Structure analysis on synthetic emerald crystals

Single crystals of emerald synthesized by means of the flux method were adopted for crystallographic analyses. Emerald crystals with a wide range of Cr³⁺-doping content up to 3.16 wt% Cr₂O₃ were examined by X-ray single crystal diffraction refinement method. The crystal structures of the emerald crystals were refined to R ₁ (all data) of 0.019–0.024 and wR ₂ (all data) of 0.061–0.073. When Cr³⁺ substitutes for Al³⁺, the main adjustment takes place in the Al-octahedron and Be-tetrahedron. The effect of substitution of Cr³⁺ for Al³⁺ in the beryl structure results in progressively lengthening of the Al–O distance, while the length of the other bonds remains nearly unchanged. The substitution of Cr³⁺ for Al³⁺ may have caused the expansion of a axis, while keeping the c axis unchanged in the emerald lattice. As a consequence, the Al–O–Si and Al–O–Be bonding angles are found to decrease, while the angle of Si–O–Be increases as the Al–O distance increases during the Cr replacement.     

电子探针和微区X射线衍射研究陕西镇安钨-铍多金属矿床中祖母绿级绿柱石

南秦岭镇安地区发现了以白钨矿-绿柱石为矿石矿物组合的矿床新类型。为查明该矿床中首次发现的翠绿色祖母绿级绿柱石的致色机理并进一步揭示其成矿机制,本文在野外地质调查的基础上,对绿柱石开展了电子探针与微区X射线衍射等矿物学研究。结果表明:矿区中首次发现的祖母绿级绿柱石,呈自形晶产于石英(方解石)脉中并与白钨矿共(伴)生。祖母绿级绿柱石从核部至边缘V2O3含量较高,分别为0.64%~0.98%和1.04%~1.42%,且有增高趋势。X射线衍射数据表明区内祖母绿为"正常"绿柱石,同时存在Al■Me2+和Be■Li两种类质同象替换机制。V为本区祖母绿主要致色元素,来自于区内碳质板岩、金云母片岩及白云质大理岩等地层,Be、Si、Al等主要元素则来自于深部酸性岩浆岩。本次发现为该矿床中钨、铍矿产资源的综合开发利用提供了基础地质资料,并为南秦岭在区域及深部继续寻找稀有金属矿指出新的找矿方向。     

Emerald deposits and occurrences: A review

Emerald, the green gem variety of beryl, is the third most valuable gemstone (after diamond and ruby). Although it is difficult to obtain accurate statistics, Colombia supplies most (an estimated 60%, worth more than $500,000,000 per year) of the world's emeralds. However there is speculation that the emerald mines in Colombia are becoming depleted. Brazil currently accounts for approximately 10% of world emerald production. Emeralds have also been mined in Afghanistan, Australia, Austria, Bulgaria, China, India, Madagascar, Namibia, Nigeria, Pakistan, South Africa, Spain, Tanzania, the United States, and Zimbabwe.Because it is difficult to obtain accurate analyses of beryllium, most published analyses of beryl are renormalized on the basis of 18 oxygen and 3 Be atoms per formula unit. The color of emerald is due to trace amounts of chromium and/or vanadium replacing aluminum at the Y site; in most cases the Cr content is much greater than that of V. To achieve charge balance, the substitution of divalent cations at the Y site is coupled with the substitution of a monovalent cation for a vacancy at a channel site.Beryl is relatively rare because there is very little Be in the upper continental crust. Unusual geologic and geochemical conditions are required for Be and Cr and/or V to meet. In the classic model, Be-bearing pegmatites interact with Cr-bearing ultramafic or mafic rocks. However in the Colombian deposits there is no evidence of magmatic activity and it has been demonstrated that circulation processes within the host black shales were sufficient to form emerald. In addition, researchers are recognizing that regional metamorphism and tectonometamorphic processes such as shear zone formation may play a significant role in certain emerald deposits.A number of genetic classification schemes have been proposed for emerald deposits. Most are ambiguous when it comes to understanding the mechanisms and conditions that lead to the formation of an emerald deposit. Studies of individual emerald deposits show that in most cases a combination of mechanisms (magmatic, hydrothermal, and metamorphic) were needed to bring Be into contact with the chromophores. This suggests the need for a more flexible classification scheme based on mode of formation. Stable isotopes can be used to estimate the contribution of each mechanism in the formation of a particular deposit. Such estimates could perhaps be more precisely defined using trace element data, which should reflect the mode of formation.Emerald may be identified in the field by color, hardness, and form. It will tend to show up in stream sediment samples but because its specific gravity is relatively low, it will not concentrate in the heavy mineral fraction. In Colombia, structural geology, the sodium content of stream sediment samples, and the lithium, sodium, and lead contents of soil samples have all been used to find emerald occurrences. Exploration for gem beryl could result in the discovery of new occurrences of non-gem beryl or other Be minerals that could become new sources of Be and Be oxide.Future efforts should go towards creating a comprehensive data base of emerald compositions (including trace elements), determination of the role of metamorphism in the formation of some emerald deposits, improved classification schemes, and more effective exploration guidelines.     

Beryl-II,a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa

The Raman and Cr³⁺ and V²⁺ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E _1g symmetry mode at 138 cm^?1 shifts negatively by ?4.57 (±0.55) cm^?1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si₆O₁₈ rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr³⁺ and V²⁺ in emerald under compression to 16.4 GPa. The R-lines of both Cr³⁺ and V²⁺ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr³⁺ split at ~13.7 GPa, and the V²⁺ R₁ slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr³⁺ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr³⁺ and V²⁺ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that extensive twinning occurs across this transition.     

The positions of H+, Li+ and Na+ impurities in beryl

Electron Paramagnetic Resonance (EPR) measurements show that Li⁺ impurities are located at two different positions in beryl, one in the crystal lattice and the other in the crystal channel. The position of the Li⁺ impurity in the lattice is generally assumed to be at the site of a missing Be²⁺ ion. It is shown that this is not the case, but that the Li⁺ ion is located in a tetrahedron formed by the oxygens of one side of the Be tetrahedron and the nearest oxygen in the channel ring. This Li site has the coordinates (0.423, 0.344, 0.167) and can only be occupied when the neighbouring Be site is empty. There are four such sites around every Be tetrahedron at the distance of 1.46 Å from the Be site. The distance from the Li site to the oxygens of the Li tetrahedron is 1.84 Å. This compares favourably with the much smaller distance of 1.65 Å in the Be tetrahedron. Protons in beryl are trapped at or near these Li sites. Na⁺ is known to be located at the 2b position at the center of the silicate rings, where it is stabilized by one water molecule located at each of the two surrounding 2a sites. This is also the position of Li⁺ in the beryl channel. It is found that the presence of Na⁺ in the ring of six oxygens reduces the radius of this ring. The Na⁺ impurity has also been supposed to be located at position 2a alone and at 2b stabilized by only one water molecule. It is now proposed that Na⁺ and H₂O are located together in the Al–Be plane when only one water molecule is associated with Na⁺. The water oxygen is located at or near 2a and Na is closer to the Be site in tetrahedral beryl and closer to the Al site in octahedral beryl. It is proposed that the water protons are also located in the Al–Be plane, which would mean that there exists a third type of water in beryl. The origin of protons and OH^? ions in beryl is discussed and it is suggested that the plugs in the beryl channels are CO ₃ ^2? ions. Diffusion of OH^? ions and natural radiation may have led to the creation of NO₃ and the blue colour of Maxixe beryl.     

云南麻栗坡祖母绿的矿物包裹体特征研究

采用偏光显微镜薄片观察、电子探针及背散射图像、阴极发光等方法,分别对伟晶岩矿脉和顺层剪切带矿脉两种产出状态的云南麻栗坡祖母绿进行了系统的包裹体特征研究。结果表明,云南麻栗坡祖母绿具有产地特征的包裹体有黑色镁电气石、含钒的白云母、具有环带的钾长石、毒砂、镁质黑云母、白钨矿包裹体。伟晶岩脉和顺层剪切带中的祖母绿均含有钾长石、钠长石、电气石、萤石、祖母绿(绿柱石)、黑云母、榍石、磷灰石、黄铁矿、绿泥石、绿帘石包裹体。白云母、方解石、石英、锆石、毒砂、闪锌矿、方铅矿、透辉石仅出现在伟晶岩脉中的祖母绿包裹体中;而白钨矿仅出现在顺层剪切带中的祖母绿包裹体中。对云南不同产状祖母绿矿物包裹体的研究不仅对祖母绿的产地鉴定具有宝石学意义,也对揭示云南麻栗坡祖母绿的成因类型具有重要意义。     

Optical absorption and electron spin resonance in blue and green natural beryl

A comparative study of blue and green beryl crystals (from the region of Governador Valadares, Minas Gerais, Brazil) using electron paramagnetic resonance (EPR) and optical absorption (OA) spectroscopy is reported. The EPR spectra show that Fe³⁺ in blue beryl occupies a substitutional Al³⁺ site and in green beryl is localized in the structural channels between two O₆ planes. On the other hand the infrared spectra show that the alkali content in the blue beryl is mostly at substitutional and/or interstitial sites and in green beryl is mostly in the structural channels. The OA spectra show two types of Fe²⁺. Thermal treatments above 200° C in green beryl cause the reduction of Fe³⁺ into Fe²⁺ accompanied by a change of color to blue. The blue beryl color does not change on heating. The kinetics of the thermal conversion of Fe³⁺ into Fe²⁺ is composed of two first order processes; the first one has an activation energy ΔE ₁=0.30 eV and the second one has an activation energy ΔE ₂=0.46 eV.     

Gemstone Mineralization in the Palghat-Cauvery Shear Zone System (Karur-Kangayam Belt), Southern India

We summarize here the occurrence of a number of semiprecious stones within a major gemstone belt in the Palghat-Cauvery shear zone system close to the northern margin of the Madurai Granulite Block, southern India. The gem mineralization in this belt includes different varieties of corundum (star ruby, sapphire), cordierite (iolite), feldspar (moonstones and sunstone of various hues), beryl (emerald, aquamarine), chrysoberyl (alexandrite), kornerupine, topaz, spinel, crystal quartz and amethyst, among others. Gem mineralisation has not been directly dated, but is associated with pegmatites that crosscut rocks metamorphosed in late Neoproterozoic/Early Cambrian times. Similar aged gem mineralization occurs south of the Achankovil Shear Zone in southern India, as well as in Sri Lanka and Madagascar and strengthen the view of a broad late Neoproterozoic-early Cambrian gemstone province in central Gondwana. The ruby mineralization within this belt can be correlated with similar occurrences in eastern Madagascar, supporting a correlation between the Malagasy Betsimisaraka suture zone and the Palghat-Cauvery shear zone system in southern India.     

Multi-stage emerald formation during Pan-African regional metamorphism: The Zabara,Sikait, Umm Kabo deposits,South Eastern desert of Egypt

The genesis of gem-quality deep green emeralds of Zabara, Sikait and Umm Kabo (South Eastern Desert, Egypt) is to date a controversial topic. The emerald-bearing biotite schists and quartz lenses are interpreted alternatively as a product of (i) thrust-fault-shear zone – controlled large scale alkali-metasomatism driven by post-magmatic fluid flow or of (ii) a large scale interaction between syntectonic pegmatitic magma or hydrothermal fluids with pre-existing basic to ultrabasic rocks, or of (iii) a syn- to post-tectonic regional metamorphism and small scale blackwall metasomatism. Detailed microstructural and chemical analyses of the Egyptian emeralds and their host rocks show that three generations of beryl can be distinguished: a colourless pegmatitic beryl; a pale green Cr-poor beryl crystallized from pegmatite-related hydrothermal fluids; and a deep green Cr- and Mg-rich emerald. The crystallization of the Cr- and Mg-rich emerald was controlled by the very local availability of Cr, Mg and Be-rich metamorphic fluids during the Pan-African tectono-thermal event. Emerald-rich quartz lenses demonstrate that those fluids locally did mobilize quartz, too. The pale green emeralds found within the pegmatites in association with colourless beryl are the product of a mobilization of colourless pegmatitic beryl and/or phenakite by late pegmatitic fluids slightly enriched in Cr by an interaction with the Cr-rich country rocks. The late pegmatitic fluids are typically Na-rich as is demonstrated by the pervasive albitization of the pegmatites. The complex interplay of magmatic and regional metamorphic events during the genesis of the Egyptian emeralds/beryls makes it impossible through stable oxygen isotope data to relate their genesis to the one or the other event.     

Experimental silicate mineral/melt partition coefficients for beryllium and the crustal Be cycle from migmatite to pegmatite

Partition coefficients (D_Be^mineral/melt) for beryllium between hydrous granitic melt and alkali feldspars, plagioclase feldspars, quartz, dark mica, and white mica were determined by experiment at 200 MPa H₂O as a function of temperature (650-900°C), activity of Be in melt (trace levels to beryl saturation), bulk composition, and thermal run direction. At trace levels, Be is compatible in plagioclase of An₃₁ (1.84 at 700°C) and muscovite (1.35 at 700°C) but incompatible in biotite (0.39-0.54 from 650-800°C), alkali feldspar (0.38-0.19 from 680-850°C), quartz (0.24 at 800°C), and albite (0.10 at 750°C). The partition coefficients are different at saturation of the melt in beryl: lower in the case of plagioclase of An₃₁ (0.89 at 700°C), muscovite (0.87 at 700°C), biotite (0.18-0.08 from 675-800°C), alkali feldspar (0.18-0.14 from 680-700°C), and quartz (0.17-0.08 from 750-800°C), but higher in the case of albite (0.37 at 750°C).With other data sources, these new partition coefficients were utilized to track, first, the distribution of Be between aluminous quartzofeldspathic source rocks and their anatectic melts, and second, the dispersion or concentration of Be in melt through igneous crystal fractionation of different magma types (e.g., S-type, I-type) up to beryl-saturated granitic pegmatites and, finally, into their hydrothermal aureoles. Among the rock-forming minerals, cordierite, calcic oligoclase, and muscovite (in this order) control the fate of Be because of the compatibility of Be in these phases. In general, beryl-bearing pegmatites can arise only after extended crystal fractionation of large magma batches (to F, fraction of melt remaining, ≤0.05); granitic magmas that originate from cordierite-bearing protoliths or that contain large modal quantities of calcic oligoclase will not achieve beryl saturation at any point in their evolution.     

Mineralogical and geochemical investigation of emerald and beryl mineralisation,Pan-African belt of Egypt: genetic and exploration aspects

Mineralogical, geochemical and fluid inclusion studies reveal two favorable environments for the localisation of beryl mineralisations in the Precambrian rocks of Egypt: (1) emerald-schist; and (2) beryl-specialised granitoid associations. Emerald occurs within the mica schists and is typically confined to the Nugrus major shear zone. However, beryl associated with granitoids occurs in pegmatite veins, greisen bodies, and cassiterite quartz veins cutting the granites and the exocontacts of the volcanosedimentary country rocks.Compositionally, emerald is of octahedral type and its cell edge is lengthened along the a-axis, while beryl associated with granitoids is normal in composition and structural constants. Emerald is thought to be formed as the result of epitactic nucleation of Be, Al and alkali-rich solutions on the mica of the schist country rocks. Fluid inclusion studies show that the solutions are saline (8–22 wt% NaCl equiv.) and the reactions proceeded in the temperature range 260–382°C. On the other hand, aqueous inclusions in beryl associated with granitoids show the following sequence of formation with decreasing temperatures and salinities: beryl pegmatite (320–480°C and 7–16 wt% NaCl equiv.)→greisen bodies (190–400°C and 4–7 wt% NaCl equiv.)→cassiterite-quartz veins (190–380°C and 2–4 wt% NaCk equiv.).This study suggests that factors such as the chemistry of the Be-bearing fluids (rather than that of the bulk host schists) and syn-tectonic intrusions of leucogranites and pegmatites (Bederiving sources) along major ductile shear zones are the important factors controlling emerald formation. However, the endogreisens and exogreisens are the most important targets characterising the metasomatically- and magmatically-specialised, Be-granitoids, respectively. The aqueous inclusions examined in greisen beryls of metasomatised granites show a shorter range of homogenisation temperatures (260–390°C) and salinities(4.8-7 wt% NaCl equiv.) as compared to those of magmatically-specialised granitoids (190–400°C and 4–7 wt% NaCl equiv.). This phenomenon can be partly attributed to the late development of the fracture system during the crystallisation history of the metasomatised granites, where little or no contribution from meteoric waters occurred.     

Study of structural and valence state of Cr and Fe in chrysoberyl and alexandrite with EPR and M?ssbauer spectroscopy

Data on the structural and valence distribution of Cr and Fe in chrysoberyl and in alexandrite, its gem variety, are given. It is shown that the Cr³⁺ line in the natural Ural and Tanzania samples is the strongest in the M1 site and for the synthetic stones, in the M2 site. During the annealing of the alexandrite crystals, Cr³⁺ passes from the smaller M1 site into the larger M2 site. The M?ssbauer spectroscopy quantitatively determined the distribution of different valence Fe ions. The various proportions of both Fe²⁺ and Fe³⁺ ions isomorphically entering the octahedral sites in the BeAl₂O₄ crystal structure were established.     

Geochemistry and geochronology of A-type Barabazar granite: Implications on the geodynamics of South Purulia Shear Zone,Singhbhum craton,Eastern India

The Barabazar granite, exposed at the northern margin of Singhbhum craton, Eastern India, occurs along the South Purulia Shear Zone (SPSZ) and is emplaced into the Palaeoproterozoic metapelites and felsic volcanics of Singhbhum Group. Geochemical, petrographical and geochronological studies on the Barabazar granite addressed in the work have wide implications on understanding the geodynamics of SPSZ during Palaeoproterozoic to Mesoproterozoic. Geochemically, Barabazar granite displays limited range of major oxides, alkali enrichment and highly fractionated features (SiO₂ > 75%; Eu/Eu* = 0.16–0.33; enrichment of K, Rb, Th, U and Nb; depletion of Ba, Sr, P and Ti). It is predominantly peraluminous (molar Al₂O₃/CaO+Na₂O+K₂O (A/CNK) =1.14–144) and contains abundant alkali feldspar, perthite, and minor plagioclase, biotite and accessory minerals. Geochemical and petrological data indicates that it is A-type granite, which formed in ‘Within plate granite’ tectonic set up. The Barabazar granite was emplaced at ca. 1771 Ma (Pb-Pb) in rift related environs and evolved by partial melting of stabilized lower/middle crust (initial ⁸⁷Sr/⁸⁶Sr = 0.7302 ± 0.0066 and μ₁ = 8.5 ± 0.5). Subsequently, the shear zone (SPSZ) developed during the closure of the riftogenic basin and was reactivated during the Grenvillian orogeny (Ca. 900–1300 Ma), resulting in rehomogenisation of the strontium isotopes and thereby yielding younger whole-rock Rb-Sr isotope age of c. 971 Ma for the Barabazar granite. Probably during this tectonic event, the Singhbhum craton (Southern India Shield) would have finally juxtaposed with Northern Indian Shield along Central Indian Tectonic Zone (CITZ) during the global Grenvillian orogeny.     

EPR investigation of NO2 and CO2 − and other radicals in beryl

A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO₂. The isoelectronic CO₂ ⁻ radical is found in the irradiated Maxixe-type beryl. The NO₂ radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO₂ ⁻ radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO₂ ⁻ radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li⁺, Na⁺, and another counter-ion, which probably is Cs⁺. The related NO₃ and CO₃ ⁻ radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO₃ is created in Maxixe beryl by a natural process, while CO₃ ⁻ in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.     

Characteristic Features of REE and Pb–Zn–Ag Mineralizations in the Na Son Deposit,Northeastern Vietnam

The Na Son deposit is a small‐scale Pb–ZnPb–Zn–Ag deposit in northeast Vietnam and consists of biotite–chlorite schist, reddish altered rocks, quartz veins and syenite. The biotite–chlorite schist is intruded by syenite. Reddish altered rocks occur as an alteration halo between the biotite–allanite‐bearing quartz veins and the biotite–chlorite schist. Allanite occurs in the biotite–allanite‐bearing quartz veins and in the proximal reddish altered rocks. Rare earth element (REE) fluorocarbonate minerals occur along fractures or at rim of allanite crystals. The later horizontal aggregates of sulfide veins and veinlets cut the earlier reddish altered rocks. The earlier Pb–Zn veins consist of a large amount of galena and lesser amounts of sphalerite, pyrite and molybdenite. The later Cu veins cutting the Pb–Zn veins include chalcopyrite and lesser amounts of tetrahedrite and pyrite. The occurrences of two‐phase H₂O–CO₂ fluid inclusions in quartz from biotite–allanite‐bearing quartz veins and REE‐bearing fluorocarbonate minerals in allanite suggest the presence of CO₂ and F in the hydrothermal fluid. The oxygen isotopic ratios of the reddish altered rocks, biotite–chlorite schist, and syenite range from +13.9 to +14.9 ‰, +11.5 to +13.3 ‰, and +10.1 to +11.6 ‰, respectively. Assuming an isotopic equilibrium between quartz (+14.6 to +15.8 ‰) and biotite (+8.6 ‰) in the biotite–allanite‐bearing quartz vein, formation temperature was estimated to be 400°C. At 400°C, δ¹⁸O values of the hydrothermal fluid in equilibrium with quartz and biotite range from +10.5 to +11.7 ‰. These δ¹⁸O values are consistent with fluid that is derived from metamorphism. Assuming an isotopic equilibrium between galena (+1.5 to +1.7 ‰) and chalcopyrite (+3.4 ‰), the formation temperature was estimated to be approximately 300°C. The formation temperature of the Na Son deposit decreased with the progress of mineralization. Based on the geological data, occurrence of REE‐bearing minerals and oxygen isotopic ratios, the REE mineralization is thought to result from interaction between biotite–chlorite schist and REE‐, CO₂‐ and F‐bearing metamorphic fluid at 400°C under a rock‐dominant condition.     

Fluid Composition, δD of Channel H2O,and δ18O of Lattice Oxygen in Beryls: Genetic Implications for Brazilian,Colombian, and Afghanistani Emerald Deposits

The fluid composition, δD of channel H₂O, and δ₁₈O of lattice oxygen have been determined in beryl and emerald from a variety of geological environments and used to constrain the origin of the parental fluids from which beryl has grown. Step-heating analyses performed by quadrupolar mass spectrometry were used to quantify the composition of the fluid phases in beryl from granitic pegmatites and greisens and emerald from Brazil, Colombia, and Afghanistan. An important conclusion is that beryl and emerald have a similar fluid composition, with concentrations of H₂O being greater than 90% of the total water in the mineral irrespective of the age of formation (2.0 Ga to 32 Ma) and tectonic settings. However, the Brazilian Santa Terezinha shear-zone emerald deposit contains abundant CO₂, up to 13 wt% of the total fluid. A second conclusion is that the channel H₂O content for some Brazilian emeralds is higher than the range defined for beryl in the literature, especially for those related to the shear-zone type (2.99 lt; H₂O < 3.16 wt%) and the pegmatite type from the Pombos, Pela Ema, and Pirenopolis deposits (2.78 < H₂O < 3.01 wt%). Colombian emeralds have very low H₂O contents (1.30 < H₂O < 1.96 wt%), among the lowest in the world.

Brazilian, Colombian, and Afghanistani emeralds have contrasting and restricted ranges of δ¹⁸O values. In Brazil, emeralds related to pegmatites have a systematic δ¹⁸O inter-deposit variability (+6.3 < δ¹⁸O < +12.4‰). The calculated δ¹⁸O of the fluid was buffered by the host ultrabasic rocks during fluid-rock interaction. Emerald and cogenetic phlogopite related to shear-zone-type deposits have a quite restricted δ¹⁸O range (+12.0 < δ¹⁸O 7lt; +12.4‰); the calculated is interpreted to represent the original isotopic composition of the hydrothermal fluid. Relative to Brazil, the δ¹⁸O of Colombian and Afghanistani emeralds shows strong enrichment in ¹⁸O (+13.4 < δ¹⁸O < +23.6‰), and the high calculated δ¹⁸O of the fluid suggests extensive reaction with 18O-rich sedimentary or metasedimentary rocks.

In Brazil, the δD composition of channels in emerald and the calculated δ¹⁸O^H₂O for phlogopite are compatible with both magmatic and metamorphic origins. A magmatic origin is supported for emeralds associated with the pegmatitic Socotó and Carnaiba deposits (mean δD = ?37.8 ± 8‰) and a metamorphic origin is suggested for the Santa Terezinha shear-zone type (mean δD = ?32.4 ± 3‰). A metamorphic origin is proposed for Colombian emeralds. Afghanistani emeralds have a δD composition of channels (mean δD = ?46.3 ± 1.3‰) that is compatible with both magmatic and metamorphic origins.     

Spectroscopic characterisation and crystal field calculations of varicoloured kyanites from Loliondo, Tanzania

Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al₂SiO₅, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr₂O₃, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H₂O with structural OH defects partially replacing the O_B (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe³⁺ (all samples), Mn³⁺ (orange and ochre) and Cr³⁺ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe³⁺ preferably occupies the Al4 site, Cr³⁺ prefers the Al1 and Al2 sites, and Mn³⁺ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me³⁺–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr³⁺ cations.     

Structural history of high-pressure metamorphic rocks in the southern vanoise massif,french alps,and their relation to alpine tectonic events

A nappe of amphibolite-facies metamorphic rocks of pre-Permian age in the southern Vanoise massif (the Arpont schist) has been affected by an Alpine HP/LT metamorphism. The first mesoscopically recognizable deformation (D₁) post-dated the high-pressure peak (jadeitic pyroxene + quartz, glaucophane + ?lawsonite), and was associated with glaucophane + epidote. D₁ produced a flat-lying schistosity and a NW-trending glaucophane lineation, and was probably associated with nappe displacement involving NW-directed subhorizontal shear. D₂ formed small-scale folds and a foliation associated with chlorite + albite. The changing parageneses during the period pre-D₁ to D₁ to D₂ suggest decreasing pressure, so that the deformation appears to have been related to the uplift history, rather than to the process of tectonic burial. D₂ was followed by a static metamorphism (green biotite + chlorite + albite), possibly of Lepontine age. SE-directed backthrusting and folding (D₃), and later differential uplift along steep faults, took place under low-grade conditions.     

Distinct ruby suite at Sardapur, Orissa: A spectroscopic investigation

Orissa is an important area for gem variety of corundum deposits in India. Spectroscopic studies, such as ESR, OAS on samples from Sardapur, Orissa, were carried out to ascertain the colour cause of corundum. Electron spin resonance (ESR) spectroscopic study was carried out on the samples to detect the presence of paramagnetic ions i.e. Fe²⁺, Fe³⁺, Ti⁴⁺, Cr³⁺ and V³⁺ etc. The variable temperature experiment carried out to observe the effect of heating on peak valence state change in paramagnetic ions. Samples were cut and polished to obtain the optical absorption spectrum (OAS) to detect the colour causing transition ions/defect centres. The samples of gem variety were step heated up to 300°C for colour enhancement studies. EPMA analysis has revealed the low chromium concentration in the rubies. The varying hues of red in the corundum are due to the presence of bivalent and trivalent iron and charge transfer process along with Cr³⁺ absorption in the 550 nm region.     

Occurrence of calcite in Sanbagawa pelitic schists: implications for the formation of garnet, rutile, oligoclase, biotite and hornblende

The frequency of occurrence of minerals in 1876 samples of Sanbagawa pelitic schist in central Shikoku is summarized on the basis of microscopic observation accompanied, in part, by use of an electron microprobe. All samples contain quartz, plagioclase, phengite, chlorite and graphite. More than 90% of samples contain clinozoisite, titanite and apatite. Garnet is present in 95% of samples from the garnet zone, and biotite is present in 64% of samples from the albite‐biotite zone. Calcite is found in about 40% of samples of the pelitic schist collected from outcrop, but occurs in 95% of the pelitic schist from drill cores. Calcite was apparently ubiquitous in the pelitic schist during the Sanbagawa metamorphism, but must have been dissolved recently by the action of surface or ground water. The mineral assemblages of the Sanbagawa pelitic schist have to be analyzed in the system with excess calcite, quartz, albite (or oligoclase), clinozoisite, graphite and fluid that is composed mainly of H₂O, CO₂ and CH₄. In the presence of calcite, reactions that produce garnet, rutile, oligoclase, biotite and hornblende, some of which define isograds of the metamorphic belt, should be written as mixed volatile equilibria that tend to take place at lower temperature than the dehydration reactions that have been proposed. The presence of calcite in pelitic schist suggests that fluid composition is a variable as important in determining mineral assemblages as pressure and temperature. Thus Ca‐bearing phases must be taken into account to analyze the phase relations of calcite‐bearing pelitic schist, even if CaO content of Sanbagawa pelitic schist is low. As calcite is a common phase, the mineral assemblages of the biotite zone pelitic schist may contravene the mineralogical phase rule and warrant further study.