Trace element evaluation of a suite of rocks from Reunion Island,Indian Ocean

Reunion Island consists of an olivine-basalt shield capped by a series of flows and intrusives ranging from hawaiite through trachyte. Eleven rocks representing the total compositional sequence have been analyzed for U, Th and REE.Eight of the rocks (group 1) have positive-slope, parallel, chondrite-normalized REE fractionation patterns. Using a computer model, the major element compositions of group 1 whole rocks and observed phenocrysts were used to predict the crystallization histories of increasingly residual liquids, and allowed semi-quantitative verification of origin by fractional crystallization of the olivine-basalt parent magma. Results were combined with mineral-liquid distribution coefficient data to predict trace element abundances, and existing data on Cr, Ni, Sr and Ba were also successfully incorporated in the model.The remaining three rocks (group 2) have nonuniform positive-slope REE fractionation patterns not parallel to group 1 patterns. Rare earth fractionation in a syenite is explained by partial melting of a source rich in clinopyroxene and/or hornblende. The other two rocks of group 2 are explained as hybrids resulting from mixing of syenite and magmas of group 1.     

Pb and Sr isotopes in volcanic rocks from the Aleutian Islands and Pribilof Islands,Alaska

The Pb and Sr isotope ratios of Plio-Pleistocene volcanic rocks from the Aleutian volcanic arc are used as tracers of the lithospheric subduction process at the converging Pacific and Bering plates. Aleutian arc lavas do not have the same Pb isotopic compositions as volcanic rocks of the subducted Pacific ocean crust or the nearby Pribilof Islands, but appear to contain an ‘old continental crustal component’ with high ²⁰⁷Pb/²⁰⁴Pb ratio, as has been found in some other volcanic arcs.⁸⁷Sr/⁸⁶Sr ratios in the Aleutian volcanic arc rocks average 0.70322, slightly higher than fresh volcanic rocks from normal ridge segments, but within the range of values from ‘Icelandic’ ridge segments, oceanic islands and the Pribolof Islands. The Pb and Sr isotopic compositions of Aleutian lavas show a positive correlation and the range of values does not change for volcanoes distributed along strike in the arc, even though the crustal type in the hanging wall of the Benioff zone changes from oceanic in the west to continental in the east. Since the basement of the continental arc segment is older than the basement of the oceanic segment, and probably has a different isotopic character, the constancy of isotopic ratios along the arc argues against contamination by wall rocks of the type exposed in the arc.A sufficient explanation for the isotopic data is the mixture of several per cent of continent-derived sediment with melt derived from the underthrust oceanic crust and overlying mantle. This small amount of contaminant is difficult to document by geophysical observations. Such a model implies extensive recycling of Ba, Pb, K and Rb through volcanism at convergent plate margins like the Aleutians.     

Trace and minor element geochemistry of the rhyolitic volcanic rocks,Central North Island,New Zealand

Analytical data are presented for the following elements: Cs, Rb, Ba, K, Sr, Ca, Na, Fe, Mg, Cu, Co, Ni, Li, Sc, V, Cr, Ga, Al, Si, La, Y, and Zr. Eight samples were analysed by the spark source method for rare earths, Tl, Pb, Hf, Sn, Nb, Mo, Bi, and In. In addition to data on rhyolitic volcanics, a small number of intermediate volcanics and eugeosynclinal sediments were analysed for comparative purposes. The following features are shown by the trace element data:

1. The rhyolitic rocks have consistently lower concentrations of most trace and minor elements when compared with recent estimates of average concentrations in granites. None of the criteria for strong fractionation (e.g. low K/Rb, Ba/Rb and K/Cs ratios) are present.
2. The data do not indicate any systematic differences between the rhyolitic lavas and ignimbrites, although the very young rhyolitic pumices are consistently more “basic” in their element concentrations compared to the other rhyolitic analyses.
3. The residual glasses (and devitrified matrices) are depleted, relative to the total rock compositions, in Fe, Mg, Ca, Sr, V, Sc, and Al, and enriched in Cs, Rb, K, Ba, and Si. Zr is depleted in the residual glasses separated from rhyolites, but not in the andesitic residual matrices.
4. The rare earth fractionation patterns of the rhyolitic and andesitic extrusives are very similar, being intermediate between chondritic and sedimentary patterns i.e., there is no evidence of strong fractionation. The rhyolitic patterns also indicate a slight Eu depletion.
5. Comparable trace and minor element behaviour (with the possible exception of Zr) seems to exist through the rhyolite-andesite compositional range. This is supported by the whole rock-residual liquid trends for the various elements studied, which broadly coincide with the observed whole rock trends, both through the rhyolitic-andesitic compositonal range, and within the rhyolitic compositional range.

The data are finally discussed in the light of the possible origin of the rhyolitic magmas. It is believed that the analytical data presented are qualitatively consistent with the recently proposed idea that the magmas are derived by partial fusion of the associated Triassic-Jurassic eugeosynclinal greywacke-argillite sedimentary sequence.     

Strontium isotopic and selected trace element variations between two Aleutian volcanic centers (Adak and Atka): implications for the development of arc volcanic plumbing systems

Major and trace element concentrations and initial ⁸⁷Sr/⁸⁶Sr ratios of lavas from the Aleutian volcanic centers of Adak and Atka have been used to study the evolution of their respective lithospheric plumbing systems. The centers are within 150 km of one another and show similar overall silica ranges (47–67%), but Adak (40 km³) is smaller than Atka (200 km³). Adak's lavas are chemically and isotopically heterogeneous (⁸⁷Sr/⁸⁶Sr:0.70285–0.70330) and two units contain lithospheric xenoliths. The lavas of the much larger Atka, on the other hand, have much less variability in major and trace elements as well as ⁸⁷Sr/⁸⁶Sr (0.70320–0.70345). We suggest that these characteristics are a measure of the relative maturity and cleanliness of the lithospheric plumbing systems that supply magma to these centers. Because Aleutian volcanic centers often remain fixed for relatively long periods of time (5 m.y.), once established, magmatic passageways are repeatedly used. Young plumbing systems are relatively cool and contain large amounts of wallrock contaminant, and ascending magmas undergo contamination as well as concurrent crystallization and fractionation. With time, however, heat and mass transfer between ascending magmas and wallrock produce thermal and chemical boundary layers that insulate subsequent magmas. In effect, the plumbing system matures. The chemical heterogeneity displayed by young, dirty systems (like Adak) reflects not only the magma source but also the wallrock encountered during ascent and possibly the effects of extensive crystal fractionation. Thus, it is the petrologic data of mature, clean systems, like Atka, that yield the most direct and unambiguous information on the ultimate origin of the lavas and their near surface evolution.     

Trace element geochemistry of the rhyolitic volcanic rocks,Central North Island,New Zealand. Phenocryst data

Data are presented for K, Ba, Sr, Rb, Li, Ga, Mg, Mn, and Fe for twelve rhyolitic plagioclases (An₂₈-An₄₆), one dacitic (An₅₃), and three andesitic plagioclases (An₆₈-An₈₁). Additional data are presented for Ga, Gr, V, Ni, Co, Sc, Y, La, Sr, and Ba for two augites, nine hypersthenes, and five hornblendes separated from the same rocks. Distribution factors have been calculated, using these data, and previously published results for coexisting groundmass compositions (=liquids).The plagioclases show a positive correlation between, and a progressive increase in K and Ba (range 0.09–0.58% and 61–610 p.p.m. respectively) with increasing Ab-content. Sr (range 465–880 p.p.m.) shows a well defined maximum between An₄₀-An₅₅. The plagioclases have extremely high K/Rb ratios (mostly > 1,000).This volcanic series is characterised by relatively Mg-rich pyroxenes and hornblendes. The augites contain higher Sc, Cr, Y, Sr, and Y relative to their coexisting hypersthenes, while the hornblendes exhibit higher Sc, V, Ba, Sr, Y, and La relative to coexisting hypersthenes. Very marked differences in concentrations of these elements exist between the rhyolitic and andesitic ferromagnesian phenocrysts. There is also evidence of a systematic distribution of Sc, V, Cr, Y, Co, and Ni between coexisting hypersthenes and hornblendes, and between these minerals and their coexisting whole rock and groundmass compositions.The data are discussed from a petrological viewpoint, as they are interpreted to indicate that the phenocrysts crystallised in the magmas in which they are found, and are not xenocrystic. No evidence of hybridisation or contamination, subsequent to the onset of crystallisation, is found.     

Strontium isotopic geochemistry of the volcanic rocks and associated megacrysts and inclusions from Ross Island and vicinity,Antarctica

Twelve whole-rock samples of volcanic rocks and a composite of 11 basanitoid samples from Ross Island and vicinity, Antarctica show a narrow range of ⁸⁷Sr/⁸⁶Sr ratios from 0.7030₅ to 0.7033₉. This range is consistent with a model of differentiation from a single parent magma, but the data allow a 30% variation in the ⁸⁷Rb/⁸⁶Sr ratio in the source region if the average ratio is less than 0.057 and if the source region has existed as a closed system for 1.5 b.y. Megacrysts of titaniferous augite, kaersutite, and anorthoclase are isotopically indistinguishable from the host volcanic rocks and therefore are probably cogenetic with the volcanic sequence. A single trachyte sample is isotopically distinct from the rest of the volcanic rocks and probably was contaminated with crustal strontium.Ultramafic and mafic nodules found in association with basanitoids and trachybasalts have ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7027₅ to 0.7057₅. Several of these nodules exhibit evidence of reaction with the melt and are isotopically indistinguishable from their hosts, but data for seven granulite-facies nodules show an apparent isochronal relationship. Although this isochron may be fortuitous, the resulting age of 158±22 m.y. is similar to ages reported for the voluminous Ferrar Dolerites, and suggests isotopic re-equilibration within the lower crust and upper mantle. These nodules are not genetically related to the Ferrar Dolerites, as evidenced by their lower initial ⁸⁷Sr/⁸⁶Sr ratios.Three ultramafic nodules are texturally and isotopically distinct from the rest of the analyzed nodules. These are friable, have larger ⁸⁷Sr/⁸⁶Sr ratios, and may represent a deeper sampling of mantle rock than the granulite-facies nodules. They were, however, derived at a shallower depth than the alkalic magma. Thus they are not genetically related to either the magma or the granulite-facies nodules.     

Trace element and isotopic evidence for REE migration and fractionation in salts next to a basalt dyke

Neodymium and Sr isotopic compositions and the rare earth elements (REE) distribution patterns have been determined in salts adjacent to a basaltic dyke along 2 parallel horizontal profiles. The salts, originally consisting of carnallite (KMgCl₃ · 6H₂O), have been transformed during basalt intrusion mainly into halite (NaCl) and sylvite (KCl) by fluids saturated in NaCl. The Sr isotope data suggests that much more fluid penetrated the upper than the lower horizon. The Nd isotope data shows that in the upper horizon, where fluid flow was stronger, Nd is essentially derived from the basalt. In contrast, in the lower horizon a strong salt Nd component is present.The REE data document in both horizons is a strong depletion of Ce, Pr, Nd, Sm and Eu with increasing distance from the basalt. This depletion of the light rare earths (LREE) is stronger in the upper horizon where fluid flow was stronger. The authors suggest that this REE fractionation is more likely due to precipitation of LREE-enriched accessory minerals such as apatite, than to differential REE solubility caused by selective REE complexation. This finding is of interest for REE behaviour in brines in general, and for the behaviour of radioactive REE and actinides in a salt repository for high-level nuclear waste in particular.     

北部湾涠洲岛及斜阳岛火山岩微量元素和同位素地球化学及其构造意义

本文在北部湾内一对姊妹火山岛即涠洲岛及斜阳岛火山地质研究基础上,进一步开展火山岩微量元素和Sr-Nd-Pb同位素,以及地幔橄榄岩Re-Os同位素地球化学研究.岛上早晚两期火山岩均为碱性玄武岩,分别属于碱性橄榄玄武岩和碧玄岩.碧玄岩为玻基斑状结构,舍地幔橄榄岩碎块(一般<1cm),表明为地幔岩浆快速喷出地表冷凝而成,岩浆上升过程中极少演化.火山岩微量元素和Sr-Nd-Pb同位素资料表明,涠洲岛及斜阳岛玄武岩与雷琼及北部湾周边、南海海盆玄武岩类似,具有亏损地幔的Sr、Nd同位素组成与Pb同位素显示的EMII富集地幔特征的Dupal异常,表明岩浆并非来自单一地幔源区,不可与OIB或MORB源区简单类比,也非地幔柱成因,而是由两个不同的地球化学组分混合而成.Re-OS同位素特征也指示地幔橄榄岩捕虏体来源于亏损的岩石圈地幔,而非核幔边界.推测涠洲岛及斜阳岛与雷琼及北部湾周边的岩浆可能是由于南海扩张后大陆裂解-软流圈地幔热物质上涌,与上覆薄而年轻的岩石圈地幔相互作用的产物.     

Boron isotopic variations in fumarolic condensates and thermal waters from Vulcano Island, Italy: Implications for evolution of volcanic fluids

Temporal variation in the isotopic composition of boron has been monitored in fumarolic condensates collected over an extended time period (1970-1996) from La Fossa crater, Volcano Island. We also report comparative boron isotopic data for representative Vulcano lavas and for shallow hydrologic samples (seawater, wells, thermal springs) from the north flank of La Fossa. Combined with concurrent chemical and isotopic (δ¹⁸O, δD) data for the fumaroles, these results indicate that the fumarolic fluids record mixing relations between three distinct fluid end members: (1) a dominantly magmatic fluid (EM1); (2) a mixture of modified seawater with magmatic fluid (EM2); and (3) an aqueous fluid produced from seawater by extensive wall-rock reaction, evaporation, and boiling (AF). Differences between the latter two end members are most clearly accentuated on the basis of the boron isotopic data. Long-term compositional variations for crater fumaroles were dominated by EM1-AF mixing between 1979-88, with progressive decrease in EM1 contribution with time, and by EM2-AF mixing between 1988-96. The exact spatial distribution of these fluid reservoirs remains unclear, but all must have been present throughout the monitoring period to account for the observed variations. Moreover, the combined B-O-H data seem to preclude important contributions from shallow meteoric reservoirs. Marked short-term variations in δ¹¹B closely coincide with episodes of local seismicity, which presumably triggered reorganization of hydrothermal circulation patterns; gradual variations over periods up to 3-4 years are associated with relatively low seismicity during which fluid circulation was likely influenced by effects of mineral precipitation on permeability of the hydrologic system.     

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO₂ range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7–7.8 ppb Pd, 0.025–0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu–Au deposits.     

Chemical and isotopic (Pb,Sr) zonation in a peraluminous granite pluton: role of fluid fractionation

The Davis Lake pluton (DLP, ~800 km²) of southwestern Nova Scotia, Canada, part of the large peraluminous South Mountain batholith of ca. 380 Ma (U/Pb zircon, Ar/Ar mica), consists of granite and subordinate topaz–muscovite leucogranite that hosts greisen tin-base metal mineralization. A new Pb–Pb isochron age for leucogranite from the most evolved part of the DLP indicates a crystallization age of 378±3.6 Ma, coincident with other radiometric ages of the DLP (Rb–Sr, Re–Os, Pb–Pb). The intrusion displays a compositional zonation defined by lead and strontium isotopic ratios, as well as some major elements (e.g., Si, F), incompatible trace elements (e.g., Li, Rb, Ta, U, Sn), and elemental ratios (e.g., K/Rb and Nb/Ta). The greisens and the leucogranites that host them are characterized by extreme radiogenic compositions for Pb and Sr, and their chemical-isotopic trends are extensions of the trends displayed by the less evolved granites. The covariations of the isotopic ratios with several major and trace elements and elemental ratios as well as the Pb–Pb and Rb–Sr isochrones indicate that all phases of the intrusion originated from a homogeneous parental magma. The granitoid magma underwent extensive fractional crystallization of feldspars, minor biotite and accessory minerals (monazite, apatite and zircon) in a compositionally zoned magma chamber that was subsequently accompanied by fluid fractionation, during which time the internally derived fluorine-rich fluids modified the Rb/Sr, U/Pb and Th/Pb ratios, leading to distinct variations of ⁸⁷Sr/⁸⁶Sr, ²⁰⁶Pb/²⁰⁴Pb, ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb isotopic ratios. These data therefore document the evolution of a granitic magma through magmatic (i.e., crystal fractionation), orthomagmatic (i.e., crystal-fluid fractionation) and hydrothermal (i.e., fluid fractionation) stages that culminated in the formation of a tin-base metal deposit. The Pb isotope data also constrain the source region for the DLP as being Avalonian basement that, by inference, must underlie much of the Meguma Terrane.Editorial responsibility: T.L. Grove     

Trace element and isotopic evidence for two types of crustal melting beneath a High Cascade volcanic center, Mt. Jefferson, Oregon

Mt. Jefferson is an andesite-dacite composite volcano in the Cascade Range, the locus of andesite and dacite-dominated volcanism for at least 1 million years. A large trace element data set for Mt. Jefferson and its surrounding mafic volcanic platform effectively rules out any fractionation based model (FC or AFC) for the generation of Mt. Jefferson andesites. Several incompatible element (Zr, Nb, Y) concentrations decrease in the range from basalt to andesite, and then increase in the range from andesite to rhyodacite. Others (Ba, Rb, La, Th) remain constant or show a slight increase in the basalt to andesite range, with modest increases from andesite to rhyodacite. Systematic variations in highly incompatible element ratios such as Ba/La and Rb/Th suggest magma mixing dominates the trace element signatures. Rhyodacites are isotopically uniform (⁸⁷Sr/⁸⁶Sr=0.70325-0.70343; ²⁰⁶Pb/²⁰⁴Pb=18.75-18.85; ‘¹⁸O=6.3ǂ.3), whereas andesite and dacite are more variable (⁸⁷Sr/⁸⁶Sr=0.70291-0.70353; ²⁰⁶Pb/²⁰⁴Pb=18.59-18.86; ‘¹⁸O=6.0ǂ.6). Typical basaltic andesite has ⁸⁷Sr/⁸⁶Sr=0.70326-0.70358, ²⁰⁶Pb/²⁰⁴Pb=18.78-18.85, and ‘¹⁸O=5.9ǂ.4. Sr-rich (>1,000 ppm) basaltic andesite is more variable (⁸⁷Sr/⁸⁶Sr=0.70300-0.70360; ²⁰⁶Pb/²⁰⁴Pb=18.70-18.89; ‘¹⁸O=5.9ǂ.4). The data define mixing arrays with one end member at ⁸⁷Sr/⁸⁶Sr=0.7029; ²⁰⁶Pb/²⁰⁴Pb=18.59, another at rhyodacite, and a third at ⁸⁷Sr/⁸⁶Sr=0.7036; ²⁰⁶Pb/²⁰⁴Pb=18.89. The first end member is defined by Sr-rich (800-1,200 ppm) andesite with high Al₂O₃, and low K₂O, Ba, and Rb/Th; the third one by K₂O- and very Sr-rich (>2,000 ppm) shoshonite. Isotopic data for basalts in northern Oregon preclude any fractionation relationship between basalt and either rhyodacite or Sr-rich andesite (e.g., the minimum ²⁰⁶Pb/²⁰⁴Pb ratio in basalt is 18.83). Considered in light of geophysical models for the Cascades, these data suggest two types of crustal melting beneath the arc. Rhyodacite may be generated at 25-30 km depth by partial melting of arc basalt-like amphibolite at 850-900 °C. Sr-rich andesite may be formed by partial melting of depleted MORB-like mafic granulite at 35-45 km depth at 1,000-1,100 °C. Experimental and REE evidence supports these interpretations as does the restriction of Sr-rich andesite in the Cascades to the area south of the 100 mW/m² heat flow contour between Mt. Jefferson and Mt. Hood. Thick crust and high heat flow are necessary to produce such andesite.     

Crystal fractionation and partial melting in the petrogenesis of a Proterozoic high-MgO volcanic suite,Ungava, Québec

There is little concensus on the relative importance of crystal fractionation and differential partial melting to the chemical diversity observed within most types of volcanic suites. A resolution to this controversy is best sought in suites containing high MgO lavas such as the Chukotat volcanics of the Proterozoic Cape Smith foldbelt, Ungava, Quebec. The succession of this volcanic suite consists of repetitive sequences, each beginning with olivine-phyric basalt (19-12 wt% MgO), grading upwards to pyroxene-phyric basalt (12-8 wt% MgO) and then, in later sequences, to plagioclase-phyric basalt (7-4 wt% MgO). Only the olivine-phyric basalts have compositions capable of equilibrating with the upper mantle and are believed to represent parental magmas for the suite. The pyroxene-phyric and plagioclase-phyric basalts represent magmas derived from these parents by the crystal fractionation of olivine, with minor chromite, clinopyroxene and plagioclase. The order of extrusion in each volcanic sequence is interpreted to reflect a density effect in which successively lighter, more evolved magmas are erupted as hydrostatic pressure wanes. The pyroxene-phyric basalts appear to have evolved at high levels in the active part of the conduit system as the eruption of their parents was in progress. The plagioclase-phyric basalts may represent residual liquids expelled from isolated reservoirs along the crust-mantle interface during the late stages of volcanic activity.A positive correlation between FeO and MgO in the early, most basic olivine-phyric basalts is interpreted to reflect progressive adiabatic partial melting in the upper mantle. Although this complicates the chemistry, it is not a significant factor in the compositional diversification of the volcanic suite. The preservation of such compositional melting effects, however, suggests that the most basic olivine-phyric basalts represent primitive magmas. The trace element characteristics of these magmas, and their derivatives, indicate that the mantle source for the Chukotat volcanics had experienced a previous melting event.     

Mid-Pleistocene lavas from the Seguam volcanic center,central Aleutian arc: closed-system fractional crystallization of a basalt to rhyodacite eruptive suite

In contrast to adjacent volcanic centers of the modern central Aleutian arc, Seguam Island developed on strongly extended arc crust. K-Ar dates indicate that mid-Pleistocene, late-Pleistocene, and Holocene eruptive phases constitute Seguam. This study focuses on the petrology of the mid-Pleistocene, 1.07–07 Ma, Turf Point Formation (TPF) which is dominated by an unusual suite of porphyritic basalt and basaltic andesite lavas with subordinate phenocryst-poor andesite to rhyodacite lavas. Increasing whole-rock FeO^*/MgO from basalt to dacite, the anhydrous Plag+Ol+Cpx±Opx±Mt phenocryst assemblage, groundmass pigeonite, and the reaction Ol+Liq=Opx preserved in the mafic lavas indicate a tholeiitic affinity. Thermometry and comparison to published phase equilibria suggests that most TPF basalts crystallized Plag+Ol+Cpx±Mt at 1160°C between about 3–5 kb (±1–2% H₂O), andesites crystallized Plag+Cpx+Opx±Mt at 1000°C between 3–4 kb with 3–5% H₂O, and dacites crystallized Plag +Cpx±Opx±Mt at 1000°C between 1–2 kb with 2–3% H₂O. All lavas crystallized at f _{o 2} close to the NNO buffer. Mineral compositions and textures indicate equilibrium crystallization of the evolved lavas; petrographic evidence of open-system mixing or assimilation is rare. MgO, CaO, Al₂O₃, Cr, Ni, and Sr abundances decrease and K₂O, Na₂O, Rb, Ba, Zr, and Pb increase with increasing SiO₂ (50–71%). LREE enrichment [(Ce/Yb)_n=1.7±0.2] characterizes most TPF lavas; total REE contents increase and Eu anomalies become more negative with increasing SiO₂. Relative to other Aleutian volcanic centers, TPF basalts and basaltic andesites have lower K₂O, Na₂O, TiO₂, Rb, Ba, Sr, Zr, Y, and LREE abundances. ⁸⁷Sr/⁸⁶Sr ratios (0.70361–0.70375) and ratios of ²⁰⁶Pb/²⁰⁴Pb (18.88–18.97), ²⁰⁷Pb/²⁰⁴Pb (15.58–15.62), ²⁰⁸Pb/²⁰⁴Pb (38.46–38.55) are the highest measured for any suite of lavas in the oceanic portion of the Aleutian arc. Conversely, Nd values (+5.8 to+6.7) are among the lowest from the Aleutians. Sr, Nd, and Pb ratios are virtually constant from basalt through rhyodacite, whereas detectable isotopic heterogenity is observed at most other Aleutian volcanic centers. Major and trace element, REE, and Sr, Nd, and Pb isotopic compositions are consistent with the basaltic andesitic, andesitic, dacitic, and rhyodacitic liquids evolving from TPF basaltic magma via closed-system fractional crystallization alone. Fractionation models suggest that removal of 80 wt% cumulate (61% Plag, 17% Cpx, 12% Opx, 7% Ol, and 3% Mt) can produce 20 wt% rhyodacitic residual liquid per unit mass of parental basaltic liquid. Petrologic and physical constraints favor segregation of small batches of basalt from a larger mid-crustal reservoir trapped below a low-density upper crustal lid. In these small magma batches, the degree of cooling, crystallization, and fractionation are functions of the initial mass of basaltic magma segregated, the thermal state of the upper crust, and the magnitude of extension. Tholeiitic magmas erupted at Seguam evolved by substantially different mechanisms than did calc-alkaline lavas erupted at the adjacent volcanic centers of Kanaga and Adak on unextended arc crust. These variable differentiation mechanisms and liquid lines of descent reflect contrasting thermal and mechanical conditions imposed by the different tectonic environments in which these centers grew. At Seguam, intra-arc extension promoted eruption of voluminous basalt and its differentiates, unmodified by interaction with lower crustal or upper mantle wallrocks.     

Trace elements and REE fractionation in subsoils developed on sedimentary and volcanic rocks: case study of the Mt. Vulture area,southern Italy

There is an increasing interest in the distribution of rare earth elements (REEs) within soils, primarily as these elements can be used to identify pedogenetic processes and because soils may be future sources for REE extraction, despite much attention should be paid to the protection and preservation of present soils. Here, we evaluate the processes that control the distribution of REEs in subsoil horizons developed over differing lithologies in an area of low anthropogenic contamination, allowing estimates of the importance of source rocks and weathering. Specifically, this study presents new data on the distribution of REEs and other trace elements, including transition and high-field-strength elements, in subsoils developed on both Quaternary silica-undersaturated volcanic rocks and Pliocene siliciclastic sedimentary rocks within the Mt. Vulture area of the southern Apennines in Italy. The subsoils in the Mt. Vulture area formed during moderate weathering (as classified using the chemical index of alteration) and contain an assemblage of secondary minerals that is dominated by trioctahedral illite with minor vermiculite. The REEs, high-field-strength elements, and transition metals have higher abundances in subsoils that developed from volcanic rocks, and pedogenesis caused the Mt. Vulture subsoils to have REE concentrations that are an order of magnitude higher than typical values for the upper continental crust. This result indicates that the distribution of REEs in soils is a valuable tool for mineral exploration. A statistical analysis of inter-elemental relationships indicates that REEs are concentrated in clay-rich fractions that also contain significant amounts of low-solubility elements such as Zr and Th, regardless of the parent rock. This suggests that low-solubility refractory minerals, such as zircon, play a significant role in controlling the distribution of REEs in soils. The values of (La/Yb)_N and (Gd/Yb)_N fractionation indices are dependent on the intensity of pedogenesis; soils in the study area have values that are higher than typical upper continental crust ratios, suggesting that soils, especially those that formed during interaction with near neutral to acidic organic-rich surface waters, may represent an important source of both light REEs and medium REEs (MREEs). In comparison, MREE/heavy REE fractionation in soils that form during moderate weathering may be affected by variations in parent rock lithologies, primarily as MREE-hosting minerals, such as pyroxenes, may control (La/Sm)_N index values. Eu anomalies are thought to be the most effective provenance index for sediments, although the anomalies within the soils studied here are not related to the alteration of primary minerals, including feldspars, to clay phases. In some cases, Eu/Eu* values may have a weak correlation with elements hosted by heavy minerals, such as Zr; this indicates that the influence of mechanical sorting of clastic particles during sedimentary transport on the Eu/Eu* values of siliciclastic sediments needs to be considered carefully.     

Observations of Li isotopic variations in the Trinity Ophiolite: Evidence for isotopic fractionation by diffusion during mantle melting

The Trinity peridotite (northern CA) contains numerous lithologic sequences consisting of dunite to harzburgite to spinel lherzolite to plagioclase lherzolite. Previous workers have documented geochemical gradients in these sequences consistent with melt-rock reaction processes occurring around dunites, interpreted to reflect conduits for melt ascent. We have undertaken a study of Li isotope compositions of clinopyroxene and some olivine within these sequences using ion probe techniques to test the hypothesis that the geochemical gradients are related to diffusive fluxing of alkali elements into or away from the melt conduit.Results show large variations in ⁷Li/⁶Li occurring in a consistent pattern across three transects from dunite to plagioclase lherzolite within the Trinity peridotite. Specifically, measurements of average δ⁷Li for single thin sections along the traverse reveal a low in δ⁷Li in the harzburgite adjacent to the dunite returning to higher values farther from the dunite with a typical offset of ∼10 per mil in the low δ⁷Li trough. This pattern is consistent with a process whereby Li isotopes are fractionated during diffusion through a melt either from the dunite conduit to the surrounding peridotite, or from the surrounding peridotite into the dunite conduit. The patterns in ⁷Li/⁶Li occur over a length scale similar to the decrease in REE concentration in these same samples. Explaining both the trace element and Li isotopic gradients requires a combined process of alkali diffusion and melt extraction.We develop a numerical model and examine several scenarios of the combined diffusion-extraction process. Using experimentally constrained values for the change in Li diffusion coefficient with isotope mass, large changes in δ⁷Li as a function of distance can be created in year to decade timescales. The addition of the melt extraction term allows larger Li concentration gradients to be developed and thus produces larger isotopic fractionations than diffusion only models. The extraction aspect of the model can also account for the observed decrease in rare earth element concentrations across the transects.     

Geochemical and isotopic characteristics of the Cretaceous Orikabe Plutonic Complex,Kitakami Mountains,Japan: magmatic evolution in a zoned pluton and significance of a subduction-related mafic parental magma

The Orikabe Plutonic Complex, northeast Japan, is a zoned pluton and one of the Cretaceous intrusions in the Circum-Pacific area. In the Main body, K-rich calc-alkaline rocks composed of marginal gabbro and a large amount of monzodiorite–quartz monzonite–monzogranite are intruded successively by innermost calc-alkaline rocks of granodiorite. The gabbro and monzodiorite–monzogranite have a continuous chemical variation, while the granodiorite has lower concentrations of K, Rb, Y, Zr, Nb and F at the same SiO₂ content. The gabbro and monzodiorite–quartz monzonite have a Rb-Sr whole-rock age of 119±12 Ma with an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.70392±0.00007. The initial ⁸⁷Sr/⁸⁶Sr ratio of the innermost granodiorite is estimated to be about 0.7042. The ¹⁸O values of fresh rocks range from +6.7 to +8.3, indicating a positive correlation with SiO₂ contents. The K-rich calc-alkaline rocks were derived through fractional crystallization from a mafic parental magma with a slightly high ¹⁸O value, implying a major contribution of a sub-arc mantle at a continental margin. Trace element modeling indicates that the source could have been a fertile lherzolite enriched in LILE and depleted in HFSE. The innermost granodiorite was the differentiation product of a distinct parental magma, suggesting the involvement of a small amount of crustal component in the source and partial melting under a more hydrous condition.Editorial responsibility: J. Hoefs     

西天山昭苏北部大哈拉军山组火山岩中辉长岩体的形成时代、地球化学特征及地质意义

西天山昭苏北部侵入于大哈拉军山组火山岩层上部的辉长岩体具有富集大离子亲石元素(Rb、Sr、Ba)、亏损高场强元素(Nb、Ta)、轻重稀土分馏等地球化学特征,与火山岩围岩具有相似的不相容元素和Sr-Nd同位素特征,其母岩浆可能由俯冲流体交代的富集岩石圈地幔部分熔融形成,晚石炭世之前南天山洋盆向伊犁-中天山板块之下的俯冲可能导致了岩石圈的富集作用。利用不相容元素进行地球化学模拟计算,结果表明辉长岩成分由50%~80%的堆晶矿物(单斜辉石、斜长石)与50%~20%的玄武质熔浆组成。辉长岩体的Cameca锆石U-Pb年龄为311.3±2.3Ma,与伊犁-中天山板块晚石炭世伊什基里克组火山岩的时代大致相当,略晚于西天山榴辉岩的峰期变质时间。辉长岩的时代进一步限定该地区大哈拉军山组火山活动应在早石炭世晚期结束,下石炭统阿克沙克组沉积岩应形成于320~311Ma之间。与辉长岩同时期的岩浆岩在伊犁-中天山板块广泛分布,形成于俯冲结束之后挤压环境向拉张环境过度的构造环境。     

The parnell quartz monzonite: A proterozoic zoned pluton in the archaean pilbara block,Western Australia

The Parnell Quartz Monzonite in the Pilbara Block of Western Australia is a Proterozoic (1731 ± 14 Ma) pluton characterized by high modal K‐feldspar and a greater abundance of hornblende relative to biotite, as is typical of Phanerozoic monzonitic rocks in eastern Australia. The only geochemical features reflecting its setting in an Archaean terrain are high Na2O, Ni and Cr. The pluton is zoned, with an increase in K‐feldspar, quartz and biotite and a decrease in plagioclase and hornblende from margin to core. Chemically, this zoning is reflected by systematic variation of CaO, K₂O, Na₂O, Sr and Rb, but ferromagnesian elements have irregular trends, implying preferential extraction of feldspars relative to mafic minerals during differentiation of the magma. The unusual geochemical trends are explained by a model involving ‘in situ’ feldspar fractionation of a K‐rich residual liquid from a mafic crystalline mush.

A parent magma similar to the average rock composition of the pluton is deduced because high ferromagnesian trace element abundances preclude extensive fractionation of mafic minerals. Geochemical and isotopic constraints suggest that the ultimate source was chemically similar to a shoshonitic basaltic andesite, that must have been emplaced beneath the eastern margin of the Pilbara Block in the Early Proterozoic. Subsequent partial melting of this postulated underplated source at ～ 1700 Ma to produce the Parnell Quartz Monzonite was probably associated with tectonism in the Gregory Range Complex.