geology and mineralogy of gem sediments and associated rocks reveal that gem minerals occur both in garnetiferous gneisses and granulites. It has been observed that PT conditions characteristic of granulite facies had favoured the formation of gem minerals such as topaz, corundum, beryl, spinel, tourmaline and zircon.

---

Resume Les travaux sur le terrain ainsi qu'au laboratoire portant sur les sédiments et les roches associes aux pierres precieuses montrent que les minéraux précieux se trouvent dans les gneiss à grenat et les granulites. Il a été observé que les conditions de pression et de température qui caractérisent le faciès des granulites ont favorise la formation des minéraux precieux tels que des topazes, corindons, béryls, spinelles, tourmalines et zircons.

     

A metallogenic survey of alkalic rocks of Mt. Somma-Vesuvius volcano

Summary Somma-Vesuvius is an alkaline volcano whose products (pumice, scoria and lava) have alkaline (Na₂O + K₂O) contents between 6 and 16 wt%, Mg number <50, SiO₂ 59–47 wt% and MgO 0–7.8 wt% (more than 50% of the samples have a content <2 wt%). Immobile-element ratios (Th/Yb, Ta/Yb, Ce/Yb) indicate a shoshonitic character, while the K₂O content (4–10 wt%) is characteristic of ultrapotassic rocks. The behavior of selected metals is discussed by grouping them on the basis of the stratigraphic sequence and differentiating the volcanic activity between plinian and interplinian (Rolandi et al., 1998; Ayuso et al., 1998). This allows observation of the variation within each formation from 25.000 y. BP to the last historic eruptive cycle (1631–1944 AD). The main processes to explain the wide distribution of the data presented are fractional crystallization of a mantle-derived magma, magma mixing, and contamination with heterogeneous lower and/or upper crust. Variation diagrams distinguish different behavior for groups of metals: Ag (0.01–0.2 ppm), Mo (1–8.8 ppm), W (1.3–13 ppm), Pb (16–250 ppm), Sb (0.2–2.6 ppm), Sc (0.2–61 ppm), Li (15–140 ppm) and Be (1–31 ppm) increase with increasing differentiation and tend to correlate with the incompatible trace elements (Th, Hf, etc). Cu (10–380 ppm), Au (2–143 ppb), Co (0.7–35.1 ppm) and Fe (1.3–6.2 wt%) decrease towards advanced stage of differentiation. Iron also identifies three magmatic groups. The ratio Fe³⁺/Fe²⁺ ranges between 0.2 and 1.8, and Fe₂O₃/(Fe₂O₃ + FeO) ranges between 0.2 and 0.8, giving rise to an oxidized environment; exceptions are in the samples belonging to the interplinian formations: I, II, medieval and 1631–1994 AD. Fluorine ranges between 0.1 and 0.4 wt% for the complete Mt. Somma-Vesuvius activity, except for the Ottaviano and Avellino plinian (0.8 wt%) events. Chlorine has a wider range, from 0.1 wt% to 1.6 wt%. Mt Somma-Vesuvius has some features similar to those of mineralized alkaline magmatic systems which coincide with the transition between subduction-related compression and extension-related to continental rifting. We infer that a prospective time for the formation of mineralization at Mt Somma-Vesuvius was during the 1631–1944 eruptive period. Received March 27, 2000; revised version accepted February 28, 2001     

岩石矿物高含量锡的测定

测锡的方法有很多,方法不同对应所要求的样品和含量也各不相同,经多方实验,发现一项能方便、准确的测量岩矿样品中高含量锡的测量方法。常规岩矿样品中高含量锡的测定一般采用苯芴酮比色法,该方法分析手续繁琐,很容易致使测定结果不太理想。本文主要讲述一种通过碱熔样品,使用原子荧光光度计对岩石样品中的锡进行检测的方法。     

Abiogenic Fischer–Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia

A detailed fluid inclusion study has been carried out on the hydrocarbon-bearing fluids found in the peralkaline complex, Lovozero. Petrographic, microthermometric, laser Raman and bulk gas data are presented and discussed in context with previously published data from Lovozero and similar hydrocarbon-bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons. CH₄-dominated inclusions have been identified in all Lovozero samples. They occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare H₂O-dominant inclusions. They are consistently observed in close association with either arfvedsonite crystals, partially replaced by aegirine, aegirine crystals or areas of zeolitization. The majority of inclusions consist of a low-density fluid with CH₄ homogenisation temperatures between −25 and −120 °C. Those in near-surface hand specimens contain CH₄+H₂ (up to 40 mol%)±higher hydrocarbons. However, inclusions in borehole samples contain CH₄+higher hydrocarbons±H₂ indicating that, at depth, higher hydrocarbons are more likely to form. Estimated entrapment temperatures and pressures for these inclusions are 350 °C and 0.2–0.7 kbar. A population of high-density, liquid, CH₄-dominant inclusions have also been recorded, mainly in the borehole samples, homogenising between −78 and −99 °C. These consist of pure CH₄, trapped between 1.2 and 2.1 kbar and may represent an early CH₄-bearing fluid overprinted by the low-density population. The microthermometric and laser Raman data are in agreement with bulk gas data, which have recorded significant concentrations of H₂ and higher hydrocarbons up to C₆H₁₂ in these samples. These data, combined with published isotopic data for the gases CH₄, C₂H₆, H₂, He and Ar indicate that these hydrocarbons have an abiogenic, crustal origin and were generated during postmagmatic, low temperature, alteration reactions of the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer–Tropsch type reactions involving an early CO₂-rich fluid and H₂ derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilímaussaq, at temperatures between 400 and 500 °C.     

Strain localization mechanisms in deep-seated layered rocks

More than 160 shear zones of the Norwegian Caledonides and Italian Southern Alps, formed under high-temperature or high-pressure conditions, are analysed with respect to mechanisms of strain localization. In metabasic rocks with a pre-existing (magmatic) layering strain localizes preferentially in mafic layers, although experiments in monomineralic rocks would predict a location in the weaker feldspar-rich layers. In addition, in some of these zones amphibole recrystallizes dynamically, whereas feldspars only show undulatory extinction. These are evidences for strength inversion between feldspars and mafic minerals. This inverse strength behaviour is caused by a reduced grain size of feldspars and sometimes amphiboles in the pre-existing mafic layers, i.e. prior to shearing. The localization of the shear zones is therefore a grain-size-sensitive process (grain-size-dependent softening), nearly independent of the composition of the deformed material. The numerous amphibole–amphibole contacts favour dynamical recrystallization by grain-boundary migration and the rare feldspar–feldspar contacts prevent or suppress the same process in feldspars. Therefore, the feigned inverse strength is mainly caused by the interaction of reduced grain size and grain-boundary effects in the original rock. This behaviour can lead to the preferential localization of shear zones in mafic layers, although they are not favourably oriented with respect to the stress system.     

Leaching rare-earth and radioactive elements from alkaline rocks of the Lovozero Massif,Kola Peninsula

The paper presents data on the leaching efficiency of rare-earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) and radioactive (Th and U) elements by various reagents from alkaline rocks of the Lovozero Massif. Element concentrations were analyzed by ICP-MS and instrumental neutral activation (INAA). A new complex technique is suggested for analyzing elements on the solid phase of polymer hydrogels. This technique makes it possible to enhance the sensitivity and selectivity of INAA when these elements are simultaneously contained in rocks. Data are presented on the selective leaching of trace elements and the application of environmentally safe reagents.     

Distribution of ammonium in minerals of metamorphic and granitic rocks

Sixty-nine analyses are given for NH₄ in minerals of metamorphic and granitic rocks mostly from the Ryoke belt, Japan. The distribution of NH₄ in coexisting minerals is quite systematic, suggesting that NH₄ is one of the stable geochemical components in high temperature processes.Biotite has the highest content of NH₄, followed by muscovite, K-feldspar and plagioclase. Pure quartz is almost free from NH₄. Calcic plagioclase contains less NH₄ than does sodic plagioclase. The partition coefficients $\text{D}{}^{\mathrm{<mtext>Pl</mtext><mtext>Bi</mtext>}}$, $\text{D}{}^{\mathrm{<mtext>Kf</mtext><mtext>Bi</mtext>}}$ and $\text{D}{}^{\mathrm{<mtext>Kf</mtext><mtext>Bi</mtext>}}$ are, on the average, 0.11, 0.38 and 0.43 respectively. The fractionation of NH₄ in these minerals is quite similar to that of Rb but much smaller than that of Cs.Distribution of NH₄ as well as those of Rb and Cs appears to be explained by its ionic radius and the shortest cation-O distances in alkali positions of minerals.     

流体晶、流体晶矿物组合、流体岩及其研究意义

流体是地球各圈层之间相互作用的纽带,在成岩、成矿过程中起着十分重要的作用。目前,流体的研究主要集中在流体对先存矿物岩石进行的交代作用方面,而对流体直接结晶形成的矿物领域研究较少。文中根据作者近几年的研究成果对从流体直接结晶而成的矿物——流体晶以及流体晶矿物组合、流体岩等的定义、特征进行了归纳总结。最新的研究结果显示：岩浆中可以含有大量的流体,这些流体来源既可以是岩浆演化富集、岩浆与围岩相互作用产生,亦可以是外部来源。因此,流体晶矿物、流体岩在自然界应该是普遍存在的。流体晶矿物的提出将深化人们对地质过程的理解,发展岩石学及矿床学的研究新领域,有利于矿床勘探和成矿预测。     

Altered rocks of the Onguren carbonatite complex in the Western Tansbaikal Region: Geochemistry and composition of accessory minerals

The paper discusses the mineralogy and geochemistry of altered rocks associated with calcite and dolomite–ankerite carbonatites of the Onguren dyke–vein complex in the Western Transbaikal Region. The alteration processes in the Early Proterozoic metamorphic complex and synmetamorphic granite hosting carbonatite are areal microclinization and riebeckitization; carbonates, phlogopite, apatite, and aegirine occur in the near-contact zones of the dolomite–ankerite carbonatite veins; and silicification is displayed within separated zones adjacent to the veins. In aluminosilicate rocks, microclinization was accompanied by an increasing content of K, Fe³⁺, Ti, Nb (up to 460 ppm), Th, Cu, and REE; Na, Ti, Fe³⁺, Mg, Nb (up to 1500 ppm), Zr (up to 2800 ppm), Ta, Th, Hf, and REE accumulated in the inner zone of the riebeckitization column. High contents of Ln _Ce (up to 11200 ppm), U (23 ppm), Sr (up to 7000 ppm), Li (up to 400 ppm), Zn (up to 600 ppm), and Th (up to 700 ppm) are typical of apatite–phlogopite–riebeckite altered rock; silicified rock contains up to (ppm): 2000 Th, 20 U, 13000 Ln _Ce, and 5000 Ва. Ilmenite and later rutile are the major Nb carriers in alkali altered rocks. These minerals contain up to 2 and 7 wt % Nb₂O₅, respectively. In addition, ferrocolumbite and aeschynite-(Ce) occur in microcline and riebeckite altered rocks. Fluorapatite containing up to 2.7 wt % (Ln _Ce)₂O₃, monazite-(Ce), cerite-(Ce), ferriallanite-(Ce), and aeschynite-(Ce) are the REE carriers in riebeckite altered rock. Bastnäsite-(Ce), rhabdophane-group minerals, and xenotime-(Y) are typical of silicified rock. Thorite, monazite-(Ce), and rhabdophane-group minerals are the Th carriers.     

Abundance and distribution of the rare-earth elements and yttrium in the rocks and minerals of the Oka carbonatite complex,Quebec

are-earth (REE) and yttrium abundances were determined, by an ion-exchange-X-ray fluorescence procedure, for whole-rock (14) and mineral (87) samples from the Oka carbonatite complex. Whole-rock and mineral data indicate a trend of total REE + Y enrichment, and relative enrichment in light REE, in the order: ultrafenites < ijolites < okaites. The sövites may show wide variations in total REE + Y concentrations, but relative REE abundance patterns will be similar. The greatest REE and Y concentrations occur in apatite, niocalite, perovskite and pyrochlore. Many of the minerals show europium anomalies (both positive and negative), and these are believed to be the result of closed system competition between the various minerals for divalent Eu. The partition coefficients for mineral pairs are quite variable, indicating that the Oka rocks were emplaced through a wide-range of physicochemical and/or nonequilibrium conditions. A reasonable model for the origin of the complex involves a limited partial melting of mantle material, emplacement of the melt in a magma chamber, crystallization of mafic minerals resulting in a residual liquid which produced ijolite and subsequently okaite, and crystallization of the carbonatites from a volatile-rich, possibly immiscible, phase.     

Uranium-enriched minerals in mesostasis areas of the Rhum layered pluton

The distribution of uranium in intercumulus minerals of the Rhum layered intrusion, Inner Hebrides, has been studied by the fission track technique. A striking feature was the frequent occurrence of intense fission track stars recorded on the organic solid state nuclear track detectors. The high uranium sources corresponding to such features were found to be small, discrete mineral phases, often not larger than 50 m in size. The phases were identified as the zirconium- or phosphorus-bearing minerals zirconolite (essentially (CaFe)(Zr)(Ti)₂O₇), baddeleyite, zircon and apatite. Although zirconolite and baddeleyite frequently coexist in mesostasis areas of lunar mare basalts, baddeleyite has been only rarely observed, and zirconolite not yet reported in terrestrial basalts, with this being the first recorded occurrence of zirconolite and baddeleyite from a terrestrial ultrabasic cumulate. From estimated uranium concentrations, all of which exceed 50 p.p.m., the uranium values decrease in the order zirconolite, baddeleyite, zircon, apatite. The mesostasis areas in which these minerals occur, are to a certain extent determined by the pre-existing cumulus mineral morphologies. Branching, or cup-shaped, olivines provide small scale hollows in which residual magmatic fluids become trapped. Such fluids clearly concentrate those elements not incorporated into the cumulus phases, e.g. uranium, phosphorus, zirconium, etc., and crystallise to give uranium-enriched minerals.     

Iron(II) oxide determination in rocks and minerals

The determination of FeO of geologic materials by modern instrumental methods (such as atomic absorption spectroscopy (AAS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), etc.) cannot distinguish between different oxidation states of elements. In many cases, the oxidation state of Fe has to be known in order to perform several chemical calculations (norms, etc.) and discuss the reactions that occur during weathering, hydrothermal alteration and other processes. A modified Wilson method is proposed, giving reproducible results in a much shorter time than the classical method. Back-titration with potassium dichromate and an Fe(II) and ammonia sulphate solution is used, after dissolution of the sample powder in a heated HF/H₃PO₄ mixture and an ammonium vanadate solution. This modified method, tested with several international reference materials, gives reliable results, equivalent to the ones cited in the literature for the reference materials.     

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.     

Transformations of ore minerals in genetically different oceanic ferromanganese rocks

Results of thermic transformations of ore minerals from genetically different oceanic ferromanganese rocks in the course of their heating up to 1000°C are considered. Manganese minerals with various types of crystalline lattice have different grades of thermic stability. Layered manganese minerals (buserite I, asbolane-buserite, and birnessite) are stable up to 120–150°C; asbolane up to 180°C, vernadite, up to ～500°C; todorokite and pyrolusite (minerals of the tunnel group), up to 600 and 670°C, respectively. Sorbed cations of heavy metals govern the transformation temperature and mineral composition of products of the calcination of ferromanganese rocks. Study of birnessite and todorokite demonstrated that genesis of ferromanganese rocks do not affect thermic properties of minerals in them.