Incompatible Trace Element Abundances Research Articles

Revisiting the Petrogenesis of Pyroclastic Glass Bead Deposits at the Apollo 15 and 17 Sites

Abstract The Apollo 15 low-titanium and Apollo 17 high-titanium pyroclastic glass beads are among the most primitive magmatically derived samples obtained from the Moon. Two key samples, the low-Ti Apollo 15426 green glass clod and the high-Ti Apollo 74220 orange glass are morphologically distinct, where the Apollo 15 beads are larger (~107 μm along maximum axis) and more fractured, and the Apollo 17 are smaller (~42 μm) and less fractured. In this study, holohyaline beads as well as crystallized beads were examined from both samples using petrography, electron microprobe analysis, and laser-ablation inductively coupled plasma mass spectrometry. Crystallized beads show compositional variability in major, minor, and trace elements and enable examination of magmatic mineral fractionation processes during cooling of both deposits. The Apollo 15426 beads experienced variable olivine crystallization, whereas the Apollo 74220 beads experienced both olivine and ilmenite crystallization. Holohyaline beads from both deposits show more limited major, minor, and trace element variability than their crystallized counterparts. Trace element abundance data for individual holohyaline beads show that in Apollo 74220, they are tightly clustered at ~30× Carbonaceous Ivuna chondrite [CI] with negative Eu anomalies and subchondritic Nb/Ta, interpreted to reflect the presence of late-stage magma ocean cumulates overturned into an otherwise primitive mantle source. Incompatible trace element abundances for holohyaline beads in 15426 are supra-chondritic from ~8× CI, to >80× CI, with pronounced relative depletions in Sr and Eu for the most incompatible element enriched beads, which represent a distinct bead group within the deposit. Apollo 15426 beads have elevated Ni and Co abundances at the edges of the beads compared to their centers. These data are interpreted to reflect a more complex magmatic evolution of the 15426 deposit, beginning with (i) initial magma generation, storage, and assimilation within shallower low- and high-Ca pyroxene bearing magma ocean cumulates (15B,C); (ii) mobilization of the earlier magmas by more recently generated primitive magmas (15A); (iii) eruption and crystallization of some beads (15D,E); and (iv) later jumbling of the deposit, possible impact contamination and addition of exotic basaltic bead components (J Group). In contrast, the 74220 data show no discernable difference between Ni and Co abundances at the edges and centers supporting prior observations for limited melt fractionation and an absence of meteoritic components. Both deposits are likely to have been formed in the presence of a transient atmosphere. Using 74220 melt compositions from this study, post-entrapment crystallization abundances range from 266 to 1130 μg/g for H2O, 36 to 68 μg/g for F, 441 to 832 μg/g for S, and 0 to 2.31 μg/g for Cl, consistent with prior studies and suggesting up to ~0.1 wt % H2O in the melt, with considerably less in the source. The role that late-stage magma ocean cumulates rich in ilmenite and high-Ca pyroxene might play in modifying this volatile element estimate, however, casts remaining doubt on the volatile element abundance and evolution of the primitive Moon.

Compositional zoning of the Otowi Member of the Bandelier Tuff, Valles caldera, New Mexico, USA

Abstract The Otowi Member of the Bandelier Tuff erupted at ca. 1.60 Ma from the Valles caldera (New Mexico, USA). It consists of as much as 400 km3 (dense rock equivalent) of strongly differentiated high-silica rhyolite and shows systematic upward variations in crystallinity, mineral chemistry, and trace element concentrations through its thickness, but the major element composition is almost constant and is near the low-pressure granite minimum. Incompatible trace elements in whole pumice fragments and glasses show well-correlated linear covariations. Upward zoning to lower abundances of incompatible trace elements is accompanied by development of overgrowths on quartz and alkali feldspar, although earlier-formed interiors of quartz and feldspar have near-constant compositions throughout the tuff, modified by cation diffusion in the case of feldspar. Melt inclusions in remnant quartz cores show diverse Pb isotope ratios, pointing to a wide range of distinct protoliths that contributed rhyolitic melt to the Otowi magma. Mineral thermometers suggest a modest temperature gradient through the melt body, perhaps of 40 °C, at the time of eruption. Chemical, textural, and mineralogical variations and volume-composition relations through the tuff are consistent with an origin for zoning by melting of a high-crystallinity cumulate layer beneath cognate supernatant liquid to produce denser, remobilized liquid of accumulative composition (i.e., the “modified mush model”). Melting may have occurred in several episodes. The latest of these episodes, probably thousands of years prior to eruption, introduced new rhyolitic liquid into the system and was associated with a thermal excursion, recorded in core compositions of pyroxene, during which much of the earlier crystal mass was dissolved. This left inherited cores and interiors of accumulated quartz and feldspar mantled with new growth having less-evolved compositions (higher Ti, Sr, and Ba). Changing solubility of zircon during cumulate melting produced a reversal of Zr concentrations. There is no clear petrologic evidence of a recharge eruption trigger; nonetheless, compositional zoning resulted mainly from repeated recharge-induced remobilization of quartz-feldspar cumulate. The Otowi system was built, evolved, and modified by several events over the course of a few hundred thousand years.

Early Eocene Arctic volcanism from carbonate-metasomatized mantle

Melilitite, nephelinite, basanite, and alkali basalt, along with phonolite differentiates, form the Freemans Cove Complex (FCC) in the south-eastern extremity of Bathurst Island (Nunavut, Canada). New 40Ar/39Ar chronology indicates their emplacement between ~ 56 and ~ 54 million years ago within a localized extensional structure. Melilitites and nephelinites, along with phonolite differentiates, likely relate to the beginning and end phases of extension, whereas alkali basalts were emplaced during a main extensional episode at ~ 55 Ma. The melilitites, nephelinites, and alkali basalts show no strong evidence for significant assimilation of crust, in contrast to some phonolites. Partial melting occurred within both the garnet- and spinel-facies mantle and sampled sources with He, O, Nd, Hf, and Os isotope characteristics indicative of peridotite with two distinct components. The first, expressed in higher degree partial melts, represents a relatively depleted component (“A”; 3He/4He ~ 8 RA, εNdi ~ + 3 εHfi ~ + 7, γOsi ~ 0). The second was an enriched component (“B” 3He/4He < 3 RA, εNdi < – 1 εHfi < + 3, γOsi > + 70) sampled by the lowest degree partial melts and represents carbonate-metasomatized peridotite. Magmatism in the FCC shows that rifting extended from the Labrador Sea to Bathurst Island and reached a zenith at ~ 55 Ma, during the Eurekan orogeny. The incompatible trace-element abundances and isotopic signatures of FCC rocks indicate melt generation occurred at the base of relatively thin lithosphere at the margin of a thick craton, with no mantle plume influence. FCC melt compositions are distinct from other continental rift magmatic provinces worldwide, and their metasomatized mantle source was plausibly formed synchronously with emplacement of Cretaceous kimberlites. The FCC illustrates that the range of isotopic compositions preserved in continental rift magmas are likely to be dominated by temporal changes in the extent of partial melting, as well as by the timing and degree of metasomatism recorded in the underlying continental lithosphere.

Petrogenesis of alkaline magmas across a continent to ocean transect, northern Ross Sea, Antarctica

The West Antarctic Rift System (WARS) is one of the world's largest active rift systems and alkaline magmatic provinces. The alkaline magmatism crosscuts oceanic and continental lithosphere but maintains generally similar Sr-Nd-Pb isotope signatures. Here we present new major-, trace- and highly siderophile-element (Os, Ir, Ru, Pt, Pd, Re) abundances and Sr-Nd-Pb-Os isotope data for a Miocene to recent WARS alkaline basalt suite from a continental-oceanic transect in the northwest Ross Sea. The samples are geochemically enriched similar to ocean island basalts, with oceanic lavas having higher absolute incompatible trace element abundances than continental lavas. The suite exhibits a large range in measured 187Re/188Os (1.7 to 1305) and age-corrected 187Os/188Os (0.1254 to 1.055) that has a positive, highly curved relationship with measured 87Sr/86Sr (0.70287–0.70331), but a negative, highly curved relationship with both measured 143Nd/144Nd (0.51280–0.51300) and 206Pb/204Pb (19.237–20.237). These data suggest that contamination by a mafic continental lithospheric component has occurred to varying degrees and exerts some control on the geochemistry of the continental lavas. Primitive lavas from the oceanic Adare Basin that have experienced negligible contamination are used to constrain the primary source of northwest Ross Sea alkaline lavas and to assess previously proposed hypotheses regarding the origin of magmatism. Explanations for the origin of WARS alkaline lavas range from plume magmatism to partial melting of continental lithospheric mantle metasomatized by subduction fluids prior to cessation of subduction of the Phoenix Plate underneath the Gondwana margin. Samples from the continental-oceanic transect, however, neither exhibit classic arc-lava geochemical signatures nor provide any evidence to support an active mantle plume source. Rather, they are geochemically enriched magmas generated through partial melting of previously subducted oceanic lithospheric mantle concomitant with continental lithospheric thinning during the Cenozoic.

Complexity and ambiguity in the relationships between major lunar crustal lithologies and meteoritic clasts inferred from major and trace element modeling

Clasts of feldspathic lithologies such as magnesian anorthosites, anorthositic troctolites, and granulites in lunar meteorites have greatly expanded knowledge of the lithologic diversity of the lunar crust. However, their origins and relationships to other major crustal lithologies such as the ferroan anorthosites, magnesian-suite, and alkali-suite are not fully understood. Here we present the results of phase equilibrium modeling using the MELTS and MAGFOX programs designed to investigate the origins of lunar crustal lithologies and petrologic connections between them. We show that the major and trace element compositions of the Mg- and alkali-suites are consistent with partial melting of hybridized sources and are inconsistent with decompression melting + assimilation models. Our results also show that the vertical trend in Mg# in mafic silicates vs. An# in plagioclase characteristic of feldspathic meteoritic lithologies and ferroan anorthosites can be produced by fractional crystallization of KREEP-free Mg-suite melts, but that these melts are not likely to contribute significantly to the composition of the global crust. Furthermore, we calculated potential parental melt compositions for these crustal lithologies using the abundances of REEs in plagioclase in FANs, the Mg- and alkali-suites, and clasts in feldspathic meteorites. Our results show that despite low bulk rock abundances of incompatible trace elements in many feldspathic lunar meteorites, parental melts with overall REE abundances similar to or in excess of KREEP are needed to reproduce the REE abundances in plagioclase in clasts from feldspathic lunar meteorites. However, the lack of a Na enrichment trend in their plagioclase compositions with decreasing Mg# requires very Na-depleted melts without a KREEP component. The available data regarding magnesian anorthosites, anorthositic troctolites, and granulites in lunar meteorites, and inferences made here regarding their parental melt compositions, lead to contradictory and ambiguous conclusions regarding their origins.

A common magma source for plutonic and volcanic rocks of The Geysers geothermal field, California: Volume and intrusive history derived from zircon

The Geysers Plutonic Complex (GPC) in the California Coast Ranges underlies one of the world's premier geothermal resources. The GPC consists of three major intrusive phases, orthopyroxene-biotite microgranite porphyry, orthopyroxene-biotite granite, and hornblende-biotite-orthopyroxene granodiorite (in sequence of emplacement). These are nearly coeval and compositionally equivalent to lavas of the overlying Cobb Mountain Volcanic Center which includes (from older to younger) rhyolite of Alder Creek, dacite of Cobb Mountain, and dacite of Cobb Valley. Zircon from GPC plutonic and associated volcanic rocks were analyzed at high spatial resolution for their trace element abundances along with oxygen and hafnium isotopic compositions. Pronounced negative Eu anomalies and high incompatible trace element (e.g., Y, Hf, and U) abundances in zircon along with low Ti-in-zircon temperatures reveal that the GPC microgranite porphyry magma was more evolved than GPC granite and granodiorite. Isotopically, GPC microgranite porphyry, granite, and granodiorite zircon crystals closely overlap (δ18O = +4.76 to +9.18; εHf = +1.4 to +10.7), but a subpopulation with elevated δ18O (∼8.05) and lower εHf (∼4.4) is only present in GPC granite and granodiorite. Zircon from coeval volcanic units share this dichotomy, with a dominant population at (δ18O = +4.92 to +9.38; εHf = +3.4 to +11.3) and a generally minor population with elevated δ18O and low εHf, which is particularly prominent in dacite of Cobb Valley. Anticorrelated δ18O and εHf values indicate progressive assimilation of Franciscan Complex basement rocks, but fractional crystallization was decoupled from crustal assimilation. Together with published U-Th-Pb geochronology, these data reveal distinct degrees of crust-mantle interaction and constrain the thermochemical conditions during different stages in the evolution of a composite intrusive body that fed the GPC and contemporaneous volcanoes. A thermal model for such a body emplaced at ∼7 km depth quantitatively matches the GPC zircon age distribution when magma accumulation started at low recharge rates (0.1 km3/ka), intermittently peaked during a brief flare-up (4 km3/ka for 50 ka), and then returned to a low recharge flux (0.1 km3/ka). This model also qualitatively explains the initial presence of small-volume, highly evolved melts forming the microgranite porphyry, followed by massive emplacement of less evolved magmas forming the GPC granite-granodiorite complex. During this second stage, crustal assimilation locally intensified due to prior thermal priming of the country rock. The total injected magma volume into the upper-crustal reservoir between c. 2.1 and 1.1 Ma amounts to ∼300 km3, which is about three to four times the known volume from geothermal well penetration into the GPC. The accumulation of large volumes of silicic magma along the western North American continental margin in the wake of the northward migrating Gorda slab edge thus appears limited to a brief (c. 50 ka) pulse of high magma influx from the mantle that was pre- and post-dated by protracted low-flux magmatism.

Pristinity and petrogenesis of eucrites

AbstractNew petrography, mineral chemistry, and whole rock major, minor, and trace element abundance data are reported for 29 dominantly unbrecciated basaltic (noncumulate) eucrites and one cumulate eucrite. Among unbrecciated samples, several exhibit shock darkening and impact melt veins, with incomplete preservation of primary textures. There is extensive thermal metamorphism of some eucrites, consistent with prior work. A “pristinity filter” of textural information, siderophile element abundances, and Ni/Co ratios of bulk rocks is used to address whether eucrite samples preserve endogenous refractory geochemical signatures of their asteroid parent body (i.e., Vesta), or could have experienced exogenous impact contamination. Based on these criteria, Cumulus Hills 04049, Elephant Moraine 90020, Grosvenor Range 95533, Pecora Escarpment 91245, and possibly Queen Alexander Range 97053 and Northwest Africa 1923 are pristine eucrites. Eucrite major element compositions and refractory incompatible trace element abundances are minimally affected by metamorphism or impact contamination. Eucrite petrogenesis examined through the lens of these elements is consistent with partial melting of a silicate mantle that experienced prior metal–silicate equilibrium, rather than as melts associated with cumulate diogenites. In the absence of the requirement of a large‐scale magma ocean to explain eucrite petrogenesis, the interior structure of Vesta could be more heterogeneous than for larger planetary bodies.

Compositional variation of mafic calc-alkaline lavas at the submarine Pausanias Volcanic Field, western South Aegean Volcanic Arc: Implications for magma formation and ascent

The calc-alkaline lavas of the submarine Pausanias Volcanic Field and the neighboring Methana peninsula represent the largest volcanic edifices of the western South Aegean Volcanic Arc (SAVA) in the Mediterranean Sea and erupted on 30–35 km thick continental crust. We report the first whole rock major and trace elements together with Sr-Nd-Pb isotope ratios for basaltic to andesitic lavas from the submarine Pausanias Volcanic Field consisting of six smaller, volcanic structures. The mafic lavas have the most primitive compositions of the SAVA with MgO of up to 9 wt% and Ni concentrations >100 ppm. The incompatible trace element abundance patterns of the Pausanias and Methana lavas overlap and have typical island arc patterns, but Pausanias lavas display a larger geochemical heterogeneity on a smaller spatial scale compared to those from Methana. The Pausanias lavas resemble those from Methana in Sr, Nd, and Pb isotopes reflecting higher sediment subduction in the western SAVA than in the central arc at Santorini. The variability of incompatible element concentrations at relatively constant isotope compositions suggests variable degrees of partial melting of a peridotite-sediment mélange diapir in the mantle wedge. The Pausanias magmas formed from a less depleted mantle source compared to the central SAVA and their ascent in an extensional basin supported relatively rapid ascent without the extensive stagnation in the crust observed in the Methana magmas. The compositional differences between Pausanias and Methana imply differences in their composition and/or transport in the mantle wedge and the crust, allowing highly variable melts to reach the surface within a spatial distance of few kilometers. • Small scale mantle heterogeneity recorded at the Pausanias Volcanic Field. • Melting of sediment-rich mélange diapirs contribute to Pausanias lavas. • At Pausanias, extension allows melts to ascend more direct through the crust compared to Methana.

REE mineralization in Siwana peralkaline granite, western India-role of fractional crystallization, hydrothermal remobilization, and feldspar-fluid interaction

Peralkaline granites from the Siwana complex in western India host mineralization of rare earth and other high field strength elements (REE/HFSE). In this study, we use textural relations, major-trace element chemistry and Li-isotope composition of minerals to constrain the magmatic evolution of the granites and the mechanism of hydrothermal REE mineralization. Three facies of peralkaline granites, viz., hypersolvus, transsolvus, and pegmatitic are identified in the Siwana complex. The hypersolvus granites constitute two mineralogical variants: clinopyroxene- and ferrorichterite-bearing. Transsolvus granites contain riebeckite-arfvedsonite and occur as patches/network of dikes in hypersolvus granites. Rayleigh crystal fractionation modelling using incompatible trace element abundances in clinopyroxene and amphibole indicates that the hypersolvus and the transsolvus granites formed after 50-85% and 98% melt crystallization, respectively. Early magmatic clinopyroxenes and ferrorichterites in the hypersolvus granites have fairly heavy δ7Li (+18.5‰ to +20.4‰) suggestive of crystallization from highly evolved magmas. Late magmatic arfvedsonites in the transsolvus granites have even heavier δ7Li (+29.7‰ to +33.8‰). Rayleigh distillation modelling using Li isotopes reveal that the hypersolvus and transsolvus granites crystallized from parental magmas that had undergone >90% fractional crystallization.The Siwana granitoids are hydrothermally altered as evidenced from pseudomorphic re-equilibration of clinopyroxene, alkali feldspar megacrysts, vein and patch perthite formation, replacement of ferrorichterite/clinopyroxene by hydrothermal aegirine, alteration of primary fluorapatite, monazite, aenigmatite, eudialyte, and vlasovite. Three stages of hydrothermal alteration are identified in the granites: stage-I alteration was brought about by highly-saline high-temperature fluid that scavenged REE, HFSE, Ti, Na, and Fe from clinopyroxene and aenigmatite. This was followed by extensive replacement of ferrorichterite and arfvedsonite by aegirine, which decreased the pH and salinity of the fluid. The third stage of alteration led to the replacement of vlasovite by calciocatapleiite, elpidite, and eudialyte and was accompanied by the replacement of alkali feldspar by aegirine, quartz, and secondary REE minerals. The bulk of the REE mineralization occurs in transsolvus granites as cerite associated with aegirine and quartz. Textural relations indicate that these minerals pseudomorph alkali feldspar. Distinct assemblages of secondary REE minerals are identified in the pyroxene- and amphibole-bearing granites-only hydroxyl-dominated REE minerals like cerite are identified in the former while late-stage replacement of cerite by bastnäsite and chevkinite is observed in the latter, the difference controlled by the extent of ferrorichterite to aegirine transformation. The precipitation of secondary REE minerals was largely triggered by pH increase due to the interaction of alkali feldspar with REE-bearing hydrothermal fluids, resulting in the replacement of alkali-feldspar with Fe-phyllosilicates.

Rare Earth Element and Incompatible Trace Element Abundances in Emeralds Reveal Their Formation Environments

Emeralds require the unusual association of typically compatible elements (Cr, V), with incompatible Be to form, and occur in complex tectonic settings associated with sediments (type IIB; Colombia) or, more commonly, with magmatism and regional metamorphism (IA). Precise rare earth element (REE) and incompatible trace element abundances are reported for a global suite of emeralds, enabling the identification of the environments in which they formed. Type IIB emeralds have nearly flat continental crust normalized REE patterns (La/YbCC = ~2), consistent with a sedimentary source origin. Type IA emerald REE patterns have upturns in the heavy REE (La/YbCC = ~0.3), a feature also shared with South African emeralds occurring in Archaean host rocks. Modeling of type IA emerald compositions indicates that they form from magmatic fluids of sedimentary (S)-type granite melts interacting with Cr, V-rich mafic–ultramafic crustal protoliths. This geochemical signature links emerald formation with continental suture zones. Diamonds, rubies, and sapphires have been considered as ‘plate tectonic gemstones’ based on mineral inclusions within them, or associations with plate tectonic indicators. Emeralds are distinct plate tectonic gemstones, recording geochemical evidence for origin within their mineral structure, and indicating that plate tectonic processes have led to emerald deposit formation since at least the Archaean.

MORB Melt Transport through Atlantis Bank Oceanic Batholith (SW Indian Ridge)

AbstractThe Atlantis Bank Oceanic Batholith is a 660 km2 gabbro massif representing the plutonic foundation of a major ridge magmatic center. It was continuously accreted, emplaced, and exposed in the rift mountains of the paleo-SW Indian Ridge from 13 to 10·3 Ma. Ocean Drilling Program (ODP) Hole 735B, drilled to 1508 m at Atlantis Bank, recovered evolved intercalated olivine and oxide gabbros representing the upper levels of the lower ocean crust. Within this section, ∼5·6 m of primitive chromian-spinel-bearing troctolites (0·1–2 m thick), with sharp modal contacts with the host gabbros, were cored between 410 and 500 m depth. Here we present new mineral (chromian spinel, clinopyroxene, olivine, and plagioclase) major and trace element and petrographic data for the troctolite suites (i.e. troctolites, clinopyroxene-rich troctolites, troctolitic gabbros) from 410 to 528 mbsf (meters below seafloor) and olivine gabbros in the 0–274 mbsf and 410–500 mbsf intervals, and examine the origin of these troctolite layers. Equilibrium melts for the troctolites are primitive to moderately evolved, with Mg# [= 100Mg/(Mg + Fe), 48–68 mol%] comparable with those of Atlantis Bank basalts. By contrast, equilibrium melts for both the 0–274 mbsf and 410–500 mbsf host olivine gabbros are highly to moderately evolved (Mg# 27–63 mol%). The 410–500 mbsf troctolite suites maintain high clinopyroxene Mg# (81–89 mol%) and mineral concentrations of compatible elements (i.e. clinopyroxene Cr2O3 0·1–1·2 wt%, Ni 151–330 μg g–1 and olivine Ni 1055–1559 μg g–1) with the increase in incompatible trace element abundances (i.e. clinopyroxene TiO2 0·3–2·1 wt%, Zr 5·8–112 μg g–1 and olivine Ti up to 293 μg g–1). Combined with abundant dissolution–reprecipitation textures, our results indicate that the troctolites were formed by the reaction between a spinel-bearing, troctolitic mush, from which they inherited the high Mg#, Ni and Cr, and percolating melts adding incompatible trace elements. Moreover, the spinel (NiO versus TiO2) and olivine (Ti versus Y) trace element compositions indicate that the troctolites were affected by low-degree Fe–Ti-rich melt metasomatism. In contrast, both the 0–274 mbsf and 410–500 mbsf olivine gabbros display a prominent decrease in clinopyroxene Mg# (from 88 to 66) and mineral compatible element concentrations (i.e. clinopyroxene Cr2O3 from 1·1 to ∼0 wt%, Ni from 208 to 34 μg g–1 and olivine Ni from 1200 to 136 μg g–1) with increasing incompatible trace element abundances (e.g. clinopyroxene Zr from 4·8 to 157 μg g–1). These features are compatible with the reactive porous flow of slightly to highly evolved melts through the cooling crystal mush zone. Our results, combined with the literature data, indicate that most olivine gabbros between 410 and 500 mbsf were formed prior to the troctolite layers. We document that the troctolites represent conduits for mid-ocean ridge basalt melt transport through the lower oceanic crust, whereas the olivine gabbros represent crystallization of a large crystal mush, recording initial gabbro emplacement, hyper- and sub-solidus deformation, and melt–rock reaction owing to upward penetrative flow of intercumulus melt.

Evolution of Intraplate Alkaline to Tholeiitic Basalts via Interaction Between Carbonated Melt and Lithospheric Mantle

AbstractIntraplate basaltic volcanism commonly exhibits wide compositional ranges from silica-undersaturated alkaline basalts to silica-saturated tholeiitic basalts. Possible mechanisms for the compositional transition involve variable degrees of partial melting of a same source, decompression melting at different mantle depths (so-called ‘lid effect’), and melt-peridotite interaction. To discriminate between these mechanisms, here we investigated major-trace elemental and Sr–Nd–Mg–Zn isotopic compositions of a suite of intraplate alkaline and tholeiitic basalts from the Datong volcanic field in eastern China. Specifically, we employed Mg and Zn isotope systematics to assess whether the silica-undersaturated melts originated from a carbonated mantle source. The alkaline basalts have young HIMU-like Sr and Nd isotopic compositions, lower δ26Mg (-0·42‰ to -0·38‰) and higher δ66Zn (0·40‰ to 0·46‰) values relative to the mantle. These characteristics were attributable to an asthenospheric mantle source hybridized by carbonated melts derived from the stagnant Pacific slab in the mantle transition zone. From alkaline to tholeiitic basalts, δ26Mg gradually increases from -0·42‰ to -0·28‰ and δ66Zn decreases from 0·46‰ to 0·28‰ with decreasing alkalinity and incompatible trace element abundances (e.g. Rb, Nb, Th and Zr). The Mg and Zn isotopic variations are significantly beyond the magnitude (&amp;lt;0·1‰) induced by different degrees of fractional crystallization and partial melting of a same mantle source, excluding magmatic differentiation, different degrees of partial melting and the ‘lid effect’ as possible mechanisms accounting for the compositional variations in the Datong basalts. There are strong, near-linear correlations of δ26Mg and δ66Zn with 87Sr/86Sr (R2=0·75 − 0·81) and 143Nd/144Nd (R2=0·83 − 0·90), suggesting an additional source for the Datong basalts. This source is characterized by pristine mantle-like δ26Mg and δ66Zn values as well as EM1-like Sr–Nd isotopic ratios, pointing towards a metasomatized subcontinental lithospheric mantle (SCLM). Isotope mixing models show that mingling between alkaline basaltic melts and partial melts from the SCLM imparts all the above correlations, which means that the SCLM must have been partially melted during melt-SCLM reaction. Our results underline that interaction between carbonated silica-undersaturated basaltic melts and the SCLM acts as one of major processes leading to the compositional diversity in intracontinental basaltic volcanism.

Late Cambrian tonalite-trondhjemite association in the eastern segment of North Qilian suture zone: petrogenesis and geodynamic implications

ABSTRACT The late Cambrian tonalite-trondhjemite association in the eastern segment of North Qilian suture zone (E. NQSZ) is important for understanding of the sub-arc magmatic process and tectonic evolution. Here we report data for feldspar-quartz porphyry and fine-grained trondhjemite with abundant tonalite enclave/interlayer from the Leigongshan (LGS) pluton, and medium-grained tonalite from the Beilinggou (BLG) pluton. Zircon U‒Pb ages suggest emplacement of the plutons at ca. 506‒481 Ma, associated with early subduction of the North Qilian Ocean. The LGS tonalite enclave/interlayers and trondhjemite hosts share many characteristics in common, including the same mineralogy and texture, similar mineral chemistry, whole-rock trace element ratio and Sr‒Nd isotopic compositions. The tonalite enclave/interlayers probably represent quenched blobs/layers of an evolved, tonalitic magma branch resulting from periodic injection of magma into the magma chamber. All the LGS-BLG tonalite-trondhjemites display low abundances of incompatible trace elements (e.g., K, Rb, Th, Zr and REE) and depleted Sr‒Nd‒Hf isotopes (87Sr/86Sr = 0.707490‒0.707840; εNd(t) = +4.0‒4.3; zircon εHf(t) = +4.0‒13.1), indicating little/no contribution of the continental crust. Geochronological and geochemical consistency between the coeval arc sodium-rich volcanic rocks and studied tonalite-trondhjemites further suggests crystal fractionation of a common basaltic parental magma. The parental magma was generated in continental-arc rifting environments due to slab rollback in the early stage of subduction.

Geochemistry and petrogenesis of the Tsirub nephelinite intrusions, southern Namibia

Field studies and geochemical analysis of a nephelinite dyke and two plug-like bodies - Tsirub (south) and Tsirub (north), occurring in southern Namibia are reported. Bulk rock geochemical analyses show that the nephelinites have limited but significant compositional variation (MgO = 8.7–12.1 wt%; Mg# = 0.61–0.71; Zr = 415–525 ppm; Nb = 152–267 ppm; Ni = 105–305 ppm; Zr/Nb = 1.8–3.1; La/Smn = 3.8–6.1). In detail, systematic minor variations in incompatible trace element abundances and ratios and Sr and Nd isotope compositions (87Sr/86Sr = 0.70335–0.70441; 143Nd/144Nd = 0.51278–0.51272) are best accounted for by small differences in degree of partial melting and some source heterogeneity. Quantitative modelling of partial melting processes indicates that compositional variations can be accounted for by low but variable degrees of partial melting (2–6%) of a peridotitic mantle. Negative K and to a lesser extent Ti, anomalies on primitive mantle normalised diagrams require melting to have occurred in the presence of minor amphibole, constraining the depth of melting to less than ~38 kbar, i.e. within the subcontinental lithospheric mantle. Heat required to raise the ambient geotherm (to ~55 mWm−2) to allow low degrees of melting of a volatile-rich (H2O–CO2 undersaturated) peridotitic lithospheric mantle is attributed to the passage of the African plate over the Vema mantle plume at 40–50 Ma. The close spatial proximity of the Tsirub nephelinite to the Dicker Willem carbonatite, Schwarzeberg nephelinite and alkaline intrusive rocks associated with the Klinghardt phonolites is taken to indicate a similar emplacement age of ~30–50 Ma and a related cause of magmatism.

Importance of the size and distribution of chemical heterogeneities in the mantle source to the variations of isotope ratios and trace element abundances in mid-ocean ridge basalts

The size and distribution of chemical heterogeneities in the mantle source affect compositions of basalts erupted on the surface. To understand the effect of size and distribution of heterogeneous mantle source on the variations of isotope ratios and incompatible trace element abundances in mid-ocean ridge basalts (MORB), we develop a time-dependent two-porosity ridge model that features disequilibrium melting and channelized melt migration in a truncated triangular melting region. We run numerical simulations for a two-component mantle that consists of the depleted mantle and enriched blobs spanning a range of enriched compositions and sizes. The volume fraction of enriched mantle varies under 10% of the mantle source and the size of the melt production area that contributes to the pooled melt is also treated as a variable. Results show that higher abundance of incompatible trace element in the enriched mantle, larger size of enriched blobs, and narrower melt pooling area produce larger variations of isotope ratios in the pooled melt. We develop an empirical scaling equation that quantifies the fluctuation of isotope ratios as a function of elemental abundance, size and average spacing of enriched heterogeneities in the source, and the width of melt pooling area. The two-standard deviation of 143Nd/144Nd, 176Hf/177Hf, 87Sr/86Sr, and 206Pb/204Pb in global MORB not affected by hotspots can be produced by melting a two-component mantle with 5.2–8.2% enriched heterogeneities of 5.1–6.7 km mean size and 7.0(±1.6), 5.3(±1.2), 2.0(±0.5), and 9.8(±2.2) times higher abundances of Nd, Hf, Sr, and Pb than the depleted mantle, respectively. Incomplete mixing of melts at the base of the lithosphere is likely important for producing the variation of incompatible trace elements in MORB. The melt erupted at the ridge axis may represent an ensemble of the melt pooled from the center of the melt pooling area and melts pooled from local areas away from the ridge axis. The present study underscores the importance of the size and distribution of mantle heterogeneities to the interpretation of isotope ratios and trace element abundances in basalts.

Distinguishing Plume and Metasomatized Lithospheric Mantle Contributions to Post-Flood Basalt Volcanism on the Southeastern Ethiopian Plateau

Abstract Magmatism in the East African Rift System (EARS) contains a spatial and temporal record of changing contributions from the Afar mantle plume, anciently metasomatized lithosphere, the upper mantle and the continental crust. A full understanding of this record requires characterizing volcanic products both within the rift valley and on its flanks. In this study, three suites of mafic, transitional to alkaline lavas, were collected over a northeast-southwest distance of ∼150 km along the southeastern Ethiopian Plateau, adjacent to the Main Ethiopian Rift. Specifically, late Oligocene to Quaternary mafic lavas were collected from Chiro, Debre Sahil and the Bale Mountains. New major element, trace element, 40Ar/39Ar ages and isotopic results (Sr, Nd, Pb, Hf, Os, He) show spatial and temporal variation in the lavas caused by dynamical changes in the source of volcanism during the evolution of the EARS. The trace element compositions of Oligocene and Miocene Chiro lavas indicate derivation from mildly depleted and nominally anhydrous lithospheric mantle, with variable inputs from the crust. Further south, Miocene Debre Sahil and alkaline Bale Mountains lavas have enriched incompatible trace element ratios (e.g. Ba/Nb = 12–43, La/SmN = 3·1–4·9, Tb/YbN = 1·6–2·4). Additionally, their 87Sr/86Sr, 143Nd/144Nd, 176Hf/177Hf and 206Pb/204Pb values trend toward a radiogenic Pb (HIMU) component. Radiogenic 187Os/188Os in these lavas correlates positively with 206Pb/204Pb and trace element indicators consistent with ancient metasomatic enrichment of their mantle source. In contrast, transitional Miocene Bale Mountains lavas have lower incompatible trace element abundances, less enriched trace element ratios (Ba/Nb ∼7, La/SmN = 2·3–2·5) and less radiogenic isotopic signatures that originate from melting garnet-bearing, anhydrous lithospheric mantle (Tb/YbN = 2·5–2·9). Pliocene and Quaternary Bale Mountains basaltic lavas are chemically and isotopically similar to Main Ethiopian Rift lavas. Trace element and isotopic indicators in both of these suites denote an amphibole-bearing source distinct from that sampled by the older Bale Mountains lavas. Isotopically, Pliocene and Quaternary Bale lavas have notably less radiogenic Sr–Nd–Pb–Hf isotopic ratios. Quaternary Bale Mountains lavas have the strongest mantle plume contribution (3He/4He = 12·1–12·5 RA), while other Bale Mountains, Debre Sahil and Chiro lavas were derived dominantly by melting of lithospheric or upper mantle sources (3He/4He = 5·1–9·1 RA). A multi-stage, regional-scale model of metasomatism and partial melting accounts for the spatial and temporal variations on the southeastern Ethiopian Plateau. Early Debre Sahil and alkaline Bale Mountains mafic lavas are melts derived from Pan-African lithosphere containing amphibole-bearing metasomes, while later transitional Bale basalts are melts of lithosphere containing anhydrous, clinopyroxene-rich veins. These ancient metasomatized domains were eventually removed through preferential melting, potentially during thermal erosion of the lithosphere or lithospheric foundering. Pliocene and Quaternary Bale Mountains lavas erupted after tectonic extension progressed throughout Ethiopia and was accompanied by increased plume influence on the volcanic products.

Melt-modified lithosphere beneath Ross Island and its role in the tectono-magmatic evolution of the West Antarctic Rift System

Mantle lithosphere influences rift system tectonic evolution, yet the age and composition of rifted lithosphere is typically difficult to constrain due to limited sampling. In the West Antarctic Rift System (WARS), Cenozoic to recent alkaline volcanic rocks yield a variety of peridotite and pyroxenite xenoliths that allow sampling of lithosphere. We report osmium and helium isotope data, elemental abundances, and petrology, for a suite of xenoliths and lavas from the Hut Point Peninsula of Ross Island. Recently (<1.3 Ma) erupted basanites yield fresh dunite and harzburgite (olivine forsterite [Fo] 90.1–88.2), lherzolite (Fo90.6–87.4), and pyroxenite xenoliths (Fo89.3–87.3). The basanite lavas contain abundant large olivine xenocrysts (Fo89.7–88.0), with more ferroan matrix olivine grains (Fo83.7–81.2) and have HIMU-like incompatible trace-element signatures. The 3He/4He ratios (6.8 ± 0.3RA; 2SD) defined by co-existing He-rich xenoliths indicate a mantle source distinct from high-3He/4He plume mantle. Pyroxenite and lherzolite xenoliths have similar relative abundances of incompatible trace elements to host lavas, whereas dunite xenoliths have refractory compositions. Melt-rock reaction occurring in the xenoliths is demonstrated by replacement by amphibole or clinopyroxene to form pyroxenite and lherzolite lithologies, or as amphibole-impregnated dunites. The 187Re187Os systematics of the lavas, pyroxenites and lherzolites define an apparent isochron, with an initial 187Os/188Os ratio of 0.1286 ± 0.0001. The initial 187Os/188Os ratio is within uncertainty of dunite and harzburgite xenolith Os isotope compositions (0.1279–0.1303). Pervasive evidence for melt-rock interaction indicates that the straight-line relationship in 187Re/188Os-187Os/188Os space is a mixing line between high Re/Os lavas with radiogenic 187Os/188Os, and dunite and harzburgite. Petrological and geochemical evidence indicates that dunite and harzburgite xenoliths represent young lithosphere, with rhenium depletion ages up to ~250 Ma. The timing of formation and composition of the Hut Point Peninsula xenoliths are consistent with both destruction and creation of mantle lithosphere during or after subduction along the Gondwana margin, prior to WARS formation. Modification of mantle lithosphere by subduction is also consistent with generation of HIMU-like metasomatized mantle reservoirs that fed Cenozoic to recent alkali volcanism of Mount Erebus and the WARS. The presence of young lithosphere within the WARS has collateral implications for rift dynamics and melting processes, especially beneath Mount Erebus, contrasting with older lithospheric mantle beneath the Trans-Antarctic Mountains and Marie Byrd Land.

Multiple reservoirs of volatiles in the Moon revealed by the isotopic composition of chlorine in lunar basalts

The isotopes of chlorine (37Cl and 35Cl) are highly fractionated in lunar samples compared to most other Solar System materials. Recently, the chlorine isotope signatures of lunar rocks have been attributed to large-scale degassing processes that occurred during the existence of a magma ocean. In this study we investigated how well a suite of lunar basalts, most of which have not previously been analyzed, conform to previous models. The Cl isotope compositions (δ37Cl (‰) = [(37Cl/35Clsample/37Cl/35ClSMOC) − 1] × 1000, where SMOC refers to standard mean ocean chloride) recorded range from ∼+7 to +14‰ (Apollo 15), +10 to +19‰ (Apollo 12), +9 to +15‰ (70017), +4 to +8‰ (MIL 05035), and +15 to +22‰ (Kalahari 009). The Cl isotopic data from the present study support the mixing trends previously reported by Boyce et al. (2015) and Barnes et al. (2016), as the Cl isotopic composition of apatites are positively correlated with bulk-rock incompatible trace element abundances in the low-Ti basalts, inclusive of low-Ti and KREEP basalts. This trend has been interpreted as evidence that incompatible trace elements, including Cl, were concentrated in the urKREEP residual liquid of the lunar magma ocean, rather than the mantle cumulates, and that urKREEP Cl had a highly fractionated isotopic composition. The source regions for the basalts were thus created by variable mixing between the mantle (Cl-poor and relatively unfractionated) and urKREEP. The high-Ti basalts show much more variability in measured Cl isotope ratios and scatter around the trend formed by the low-Ti basalts. Most of the data for lunar meteorites also fits the mixing of volatiles in their sources, but Kalahari 009, which is highly depleted in incompatible trace elements, contains apatites with heavily fractionated Cl isotopic compositions. Given that Kalahari 009 is one of the oldest lunar basalts and ought to have been derived from very early-formed mantle cumulates, a heavy Cl isotopic signature is likely not related to its mantle source, but more likely to magmatic or secondary alteration processes, perhaps via impact-driven vapor metasomatism of the lunar crust.

Parental Magma Composition of the Main Zone of the Bushveld Complex: Evidence fromin situLA-ICP-MS Trace Element Analysis of Silicate Minerals in the Cumulate Rocks

In situ trace element analysis of cumulus minerals may provide a clue to the parental magma from which the minerals crystallized. However, this is hampered by effects of the trapped liquid shift (TLS). In the Main Zone (MZ) of the Bushveld Complex, the Ti content in plagioclase grains shows a clear increase from core to rim, whereas most other elements [e.g. rare earth elements (REE), Zr, Hf, Pb] do not. This is different from the prominent intra-grain variation of all trace elements in silicate minerals in mafic dikes, which have a faster cooling rate. We suggest that crystal fractionation of trapped liquid occurred in the MZ of Bushveld and the TLS may have modified the original composition of the cumulus minerals for most trace elements except Ti during slow cooling. Quantitative model calculations suggest that the influence of the TLS depends on the bulk partition coefficient of the element. The effect on highly incompatible elements is clearly more prominent than that on moderately incompatible and compatible elements because of different concentration gradients between cores and rims of cumulate minerals. This is supported by the following observations in the MZ of Bushveld: (1) positive correlation between Cr, Ni and Mg# of clinopyroxene and orthopyroxene; (2) negative correlation between moderately incompatible elements (e.g. Mn and Sc in clinopyroxene and orthopyroxene; Sr, Ba and Eu in plagioclase); but (3) poor correlation between highly incompatible elements and Mg# of clinopyroxene and orthopyroxene or An# of plagioclase. Modeling suggests that the extent of the TLS for a trace element is also dependent on the initial fraction of the primary trapped liquid, with strong TLS occurring if the primary trapped liquid fraction is high. This is supported by the positive correlation between highly incompatible trace element abundances in cumulus minerals and whole-rock Zr contents. We have calculated the composition of the parental magma of the MZ of the Bushveld Complex. The compatible and moderately incompatible element contents of the calculated parental liquid are generally similar to those of the B3 marginal rocks, but different from those of the B1 and B2 marginal rocks. For the highly incompatible elements, we suggest that the use of the sample with the lowest whole-rock Zr content and the least degree of TLS is the best approach to obtain the parental magma composition. The heavy REE contents of the magma calculated from orthopyroxene are similar to those of B3 rocks and lower than those of B2 rocks. The calculated REE contents from clinopyroxene are generally significantly higher than for B2 or B3 rocks, and those from plagioclase are in the lower level of B2, but slightly higher than for B3. However, the calculated REE patterns for both clinopyroxene and plagioclase show strong negative Eu anomalies, which are at the lower level of the B2 field and within the B3 field, respectively. We suggest that Eu may be less affected by TLS than other REE owing to its higher bulk compatibility. Based on this and the fact that the calculated REE contents of the parental magma should be higher than the real magma composition owing to some degree of crystal fractionation and TLS, even for the sample with the lowest amount of trapped liquid, we propose that a B3 type liquid is the most likely parental magma to the MZ of the Bushveld Complex. In the lowermost part of the MZ, there is involvement of the Upper Critical Zone (UCZ) magma.

The trace element and Sr-Nd-Pb isotope geochemistry of Juan Fernandez lavas reveal variable contributions from a high-3He/4He mantle plume

The Juan Fernandez Islands in the southeastern Pacific are an atypical linear volcanic chain that exhibits a considerable range in 3He/4He ratios (8 to 18 RA, where RA is the 3He/4He ratio of air), but limited ranges of 87Sr/86Sr and 143Nd/144Nd. Here we report new trace element abundance data and Sr-Nd-Pb isotope data for mafic lavas previously analyzed for their 3He/4He and He contents from the two main islands of Robinson Crusoe and Alexander Selkirk. Lavas from these islands have been previously grouped based on geochemical and petrological classification into Group I and III basalts, and Group II basanites. In general, samples have overlapping Sr-Nd-Pb isotope compositions that suggest a common, albeit slightly heterogeneous mantle source. In detail, the Group I and III tholeiitic and alkalic basalts have nearly identical incompatible trace element patterns, whereas the Group II basanites show elevated incompatible trace element abundances. Major and incompatible trace element modeling indicates that Group III basalts (3He/4He=7.8–9.5 RA) from younger Alexander Selkirk Island were produced by the highest degree of partial melting (>10%) of a common mantle source, followed by Group I basalts (13.6–18.0 RA) and Group II basanites (11.2–12.5 RA) from older Robinson Crusoe Island. The 206Pb/204Pb of Group I basalts and Group II basanites are slightly more radiogenic and limited in range (19.163 to 19.292) compared with those of Group III (18.939 to 19.221). The Group I and II lavas from Robinson Crusoe are consistent with an origin from the so-called focus zone (FOZO) mantle component, whereas the Alexander Selkirk basalts additionally contain contributions from a less-enriched or relatively depleted mantle component. Juan Fernandez lavas reveal limited ranges of Sr-Nd-Pb isotopes but variable 3He/4He as their parental magmas originated mainly from the FOZO component with high 3He/4He (>9 RA) and variably polluted with a depleted component with lower 3He/4He (ca. 8 RA). Contributions from high-3He/4He mantle sources to ocean island basalts can therefore vary both spatially and temporally, over meter to kilometer lengths and hundred to million-year time scales, and may not be strongly correlated to radiogenic lithophile isotope systematics.