Alpha-decay damage in minerals of the pyrochlore group

X-ray diffraction analysis and transmission electron microscopy have been used to study the effects of alpha-decay damage in pyrochlore group minerals, characterized by the general formula A _1?m B ₂O₆(O,OH,F)_1?n ·pH₂O. As defined by the XRD intensity ratio I/I ₀ , both the saturation dose (for which I/I ₀ =0.1?0.0) and the dose which signifies the initial loss of crystallinity (for which I/I ₀ =1.0?0.8) increase as a function of geologic age. The increase is attributed to annealing of isolated alpha-recoil tracks back to the original crystalline structure. The tracks have calculated mean lives, τ_a, on the order of 10⁸ years. In contrast, minerals which remain crystalline (e.g., uraninite, UO₂) despite doses of up to 10¹⁸ alpha-events/mg have mean alpha-recoil track lives ≈10⁴ years (Eyal and Fleischer 1985). After correcting the calculated dose for annealing of alpha-recoil damage, I/I ₀ is observed to decrease exponentially to zero over the dose range 0.02–1.0 × 10¹⁶ alpha-events/mg. The relationship between I/I ₀ and “corrected” dose was used to calculate an average alpha-recoil track diameter of 4.6 nm, in which < 2600 atoms are displaced. XRD line broadening due to strain dominates the first half of the crystalline-to-metamict transition, reaching a maximum of 0.003, then decreasing to < 0.001. Line broadening due to decreasing crystallite size dominates the latter half of the transition. Estimated crystallite dimensions decrease from 450 nm to < 15 nm prior to reaching the fully metamict state. With increasing dose HRTEM images of microlites from the Harding pegmatite sequentially exhibit: 1) mottled diffraction contrast, 2) isolated 1–5 nm aperiodic areas, 3) coexisting aperiodic and crystalline areas, 4) relict “islands” of crystalline material in an aperiodic matrix, and 5) complete loss of lattice fringe periodicity. With no consideration given to alpha-recoil track fading, the transition covers a dose range of 0.04–1.7 × 10¹⁷ alpha-events/mg. Using a value of τ_a=10⁸ years, this dose range is corrected down to 0.02–1.2 × 10¹⁶ alpha-events/mg. The metamict state is characterized by a range of M-M and M-O distances which give rise to bands of diffuse scattering centered at 0.30 nm and 0.18 nm, respectively, in x-ray and electron diffraction patterns. Random image contrast shown by HRTEM is consistent with a random network type structure, an interpretation supported by EXAFS/XANES studies (Greegor et al. 1985a, b, 1987). The structure of metamict pyrochlore consists of an aperiodic framework of corner-sharing B-O polyhedra. Compared to the crystalline precursor, the metamict state displays a reduced M-O coordination number and mean bond length, increased distortion of the B-site, and a slight increase in the average M-M distance.     

Evolution of chemical composition of pyrochlore group minerals from phoscorites and carbonatites of the Khibina alkaline massif

Phoscorites and carbonatites of the Khibina alkaline massif, Russia contain three minerals of the pyrochlore group. They are, in order of crystallization: uranpyrochlore and pyrochlore in the phoscorites, and pyrochlore and bariopyrochlore in late calcite carbonatites. Early calcite carbonatites also contain uranpyrochlore and pyrochlore, but they are xenocrysts derived from the phoscorites. Alteration of the pyrochlore group minerals led to increasing U, Ti and water contents and decreasing Na, Ca, Nb and F contents. Crystallization of zoned uranpyrochlore to pyrochlore crystals in the phoscorites is explained by the experiments of Ryabchikov and Hamilton (1993, 1994) on the interaction of carbonate-phosphate melts with mantle peridotites.     

Synthetic minerals with the pyrochlore and garnet structures for immobilization of actinide-containing wastes

Complex oxides of the pyrochlore (space groups Fd3m, ^[8]A₂ ^[6]B₂O₇) and garnet (Ia3d, ^[8]A₃ ^[6]B₂ ^[4]T₃O₁₂) structures (“A” = Ca²⁺, Ln^3+/4+, An^3+/4+; “B” = (Ti, Sn, Hf, and Zr)⁴⁺ in pyrochlore, and Al³⁺, Ga³⁺, and Fe³⁺ in garnet alone; “T” = (Al³⁺, Ga³⁺, and Fe³⁺) are promising matrices for actinide-bearing wastes. In order to identify optimal compositions of these phases, their isomorphic capacity with respect to REE, actinides, and other components of wastes was examined. The long-term behavior of the matrix at a repository was predicted based on data obtained on the behavior of pyrochlores and garnets under ion irradiation and ²⁴⁴Cm decay and on the determined leaching rates of REE from the matrices because of their interaction with aqueous solutions, including that after amorphization. In order to propose efficient synthesis techniques, samples prepared with the use of various methods were studied. The possibility of incorporating long-lived decay products of ⁹⁹Tc into the crystalline matrices was analyzed.     

The sodalite group of minerals

The results of a study of the chemical composition, cell parameters, density and refractive index of two sodalites and twenty five members of the nosean-haüyne solid solution series are given. It is evident from this study that potassium is a significant component substituting in the nosean-haüyne series, and that the cell edge shows a linear variation with the K₂O content. The space groups of the minerals have been determined, and it is proposed that the space group be used as the criterion to distinguish nosean (space group P¯43m) from haüyne (space group P¯43n), owing to the lack of a suitable criterion in the composition, density, or refractive index of these minerals. Sharp compositional zoning in nosean and haüyne is reported. Data on the superstructure reflections of certain of the minerals are given and discussed. Finally means of identifying sodalite, nosean, and haüyne are suggested.     

Iron in the minerals of the sodalite group

The study of the problem of the black coloration of feldspathoids of the sodalitic group (nosean, haüyne, sodalite) reveals iron as a main factor.A statistical study of the global compositions of these minerals proves that their enriching inFe is accompanied by a decrease in Al, but also by an increase in Si.A substitution of Fe⁺⁺⁺ to Al in the structure in the feldspathoids is suggested.The analysis with an electron microprobe confirms this hypothesis and allows us to state a fondamental difference between the formation of miaskitic phonolites rich in Fe⁺⁺ and that of agpaitic phonolites rich in Fe⁺⁺⁺.     

Boron in magnesium minerals of the humite group

Based on microprobe analysis and IR-spectroscopy of a representative collection of magnesium minerals of the humite group (282 samples from 80 various geological-genetic occurrences all over the world), it was shown for the first time that these minerals typically concentrate trace boron (from 0.5 to 4.9 wt % B₂O₃ in 63 samples). The diagnostic bands of B-O stretching vibrations in IF-spectra of magnesium minerals of the humite group occur within the 1170–1190, 1262–1289, and 1306–1331 cm^?1 ranges and are regularly shifted to the low frequencies in a norbergite-chondrodite-humite-clinohumite series. Boron isomorphically replaces silicon in tetrahedra, probably, by Pertsev’s scheme: Si⁴⁺ + O^2? → B³⁺ + (F,OH)^?.     

Rare minerals of the spinel group in ultrabasites from Bulgaria

Summary Chromite mineralization was found during a detailed geological mapping, carried out in 1962, in the region of the Seven Lakes, Northern Rila Mountain. Mineralogical studies showed that the ore minerals of this mineralization are of a great variety, and are members of the little known group of ferrospinels with varying chromium-, aluminium- and magnesium-content. Only three minerals are described in the present paper. They are well defined varieties, differing from one another by their chemical composition and physical properties.

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Seltene Vertreter der Spinell-Gruppe in Ultrabasiten von Bulgarien

Zusammenfassung Bei einer detaillierten geologischen Kartierung im Gebiet der Sieben Seen, nördliches Rila-Gebirge, wurden im Jahre 1962 Chromit-Mineralisationen gefunden. Die mineralogische Bearbeitung zeigte, daß die Erzminerale dieser Mineralisation stark variieren und daß sie zu der noch wenig bekannten Gruppe der Ferrospinelle mit wechselndem Chrom-, Aluminium- und Magnesiumgehalt gehören. In der vorliegenden Arbeit werden nur drei Glieder beschrieben. Es handelt sich um gut definierte Varietäten, die sich in der chemischen Zusammensetzung und in den physikalischen Eigenschaften unterscheiden.

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With 6 Figures     

First find of nephrite with accessory minerals of the platinum group

The relic minerals of the platinum group (MPG) were found for the first time in nephrite of tremolite–diopside composition associated genetically with the boninite dike of the Gorlyk-Gol deposit. This latter is confined to a segment of the zone of serpentinite mélange in the southern part of the Ospinsko–Kitoi ultrabasite massif in the East Sayan ophiolite belt. The micro- and nanophases of MPG were identified: rutheniridosmine with Ni and Fe admixtures, ruthenium, rutheniridium, iridoarsenite, omeiite, and laurite. The MPG sources are chromium spinels from harzburgites and dunites of the Ospinsko–Kitoi massif subjected to deforming transformations in the zone of the serpentinite mélange.     

LIBS analysis of geomaterials: Geochemical fingerprinting for the rapid analysis and discrimination of minerals

Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique capable of real-time, essentially non-destructive determination of the elemental composition of any substance (solid, liquid, or gas). LIBS, which is presently undergoing rapid research and development as a technology for geochemical analysis, has attractive potential as a field tool for rapid man-portable and/or stand-off chemical analysis. In LIBS, a pulsed laser beam is focused such that energy absorption produces a high-temperature microplasma at the sample surface resulting in the dissociation and ionization of small amounts of material, with both continuum and atomic/ionic emission generated by the plasma during cooling. A broadband spectrometer-detector is used to spectrally and temporally resolve the light from the plasma and record the intensity of elemental emission lines. Because the technique is simultaneously sensitive to all elements, a single laser shot can be used to track the spectral intensity of specific elements or record the broadband LIBS emission spectra, which are unique chemical ‘fingerprints’ of a material. In this study, a broad spectrum of geological materials was analyzed using a commercial bench-top LIBS system with broadband detection from ∼200 to 965 nm, with multiple single-shot spectra acquired. The subsequent use of statistical signal processing approaches to rapidly identify and classify samples highlights the potential of LIBS for ‘geochemical fingerprinting’ in a variety of geochemical, mineralogical, and environmental applications that would benefit from either real-time or in-field chemical analysis.     

Optical and mössbauer study of minerals of the eudialyte group

Twelve eudialyte specimens from the Khibini alkaline complex (Kola peninsula, USSR) have been studied by optical and Mössbauer spectroscopy methods. It has been found that in optically positive eudialytes Fe is mainly represented by Fe²⁺ ions in a rare planar four-fold coordination (Mössbauer hyperfine parameters — isomer shift IS=1.08 mm/s and quadrupole splitting QS=0.34 mm/s). It is these ions, not Mn³⁺ as it was assumed before, that are responsible for the crimson-red colour of eudialyte. In the optically negative red-brown and yellow-brown eudialytes (eucolites) Fe²⁺ ions are contained also in a tetragonal pyramid based on the above planar quadrangle (IS=1.33 mm/s and QS=2.24 mm/s). Major attention has been paid to an explanation of the colour and crystal-chemical features of optically positive in comparison with optically negative varieties of eudialytes.     

Geochemical characteristics of vanadium in rocks and minerals from Ningwu district,China

Based upon a fairly large body of data available on vanadium in rocks and minerals from the Ningwu district of China, the distribution patterns of vanadium have been substantiated in igneous and terrestrial volcanic rocks. Also discussed are geochemical behaviors of vanadium and favorable conditions for mineralization of this element during different geological processes.     

准噶尔盆地南缘中-新生界粘土矿物地球化学特征及其物源分析

准噶尔盆地南缘中-新生界地层主要分布于准噶尔盆地南缘与天山耦合部位。通过X射线荧光光谱（XRF）和电感耦合等离子体质谱（ICP-MS）对准噶尔盆地南缘中-新生界沉积岩样品进行了测试。本文根据样品中常量元素、微量元素及稀土元素（REE）特征以及特征元素比值等地球化学参数,探讨了准噶尔盆地南缘中-新生界物源区构造背景、物源性质及风化程度。通过常量、微量元素构造判别图（含量及比值）判断得出中-新生界沉积岩源岩以长英质岩石为主,构造背景为活动性大陆边缘。准噶尔盆地南缘中-新生界具有较低化学蚀变指数（CIA）和较高成分成熟度变化指数（ICV）的特征,分布范围分别为52～89、0.37～1.82,反映准南中-新生界物源区古风化程度低、沉积物成分成熟度低,表明物源区构造活动强烈,属于快速剥蚀和搬运的构造环境。     

Gold and platinum group minerals in placers of the South Urals: Composition,microinclusions of ore minerals and primary sources

Gold and platinum group minerals from the gold placers of the South Urals are studied in order to identify the metal sources. In placers from the Main Uralian fault zone (MUF), the primary gold contains Ag (up to 29 wt.%), Cu (up to 2 wt.%) and Hg (up to 4 wt.%) and its fineness ranges from 538 to 997‰. Tetra-auricupride and cupriferous gold (up to 20 wt.% Cu) are common for the Nizhny Karabash placer of the MUF zone. In the eastern part of the South Urals, the placer gold is mainly characterized by high fineness of 900–1000‰ and low Cu contents (max 1.38 wt.%). Most of the placer gold grains consist of the primary domains, which are rimmed by secondary high-fineness gold with diffuse and clear boundaries. The secondary gold also develops along the shear dislocations of primary gold. Gold contains microinclusions of geerite, balkanite, chalcopyrite, Se-bearing galena, sphalerite, pyrite, pyrrhotite, arsenopyrite and hematite.Twenty four (including five unnamed) platinum group minerals (PGMs) were found in 28 placers; those from the Kialim and Maly Iremel placers of the Miass placer zone were studied in details. In the Kialim placer, ruthenium is most abundant PGM, which hosts microinclusions of isoferroplatinum, ferroan platinum, laurite, cupriferous gold, a mineral similar in composition to tolovkite, heazlewoodite and unnamed RhSbS phase. The osmium contains microinclusions of erlichmanite and laurite. The iridium grains hosts various sulfides and arsenides of platinum group elements (PGEs). The inclusion-free PGMs form Ru compositional trend in contrast to Os–Ru trend of the Ir-depleted inclusion-hosted PGMs. The isoferroplatinum from the Maly Iremel placer hosts laurite, rhodarsenite, bowieite, a mineral similar in composition to miassite and unnamed sulfide of Pt (Pt_1.11S_2.00) and antimonide of Pd ((Pd_2.41Rh_0.43Fe_0.17)_3.01(Sb_0.91Te_0.09)_1.00). Ruthenium is a host to isoferroplatinum, PGE sulfides and arsenides, and heazlewoodite. Osmium contains microinclusions of ferroan platinum; iridium is a host to a mineral similar in composition to hongshiite. Three types of PGM intergrowths were identified in the Maly Iremel samples: (1) the intergrowths of platy grains of ruthenium with isoferroplatinum and a mineral similar in composition to tulameenite; (2) the open-latticework intergrowths of platy crystals of ruthenium with interstitial aggregates made up of gold, isoferroplatinum and a mineral similar in composition to xingzhongite and (3) the intergrowths of osmium and irarsite and iridarsenite, which are developed along cleavage of the osmium grains. Nickel sulfides associated with some PGMs contain Ru (11.32 wt.%) and Rh (2.21 wt.%) in millerite and Ir (31.00 wt.%), Ru (5.81 wt.%) and Rh (2.87 wt.%) in vaesite.The primary metal sources were determined on the basis of the mineral assemblages and composition of minerals, taking into account the nearby mineral deposits and directions of rivers. The rodingite-associated gold, gold-bearing massive sulfide and chromite deposits are major sources of gold and PGMs in placers of the Miass placer zone confined to the MUF structure of the South Urals. In the southern part of this structure, gold was mainly originated from orogenic gold–sulfide deposits associated with volcanic/volcaniclastic rocks and listvenite-associated gold deposits. The placer PGMs were derived from the adjacent ultramafic massifs of ophiolitic origin. The distance between the placers and primary deposits varies from 2 to 5 km (up to 20 km in the extended valley of the Miass River). Usage of ore microinclusions and associated PGMs in study of placer gold is far more advanced than an ordinary consideration of gold composition alone. This approach allowed us to identify the concrete sources for individual placers and to predict some mineralogical findings in already known primary occurrences.     

Geochemical evidence for diversity of dust sources in the southwestern United States

Several potential dust sources, including generic sources of sparsely vegetated alluvium, playa deposits, and anthropogenic emissions, as well as the area around Owens Lake, California, affect the composition of modern dust in the southwestern United States. A comparison of geochemical analyses of modern and old (a few thousand years) dust with samples of potential local sources suggests that dusts reflect four primary sources: (1) alluvial sediments (represented by Hf, K, Rb, Zr, and rare-earth elements, (2) playas, most of which produce calcareous dust (Sr, associated with Ca), (3) the area of Owens (dry) Lake, a human-induced playa (As, Ba, Li, Pb, Sb, and Sr), and (4) anthropogenic and/or volcanic emissions (As, Cr, Ni, and Sb). A comparison of dust and source samples with previous analyses shows that Owens (dry) Lake and mining wastes from the adjacent Cerro Gordo mining district are the primary sources of As, Ba, Li, and Pb in dusts from Owens Valley. Decreases in dust contents of As, Ba, and Sb with distance from Owens Valley suggest that dust from southern Owens Valley is being transported at least 400 km to the east. Samples of old dust that accumulated before European settlement are distinctly lower in As, Ba, and Sb abundances relative to modern dust, likely due to modern transport of dust from Owens Valley. Thus, southern Owens Valley appears to be an important, geochemically distinct, point source for regional dust in the southwestern United States.     

角闪石族和辉石族矿物的系统矿物学分类命名

角闪石族和辉石族矿物是链状硅酸盐矿物的重要组成部分,它们中的许多矿物种属于造岩矿物和/或工业矿物,具有重要的成因矿物研究意义和工业应用开发价值。国内学者对它们的分类命名和基本系统认识主要源自于王璞等(1984)编著的《系统矿物学》。随着科学技术发展和矿物学研究的不断深入,原有的矿物基础资料和分类命名都在不断更新与完善,迄今已有专业学术机构和学者在不同年代陆续发表了不同版本对该两类矿物的修订或修改意见,但一直没有统一整合,导致在涉及该两类矿物的应用研究中,在分类命名上与国际标准不统一。根据本课题组在国家公益性行业科研专项项目(新编《系统矿物学》)所承担的研究任务和当前国内外研究进展,本文系统归纳、梳理并综述了角闪石族和辉石族矿物的分类方案和命名原则,使分类命名统一标准、原则和认识并与国际接轨,这有利于该两类矿物的理论研究与开发应用,更好地支撑地质学及相关学科的研究与发展。