Trace element and isotopic variations in a zoned pluton and associated volcanic rocks,Unalaska Island,Alaska: A model for fractionation in the Aleutian calcalkaline suite

Trace elements, including rare earth elements (REE), exhibit systematic variations in plutonic rocks from the Captains Bay pluton which is zoned from a narrow gabbroic rim to a core of quartz monzodiorite and granodiorite. The chemical variations parallel those in the associated Aleutian calcalkaline volcanic suite. Concentrations of Rb, Y, Zr and Ba increase as Sr and Ti decrease with progressive differentiation. Intermediate plutonic rocks are slightly enriched in light REE (La/Yb=3.45–9.22), and show increasing light REE fractionation and negative Eu anomalies (Eu/Eu^*=1.03–0.584). Two border-zone gabbros have similar REE patterns but are relatively depleted in total REE and have positive Eu anomalies; indicative of their cumulate nature. Initial ⁸⁷Sr/⁸⁶Sr ratios in 8 samples (0.70299 to 0.70377) are comparable to those of volcanic rocks throughout the arc and suggest a mantle source for the magmas. Oxygen isotopic ratios indicate that many of the intermediate plutonic rocks have undergone oxygen isotopic exchange with large volumes of meteoric water during the late stages of crystallization; however no trace element or Sr isotopic alteration is evident.Major and trace element variations are consistent with a model of inward fractional crystallization of a parental high-alumina basaltic magma at low pressures (6 kb). Least-squares approximations and trace element fractionation calculations suggest that differentiation in the plutonic suite was initially controlled by the removal of calcic plagioclase, lesser pyroxene, olivine and Fe-Ti oxides but that with increasing differentiation and water fugacity the removal of sub-equal amounts of sodic plagioclase and hornblende with lesser Fe-Ti oxides effectively drove residual liquids toward dacitic compositions. Major and trace element compositions of aplites which intrude the pluton are not adequately explained by fractional crystallization. They may represent partial melts derived from the island arc crust. Similarities in Sr isotopes, chemical compositions and differentiation trends between the plutonic series and some Aleutian volcanic suites indicates that shallow-level fractional crystallization is a viable mechanism for generating the Aleutian calcalkaline rock series.LDGO Contribution no. 2964     

Chemistry,mineralogy and petrology of an eclogite from the type locality (Saualpe,Austria)

An eclogite and five of its coexisting minerals (omphacite, garnet, carinthine, kyanite and zoisite) from the probable type locality of eclogites (Kupplerbrunn, Saualpe, Austria) described by Haüy (1822) have been analysed. Optical and X-ray data for these minerals are also given. Comparison of the Kupplerbrunn rock with those of other eclogites from the Saualpe region indicates they all have roughly similar compositions. When plotted on an A-C-F diagram the majority of these analyses fall in the region of kyanite-bearing eclogites suggested by Tilley (1936) although the Kupplerbrunn rock is the only sample containing kyanite; the others containing zoisite. The garnet and omphacite compositions of the Kupplerbrunn rock differ markedly from those of other Saualpe eclogites, possibly due to different metamorphic conditions of their formation. Carinthine analyses are all very similar for eclogites from Saualpe. On the basis of geological, analytical and limited experimental evidence, it is postulated that the Kupplerbrunn eclogite was derived from an original gabbroic rock low in water content such that amphibole and zoisite formed from plagioclase, pyroxene and water; omphacite, garnet and kyanite formed from plagioclase and pyroxene, once all the water was used up in the form of amphibole and zoisite. These reactions are believed to have taken place at 5–8 kb pressure at around 600° C; a value close to that suggested by Lodemann (1966) from field data.     

Cumulate xenoliths from St. Vincent, Lesser Antilles Island Arc: a window into upper crustal differentiation of mantle-derived basalts

In order to shed light on upper crustal differentiation of mantle-derived basaltic magmas in a subduction zone setting, we have determined the mineral chemistry and oxygen and hydrogen isotope composition of individual cumulus minerals in plutonic blocks from St. Vincent, Lesser Antilles. Plutonic rock types display great variation in mineralogy, from olivine–gabbros to troctolites and hornblendites, with a corresponding variety of cumulate textures. Mineral compositions differ from those in erupted basaltic lavas from St. Vincent and in published high-pressure (4–10 kb) experimental run products of a St. Vincent high-Mg basalt in having higher An plagioclase coexisting with lower Fo olivine. The oxygen isotope compositions (δ¹⁸O) of cumulus olivine (4.89–5.18‰), plagioclase (5.84–6.28‰), clinopyroxene (5.17–5.47‰) and hornblende (5.48–5.61‰) and hydrogen isotope composition of hornblende (δD = −35.5 to −49.9‰) are all consistent with closed system magmatic differentiation of a mantle-derived basaltic melt. We employed a number of modelling exercises to constrain the origin of the chemical and isotopic compositions reported. δ¹⁸O_Olivine is up to 0.2‰ higher than modelled values for closed system fractional crystallisation of a primary melt. We attribute this to isotopic disequilibria between cumulus minerals crystallising at different temperatures, with equilibration retarded by slow oxygen diffusion in olivine during prolonged crustal storage. We used melt inclusion and plagioclase compositions to determine parental magmatic water contents (water saturated, 4.6 ± 0.5 wt% H₂O) and crystallisation pressures (173 ± 50 MPa). Applying these values to previously reported basaltic and basaltic andesite lava compositions, we can reproduce the cumulus plagioclase and olivine compositions and their associated trend. We conclude that differentiation of primitive hydrous basalts on St. Vincent involves crystallisation of olivine and Cr-rich spinel at depth within the crust, lowering MgO and Cr₂O₃ and raising Al₂O₃ and CaO of residual melt due to suppression of plagioclase. Low density, hydrous basaltic and basaltic andesite melts then ascend rapidly through the crust, stalling at shallow depth upon water saturation where crystallisation of the chemically distinct cumulus phases observed in this study can occur. Deposited crystals armour the shallow magma chamber where oxygen isotope equilibration between minerals is slowly approached, before remobilisation and entrainment by later injections of magma.     

Sub-volcanic infiltration and syn-eruptive quenching of liquids in cumulate wall-rocks: the example of the gabbroic nodules of Stromboli (Aeolian Islands, Italy)

Summary ¶Fine- to coarse-grained plutonic nodules within the Petrazza pyroclastics (Paleo-Stromboli I period) consist of gabbroic rocks with variable amounts of interstitial material. They are characterised by cumulate textures and low pressure modal mineralogy formed by plagioclase (An_96–87)+clinopyroxene (Mg-v 82–94)+olivine (Fo_83–74)±amphibole±opaque minerals; the interstitial material consists of newly crystallised microlites (quenching) of plagioclase (An_73–55)+amphibole+clinopyroxene±olivine±biotite±opaques and highly variable amounts of residual glasses that range in composition from shoshonite and high-K basaltic andesite to high-K andesite and latite. The interstitial material has a relatively high but variable degree of vesicularity. The whole rock incompatible element abundances are lower than – but the patterns are typical of – in subduction related magmas and the incompatible trace-elements are well correlated with the amount of the interstitial material. The Sr, Pb and Nd isotopic ratios resemble those of the extrusive rocks of Stromboli older series and the mineral chemistry of the gabbros is similar to that of the HKCA Paleo-Stromboli lavas. Modal mineralogy, mineral chemistry and chemical-isotopic whole rock compositions suggest that the cumulus portions of the gabbroic nodules crystallised from basaltic magmas compositionally compatible with those erupted by Stromboli volcano. The interstitial material does not represent the residual liquid after in situ crystallisation of the gabbros; it is also distinct from the juvenile host andesite magma. Textural evidence, Fe–Mg mineral/liquid partioning and mass balance calculations indicate that the interstitial material (quench crystals and vesicular glass) derived from infiltrated hydrous basaltic liquid undercooling and vesiculation of which occurred during the eruption of the Petrazza pyroclastics.Received April 17, 2002; revised version accepted November 14, 2002 Published online June 2, 2003     

Geochemical constraints of the eclogite and granulite facies metamorphism as recognized in the Raobazhai complex from North Dabie Shan,China

A combined study of major and trace elements, fluid inclusions and oxygen isotopes has been carried out on garnet pyroxenite from the Raobazhai complex in the North Dabie Terrane (NDT). Well‐preserved compositional zoning with Na decreasing and Ca and Mg increasing from the core to rim of pyroxene in the garnet pyroxenite indicates eclogite facies metamorphism at the peak metamorphic stage and subsequent granulite facies metamorphism during uplift. A P–T path with substantial heating (from c. 750 to 900 °C) after the maximum pressure reveals a different uplift history compared with most other eclogites in the South Dabie Terrane (SDT). Fluid inclusion data can be correlated with the metamorphic grade: the fluid regime during the peak metamorphism (eclogite facies) was dominated by N₂‐bearing NaCl‐rich solutions, whereas it changed into CO₂‐dominated fluids during the granulite facies retrograde metamorphism. At a late retrograde metamorphic stage, probably after amphibolite facies metamorphism, some external low‐salinity fluids were involved. In situ UV‐laser oxygen isotope analysis was undertaken on a 7 mm garnet, and impure pyroxene, amphibole and plagioclase. The nearly homogeneous oxygen isotopic composition (δ¹⁸O_VSMOW = c. 6.7‰) in the garnet porphyroblast indicates closed fluid system conditions during garnet growth. However, isotopic fractionations between retrograde phases (amphibole and plagioclase) and garnet show an oxygen isotopic disequilibrium, indicating retrograde fluid–rock interactions. Unusual MORB‐like rare earth element (REE) patterns for whole rock of the garnet pyroxenite contrast with most ultra‐high‐pressure (UHP) eclogites in the Dabie‐Sulu area. However, the age‐corrected initial ε_Nd(t) is ? 2.9, which indicates that the protolith of the garnet pyroxenite was derived from an enriched mantle rather than from a MORB source. Combined with the present data of oxygen isotopic compositions and the characteristic N₂ content in the fluid inclusions, we suggest that the protolith of the garnet pyroxenite from Raobazhai formed in an enriched mantle fragment, which has been exposed to the surface prior to the Triassic metamorphism.     

Oxygen isotope fractionation and disequilibrium displayed by some granulite facies rocks from the Fraser Range,Western Australia

The granulites of the Fraser Range are assumed to have formed in a carbon-rich fluid, and are generally devoid of hornblende, and lack obvious hydrous retrograde features. In these granulites, pyroxene, garnet, plagioclase and quartz are the minerals most likely to retain the oxygen isotope ratios fixed at an early stage of initial granulite metamorphism. Temperature estimates using these minerals commonly suggest that oxygen isotopic exchange ceased in the range 600 to 680°C. The peak metamorphic temperature was probably ～ 850°C as based on the stability fields of the coexisting minerals and some cation temperatures from coexisting pyroxenes in these rocks. Ilmenite may be slightly out of isotopic equilibrium with the other minerals. Thus, grains of quartz, feldspar, pyroxene and ilmenite have suffered considerable oxygen isotopic exchange during the retrogressive phase of the metamorphism, in spite of the fact that very little water was present in these granulites. The observed deviation from the peak metamorphic temperatures can be explained by essentially closed system solid-state diffusion (on at least a scale of centimetres) during slow cooling of the rocks from ~850 to 650°C, followed by more rapid cooling down to ～ 300°C. Such an explanation is not at variance with the radiometric data available for rocks from the area, which suggest that the latter phase could have involved uplift rates of ?0.5 mm/yr for a period of about 40 Ma. Wholerock δ¹⁸O values on non-quartzose mafic granulites, about 7.2%., fall within the range of basalts affected by seafloor weathering.     

The role of H2O during crystallization of primitive arc magmas under uppermost mantle conditions and genesis of igneous pyroxenites: an experimental study

Exposed, subduction-related magmatic arcs commonly include sections of ultramafic plutonic rocks that are composed of dunite, wehrlite, and pyroxenite. In this experimental study we examined the effects of variable H₂O concentration on the phase proportions and compositions of igneous pyroxenites and related ultramafic plutonic rocks. Igneous crystallization experiments simulated natural, arc magma compositions at 1.2 GPa, corresponding to conditions of the arc lower crust. Increasing H₂O concentration in the liquid changes the crystallization sequence. Low H₂O concentration in the liquid stabilizes plagioclase earlier than garnet and amphibole while derivative liquids remain quartz normative. Higher H₂O contents (>3%) suppress plagioclase and lead to crystallization of amphibole and garnet thereby producing derivative corundum normative andesite liquids. The experiments show that alumina in the liquid correlates positively with Al in pyroxene, as long as no major aluminous phase crystallizes. Extrapolation of this correlation to natural pyroxenites in the Talkeetna and Kohistan arc sections indicates that clinopyroxenes with low Ca-Tschermaks component represent near-liquidus phases of primitive, Si-rich hydrous magmas. Density calculations on the residual solid assemblages indicate that ultramafic plutonic rocks are always denser than upper mantle rocks in the order of 0.05 to 0.20 g/cm³. The combination of high pressure and high H₂O concentration in the liquid suppresses plagioclase crystallization, so that ultramafic plutonic rocks form over a significant proportion of the crystallization interval (up to 50% crystallization of ultramafic rocks from initial, mantle-derived liquids). This suggests that in subduction-related magmatic arcs the seismic Moho might be shallower than the petrologic crust/mantle transition. It is therefore possible that calculations based on seismic data have overestimated the normative plagioclase content (e.g., SiO₂, Al₂O₃) of igneous crust in arcs.     

Oxygen isotopic studies of the interaction between xenoliths and mafic magma, Voisey’s Bay Intrusion, Labrador, Canada

Sulfide mineralization in the Voisey’s Bay Intrusion, Labrador, Canada, is closely associated with country rock xenoliths that have extensively reacted with basaltic magma. In order to better understand the processes that control the assimilation of country rocks by mafic magma, a detailed study of oxygen isotope systematics related to magma-country rock interaction in the Voisey’s Bay area was undertaken. Protracted interaction of the xenoliths with magma produced refractory mineral assemblages in the xenoliths (2-10 cm in diameter) composed of Ca-rich plagioclase, corundum, hercynite, and minor magnetite. Overgrowth rims of plagioclase and biotite that surround most xenoliths separate the restites from the enclosing igneous matrix. The δ¹⁸O values of minerals from regionally metamorphosed pelitic and quartzofeldspathic protoliths are: plagioclase (8.7-12.3‰), orthoclase (9.5-9.8‰), biotite (5.2-8.7‰), garnet (8.3-10.8‰), pyroxene (8.0-10.1‰), and quartz (9.6-14.0). The δ¹⁸O values of minerals from the hornfels in the contact aureole of the intrusion are consistent with modeling which indicates that as a result of essentially closed system contact metamorphism oxygen isotope values should differ only slightly from those of the protoliths. Hercynite, plagioclase, and corundum separates from the xenoliths have δ¹⁸O values that vary from 2.9‰ to 10.5‰, 5.6‰ to 10.9‰, and 2.0‰ to 6.8‰, respectively. Although a siliceous ¹⁸O-enriched melt has been lost from the xenoliths, corundum, and feldspar δ¹⁸O values are significantly lower than expected through melt loss alone. The relatively low δ¹⁸O values of minerals from the xenoliths may be a function of incomplete isotopic exchange with surrounding mafic magma which had a δ¹⁸O value of ∼5.5‰ to 6.0‰. The high-¹⁸O melt that was released from the xenoliths is partially recorded in the plagioclase overgrowth on the margin of the xenoliths (δ¹⁸O values from 6.2‰ to 10.7‰), and in hercynite that replaced corundum. However, mass balance calculations indicate that a portion of the partial melt must have been transferred to magma that was moving through the conduit system. δ¹⁸O and δD values of biotite surrounding the plagioclase overgrowth range from 5.0‰ to 6.2‰ and −58‰ to −80‰, respectively. These data suggest that the outermost rim associated with many xenoliths has closely approached isotopic equilibrium with uncontaminated mafic magma. The current gabbroic to troctolitic matrix of the xenoliths shows no evidence for contamination by the high-¹⁸O partial melt from the xenoliths. The feldspar and biotite overgrowths on the xenoliths that formed after the motion of the xenoliths relative to the magma had stopped prevented further isotopic exchange between the xenoliths and final magma. The minerals within the xenoliths are not in oxygen isotopic equilibrium with each other, due in part to rapid thermal equilibration, partial melting, and partial exchange with flow through magma.     

小秦岭东吉口印支期辉石正长岩年代学及其地质意义

东吉口辉石正长岩是小秦岭地区此前唯一获得加里东期年龄的岩体,呈不规则卵圆状侵入于古元古代太华群高级变质岩中,发育弱片麻理。详细的岩相学观察发现,岩体内部可以分为两种具不同结构特征的岩性,从野外接触关系来看:细粒辉石正长岩形成较早,发育烘烤边;中粒含斑辉石正长岩略晚,发育冷凝边。二者的矿物均由斜长石、钾长石、辉石、角闪石、石英等组成,斑晶主要为辉石和斜长石,辉石和角闪石均发生退变质作用。细粒辉石正长岩LA-ICP-MS锆石U-Pb测年结果为(214.8±3.1) Ma（MSWD=0.48）,中粒含斑辉石正长岩为(212.9±3.1) Ma（MSWD=5.6）,均形成于晚三叠世印支期,而不是此前认为的加里东期。这一组年龄表明,小秦岭地区加里东期岩浆活动可能极其微弱,或者不存在该期岩浆活动。总结前人资料,发现东吉口辉石正长岩的形成时代与小秦岭印支期成矿事件同时,印支期岩浆活动与洋陆俯冲转为陆陆碰撞作用有关,强烈的壳幔相互作用导致了深部物质的上涌,岩浆活动为金的富集提供了热驱动力。     

The oxygen isotope geochemistry of igneous rocks

Oxygen isotope analyses have been obtained for 443 igneous rock and mineral samples from various localities throughout the world. Detailed studies were made on the Medicine Lake, Newberry, Lassen, Clear Lake, S. E. Guatemala, Hawaii and Easter I. volcanic complexes and on the Bushveld, Muskox, Kiglapait, Guadalupe, Duluth, Nain, Egersund, Lac St. Jean, Laramie, Skaergaard, Mull, Skye, Ardnamurchan and Alta, Utah plutonic complexes, as well as upon several of the zoned ultramafic intrusions of S. E. Alaska. Basalts, gabbros, syenites and andesites are very uniform in O¹⁸/O¹⁶, commonly with δ-values of 5.5 to 7.0 per mil. Many rhyolite obsidians, particularly those from oceanic areas and the Pacific Coast of the United States, also lie in this range; this indicates that such obsidians are differentiates of basaltic or andesitic magma at high temperatures (about 1,000° C). They cannot represent melted sialic crust. The only plutonic granites with such low δ-values are some of the hypersolvus variety, suggesting that these also might form by fractional crystallization. Obsidians from the continental interior, east of the quartz-diorite line, have higher δ-values. This is compatible with their having assimilated O¹⁸-rich sialic crust. A correlation generally exists between the O¹⁸/O¹⁶ ratios of SiO₂-rich differentiates and the chemical trends in volcanic complexes. High O¹⁸/O¹⁶ ratios accompany those trends having the lower Fe/Mg ratios, while ferrogabbro trends are associated with depletion in O¹⁸. Variations in oxygen fugacity may be responsible for these effects, as abundant early precipitation of magnetite should lead to both O¹⁸-enrichment and Fe-depletion in later differentiates. Plutonic granites have higher O¹⁸/O¹⁶ ratios than their volcanic equivalents, because (a) their differentiation occurred at much lower temperatures, or (b) they are in large part derived from O¹⁸-rich sialic crust by partial melting or assimilation. Also, the oxygen isotope fractionations among coexisting minerals are distinctly larger in plutonic rocks than in volcanic rocks. This is in keeping with their lower crystallization temperatures and their longer cooling history, which promotes post-crystallization oxygen isotope exchange. Hydrated obsidians and perlites have δO¹⁸-values that are much different from their primary, magmatic values. A correlation exists between D/H and O¹⁸/O¹⁶ ratios in hydrated volcanic glass from the western U.S.A., proving that the isotopic compositions are a result of exchange with meteoric waters. The O¹⁸ contents of the glasses appear to be about 25 per mil higher than their associated waters; hence, these hydrated glasses have not simply absorbed H₂O, but they have exchanged with large quantities of it. The igneous rocks from Mull, Skye, Ardnamurchan and the Skaergaard intrusion are all abnormally depleted in O¹⁸ relative to “normal” igneous rocks. This is a result of their having exchanged at high temperatures with meteoric water that was apparently abundant in the highly jointed plateau lavas into which these igneous rocks were intruded. In part, this exchange occurred with liquid magma and in part with the crystalline rock; in the latter case the feldspar was more easily exchanged and has become much more depleted in O¹⁸ than has coexisting quartz or pyroxene. The later differentiates of the Muskox intrusion are markedly O¹⁸-rich, but this is not a result of fractional crystallization. It is in large part a result of deuteric exchange between feldspars and an oxygen-bearing fluid (H₂O ?) that was either O¹⁸-rich or had a relatively low temperature. This phenomenon was also observed in a number of granophyres from other localities, particularly those containing brick-red alkali feldspar. The exchanged feldspars in all these examples are turbid or cloudy, and may be filled with hematite dust. It is concluded that most such feldspar in nature is the result of deuteric exchange and is probably drastically out of oxygen isotopic equilibrium with its coexisting quartz.     

Fluid infiltration effects on stable isotope systematics of the Susurluk skarn deposit,NW Turkey

A calcic skarn deposit occurs along the contact zone between Oligo-Miocene Çatalda? Granitoid and Mesozoic limestones in Susurluk, northwestern Turkey. The skarn zone with little or no retrograde stage is represented by fluid inclusions with high homogenization temperatures (up to >600 °C) and a wide range of salinity (12 to >70 wt.% NaCl). Pluton-derived fluids facilitated occurrence of continuous prograde reactions in the country rocks (particularly in the proximal zone) and oxygen isotopic depletion in calc-silicate and calcite minerals. δ¹⁸O of anhydrous minerals within proximal and distal zones indicate that skarn-forming fluids had a magmatic origin. The δ¹⁸O values are 5.93–9.08‰ (mean 6.8‰) for garnet, 4.08–9.94‰ (mean 6.4‰) for pyroxene, 4.89–7.92‰ (mean 6.4‰) for wollastonite and 6.65–8.28‰ (mean 7.5‰) for vesuvianite. Temperatures estimated by isotopic compositions of mineral pairs are significantly lower than those measured from the fluid inclusions, indicating that isotopic equilibrium is not preserved between the skarn minerals. δ¹⁸O and δ¹³C values are systematically depleted from marbles to skarn carbonates. Calc-silicate forming reactions and permeability increase triggered by volatilization and consequent strong infiltration of H₂O-rich siliceous fluids into the system promoted fluid–rock interaction causing isotopic resetting and isotopic depletion of silicates (e.g. pyroxene and wollastonite) and skarn calcites.     

Important role of hornblende fractionation in generating the adakitic magmas in Tongling,Eastern China: evidence from amphibole megacryst and cumulate xenoliths and host gabbros

ABSTRACT

Tongling, in eastern China, is an area well-known for intra-plate adakites. Here, we present the mineral chemistry and zircon U–Pb ages for amphibole cumulate xenoliths, the mineral chemistry of amphibole megacrysts, and the whole–rock chemistry, zircon U–Pb age and Sr–Nd isotopic compositions of host gabbros from Tongling. Zircon U–Pb dating yields a crystallization age of 120.6 ± 1.2 Ma (MSWD = 4.2) for the host gabbros, which are characteristically depleted in high field strength elements (Nb, Ta, and Ti) and enriched in large ion lithophile elements (Ba and Sr), with εNd (t) of ?3.00 to ?4.52 and initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7068–0.7072, suggesting an enriched mantle source. Parental melts, as estimated from average amphibole megacryst and cumulate compositions, have Mg# values of 26–33, are enriched in Ba, Th, U, and Nd, and depleted in Nb, Ta, Zr, Hf, and Ti, similar to 136 Ma mafic magmas in Tongling. Zircon U–Pb dating yields a crystallization age of 135.4 ± 1.0 Ma (MSWD = 1.6) for the amphibole cumulates. It is concluded that the Tongling adakitic rocks were formed by polybaric crystallization involving early high-pressure intracrustal fractional crystallization of cumulates comprising hornblende and clinopyroxene, and late low-pressure fractional crystallization of hornblende and plagioclase phenocrysts. The flat subduction of Pacific plate and its subsequent foundering during the Cretaceous may have triggered the generation of extensive adakitic magmas and lithospheric thinning in the Lower Yangtze Region.     

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

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

The Lac Des Iles Palladium Deposit,Ontario, Canada part I. The effect of variable alteration on the Offset Zone

The recently discovered Offset Zone of the Mine Block Intrusion of the Lac des Iles Complex hosts palladium mineralization with unusually high Pd/Pt and Pd/Ir ratios in rocks that range from relatively unaltered norite to amphibolites and chlorite–actinolite–talc schist. Quantitative assessment of the effect of progressive alteration using mineral modes was done using total silicate H₂O as a monitor of reaction progress (ξ = moles H₂O added to form alteration minerals per 100 g of rock). Major mineral modal variations define three reaction regions: (1) ξ?=?0.00–0.03, characterized by epidote/clinozoisite formation and some amphibole; (2) ξ?=?0.03–0.23, characterized by formation of chlorite, amphibole, quartz muscovite/sericite, and calcite after plagioclase?+?pyroxene; and (3) ξ?=?0.23–0.28, characterized by the formation of talc after earlier formed amphibole. Epidote occurs as an incongruent product from the destruction of plagioclase that is itself lost as the reaction proceeds. Pyroxene is altered at about twice the rate of plagioclase, resulting in pyroxene-rich protoliths to be more altered than those relatively enriched in plagioclase. Major elements variations largely reflect variations in the plagioclase/pyroxene ratio of the protolith, but compositional trends suggest a loss of Na with reaction progress. The base metal sulfides chalcopyrite, pyrrhotite, and pentlandite show decreasing abundance with reaction progress, forming pyrite (± magnetite) as an intermediate reaction product that also is lost as the reaction proceeds. Millerite is overall low but increases slightly. A more limited data set on the platinum-group minerals suggests that platinum-group element (PGE)-arsenides increase whereas PGE-sulfides and PGE-Bi-tellurides decrease with reaction progress. Assuming ore element concentrations in the protolith were constant and similar to relatively fresh norites, Pd increases modestly, by 5 %, whereas Pt decreases by about 65 % in the most altered rocks. Similarly, Cu, Au, and S decrease by 60, 82, and 94 %, respectively, in the most altered rocks. The antithetical behavior of Pd and the fact that Pd enrichment is not seen in altered dikes suggest that the Pd originally was enriched in the more melanocratic protoliths that are most extensively altered and that Pd also was lost in part. These results are consistent with the mineralization having been a high-temperature event that predated the amphibolite/greenschist alteration.     

Petrogenesis of the ~740 Korab Kansi mafic-ultramafic intrusion,South Eastern Desert of Egypt: Evidence of Ti-rich ferropicritic magmatism

The Neoproterozoic Korab Kansi mafic-ultramafic intrusion is one of the largest (100 km²) intrusions in the Southern Eastern Desert of Egypt. The intrusion consists of Fe-Ti-bearing dunite layers, amphibole peridotites, pyroxenites, troctolites, olivine gabbros, gabbronorites, pyroxene gabbros and pyroxene-hornblende gabbros, and also hosts significant Fe-Ti deposits, mainly as titanomagnetite-ilmenite. These lithologies show rhythmic layers and intrusive contacts against the surrounding granites and ophiolitic-island arc assemblages. The wide ranges of olivine forsterite contents (Fo_67.9-85.7), clinopyroxene Mg# (0.57–0.95), amphibole Mg# (0.47–0.88), and plagioclase compositions (An_85.8-40.9) indicate the role of fractional crystallization in the evolution from ultramafic to mafic rock types. Clinopyroxene (Cpx) has high REE contents (2–30 times chondrite) with depleted LREE relative to HREE, like those crystallized from ferropicritic melts generated in an island-arc setting. Melts in equilibrium with Cpx also resemble ferropicrites crystallized from olivine-rich mantle melts. Cpx chemistry and its host rock compositions have affinities to tholeiitic and calc-alkaline magma types. Compositions of mafic-ultramafic rocks are depleted in HFSE (e.g. Nb, Ta, Zr, Th and U) relative to LILE (e.g. Li, Rb, Ba, Pb and Sr) due to the addition of subduction-related hydrous fluids (rich in LILE) to the mantle source, suggesting an island-arc setting. Fine-grained olivine gabbros may represent quenched melts approximating the primary magma compositions because they are typically similar in assemblage and chemistry as well as in whole-rock chemistry to ferropicrites. We suggest that the Korab Kansi intrusion crystallized at temperatures ranging from ~700 to 1100 °C from ferropicritic magma derived from melting of metasomatized mantle at <5 Kbar. These hydrous ferropicritic melts were generated in the deep mantle and evolved by fractional crystallization under high ƒO₂ at relatively shallow depth. Fractionation formed calc-alkaline magmas during the maturation of an island arc system, reflecting the role of subduction-related fluids. The interaction of metasomatized lithosphere with upwelling asthenospheric melts produced the Fe and Ti-rich ferropicritic parental melts that are responsible for precipitating large quantities of Fe-Ti oxide layers in the Korab Kansi mafic-ultramafic intrusion. The other factors controlling these economic Fe-Ti deposits beside parental melts are high oxygen fugacity, water content and increasing degrees of mantle partial melting. The generation of Ti-rich melts and formation of Fe-Ti deposits in few layered intrusions in Egypt possibly reflect the Neoproterozoic mantle heterogeneity in the Nubian Shield. We suggest that Cryogenian-Tonian mafic intrusions in SE Egypt can be subdivided into Alaskan-type intrusions that are enriched in PGEs whereas Korab Kansi-type layered intrusions are enriched in Fe-Ti-V deposits.     

Kinetic theory of oxygen isotopic exchange between minerals and water

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in “closed” and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on δ-δ plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (δ), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated.     

Rocks mineralogy controls the metasomatic activities: an indication from water/rock ratio modeling

The final ratio equation of an isotopic element in a rock, derived from water/rock formula of McCulloch et al. Earth Planet Sci Lett 46:201-211, 1980, McCulloch et al. J Geophys Res 86:B4 2721-2735, 1981 is used to assess the behavior of diverse suites of rocks towards the alteration effect, and what implications can give about hydrothermal alteration in terms of isotopic compositions. Due to their higher Sr and lower Nd initial ratios than seawater, rocks of metamorphic and sedimentary signatures such as carbonates and Precambrian basement rocks show similar but inverse mixing curves compared with igneous rocks. Sr composition of rocks immediately alters by seawater, while Nd composition keeps unchanged until large volumes of water are added. Although, this can be attributed to the very low Nd concentration in seawater, it indicates that Nd-exchange may only take place under seawater, possibly hydrothermally by circulated seawater, and Nd-concentration of less altered crustal rocks are apparently primary. The isotopic composition and rock mineralogy seem to be the main factors controlling the volume of water required to cause isotopic alteration in rocks. Crustal rocks require higher water volumes due to their relatively low temperature minerals, whereas, mantle peridotites mainly consist of residual olivine minerals that are highly susceptible to alteration and lack of Sr and Nd compositions, and so need less amount of water for metasomatism. This property reduces the limited penetration effect as the mafic affinity increases at depth in the oceanic crust, and enables modified (probably acidified) circulated fluids to maintain ion exchanging and leaching throughout their passageway.     

Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.     

Crustal xenoliths from Calbuco Volcano,Andean Southern Volcanic Zone: implications for crustal composition and magma-crust interaction

Crustal xenoliths in the 1961 andesite flow of Calbuco Volcano, in the southern Southern Volcanic Zone (SSVZ) of the Andes, consist predominantly of pyroxene granulites and hornblende gabbronorites. The granulites contain plagioclase+pyroxene+magnetite±amphibole, and have pronounced granoblastic textures. Small amounts of relict amphibole surrounded by pyroxene-plagioclase-magnetite-glass symplectites are found in some specimens. These and similar textures in the gabbronorites are interpreted as evidence of dehydration melting. Mineral and bulk rock geochemical data indicate that the granulites are derived from an incompatible trace element depleted basaltic protolith that underwent two stages of metamorphism: a moderate pressure, high temperature stage accompanied by melting and melt extraction from some samples, followed by thermal metamorphism after entrainment in the Calbuco andesite lavas. High _Nd ^T values (+4.0 to +8.6), Nd-isotope model ages of 1.7–2.0 Ga, and trace element characteristics like chondrite normalized La/Yb< and La/Nb1 indicate that the protoliths were oceanic basalts. Similar oceanic metabasalts of greenschist to amphibolite facies are found in the Paleozoic metamorphic belt that underlies the Chilean coastal ranges. Mineral and bulk rock compositions of the gabbronorite xenoliths indicate that they are cognate, crystallizing from the basaltic andesite magma at Calbuco. Crystallization pressures for the gabbros based on total Al contents in amphibole are 6–8 kbar. These pressures point to middle to lower crustal storage of the Calbuco magma. Neither granulite nor gabbro xenoliths have the appropriate geochemical characteristics to be contaminants of Calbuco andesites, although an ancient sedimentary contaminant is indicated by the lava compositions. The presence of oceanic metabasaltic xenoliths, together with the sedimentary isotopic imprint, suggests that the lower crust beneath the volcano is analogous to the coastal metamorphic belt, which is an accretionary complex of intercalated basalts and sediments that formed along the Paleozoic Gondwanan margin. If this is the case, the geochemical composition of the lower and middle crust beneath the SSVZ is significantly different from that of most recent SSVZ volcanic rocks.     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.