Oxygen isotope constraints on the petrogenesis of the Sybille intrusion of the Proterozoic Laramie Anorthosite Complex

The origin of monzonitic intrusions that are associated with Proterozoic massif-type anorthosite complexes is controversial. A detailed oxygen isotope study of the Sybille intrusion, a monzonitic intrusion of the Laramie Anorthosite Complex (Wyoming), indicates that either derivation from a basaltic magma of mantle origin with a metasedimentary component (∼20%) incorporated early in its magmatic history, or a partial melt of lower crustal rocks is consistent with the data. The oxygen isotope compositions of plagioclase, pyroxene and zircon from the Sybille monzosyenite, the dominant rock type in the Sybille intrusion, were analyzed in order to establish the isotopic composition of the source of the magma. Plagioclase δ¹⁸O values range from 6.77 to 9.17‰. We interpret the higher plagioclase δ¹⁸O values (average 8.69 ± 0.30‰, n = 19) to be magmatic in origin, lower plagioclase δ¹⁸O values (average 7.51 ± 0.44‰, n = 22) to be the result of variable subsolidus alteration, and pyroxene δ¹⁸O values (average 6.34 ± 0.38‰, n = 19) to be the result of closed-system diffusional exchange during cooling. Low magnetic zircons, which have been shown to retain magmatic oxygen isotope values despite high grade metamorphism and extensive subsolidus hydrothermal alteration, have δ¹⁸O values (7.40 ± 0.24‰, n = 11) which are consistent with our interpretation of the plagioclase and pyroxene results. Oxygen isotope data from all three minerals indicate that the magmatic oxygen isotope composition of the Sybille intrusion is enriched in ¹⁸O relative to the composition of average or “normal” mantle-derived magmas. This enrichment is approximately twice the oxygen isotope enrichment that could result from closed-system fractionation, rendering a closed-system, comag- matic petrogenetic model between the Sybille intrusion and the mantle-derived anorthositic lithologies of the Laramie Anorthosite Complex improbable. Received: 7 April 1998 / Accepted: 19 January 1999     

The origin of hydrous,high-δ<Superscript>18</Superscript>O voluminous volcanism: diverse oxygen isotope values and high magmatic water contents within the volcanic record of Klyuchevskoy volcano,Kamchatka, Russia

Klyuchevskoy volcano, in Kamchatka’s subduction zone, is one of the most active arc volcanoes in the world and contains some of the highest δ¹⁸O values for olivines and basalts. We present an oxygen isotope and melt inclusion study of olivine phenocrysts in conjunction with major and trace element analyses of ¹⁴C- and tephrochronologically-dated tephra layers and lavas spanning the eruptive history of Klyuchevskoy. Whole-rock and groundmass analyses of tephra layers and lava samples demonstrate that both high-Mg (7–12.5 wt% MgO) and high-Al (17–19 wt% Al₂O₃, 3–6.5 wt% MgO) basalt and basaltic andesite erupted coevally from the central vent and flank cones. Individual and bulk olivine δ¹⁸O range from normal MORB values of 5.1‰ to values as high as 7.6‰. Likewise, tephra and lava matrix glass have high-δ¹⁸O values of 5.8–8.1‰. High-Al basalts dominate volumetrically in Klyuchevskoy’s volcanic record and are mostly high in δ¹⁸O. High-δ¹⁸O olivines and more normal-δ¹⁸O olivines occur in both high-Mg and high-Al samples. Most olivines in either high-Al or high-Mg basalts are not in oxygen isotopic equilibrium with their host glasses, and Δ¹⁸O_{olivine–glass} values are out of equilibrium by up to 1.5‰. Olivines are also out of Fe–Mg equilibrium with the host glasses, but to a lesser extent. Water concentrations in olivine-hosted melt inclusions from five tephra samples range from 0.4 to 7.1 wt%. Melt inclusion CO₂ concentrations vary from below detection (<50 ppm) to 1,900 ppm. These values indicate depths of crystallization up to ~17 km (5 kbar). The variable H₂O and CO₂ concentrations likely reflect crystallization of olivine and entrapment of inclusions in ascending and degassing magma. Oxygen isotope and Fe–Mg disequilibria together with melt inclusion data indicate that olivine was mixed and recycled between high-Al and high-Mg basaltic melts and cumulates, and Fe–Mg and δ¹⁸O re-equilibration processes were incomplete. Major and trace elements in the variably high-δ¹⁸O olivines suggest a peridotite source for the parental magmas. Voluminous, highest in the world with respect to δ¹⁸O, and hydrous basic volcanism in Klyuchevskoy and other Central Kamchatka depression volcanoes is explained by a model in which the ascending primitive melts that resulted from the hydrous melt fluxing of mantle wedge peridotite, interacted with the shallow high-δ¹⁸O lithospheric mantle that had been extensively hydrated during earlier times when it was part of the Kamchatka forearc. Following accretion of the Eastern Peninsula terrains several million years ago, a trench jump eastward caused the old forearc mantle to be beneath the presently active arc. Variable interaction of ascending flux-melting-derived melts with this older, high-δ¹⁸O lithospheric mantle has produced mafic parental magmas with a spectrum of δ¹⁸O values. Differentiation of the higher δ¹⁸O parental magmas has created the volumetrically dominant high-Al basalt series. Both basalt types incessantly rise and mix between themselves and with variable in δ¹⁸O cumulates within dynamic Klyuchevskoy magma plumbing system, causing biannual eruptions and heterogeneous magma products. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mesoproterozoic olivine gabbronorites of the Bashkirian anticlinorium,the South Urals: Parental melts and specifics of magma evolution

This paper is devoted to detailed study of picritic rocks (olivine melanogabbronorites) and comagmatic gabbrodolerites from sills and dikes in the central part of the Bashkirian meganticlinorium. These rocks are ascribed to the Kama-Belsk magmatic province (KBP) that was formed in the eastern East European Platform (EEP) in the Mesoproterozoic time. The study of minerals (EMPA, SIMS), rocks, and their oxygen isotope compositions showed the contribution of crustal contamination, fractional crystallization and cumulus processes in their formation. The geochemical indicators of crustal contamination (Nb/Nb*, (Nb/La) _n , δ¹⁸O, and others) show strong variations, which indicates uneven crustal contribution in the parental melts during rock formation (10–25%). The study of weakly contaminated (δ¹⁸O = 5.3‰) olivine melanogabbronorites (MgO = 22.55 wt %) from the small Ishlya-1 subvolcanic body, which contain subordinate amount of cumulus (24%), high-magnesian olivine (Fo91.3), and high-Cr spinel (cr# 0.67), as well as HREE depleted clinopyroxenes, allowed us to retrieve the composition of parental melt. The latter contained about 20 wt % MgO and was formed by 19–26% melting of mantle source (potential mantle temperature T _m of 1530–1545°C). Geochemical characteristics of KBP reflect the formation of primary melts by melting of mantle column at different depths, mixing of the melts, and significant contamination by crustal material. The dominant role in the formation of the rocks of the Ishlya area and Mashak Complex was played by derivatives of spinel peridotites, while the rocks of the Bakal-Satka area were derived from garnet peridotites.     

The origin of high-Mg magmas in Mt Shasta and Medicine Lake volcanoes,Cascade Arc (California): higher and lower than mantle oxygen isotope signatures attributed to current and past subduction

We report the oxygen isotope composition of olivine and orthopyroxene phenocrysts in lavas from the main magma types at Mt Shasta and Medicine Lake Volcanoes: primitive high-alumina olivine tholeiite (HAOT), basaltic andesites (BA), primitive magnesian andesites (PMA), and dacites. The most primitive HAOT (MgO > 9 wt%) from Mt. Shasta has olivine δ¹⁸O (δ¹⁸O_Ol) values of 5.9–6.1‰, which are about 1‰ higher than those observed in olivine from normal mantle-derived magmas. In contrast, HAOT lavas from Medicine Lake have δ¹⁸O_Ol values ranging from 4.7 to 5.5‰, which are similar to or lower than values for olivine in equilibrium with mantle-derived magmas. Other magma types from both volcanoes show intermediate δ¹⁸O_Ol values. The oxygen isotope composition of the most magnesian lavas cannot be explained by crustal contamination and the trace element composition of olivine phenocrysts precludes a pyroxenitic mantle source. Therefore, the high and variable δ¹⁸O_Ol signature of the most magnesian samples studied (HAOT and BA) comes from the peridotitic mantle wedge itself. As HAOT magma is generated by anhydrous adiabatic partial melting of the shallow mantle, its 1.4‰ range in δ¹⁸O_Ol reflects a heterogeneous composition of the shallow mantle source that has been influenced by subduction fluids and/or melts sometime in the past. Magmas generated in the mantle wedge by flux melting due to modern subduction fluids, as exemplified by BA and probably PMA, display more homogeneous composition with only 0.5‰ variation. The high-δ¹⁸O values observed in magnesian lavas, and principally in the HAOT, are difficult to explain by a single-stage flux-melting process in the mantle wedge above the modern subduction zone and require a mantle source enriched in ¹⁸O. It is here explained by flow of older, pre-enriched portions of the mantle through the slab window beneath the South Cascades.     

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     

Distribution of oxygen isotopes in rocks and minerals from the critical zone of the Ioko-Dovyren pluton

The oxygen isotopic composition was studied in minerals and rocks from the critical zone of the Ioko-Dovyren layered pluton. The δ¹⁸O values vary from +5.4 to +6.1‰ in rocks, from +4.8 to +5.8‰ in olivine, from +5.5 to 6.5‰ in pyroxene, and from +5.8 to +6.9‰ in plagioclase and fall into the interval of mantle values for continental mafic and ultramafic rocks. A decrease in δ¹⁸O could have been caused by penetration of meteoric water. Postmagmatic (retrograde) oxygen isotopic redistribution in the slowly cooling rocks is responsible for disturbance of oxygen isotope equilibria in the coexisting minerals, which were crystallized from the same magma at a high temperature. The nonequilibrium oxygen isotopic composition in the associated minerals and calculated temperature of the final isotopic equilibration do not contradict the model of “fluid” formation of low-sulfide PGE mineralization in the Ioko-Dovyren layered pluton.     

Melt/rock interaction in remains of refertilized Archean lithospheric mantle in Jiaodong Peninsula, North China Craton: Li isotopic evidence

Li contents and its isotopes of minerals in mantle peridotite xenoliths from late Cretaceous mafic dikes, analyzed in situ by Cameca IMS-1280, reveal the existence of melt/rock interaction in remains of refertilized Archean lithospheric mantle in Qingdao, Jiaodong Peninsula, North China Craton. Two groups of peridotites exist, i.e., low-Mg# lherzolite and high-Mg# harzburgites. The low-Mg# lherzolite has a relatively homogeneous Li concentration (ol: 2.01–2.11 ppm; opx: 1.77–1.88 ppm; cpx: 1.75–1.93 ppm) and Li isotopic composition (δ⁷Li in ol: 4.2–7.6‰; in opx: 6.0–8.3‰; in cpx: 5.3–8.4‰). The similarity in δ⁷Li value to the fresh MORB provides further evidence for the argument that the low-Mg# lherzolite could be the fragment of the newly accreted lithospheric mantle. The high-Mg# harzburgites have heterogeneous Li abundances (ol: 0.83–2.09 ppm; opx: 0.92–1.94 ppm; cpx: 1.12–4.89 ppm) and Li isotopic compositions (δ⁷Li in ol: −0.5 to +11.5‰; in opx: −6.2 to +11.1‰; in cpx: −34.3 to +10.1‰), showing strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The cores of most minerals in these high-Mg# harzburgites have relatively homogeneous δ⁷Li values, which are higher than those of fresh MORB, but similar to those previously reported for arc lavas. These harzburgites have enriched trace elemental and Sr–Nd isotopic compositions. These observations indicate that in the early Mesozoic the lithospheric mantle beneath the southeastern North China Craton was similar to that in arc settings, which is metasomatized by subducted crustal materials. Extremely low δ⁷Li preserved in cpxs requires diffusive fractionation of Li isotopes from later-stage melt into the minerals. Thus, the Li data provide further evidence that the Archean refractory lithospheric mantle represented by the high-Mg# harzburgites was refertilized through melt/rock interaction and transformed to the Mesozoic less refractory and incompatible element and Sr–Nd isotopes enriched lithospheric mantle.     

Historic magmatism on the Reykjanes Peninsula,Iceland: a snap-shot of melt generation at a ridge segment

We present new compositional data on a suite of historic lava flows from the Reykjanes Peninsula, Iceland. They were erupted over a short time period between c. 940 and c. 1340 ad and provide a snap-shot view of melt generation and evolution processes beneath this onshore, 65 km long, ridge segment. The lavas are tholeiitic basalts (MgO 6.5–9.2 wt%) and sparsely (≪5%) olivine and/or plagioclase phyric (±trace clinopyroxene). Individual eruptive events show remarkable compositional homogeneity. Despite a limited variation in Sr–Nd isotope compositions, high-precision double-spike Pb isotope data show tight coherent arrays that, together with correlations with incompatible trace element ratios, indicate control by binary mixing processes. Poor correlations with elemental abundances require that this mixing took place prior to extensive fractional crystallisation. Olivines in the historic lavas have light δ¹⁸O values (+4.2 to +4.3‰), which is likely to be a feature of the enriched mantle source to Reykjanes Peninsula lavas. High precision Pb isotope analyses of other post-glacial Reykjanes Peninsula lavas show significant variability in ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb at lower ²⁰⁶Pb/²⁰⁴Pb values than in the historic lavas. This variation demonstrates that at least three compositionally distinct components within the mantle are required to explain the Pb isotope variations within the Reykjanes Peninsula as a whole. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Anorthositic Rocks of the Duluth Complex: Examples of Rocks Formed from Plagioclase Crystal Mush

Anorthositic rocks compose 35–40% of the Middle Proterozoic(Keweenawan; 1?1 Ga) Duluth Complex—a large, compositemafic body in northeastern Minnesota that was intruded beneatha comagmatic volcanic edifice during the formation of the Midcontinentrift system. Anorthositic rocks, of which six general lithologictypes occur in one area of the complex, are common in an earlyseries of intrusions. They are characterized on a local scale(meters to kilometers) by nonstratiform distribution of rocktypes, variably oriented plagioclase lamination, and compositeintrusive relationships. Variably zoned, subhedral plagioclaseof nearly constant average An (60) makes up 82–98% ofthe anorthositic rocks. Other phases include granular to poikiliticolivine (Fo_66–38), poikilitic clinopyrox-ene (En'_73–37),subpoikilitic Fe-Ti oxides, and various late-stage and secondaryminerals. Whole-rock compositions of anorthositic rocks are modelled bymass balance to consist of three components: cumulus plagioclase(70–95 wt.%), minor cumulus olivine (0–5%), anda gabbroic postcumulus assemblage (5–27%) representinga trapped liquid. The postcumulus assemblage has textural andcompositional characteristics which are consistent with crystallizationfrom basaltic magma ranging from moderately evolved olivinetholeiite to highly evolved tholeiite (mg=60–25). Sympatheticvariations of mg in plagioclase and in mafic minerals suggestthat cumulus plagioclase, though constant in An, was in approximateequilibrium with the variety of basaltic magma compositionswhich produced the postcumulus assemblages. Standard models of mafic cumulate formation by fractional crystallizationof basaltic magmas in Duluth Complex chambers, although ableto explain the petrogenesis of younger stratiform troctoliticto gabbroic intrusions, are inadequate to account for the field,petrographic, and geochemical characteristics of the anorthositicrocks. Rather, we suggest an origin by multiple intrusions ofplagioclase crystal mushes—basaltic magmas charged withas much as 60% intratelluric plagioclase. The high concentrationsof cumulus plagioclase (70–95%) estimated to compose theanorthositic rocks may reflect expulsion of some of the transportingmagma during emplacement or early postcumulus crystallizationof only plagioclase from evolved hyperfeldspathic magma. Althoughthe evolved compositions of anorthositic rocks require significantfractionation of mafic minerals, geophysical evidence indicatesthat ultramafic rocks are, as exposure implies, rare in theDuluth Complex and implies that plagioclase crystal mushes werederived from deeper staging chambers. This is consistent withinterpretations of olivine habit and plagioclase zoning. Moreover,plagioclase could have been segregated from coprecipitatingmafic phases in such lower crustal chambers because of the buoyancyof plagioclase in basaltic magmas at high pressure. The geochemicaleffects of plagioclase suspension in basaltic magmas are consistentwith observed compositions of cumulus plagioclase in the anorthositicrocks and with the geochemical characteristics of many comagmaticbasalts. The petrogenesis of the anorthositic rocks and theoverall evolution of Keweenawan magmas can be related to thedynamics of intracontinental rift formation.     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

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.     

Oxygen isotope geochemistry of the Granite Harbour Intrusives, Wilson Terrane, Northern Victoria Land, Antarctica

Summary The oxygen and strontium isotope compositions of the Cambro-Ordovician granitoids cropping out in the Wilson Terrane (Granite Harbour Intrusives–GHI) constrain the petrological evolution of the magmatism in Antarctica, related to the Ross Orogeny. The measured δ¹⁸O_WR values of these intrusives define three different compositional groups: the metaluminous rocks (MAG), with δ¹⁸O_WR ranging from 6.9 (olivine gabbro) to 11.4‰ (monzogranite); the unaltered peraluminous granites (PAG), having δ¹⁸O_WR values ranging from 10.6 to 13.2‰, and the foliated peraluminous leucogranites (SKG), characterised by δ¹⁸O_WR values above 14‰. The analysis of equilibrium mineral assemblages indicates that the high δ¹⁸O_WR values are magmatic and unaffected by low-temperature processes. A few peraluminous granites sampled in the vicinity of Cenozoic intrusions show anomalously low δ¹⁸O_WR, due to meteoric-hydrothermal alteration. The isotopic data indicate that the coeval and spatially related metaluminous mafic and felsic intrusives forming the GHI were not comagmatic: the mafic and intermediate rocks were likely derived from lower crustal contamination of a pristine basaltic magma; their δ¹⁸O_WR values were also increased during emplacement, due to the interaction with the adjacent ¹⁸O-rich hydrous felsic magmas (mixing). Oxygen isotope data indicate that the crustal sources producing the Granite Harbour intrusives were not homogeneous: the felsic metaluminous intrusives were produced by partial melting of fertile rock with possible igneous origin, whereas partial melting of a metapelitic source rock is claimed for the genesis of the peraluminous granites. Received February 9, 2001; revised version accepted August 10, 2001     

Geology and vein tin mineralization in the Dadoushan deposit,Gejiu district,SW China

Vein-type tin mineralization in the Dadoushan deposit, Laochang ore field, Gejiu district, SW China, is predominantly hosted in Triassic carbonate rocks (Gejiu Formation) over cupolas of the unexposed Laochang equigranular granite intrusion. The most common vein mineral is tourmaline, accompanied by skarn minerals (garnet, diopside, epidote, phlogopite) and beryl. The main ore mineral is cassiterite, accompanied by minor chalcopyrite, pyrrhotite, and pyrite, as well as scheelite. The tin ore grade varies with depth, with the highest grades (~1.2 % Sn) prevalent in the lower part of the vein zone. Muscovite ⁴⁰Ar–³⁹Ar dating yielded a plateau age of 82.7 ± 0.7 Ma which defines the age of the vein-type mineralization. Measured sulfur isotope compositions (δ ³⁴S = −4.1 to 3.9 ‰) of the sulfides (arsenopyrite, chalcopyrite, pyrite, and pyrrhotite) indicate that the sulfur in veins is mainly derived from a magmatic source. The sulfur isotope values of the ores are consistent with those from the underlying granite (Laochang equigranular granite, −3.7 to 0.1 ‰) but are different from the carbonate wall rocks of the Gejiu Formation (7.1 to 11.1 ‰). The calculated and measured oxygen and hydrogen isotope compositions of the ore-forming fluids (δ ¹⁸O_H2O = −2.4 to 5.5 ‰, δD = −86 to −77 ‰) suggest an initially magmatic fluid which gradually evolved towards meteoric water during tin mineralization.     

Mineral inclusions in sublithospheric diamonds from Collier 4 kimberlite pipe, Juina, Brazil: subducted protoliths, carbonated melts and primary kimberlite magmatism

We report on a suite of diamonds from the Cretaceous Collier 4 kimberlite pipe, Juina, Brazil, that are predominantly nitrogen-free type II crystals showing complex internal growth structures. Syngenetic mineral inclusions comprise calcium- and titanium-rich phases with perovskite stoichiometry, Ca-rich majoritic-garnet, clinopyroxene, olivine, TAPP phase, minerals with stoichiometries of CAS and K-hollandite phases, SiO₂, FeO, native iron, low-Ni sulfides, and Ca–Mg-carbonate. We divide the diamonds into three groups on the basis of the carbon isotope compositions (δ¹³C) of diamond core zones. Group 1 diamonds have heavy, mantle-like δ¹³C (−5 to −10‰) with mineral inclusions indicating a transition zone origin from mafic protoliths. Group 2 diamonds have intermediate δ¹³C (−12 to −15‰), with inclusion compositions indicating crystallization from near-primary and differentiated carbonated melts derived from oceanic crust in the deep upper mantle or transition zone. A ²⁰⁶Pb/²³⁸U age of 101 ± 7 Ma on a CaTiSi-perovskite inclusion (Group 2) is close to the kimberlite emplacement time (93.1 ± 1.5 Ma). Group 3 diamonds have extremely light δ¹³C (−25‰), and host inclusions have compositions akin to high-pressure–temperature phases expected to be stable in pelagic sediments subducted to transition zone depths. Collectively, the Collier 4 diamonds and their inclusions indicate multi-stage, polybaric growth histories in dynamically changing chemical environments. The young inclusion age, the ubiquitous chemical and isotopic characteristics indicative of subducted materials, and the regional tectonic history, suggest a model in which generation of sublithospheric diamonds and their inclusions, and the proto-kimberlite magmas, are related genetically, temporally and geographically to the interaction of subducted lithosphere and a Cretaceous plume.     

Crystallization of primitive basaltic magmas at crustal pressures and genesis of the calc-alkaline igneous suite: experimental evidence from St Vincent,Lesser Antilles arc

Near-liquidus crystallization experiments have been carried out on two basalts (12.5 and 7.8 wt% MgO) from Soufriere, St Vincent (Lesser Antilles arc) to document the early stages of differentiation in calc-alkaline magmas. The water-undersaturated experiments were performed mostly at 4 kbar, with 1.6 to 7.7 wt% H₂O in the melt, and under oxidizing conditions (ΔNNO = −0.8 to +2.4). A few 10 kbar experiments were also performed. Early differentiation of primitive, hydrous, high-magnesia basalts (HMB) is controlled by ol + cpx + sp fractionation. Residual melts of typical high-alumina basalt (HAB) composition are obtained after 30–40% crystallization. The role of H₂O in depressing plagioclase crystallization leads to a direct relation between the Al₂O₃ content of the residual melt and its H₂O concentration, calibrated as a geohygrometer. The most primitive phenocryst assemblage in the Soufriere suite (Fo_89.6 olivine, Mg-, Al- and Ti-rich clinopyroxene, Cr–Al spinel) crystallized from near-primary (Mg# = 73.5), hydrous (∼5 wt% H₂O) and very oxidized (ΔNNO = +1.5–2.0) HMB liquids at middle crustal pressures and temperatures from ∼1,160 to ∼1,060°C. Hornblende played no role in the early petrogenetic evolution. Derivative HAB melts may contain up to 7–8 wt% dissolved H₂O. Primitive basaltic liquids at Soufriere, St Vincent, have a wide range of H₂O concentrations (2–5 wt%).     

Oxygen isotope evidence for subduction and rift-related mantle metasomatism beneath the Colorado Plateau–Rio Grande rift transition

Spinel lherzolite and pyroxenite xenoliths from the Rio Puerco Volcanic Field, New Mexico, were analyzed for oxygen isotope ratios by laser fluorination. In lherzolites, olivine δ¹⁸O values are high (+5.5‰), whereas δ¹⁸O values for pyroxenes are low (cpx=+5.1‰; opx=+5.4‰) compared to average mantle values. Pyroxenite δ¹⁸O values (cpx=+5.0‰; opx=+5.3‰) are similar to those of the lherzolites and are also lower than typical mantle oxygen isotope compositions. Texturally and chemically primary calcite in pyroxenite xenoliths is far from isotopic equilibrium with other phases, with δ¹⁸O values of +21‰. The isotopic characteristics of the pyroxenite xenoliths are consistent with a petrogenetic origin from mixing of lherzolitic mantle with slab-derived silicate and carbonatite melts. The anomalously low δ¹⁸O in the pyroxenes reflects metasomatism by a silicate melt from subducted altered oceanic crust, and high δ¹⁸O calcite is interpreted to have crystallized from a high δ¹⁸O carbonatitic melt derived from subducted ophicarbonate. Similar isotopic signatures of metasomatism are seen throughout the Rio Puerco xenolith suite and at Kilbourne Hole in the southern Rio Grande rift. The discrete metasomatic components likely originated from the subducted Farallon slab but were not mobilized until heating associated with Rio Grande rifting occurred. Oxygen diffusion modeling requires that metasomatism leading to the isotopic disequilibrium between calcite and pyroxene in the pyroxenites occurred immediately prior to entrainment. Melt infiltration into spinel-facies mantle (xenoliths) prior to eruption was thus likely connected to garnet-facies melting that resulted in eruption of the host alkali basalt.     

Multistage melt/fluid-peridotite interactions in the refertilized lithospheric mantle beneath the North China Craton: constraints from the Li–Sr–Nd isotopic disequilibrium between minerals of peridotite xenoliths

Elemental and Li–Sr–Nd isotopic data of minerals in spinel peridotites hosted by Cenozoic basalts allow us to refine the existing models for Li isotopic fractionation in mantle peridotites and constrain the melt/fluid-peridotite interaction in the lithospheric mantle beneath the North China Craton. Highly elevated Li concentrations in cpx (up to 24 ppm) relative to coexisting opx and olivine (<4 ppm) indicate that the peridotites experienced metasomatism by mafic silicate melts and/or fluids. The mineral δ⁷Li vary greatly, with olivine (+0.7 to +5.4‰) being isotopically heavier than coexisting opx (−4.4 to −25.9‰) and cpx (−3.3 to −21.4‰) in most samples. The δ⁷Li in pyroxenes are considerably lower than the normal mantle values and show negative correlation with their Li abundances, likely due to recent Li ingress attended by diffusive fractionation of Li isotopes. Two exceptional samples have olivine δ⁷Li of −3.0 and −7.9‰, indicating the existence of low δ⁷Li domains in the mantle, which could be transient and generated by meter-scale diffusion of Li during melt/fluid-peridotite interaction. The ¹⁴³Nd/¹⁴⁴Nd (0.5123–0.5139) and ⁸⁷Sr/⁸⁶Sr (0.7018–0.7062) in the pyroxenes also show a large variation, in which the cpx are apparently lower in ⁸⁷Sr/⁸⁶Sr and slightly higher in ¹⁴³Nd/¹⁴⁴Nd than coexisting opx, implying an intermineral Sr–Nd isotopic disequilibrium. This is observed more apparently in peridotites having low ⁸⁷Sr/⁸⁶Sr and high ¹⁴³Nd/¹⁴⁴Nd ratios than in those with high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd, suggesting that a relatively recent interaction existed between an ancient metasomatized lithospheric mantle and asthenospheric melt, which transformed the refractory peridotites with highly radiogenic Sr and unradiogenic Nd isotopic compositions to the fertile lherzolites with unradiogenic Sr and radiogenic Nd isotopic compositions. Therefore, we argue that the lithospheric mantle represented by the peridotites has been heterogeneously refertilized by multistage melt/fluid-peridotite interactions.     

Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

Chemical evolution of basalts from 23°N along the mid-Atlantic ridge: evidence from melt inclusions

The chemical compositions of melt inclusions in a primitive and an evolved basalt recovered from the mid-Atlantic ridge south of the Kane Fracture Zone (23°–24°N) are determined. The melt inclusions are primitive in composition (0.633–0.747 molar Mg/(Mg+Fe²⁺), 1.01–0.68 wt% TiO₂) and are comparable to other proposed parental magmas except in having higher Al₂O₃ and lower CaO. The primitive melt inclusion compositions indicate that the most primitive magmas erupted in this region are not near primary magma compositions. Olivine and plagioclase microphenocrysts are close to exchange equilibrium with their respective basalt glasses, whose compositions are displaced toward olivine from 1 atm three phase saturation. The most primitive melt inclusion compositions are close to exchange equilibrium with the anorthitic cores of zoned plagioclases (An_78.3-An_83.1; the hosts for the melt inclusions in plagioclase) and with olivines more forsteritic (Fo₈₉-Fo₉₁) than the olivine microphenocrysts (the hosts for the melt inclusions in olivine). Xenocrystic olivine analyzed is Fo₈₉ but contains no melt inclusions. These observations indicate that olivines have exchanged components with the melt after melt inclusion entrapment, whereas plagioclase compositions have remained the same since melt inclusion entrapment. Common denominator element ratio diagrams and oxide versus oxide variation diagrams show that the melt inclusion compositions, which represent liquids higher along the liquid line of descent, are related to the glass compositions by the fractionation of olivine, plagioclase and clinopyroxene (absent from the mincral assemblage), probably occurring at elevated pressures. A model is proposed whereby clinopyroxene segregates from the melt at elevated pressures (to account for its absence in the erupted lavas that have the chemical imprint of clinopyroxene fractionation). Zoned plagioclases in the erupted lavas are thought to be survivors of decompressional melting during magma ascent. Since similar primitive melt inclusions occur in olivine microphenocrysts and in the cores of zoned plagioclases, any model must account for all phases present.     

Mineralogical, fluid inclusion, and stable isotope constraints on mechanisms of ore deposition at the Samgwang mine (Republic of Korea)—a mesothermal, vein-hosted gold–silver deposit

The Samgwang mine is located in the Cheongyang gold district (Cheonan Metallogenic Province) of the Republic of Korea. It consists of eight massive, gold-bearing quartz veins that filled NE- and NW-striking fractures along fault zones in Precambrian granitic gneiss of the Gyeonggi massif. Their mineralogy and paragenesis allow two separate vein-forming episodes to be recognized, temporally separated by a major faulting event. The ore minerals occur in quartz and calcite of stage I, associated with fracturing and healing of veins. Hydrothermal wall-rock alteration minerals of stage I include Fe-rich chlorite (Fe/(Fe+Mg) ratios 0.74-0.81), muscovite, illite, K-feldspar, and minor arsenopyrite, pyrite, and carbonates. Sulfide minerals deposited along with electrum during this stage include arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, galena, argentite, pyrargyrite, and argentian tetrahedrite. Only calcite was deposited during stage II. Fluid inclusions in quartz contain three main types of C–O–H fluids: CO₂-rich, CO₂–H₂O, and aqueous inclusions. Quartz veins related to early sulfides in stage I were deposited from H₂O–NaCl–CO₂ fluids (1,500–5,000 bar, average 3,200) with T _htotal values of 200°C to 383°C and salinities less than about 7 wt.% NaCl equiv. Late sulfide deposition was related to H₂O–NaCl fluids (140–1,300 bar, average 700) with T _htotal values of 110°C to 385°C and salinities less than about 11 wt.% NaCl equiv. These fluids either evolved through immiscibility of H₂O–NaCl–CO₂ fluids as a result of a decrease in fluid pressure, or through mixing with deeply circulated meteoric waters as a result of uplift or unloading during mineralization, or both. Measured and calculated sulfur isotope compositions (δ³⁴S_H2S = 1.5 to 4.8‰) of hydrothermal fluids from the stage I quartz veins indicate that ore sulfur was derived mainly from a magmatic source. The calculated and measured oxygen and hydrogen isotope compositions (δ¹⁸O_H2O = −5.9‰ to 10.9‰, δD = −102‰ to −87‰) of the ore-forming fluids indicate that the fluids were derived from magmatic sources and evolved by mixing with local meteoric water by limited water–rock exchange and by partly degassing in uplift zones during mineralization. While most features of the Samgwang mine are consistent with classification as an orogenic gold deposit, isotopic and fluid chemistry indicate that the veins were genetically related to intrusions emplaced during the Jurassic to Cretaceous Daebo orogeny.