Showing papers on "Incompatible element published in 2013"

Origin and age of the earliest Martian crust from meteorite NWA 7533

Abstract: Chemical analysis of the meteorite NWA 7533 indicates that it may be a Martian regolith breccia and, if so, that the crust of Mars may have formed in the first 100 million years of the planet’s history. This paper identifies the NWA 7533 meteorite from Northwest Africa as the first sample of Martian highlands rock in the meteorite collection. Munir Humayun and co-authors show that NWA 7533 has a composition indicative of a highlands breccia. It also contains zircons more than 4.4 billion years old, implying that early crustal differentiation on Mars occurred in the first 100 million years of its history, coeval with earliest crust formation on the Moon and the Earth. The ancient cratered terrain of the southern highlands of Mars is thought to hold clues to the planet’s early differentiation1,2, but until now no meteoritic regolith breccias have been recovered from Mars. Here we show that the meteorite Northwest Africa (NWA) 7533 (paired with meteorite NWA 70343) is a polymict breccia consisting of a fine-grained interclast matrix containing clasts of igneous-textured rocks and fine-grained clast-laden impact melt rocks. High abundances of meteoritic siderophiles (for example nickel and iridium) found throughout the rock reach a level in the fine-grained portions equivalent to 5 per cent CI chondritic input, which is comparable to the highest levels found in lunar breccias. Furthermore, analyses of three leucocratic monzonite clasts show a correlation between nickel, iridium and magnesium consistent with differentiation from impact melts. Compositionally, all the fine-grained material is alkalic basalt, chemically identical (except for sulphur, chlorine and zinc) to soils from Gusev crater. Thus, we propose that NWA 7533 is a Martian regolith breccia. It contains zircons for which we measured an age of 4,428 ± 25 million years, which were later disturbed 1,712 ± 85 million years ago. This evidence for early crustal differentiation implies that the Martian crust, and its volatile inventory4, formed in about the first 100 million years of Martian history, coeval with earliest crust formation on the Moon5 and the Earth6. In addition, incompatible element abundances in clast-laden impact melt rocks and interclast matrix provide a geochemical estimate of the average thickness of the Martian crust (50 kilometres) comparable to that estimated geophysically2,7.

Major and trace element composition of the high 3He/4He mantle: Implications for the composition of a nonchonditic Earth

Abstract: [1] The bulk composition of the silicate portion of the Earth (BSE) has long been assumed to be tied to chondrites, in which refractory, lithophile elements like Sm and Nd exist in chondritic relative abundances. However, the 142Nd/144Nd ratios of modern terrestrial samples are 18 ± 5 ppm higher than the ordinary-chondrite reservoir, and this challenges the traditional BSE model. Here we investigate a hypothesis that this terrestrial 142Nd excess is related to a Sm/Nd ratio 6% higher than chondritic. This Sm/Nd ratio yields a superchondritic 143Nd/144Nd (∼0.5130) similar to that identified in the highest 3He/4He mantle reservoir, and we argue that this reservoir represents the BSE composition for lithophile elements. We develop a compositional model for BSE in which the elevated Sm/Nd requires a shift of 143Nd/144Nd from 0.51263 (chondritic) to 0.51300. The new BSE composition is depleted in highly incompatible elements, including K, relative to the chondrite-based BSE, and offers a solution the “missing” 40Ar paradox. This BSE compositional model requires that >83% of the mantle is depleted to form continental crust. It also implies a ∼30% reduction in BSE U, Th and K, and therefore in the current rate of radiogenic heating and, thus, a proportional increase in the heat flow delivered to surface by plate tectonics. We explore thermal history models including effects related to a newly recognized evolution in the style of plate tectonics over Earth history: The lower radiogenic heat production may delay the onset of core convection and dynamo action to as late as 3.5 Gyr.

Orogenic climax of Earth: the 1.2-1.1 Ga Grenvillian superevent

Abstract: The rate of growth of the continental crust is controversial. We present an evaluation of time-constrained analyses of oxygen isotopes in zircon grains and incompatible element (Zr, Th) concentrations in magmatic rocks to test for variations in the degree of crustal recycling through geological time. The data indicate a rise in these geochemical proxies from ca. 3.0 Ga to a statistically significant peak at 1.2–1.1 Ga during the amalgamation of supercontinent Rodinia, and a decrease thereafter. When combined with other geological and geophysical observations, the data are interpreted as a consequence of an unprecedented level of crustal recycling and sediment subduction during Rodinia assembly, arising from a "Goldilocks" (i.e., just right) combination of larger, thicker plates on a warmer Earth with more rapid continental drift relative to modern Earth. The subsequent decrease in δ 18 O, Zr, and Th measurements is interpreted to reflect decreasing drift rates on a cooling Earth.

TTG-type plutonic rocks formed in a modern arc batholith by hydrous fractionation in the lower arc crust

Abstract: We present the geochemistry and intrusion pressures of granitoids from the Kohistan batholith, which represents, together with the intruded volcanic and sedimentary units, the middle and upper arc crust of the Kohistan paleo-island arc. Based on Al-in-hornblende barometry, the batholith records intrusion pressures from ~0.2 GPa in the north (where the volcano-sedimentary cover is intruded) to max. ~0.9 GPa in the southeast. The Al-in-hornblende barometry demonstrates that the Kohistan batholith represents a complete cross section across an arc batholith, reaching from the top at ~8–9 km depth (north) to its bottom at 25–35 km (south-central to southeast). Despite the complete outcropping and accessibility of the entire batholith, there is no observable compositional stratification across the batholith. The geochemical characteristics of the granitoids define three groups. Group 1 is characterized by strongly enriched incompatible elements and unfractionated middle rare earth elements (MREE)/heavy rare earth element patterns (HREE); Group 2 has enriched incompatible element concentrations similar to Group 1 but strongly fractionated MREE/HREE. Group 3 is characterized by only a limited incompatible element enrichment and unfractionated MREE/HREE. The origin of the different groups can be modeled through a relatively hydrous (Group 1 and 2) and of a less hydrous (Group 3) fractional crystallization line from a primitive basaltic parent at different pressures. Appropriate mafic/ultramafic cumulates that explain the chemical characteristics of each group are preserved at the base of the arc. The Kohistan batholith strengthens the conclusion that hydrous fractionation is the most important mechanism to form volumetrically significant amounts of granitoids in arcs. The Kohistan Group 2 granitoids have essentially identical trace element characteristics as Archean tonalite–trondhjemite–granodiorite (TTG) suites. Based on these observations, it is most likely that similar to the Group 2 rocks in the Kohistan arc, TTG gneisses were to a large part formed by hydrous high-pressure differentiation of primitive arc magmas in subduction zones.

Petrogenesis of the Lower Zone Olivine-Rich Cumulates Beneath the Platreef and Their Correlation with Recognized Occurrences in the Bushveld Complex

Abstract: Previously unknown Lower zone ultramafic sequences are described beneath the Platreef in the northern limb of the Bushveld Complex (South Africa). The Lower zone is separated from the overlying mineralized Platreef sequence by intervals of country rocks, which are represented by granofels (agmatites) and shales and include thin sills of fine-grained Marginal zone norite and pyroxenite. The chemical compositions of olivine and orthopyroxene in the Lower zone of the northern limb are more primitive than those established for the western and eastern limb and indicate that the Bushveld parental magma should be more Mg rich than previously suggested and therefore may have been able to dissolve more Cr than indicated by known Marginal chilled rock compositions. Olivine and orthopyroxene compositions show multiple reversals within the Lower zone sections which are accompanied by coherent reversals in the Cu/Pd ratio. The style of reversals is consistent with a gradual mixing of fresh magma with more evolved resident liquid in the chamber. Olivine and orthopyroxene contain higher Ni in sulfide-poor Lower zone sequences and are Ni depleted in mineralized rocks, whereas the degree of sulfide mineralization correlates with the S content in the country rock. Assimilation of sedimentary sulfur resulted in sulfide saturation and formation of Ni-depleted silicates in ultramafic rocks. The extremely high Ni content in olivine (up to 0.66 wt % NiO at Mg # = 88) from S-poor ultramafic rocks is attributed to Ni enrichment in residual melt after massive crystallization of Ni-poor orthopyroxene adcumulates. Trace element compositions of the most primitive cumulates and minerals confirm that the enrichment of primary melt of the Bushveld Complex in some incompatible elements is an initial feature of its anomalous mantle source.

The Transition-Zone Water Filter Model for Global Material Circulation: Where Do We Stand?

Abstract: Materials circulation in Earth's mantle will be modified if partial melting occurs in the transition zone. Melting in the transition zone is plausible if a significant amount of incompatible components is present in Earth's mantle. We review the experimental data on melting and melt density and conclude that melting is likely under a broad range of conditions, although conditions for dense melt are more limited. Current geochemical models of Earth suggest the presence of relatively dense incompatible components such as K 2 O and we conclude that a dense melt is likely formed when the fraction of water is small. Models have been developed to understand the structure of a melt layer and the circulation of melt and volatiles. The model suggests a relatively thin melt-rich layer that can be entrained by downwelling current to maintain "steady-state" structure. If deep mantle melting occurs with a small melt fraction, highly incompatible elements including hydrogen, helium and argon are sequestered without much effect on more compatible elements. This provides a natural explanation for many paradoxes including (i) the apparent discrepancy between whole mantle convection suggested from geophysical observations and the presence of long-lived large reservoirs suggested by geochemical observations, (ii) the helium/heat flow paradox and (iii) the argon paradox. Geophysical observations are reviewed including electrical conductivity and anomalies in seismic wave velocities to test the model and some future directions to refine the model are discussed.

The missing link between granites and granitic pegmatites

Abstract: In this contribution we provide evidence for the extraction of volatile and incompatible element enriched melts from common granites, which provides a mechanism which show that a large proportion of granitic pegmatites are genetically directly connected to a main granite body. In granites there are often two principal types of melt inclusions: (i) melt inclusions which represent the bulk chemistry of the granite and (ii) melt inclusions with a composition strongly divergent from this composition. In the Variscan Erzgebirge granites this type is characterized by extremely high fluorine concentration. However, in other geodynamic settings inclusions in granites can contain high concentrations of other elements which may take over the function of fluorine. From textural relationships this inclusion type represents intergranular melts enriched in all elements incompatible with the ideal haplogranite system. Due to the high volatile content of such melts the viscosity can be as much as several orders of magnitude lower than the quasi-solid bulk system and can therefore move rapidly through the partially or totally crystallized host, and flow together into a separate system forming pegmatite bodies inside or outside the granite body. Another important effect of the high volatile content is the phase separation resulting from the speciation change from OH- → H2O or CO32- → CO2 due to temperature and/or pressure changes at different locations within the granite-intergranular melt system. Since melt inclusions provide a means of conserving original undegassed compositions they are therefore important evidence for closing the gap between granites and granitic pegmatites. The paper is dedicated to two Czech colleagues - Petr Cerný and Milan Novak who have devoted their life to the study of granitic pegmatites.

Melt– and Fluid–Rock Interaction in Supra-Subduction Lithospheric Mantle: Evidence from Andesite-hosted Veined Peridotite Xenoliths

Abstract: We report petrographic, major and trace element data for xenoliths from the andesitic Avacha volcano (Kamchatka), which host orthopyroxene (opx)-rich veins of mantle origin formed either by rapid crystallization of intruded melts or by their interaction with the host harzburgite. Studies of such veins may give better insights into sub-arc mantle processes (in particular on a millimetre to centimetre scale) than those of (1) arc xenoliths that do not preserve solidified initial metasomatizing agents, (2) massif peridotites, probably modified during their emplacement, or (3) arc magmatic rocks, which provide indirect information. We seek to trace the evolution of these agents as they react with the host peridotite and to assess their impact on the wall-rocks. The veins cross-cut spinel harzburgite and consist mainly of opx with minor olivine, clinopyroxene (cpx) and/or amphibole. We identify 'rapidly crystallized' veins that cut wall-rock olivine without petrographic evidence of reaction, and 'reactive' veins subdivided into 'thick' (0*5-1 mm) and 'thin' (<€0*5 mm). Minerals in the rapidly crystallized veins are depleted in rare earth elements (REE) and high field strength elements (HFSE) and enriched in fluid-mobile elements relative to REE. Minerals in the reactive veins have higher Ti, Al, Cr and alkalis than minerals in the rapidly crystallized veins, as well as highly variable trace element abundances, especially in reaction zones, thin veins and related metasomatic pockets in the host peridotite. They commonly show U-shaped REE patterns and positive Zr and Hf spikes in normalized trace element patterns. Our data, supported by recent reports, show that the rapidly crystallized veins formed between 1200°C and 900°C from a liquid derived by fluid-fluxed melting of a refractory (harzburgitic) mantle source depleted in heavy REE. The reactive veins formed via 'fractionation-reactive percolation' from fractionated hydrous derivatives of the melts that precipitated the rapidly crystallized veins. These liquids re-equilibrated with the host through diffusion and fluid-assisted dissolution-precipitation reactions, whose end-products are thin reactive veins and metasomatic pockets with distinctive U-shaped REE patterns and Zr-Hf spikes. Some Avacha xenoliths contain veins of Fe-rich amphibole deposited from the host magma that penetrated fractures in the peridotite fragments during their transport to the surface. These products of contamination were mistakenly attributed to mantle metasomatism in previous studies of other suites of Avacha mantle xenoliths. Trace element abundances in such veins are higher than for reactive veins of mantle origin, but both have similar trace element patterns (U-shaped REE patterns and Zr-Hf spikes) suggesting that 'fractionation-reactive percolation' also took place during their formation and is common during interaction of refractory peridotites with percolating melts and fluids. Metasomatic pockets of cpx and amphibole replacing coarse opx and spinel in the host peridotites commonly occur in the vicinity of fractures that lead to reactive opx-rich veins. The cpx and amphiboles in the pockets show progressive depletion in middle REE and HFSE at constant light REE and/or large ion lithophile elements away from the veins towards the host. This indicates that residual hydrous fluids expelled from the source veins enriched the wall-rock peridotites in incompatible elements but were progressively modified by reaction with the host with increasing percolation distance. This process produces disseminated pockets of metasomatic minerals with a broad range of compositions from a single initial liquid and strongly affects the trace element budgets of the harzburgite xenoliths from Avacha. We show that melts and fluids are likely to undergo profound transformation as they travel through and react with the refractory host mantle, even on a millimetre to centimetre scale. The composition of the initial metasomatizing agents can only be inferred from the composition of the metasomatic phases in mantle rocks combined with appropriate partition coefficients if these phases come from well-equilibrated mineral assemblages located close to melt and/or fluid sources.

Geochemical constraints on komatiite volcanism from Sargur Group Nagamangala greenstone belt, western Dharwar craton, southern India: Implications for Mesoarchean mantle evolution and continental growth

Abstract: We present field, petrographic, major and trace element data for komatiites and komatiite basalts from Sargur Group Nagamangala greenstone belt, western Dharwar craton. Field evidences such as crude pillow structure indicate their eruption in a marine environment whilst spinifex texture reveals their komatiite nature. Petrographic data suggest that the primary mineralogy has been completely altered during post-magmatic processes associated with metamorphism corresponding to greenschist to lower amphibolite facies conditions. The studied komatiites contain serpentine, talc, tremolite, actinolite and chlorite whilst tremolite, actinolite with minor plagioclase in komatiitic basalts. Based on the published Sm-Nd whole rock isochron ages of adjoining Banasandra komatiites (northern extension of Nagamangala belt) and further northwest in Nuggihalli belt and Kalyadi belt we speculate ca. 3.2–3.15 Ga for komatiite eruption in Nagamangala belt. Trace element characteristics particularly HFSE and REE patterns suggest that most of the primary geochemical characteristics are preserved with minor influence of post-magmatic alteration and/or contamination. About 1/3 of studied komatiites show Al-depletion whilst remaining komatiites and komatiite basalts are Al-undepleted. Several samples despite high MgO, (Gd/Yb)N ratios show low CaO/Al2O3 ratios. Such anomalous values could be related to removal of CaO from komatiites during fluid-driven hydrothermal alteration, thus lowering CaO/Al2O3 ratios. The elemental characteristics of Al-depleted komatiites such as higher (Gd/Yb)N (>1.0), CaO/Al2O3 (>1.0), Al2O3/TiO2 ( 18) together with higher HREE, Y, Zr suggest their derivation from shallower upper mantle without garnet involvement in residue. The observed chemical characteristics (CaO/Al2O3, Al2O3/TiO2, MgO, Ni, Cr, Nb, Zr, Y, Hf, and REE) indicate derivation of the komatiite and komatiite basalt magmas from heterogeneous mantle (depleted to primitive mantle) at different depths in hot spot environments possibly with a rising plume. The low content of incompatible elements in studied komatiites suggest existence of depleted mantle during ca. 3.2 Ga which in turn imply an earlier episode of mantle differentiation, greenstone volcanism and continental growth probably during ca. 3.6–3.3 Ga which is substantiated by Nd and Pb isotope data of gneisses and komatiites in western Dharwar craton (WDC).

Magmatic processes in the Bishop Tuff rhyolitic magma based on trace elements in melt inclusions and pumice matrix glass

Abstract: To investigate the origin of compositional zonation in the Bishop Tuff magma body, we have analyzed trace elements in the matrix glass of pumice clasts and in quartz-hosted melt inclusions. Our results show contrasting patterns for quartz in different parts of the Bishop Tuff. In all samples from the early part of the eruption, trace element compositions of matrix glasses are similar to but slightly more evolved than quartz-hosted melt inclusions. This indicates a cogenetic relationship between quartz crystals and their surrounding matrix glass, consistent with in situ crystallization. The range of incompatible element concentrations in melt inclusions and matrix glass from single pumice clasts requires 16–20 wt% in situ crystallization. This is greater than the actual crystal content of the pumices (<15 % crystals). In contrast to the pattern for the early pumices, pyroclastic flow samples from the middle part of the eruption show contrasting trends: In some clasts, the matrix is more evolved than the inclusions, whereas in other clasts, the matrix is less evolved. In the late Bishop Tuff, all crystal-rich samples have matrix glasses that are less evolved than the melt inclusions. Trace element abundances indicate that the cores of quartz in the late Bishop Tuff crystallized from more differentiated rhyolitic magma that was similar in many ways, yet distinct from the early-erupted Bishop Tuff. Our results are compatible with a model of secular incremental zoning (Hildreth and Wilson in Compositional zoning of the Bishop Tuff. J Petrol 48(5):951–999, 2007), in which melt batches from underlying crystal mush rise to various levels in a growing magma body according to their buoyancy. Early- and middle-erupted quartz crystallized from highly evolved rhyolitic melt, but then some parts of the middle-erupted magma were invaded by less differentiated rhyolite such that the matrix melt at the time of eruption was less evolved than the melt inclusions. A similar process occurred but to a greater extent in magma that erupted to form the late Bishop Tuff. In addition, there was a final, major magma mixing event in the late magma that formed Ti-rich rims on quartz and Ba-rich rims on sanidine, trapped less evolved rhyolitic melt inclusions, and resulted in dark and swirly crystal-poor pumice that is a rare type throughout much of the Bishop Tuff.

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

Abstract: 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 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.

Formation of U-depleted rhyolite from a basanite at El Hierro, Canary Islands

Abstract: Phonolite and trachyte are the felsic magmas of the alkaline magma suites, which characterize the Canary Islands. The October 2011 submarine eruption off El Hierro, the westernmost island, nevertheless, produced a small volume of rhyolitic magma. The rhyolite occurred as highly vesicular, white coloured pumices enveloped in and mingled with darker coloured basanitic pumice. The basanitic pumice is relatively crystal poor with a few euhedral olivines (mostly Fo77–79), clinopyroxenes and Fe-rich spinels, whereas very rare olivine of same composition is found together with equally rare Fe-sulphide and FeTi-rich oxides in the rhyolite. The Fe–Mg exchange equilibrium in the oxides permits to calculate an equilibrium temperature of 970–890 °C for the rhyolite, in agreement with quartz-melt equilibrium at ca. 930 °C. A striking mineralogical feature of the rhyolite is the presence of rounded to contorted grains of milky quartz, which are xenocrysts incorporated and partly dissolved into the magma. Analyses of residual volatile concentrations in the glasses show that the rhyolite melt was highly degassed, whereas the basanitic glass still has important halogen concentrations. Trace element patterns of the mafic glasses and their elevated incompatible element concentrations are typical of the western Canary Island basanites. In contrast, the trace element composition of the rhyolite shows surprisingly low concentrations for all elements except the most incompatible ones (e.g. Rb, Ba, K and Th). All other measured LILE, HFSE and REE have significantly lower concentration than the basanitic counterpart that can be explained by fractionation of accessory phases (1 % apatite, 1 % sphene and 0.1 % zircon). Surprisingly, low U concentration is presumably related to elevated oxygen fugacity in the rhyolite, causing U to be in a hexavalent state, and fluxing of F-rich gas leading to volatilization of UF6, known to emanate at low temperature. The results suggest that a gas-rich basanitic melt remobilized a small volume of stagnant rhyolitic melt formed by incorporation of approximately 10 % quartz-rich sediment into a late differentiate of trachytic composition. Sediments at the interface of an old oceanic crust adjacent to a continental shield and younger volcanic island are likely to act as magma traps were sediment assimilation may alter the mantle-derived magma composition. Quartz assimilation thus explains the production of rhyolite magma in a volcanic island characterized by an alkaline magma series from primitive basanites to trachytes.

Plio-Pleistocene basanitic and melilititic series of the Bohemian Massif : K-Ar ages, major/trace element and Sr-Nd isotopic data

Abstract: The Plio-Pleistocene volcanic rocks of the Bohemian Massif comprise a compositional spectrum involving two series: an older basanitic series (6.0–0.8 Ma) and a younger, melilititic series (1.0–0.26 Ma). The former consists of relatively undifferentiated basaltic rocks, slightly silica-undersaturated, with Mg# ranging from 62 to almost primitive mantle-type values of 74. The major and trace element characteristics correspond to those of primitive intra-plate alkaline volcanic rocks from a common sub-lithospheric mantle source (European Asthenospheric Reservoir – EAR) including positive Nb, and negative K and Pb anomalies. 87Sr/86Sr ratios of 0.7032–0.7034 and 143Nd/144Nd of 0.51285–0.51288 indicate a moderately depleted mantle source as for other mafic rocks of the central European volcanic province with signs of HIMU-like characteristics commonly attributed to recycling of subducted oceanic crust in the upper mantle during the Variscan orogeny. The melilititic series is characterized by higher degrees of silica-undersaturation, and high Mg# of 68–72 values, compatible with primitive-mantle-derived compositions. The high OIB-like Ce/Pb (19–47) and Nb/U (32–53) ratios indicate that assimilation of crustal material was negligible. In both series, concentrations of incompatible elements are mildly elevated and 87Sr/86Sr ratios (0.7034–0.7036) and 143Nd/144Nd ratios (0.51285–0.51288) overlap. Variations in incompatible element concentrations and isotopic compositions in the basanitic series and melilititic series can be explained by a lower degree of mantle melting for the latter with preferential melting of enriched mantle domains. The Sr and Nd isotopic compositions of both rock series are similar to those of the EAR. Minor differences in geochemical characteristics between the two series may be attributed to: (i) to different settings with respect to crust and lithospheric mantle conditions in (a) Western Bohemia (WB) and (b) Northeastern Bohemia (NEB) and the Northern Moravia and Silesia (NMS) areas, (ii) a modally metasomatized mantle lithosphere in WB in contrast to cryptically metasomatized domains in the NEB and NMS, (iii) different degrees of partial melting with very low degrees in WB but higher degrees in NEB and NMS. The geochemical and isotopic similarity between the Plio-Pleistocene volcanic rocks and those of the late Cretaceous and Cenozoic (79–6 Ma) suggests that their magmas came from compositionally similar mantle sources, that underwent low degrees of melting over an interval of ∼80 Ma. The Oligocene to Miocene basanitic series that accompanied the Plio-Pleistoicene basanitic series in the NMS region indicate that they shared a common mantle source. There is no geochemical evidence for thermal erosion of the lithospheric mantle or significant changes in mantle compositions within the time of a weak thermal perturbation in the asthenospheric mantle. These perturbations were caused by a dispersed mantle plume or passively upwelling asthenosphere in zones of lithospheric thinning.

The Behavior of Metals (Pb, Zn, As, Mo, Cu) During Crystallization and Degassing of Rhyolites from the Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand

Abstract: TThe Taupo Volcanic Zone (TVZ), New Zealand is a region of voluminous and frequent rhyolitic volcanism and widespread geothermal activity. Additionally, the hydrothermal systems of the TVZ contain relatively high concentrations of base and precious metals. Here we present an extensive dataset of major element, volatile, and trace element (including Pb, Zn, As, Mo, Cu) abundances in melt inclusions, pumice glasses and minerals from eight eruptions within the Okataina Volcanic Center (OVC) of the TVZ to investigate the behavior of metals during melt evolution. The high-SiO2 rhyolites of the OVC contain high concentrations of volatiles (≤6 wt % H2O, ≤0·25 wt % Cl) and underwent significant degassing prior to and during eruption. The OVC melts contain moderate concentrations of metals (11–24 ppm Pb, 20–50 ppm Zn, 2–7 ppm As, <2·5 ppm Mo, <~5 ppm Cu). Ferromagnesian minerals (amphibole, biotite and orthopyroxene) in the OVC pumice have high concentrations of Zn (≤1500 ppm), and plagioclase and biotite contain moderate amounts of Pb (≤11 ppm). The melt inclusion and pumice glass trace element data reveal complex histories of magma mixing and mingling prior to eruption; however, discrete melt batches are easily identified based on trace element geochemistry. Variations in incompatible trace elements within these melt batches suggest that the OVC rhyolites underwent at least ∼20–25% fractional crystallization during quartz crystallization and melt inclusion entrapment (at pressures of ∼100–200 MPa) and little to no crystallization (≤5%) during ascent and eruption. Comparison of melt inclusion metal and incompatible element (e.g. U) concentrations reveals that melt Pb, Mo and As increase, whereas melt Zn decreases, during fractional crystallization at depth (∼100–200 MPa). These observations can be explained by minor partitioning of the metals Pb, Mo and As into the fractionating minerals and stronger partitioning of Zn into the ferromagnesian phases, supported by calculated metal D values and analyzed metal concentrations in OVC minerals. Interestingly, throughout both deep, vapor-saturated crystallization and during extensive degassing during magma ascent and eruption (as recorded by pumice glasses), the metals analyzed here do not appear to partition appreciably into the vapor. We propose that the lack of volatility of the metals analyzed in this study can be attributed to a combination of several factors. First, vapor–melt partitioning requires the presence of ligands—commonly Cl, S and OH—with which the metals may complex. Given the low Cl/H2O ratios in the OVC melts and the extensive degassing of H2O compared with Cl, it seems likely that the rhyolites would have exsolved H2O-rich vapor with insufficient Cl to transport metals (in particular Pb and Zn) into the vapor phase, either at depth or during magma ascent. Second, the overall small volumes of vapor present during crystallization at pressures of 100–200 MPa would have impeded significant vapor–melt partitioning of the metals. Finally, the estimated very rapid ascent of the OVC melts from depths of 4–8 km suggests that there was insufficient time at low pressure for diffusion of metals out of the melt. These results imply that there may be an indirect connection between the rhyolites and the metals of the hydrothermal systems of the TVZ. As the metals, and other species such as Cl, remain in the rhyolitic magmas upon eruption, they are available in the large volumes of rhyolite emplaced in the upper crust of the TVZ for leaching by heated meteoric waters.