Zircon U-Pb and Hf isotope constraints on crustal melting associated with the Emeishan mantle plume

SHRIMP zircon U-Pb dates, combined with in-situ Hf isotopic data, provide new constraints on the petrogenesis and protolith of peralkaline, metaluminous and peraluminous intrusions and rhyolitic tuffs in the Emeishan large igneous province, with significant bearing on crustal melting associated with mantle plumes. Syenite and A-type granitic intrusions from Huili, Miyi and Taihe in the center of this large igneous province yield U-Pb dates at ∼260 Ma, consistent with the ages obtained for mafic layered intrusions in the same province. Zircon from these rocks exhibits a wide range of initial Hf isotope ratios (ε_Hf(t) = −1.4 to +13.4), with corresponding T_DM1 of 400-900 Ma. The highest ε_Hf(t) value is only marginally lower than that of depleted mantle reservoir at 260 Ma, suggesting that their source is primarily juvenile crust added during Emeishan volcanism, with incorporation of variable amounts of Neoproterozoic crust. The trigger of crustal melting is most likely related to advective heating associated with magmatic underplating. In contrast, the 255-251 Ma peraluminous granites from Ailanghe and 238 Ma rhyolitic tuff from Binchuan, have negative initial ε_Hf values of −1.3 to −4.4, and of −7.7 to −14, respectively. Hf isotopic model ages and presence of inherited zircons indicate their derivation from Mesoproterozoic and Paleoproterozoic crust, respectively. Given the time lag relative to the plume impact (∼260 Ma) and insignificant mantle contribution to 255-238 Ma magmatism, conductive heating is suggested as the trigger of crustal melting that resulted in formation of delayed felsic magmas. The involvement of older crust in younger felsic magmas is consistent with upward heat transfer to the lithosphere during plume impregnation, if the age of crust is inversely stratified, i.e., changes from Paleoproterozoic to Mesoproterozoic to Neoproterozoic to Permian with increasing depth. Such crust may have resulted from episodic, downward crustal growth during the evolution of the western Yangtze Craton.     

Crustal thickening prior to 38 Ma in southern Tibet: Evidence from lower crust-derived adakitic magmatism in the Gangdese Batholith

The petrogenesis and geodynamic implications of the Cenozoic adakites in southern Tibet remain topics of debate. Here we report geochronological and geochemical data for host granites and mafic enclaves from Wolong in the eastern Gangdese Batholith, southern Tibet. Zircon LA-ICP-MS dating indicates that the Wolong host granites and enclaves were synchronously emplaced at ca. 38 Ma. The host granites are medium- to high-K calc-alkaline, metaluminous (A/CNK = 0.93-0.96), with high Al₂O₃ (15.47-17.68%), low MgO (0.67-1.18%), very low abundances of compatible elements (e.g., Cr = 3.87-8.36 ppm, Ni = 3.04-5.71 ppm), and high Sr/Y ratios (127-217), similar to those typical of adakite. The mafic enclaves (SiO₂ = 51.08-56.29%) have 3.83-5.02% MgO and an Mg^# of 48-50, with negative Eu anomalies (δEu = 0.59-0.79). The Wolong host granites and enclaves have similar Sr-Nd isotopic compositions (initial ⁸⁷Sr/⁸⁶Sr = 0.7053-0.7055, ε_Nd(t) = − 2.7 to − 1.4), with varying zircon ε_Hf(t) values, ranging from + 6.0 to + 12.6. A comprehensive study of the data available for adakitic rocks from the Gangdese Batholith indicates that the Wolong adakitic host granites were derived from partial melting of a thickened lower crust, while the parental magmas of the mafic enclaves were most likely derived from lithospheric mantle beneath southern Tibet. The Wolong granitoids are interpreted as the result of mixing between the thickened lower crust-derived melts and lithospheric mantle-derived mafic melts, which are likely the protracted magmatic response to the break-off of the Neo-Tethyan oceanic slab at about 50 Ma. Our results suggest that the crustal thickening in southern Tibet occurred prior to ~ 38 Ma, and support the general view that the India-Asia collision must have occurred before 40 Ma.     

Timing and source constraints on the relationship between mafic and felsic intrusions in the Emeishan large igneous province

Several I- and A-type granite, syenite plutons and spatially associated, giant Fe-Ti-V deposit-bearing mafic-ultramafic layered intrusions occur in the Pan-Xi (Panzhihua-Xichang) area within the inner zone of the Emeishan large igneous province (ELIP). These complexes are interpreted to be related to the Emeishan mantle plume. We present LA-ICP-MS and SIMS zircon U-Pb ages and Hf-Nd isotopic compositions for the gabbros, syenites and granites from these complexes. The dating shows that the age of the felsic intrusive magmatism (256.2 ± 3.0-259.8 ± 1.6 Ma) is indistinguishable from that of the mafic intrusive magmatism (255.4 ± 3.1-259.5 ± 2.7 Ma) and represents the final phase of a continuous magmatic episode that lasted no more than 10 Myr. The upper gabbros in the mafic-ultramafic intrusions are generally more isotopically enriched (lower ε_Nd and ε_Hf) than the middle and lower gabbros, suggesting that the upper gabbros have experienced a higher level of crustal contamination than the lower gabbros. The significantly positive ε_Hf(t) values of the A-type granites and syenites (+4.9 to +10.8) are higher than those of the upper gabbros of the associated mafic intrusion, which shows that they cannot be derived by fractional crystallization of these bodies. They are however identical to those of the mafic enclaves (+7.0 to +11.4) and middle and lower gabbros, implying that they are cogenetic. We suggest that they were generated by fractionation of large-volume, plume-related basaltic magmas that ponded deep in the crust. The deep-seated magma chamber erupted in two stages: the first near a density minimum in the basaltic fractionation trend and the second during the final stage of fractionation when the magma was a low density Fe-poor, Si-rich felsic magma. The basaltic magmas emplaced in the shallow-level magma chambers differentiated to form mafic-ultramafic layered intrusions accompanied by a small amount of crustal assimilation through roof melting. Evolved A-type granites (synenites and syenodiorites) were produced dominantly by crystallization in the deep crustal magma chamber. In contrast, the I-type granites have negative ε_Nd(t) [−6.3 to −7.5] and ε_Hf(t) [−1.3 to −6.7] values, with the Nd model ages () of 1.63−1.67 Ga and Hf model ages () of 1.56−1.58 Ga, suggesting that they were mainly derived from partial melting of Mesoproterozoic crust. In combination with previous studies, this study also shows that plume activity not only gave rise to reworking of ancient crust, but also significant growth of juvenile crust in the center of the ELIP.     

Sm and Gd isotopic shifts of Apollo 16 and 17 drill stem samples and their implications for regolith history

The isotopic compositions of Sm and Gd in lunar regolith samples from the Apollo 16 and 17 deep drill stems showed clear isotopic shifts in ¹⁵⁰Sm /¹⁴⁹Sm (ε = +124 to +191 for A-16, and +37 to +111 for A-17) and ¹⁵⁸Gd/¹⁵⁷Gd (ε = +107 to +169 for A-16, and +31 to +84 for A-17) corresponding to neutron fluences of (5.68-9.03) × 10¹⁶ n cm⁻² for A-16 and (1.85-5.04) × 10¹⁶ n cm⁻² for A-17. The depth profiles of neutron fluences suggest that the regoliths at both sites were due to incomplete mixing of three different slabs which experienced individual two-stage irradiation before and after deposition of the upper slabs. The variations in REE compositions provide chemical evidence for incompletely vertical mixing of regoliths especially at upper layers of the two sites. The thermal neutron energy index estimated from the combination of Sm and Gd isotopic shifts, defined as ε_Sm/ε_Gd, shows a small variation (0.61-0.64) in the A-16 core except for the surface layer. On the other hand, a large variation in ε_Sm/ε_Gd = 0.67 to 0.83 in the A-17 core may result from complicated history such as two-stage irradiation and incomplete mixing during the gardening processes. Isotopic enrichments of ¹⁵²Gd and ¹⁵⁴Gd correlated with Eu/Gd elemental abundances and neutron fluences were also observed in almost all of 15 samples, showing evidence of neutron-capture from ¹⁵¹Eu and ¹⁵³Eu, respectively.     

Joint determination of K decay constants and Ar∗/K for the Fish Canyon sanidine standard, and improved accuracy for Ar/Ar geochronology

⁴⁰Ar/³⁹Ar and K-Ar geochronology have long suffered from large systematic errors arising from imprecise K and Ar isotopic data for standards and imprecisely determined decay constants for the branched decay of ⁴⁰K by electron capture and β⁻ emission. This study presents a statistical optimization approach allowing constraints from ⁴⁰K activity data, K-Ar isotopic data, and pairs of ²³⁸U-²⁰⁶Pb and ⁴⁰Ar/³⁹Ar data for rigorously selected rocks to be used as inputs for estimating the partial decay constants (λ_ε and λ_β) of ⁴⁰K and the ⁴⁰Ar∗/⁴⁰K ratio (κ_FCs) of the widely used Fish Canyon sanidine (FCs) standard. This yields values of κ_FCs = (1.6418 ± 0.0045) × 10⁻³, λ_ε = (0.5755 ± 0.0016) × 10⁻¹⁰ a⁻¹ and λ_β = (4.9737 ± 0.0093) × 10⁻¹⁰ a⁻¹. These results improve uncertainties in the decay constants by a factor of >4 relative to values derived from activity data alone. Uncertainties in these variables determined by our approach are moderately to highly correlated (cov(κ_FCs, λ_ε) = 7.1889 × 10⁻¹⁹, cov(κ_FCs, λ_β) = −7.1390 × 10⁻¹⁹, cov(λ_ε, λ_β) = −3.4497 × 10⁻²⁶) and one must take account of the covariances in error propagation by either linear or Monte Carlo methods. ⁴⁰Ar/³⁹Ar age errors estimated from these results are significantly reduced relative to previous calibrations. Also, age errors are smaller for a comparable level of isotopic measurement precision than those produced by the ²³⁸U/²⁰⁶Pb system, because the ⁴⁰Ar/³⁹Ar system is now jointly calibrated by both the ⁴⁰K and ²³⁸U decay constants, and because λ_ε(⁴⁰K) < λ(²³⁸U). Based on this new calibration, the age of the widely used Fish Canyon sanidine standard is 28.305 ± 0.036 Ma. The increased accuracy of ⁴⁰Ar/³⁹Ar ages is now adequate to provide meaningful validation of high-precision U/Pb or astronomical tuning ages in cases where closed system behavior of K and Ar can be established.     

Paleoenvironmental implications of taxonomic variation among δN values of chloropigments

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ¹⁵N values of chloropigments of photosynthetic organisms to determine the corresponding δ¹⁵N values of biomass - and by extension, surface waters - the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth’s history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N₂, NO₃⁻, and NH₄⁺ as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ¹⁵N_biomass − δ¹⁵N_{chloropigment}) for prokaryotes, with average values for species ranging from −12.2‰ to +11.7‰. We define this difference as ε_por, a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of ε_por reflect chloropigments that are ¹⁵N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of ε_por for freshwater cyanobacterial species is −9.8 ± 1.8‰, while for marine cyanobacteria it is −0.9 ± 1.3‰. These isotopic effects group environmentally but not phylogenetically, e.g., ε_por values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of ε_por for eukaryotic algae (range = 4.7-8.7‰) are similar to previous reports for pure cultures. For all taxa studied, values of ε_por do not depend on the type of nitrogen substrate used for growth. The observed environmental control of ε_por suggests that values of ε_por could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.     

The Lithium, Boron and Beryllium content of serpentinized peridotites from ODP Leg 209 (Sites 1272A and 1274A): Implications for lithium and boron budgets of oceanic lithosphere

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 μg g⁻¹) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 μg g⁻¹), depleted in Li (most values below 1 μg g⁻¹) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 μg g⁻¹), H₂O and Cl contents and to lower Li contents (0.07-3.37 μg g⁻¹) of peridotites, implying that—contrary to alteration of oceanic crust—B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m × 1 m × thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.     

In situ U-Pb, O and Hf isotopic compositions of zircon and olivine from Eoarchaean rocks, West Greenland: New insights to making old crust

The sources and petrogenetic processes that generated some of the Earth’s oldest continental crust have been more tightly constrained via an integrated, in situ (U-Pb, O and Hf) isotopic approach. The minerals analysed were representative zircon from four Eoarchaean TTG tonalites and two felsic volcanic rocks, and olivine from one harzburgite/dunite of the Itsaq Gneiss Complex (IGC), southern West Greenland. The samples were carefully chosen from localities with least migmatisation, metasomatism and strain. Zircon was thoroughly characterized prior to analysis using cathodoluminescence, scanning electron, reflected and transmitted light imaging. The zircon from all but one sample showed only minor post-magmatic recrystallisation. ²⁰⁷Pb/²⁰⁶Pb dating of oscillatory-zoned zircon using SHRIMP RG (n = 142) indicates derivation of the felsic igneous rocks from different batches of magma at 3.88, 3.85, 3.81, 3.80 and 3.69 Ga.Analyses of ¹⁸O/¹⁶O compositions of olivine from a harzburgite/dunite (n = 8) using SHRIMP II in multi-collector mode, indicate that the oxygen isotopic composition of this sample of Eoarchaean mantle (δ¹⁸O_Ol = 6.0 ± 0.4‰) was slightly enriched in ¹⁸O, but not significantly different from that of the modern mantle. Zircon δ¹⁸O measurements from the six felsic rocks (n = 93) record mean or weighted mean compositions ranging from 4.9 ± 0.7‰ to 5.1 ± 0.4‰, with recrystallised domains showing no indication of oxygen isotopic exchange during younger tectonothermal events. δ¹⁸O_Zr compositions indicate that the primary magmas were largely in equilibrium with the mantle or mantle-derived melts generated at similar high temperatures, while calculated tonalite δ¹⁸O_WR compositions (6.7-6.9‰) resemble those of modern adakites.LA-MC-ICPMS zircon ¹⁷⁶Hf/¹⁷⁷Hf analyses were obtained from six samples (n = 122). Five samples record weighted mean initial ε_Hf compositions ranging from to 0.5 ± 0.6 to −0.1 ± 0.7 (calculated using λ¹⁷⁶Lu = 1.867 × 10⁻¹¹ yr⁻¹), while one sample records a composition of 1.3 ± 0.7, indicating the magmas were generated from a reservoir with a time averaged, near chondritic Lu/Hf. The derivation of TTG magmas from a chondritic Lu/Hf source implies either that there was not voluminous continental crustal growth nor major mantle differentiation leading to Lu/Hf fractionation during the Hadean or Eoarchaean, or alternatively that rapid recycling of an early formed crust allowed the early mantle to maintain a chondritic Lu/Hf.Previous studies have demonstrated that ancient TTG rocks were mostly produced by dehydration melting of mafic rocks within the stability field of garnet, probably in flatly-subducted or buried oceanic crust. The oxygen isotopic signatures measured here at high spatial resolution allow the source materials to be better defined. Melting of a mixed mafic source consisting of ∼80% unaltered gabbro (δ¹⁸O_WR = 5.5‰) with ∼20% hydrothermally altered gabbro/basalt (δ¹⁸O_WR = 4.0‰) would produce tonalite magmas within the average compositional range observed. ¹⁸O-enriched components such as altered shallow basaltic oceanic crust and pelagic or continental sediments were not present in the sources of these TTG melts. The absence of high ¹⁸O signatures may indicate either the rarity of low temperature altered sediments, or their effective removal from the down-going slab.     

Geochemistry and C–O and Nd–Sr isotope characteristics of the 2.4 Ga Hogenakkal carbonatites from the South Indian Granulite Terrane: evidence for an end-Archaean depleted component and mantle heterogeneity

ABSTRACT

The South Indian Granulite Terrane (SGT) is a collage of Archaean to Neoproterozoic age granulite facies blocks that are sutured by an anastomosing network of large-scale shear systems. Besides several Neoproterozoic carbonatite complexes emplaced within the Archaean granulites, there are also smaller Paleoproterozoic (2.4 Ga, Hogenakkal) carbonatite intrusions within two NE-trending pyroxenite dikes. The Hogenakkal carbonatites, further discriminated into sövite and silicate sövite, have high Sr and Ba contents and extreme light rare earth element (LREE) enrichment with steep slopes typical of carbonatites. The C- and O-isotopic ratios [δ¹³C_VPDB = ?6.7 to ?5.8‰ and δ¹⁸O_VSMOW = 7.5–8.7‰ except a single ¹⁸O-enriched sample (δ¹⁸O = 20.0‰)] represent unmodified mantle compositions. The εNd values indicate two groupings for the Hogenakkal carbonatites; most samples show positive εNd values, close to CHUR (εNd = ?0.35 to 2.94) and named high-εNd group while the low-εNd group samples show negative values (?5.69 to ?8.86), corresponding to depleted and enriched source components, respectively. The ⁸⁷Sr/⁸⁶Sr_i ratios of the two groups also can be distinguished: the high-εNd ones have low ⁸⁷Sr/⁸⁶Sr_i ratios (0.70161–0.70244) while the low-εNd group shows higher ratios (0.70247–0.70319). We consider the Nd–Sr ratios as primary and infer derivation from a heterogeneous mantle source. The emplacement of the Hogenakkal carbonatites may be related to Paleoproterozoic plume induced large-scale rifting and fracturing related to initiation of break-up of the Neoarchean supercontinent Kenorland.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

Diffusion of HTO,Cl and I in Upper Toarcian argillite samples from Tournemire: Effects of initial iodide concentration and ionic strength

Diffusion parameters for HTO, ³⁶Cl⁻_, and ¹²⁵I⁻ were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I⁻ interaction with Upper Toarcian argillite and to verify the effects of initial I⁻ concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl⁻ and I⁻ diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers’ diffusive behaviour. The results show that the effective diffusion coefficient (D_e) and diffusion accessible porosity (ε_a) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L⁻¹ are: D_e = 2.35–2.50 × 10⁻¹¹ m² s⁻¹ and ε_a = 12.0–15.0% for HTO, and D_e = 14.5–15.5 × 10⁻¹³ m² s⁻¹ and ε_a = 2.5–2.9% for ³⁶Cl⁻. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (D_e) and rock capacity factor (α) obtained for ¹²⁵I are: D_e = 7.00–8.60 × 10⁻¹³ m² s⁻¹ and α = 4.3–7.2%. Such values make it possible to calculate low ¹²⁵I distribution ratios (0.0057 < R_D < 0.0192 mL g⁻¹) which confirm the trend indicating that the ¹²⁵I rock capacity factor increases with the decrease of the initial I⁻ concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L⁻¹). No evolution of HTO diffusion parameters was observed. The anionic tracers’ effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for ¹²⁵I and ³⁶Cl. Whatever the ionic strength of the synthetic solution used, ¹²⁵I exhibited D_e values two times lower than those of ³⁶Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying ¹²⁵I sorption and postulating that ³⁶Cl and ¹²⁵I would diffuse in the same porosity. In other terms, at Tournemire, ¹²⁵I sorption could be more pronounced than previously indicated.     

Rhenium-osmium isotope and platinum-group elements in the Xinjie layered intrusion, SW China: Implications for source mantle composition, mantle evolution, PGE fractionation and mineralization

The Xinjie mafic-ultramafic layered intrusion in the Emeishan large igneous province (ELIP) hosts Cu-Ni-platinum group element (PGE) sulfide ore layers within the lower part and Fe-Ti-V oxide-bearing horizons within the middle part. The major magmatic Cu-Ni-PGE sulfide ores and spatially associated cumulate rocks are examined for their PGE contents and Re-Os isotopic systematics. The samples yielded a Re-Os isochron with an age of 262 ± 27 Ma and an initial ¹⁸⁷Os/¹⁸⁸Os of 0.12460 ± 0.00011 (γ_Os(t) = −0.5 ± 0.1). The age is in good agreement with the previously reported U-Pb zircon age, indicating that the Re-Os system remained closed for most samples since the intrusion emplacement. They have near-chondritic γ_Os(t) values ranging from −0.7 to −0.2, similar to those of the Lijiang picrites and Song Da komatiites. Exceptionally, two samples from the roof zone and one from upper sequence exhibit radiogenic γ_Os(t) values (+0.6 to +8.6), showing minor contamination by the overlying Emeishan basalts.The PGE-rich ores contain relatively high PGE and small amounts of sulfides (generally less than 2%) and the abundance of Cu and PGE correlate well with S, implying that the distribution of these elements is controlled by the segregation and accumulation of a sulfide liquid. Some ore samples are poor in S (mostly <800 ppm), which may due to late-stage S loss caused by the dissolution of FeS from pre-existing sulfides through their interaction with sulfide-unsaturated flowing magma. The combined study shows that the Xinjie intrusion may be derived from ferropicritic magmas. The sharp reversals in Mg#, Cr/FeO_T and Cr/TiO₂ ratios immediately below Units 2-4, together with high Cu/Zr ratios decreasing from each PGE ore layer within these cyclic units, are consistent with multiple magma replenishment episodes. The sulfides in the cumulate rocks show little evidence of PGE depletion with height and thus appear to have segregated from successive inputs of fertile magma. This suggests that the Xinjie intrusion crystallized from in an open magma system, e.g., a magma conduit. The compositions of the disseminated sulfides in most samples can be modeled by applying an R factor (silicate-sulfide mass ratio) of between 1000 and 8000, indicating the segregation of only small amounts of sulfide liquid in the parental ferropicritic magmas. Thus, continuous mixing between primitive ferropicritic magma and differentiated resident magma could lead to crystallization of chromite, Cr-bearing magnetite and subsequently abundant Fe-Ti oxides, thereby the segregation of PGE-rich Cu-sulfide.When considered in the light of previous studies on plume-derived komatiites and picrites worldwide, the close-to-chondritic Os isotopic composition for most Xinjie samples, Lijiang picrites and Song Da komatiites suggest that the ferropicritic magma in the ELIP were generated from a plume. This comprised recycled Neoproterozic oceanic lithosphere, including depleted peridotite mantle embedded with geochemically enriched domains. The ascending magmas thereafter interacted with minor (possibly <10%) subducted/altered oceanic crust. This comparison suggests that the komatiitic melts in the ELIP originated from a greater-than normal degree of melting of incompatible trace element depleted, refractory mantle components in the plume source.     

CO2 solubility in Martian basalts and Martian atmospheric evolution

To understand possible volcanogenic fluxes of CO₂ to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO₂ solubility. CO₂ contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe³⁺/Fe^T was measured by Mössbauer spectroscopy. The CO₂ contents of glasses show no dependence on Fe³⁺/Fe^T and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO₂ contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol⁻¹ cm⁻² for the integrated area under the carbonate doublet at 1430 and 1520 cm⁻¹. The experimentally determined CO₂ solubilities allow calibration of the thermodynamic parameters governing dissolution of CO₂ vapor as carbonate in silicate melt, K_II, (Stolper and Holloway, 1988) as follows: , ΔV⁰ = 20.85 ± 0.91 cm³ mol⁻¹, and ΔH⁰ = −17.96 ± 10.2 kJ mol⁻¹. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO₂ dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and f_O2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO₂ contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO₂ at IW and 0.24 wt.% of CO₂ at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO₂ to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO₂ to an early Martian greenhouse is plausible.     

Effects of aridity and vegetation on plant-wax δD in modern lake sediments

We analyzed the deuterium composition of individual plant-waxes in lake sediments from 28 watersheds that span a range of precipitation D/H, vegetation types and climates. The apparent isotopic fractionation (ε_a) between plant-wax n-alkanes and precipitation differs with watershed ecosystem type and structure, and decreases with increasing regional aridity as measured by enrichment of ²H and ¹⁸O associated with evaporation of lake waters. The most negative ε_a values represent signatures least affected by aridity; these values were −125 ± 5‰ for tropical evergreen and dry forests, −130‰ for a temperate broadleaf forest, −120 ± 9‰ for the high-altitude tropical páramo (herbs, shrubs and grasses), and −98 ± 6‰ for North American montane gymnosperm forests. Minimum ε_a values reflect ecosystem-dependent differences in leaf water enrichment and soil evaporation. Slopes of lipid/lake water isotopic enrichments differ slightly with ecosystem structure (i.e. open shrublands versus forests) and overall are quite small (slopes = 0-2), indicating low sensitivity of lipid δD variations to aridity compared with coexisting lake waters. This finding provides an approach for reconstructing ancient precipitation signatures based on plant-wax δD measurements and independent proxies for lake water changes with regional aridity. To illustrate this approach, we employ paired plant-wax δD and carbonate-δ¹⁸O measurements on lake sediments to estimate the isotopic composition of Miocene precipitation on the Tibetan plateau.     

Boron cycling by subducted lithosphere; insights from diamondiferous tourmaline from the Kokchetav ultrahigh-pressure metamorphic belt

Subduction of lithosphere, involving surficial materials, into the deep mantle is fundamental to the chemical evolution of the Earth. However, the chemical evolution of the lithosphere during subduction to depth remains equivocal. In order to identify materials subjected to geological processes near the surface and at depths in subduction zones, we examined B and Li isotopes behavior in a unique diamondiferous, K-rich tourmaline (K-tourmaline) from the Kokchetav ultrahigh-pressure metamorphic belt. The K-tourmaline, which includes microdiamonds in its core, is enriched in ¹¹B relative to ¹⁰B (δ¹¹B = −1.2 to +7.7) and ⁷Li relative to ⁶Li (δ⁷Li = −1.1 to +3.1). It is suggested that the K-tourmaline crystallized at high-pressure in the diamond stability field from a silicate melt generated at high-pressure and temperature conditions of the Kokchetav peak metamorphism. The heavy isotope signature of this K-tourmaline differs from that of ordinary Na-tourmalines in crustal rocks, enriched in the light B isotope (δ¹¹B = −16.6 to −2.3), which experienced isotope fractionation through metamorphic dehydration reactions. A possible source of the heavy B-isotope signature is serpentine in the subducted lithospheric mantle. Serpentinization of the lithospheric mantle, with enrichment of heavy B-isotope, can be produced by normal faulting at trench-outer rise or trench slope regions, followed by penetration of seawater into the lithospheric mantle. Serpentine breakdown in the lithospheric mantle subducted in subarc regions likely provided fluids with the heavy B-isotope signature, which was acquired during the serpentinization prior to subduction. The fluids could ascend and cause partial melting of the overlying crustal layer, and the resultant silicate melt could inherit the heavy B-isotope signature. The subducting lithospheric mantle is a key repository for modeling the flux of fluids and associated elements acquired at a near the surface into the deep mantle.     

Low stable carbon isotope fractionation by coccolithophore RubisCO

The ¹³C/¹²C ratio of carbon compounds is used to identify sources and sinks in the global carbon cycle. However, the relatively enriched ¹³C content observed for marine organic carbon remains enigmatic. The majority of oceanic carbon is fixed by algae and cyanobacteria via the Calvin-Benson-Bassham cycle, yet isotopic discrimination by the CO₂ fixation enzyme, RubisCO (ribulose 1,5-bisphosphate carboxylase/oxygenase), has only been measured for a single marine cyanobacterium. Different forms of RubisCO occur in different phytoplankton species (overall amino acid identity varying by as much as ∼75%) and thus may vary in the degree to which they fractionate carbon. Here we measured isotope discrimination by RubisCO from the coccolithophore Emiliania huxleyi, a cosmopolitan species used as a marine algal model.E. huxleyi RubisCO discriminated substantially less (ε = 11.1‰) against ¹³CO₂ than other RubisCO enzymes (18-29‰), despite having Michaelis-Menten kinetic parameters (K_CO2 = 72 μM; V_max = 0.66 μmol min⁻¹ mg⁻¹ protein) similar to those measured for RubisCO enzymes from different organisms. If widespread, decreased isotope discrimination of ¹³C by phytoplankton RubisCO may be a major factor influencing the enriched ¹³C content of marine organic carbon. This finding emphasizes the necessity of (a) determining ε values for RubisCOs of other marine phytoplankton and (b) re-evaluation of δ¹³C values from physiological, environmental, and geological studies.     

Geology, petrochemistry, and genesis of the bimodal lavas of Osham Hill, Saurashtra, northwestern Deccan Traps

The Saurashtra region in the northwestern Deccan continental flood basalt province (India) is notable for compositionally diverse volcano-plutonic complexes and abundant rhyolites and granophyres. A lava flow sequence of rhyolite-pitchstone-basaltic andesite is exposed in Osham Hill in western Saurashtra. The Osham silicic lavas are Ba-poor and with intermediate Zr contents compared to other Deccan rhyolites. The Osham silicic lavas are enriched in the light rare earth elements, and have ε_Nd (t = 65 Ma) values between −3.1 and −6.5 and initial ⁸⁷Sr/⁸⁶Sr ratios of 0.70709-0.70927. The Osham basaltic andesites have initial ε_Nd values between +2.2 and −1.3, and initial ⁸⁷Sr/⁸⁶Sr ratios of 0.70729-0.70887. Large-ion-lithophile element concentrations and Sr isotopic ratios may have been affected somewhat by weathering; notably, the Sr isotopic ratios of the silicic and mafic rocks overlap. However, the Nd isotopic data indicate that the silicic lavas are significantly more contaminated by continental lithosphere than the mafic lavas. We suggest that the Osham basaltic andesites were derived by olivine gabbro fractionation from low-Ti picritic rocks of the type found throughout Saurashtra. The isotopic compositions, and the similar Al₂O₃ contents of the Osham silicic and mafic lavas, rule out an origin of the silicic lavas by fractional crystallization of mafic liquids, with or without crustal assimilation. As previously proposed for some Icelandic rhyolites, and supported here by MELTS modelling, the Osham silicic lavas may have been derived by partial melting of hot mafic intrusions emplaced at various crustal depths, due to heating by repetitively injected basalts. The absence of mixing or mingling between the rhyolitic and basaltic andesite lavas of Osham Hill suggests that they reached the surface via separate pathways.     

U-Pb and Lu-Hf isotope record of detrital zircon grains from the Limpopo Belt - Evidence for crustal recycling at the Hadean to early-Archean transition

Detrital zircon grains from Beit Bridge Group quartzite from the Central Zone of the Limpopo Belt near Musina yield mostly ages of 3.35-3.15 Ga, minor 3.15-2.51 Ga components, and numerous older grains grouped at approximately 3.4, 3.5 and 3.6 Ga. Two grains yielded concordant Late Hadean U-Pb ages of 3881 ± 11 Ma and 3909 ± 26 Ma, which are the oldest zircon grains so far found in Africa. The combined U-Pb and Lu-Hf datasets and field relationships provide evidence that the sedimentary protolith of the Beit Bridge Group quartzite was deposited after the emplacement of the Sand River Gneisses (3.35-3.15 Ga), but prior to the Neoarchean magmatic-metamorphic events at 2.65-2.60 Ga. The finding of abundant magmatic zircon detritus with concordant U-Pb ages of 3.35-3.15 Ga, and ¹⁷⁶Hf/¹⁷⁷Hf of 0.28066 ± 0.00004 indicate that the Sand River Gneiss-type rocks were a predominant source. In contrast, detrital zircon grains older than approximately 3.35 Ga were derived from the hinterland of the Limpopo Belt; either from a so far unknown crustal source in southern Africa, possibly from the Zimbabwe Craton and/or a source, which was similar but not necessarily identical to the one that supplied the Hadean zircons to Jack Hills, Western Australia. The Beit Bridge Group zircon population at >3.35 Ga shows a general εHf_t increase with decreasing age from εHf_3.9Ga = −6.3 to εHf_3.3-3.1Ga = −0.2, indicating that Hadean crust older than 4.0 Ga (T_DM = 4.45-4.36 Ga) was rejuvenated during magmatic events between >3.9 and 3.1 Ga, due to a successive mixing of crustal rocks with mantle derived magmas. The existence of a depleted mantle reservoir in the Limpopo’s hinterland is reflected by the ∼3.6 Ga zircon population, which shows εHf_3.6Ga between −4.6 and +3.2. In a global context, our data suggest that a long-lived, mafic Hadean protocrust with some tonalite-trondhjemite-granodiorite constituents was destroyed and partly recycled at the Hadean/Archean transition, perhaps due to the onset of modern-style plate tectonics.     

U-Th-Pb and Lu-Hf isotopic constraints on the evolution of sub-continental lithospheric mantle, French Massif Central

We have carried out a Pb double-spike and Lu-Hf isotope study of clinopyroxenes from spinel-facies mantle xenoliths entrained in Cenozoic intraplate continental volcanism of the French Massif Central (FMC). U-Th-Pb and Lu-Hf isotope systematics verify the existence of different lithospheric domains beneath the northern and southern FMC. Northern FMC clinopyroxenes have extreme Lu/Hf ratios and ultra-radiogenic Hf (ε_Hf = +39.6 to +2586) that reflect ∼15-25% partial melting in Variscan times (depleted mantle model ages ∼360 Ma). Zr, Hf and Th abundances in these clinopyroxenes are low and unaffected by hydrous/carbonatitic metasomatism that overprinted LILE and light REE abundances and caused decoupling of Lu/Hf-Sm/Nd ratios and Nd-Hf isotopes (ε_Nd = +2.1 to +91.2). Pb isotopes of northern FMC clinopyroxenes are radiogenic (²⁰⁶Pb/²⁰⁴Pb > 19), and typically more so than the host intraplate volcanic rocks. ²³⁸U/²⁰⁴Pb ratios range from 17 to 68, and most samples have distinctively low ²³²Th/²³⁸U (<1) and ²³²Th/²⁰⁴Pb (3-22). Clinopyroxenes from southern FMC lherzolites are generally marked by overall incompatible trace element enrichment including Zr, Hf and Th abundances, and have Pb isotopes that are similar to or less radiogenic than the host volcanic rocks. Hf isotope ratios are less radiogenic (ε_Hf = +5.4 to +41.5) than northern FMC mantle and have been overprinted by silicate-melt-dominated metasomatism that affected this part of FMC mantle. Major element and Lu concentrations of clinopyroxenes from southern FMC harzburgites are broadly similar to northern FMC clinopyroxenes and suggest they experienced similar degrees of melt extraction as northern FMC mantle. ²³⁸U/²⁰⁴Pb (53-111) and ²³²Th/²⁰⁴Pb ratios (157-355) of enriched clinopyroxenes from the southern FMC are extreme and significantly higher than the intraplate volcanic rocks. In summary, mantle peridotites from different parts of the FMC record depletion at ∼360 Ma during Variscan subduction, followed by differing styles of enrichment. Northern FMC mantle was overprinted by a fluid/carbonatitic metasomatic agent that carried elements like U, Pb, Sr and light REE. In contrast, much of the southern FMC mantle was metasomatised by a small-degree partial silicate melt resulting in enrichment of all incompatible trace elements. The extreme mantle ²³⁸U/²⁰⁴Pb (northern and southern FMC), ²³²Th/²³⁸U (northern FMC) and ²³²Th/²⁰⁴Pb ratios (southern FMC), coupled with unremarkable present-day Pb isotope ratios, constrain the timing of enrichment. Mantle metasomatism is a young feature related to melting of the upwelling mantle responsible for Cenozoic FMC volcanism, rather than subduction-related metasomatism intimately associated with mantle depletion during the Variscan orogeny. The varying metasomatic styles relate to pre-existing variations in the thickness of the continental lithospheric lid, which controlled the extent to which upwelling mantle could ascend and melt. In the northern FMC, a thicker and more refractory lithospheric lid (?80 km) only allowed incipient degrees of melting resulting in fluid/carbonatitic metasomatism of the overlying sub-continental lithospheric mantle. The thinner lithospheric lid of the southern FMC (?70 km) allowed larger degrees of melting and resulted in silicate-melt-dominated metasomatism, and also focused the location of the volcanic fields of the FMC above this region.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.