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.     

Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ²⁵Mg = −0.14 ± 0.06; δ²⁶Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ⁷Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ⁷Li = 3.5 ± 0.5‰, δ²⁵Mg = −0.10 ± 0.03‰ and δ²⁶Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ⁷Li and δ²⁶Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ⁷Li and δ²⁶Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ⁷Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ⁷Li seen in some oceanic basalts.     

Iron isotope variations in Holocene sediments of the Gotland Deep, Baltic Sea

Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in δ⁵⁶Fe (differences in the ⁵⁶Fe/⁵⁴Fe ratio relative to the IRMM-14 standard) from −0.27 ± 0.09‰ to +0.21 ± 0.08‰. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean δ⁵⁶Fe of +0.08 ± 0.13‰, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean δ⁵⁶Fe of −0.14 ± 0.19‰. Negative correlations of the δ⁵⁶Fe values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of −1.06 ± 0.20‰ for δ⁵⁶Fe. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved δ⁵⁶Fe value of about −1.4‰ to −0.9‰. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive δ⁵⁶Fe values.     

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‰).     

Lithium isotopes in Guatemalan and Franciscan HP-LT rocks: Insights into the role of sediment-derived fluids during subduction

High-pressure, low-temperature (HP-LT) rocks from a Cretaceous age subduction complex occur as tectonic blocks in serpentinite mélange along the Motagua Fault (MF) in central Guatemala. Eclogite and jadeitite among these are characterized by trace element patterns with enrichments in fluid mobile elements, similar to arc lavas. Eclogite is recrystallized from MORB-like altered oceanic crust, presumably at the boundary between the down-going plate and overlying mantle wedge. Eclogite geochemistry, mineralogy and petrography suggest a two step petrogenesis of (1) dehydration during prograde metamorphism at low temperatures (<500 °C) followed by (2) partial rehydration/fertilization at even lower T during exhumation. In contrast, Guatemalan jadeitites are crystallized directly from low-T aqueous fluid as veins in serpentinizing mantle during both subduction and exhumation. The overall chemistry and mineralogy of Guatemalan eclogites are similar to those from the Franciscan Complex, California, implying similar P-T-x paths.Li concentrations (?90 ppm) in mineral separates and whole rocks (WR) from Guatemalan and Franciscan HP-LT rocks are significantly higher than MORB (4-6 ppm), but similar to HP-LT rocks globally. Li isotopic compositions range from −5‰ to +5‰ for Guatemalan HP-LT rocks, and −4‰ to +1‰ for Franciscan eclogites, overlapping previous findings for other HP-LT suites. The combination of Li concentrations greater than MORB, and Li isotopic values lighter than MORB are inconsistent with a simple dehydration model. We prefer a model in which Li systematics in Guatemalan and Franciscan eclogites reflect reequilibration with subduction fluids during exhumation. Roughly 5-10% of the Li in these fluids is derived from sediments.Model results predict that the dehydrated bulk ocean crust is isotopically lighter (δ⁷Li ? +1 ± 3‰) than the depleted mantle (∼+3.5 ± 0.5‰), while the mantle wedge beneath the arc is the isotopic complement of the bulk crust. A subduction fluid with an AOC-GLOSS composition over the full range of model temperatures (50-600 °C) gives an average fluid δ⁷Li (∼+7 ± 5‰ 1σ) that is isotopically heavier than the depleted mantle. If the lowest temperature steps are excluded (50-260 °C) as too cold to participate in circulation of the mantle wedge, then the average subduction fluid (δ⁷Li = +4 ± 2.3‰ 1σ, is indistinguishable from depleted mantle. Because of the relatively compatible nature of Li in metamorphic minerals, the most altered part of the crust (uppermost extrusives), may retain a Li isotopic signature (∼+5 ± 3‰) heavier than the bulk crust. The range of Li isotopic values for OIB, IAB and MORB overlap, making it is difficult to resolve which of these components may contribute to the recycled component in the mantle using δ⁷Li alone.     

The origin and history of ordinary chondrites: A study by iron isotope measurements of metal grains from ordinary chondrites

Chondrules and chondrites provide unique insights into early solar system origin and history, and iron plays a critical role in defining the properties of these objects. In order to understand the processes that formed chondrules and chondrites, and introduced isotopic fractionation of iron isotopes, we measured stable iron isotope ratios ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe in metal grains separated from 18 ordinary chondrites, of classes H, L and LL, ranging from petrographic types 3-6 using multi-collector inductively coupled plasma mass spectrometry. The δ⁵⁶Fe values range from −0.06 ± 0.01 to +0.30 ± 0.04‰ and δ⁵⁷Fe values are −0.09 ± 0.02 to +0.55 ± 0.05‰ (relative to IRMM-014 iron isotope standard). Where comparisons are possible, these data are in good agreement with published data. We found no systematic difference between falls and finds, suggesting that terrestrial weathering effects are not important in controlling the isotopic fractionations in our samples. We did find a trend in the ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe isotopic ratios along the series H, L and LL, with LL being isotopically heavier than H chondrites by ∼0.3‰ suggesting that redox processes are fractionating the isotopes. The ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe ratios also increase with increasing petrologic type, which again could reflect redox changes during metamorphism and also a temperature dependant fractionation as meteorites cooled. Metal separated from chondrites is isotopically heavier by ∼0.31‰ in δ⁵⁶Fe than chondrules from the same class, while bulk and matrix samples plot between chondrules and metal. Thus, as with so many chondrite properties, the bulk values appear to reflect the proportion of chondrules (more precisely the proportion of certain types of chondrule) to metal, whereas chondrule properties are largely determined by the redox conditions during chondrule formation. The chondrite assemblages we now observe were, therefore, formed as a closed system.     

Magnesium isotopic composition of the Earth and chondrites

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ²⁵Mg and ±0.07‰ on δ²⁶Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL).Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ²⁵Mg = −0.13 ± 0.05 (2SD) and δ²⁶Mg = −0.26 ± 0.07 (2SD) for global oceanic basalts (n = 110) and δ²⁵Mg = −0.13 ± 0.03 (2SD) and δ²⁶Mg = −0.25 ± 0.04 (2SD) for global peridotite xenoliths (n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ²⁵Mg = −0.15 ± 0.04 (2SD) and δ²⁶Mg = −0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes.Collectively, the Mg isotopic composition of the Earth’s mantle, based on oceanic basalts and peridotites, is estimated to be −0.13 ± 0.04 for δ²⁵Mg and −0.25 ± 0.07 for δ²⁶Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.     

Silicon isotope fractionation during magmatic differentiation

The Si isotopic composition of Earth’s mantle is thought to be homogeneous (δ³⁰Si = −0.29 ± 0.08‰, 2 s.d.) and not greatly affected by partial melting and recycling. Previous analyses of evolved igneous material indicate that such rocks are isotopically heavy relative to the mantle. To understand this variation, it is necessary to investigate the degree of Si isotopic fractionation that takes place during magmatic differentiation. Here we report Si isotopic compositions of lavas from Hekla volcano, Iceland, which has formed in a region devoid of old, geochemically diverse crust. We show that Si isotopic composition varies linearly as a function of silica content, with more differentiated rocks possessing heavier isotopic compositions. Data for samples from the Afar Rift Zone, as well as various igneous USGS standards are collinear with the Hekla trend, providing evidence of a fundamental relationship between magmatic differentiation and Si isotopes. The effect of fractionation has been tested by studying cumulates from the Skaergaard Complex, which show that olivine and pyroxene are isotopically light, and plagioclase heavy, relative to the Si isotopic composition of the Earth’s mantle. Therefore, Si isotopes can be utilised to model the competing effects of mafic and felsic mineral fractionation in evolving silicate liquids and cumulates.At an average SiO₂ content of ∼60 wt.%, the predicted δ³⁰Si value of the continental crust that should result from magmatic fractionation alone is −0.23 ± 0.05‰ (2 s.e.), barely heavier than the mantle. This is, at most, a maximum estimate, as this does not take into account weathered material whose formation drives the products toward lighter δ³⁰Si values. Mass balance calculations suggest that removal of continental crust of this composition from the upper mantle will not affect the Si isotopic composition of the mantle.     

Li isotope fractionation in peridotites and mafic melts

We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of ⁷Li/⁶Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ⁷Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ⁷Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ⁷Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ⁷Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ⁷Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ⁷Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.     

Silicon isotopes in the inner Solar System: Implications for core formation, solar nebular processes and partial melting

We report Si isotopic data on a suite of terrestrial mantle-derived samples, meteorites and a lunar sample. Our data on co-existing mantle minerals, peridotites and basalts demonstrate lack of any resolvable high temperature fractionation during igneous processes. We show that the δ³⁰Si of the bulk silicate Earth (BSE) is identical, within analytical uncertainties, to carbonaceous and ordinary chondrites (CHUR). Based on our data the difference between δ³⁰Si_BSE and δ³⁰Si_CHUR is 0.035 ± 0.035. Whole-rock differentiated meteorites from different parent bodies (Mars, Vesta) and a lunar breccia sample also show similar δ³⁰Si suggesting broad-scale Si isotope homogeneity in the inner Solar System with an average δ²⁹Si = −0.20 ± 0.01 and δ³⁰Si = −0.39 ± 0.02 relative to the NBS28 Si isotope standard.A difference between δ³⁰Si_BSE and δ³⁰Si_CHUR of 0.035, as observed in our study, translates to less than 1.67 wt.% Si in the core considering a continuous accretion model whereas estimates using a batch model are even lower. Within uncertainties (±0.035‰) in the δ³⁰Si difference between the BSE and CHUR, a maximum of 3.84 wt.% Si could be present in the Earth’s core whereas at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, there is no requirement of Si in the Earth’s core. Such low Si in the core necessitates the presence of other light elements in the core to explain its density deficit. Our data also places constraints on the oxidation state of the Earth’s mantle during core segregation. The uncertainties in estimating the concentration of oxidized Fe in the mantle during the first 90% of accretion arise from uncertainties in the estimates of the equilibrium partition coefficient of silicon between metal and silicate at conditions relevant to core formation. For δ³⁰Si_BSE-δ³⁰Si_CHUR = 0.035 ± 0.035, the concentration of oxidized Fe in the mantle during the first 90% of accretion could be as low as ∼1%. However, at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, the Si isotope data do not require any change in the mantle concentration of oxidized Fe during accretion from the present day value of 6.26%.     

Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon

Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km³ of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H₂O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ³⁴S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ³⁴S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H₂O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ³⁴S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ³⁴S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H₂O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H₂O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ¹⁸O values, have elevated δ³⁴S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ³⁴S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).     

Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

This study investigates the application of sulphur isotope ratios (δ³⁴S) in combination with carbon (δ¹³C) and nitrogen (δ¹⁵N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ³⁴S values were found. The δ³⁴S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ³⁴S values of the fish were clustered and ³⁴S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly ³⁴S-depleted sulphur influenced the soil. The humans show the largest range of δ³⁴S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ³⁴S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R² = 0.71; p < 0.0001) between their δ¹⁵N and δ³⁴S compositions. These δ³⁴S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ³⁴S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.     

Pt-Re-Os and Sm-Nd isotope and HSE and REE systematics of the 2.7 Ga Belingwe and Abitibi komatiites

High-precision Pt-Re-Os and Sm-Nd isotope and highly siderophile element (HSE) and rare earth element (REE) abundance data are reported for two 2.7 b.y. old komatiite lava flows, Tony’s flow (TN) from the Belingwe greenstone belt, Zimbabwe, and the PH-II flow (PH) from Munro Township in the Abitibi greenstone belt, Canada. The emplaced lavas are calculated to have contained ∼25% (TN) and ∼28% (PH) MgO. These lavas were derived from mantle sources characterized by strong depletions in highly incompatible lithophile trace elements, such as light REE (Ce/Sm_N = 0.64 ± 0.02 (TN) and 0.52 ± 0.01 (PH), ε¹⁴³Nd(T) = +2.9 ± 0.2 in both sources). ¹⁹⁰Pt-¹⁸⁶Os and ¹⁸⁷Re-¹⁸⁷Os isochrons generated for each flow yield ages consistent with respective emplacement ages obtained using other chronometers. The calculated precise initial ¹⁸⁶Os/¹⁸⁸Os = 0.1198318 ± 3 (TN) and 0.1198316 ± 5 (PH) and ¹⁸⁷Os/¹⁸⁸Os = 0.10875 ± 17 (TN) and 0.10873 ± 15 (PH) require time-integrated ¹⁹⁰Pt/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os of 0.00178 ± 11 and 0.407 ± 8 (TN) and 0.00174 ± 18 and 0.415 ± 5 (PH). These parameters, which by far represent the most precise and accurate estimates of time-integrated Pt/Os and Re/Os of the Archean mantle, are best matched by those of enstatite chondrites. The data also provide evidence for a remarkable similarity in the composition of the sources of these komatiites with respect to both REE and HSE. The calculated absolute HSE abundances in the TN and PH komatiite sources are within or slightly below the range of estimates for the terrestrial Primitive Upper Mantle (PUM). Assuming a chondritic composition of the bulk silicate Earth, the strong depletions in LREE, yet chondritic Re/Os in the komatiite sources are apparently problematic because early Earth processes capable of fractionating the LREE might also be expected to fractionate Re/Os. This apparent discrepancy could be reconciled via a two-stage model, whereby the moderate LREE depletion in the sources of the komatiites initially occurred within the first 100 Ma of Earth’s history as a result of either global magma ocean differentiation or extraction and subsequent long-term isolation of early crust, whereas HSE were largely added subsequently via late accretion. The komatiite formation, preceded by derivation of basaltic magmas, was a result of second-stage, large-degree dynamic melting in mantle plumes.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).     

Environmental memory and a possible seasonal bias in the stable isotope composition of (U-Th)/He-dated goethite from the Canadian Arctic

Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ¹⁸O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ¹⁸O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ¹⁸O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ¹⁸O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ¹³C value of the Fe(CO₃)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO₂ derived primarily from oxidation of relict Eocene wood with δ¹³C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of ¹³C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ¹⁸O record of the latest Miocene/Pliocene Arctic climate.     

O/O and D/H in goethite from a North American Oxisol of the Early Eocene climatic optimum

An Early Eocene Oxisol in the Ione Formation of California formed in a coastal continental weathering environment at a paleolatitude of ∼38°N. The dominant minerals in the Oxisol are goethite, quartz, and kaolinite. Material balance calculations were applied to new measurements of chemical composition, D/H, and ¹⁸O/¹⁶O ratios of Oxisol samples to determine the δD (−150 ± 3‰) and δ¹⁸O (−2.4 ± 0.3‰) values of the goethite (α-FeOOH). These data, in combination with the global meteoric water line (MWL), yielded an isotopic temperature of 21(±4) °C. The nominal value of 21 °C contrasts with the modern mean annual temperature (MAT) of 16 °C in that area. The warmer temperature is consistent with formation of the goethite during the Early Eocene climatic optimum. The isotopic composition of the goethite and a temperature of 21 °C imply ancient water with a δD value of −61(±4)‰ and a δ¹⁸O value of −8.9(±0.5)‰. This Early Eocene δ¹⁸O (or δD) value is more negative than values in the range of isotopic scatter observed for modern global precipitation at sites with a MAT of 21 °C.At times of warm global climates, the location of a near-surface atmospheric isotherm would generally shift relative to its location under modern climatic conditions. A simple Rayleigh-type condensation model indicates that, if one “follows the isotherm”, the associated scatter in δD and δ¹⁸O of precipitation in very warm global climates should shift (for a given isotherm) to more negative values that may be detectable in proxy records. The isotopic results from the goethite of the Early Eocene Oxisol appear to add to evidence in support of this idea.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

Interpreting the Ca isotope record of marine biogenic carbonates

An 18 million year record of the Ca isotopic composition (δ^44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ^44/42Ca in this record averages +0.37 ± 0.05 (1σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ^44/42Ca (i.e., by 0.06 ± 0.06‰ (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ^44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ^44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (Δ_sed) results in unrealistically large variations in the total mass of Ca²⁺ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ^44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δ_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ^44/42Ca_w and Δ_sed have been established, modeling the Ca²⁺ content of seawater from Ca isotope curves should be approached cautiously.     

Lithium isotopic systematics of peridotite xenoliths from Hannuoba, North China Craton: Implications for melt-rock interaction in the considerably thinned lithospheric mantle

Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ⁷Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ⁷Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ⁷Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ⁷Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ⁷Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.     

The major ion, δCa, δCa, and δMg geochemistry of granite weathering at pH = 1 and T = 25 °C: power-law processes and the relative reactivity of minerals

We dissolved Boulder Creek Granodiorite in a plug flow reactor for 5794 h at pH = 1 and T = 25 °C. The primary purpose of the experiment was to identify controls on dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values during granite weathering. Herein, we also examine the origin of Ca and Mg isotopic variability among minerals composing the Boulder Creek Granodiorite, and we constrain fundamental characteristics of granite weathering important for quantifying the elemental and isotopic geochemistry of the reactor output. Nine Ca-bearing minerals display an 8.80‰ range of δ^44/40Ca values and a 0.51‰ range of δ^44/42Ca values. Three Mg-bearing minerals display a 1.53‰ range of δ^26/24Mg values. These ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks. Most of the δ^44/40Ca variability reflects ⁴⁰Ca enrichment in K-feldspar, and to a lesser extent, biotite, due to the radioactive decay of ⁴⁰K over the 1.7 Ga age of the rock, whereas the entire range of δ^44/42Ca values reflects mass-dependent isotope fractionation during igneous differentiation and crystallization. The range of δ^26/24Mg values may represent either fractionation during the chloritization of biotite or interaction of the Boulder Creek Granodiorite with Mg-rich metamorphic fluids having low δ^26/24Mg values.The elemental and isotopic composition of the reactor output varied substantially during the experiment. We synthesize the mineralogical and fluid data using coupled mass-conservation equations solved at non-steady-state. Model calculations reveal an intricate balance between increasing specific surface area and decreasing mineral concentrations. While surface area normalized dissolution rate constants were time-invariant, specific surface area increased as a power-law function of time through positive feedbacks between mechanical disaggregation, chemical dissolution, and mineral depletion. Variations in dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values reflect conservative mixing rather than fractionation. Apatite and calcite initially control δ^44/40Ca and δ^44/42Ca values, followed by biotite, titanite, epidote, hornblende, and plagioclase. The release of radiogenic ⁴⁰Ca clearly defines the period where biotite dissolution dominates. The brucite layer of chlorite initially controls δ^26/24Mg values, followed by biotite, the TOT layer of chlorite, and hornblende. Through direct isotopic tracking, these results demonstrate that trace minerals, such as apatite and calcite in the case of Ca and brucite in the case of Mg, dominate elemental release during the incipient stages of granite weathering. The results further show that biotite dissolution dominates the middle stages of granite weathering and that plagioclase dissolution only becomes important during relatively late stages. The Ca and Mg isotope variations associated with these stages are distinct and potentially resolvable in soil mineral weathering studies.