Vanadium-rich ruby and sapphire within Mogok Gemfield,Myanmar: implications for gem color and genesis

Rubies and sapphires are of both scientific and commercial interest. These gemstones are corundum colored by transition elements within the alumina crystal lattice: Cr³⁺ yields red in ruby and Fe²⁺, Fe³⁺, and Ti⁴⁺ ionic interactions color sapphires. A minor ion, V³⁺ induces slate to purple colors and color change in some sapphires, but its role in coloring rubies remains enigmatic. Trace element and oxygen isotope composition provide genetic signatures for natural corundum and assist geographic typing. Here, we show that V can dominate chromophore contents in Mogok ruby suites. This raises implications for their color quality, enhancement treatments, geographic origin, exploration and exploitation and their comparison with rubies elsewhere. Precise LA-ICP-MS analysis of ruby and sapphire from Mogok placer and in situ deposits reveal that V can exceed 5,000 ppm, giving V/Cr, V/Fe and V/Ti ratios up to 26, 78, and 97 respectively. Such values significantly exceed those found elsewhere suggesting a localized geological control on V-rich ruby distribution. Our results demonstrate that detailed geochemical studies of ruby suites reveal that V is a potential ruby tracer, encourage comparisons of V/Cr-variation between ruby suites and widen the scope for geographic typing and genesis of ruby. This will allow more precise comparison of Asian and other ruby fields and assist confirmation of Mogok sources for rubies in historical and contemporary gems and jewelry.     

Geochemical and oxygen isotope signatures of mantle corundum megacrysts from the Mbuji-Mayi kimberlite,Democratic Republic of Congo,and the Changle alkali basalt,China

Oxygen isotope signatures of ruby and sapphire megacrysts, combined with trace-element analysis, from the Mbuji-Mayi kimberlite, Democratic Republic of Congo, and the Changle alkali basalt, China, provide clues to specify their origin in the deep Earth. At Mbuji-Mayi, pink sapphires have δ¹⁸O values in the range 4.3 to 5.4‰ (N = 10) with a mean of 4.9 ± 0.4‰, and rubies from 5.5 to 5.6‰ (N = 3). The Ga/Mg ratio of pink sapphires is between 1.9 and 3.9, and in rubies, between 0.6 and 2.6. The blue or yellow sapphires from Changle have δ¹⁸O values from 4.6 to 5.2 ‰, with a mean of 4.9 ± 0.2‰ (N = 9). The Ga/Mg ratio is between 5.7 and 11.3. The homogenous isotopic composition of ruby suggests a derivation from upper mantle xenoliths (garnet lherzolite, pyroxenite) or metagabbros and/or lower crustal garnet clinopyroxenite eclogite-type xenoliths included in kimberlites. Data from the pink sapphires from Mbuji-Mayi suggest a mantle origin, but different probable protoliths: either subducted oceanic protolith transformed into eclogite with δ¹⁸O values buffered to the mantle value, or clinopyroxenite protoliths in peridotite. The Changle sapphires have a mantle O-isotope signature. They probably formed in syenitic magmas produced by low degree partial melting of a spinel lherzolite source. The kimberlite and the alkali basalt acted as gem conveyors from the upper mantle up to the surface.     

Oxygen isotope systematics of gem corundum deposits in Madagascar: relevance for their geological origin

The oxygen isotopic composition of gem corundum was measured from 22 deposits and occurrences in Madagascar to provide a gemstone geological identification and characterization. Primary corundum deposits in Madagascar are hosted in magmatic (syenite and alkali basalt) and metamorphic rocks (gneiss, cordieritite, mafic and ultramafic rocks, marble, and calc-silicate rocks). In both domains the circulation of fluids, especially along shear zones for metamorphic deposits, provoked in situ transformation of the corundum host rocks with the formation of metasomatites such as phlogopite, sakenite, and corundumite. Secondary deposits (placers) are the most important economically and are contained in detrital basins and karsts. The oxygen isotopic ratios (¹⁸O/¹⁶O) of ruby and sapphire from primary deposits are a good indicator of their geological origin and reveal a wide range of δ¹⁸O (Vienna Standard Mean Ocean Water) between 1.3 and 15.6‰. Metamorphic rubies are defined by two groups of δ¹⁸O values in the range of 1.7 to 2.9‰ (cordieritite) and 3.8 to 6.1‰ (amphibolite). “Magmatic” rubies from pyroxenitic xenoliths contained in the alkali basalt of Soamiakatra have δ¹⁸O values ranging between 1.3 and 4.7‰. Sapphires are classified into two main groups with δ¹⁸O in the range of 4.7 to 9.0‰ (pyroxenite and feldspathic gneiss) and 10.7 to 15.6‰ (skarn in marble from Andranondambo). The δ¹⁸O values for gem corundum from secondary deposits have a wide spread between −0.3 and 16.5‰. The ruby and sapphire found in placers linked to alkali basalt environments in the northern and central regions of Madagascar have consistent δ¹⁸O values between 3.5 and 6.9‰. Ruby from the placers of Vatomandry and Andilamena has δ¹⁸O values of 5.9‰, and between 0.5 and 4.0‰, respectively. The placers of the Ilakaka area are characterized by a huge variety of colored sapphires and rubies, with δ¹⁸O values between −0.3 and 16.5‰, and their origin is debated. A comparison with oxygen isotope data obtained on gem corundum from Eastern Africa, India, and Sri Lanka is presented. Giant placer deposits from Sri Lanka, Madagascar, and Tanzania have a large variety of colored sapphires and rubies with a large variation in δ¹⁸O due to mingling of corundum of different origin: mafic and ultramafic rocks for ruby, desilicated pegmatites for blue sapphire, syenite for yellow, green, and blue sapphire, and skarn in marbles for blue sapphire.     

红外光谱-显微共焦激光拉曼光谱研究天然红宝石和蓝宝石中含水矿物包裹体特征

天然红宝石和蓝宝石的包裹体中常见典型的含水矿物包裹体,这些含水矿物包裹体容易受外界环境升温而发生改变。微量含水矿物包裹体变化会对红宝石和蓝宝石的物理和化学性质产生明显影响,该性质为宝石热处理的鉴定提供了检测思路。本文采集了天然红宝石和蓝宝石样品,用显微镜放大观察包裹体特征,结合红外光谱与显微共焦激光拉曼光谱测试研究了含水矿物包裹体的特征。结果表明:天然红宝石和蓝宝石样品中含水矿物包裹体的外观轮廓清晰,晶形完整;红外光谱在2000～3700cm~(-1)附近显示出2105～2110cm~(-1)和1977～1985cm~(-1)硬水铝石和3619cm~(-1)和3696cm~(-1)高岭石等水(H_2O或—OH等)的特征吸收峰;拉曼光谱中可见角闪石、云母、磷灰石和长石等结晶度较好的典型含水矿物包裹体的特征拉曼位移。该系列特征揭示了红宝石和蓝宝石样品中含有水的特征,可作为红宝石和蓝宝石天然成因且未经过热处理的鉴定依据。     

Trace-element contents and cathodoluminescence of “trapiche” rubies from Mong Hsu, Myanmar (Burma): geological significance

Summary ?Mong Hsu rubies of the “trapiche” type are sporadically seen in the gem market. However, they have never been described in the field. The study of the nature of solid inclusions, the variation of trace-element contents, as well as the cathodoluminescence behaviour of six “trapiche” rubies permit the conclusion that these rubies crystallised in the same geological environment (marble-type deposit) as the normal rubies from Mong Hsu: (1) Cr and V are the main chromophorous elements in both ruby types; they act, together with Ti, as activators or quenchers for cathodoluminescence; (2) calcite, dolomite, rutile, mica, diaspore, apatite, chlorite, and feldspar are solid inclusions found in both ruby types; (3) the presence of bastn?site in trapiche ruby and fluorite in non-trapiche ruby indicates the circulation of F-bearing fluids during ruby deposition; (4) the distribution of trace-element contents in the crystal is similar for both ruby types. In the Cr₂O₃ vs. Fe₂O₃ and Cr₂O₃ vs. Fe₂O₃/TiO₂ diagrams, the population fields of Mong Hsu “trapiche” and non-“trapiche” rubies overlap. They are distinct from those of rubies and sapphires hosted in basalts from South-east Asia. Received October 30, 2001; revised version accepted March 25, 2002     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Calibration of oxygen isotope fractionation and calcite-corundum thermometry in emery at Naxos,Greece

Corundum (Crn), including sapphire, occurs in emery pods surrounded by marble on the island of Naxos, Greece. The emery formed from bauxite deposited in karst that was metamorphosed to 400–700°C at 20–15 Ma. Many of these rocks initially appeared well suited for refractory accessory mineral (RAM) thermometry, which uses oxygen isotope fractionation between a RAM – corundum – and a modally dominant phase with faster diffusion of oxygen – calcite (Cc) – to determine peak metamorphic temperatures. However, previous attempts at oxygen isotope thermometry were confounded by highly variable fractionations (Δ¹⁸O) measured at mm-scale and the uncertain calibration of Δ¹⁸O(Cc-Crn) versus temperature. Secondary ion mass spectrometry (SIMS) permits in situ analysis of δ¹⁸O in corundum and calcite at the 10-μm scale in adjacent grains where textures suggest peak metamorphic equilibrium was attained. SIMS analyses of adjacent mineral pairs in eight rocks yield values of Δ(Cc-Crn) that systematically decrease from 7.2 to 2.9‰ at higher metamorphic grade. Pairing these data with independent temperature estimates from mineral isograds yields an empirical calibration of 1,000 lnα(Cc-Crn) = 2.72 ± 0.3 × 10⁶/T² (T in K). The new fractionations (2.7‰ at 1,000 K) are significantly smaller than those calculated from the modified increment method (6.5‰ at 1,000 K; Zheng, Geochimica et Cosmochimica Acta, 1991, 55:2299–2307; Zheng, Mineral Mag, 1994, 58A:1000–1001), which yield unreasonably high temperatures of 630 to 1,140°C when applied to the new Naxos data. The new calibration of Δ(Cc-Crn) can be combined with published fractionations to calculate A-factors for corundum versus a range of 14 other minerals. These new fractionation factors can be used for thermometry or to constrain the genesis of corundum. A compilation of gem corundum δ¹⁸O values shows that many igneous sapphires, including important deposits of basalt-associated sapphire, are mildly elevated in δ¹⁸O relative to the calculated range in equilibrium with mantle values (4.4–5.7‰) and formed from evolved magmas.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Geology and D-O-C Isotope Systematics of the Tieluping Silver Deposit,Henan, China: Implications for Ore Genesis

The Tieluping silver deposit, which is sited along NE-trending faults within the high-grade metamorphic basement of the Xiong‘er terrane, is part of an important Mesozoic orogenic-type Ag-Pb and Au belt recently discovered. Ore formation includes three stages: Early (E), Middle (M) and Late (L), which include quartz-pyrite (E),polymetallic sulfides (M) and carbonates (L), respectively. The E-stage fluids are characterized by δD=-90%c,δ^13CCO2=2.0‰ and δ^18O=9‰ at 373℃, and are deeply sourced; the L-stage fluids, with δD=-70‰, δ^13C CO2=-1.3%c and δ^18O=-2‰, are shallow-sourced meteoric water; whereas the M-stage fluids, with δD=-109‰, δ^13C CO2=0.1%c and δ^18O2‰, are a mix of deep-sourced and shallow-sourced fluids. Comparisons of the D-O-C isotopic systematics of the Estage ore-forming fluids with the fluids derived from Mesozoic granites, Archean-Paleoproterozoic metamorphic basement and Paleo-Mesoproterozoic Xiong‘er Group, show that these units cannot generate fluids with the measured isotopic composition (high δ^180 and δ^13C ratios and low δD ratios) characteristic of the ore-forming fluids. This suggests that the E-stage ore-forming fluids originated from metamorphic devolatilization of a carbonate-shale-chert lithological association, locally rich in organic matter, which could correspond to the Meso-Neoproterozoic Guandaokou and Luanchuan Groups, rather than to geologic units in the Xiong‘er terrane, the lower crust and the mantle. This supports the view that the rocks of the Guandaokou and Luanchuan Groups south of the Machaoying fault might be the favorable sources. A tectonic model that combines collisional orogeny, metallogeny and hydrothermal fluid flow is proposed to explain the formation of the Tieluping silver deposit. During the Mesozoic collision between the South and North China paleocontinents, a crustal slab containing a lithological association consisting of carbonate-shale-chert, locally rich in organic matter (carbonaceous shale) was thrust northwards beneath the Xiong‘er terrane along the Machaoying fault.Metamorphic devolatilization of this underthrust slab provided the ore-forming fluids to develop the Au-Ag-(Pb-Zn) ore belt, which includes the Tieluping silver deposit.     

Geology, Fluid Inclusion and Isotopic Study of the Neoproterozoic Suoi Thau Copper Deposit, Northwest Vietnam

The Sin Quyen-Lung Po district is an important Cu metallogenic province in Vietnam, but there are few temporal and genetic constraints on deposits from this belt. Suoi Thau is one of the representative Cu deposits associated with granitic intrusion. The deposit consists of ore bodies in altered granite or along the contact zone between granite and Proterozoic meta-sedimentary rocks. The Cu-bearing intrusion is sub-alkaline I-type granite. It has a zircon U-Pb age of ~776 Ma, and has subduction-related geochemical signatures. Geochemical analysis reveals that the intrusion may be formed by melting of mafic lower crust in a subduction regime. Three stages of alteration and mineralization are identified in the Suoi Thau deposit, i.e., potassic alteration; silicification and Cu mineralization; and phyllic alteration. Two-phase aqueous fluid inclusions in quartz from silicification stage show wide ranges of homogenization temperatures(140–383℃) and salinities(4.18wt%–19.13wt%). The high temperature and high salinity natures of some inclusions are consistent with a magmatic derivation of the fluids, which is also supported by the H-O-S isotopes. Fluids in quartz have δD values of –41.9‰ to –68.8‰. The fluids in isotopic equilibrium with quartz have δ~(18)O values ranging from 7.9‰ to 9.2‰. These values are just plotted in the compositional field of magmatichydrothermal fluids in the δD_(water) versus δ~(18)O_(water) diagram. Sulfide minerals have relatively uniform δ~(34)S values from 1.84‰ to 3.57‰, which is supportive of a magmatic derivation of sulfur. The fluid inclusions with relatively low temperatures and salinities most probably represent variably cooled magmatic-hydrothermal fluids. The magmatic derivation of fluids and the close spatial relationship between Cu ore bodies and intrusion suggest that the Cu mineralization most likely had a genetic association with granite. The Suoi Thau deposit, together with other deposits in the region, may define a Neoproterozoic subduction-related ore-forming belt.     

Late Cryogenian magmatic activity in the North Lhasa terrane,Tibet: Implication of slab break-off process

The North Lhasa terrane in Tibet is generally interpreted to be paleotectonically unrelated to the East African Orogen (EAO) and is instead thought to have derived from northeastern India or northwestern Australia. In this study, we present petrogenetic and geochronological results pertaining to the analysis of gabbros (ca. 652 Ma), diorites (ca. 658 and 646 Ma), and tonalites (ca. 652 Ma) from the North Lhasa terrane. The gabbros are calc-alkaline and exhibit arc-like geochemical features. Low positive zircon ε_Hf(t) values (+1.0 to +3.8), high zircon δ¹⁸O (6.25‰ to 7.94‰), and low negative whole-rock ε_Nd(t) values (−3.5 to −1.4) indicate that the gabbros were derived from the lithospheric mantle, with geochemical modification by a subduction component. The diorite suite is characterized by a wide range of whole-rock chemistries (e.g., SiO₂ = 51.33–61.98 wt%) and Hf–O–Sr isotopic compositions (ε_Hf(t) = −10.8 to −0.1; δ¹⁸O = 5.17‰ to 7.11‰; I_Sr = 0.706 to 0.710), and negative whole-rock ε_Nd(t) values (−7.0 to −4.7). These diorites are geochemically similar to OIB and are interpreted to be products of the partial melting of a relatively deep mantle source (>85 km) prior to extensive modification by continental crustal material. The tonalites are adakitic and have moderate Mg^# values (47–54), low compatible element abundances, positive zircon ε_Hf(t) values (+3.4 to +6.2), high I_Sr values (0.714 to 0.715), and small negative whole-rock ε_Nd(t) values (−1.6 to −0.4). These tonalites most likely formed by the melting of thickened Mesoproterozoic continental crust. The generation of these ca. 650 Ma magmatic rocks was related to slab break-off in a collision zone. By integrating the findings of previous studies with the data of the present study, we suggest that the North Lhasa terrane was most likely located in the northern segment of the EAO in paleotectonic reconstructions of the Gondwana supercontinent.     

The oxygen isotopic composition as an indicator of the genesis of “Basaltic” corundum

This paper reports an oxygen isotopic study of corundums and associated minerals from the Yogo lamprophyres (Montana, US), plagioclase-corundum inclusions in alkali basalt (Tunkin depression, Russia), and from modern alluvium of Podgelbanochnyi alkaline basaltic volcano (Primorye, Russia). It is shown that all sapphires genetically related to mafic magmatic rocks have a similar oxygen isotopic composition (the variations of δ¹⁸O are within 2.5‰) with most values plotting between +4.5 and +7.0‰ SMOW. The oxygen isotopic ratios in the associated minerals (olivines, pyroxenes, mica, and others) and host rocks are plotted in the same interval. This indicates that the sapphire crystallized during evolution of the parental mafic magma. However, there are xenogenic corundums, which were only transported by basaltic magma to the Earth’s surface. They have a sharply distinct oxygen isotopic composition, which suggests their disequilibrium with the host lavas, and, correspondingly, a different genetic nature.     

Channelized fluids in subducted continental crust: constraints from δD–δ18O of quartz and fluid inclusions in quartz veins from the Chinese Continental Scientific Drilling Project

Fluid inclusions hosted by quartz veins in high-pressure to ultrahigh-pressure (HP-UHP) metamorphic rocks from the Chinese Continental Scientific Drilling (CCSD) Project main drillhole have low, varied hydrogen isotopic compositions (δD?=??97‰ to??69‰). Quartz δ¹⁸O values range from??2.5‰ to 9.6‰; fluid inclusions hosted in quartz have correspondingly low δ¹⁸O values of??11.66‰ to 0.93‰ (T _h?=?171.2～318.8°C). The low δD and δ¹⁸O isotopic data indicate that protoliths of some CCSD HP-UHP metamorphic rocks reacted with meteoric water at high latitude near the surface before being subducted to great depth. In addition, the δ¹⁸O of the quartz veins and fluid inclusions vary greatly with the drillhole depth. Lower δ¹⁸O values occur at depths of ～900–1000 m and ～2700 m, whereas higher values characterize rocks at depths of about 1770 m and 4000 m, correlating roughly with those of wall-rock minerals. Given that the peak metamorphic temperature of the Dabie-Sulu UHP metamorphic rocks was about 800°C or higher, much higher than the closure temperature of oxygen isotopes in quartz under wet conditions, such synchronous variations can be explained by re-equilibration. In contrast, δD values of fluid inclusions show a different relationship with depth. This is probably because oxygen is a major element of both fluids and silicates and is much more abundant in the quartz veins and silicate minerals than is hydrogen. The oxygen isotope composition of fluid inclusions is evidently more susceptible to late-stage re-equilibration with silicate minerals than is the hydrogen isotope composition. Therefore, different δD and δ¹⁸O patterns imply that dramatic fluid migration occurred, whereas the co-variation of oxygen isotopes in fluid inclusions, quartz veins, and wall-rock minerals can be better interpreted by re-equilibration during exhumation.

Quartz veins in the Dabie-Sulu UHP metamorphic terrane are the product of high-Si fluids. Given that channelized fluid migration is much faster than pervasive flow, and that the veins formed through precipitation of quartz from high-Si fluids, the abundant veins indicate significant fluid mobilization and migration within this subducted continental slab. Many mineral reactions can produce high-Si fluids. For UHP metamorphic rocks, major dehydration during subduction occurred when pressure–temperature conditions exceeded the stability of lawsonite. In contrast, for low-temperature eclogites and other HP metamorphic rocks with peak metamorphic P–T conditions within the stability field of lawsonite, dehydration and associated high-Si fluid release may have occurred as hydrous minerals were destabilized at lower pressure during exhumation. Because subduction is a continuous process whereas only a minor fraction of the subducted slabs returns to the surface, dehydration during underflow is more prevalent than exhumation even in subducted continental crust, which is considerably drier than altered oceanic crust.     

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.     

Hydrothermal flow systems in the Midcontinent Rift: oxygen and hydrogen isotopic studies of the North Shore Volcanic Group and related hypabyssal sills,Minnesota

Rift-related lavas of the North Shore Volcanic Group (NSVG) are intruded by plutonic rocks of the Duluth Complex along the unconformity between the NSVG and the underlying Proterozoic metasedimentary rocks (Animikie Group) and Archean volcano-sedimentary and plutonic rocks. Heat associated with the emplacement of the mafic intrusions generated fluid flow in the overlying plateau lavas. δ¹⁸O values for whole rocks from the NSVG and hypabyssal sills range from 5.5 to 17.7‰ and 5.3 to 11.5‰, respectively, and most values are higher than those considered “normal” for basaltic rocks (5.4 to 6.0‰). In general, there is a positive correlation between whole rock δ¹⁸O and water content, which suggests that elevated δ¹⁸O values are related primarily to secondary mineral growth and isotopic exchange during hydrothermal alteration and metamorphism. δ¹⁸O_H2O values computed from amygdule-filling minerals such as smectite, chlorite, and epidote found in low- to high-temperature metamorphic zones range from ∼−1 to 6‰ with an average value of ∼3‰. Smectite in the lower-grade zones gives computed δD_H2O values between −26 and −83‰, whereas epidote in the higher-grade zones gives δD_H2O values of −15 to 6‰. Fluid isotopic compositions computed from epidote and smectite values are suggestive of the involvement of at least two fluids during the early stages of amygdule filling. Fluid δD and δ¹⁸O values determined from epidote at the higher metamorphic grades indicate that seawater dominated the deeper portions of the system where greenschist facies assemblages and elevated δ¹⁸O values were produced in flow interiors, as well as margins. Smectite isotopic compositions suggest that meteoric water was predominant in the shallower portions of the system. The increase in δ¹⁸O values of massive flow interiors with depth is interpreted as a result of rock interaction with a fluid of constant oxygen isotopic composition with increasing temperature. The stable isotopic data are supportive of previous suggestions that seawater was involved in the hydrothermal system associated with the Midcontinent Rift. Although the origin of the seawater remains problematic, it appears that marine incursions may have occurred during the late stages of Portage Lake volcanism, and periodically thereafter.     

Oxygen isotopes in the Cretaceous-Paleogene granites of Primorye and some problems of their genesis

The Cretaceous-Paleogene granites of the Eastern Sikhote Alin volcanic belt (ESAVB) and Late Cretaceous granitoids of the Tatibin Series (Central Sikhote Alin) are subdivided into three groups according to their oxygen isotope composition: group I with δ¹⁸O from +5.5 to +6.5‰, group II with δ¹⁸O from +7.6 to +10.2‰, and group III with less than +4.5‰. Group I rocks are similar in oxygen isotope composition to that of oceanic basalts and can be derived by melting of basaltic crust. Group II (rocks of the Tatibin Series) have higher δ¹⁸O, which suggests that their parental melts were contaminated by sedimentary material. The low ¹⁸O composition of group III rocks can be explained by their derivation from ¹⁸O-depleted rocks or by subsolidus isotopic exchange with low-¹⁸O fluid or meteoric waters. The relatively low δ¹⁸O and ⁸⁷Sr/⁸⁶Sr in the granitoids of Primorye suggest their derivation from rocks with a short-lived crustal history and can result from the following: (1) melting of sedimentary rocks enriched in young volcanic material that was accumulated in the trench along the transform continental margin (granites of the Tatibin Series) and (2) melting of a mixture of abyssal sediments, ocean floor basalts, and upper mantle in the lithospheric plate that subsided beneath the continent in the subduction zone (granites of the ESAVB).     

Genesis of the Weiquan Ag–Polymetallic Deposit in East Tianshan, China: Evidence from Zircon U–Pb Geochronology and C–H–O–S–Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ~(13)C values of the calcite samples range from-2.5‰ to 2.3‰, the δ~(18)O_(H2 O) and δD_(VSMOW) values of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ~(13)C, δ~(18)O_(H2 O) and δD_(V-SMOW) values of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ~(34)S_(V-CDT) values of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.     

Carbon and oxygen isotopes in the Frasnian–Famennian section of the Kuznetsk basin (southern West Siberia)

The first detailed isotope-geochemical study of carbonate deposits has been performed in the Lower Famennian stratotype section of the northwestern Kuznetsk Basin (Kosoy Utyos), which was localized in the middle latitudes of the Northern Hemisphere in the Late Devonian. The δ¹³C_carb, δ¹³C_org, and δ¹⁸O variation curves were constructed for the section deposits. Geochemical and petrographic studies of carbonates allowed allocation of samples that underwent postsedimentation alteration and exclude them from further interpretation. Compared with coeval sections in the other world's regions, the Kosoy Utyos section is characterized by higher δ¹³C_carb values, up to 5.4‰, whereas the maximum value in subequatorial area sections is 4‰. The isotope shift amplitude of the studied section reaches 4.6‰, which is 1.5‰ higher than those in other regions. The δ¹⁸O values are 3‰ lower than the ones of the world's coeval sections. The results obtained show that δ¹³C and δ¹⁸O variation trends differ from those of coeval subequatorial sections. The high shift amplitude and maximum δ¹³C_carb values in the Kosoy Utyos section are due to the shallow-water carbonate sedimentation environments on the Siberian continental shelf and, probably, the lower temperatures of waters in the middle latitudes as compared with the subequatorial areas.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Oxygen isotope zoning in garnets from Franciscan eclogite blocks: evidence for rock–buffered fluid interaction in the mantle wedge

The oxygen isotope compositions of eclogite and amphibolite garnets from Franciscan Complex high-grade blocks and actinolite rinds encasing the blocks were determined to place constraints on their fluid histories. SIMS oxygen isotope analysis of single garnets from five eclogite blocks from three localities (Ring Mountain, Mount Hamilton, and Jenner Beach) shows an abrupt decrease in the δ¹⁸O value by ~1–3 ‰ from core to rim at a distance of ~120 ± 50 μm from the rim in nine out of the 12 garnets analyzed. In contrast, amphibolite garnets from one block (Ring Mountain) analyzed show a gradual increase in δ¹⁸O value from core to rim, implying a different history from that of the eclogite blocks. Values of δ¹⁸O in eclogite garnet cores range from 5.7 to 11.6 ‰, preserving the composition of the eclogite protolith. The abrupt decrease in the δ¹⁸O values of the garnet rims to values ranging from 3.2 to 11.2 ‰ suggests interaction with a lower δ¹⁸O fluid during the final stages of growth during eclogite facies metamorphism (450–600 °C). We hypothesize that this fluid is sourced from the serpentinized mantle wedge. High Mg, Ni, and Cr contents of actinolite rinds encasing the blocks also support interaction with ultramafic rock. Oxygen isotope thermometry using chlorite and phengite versus actinolite of rinds suggests temperatures of 185–240 °C at Ring Mountain and Mount Hamilton. Rind formation temperatures together with the lower δ¹⁸O garnet rims suggest that the blocks were in contact with ultramafic rock from the end of garnet growth through low-temperature retrogression. We suggest a tectonic model in which oceanic crust is subducted at the initiation of subduction and becomes embedded in the overlying mantle wedge. As subduction continues, metasomatic exchange between high-grade blocks and surrounding ultramafic rock is recorded in low δ¹⁸O garnet rims, and later as temperatures decrease, with rind formation.