Coupling of Redox Conditions of Mantle Melting and Copper and Sulfur Contents in Primary Magmas of the Tolbachinsky Dol (Kamchatka) and Juan de Fuca Ridge (Pacific Ocean)

The compositions of parental melts of Tolbachinsky Dol (Kamchatka) basalts were estimated from the compositions of olivine-hosted (Fo_90.5-83.1) primitive melt inclusions in the rocks of the Northern breakthrough of the Great Tolbachik Fissure Eruption (1975 A.C.) and of the late-Holocene cone “1004”. The parental melts contain 100–150 ppm Cu and 0.16–0.30 wt % S. These concentrations are much higher than those determined for the initial magmas of mid-ocean ridge basalts (MORB), for example of the Juan de Fuca ridge (Cu = 55–105 ppm, S=0.09–0.12 wt %). Modeling of mantle melting under variable redox conditions demonstrated that the high Cu and S contents in the Tolbachinsky Dol melts can be obtained by 6–12% melting of DMM-like source under oxidized conditions (ΔQFM = +1.2 ± 0.1) and do not require a significant (>30–35% for S) subduction-related influx of these elements to the mantle source. The high contents of Cu and S in the Tolbachinsky Dol melts are largely explained by the increase of sulfide solubility in a silicate melt under oxidized conditions. In contrast, relatively reduced (ΔQFM ～ 0) conditions of MORB generation result in low contents of Cu and S in their initial magmas. The estimated ΔQFM values agree well with the data obtained using the Cr-spinel–olivine oxybarometer. The high oxygen potential of Tolbachinsky Dol primary magmas is inherited by more evolved magmas, thus favouring Cu enrichment up to 270 ppm during magma fractionation, approaching maximum copper contents in the global systematics of island-arc rocks.     

Garnet-Pyroxenite-Derived End-Member Magma Type in Kamchatka: Evidence from Composition of Olivine and Olivine-Hosted Melt Inclusions in Holocene Rocks of Kekuknaisky Volcano

Late Quaternary volcanoes of Sredinny Range (Kamchatka) attract geoscientists’ attention by their unusual geochemical features and geodynamic setting. They produced volcanic rocks that are enriched relative to N-MORB in most of incompatible trace elements (except HREE), including strong enrichment in large-ion lithophile elements, and show a negative Nb–Ta anomaly, which is typical for rocks formed in supra-subduction settings. However, modern subduction of the Pacific Plate does not reach the most part of Sredinny Range, as inferred by mapping of Wadati–Benioff zone or seismic tomography. We constrain the source of parental magmas for Sredinny Range volcanic rocks by combining major and trace element geochemical data for olivine and naturally quenched olivine-hosed melt inclusions for Holocene tephra layers of the Kekuknaisky field. Composition of the most magnesian olivine (Ni > 2000 ppm, Fe/Mn ≈ 75 at Mg# ~ 84–85 mol %) and geochemical characteristics of the most primitive melts (FC3MS = 0.61 ± 0.04 (2s)) are consistent with their derivation from a pyroxenite source, while elevated LREE/HREE ratios in lavas indicate that it contained garnet. This garnet-bearing pyroxenite likely originated from the lower crust or lithospheric mantle. Its melting could have occurred due to delamination and sinking into the hotter mantle.     

The origin and evolution of the parental magmas of frontal volcanoes in Kamchatka: Evidence from magmatic inclusions in olivine from Zhupanovsky volcano

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69–84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (∼70% crystallization) of the parental melt (∼46.4 wt % SiO₂, ∼2.5 wt % H₂O, ∼0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of ΔFMQ = 0.9–1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx: (Crt-Mt) ∼ 13: 54: 24: 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO₂, Na₂O, and K₂O and depleted in MgO, CaO, and Al₂O₃. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H₂O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (∼45 wt % SiO₂) picrobasalt (∼14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ∼8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20–30°C lower than the solidus temperature of “dry” peridotite (1230–1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760–810°C and pressures of ∼3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H₂O-rich fluid to higher temperature H₂O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100–125 km beneath Kamchatka was estimated at 4°C/km.     

Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth’s upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 µg/g F and 0.14–0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.     

Zinc,Copper, and Lead Geochemistry of Oceanic Igneous Rocks—Ridges,Islands, and Arcs

Variations in the abundances of Zn, Cu, and Pb are found to be useful in identifying tectonic regimes and separating oceanisland basalts into enriched- and depleted-source categories. The average Zn, Cu, and Pb contents of normal mid-ocean ridge basalts (N-MORB) are 84, 70, and 0.35 ppm, respectively. Differences in average Zn contents for various ridges reflect more the varying degrees of differentiation than variations of Zn content in the source rocks. At a Mg# of 70, or Mg#₇₀, which is taken to represent primitive MORB, many MORB sequences converge at a Zn content of 58 ± 6 ppm, which is close to the value for primitive mantle (50 ppm) and ordinary chondrites (～55 ppm). Values of 0.1 to 0.15 ppm Pb in MORB at Mg#₇₀, best defined at the superfast-spreading Southern East Pacific Rise, are similar to estimates of Pb in the primitive mantle (0.12 to 0.18 ppm). They also are near the lower end of the range for ordinary chondrites. The very slow spreading Southwest Indian Ocean Ridge has a sequence with higher Pb contents, in addition to a more normal sequence, which has a visual best value of 0.4 ppm Pb at Mg#₇₀. With the exception of the Walvis Ridge, Zn and Cu appear to be little affected by proximity to hotspots (i.e., E-MORB); however, Pb contents are higher and average about 0.6 ppm.

Both Zn and Pb in MORB are incompatible elements (i.e., favor the melt), but Cu is a compatible element. At Mg#₇₀, there is the suggestion of a value of 100 ppm for Cu, with lower values possibly representing partial removal of sulfides and their associated Cu from the source. Nonetheless, Cu contents of primitive MORB tend to be much higher than even high estimates for the primitive mantle (28 ppm), and are closer to ordinary chondrites (～90 ppm). Therefore, Zn, Cu, and Pb all approximate chondritic values in the primitive MORB melt.

Average contents of Zn, Cu, and Pb in oceanic island basalts (OIB) are 115, 62, and 3.2 ppm, respectively. At Mg#₇₀, values of Zn and Cu are similar to the respective averages for OIB, with Zn higher and Cu lower than MORB. At a Mg# of ～40, however, OIB and MORB tend to have similar Zn contents. With further differentiation, OIB trachytes can contain >200 ppm Zn. Unlike MORB, OIB can differentiate to high Cu contents of 200 ppm at Mg#s of 40 to 60. In contrast to Zn and Cu, Pb regresses to a value of 0.83 ppm at Mg#₇₀ for Hawaiian and Reunion volcanics, which is much less than the average value for Pb in OIB volcanics, but higher than for MORB.

Average Zn, Cu, and Pb contents of magmatic-arc basalts are 77, 108, and 1.9 ppm, respectively. In basalts, Zn tends to be incompatible, but a dual incompatible and compatible behavior can occur at high SiO₂ contents. Dacites may average near 55 ppm Zn, but peralkalic rhyolite can contain >300 ppm Zn. A dual compatible and incompatible nature occurs for Cu. Most common, particularly in submarine volcanics, is a compatible trend, with a Cu content of around 80 ppm at a Mg# of 60, which decreases to less than 40 ppm at a Mg# of 30. The incompatible trend of increasing Cu can achieve >200 ppm at a Mg# of 30, leaving a gap approaching 100 ppm at that Mg#. The gap is less obvious on a plot of Cu vs. SiO₂, but is still there. The compatible trend is proposed to result from sulfur-saturated magmas, whereas the incompatible trend is believed to result from sulfur-deficient magmas. Support for this hypothesis is found in sparse sulfur-isotope data. Zn and Cu both can be incompatible over an extended range of Mg#s or silica content. When Zn and Cu are both compatible, Cu decreases more than twice as rapidly as Zn.

Primitive magmas at Mg#₇₀ average about 50 ppm Zn for submarine Mariana arc basalts and 58 ppm for forearc boninites, contents close to MORB values. Mariana arc basalts have a Zn content of ～45 ppm estimated at Mg#₇₀. Cu varies more widely than Zn in primitive magmas, being about 50 ppm Cu for Mariana Islands volcanics and 120 ppm for Kermadec Islands volcanics, a range broadly around MORB values. Average Pb contents are 1.9 ppm for island-arc tholeiites, 5.6 ppm for high-Al basalt, and 3.2 ppm for alkali basalt with average boninite of approximately 1.8 ppm. Back-arc-basin basalts in the deepest parts of the Mariana trough have Pb contents of 0.45 ppm, but more shallow parts may exceed 1.0 ppm Pb. Although the lower contents are similar to MORB values, the ²⁰⁸Pb/²⁰⁴Pb values are greater than Pacific Ocean MORB. At Mg#₇₀ for rocks from the Tonga and Kermadec island arcs, the Pb content is about 0.1 ppm, similar to MORB.     

Constraints from melt inclusions and their host olivines on the petrogenesis of Oligocene-Early Miocene Xindian basalts, Chifeng area, North China Craton

The geochemical characteristics of melt inclusions and their host olivines provide important information on the processes that create magmas and the nature of their mantle and crustal source regions. We report chemical compositions of melt inclusions, their host olivines and bulk rocks of Xindian basalts in Chifeng area, North China Craton. Compositions of both bulk rocks and melt inclusions are tholeiitic. Based on petrographic observations and compositional variation of melt inclusions, the crystallizing sequence of Xindian basalts is as follows: olivine (at MgO > ~5.5 wt%), plagioclase (beginning at MgO = ~5.5 wt%), clinopyroxene and ilmenite (at MgO < 5.0 wt%). High Ni contents and Fe/Mn ratios, and low Ca and Mn contents in olivine phenocrysts, combining with low CaO contents of relatively high MgO melt inclusions (MgO > 6 wt%), indicate that Xindian basalts are possibly derived from a pyroxenite source rather than a peridotite source. In the CS-MS-A diagram, all the high MgO melt inclusions (MgO > 6.0 wt%) project in the field between garnet + clinopyroxene + liquid and garnet + clinopyroxene + orthopyroxene + liquid near 3.0 GPa, further suggesting that residual minerals are mainly garnet and clinopyroxene, with possible presence of orthopyroxene, but without olivine. Modeling calculations using MELTS show that the water content of Xindian basalts is 0.3–0.7 wt% at MgO = 8.13 wt%. Using 20–25 % of partial melting estimated by moderately incompatible element ratios, the water content in the source of Xindian basalts is inferred to be ≥450 ppm, much higher than 6–85 ppm in dry lithospheric mantle. The melting depth is inferred to be ~3.0 GPa, much deeper than that of tholeiitic lavas (<2.0 GPa), assuming a peridotite source with a normal mantle potential temperature. Such melting depth is virtually equal to the thickness of lithosphere beneath Chifeng area (~100 km), suggesting that Xindian basalts are derived from the asthenospheric mantle, if the lithospheric lid effect model is assumed.     

Peridotites from the Kamchatsky Mys: evidence of oceanic mantle melting near a hotspot

A suite of mantle peridotites sampled in the Kamchatsky Mys includes spinel lherzolite, clinopyroxene-bearing harzburgite, and harzburgite. Mineral chemistry of olivine, chromian spinel, and clinopyroxene show strongly correlated element patterns typical of peridotite formed by 8% to more than 22% partial melting. Clinopyroxene in the Kamchatka peridotites is compositionally different from that of both abyssal and suprasubduction varieties: Clinopyroxene in lherzolite is depleted in LREE relative to abyssal peridotite and that in harzburgite has very low LREE and Sr unlike the subduction-related counterpart. These composition features indicate that the rocks ultra-depleted in basaltic components originated in the vicinity of a hotspot, possibly, proto-Hawaiian plume, which provided high temperature and melting degree of the MORB source mantle at mid-ocean ridge.     

Noble Metal Concentrations in Shoshonitic Lamprophyres: Analysis of the Weekend Dykes, Eastern Shore, Nova Scotia, Canada

Devonian, spessartite dykes, known as the Weekend dykes, onthe Eastern Shore of Nova Scotia contain panidiomorphic texturesand mineral (amphibole, clinopyroxene, and biotite) compositionstypical of shoshonitic lamprophyres. The major element and traceelement geochemistry of the Weekend dykes is also representativeof shoshonitic lamprophyres with high large ion lithophile elementconcentrations (LILE, e.g., Rb, K, and Ba) relative to the lightrare earth elements (LREE, e.g., La) and very low Nb and Ti.Only Ta concentrations are uncharacteristically high relativeto Nb and Ti. The dykes are variably evolved but many samplesshow primitive compositions with high mgnumber [>0.70, wheremg-number=Mg/(Mg+09total Fe) atomic] high MgO and Ni concentrations(>10 wt.% and 150 ppm, respectively), and low heavy REE concentrations.All noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir)tend to be lower in evolved samples than in primitive rocks,suggesting that evolved magmas were efficiently scavenged byimmiscible sulphide globules and that shoshonitic lamprophyreplutons may hold economic promise for the platinum-group elements(PGE). Noble metal abundances in even the most primitive rocksare low compared with many basaltic rocks excepting mid-oceanridge basalt (MORB). This makes doubtful the idea that Megumagroup mesothermal gold deposits, which are spatially and temporallyassociated with the dykes, derived their gold from the lamprophyres.Models that explain PGE concentrations and Pd/Ir ratios in awide variety of mafic rocks suggest that the low noble metalabundances probably reflect metal retention in mantle sulphides,olivine, and PGE alloys at low percentages of melting. However,noble metal abundances are higher than expected if the oceanicslab was involved in the melting process or if the source regionresembled that for most MORB, which appears to have low PGE.Mantle metasomatism represents an unlikely explanation for thePGE abundances, which are equivalent to those expected in alkalinehot-spot magmas. The high PGE abundances of hot-spot magmas(compared with MORB) may be related to the incorporation ofcore materials in deep mantle plumes. Presumably the hot-spotlikemantle became part of the subcontinental lithospheric mantlebefore the subduction and transpressional event that producedthe shoshonitic magmas.     

Trace element partitioning between mica- and amphibole-bearing garnet lherzolite and hydrous basanitic melt: 2. Tasmanian Cainozoic basalts and the origins of intraplate basaltic magmas

Oligocene volcanics from Oatlands in Tasmania, Australia, include olivine tholeiites, alkali olivine basalts, nepheline basanites and olivine nephelinites. They have compositional characteristics that are typical of intraplate basalts worldwide. They are generally enriched in incompatible elements relative to the primitive mantle and are strongly enriched in Nb, Ta and light rare earths, but not heavy rare earths. At the same time, they have Sr and Nd isotope compositions that are similar to those in some incompatible-element-depleted mid-ocean ridge basalts (E-type MORB). Experimentally obtained mineral/melt partition coefficients for an Oatlands basanite allow the relative concentrations of incompatible elements in the volcanics to be produced by small degrees of melting (≤1%) of a source similar to the E-type MORB source of Workman and Hart (2005). However, the absolute concentrations that can be achieved in this way are much less than present in the most incompatible-element-enriched basanites and nephelinites at Oatlands. This contradiction can be explained by open-system melting under the influence of a conductive geotherm. This would have involved upwardly migrating near-solidus melts from the asthenosphere cooling along a sub-adiabatic geotherm. Cooling of the melts would have caused them to re-crystallize and accumulate in the overlying mantle, thereby enriching both the new host rocks and any residual melts in incompatible elements. This would also have increased the buoyancy of the host rocks leading to upwelling and further (decompression) melting of incompatible-element-enriched peridotite. We were able to use our partition coefficients to quantitatively model the development of incompatible-element enrichments in the Oatlands magmas by these processes. Our explanation is consistent with the characteristically scattered but widespread distributions and long time scales of intraplate volcanism in a broad variety of tectonic settings. This is because the conditions required to initiate volcanism (i.e. those of near-solidus melting of the asthenosphere) are relatively easy to produce and can therefore be caused by both near-surface tectonics and deeper mantle processes. Furthermore, the super-enrichments of incompatible elements in some intraplate volcanics can be attributed to the influence of normal geothermal gradients on melting processes. Without the very strong fractionation imposed by this combination of factors, the Oatlands volcanics would more closely resemble mid-ocean-ridge basalts.     

South-to-north pyroxenite–peridotite source variation correlated with an OIB-type to arc-type enrichment of magmas from the Payenia backarc of the Andean Southern Volcanic Zone (SVZ)

New high-precision minor element analysis of the most magnesian olivine cores (Fo_85–88) in fifteen high-MgO (Mg#_66–74) alkali basalts or trachybasalts from the Quaternary backarc volcanic province, Payenia, of the Andean Southern Volcanic Zone in Argentina displays a clear north-to-south decrease in Mn/Fe_ol. This is interpreted as the transition from mainly peridotite-derived melts in the north to mainly pyroxenite-derived melts in the south. The peridotite–pyroxenite source variation correlates with a transition of rock compositions from arc-type to OIB-type trace element signatures, where samples from the central part of the province are intermediate. The southernmost rocks have, e.g., relatively low La/Nb, Th/Nb and Th/La ratios as well as high Nb/U, Ce/Pb, Ba/Th and Eu/Eu* = 1.08. The northern samples are characterized by the opposite and have Eu/Eu* down to 0.86. Several incompatible trace element ratios in the rocks correlate with Mn/Fe_ol and also reflect mixing of two geochemically distinct mantle sources. The peridotite melt end-member carries an arc signature that cannot solely be explained by fluid enrichment since these melts have relatively low Eu/Eu*, Ba/Th and high Th/La ratios, which suggest a component of upper continental crust (UCC) in the metasomatizing agent of the northern mantle. However, the addition to the mantle source of crustal materials or varying oxidation state cannot explain the variation in Mn and Mn/Fe of the melts and olivines along Payenia. Instead, the correlation between Mn/Fe_ol and whole-rock (wr) trace element compositions is evidence of two-component mixing of melts derived from peridotite mantle source enriched by slab fluids and UCC melts and a pyroxenite mantle source with an EM1-type trace element signature. Very low Ca/Fe ratios (~1.1) in the olivines of the peridotite melt component and lower calculated partition coefficients for Ca in olivine for these samples are suggested to be caused by higher H₂O contents in the magmas derived from subduction zone enriched mantle. Well-correlated Mn/Fe ratios in the wr and primitive olivines demonstrate that the Mn/Fe_wr of these basalts that only fractionated olivine and chromite reflects the Mn/Fe of the primitive melts and can be used as a proxy for the amount of pyroxenite melt in the magmas. Using Mn/Fe_wr for a large dataset of primitive Payenia rocks, we show that decreasing Mn/Fe_wr is correlated with decreasing Mn and increasing Zn/Mn as expected for pyroxenite melts.     

Petrogenetic processes in the ultramafic, alkaline and carbonatitic magmatism in the Kola Alkaline Province: A review

Igneous rocks of the Devonian Kola Alkaline Carbonatite Province (KACP) in NW Russia and eastern Finland can be classified into four groups: (a) primitive mantle-derived silica-undersaturated silicate magmas; (b) evolved alkaline and nepheline syenites; (c) cumulate rocks; (d) carbonatites and phoscorites, some of which may also be cumulates. There is no obvious age difference between these various groups, so all of the magma-types were formed at the same time in a relatively restricted area and must therefore be petrogenetically related. Both sodic and potassic varieties of primitive silicate magmas are present. On major element variation diagrams, the cumulate rocks plot as simple mixtures of their constituent minerals (olivine, clinopyroxene, calcite, etc). There are complete compositional trends between carbonatites, phoscorites and silicate cumulates, which suggests that many carbonatites and phoscorites are also cumulates. CaO / Al₂O₃ ratios for ultramafic and mafic silicate rocks in dykes and pipes range up to 5, indicating a very small degree of melting of a carbonated mantle at depth. Damkjernites appear to be transitional to carbonatites. Trace element modelling indicates that all the mafic silicate magmas are related to small degrees of melting of a metasomatised garnet peridotite source. Similarities of the REE patterns and initial Sr and Nd isotope compositions for ultramafic alkaline silicate rocks and carbonatites indicate that there is a strong relationship between the two magma-types. There is also a strong petrogenetic link between carbonatites, kimberlites and alkaline ultramafic lamprophyres. Fractional crystallisation of olivine, diopside, melilite and nepheline gave rise to the evolved nepheline syenites, and formed the ultramafic cumulates. All magmas in the KACP appear to have originated in a single event, possibly triggered by the arrival of hot material (mantle plume?) beneath the Archaean/Proterozoic lithosphere of the northern Baltic Shield that had been recently metasomatised. Melting of the carbonated garnet peridotite mantle formed a spectrum of magmas including carbonatite, damkjernite, melilitite, melanephelinite and ultramafic lamprophyre. Pockets of phlogopite metasomatised lithospheric mantle also melted to form potassic magmas including kimberlite. Depth of melting, degree of melting and presence of metasomatic phases are probably the major factors controlling the precise composition of the primary melts formed.     

Origin of the Tertiary basaltic volcanism in the northern Hessian Depression

Volcanic activity started about 20 Ma before present with quartz tholeiites (QTh), had a climax with alkali olivine basalts (AOB) 13 to 14 Ma ago and ended 7 Ma ago with nepheline basanites (NB) and olivine nephelinites (ON). AOB covers 73% of the volcanic area. About 250 basalts and peridotite xenoliths were sampled for investigation. An upper mantle layer ranging from about 90 to 60 km depth has been conditioned for a preferential alkali basalt production by advection of H₂O-CO₂-fluids containing Si, Al, Ca, K, Na, P as major constituents beside numerous incompatible minor elements. At the onset of the geodynamically triggered mantle conditioning locally restricted diapirism into shallow depth has caused formation of olivine tholeiite magmas (OTh) at about 1,300° C by partial melting. All of these OTh primary melts intruded due to a favourable compressibility into granulites of the lower crust. The rare QTh basalts are their derivative magmas which have been slightly contaminated in the crust. Magmas of the subsequent alkali basaltic volcanism (AOB, bAOB, NB, ON, MON) formed by in-situ partial melting at about 75 to 90 km depth after depression of the peridotite solidi by fluids to temperatures 1,200° C. Except many AOB these magmas are primary melts as characterized by olivine/melt distribution coefficients of Mg/Fe²⁺ (K _D=0.29 to 0.34), by Ni concentrations (260 to 330 ppm) and the occurrence of peridotite xenoliths. Rapid rise of gas charged melts due to saturation in CO₂ prevented separation of olivine etc. and of xenoliths. The sequence of magmas from OTh to ON (or MON) is formed from decreasing proportions of orthopyroxene (opx) and increasing contributions of clinopyroxene (cpx) and phlogopite (ph) at almost equal proportions of spinel (sp). Incongruent melting of opx (and cpx) for OTh, AOB, NB and ON is correlated with precipitation of olivine. The average xenolith composition (73% ol, 18% opx, 7% cpx, 1.1% sp and 1.3/0.5% ph) was used to model the sources of the investigated melts by 9 incompatible elements and to calculate degrees of partial melting. The occurrence of garnet cannot be reliably excluded by modelling on the basis of HREE distribution coefficients. The average xenolith composition was used for modelling because of its resemblance with worldwide sampled depleted mantle inclusions. For avoiding to exhaust at least one mineral of the model mantle in the support of the norm composition of OTh, AOB, NB and MON magmas the degrees of partial melting cannot exceed 12.5%, 6%, 6% and 4% respectively. Mantle containing about 500 ppm K (and the correlated incompatible elements), like the average of 36 xenoliths, allows to explain the formation of OTh magmas. AOB, NB and ON melts require peridotite with slightly less than 1,500 ppm K, 670 ppm P and proportions of the correlated elements LREE, Sr, Ba, Zr, Rb, Cs, Ta, Th, Hf, U, which are higher than their abundance in primitive mantle rocks. About 20% of the xenoliths have this composition. Metasomatism of fluids with these elements must have been an immediate precursor of the alkali basaltic volcanism. Otherwise the preservation of a local disequilibrium in ⁸⁷Sr/⁸⁶Sr ratios between cpx cores and total rock at upper mantle temperatures cannot be explained.     

Partitioning of Ni between olivine and siliceous eclogite partial melt: experimental constraints on the mantle source of Hawaiian basalts

Olivine is abundant in Earth’s upper mantle and ubiquitous in basaltic lavas, but rarely occurs in eclogite. Partial melts of eclogite are, therefore, not in equilibrium with olivine, and will react with peridotite as they migrate through the upper mantle. If such melts erupt at Earth’s surface, their compositions will be highly modified and they may be olivine-saturated. We investigated experimentally the reaction between olivine and siliceous eclogite partial melt, and determined element partitioning between olivine and the melt produced by this reaction. Our results demonstrate that mixing of reacted eclogite partial melt with primitive basalt is capable of producing the positive correlation between melt SiO₂ content and olivine Ni content observed in some Hawaiian lavas. Experiments were carried out by equilibrating eclogite partial melt or basalt with San Carlos olivine at 1 bar and 1,201–1,350°C. Our results show that eclogite partial melts equilibrated with mantle olivine retain their high SiO₂, low FeO and MgO characteristics. Further, olivine-melt partition coefficients for Ni measured in these experiments are significantly larger than for basalt. Mixing of these melts with primitive Hawaiian tholeiitic lavas results in crystallization of high-Ni olivines similar to those in Makapuu-stage Koolau lavas, even though the mixed magmas have only moderate Ni contents. This results from a hyperbolic increase of the Ni partition coefficient with increasing polymerization of the mixed melt. Note that while eclogite partial melt in contact with peridotite will equilibrate with pyroxene as well as olivine, this will have the effect of buffering the activity of SiO₂ in the reacted melt at a higher level. Therefore, an eclogite partial melt equilibrated with harzburgite will have higher SiO₂ than one equilibrated with dunite, enhancing the effects observed in our experiments. Our results demonstrate that an olivine-free “hybrid” pyroxenite source is not required to explain the presence of high-Ni olivines in Hawaiian lavas and, therefore, indicate that the proportion of eclogite in the Hawaiian plume is less than has been estimated in recent studies.     

Nickel content of basaltic magmas: identification of primary magmas and a measure of the degree of olivine fractionation

Available NiO analyses of olivine in peridotites of probable mantle origin are consistent in giving values around 0.40 weight per cent. Assuming that basaltic magma forming from the mantle was in equilibrium with such peridotitic olivine, the NiO content of primary basaltic magmas is estimated to be about 0.030–0.050 weight per cent. The fractionation behaviour of nickel in basaltic magma due to the crystallization of olivine has been calculated using constant NiMg and FeMg exchange partition coefficients between olivine and magma. It is shown that the NiO content of both magma and olivine decreases by 50 per cent after fractional crystallization of 6–12 per cent of olivine. The nickel distribution in some basaltic rocks and olivines is examined in the light of these results, and it is suggested that basaltic magmas, such as some of the ocean-floor basalt and the Hawaiian tholeiite and alkali basalts, represent primary magmas from mantle peridotites.     

The composition and formation of Miocene tholeiites in the Central European Cenozoic plume volcanism (CECV)

Tholeiites accompanying a majority of alkali basalts are restricted to the highly productive central part of the CECV plume activity in Vogelsberg and Hessian Depression. They mainly occur as quartz tholeiites which according to experiments of partial melting and material balances are products of olivine tholeiitic primary melts. The differentiation from olivine to quartz tholeiitic melts took place in lower crustal magma chambers where olivine tholeiitic melt intruded due to a density comparable with that of the country rocks. The fractionation due to separation of olivine and some clinopyroxene caused contamination of tholeiite magmas by tonalitic partial melts from the wall rocks of the magma chambers. The latter process is indicated by relatively high Rb, K and Pb and low Nb concentrations and by Nd, Sr and Pb isotopes. Contaminating crustal melts, which roughly attained a proportion of 10%, contained very low ¹⁴³Nd/¹⁴⁴Nd ratios from a Nd/Sm fractionation as old as 2.6 Ga. This is the first evidence from mafic rocks of this high age in the lower crust beneath Central Europe. Modelling with incompatible elements allows to recognize olivine tholeiites as products of about 1% partial melting of plume rocks consisting of 35% primitive and 65% depleted mantle materials. The production of tholeiites other than alkali basalts is restricted to the highest plume activity and the largest fraction of MORB type source rocks. Received: 10 December 1999 / Accepted: 23 June 2000     

Partial melting of secondary pyroxenite at 1 and 1.5 GPa,and its role in upwelling heterogeneous mantle

We performed partial melting experiments at 1 and 1.5 GPa, and 1180–1400 °C, to investigate the melting under mantle conditions of an olivine-websterite (GV10), which represents a natural proxy of secondary (or stage 2) pyroxenite. Its subsolidus mineralogy consists of clinopyroxene, orthopyroxene, olivine and spinel (+garnet at 1.5 GPa). Solidus temperature is located between 1180 and 1200 °C at 1 GPa, and between 1230 and 1250 °C at 1.5 GPa. Orthopyroxene (±garnet), spinel and clinopyroxene are progressively consumed by melting reactions to produce olivine and melt. High coefficient of orthopyroxene in the melting reaction results in relatively high SiO₂ content of low melt fractions. After orthopyroxene exhaustion, melt composition is controlled by the composition of coexisting clinopyroxene. At increasing melt fraction, CaO content of melt increases, whereas Na₂O, Al₂O₃ and TiO₂ behave as incompatible elements. Low Na₂O contents reflect high partition coefficient of Na between clinopyroxene and melt (\(D_{{{\text{Na}}_{ 2} {\text{O}}}}^{{{\text{cpx}}/{\text{liquid}}}}\)). Melting of GV10 produces Quartz- to Hyperstene-normative basaltic melts that differ from peridotitic melts only in terms of lower Na₂O and higher CaO contents. We model the partial melting of mantle sources made of different mixing of secondary pyroxenite and fertile lherzolite in the context of adiabatic oceanic mantle upwelling. At low potential temperatures (T _P < 1310 °C), low-degree melt fractions from secondary pyroxenite react with surrounding peridotite producing orthopyroxene-rich reaction zones (or refertilized peridotite) and refractory clinopyroxene-rich residues. At higher T _P (1310–1430 °C), simultaneous melting of pyroxenite and peridotite produces mixed melts with major element compositions matching those of primitive MORBs. This reinforces the notion that secondary pyroxenite may be potential hidden components in MORB mantle source.     

The systematics of lithium abundances in young volcanic rocks

Lithium is a moderately incompatible trace element in magmatic systems. High precision analyses for lithium conducted on well characterized suites of MORB and ocean island basalts suggest a bulk distribution coefficient of 0.25−0.35 and behavior which is similar to Yb during low pressure fractionation and V during melting, as long as garnet is not an important residual phase. Data for peridotites and basalts suggest a mantle lithium content of about 1.9 ppm and show that significant concentrations of lithium reside in olivine and orthopyroxene, resulting in unusual inter-mineral partitioning of Li and complex relationships between lithium and other incompatible trace elements.The lithium abundances of arc basalts are similar to those of MORB, but their Li/Yb ratios are considerably higher. The high Li/Yb suggests the addition of a Li-rich component to arc sources; relatively low Yb abundances are consistent with the derivation of some arc magmas by larger extents of melting or from a more depleted source than MORB. Although Li is enriched at arcs, K is enriched more, leading to elevated K/Li ratios in arc volcanics. The high K/Li and relatively low La/Yb of primitive arc basalts requires either incorporation of altered ocean crust into arc magma sources, or selective removal of K and Li from subducted sediments. Bulk incorporation of sediments alone does not explain the Li systematics.Data from primitive MORB indicate a relatively low (3–4 ppm) Li content for new oceanic crust. Thus, the Li flux from the ocean crust is probably <1 × 10¹¹ g/yr, and the oceanic crust may not be an important net source in the oceanic budget of lithium.     

Petrology of the parental melts and mantle sources of Siberian trap magmatism

Based on the investigation of olivine phenocrysts and melt and spinel inclusions in them from the picrites of the Gudchikhinsky Formation and olivine phenocrysts and the whole-rock geochemistry from the Tuklonsky and Nadezhdinsky formations of the Noril’sk region, the compositions and conditions of formation and evolution of the parental melts and mantle sources of Siberian trap magmatism were evaluated. Olivine phenocrysts from the samples studied are enriched in Ni and depleted in Mn compared with olivines equilibrated with the products of peridotite melting, which suggests a considerable role of a nonperidotitic component (olivine-free pyroxenite) in their mantle source. The onset of Siberian trap magmatism (Gudchikhinsky Formation) was related to the melting of pyroxenite produced by the interaction of ancient recycled oceanic crust with mantle peridotite. During the subsequent evolution of the magmatic system (development of the Tuklonsky and Nadezhdinsky formations), the fraction of the pyroxenite component in the source region decreased rapidly (to 40 and 60%, respectively) owing to the entrainment of peridotite material into the melting zone. The formation of magmas was significantly affected by the contamination by continental crustal material. The primitive magmas of the Gudchikhinsky Formation crystallized under near-surface conditions at temperatures of 1250–1170°C and oxygen fugacities 2.5–3.0 orders of magnitude below the Ni-NiO buffer. Simultaneously, the magmas were contaminated by continental silicic rocks and evaporites. The parental magmas of the Gudchikhinsky rocks corresponded to tholeiitic picrites with 11–14 wt % MgO. They were strongly undersaturated in sulfur, contained less than 0.25 wt % water and carbon dioxide, and were chemically similar to the Hawaiian tholeiites. They were produced by melting of a pyroxenite source at depths of 130–180 km in a mantle plume with a potential temperature of 1500–1580°C. The presence of low melting temperature pyroxenite material in the source of Siberian trap magmas promoted the formation of considerable volumes of melt under the thick continental lithosphere, which could trigger its catastrophic collapse. The contribution of pyroxenite-derived melt to the magmas of the Siberian trap province was no less than 40–50%. This component, whose solid residue was free of sulfides and olivine, played a key role in the origin of high contents of Ni, Cu, and Pt-group elements and low sulfur contents in the parental trap magmas and prevented the early dispersion of these elements at the expense of sulfide melt fractionation. The high contents of Cl in the magmas resulted in considerable HCl emission into the atmosphere and could be responsible for the mass extinction at the Paleozoic-Mesozoic boundary.     

Petrogenesis of Tertiary Mafic Alkaline Magmas in the Hocheifel, Germany

Primitive nephelinites and basanites from the Tertiary Hocheifelarea of Germany (part of the Central European Volcanic Province;CEVP) have high Mg-number (>0·64), high Cr and Nicontents and strong light rare earth element enrichment butsystematic depletion in Rb, K and Ba relative to trace elementsof similar compatibility in anhydrous mantle. Alkali basaltsand more differentiated magmatic rocks have lower Mg-numberand lower abundances of Ni and Cr, and have undergone fractionationof mainly olivine, clinopyroxene, Fe–Ti oxide, amphiboleand plagioclase. Some nephelinites and basanites approach theSr–Nd–Pb isotope compositions inferred for the EAR(European Asthenospheric Reservoir) component. The Nd–Sr–Pbisotope composition of the differentiated rocks indicates thatassimilation of lower crustal material has modified the compositionof the primary mantle-derived magmas. Rare earth element meltingmodels can explain the petrogenesis of the most primitive maficmagmatic rocks in terms of mixing of melt fractions from anamphibole-bearing garnet peridotite source with melt fractionsfrom an amphibole-bearing spinel peridotite source, both sourcescontaining residual amphibole. It is inferred that amphibolewas precipitated in the asthenospheric mantle beneath the Hocheifel,close to the garnet peridotite–spinel peridotite boundary,by metasomatic fluids or melts from a rising mantle diapir orplume. Melt generation with amphibole present suggests relativelylow mantle potential temperatures (<1200°C); thus themantle plume is not thermally anomalous. A comparison of recentlypublished Ar/Ar ages for Hocheifel basanites with the geochemicaland isotopic composition of samples from this study collectedat the same sample sites indicates that eruption of earlierlavas with an EM signature was followed by the eruption of laterlavas derived from a source with EAR or HIMU characteristics,suggesting a contribution from the advancing plume. Thus, theHocheifel area represents an analogue for magmatism during continentalrift initiation, during which interaction of a mantle plumewith the overlying lithosphere may have led to the generationof partial melts from both the lower lithosphere and the asthenosphere. KEY WORDS: alkali basalts; continental volcanism; crustal contamination; partial melting; Eifel, Germany     

Cryptic crustal contamination of MORB primitive melts recorded in olivine-hosted glass and mineral inclusions

The origin of compositional heterogeneities among the magmas parental to mid-ocean ridge basalts (MORB) was investigated using a single rock piece of the olivine-phyric basalt from 43°N, Mid-Atlantic Ridge (AII D11-177). The exceptional feature of this sample is presence of very primitive olivine crystals (90–91 mol% Fo) that are significantly variable in terms of CaO (0.15–0.35 wt%). A population of low-Ca olivine (0.15–0.25 wt% CaO) is also notably distinct from high-Ca olivine population in AII D11-177, and primitive MORB olivine in general, in having unusual assemblage of trapped mineral and glass inclusions. Mineral inclusions are represented by high-magnesian (Mg# 90.7–91.1 mol%) orthopyroxene and Cr-spinel, distinctly enriched in TiO₂ (up to 5 wt%, c.f. <1 wt% in common MORB spinel). Glass inclusions associated with orthopyroxene and high-Ti Cr-spinel have andesitic compositions (53–58 wt% SiO₂). Compared to the pillow-rim glass and “normal” MORB inclusions, the Si-rich glass inclusions in low-Ca olivine have strongly reduced Ca and elevated concentrations of Ti, Na, K, P, Cl, and highly incompatible trace elements. Strong variability is recorded among glass inclusions within a single olivine phenocrysts. We argue that the observed compositional anomalies are mineralogically controlled, and thus may arise from the interaction between hot MORB magmas and crystal cumulates in the oceanic crust or magma chamber.