Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

Deciphering the source and contamination history of peraluminous magmas using δ18O of accessory minerals: examples from garnet-bearing plutons of the Sierra Nevada batholith

Peraluminous granitoids provide critical insight as to the amount and kinds of supracrustal material recycled in the central Sierra Nevada batholith, California. Major element concentrations indicate Sierran peraluminous granitoids are high-SiO₂ (68.9–76.9) and slightly peraluminous (average molar Al₂O₃/(CaO + Na₂O + K₂O)=1.06). Both major and trace element trends mimic those of other high-silica Sierran plutons. Garnet (Grt) in the peraluminous plutons is almandine–spessartine-rich and of magmatic origin. Low grossular contents are consistent with shallow (<4 kbar) depths of garnet crystallization. Metasediments of the Kings Sequence commonly occur as wallrocks associated with the plutons, including biotite schists that are highly peraluminous (A/CNK=2.25) and have high whole rock (WR) δ¹⁸O values (9.6–21.8‰, average=14.5±2.9‰, n=26). Ultramafic wallrocks of the Kings–Kaweah ophiolite have lower average δ¹⁸O (7.1±1.3‰, n=9). The δ¹⁸O(WR) of the Kings Sequence is variable from west to east. Higher δ¹⁸O values occur in the west, where quartz in schists is derived from marine chert; values decrease eastward as the proportion of quartz from igneous and metamorphic sources increases. Peraluminous plutons have high δ¹⁸O(WR) values (9.5–13‰) consistent with supracrustal enrichment of their sources. However, relatively low initial ⁸⁷Sr/⁸⁶Sr values (0.705–0.708) indicate that the supracrustal component in the source of peraluminous magmas was dominantly altered ocean crust and/or greywacke. Also, plutons lack or have very low abundances (<1% of grains) of inherited zircon (Zrc) cores. Average δ¹⁸O(Zrc) is 7.9‰ in peraluminous plutons, a higher value than in coeval metaluminous plutons (6–7‰). Diorites associated with peraluminous plutons also have high δ¹⁸O(Zrc), 7.4–8.3‰, which is consistent with the diorites being derived from a similar source. Magmatic garnet has variable δ¹⁸O (6.6–10.5‰, avg.=7.9‰) due to complex contamination and crystallization histories, evidenced by multiple garnet populations in some rocks. Comparison of δ¹⁸O(Zrc) and δ¹⁸O(Grt) commonly reveals disequilibrium, which documents evolving magma composition. Minor (5–7%) contamination by high δ¹⁸O wallrocks occurred in the middle and upper crust in some cases, although low δ¹⁸O wallrock may have been a contaminant in one case. Overall, oxygen isotope analysis of minerals having slow oxygen diffusion and different times of crystallization (e.g., zircon and garnet), together with detailed textural analysis, can be used to monitor assimilation in peraluminous magmas. Moreover, oxygen isotope studies are a valuable way to identify magmatic versus xenocrystic minerals in igneous rocks. Electronic Supplementary Material Supplementary material is available for this article at     

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.     

4.4 billion years of crustal maturation: oxygen isotope ratios of magmatic zircon

Analysis of δ¹⁸O in igneous zircons of known age traces the evolution of intracrustal recycling and crust-mantle interaction through time. This record is especially sensitive because oxygen isotope ratios of igneous rocks are strongly affected by incorporation of supracrustal materials into melts, which commonly have δ¹⁸O values higher than in primitive mantle magmas. This study summarizes data for δ¹⁸O in zircons that have been analyzed from 1,200 dated rocks ranging over 96% of the age of Earth. Uniformly primitive to mildly evolved magmatic δ¹⁸O values are found from the first half of Earth history, but much more varied values are seen for younger magmas. The similarity of values throughout the Archean, and comparison to the composition of the “modern” mantle indicate that δ¹⁸O of primitive mantle melts have remained constant (±0.2‰) for the past 4.4 billion years. The range and variability of δ¹⁸O in all Archean zircon samples is subdued (δ¹⁸O(Zrc)=5–7.5‰) ranging from values in high temperature equilibrium with the mantle (5.3± 0.3‰) to slightly higher, more evolved compositions (6.5–7.5‰) including samples from: the Jack Hills (4.4–3.3 Ga), the Beartooth Mountains (4.0–2.9 Ga), Barberton (3.5–2.7 Ga), the Superior and Slave Provinces (3.0 to 2.7 Ga), and the Lewisian (2.7 Ga). No zircons from the Archean have been analyzed with magmatic δ¹⁸O above 7.5‰. The mildly evolved, higher Archean values (6.5–7.5‰) are interpreted to result from exchange of protoliths with surface waters at low temperature followed by melting or contamination to create mildly elevated magmas that host the zircons. During the Proterozoic, the range of δ¹⁸O(Zrc) and the highest values gradually increased in a secular change that documents maturation of the crust. After ∼1.5 Ga, high δ¹⁸O zircons (8 to >10‰) became common in many Proterozoic and Phanerozoic terranes reflecting δ¹⁸O(whole rock) values from 9 to over 12‰. The appearance of high δ¹⁸O magmas on Earth reflects nonuniformitarian changes in the composition of sediments, and rate and style of recycling of surface-derived material into magmas within the crust. Electronic Supplementary Material Supplementary material is available for this article at     

Ultrahigh-pressure metamorphic rocks from the Chinese Continental Scientific Drilling Project: II Oxygen isotope and fluid inclusion distributions through vertical sections

In order to reconstruct the formation and exhumation mechanisms of UHP metamorphic terrains, the Chinese Continental Scientific Drilling Program (CCSD) has been carried out in Donghai of the Dabie-Sulu ultrahigh-pressure (UHP) metamorphic belt, East China. Eclogite, gneiss, amphibolite (retrograded from eclogite), ultramafic rocks, and minor schist and quartzite have been drilled. Aiming to reveal the fluid behaviour in a vertical sequence of an UHP slab, we investigated fluid inclusion and oxygen isotope characteristics of selected drillcores from the main hole and the pilot-holes PP2 and ZK 703 of the CCSD. More than 540 laser-ablation oxygen isotope analyses on garnet, omphacite, quartz, kyanite, amphibole, phengite, rutile, epidote, amphibole, plagioclase, and biotite from various rocks in the depth range of 0–3,000 m (mainly eclogite and gneiss) show that the investigated rocks can be divided into two groups: ¹⁸O-depleted rocks (as low as δ¹⁸O = −7.4‰ for garnet) indicate interaction with cold climate meteoric waters, whereas ¹⁸O-normal rocks (with bulk δ¹⁸O > +5.6‰) have preserved the O-isotopic compositions of their protoliths. Meteoric water/rock interaction has reached depths of at least 2,700 m. Oxygen isotope equilibrium has generally been achieved. Isotopic compositions of mineral phases are homogeneous on a mm to cm scale regardless of lithology, but heterogeneous on the scale of a few metres. Oxygen isotope distributions in the vertical sections favour an “in situ” origin of the UHP metamorphic rocks. The very negative δ¹⁸O eclogites usually have higher hydroxyl-mineral contents than the normal δ¹⁸O rocks, indicating higher water content during UHP metamorphism. Fluid inclusion data suggest that rocks with depleted ¹⁸O compositions have had different fluid histories compared to those with normal δ¹⁸O values. Rocks with depleted ¹⁸O mainly have primary medium-to-high salinity inclusions in omphacite, kyanite and quartz, and abundant secondary low-salinity or pure water inclusions in quartz, indicating a high-salinity-brine-dominated fluid system during peak UHP metamorphism; no carbonic inclusions have been identified in these rocks. By contrast, primary very high-density CO₂ inclusions are commonly found in the rocks with normal δ¹⁸O values. These observations suggest that fluid and oxygen isotope composition of minerals are related and reflect variable degrees of alterations of the Dabie-Sulu UHP metamorphic rocks.     

Magmatic zircon oxygen isotopes of 1.88–1.87 Ga orogenic and 1.65–1.54 Ga anorogenic magmatism in Finland

Summary Oxygen isotope ratios of igneous zircon from magmatic rocks in Finland provide insights into the evolution and growth of the Precambrian crust during the Svecofennian orogeny. These data preserve magmatic δ¹⁸O values and correlate with major discontinuities in the lower crust. Oxygen isotope ratios of zircon across the 1.88–1.87 Ga Central Finland granitoid complex (CFGC) range from 5.50‰ to 6.84‰, except for three plutons in contact with the adjacent greenstone and metasedimentary belts (δ¹⁸O(Zrc) = 7.60‰–7.78‰). There is a systematic variation in δ¹⁸O(Zrc) with respect to geographic location in the CFGC, ranging from 6.60±0.23‰ (σ) in the northeast to 5.90±0.40‰ in the west-southwest. These values correlate with a change in crustal thickness and shift in geochemical composition. The oxygen isotope composition of the 1.65–1.54 Ga rapakivi granites and related rocks in southern Finland show a decreasing trend from north to south, independent of their emplacement age. The southern anorogenic granite group has an average δ¹⁸O in zircon of 6.14±0.07‰ and the northern anorogenic group has an average δ¹⁸O in zircon of 8.14±0.59‰. This difference reflects the boundary between island arc terrains accreted during the Paleoproterozoic. Deceased     

<Superscript>18</Superscript>O/<Superscript>16</Superscript>O and V/Cr ratios in gem tsavorites from the Neoproterozoic Mozambique metamorphic belt: a clue towards their origins?

The combination of oxygen isotope composition with V–Cr–Mn trace element concentrations of V-bearing garnets (tsavorites) originating from the main deposits of the Neoproterozoic Mozambique Metamorphic Belt is reported for the first time. The database enables the identification of the geological and geographical sources of the main productive areas from northern and southern Tanzania, Kenya, and Madagascar. Three consistent sets of δ¹⁸O values between 9.5‰ and 11.0‰, 11.6‰ and 14.5‰, and 15.5‰ and 21.1‰ have been recognized for primary deposits hosted in graphitic gneisses related to the Neoproterozic metasedimentary series. The δ¹⁸O value of tsavorite is a good tracer of the environment of its formation; the δ¹⁸O of the fluid in equilibrium with tsavorite was buffered by the host rock during metamorphism and fluid-rock interaction. This study is a first step in characterizing the geochemistry of gem tsavorite from most of the deposits and occurrences worldwide.     

Petrography and geochemistry of eclogites from the Mir kimberlite,Yakutia, Russia

 Diamond-bearing eclogites are an important component of the xenoliths that occur in the Mir kimberlite, Siberian platform, Russia. We have studied 16 of these eclogite xenoliths, which are characterized by coarse-grained, equigranular garnet and omphacite. On the basis of compositional variations in garnet and clinopyroxene, this suite of eclogites can be divided into at least two groups: a high-Ca group and a low-Ca group. The high-Ca group consists of high-Ca garnets in equilibrium with pyroxenes that have high Ca-ratios [Ca/(Ca+Fe+Mg)] and high jadeite contents. These high-Ca group samples have high modal% garnet, and garnet grains often are zoned. Garnet patches along rims and along amphibole- and phlogopite-filled veins have higher Mg and lower Ca contents compared to homogeneous cores. The low-Ca group consists of eclogites with low-Ca garnets in equilibrium with pyroxenes with a low Ca-ratio, but variable jadeite contents. These low-Ca group samples typically have low modal% of garnet, and garnets are rarely compositionally zoned. Three samples have mineralogic compositions and modes transitional to the high- and low-Ca groups. We have arbitrarily designated these samples as the intermediate-Ca group. The rare-earth-element (REE) contents of garnet and clinopyroxene have been determined by ion microprobe. Garnets from the low-Ca group have low LREE contents and typically have [Dy/Yb]_n < 1. The high-Ca group garnets have higher LREE contents and typically have [Dy/Yb]_n > 1. Garnets from the intermediate-Ca group have REE contents between the high- and low-Ca groups. Clinopyroxenes from the low-Ca group have convex-upward REE patterns with relatively high REE contents (ten times chondrite), whereas those from the high-Ca group have similar convex-upward shapes, but lower REE contents, approximately chondritic. Reconstructed bulk-rock REE patterns for the low-Ca group eclogites are relatively flat at approximately ten times chondrite. In contrast, the high-Ca group samples typically have LREE-depleted patterns and lower REE contents. The δ¹⁸O values measured for garnet separates range from 7.2 to 3.1‰. Although there is a broad overlap of δ¹⁸O between the low-Ca and high-Ca groups, the low-Ca group samples range from mantle-like to high δ¹⁸O values (4.9 to 7.2‰), and the high-Ca group garnets range from mantle-like to low δ¹⁸O values (5.3 to 3.1‰). The oxygen isotopic compositions of two of the five high-Ca group samples and four of the eight low-Ca group eclogites are consistent with seawater alteration of basaltic crust, with the low-Ca group eclogites representative of low-temperature alteration, and the high-Ca group samples representative of high-temperature hydrothermal seawater alteration. We interpret the differences between the low- and high-Ca group samples to be primarily a result of differences in the protoliths of these samples. The high-Ca group eclogites are interpreted to have protoliths similar to the mid to lower sections of an ophiolite complex. This section of oceanic crust would be dominated by rocks which have a significant cumulate component and would have experienced high-temperature seawater alteration. Such cumulate rocks probably would be LREE-depleted, and can be Ca-rich because of plagioclase or clinopyroxene accumulation. The protoliths of the low-Ca group eclogites are interpreted to be the upper section of an ophiolite complex. This section of oceanic crust would consist mainly of extrusive basalts that would have been altered by seawater at low temperatures. These basaltic lavas would probably have relatively flat REE patterns, as seen for the low-Ca group eclogites. Received: 10 July 1995 / Accepted: 17 May 1996     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.     

Uniformly mantle-like δ<Superscript>18</Superscript>O in zircons from oceanic plagiogranites and gabbros

Lower ocean crust is primarily gabbroic, although 1–2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater–rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform δ¹⁸O with an average value of 5.2 ± 0.5‰ (2SD). The average δ¹⁸O(Zrc) would be in magmatic equilibrium with unaltered MORB [δ¹⁸O(WR) ~ 5.6–5.7‰], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured δ¹⁸O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like δ¹⁸O(Zrc) requires melting and zircon crystallization prior to significant amounts of water–rock interactions that alter the protolith δ¹⁸O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal environments. Many of the >3.9 Ga zircons have mildly elevated δ¹⁸O (6.0–7.5‰), but such values have not been identified in any zircons from the large sample suite examined here. The difference in δ¹⁸O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Stable isotope study of the Archaean rocks of the Vredefort impact structure,central Kaapvaal Craton,South Africa

The Vredefort dome in the Kaapvaal Craton was formed as a result of the impact of a large meteorite at 2.02 Ga. The central core of Archaean granitic basement rocks is surrounded by a collar of uplifted and overturned strata of the Witwatersrand Supergroup, exposing a substantial depth section of the Archaean crust. Orthogneisses of the core show little variation in whole-rock δ ¹⁸O value, with the majority being between 8 and 10‰, with a mean of 9.2‰ (n = 35). Quartz and feldspar have per mil differences that are consistent with O-isotope equilibrium at high temperatures, suggesting minimal interaction with fluids during subsequent cooling. These data refute previous suggestions that the Outer Granite Gneiss (OGG) and Inlandsee Leucogranofels (ILG) of the core represent middle and lower crust, respectively. Granulite-facies greenstone remnants from the ILG have δ ¹⁸O values that are on average 1.5‰ higher than the ILG host rocks and are unlikely, therefore, to represent the residuum from the partial melting event that formed the host rock. Witwatersrand Supergroup sedimentary rocks of the collar, which were metamorphosed at greenschist-to amphibolite-facies conditions, generally have lower δ ¹⁸O values than the core rocks with a mean value for metapelites of 7.7‰ (n = 45). Overall, through an ∼20 km thick section of crust, there is a general increase in whole-rock δ ¹⁸O value with increasing depth. This is the reverse of what is normal in the crust, largely because the collar rocks have δ ¹⁸O values that are unusually low in comparison with metamorphosed sedimentary rocks worldwide. The collar rocks have δD values ranging from −35 to −115‰ (average −62‰, n = 29), which are consistent with interaction with water of meteoric origin, having a δD of about −25 to −45‰. We suggest that fluid movement through the collar rocks was enhanced by impact-induced secondary permeability in the dome structure. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Imprint of meteoric water on the stable isotope compositions of igneous and secondary minerals,Kap Edvard Holm Complex,East Greenland

 Hydrogen and oxygen isotope analyses have been made of hydrous minerals in gabbros and basaltic xenoliths from the Eocene Kap Edvard Holm intrusive complex of East Greenland. The analyzed samples are of three types: (1) primary igneous hornblendes and phlogopites that crystallized from partial melts of hydrothermally altered basaltic xenoliths, (2) primary igneous hornblendes that formed during late–magmatic recrystallization of layered gabbroic cumulates, and (3) secondary actinolite, epidote and chlorite that formed during subsolidus alteration of both xenoliths and gabbros. Secondary actinolite has a δ¹⁸O value of −5.8‰ and a δD value of −158‰. These low values reflect subsolidus alteration by low–δ¹⁸O, low–δD hydrothermal fluids of meteoric origin. The δD value is lower than the −146 to −112‰ values previously reported for amphiboles from other early Tertiary meteoric–hydrothermal systems in East Greenland and Scotland, indicating that the meteoric waters at Kap Edvard Holm were isotopically lighter than typical early Tertiary meteoric waters in the North Atlantic region. This probably reflects local climatic variations caused by formation of a major topographic dome at about the time of plutonism and hydrothermal activity. The calculated isotopic composition of the meteoric water is δD=−110 ± 10‰, δ¹⁸O ≈−15‰. Igneous hornblendes and phlogopites from pegmatitic pods in hornfelsed basaltic xenoliths have δ¹⁸O values between −6.0 and −3.8‰ and δD values between −155 and −140‰. These are both much lower than typical values of fresh basalts. The oxygen isotope fractionations between pegmatitic hornblendes and surrounding hornfelsic minerals are close to equilibrium fractionations for magmatic temperatures, indicating that the pegmatites crystallized from low–δ¹⁸O partial melts of xenoliths that had been hydrothermally altered and depleted in ¹⁸O prior to stoping. The pegmatitic minerals may have crystallized with low primary δD values inherited from the altered country rocks, but these values were probably overprinted extensively by subsolidus isotopic exchange with low–δD meteoric–hydrothermal fluids. This exchange was facilitated by rapid self–diffusion of hydrogen through the crystal structures. Primary igneous hornblendes from the plutonic rocks have δ¹⁸O values between +2.0 and +3.2‰ and δD values between −166 and −146‰. The ¹⁸O fractionations between hornblendes and coexisting augites are close to equilibrium fractionations for magmatic temperatures, indicating that the hornblendes crystallized directly from the magma and subsequently underwent little or no oxygen exchange. The hornblendes may have crystallized with low primary δD values, due to contamination of the magma with altered xenolithic material, but the final δD values were probably controlled largely by subsolidus isotopic exchange. This inference is based partly on the observation that coexisting plagioclase has been extensively depleted in ¹⁸O via a mineral–fluid exchange reaction that is much slower than the hydrogen exchange reaction in hornblende. It is concluded that all hydrous minerals in the study area, whether igneous or secondary, have δD values that reflect extensive subsolidus isotopic equilibration with meteoric–hydrothermal fluids. Received: 22 March 1994 / Accepted: 26 January 1995     

A comparative study on isotopic composition of precipitation in wet tropic and semi-arid stations across southern India

Isotopic composition of monthly composite precipitation samples from Kozhikode (n = 31), a wet tropic station and Hyderabad (n = 25), a semi-arid station across southern India were studied for a period of four years from 2005 to 2008. During the study period, the Kozhikode station recorded an average rainfall of 3500 mm while the Hyderabad station showed an average rainfall of 790 mm. The average stable isotope values in precipitation at the Kozhikode station were δ ¹⁸O = −3.52‰, d-excess = 13.72‰; δ ¹⁸O = −2.94‰, d-excess = 10.57‰; and δ ¹⁸O = −7.53‰, d-excess = 13.79‰, respectively during the pre-monsoon (March–May), monsoon (June–September) and post-monsoon (October–February) seasons. For the Hyderabad station, the average stable isotope values were δ ¹⁸O = −5.88‰, d-excess = 2.34‰; δ ¹⁸O = −4.39‰, d-excess = 9.21‰; and δ ¹⁸O = −8.69‰, d-excess = 14.29‰, respectively for the three seasons. The precipitation at the two stations showed distinctive isotopic signatures. The stable isotopic composition of precipitation at the Hyderabad station showed significant variations from the global trend while the Kozhikode station almost followed the global value. These differences are mainly attributed to the latitudinal differences of the two stations coupled with the differences in climatic conditions.     

Oxygen isotopic composition of quartz veins and host rocks at the Sukhoi Log deposit,Russia

The relationships between the δ¹⁸O of quartz veins and veinlets pertaining to the main stage of gold mineralization at the Sukhoi Log deposit and metasomatically altered host slates are estimated. The oxygen isotopic composition of veined quartz and host slates is not uniform. The δ¹⁸O of quartz veins from the Western, Central, and Sukhoi Log areas of the deposit vary from +16 to + 18 ‰. The δ¹⁸O range of metasomatically altered slates in the Western and Sukhoi Log areas attains 6 ‰. The δ¹⁸O of quartz veins are always higher than those of host slates by 3–7‰. The regular difference in the δ¹⁸O between quartz veins and host slates indicates that the oxygen isotopic composition of the ore-bearing fluid forming the system of quartz veins and veinlets at the Sukhoi Log deposit could have formed as a result of interaction with silicate rocks, for instance, terrigenous slates enriched in δ¹⁸O. Such interaction, however, took place at deeper levels of the Sukhoi Log deposit. It is suggested that the fluid phase participating in the formation of the vein and veinlet system had initially high δ¹⁸O(>+10‰) due to interaction with the rocks enriched in δ¹⁸O at a low fluid/rock ratio. The oxygen isotope data indicate that the fluid participating in the formation of gold mineralization at the Sukhoi Log deposit was not in equilibrium with igneous rocks at high temperatures.     

Do S-type granites commonly sample infracrustal sources? New results from an integrated O, U–Pb and Hf isotope study of zircon

In contrast to I-type granites, which commonly comprise infracrustal and supracrustal sources, S-type granites typically incorporate predominantly supracrustal sources. The initial aim of this study was to identify the sources of three Scottish Caledonian (~460 Ma) S-type granites (Kemnay, Cove and Nigg Bay) by conducting oxygen, U–Pb and Hf isotope analyses in zircon in order to characterise one potential end-member magma involved in the genesis of the voluminous late Caledonian (~430–400 Ma) I-type granites. Field, whole-rock geochemical and isotopic data are consistent with the generation of the S-type granites by melting their Dalradian Supergroup country rocks. While Hf isotope compositions of magmatic zircon, U–Pb data of inherited zircons, and high mean zircon δ¹⁸O values of 9.0 ± 2.7‰ (2SD) and 9.8 ± 2.0‰ for the Kemnay and Cove granites support this model, the Nigg Bay Granite contains zircons with much lower δ¹⁸O values (6.8 ± 2.1‰), similar to those found in Scottish I-type granites. This suggests that the Nigg Bay Granite contains low-δ¹⁸O material representing either altered supracrustal material, or more likely, an infracrustal source component with mantle-like δ¹⁸O. Mixing trends in plots of δ¹⁸O vs. εHf for S-type granite zircons indicate involvement of at least two sources in all three granites. This pilot study of Scottish Caledonian S-type granites demonstrates that, while field and whole-rock geochemical data are consistent with local melting of only supracrustal sources, the oxygen isotopic record stored in zircon reveals a much more complex petrogenetic evolution involving two or more magma sources.     

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.     

Genesis of sediment-hosted stratiform copper–cobalt mineralization at Luiswishi and Kamoto, Katanga Copperbelt (Democratic Republic of Congo)

The sediment-hosted stratiform Cu–Co mineralization of the Luiswishi and Kamoto deposits in the Katangan Copperbelt is hosted by the Neoproterozoic Mines Subgroup. Two main hypogene Cu–Co sulfide mineralization stages and associated gangue minerals (dolomite and quartz) are distinguished. The first is an early diagenetic, typical stratiform mineralization with fine-grained minerals, whereas the second is a multistage syn-orogenic stratiform to stratabound mineralization with coarse-grained minerals. For both stages, the main hypogene Cu–Co sulfide minerals are chalcopyrite, bornite, carrollite, and chalcocite. These minerals are in many places replaced by supergene sulfides (e.g., digenite and covellite), especially near the surface, and are completely oxidized in the weathered superficial zone and in surface outcrops, with malachite, heterogenite, chrysocolla, and azurite as the main oxidation products. The hypogene sulfides of the first Cu–Co stage display δ³⁴S values (−10.3‰ to +3.1‰ Vienna Canyon Diablo Troilite (V-CDT)), which partly overlap with the δ³⁴S signature of framboidal pyrites (−28.7‰ to 4.2‰ V-CDT) and have ∆³⁴S_SO4-Sulfides in the range of 14.4‰ to 27.8‰. This fractionation is consistent with bacterial sulfate reduction (BSR). The hypogene sulfides of the second Cu–Co stage display δ³⁴S signatures that are either similar (−13.1‰ to +5.2‰ V-CDT) to the δ³⁴S values of the sulfides of the first Cu–Co stage or comparable (+18.6‰ to +21.0‰ V-CDT) to the δ³⁴S of Neoproterozoic seawater. This indicates that the sulfides of the second stage obtained their sulfur by both remobilization from early diagenetic sulfides and from thermochemical sulfate reduction (TSR). The carbon (−9.9‰ to −1.4‰ Vienna Pee Dee Belemnite (V-PDB)) and oxygen (−14.3‰ to −7.7‰ V-PDB) isotope signatures of dolomites associated with the first Cu–Co stage are in agreement with the interpretation that these dolomites are by-products of BSR. The carbon (−8.6‰ to +0.3‰ V-PDB) and oxygen (−24.0‰ to −10.3‰ V-PDB) isotope signatures of dolomites associated with the second Cu–Co stage are mostly similar to the δ¹³C (−7.1‰ to +1.3‰ V-PDB) and δ¹⁸O (−14.5‰ to −7.2‰ V-PDB) of the host rock and of the dolomites of the first Cu–Co stage. This indicates that the dolomites of the second Cu–Co stage precipitated from a high-temperature, host rock-buffered fluid, possibly under the influence of TSR. The dolomites associated with the first Cu–Co stage are characterized by significantly radiogenic Sr isotope signatures (0.70987 to 0.73576) that show a good correspondence with the Sr isotope signatures of the granitic basement rocks at an age of ca. 816 Ma. This indicates that the mineralizing fluid of the first Cu–Co stage has most likely leached radiogenic Sr and Cu–Co metals by interaction with the underlying basement rocks and/or with arenitic sedimentary rocks derived from such a basement. In contrast, the Sr isotope signatures (0.70883 to 0.71215) of the dolomites associated with the second stage show a good correspondence with the ⁸⁷Sr/⁸⁶Sr ratios (0.70723 to 0.70927) of poorly mineralized/barren host rocks at ca. 590 Ma. This indicates that the fluid of the second Cu–Co stage was likely a remobilizing fluid that significantly interacted with the country rocks and possibly did not mobilize additional metals from the basement rocks.     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Chemical and mineralogical heterogeneity in the basal zone of the Partridge River Intrusion: implications for the origin of Cu–Ni sulfide mineralization in the Duluth Complex,midcontinent rift system

Copper–nickel sulfide mineralization in the Partridge River Intrusion of the 1.1 Ga Duluth Complex is restricted primarily to a 100 m thick zone near the base of the intrusion, which is heterogeneous at meter scales in terms of both sulfide contents and rock types, which include dunite, melatroctolite, troctolite, leucotroctolite, gabbro, olivine gabbro, gabbronorite, and rare norite. Olivine-rich troctolites and melatroctolites appear to have required mineral accumulation on a substrate, whereas augite troctolite and gabbros are thought to have formed via in situ crystallization of magmas ranging in composition from high-Al olivine tholeiite to high-Ti tholeiite. δ¹⁸O values of orthopyroxene-poor rocks in the Partridge River Intrusion range from 5.2 to 6.7‰. δ¹⁸O values of 6.7‰ are consistent with less than 20% contamination by high-¹⁸O metasedimentary country rock, either via devolatilization or local partial melting. Rocks with greater than ∼15% orthopyroxene, gabbronorites, and norites, are characterized by δ¹⁸O values in excess of 6.9‰, and required the assimilation of larger amounts of siliceous country rocks. Sulfur isotopic values in leucotroctolitic rocks that contain less than ∼400 ppm S and that overlie the basal zone range between −1.5 and 2‰, values that are consistent with those of mantle-derived sulfur. In contrast, δ³⁴S values in the basal zone range from −1.4 to 10.5‰, where the ³⁴S-enriched samples require an input of sulfur from metasedimentary country rocks. δ³⁴S values of the rocks in the basal zone correlate with variations in olivine Fo content but not with S abundance. The wide range in δ³⁴S values of rocks in the basal zone strongly suggests that magmas interacted with layers in the sedimentary country rocks that were themselves characterized by variable sulfide contents and δ³⁴S values. The S isotopic data suggest that the heterogeneity observed in the basal zone results from the emplacement of relatively thin sheets of compositionally distinct magma. All rock types present in the basal zone can be produced as a result of variable degrees of fractionation of a parental high-Al olivine tholeiite, followed by varying degrees of contamination of derivative liquids by country rocks. The S-contamination process was essential for the development of Cu–Ni mineralization, and was restricted to the earliest stages in the development of the Duluth Complex at a time when volatile species such as S and H₂O, and low-T partial melts of country rocks, were available to magmas. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.