Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ¹⁸O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO₂, Al₂O₃). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ⁵⁶Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ¹⁸O and δ⁵⁶Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ⁵⁶Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ¹⁸O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ¹⁸O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ¹⁸O and δ⁵⁶Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).     

Basaltic magmatism on the Moon: A perspective from volcanic picritic glass beads

It is widely accepted that basaltic magmas are products of partial fusion of periodotite within planetary mantles. As such, they provide valuable insights into the composition, structure, and processes of planetary interiors. Those compositions which approach primary melt compositions provide the most direct information about planetary interiors and serve as a starting point to understand basaltic evolution. Within the collection of lunar samples returned by the Apollo and Luna missions are homogeneous, picritic glass beads of volcanic origin. These picritic glasses are our closest approximations to primary magmas. As such, these glass beads provide a unique perspective concerning the origin of mare basalts, the characteristics of the lunar interior, and processes in the early differentiation of the Moon. We have obtained trace element data for these picritic glasses using SIMS techniques. These data and literature isotopic and experimental data on the picritic glasses are placed within the framework of mare basaltic magmatism.The volcanic glasses are very diverse in their trace element characteristics, for example, they have a wide range of REE pattern shapes and concentrations. Like the crystalline mare basalts, all picritic glasses have a negative Eu anomaly. Unlike the crystalline mare basalts, there is little correlation between the size of the Eu anomaly and overall REE concentrations. Trace element differences among the various glasses suggests that a KREEP component was incorporated into their mantle source. This implies large scale mixing of the “Lunar Magma Ocean”-derived cumulate pile. Subtle differences among glasses suggest that local mixing of sources may also have been an important process. Preservation of subtle chemical differences in the picritic glasses and crystalline basalts may be interpreted as indicating that they were produced by small to moderate degrees of partial melting and that the lunar mantle did not experience extensive melting during episodes of mare volcanism.Several lines of evidence are consistent with the view that the picritic glasses were derived from mantle sources that were compositionally distinct from the sources for crystalline mare basalts. These are parallel, but no common, liquid lines of descent; chemical differences between picritic glasses and the more primitive crystalline mare basalts; experimental studies indicating that the picritic glasses are multiply saturated at depths greater than that of the mare basalts; differences in lead isotopic data; and the mode of eruption (i.e., fire fountaining for glass beads). These data also provide circumstantial evidence that suggests that the picritic glasses were derived from a source somewhat more volatile-rich than that of the mare basalts.Several petrogenetic models are suggested by the trace element characteristics of the picritic glasses:

• 1.(1) Partial melting of heterogeneous lunar mantle at depths greater than 300 km to produce the parental magmas (picritic) for both the mare basalts and picritic glasses. Picritic magmas represented by glass beads were erupted to the surface with small degrees of fractional crystallization while mare basalts were produced by larger degrees of fractional crystallization (15–30%) of similar (but not identical) picritic magmas.
• 2.(2) Picritic magmas represented by the glass beads were generated at depths greater than 400 km in a volatile-enriched (relative to the mare basalt source) heterogeneous mantle while mare basalts are fractional crystallization products of picritic magmas generated at depths of less than 400 km.
• 3.(3) The picritic magmas represented by the glass beads represent polybaric melting that initiated at depths of at least 1000 km. A primitive mantle component or less processed cumulate mantle components may have been involved in the generation of the picritic glasses in any of these models.

     

Geochemical diversity in submarine HIMU basalts from Austral Islands, French Polynesia

We present the first report of geochemical data for submarine basalts collected by a manned submersible from Rurutu, Tubuai, and Raivavae in the Austral Islands in the South Pacific, where subaerial basalts exhibit HIMU isotopic signatures with highly radiogenic Pb isotopic compositions. With the exception of one sample from Tubuai, the ⁴⁰Ar/³⁹Ar ages of the submarine basalts show no significant age gaps between the submarine and subaerial basalts, and the major element compositions are indistinguishable at each island. However, the variations in Pb, Sr, Nd, and Hf isotopic compositions in the submarine basalts are much larger than those previously reported in subaerial basalts. The submarine basalts with less-radiogenic Pb and radiogenic Nd and Hf isotopic compositions show systematically lower concentrations in highly incompatible elements than the typical HIMU basalts. These geochemical variations are best explained by a two-component mixing process in which the depleted asthenospheric mantle was entrained by the mantle plume from the HIMU reservoir during its upwelling, and the melts from the HIMU reservoir and depleted asthenospheric mantle were then mixed in various proportions. The present and compiled data demonstrate that the HIMU reservoir has a uniquely low ¹⁷⁶Hf/¹⁷⁷Hf decoupled from ¹⁴³Nd/¹⁴⁴Nd, suggesting that it was derived from an ancient subducted slab. Moreover, the Nd/Hf ratios of the HIMU basalts and curvilinear Nd–Hf isotopic mixing trend require higher Nd/Hf ratios for the melt from the HIMU reservoir than that from the depleted mantle component. Such elevated Nd/Hf ratios could reflect source enrichment by a subducted slab during reservoir formation.     

The origin of geochemical diversity of lunar mantle sources inferred from the combined U-Pb, Rb-Sr, and Sm-Nd isotope systematics of mare basalt 10017

The results of our combined U-Pb, Rb-Sr, and Sm-Nd isotope study of mare basalt 10017 contribute to the understanding of the petrogenetic processes involved in the origin of geochemical diversity in lunar mare basalt sources, as well as the U-Pb isotope systematics of the Moon. The Rb-Sr, Sm-Nd, and ²³⁸U-²⁰⁶Pb isotope systems yield concordant crystallization ages of 3.633 ± 0.057 Ga, 3.678 ± 0.069 Ga, and 3.616 ± 0.098 Ga, respectively. The ²³⁵U-²⁰⁷Pb isochron yields an older, though still concordant, age of 3.80 ± 0.12 Ga. Neither the ²⁰⁶Pb-²⁰⁷Pb system nor U-Pb concordia system yields an age for 10017 that is concordant with the age determined from the Sm-Nd, Rb-Sr, and ²³⁸U-²⁰⁶Pb systems. The initial ⁸⁷Sr/⁸⁶Sr of 10017 is 0.69941 ± 7 and the initial ε_Nd is +3.2 ± 0.4. Initial Pb isotopic compositions, determined from the U-Pb isochrons, are ²⁰⁶Pb/²⁰⁴Pb_i = 31 ± 11 and ²⁰⁷Pb/²⁰⁴Pb_i = 34 ± 15. Together, these initial Pb compositions constrain the μ value of the 10017 source to be 70 ± 30, assuming a single-stage Pb growth model. This is considerably lower than μ values typically estimated for mare basalt sources (∼100-600). Regardless, the μ values calculated for the sources of mare basalts, as well as other lunar samples, show a range that is larger than can be explained by fractionation of U from Pb solely by crystallization of silicate phases and ilmenite during magma ocean solidification and formation of lunar mantle sources. The U-Pb isotope systematics may reflect late-stage formation of a sulfide phase, which strongly fractionates Pb from U but has minimal effect on Rb/Sr or Sm/Nd compositions, during crystallization of the lunar magma ocean.     

Antarctic lunar meteorites Yamato-793169, Asuka-881757, MIL 05035, and MET 01210 (YAMM): Launch pairing and possible cryptomare origin

The Antarctic lunar meteorite Meteorite Hills (MET) 01210 is a polymict regolith breccia, dominantly composed of mare basalt components. One relatively large (2.7 × 4.7 mm) basalt clast in MET 01210 (MET basalt) shows remarkable mineralogical similarities to the lunar-meteorite crystalline mare basalts Yamato (Y)-793169, Asuka (A)-881757, and Miller Range (MIL) 05035. All four basalts have similar rock texture, mineral assemblage, mineral composition, pyroxene crystallization trend, and pyroxene exsolution lamellae. The estimated TiO₂ contents (∼2.0 wt%) of the MET basalt and MIL 05035 are close to the bulk-rock TiO₂ contents of Y-793169 and A-881757. These similarities suggest that Y-793169, A-881757, MIL 05035, and the MET basalt came from the same basalt flow, which we designate the YAMM basalt. The source-basalt pairing of the YAMM is also supported by their similar REE abundances, crystallization ages (approx. 3.8-3.9 Ga), and isotopic compositions (low U/Pb, low Rb/Sr, and high Sm/Nd). The pyroxene exsolution lamellae, which are unusually coarse (up to a few microns) by mare standards, imply a relatively slow cooling in an unusually thick lava and/or subsequent annealing within a cryptomare. Reported noble gas and CRE data with close launch ages (∼1 Ma) and ejection depths (deeper than several meters) among the four meteorites further indicate their simultaneous ejection from the moon. Despite the marginally close terrestrial ages, pairing in the conventional Earth-entry sense seems unlikely because of the remote recovery sites among the YAMM meteorites.The high abundance (68%) of mare components in MET 01210 estimated from a two-component mixing model calculation could have resulted from either lateral mixing at a mare-highland boundary or vertical mixing in a cryptomare. The proportion of mare materials in MET 01210 is greater than in Apollo core samples at the mare-highland boundary. The burial depth (>several meters deep) inferred from the lack of surface irradiation of MET 01210 exceeds the typical mare regolith thickness (a few meters). Thus, the source of the YAMM meteorites is likely a terrain of locally high mare-highland mixing within a cryptomare. We searched for a possible source crater of the YAMM meteorites within the well-defined cryptomare, based on the multiple constraints obtained from this study and published data. An unnamed 1.4 km-diameter crater (53°W, 44.5°S) on the floor of the Schickard crater is the most suitable source for the YAMM meteorites.The ²³⁸U/²⁰⁴Pb (μ) value of the YAMM basalts is extremely low, relative to those of the Apollo mare basalts, but comparable to those of the Luna 24 very low-Ti basalts. The low-μ source indicates a derivation from a less differentiated mantle with a lack of KREEP components. Although the chemical sources of materials and heat source of melting might be independent, the heat source that generated the source magma of the YAMM and Luna 24 basalts may not be related to KREEP, unlike the case of the Apollo basalts. The distinct chemical and isotopic compositions of mantle sources between the Apollo basalts and the YAMM/Lunar 24 basalts imply differences in mantle composition and thermal evolution between the Procellarum KREEP Terrane (PKT) and non-PKT regions of the nearside.     

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios (0.268–0.892) together with their respective Sr–Nd–Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle “hybridization”, metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5–25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re–Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu–Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.     

REE characteristics and Nd isotopic compositions of Lunar pristine rocks：Implications for petrogenesis of pristine rocks and source regions

This paper compile the rare-earth elements and Nd isotope data for lunar pristine rocks from investiga-tions in recent years. Using these data, we compared the REE characteristics of lunar pristine rocks and Nd isotopic compositions of their source regions. Based on the Lunar Magma Ocean model, we then studied their formation and petrogenetic correlations of Mg suite, alkali suite, and KREEP, with especial emphasis on the importance of assimi-lation during early magmatism. And Nd isotopic compositions of mare basalt samples suggest that mantle sources of mare basalts should be heterogeneous, which has not yet been explained by several current models.     

The oxygen isotope composition, petrology and geochemistry of mare basalts: Evidence for large-scale compositional variation in the lunar mantle

To investigate the formation and early evolution of the lunar mantle and crust we have analysed the oxygen isotopic composition, titanium content and modal mineralogy of a suite of lunar basalts. Our sample set included eight low-Ti basalts from the Apollo 12 and 15 collections, and 12 high-Ti basalts from Apollo 11 and 17 collections. In addition, we have determined the oxygen isotopic composition of an Apollo 15 KREEP (K - potassium, REE - Rare Earth Element, and P - phosphorus) basalt (sample 15386) and an Apollo 14 feldspathic mare basalt (sample 14053). Our data display a continuum in bulk-rock δ¹⁸O values, from relatively low values in the most Ti-rich samples to higher values in the Ti-poor samples, with the Apollo 11 sample suite partially bridging the gap. Calculation of bulk-rock δ¹⁸O values, using a combination of previously published oxygen isotope data on mineral separates from lunar basalts, and modal mineralogy (determined in this study), match with the measured bulk-rock δ¹⁸O values. This demonstrates that differences in mineral modal assemblage produce differences in mare basalt δ¹⁸O bulk-rock values. Differences between the low- and high-Ti mare basalts appear to be largely a reflection of mantle-source heterogeneities, and in particular, the highly variable distribution of ilmenite within the lunar mantle. Bulk δ¹⁸O variation in mare basalts is also controlled by fractional crystallisation of a few key mineral phases. Thus, ilmenite fractionation is important in the case of high-Ti Apollo 17 samples, whereas olivine plays a more dominant role for the low-Ti Apollo 12 samples.Consistent with the results of previous studies, our data reveal no detectable difference between the Δ¹⁷O of the Earth and Moon. The fact that oxygen three-isotope studies have been unable to detect a measurable difference at such high precisions reinforces doubts about the giant impact hypothesis as presently formulated.     

Pb,Sr and 10Be isotopic studies of volcanic rocks from the Northern Mariana Islands. Implications for magma genesis and crustal recycling in the Western Pacific

We report Sr and Pb isotope analyses for an extensive suite of volcanic rocks from the N. Mariana arc together with Sr and Pb isotope analyses of sediments from the nearby Mariana and Nauru basins. In addition ten of the most recent volcanic samples were analysed for ¹⁰Be.The Sr isotope compositions cluster tightly around ${}^{87}\text{Sr}{}^{86}\text{Sr}$ = 0.7035 being slightly but significantly higher than the Pacific ocean floor basalts on either side of the arc and agreeing well with previous data. In contrast, the large number of new Pb isotopic data presented significantly extends the observed range of Pb isotope compositions for volcanic rocks from the Mariana arc to more radiogenic compositions. The concentrations of ¹⁰Be were very low (< 0.5 × 10⁶ atom g^?1).These new data require either that the Pb and Sr isotopic compositions of the Mariana sub-arc mantle be substantially different from those of the mantle source of ocean floor basalts on either side of the arc, or that the enrichment in radiogenic Pb and Sr relative to the values observed in Pacific ocean floor basalts be related to the subduction process. We prefer the latter hypothesis in which radiogenic Sr and Pb in ocean floor sediments are added to M.O.R.B. type mantle either by direct assimilation of the sediments in partial melts or, more probably, by transfer in a fluid phase into the zone of magma production. The low ¹⁰Be concentrations observed suggest the removal of at least the top few metres of sediment during subduction.     

A high field strength element perspective on early lunar differentiation

Lunar rocks are inferred to tap the different fossil cumulate layers formed during crystallisation of a lunar magma ocean (LMO). A coherent dataset, including Zr isotope data and high precision HFSE (W, Nb, Ta, Zr, Hf) and REE (Nd, Sm, Lu) data, all obtained by isotope dilution, can now provide new insights into the processes active during LMO crystallisation and during the petrogenesis of lunar magmas. Measured ⁹²Zr and ⁹¹Zr abundances agree with the terrestrial value within 0.2 ε-units. Incompatible-trace-element enriched rocks from the Procellarum KREEP Terrane (PKT) display Nb/Ta and Zr/Hf above the bulk lunar value (ca. 17), and mare basalts display lower ratios, generally confirming the presence of complementary enriched and depleted mantle reservoirs on the Moon. The full compositional spectrum of lunar basalts, however, also requires interaction with ilmenite-rich layers in the lunar mantle. Notably, the high-Ti mare basalts analysed display the lowest Nb/Ta and Zr/Hf of all lunar rocks, and also higher Sm/Nd at similar Lu/Hf than low-Ti basalts. The high-Ti basalts also exhibit higher and strongly correlated Ta/W (up to 25) and Hf/W (up to 140), at similar W contents, which is difficult to reconcile with ortho- and clinopyroxene-controlled melting. Altogether, these patterns can be explained via assimilation of up to ca. 20% of ilmenite- and clinopyroxene-rich LMO cumulates by more depleted melts from the lower lunar mantle. Direct melting of ilmenite-rich cumulates or the possible presence of residual metals in the lunar mantle both cannot easily account for the observed Ta/W and Hf/W patterns. Cumulate assimilation is also a viable mechanism that can partially buffer the Lu/Hf of mare basalts at relatively low values while generating variable Sm/Nd. Thus, the dichotomy between low Lu/Hf of lunar basalts and high time integrated source Lu/Hf as inferred from Hf isotope compositions can potentially be explained. The proposed assimilation model also has important implications for the short-lived nuclide chronology of the Earth-Moon system. The new Hf/W and Ta/W data, together with a compilation of existing W-Th-U data for lunar rocks, indicate that the terrestrial and lunar mantles are indistinguishable in their Hf/W. Virtually identical εW and Hf/W in the terrestrial and lunar mantle suggest a strong link between final core-mantle equilibration on Earth and the Moon forming giant impact. Previously, linear arrays of lunar samples in ¹⁸²W vs. Hf/W and ¹⁴²Nd vs. Sm/Nd spaces have been interpreted as isochrons, arguing for LMO crystallisation as late as 250 Myrs after solar system formation. Based on the proposed assimilation model, the ¹⁸²W and ¹⁴²Nd in many lunar magmas can be shown to be decoupled from their ambient Hf/W and Sm/Nd source compositions. As a consequence, the ¹⁸²W vs. Hf/W and ¹⁴²Nd vs. Sm/Nd arrays would constitute mixing lines rather than isochrons. Hence, the lunar ¹⁸²Hf-¹⁸²W and ¹⁴⁶Sm-¹⁴²Nd data would be fully consistent with an “early” crystallisation age of the LMO, even as early as 50 Myrs after solar system formation when the Moon was probably formed.     

Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Os, Pb, and Nd isotope geochemistry of the Permian Emeishan continental flood basalts: Insights into the source of a large igneous province

The nature of the source of continental flood basalts (CFB) is a highly debated topic. Proposed mantle sources for CFBs, including both high- and low-Ti basalts, include subcontinental lithospheric mantle (SCLM), asthenospheric mantle, and deep, plume-related mantle. Re-Os isotope systematics can offer important constraints on the sources of both ocean island basalts (OIB) and CFB, and may be applied to distinguish different possible melt sources. This paper reports the first Re-Os isotope data for the Late Permian Emeishan large igneous province (LIP) in Southwest China. Twenty one CFB samples including both low- and high-Ti basalts from five representative sites within the Emeishan LIP have been analyzed for Os, Nd, and Pb isotopic compositions. The obtained Os data demonstrate that crustal assimilation affected Os isotopic compositions of some Emeishan basalt samples with low Os concentrations but not all of the samples, and the Emeishan basalts with high Os contents likely experienced the least crustal contamination. The low and high-Ti basalts yield distinct Os signatures in terms of ¹⁸⁷Os/¹⁸⁸Os and Os content. The low-Ti basalt with the highest Os concentration (400 ppt) has a radiogenic Os isotopic composition (γOs(t), +6.5), similar to that of plume-derived OIB. Because the Os isotopic composition of basalts with relatively high Os concentrations (typically >50 ppt) likely represents that of their mantle source, this result implies a plume-derived origin for the low-Ti basalts. On the other hand, the high-Ti basalts with high Os concentration (over 50 ppt) have unradiogenic Os isotopic signatures (γOs(t) values range from −0.8 to −1.4), suggesting that a subcontinental lithosphere mantle (SCLM) component most likely contributed to the generation of these magmas. Combining Pb and Nd isotopic tracers with the Os data, we demonstrate that the low-Ti basaltic magmas in the Emeishan CFB were mainly sourced from a mantle plume reservoir, whereas the high-Ti basaltic magmas were most likely derived from a SCLM reservoir or were contaminated by a significant amount of lithospheric mantle material during plume-related magma ascent through the SCLM.     

Petrogenesis of isotopically unusual Pliocene olivine leucitites from Deep Springs Valley, California

High-K mafic alkalic lavas (5.4 to 3.2 wt% K₂O) from Deep Springs Valley, California define good correlations of increasing incompatible element (e.g., Sr, Zr, Ba, LREE) and compatible element contents (e.g., Ni, Cr) with increasing MgO. Strontium and Nd isotope compositions are also correlated with MgO; ⁸⁷Sr/⁸⁶Sr ratios decrease and ɛ_Nd values increase with decreasing MgO. The Sr and Nd isotope compositions of these lavas are extreme compared to most other continental and oceanic rocks; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7121 to 0.7105 and ɛ_Nd values range from −16.9 to −15.4. Lead isotope ratios are relatively constant, ²⁰⁶Pb/²⁰⁴Pb ∼17.2, ²⁰⁷Pb/²⁰⁴Pb ∼15.5, and ²⁰⁸Pb/²⁰⁴Pb ∼38.6. Depleted mantle model ages calculated using Sr and Nd isotopes imply that the reservoir these lavas were derived from has been distinct from the depleted mantle reservoir since the early Proterozoic. The Sr-Nd-Pb isotope variations of the Deep Springs Valley lavas are unique because they do not plot along either the EM I or EM II arrays. For example, most basalts that have low ɛ_Nd values and unradiogenic ²⁰⁶Pb/²⁰⁴Pb ratios have relatively low ⁸⁷Sr/⁸⁶Sr ratios (the EM I array), whereas basalts with low ɛ_Nd values and high ⁸⁷Sr/⁸⁶Sr ratios have radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios (the EM II array). High-K lavas from Deep Springs Valley have EM II-like Sr and Nd isotope compositions, but EM I-like Pb isotope compositions. A simple method for producing the range of isotopic and major- and trace-element variations in the Deep Springs Valley lavas is by two-component mixing between this unusual K-rich mantle source and a more typical depleted mantle basalt. We favor passage of MORB-like magmas that partially fused and were contaminated by potassic magmas derived from melting high-K mantle veins that were stored in the lithospheric mantle. The origin of the anomalously high ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios and low ɛ_Nd values and ²⁰⁶Pb/²⁰⁴Pb ratios requires addition of an old component with high Rb/Sr and Th/Pb ratios but low Sm/Nd and U/Pb ratios into the mantle source region from which these basalts were derived. This old component may be sediments that were introduced into the mantle, either during Proterozoic subduction, or by foundering of Proterozoic age crust into the mantle at some time prior to eruption of the lavas. Received: 28 February 1997 / Accepted: 9 July 1998     

Elemental and isotopic variations in subduction related basalts: evidence for a three component model

Subduction related basalts display wide ranges in large ion lithophile element ratios (e.g., Rb/Ba and Rb/ Sr) which are unlikely to result from mixing, but suggest a role for small degree partial melting of a relatively Rb-poor mantle wedge source. However, these variations do not correlate with other trace element criteria, such as the depletions of high field strength elements (HFSE) and light rare earth elements (LREE) relative to the LILE, which characterise subduction related magmatism. Integration of radiogenic isotope and trace element data demonstrates that the elemental enrichment cannot be simply related to two component mixtures inferred from isotopic variations. Thus a minimum of three components is required to describe the geochemistry of subduction zone basalts. Two are subduction related: high Sr/Nd material is derived from the dehydration of subducted basaltic ocean crust, and a low Sr/Nd component is thought to be from subducted terrigenous sediment. The third component is in the mantle wedge, it is usually similar to the source of MORB, particularly in its isotopic composition. However, in some cases, notably continental areas, more enriched mantle wedge material with relatively high ⁸⁷Sr/⁸⁶Sr, low ¹⁴³Nd/¹⁴⁴Nd and elevated incompatible trace element contents may be involved Mixing of these three components is capable of producing both the entire range of Sr, Nd and Pb isotope signatures observed in destructive margin basalts, and their distinctive trace element compositions. The isotope differences between Atlantic and Pacific island arc basalts are attributed to the isotope compositions of sediments in the two oceans.     

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene,olivine, armalcolite,ilmenite, and silicate glass during mare basalt petrogenesis

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO₂) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti³⁺ under fO₂ conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% ^[IV]Ti⁴⁺ in the pyroxene. In addition, our results can help to better constrain the Ti³⁺/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.     

Geological and C–O–S–Pb–Sr isotopic constraints on the origin of the Qingshan carbonate-hosted Pb–Zn deposit,Southwest China

Located in the western Yangtze Block, the Qingshan Pb–Zn deposit, part of the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province, contains 0.3 million tonnes of 9.86 wt.% Pb and 22.27 wt.% Zn. Ore bodies are hosted in Carboniferous and Permian carbonate rocks, structurally controlled by the Weining–Shuicheng anticline and its intraformational faults. Ores composed of sphalerite, galena, pyrite, dolomite, and calcite occur as massive, brecciated, veinlets, and disseminations in dolomitic limestones.

The C–O isotope compositions of hydrothermal calcite and S–Pb–Sr isotope compositions of Qingshan sulphide minerals were analysed in order to trace the sources of reduced sulphur and metals for the Pb–Zn deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from –5.0‰ to –3.4‰ and +18.9‰ to +19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid had a mixed origin of mantle, marine carbonate rocks, and sedimentary organic matter. δ³⁴S values of sulphide minerals range from +10.7‰ to +19.6‰, similar to Devonian-to-Permian seawater sulphate (+20‰ to +35‰) and evaporite rocks (+23‰ to +28‰) in Carboniferous-to-Permian strata, suggesting that the reduced sulphur in hydrothermal fluids was derived from host-strata evaporites. Ores and sulphide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.561 to 18.768, ²⁰⁷Pb/²⁰⁴Pb = 15.701 to 15.920, and ²⁰⁸Pb/²⁰⁴Pb = 38.831 to 39.641) that plot in the upper crust Pb evolution curve, and are similar to those of Devonian-to-Permian carbonate rocks. Pb isotope compositions suggest derivation of Pb metal from the host rocks. ⁸⁷Sr/⁸⁶Sr ratios of sphalerite range from 0.7107 to 0.7136 and (⁸⁷Sr/⁸⁶Sr)_200Ma ratios range from 0.7099 to 0.7126, higher than Sinian-to-Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than Proterozoic basement rocks. This indicates that the ore strontium has a mixture source of the older basement rocks and the younger cover sequence. C–O–S–Pb–Sr isotope compositions of the Qingshan Pb–Zn deposit indicate a mixed origin of the ore-forming fluids and metals.     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

Oxygen isotope signatures in olivines from São Miguel (Azores) basalts: implications for crustal and mantle processes

Oxygen isotope ratios were measured in olivines from eight São Miguel basalt lavas. With one exception (4.57‰), the olivines are indistinguishable from one another with an average δ¹⁸O of 4.92±0.03‰ (1σ). This value is slightly lower than that characteristic of upper mantle peridotite and MORB olivines (5.2±0.2‰). Assimilation of ≥10–20% of high-temperature altered lower oceanic crust or 4–9% hydrothermally altered volcanic edifice rocks could produce the low δ¹⁸O signatures in the São Miguel olivines; both of these assimilation models are permitted by the trace element and radiogenic isotope variations in the São Miguel basalts. However, the limited variation in δ¹⁸O despite eruption of the basalts through compositionally and tectonically variable lithosphere, and the lack of correlation of δ¹⁸O with olivine forsterite content, are more easily explained if the olivine δ¹⁸O signatures are inherited from their mantle source. If the δ¹⁸O signatures reflect mantle source compositions, then the relatively low and uniform δ¹⁸O signatures allow constraints to be placed on the origin of the mantle sources beneath São Miguel. Extreme variations in radiogenic isotope signatures have previously been attributed to two component source mixing between a predominant Azores plume source with mild HIMU-like characteristics, and an EMII-type mantle with very radiogenic Sr. The low δ¹⁸O signatures in the São Miguel basalt olivines suggest that the predominant Azores plume source contains >10% hydrothermally altered recycled oceanic crust. The limited variation in δ¹⁸O is consistent with a component of recycled sediment in the São Miguel EMII-type source, although, unlike the case for other EMII OIB (e.g. Samoa and Society), the relatively low δ¹⁸O signatures in São Miguel restrict any involvement of recycled sediment to <2% of a relatively low δ¹⁸O and very radiogenic Sr or high Rb/Sr sediment. Involvement of several percent metasomatized subcontinental lithospheric mantle could alternatively produce the EMII-type Sr–Nd–Pb isotope signatures without significantly affecting the plume-related low δ¹⁸O signatures. The São Miguel δ¹⁸O data are thus consistent with mixing between a low δ¹⁸O Azores plume source with a component of subducted, hydrothermally altered lower oceanic crust, and either minor recycled sediment or localized EMII-rich delaminated subcontinental lithospheric mantle. The latter could have been introduced into the lithosphere or shallow asthenosphere during opening of the Atlantic ocean basin.     

Combined Sr,Nd, Pb and Li isotope geochemistry of alkaline lavas from northern James Ross Island (Antarctic Peninsula) and implications for back-arc magma formation

We present a comprehensive geochemical data set for a suite of back-arc alkaline volcanic rocks from James Ross Island Volcanic Group (JRIVG), Antarctic Peninsula. The elemental and isotopic (Sr, Nd, Pb and Li) composition of these Cenozoic basalts emplaced east of the Antarctic Peninsula is different from the compositions of the fore-arc alkaline volcanic rocks in Southern Shetlands and nearby Bransfield Strait. The variability in elemental and isotopic composition is not consistent with the JRIVG derivation from a single mantle source but rather it suggests that the magma was mainly derived from a depleted mantle with subordinate OIB-like enriched mantle component (EM II). The isotopic data are consistent with mantle melting during extension and possible roll-back of the subducted lithosphere of the Antarctic plate. Magma contamination by Triassic–Early Tertiary clastic sediments deposited in the back-arc basin was only localized and affected Li isotopic composition in two of the samples, while most of the basalts show very little variation in δ⁷Li values, as anticipated for “mantle-driven” Li isotopic composition. These variations are difficult to resolve with radiogenic isotope systematics but Li isotopes may prove sensitive in tracking complex geochemical processes acting through the oceanic crust pile, including hydrothermal leaching and seawater equilibration.     

Early crustal building processes on the moon: Models for the petrogenesis of the magnesian suite

The plutonic rocks of the magnesian suite (Mg-suite) represent the period of lunar basaltic magmatism and crustal growth (∼4.46 to 4.1 Ga) that immediately followed the initial differentiation of the Moon by magma ocean (LMO) formation and crystallization. The volume and distribution of the Mg-suite and its petrogenetic relationship to latter stages of lunar magmatism (mare basalts) remains obscure. These plutonic rocks exhibit a range of compositions and include ultramafics, troctolites, spinel troctolites, norites, and gabbronorites. A distinguishing characteristic of this suite is that they contain some of the most magnesium-rich phases (Fo_95-90) that had crystallized from lunar magmas, yet they also are significantly enriched in an incompatible element component referred to as KREEP (a late-stage product of LMO crystallization containing abundant potassium (K), rare earth elements (REE), phosphorous (P), uranium, and thorium). Ion microprobe analyses of individual mineral phases (olivine, pyroxene, and plagioclase) from the Mg-suite have shown some very unexpected characteristics that have profound implications on the origin of these basaltic magmas. Although the Mg-suite lithologies are typified by silicates with relatively high Mg′, early liquidus phases such as olivine are fairly low in Ni, Co, and Cr relative to more iron-rich olivines in the younger mare basalts. The high Y and Ti/Y in early phases such as olivine and orthopyroxene indicate that the parental basaltic melts were high in incompatible elements and contained an “ilmenite fractionation” signature. However, the Y in olivine from many of the troctolites and ultramafic lithologies are only slightly greater than that of the olivine in the mare basalts whereas olivine in the norites, gabbronorites, and Apollo 14 troctolites are exceedingly high. The KREEP component may have been added to the Mg-suite parent magmas by assimilation or mixing into the mantle source. The volume of KREEP required to be added to the parental magmas of the Mg-suite tends to favor the latter mechanism for KREEP incorporation. The extremely high abundances of KREEP in the norites and gabbronorites are a product of substantial crystallization (40% to 70%) of KREEP-enriched Mg-suite parental magmas. Basaltic magmatism associated with KREEP extended for over 1.5 billion years and appears to have changed over time. The early stages of this style of lunar magmatism (Mg-suite) appear to represent melting of early LMO cumulates with low abundances of Ni, Co, Cr, and V. Later stages of KREEP-rich basaltic magmatism seemed to clearly involve melting of a variety of LMO cumulate assemblages with higher incompatible element enrichment. It appears that the heat derived from the KREEP component was instrumental in at least initiating melting of the lunar mantle over this period of time.