Isotopic Composition Of Mg Research Articles

Effect of Endotoxemia Induced by Intraperitoneal Injection of Lipopolysaccharide on the Mg isotopic Composition of Biofluids and Tissues in Mice.

Endotoxemia induced in vivo in mice by intraperitoneal injection of lipopolysaccharide (LPS) leads to (neuro)inflammation and sepsis. Also the homeostasis of mineral elements can be altered through mechanisms that still are poorly understood. The isotopic composition of Mg and the concentrations of the minor elements Ca, K, Mg, Na, P, and S were determined in biological fluids and tissues of young (14–28 weeks) and aged (40–65 weeks) LPS-injected mice and age-matched controls to reveal potential effects of the LPS-induced infection. Blood plasma of young and aged LPS-injected mice showed a heavy Mg isotopic composition, as well as elevated Mg and P concentrations, compared to matched controls. The plasma Mg isotopic composition was correlated with the P concentration in aged mice. Also the liver Mg isotopic composition was strongly affected in the young and aged LPS-injected mice, while for aged mice, an additional effect on the urine Mg isotopic composition was established. These observations were hypothetically associated with liver inflammation and/or hepatotoxicity, and reduced urinary Mg excretion, respectively. Also a regional endotoxin-induced difference was observed in the brain Mg isotopic composition for the aged mice only, and was attributed to potential disruption of the blood-brain barrier.

The Mg isotope signature of marine Mg-evaporites

Marine Mg-evaporites are a small oceanic sink of magnesium, precipitating only from extremely evaporated brines. The isotopic composition of Mg in seawater, δ26Mgseawater, has recently been shown to be an effective tool for reconstructing the Mg budget of the modern and past oceans. However, estimations of the Mg isotope fractionation between the Mg-evaporites and their precipitating solution are required for full quantification of the isotope effect of the evaporitic sink on δ26Mgseawater, as well as for utilizing ancient evaporitic sequences as an archive for past δ26Mgseawater. Here, we estimate the Mg isotope fractionation between Mg-evaporites and modern marine-derived brine along the course of seawater evaporation, up to degree evaporation of >200. The sequence of Mg-salts included epsomite (MgSO4·7H2O), kainite (KMgClSO4·3H2O), carnallite (KMgCl3·6H2O), kieserite (MgSO4·H2O) and bischofite (MgCl2·6H2O).The following isotope fractionation values, either negative or positive, were calculated from the isotope difference between the salt and its precipitating brine, and from the evolution of δ26Mg in the brine throughout the evaporation: Δcarnallite-brine = +1.1‰, Δepsomite-brine = +0.59‰, Δbischofite-brine = +0.33‰, Δkieserite-brine = −0.2‰ and Δkainite-brine = −1.3‰. Magnesium isotopic compositions determined on minerals from different ages in the geological record corroborate well these results. Due to precipitation of multi-mineral assemblages having isotope fractionation values of opposing signs, the δ26Mg value of the brine changes only slightly (<0.5‰) throughout the evaporation path, despite the considerable Mg removal (>50%). The isotope fractionations are shown to correlate with the number of water molecules coordinated to the Mg2+ and with Mg-O bond length in the mineral lattice.Given these isotope fractionations, it is calculated that a volume of 0.4 · 106–0.8 · 106 Km3 of a mono-mineral assemblage of kainite or carnallite needs to precipitate in order to change seawater δ26Mg by only 0.1‰. This huge volume is by far larger than the volume of these minerals known to date in the global geological record. Therefore, it is concluded that the impact of Mg-evaporites formation on δ26Mgseawater has been insignificant since the Proterozoic. The results of this study suggest that the Mg isotopic composition of Mg-evaporites preserved in the geological record of evaporitic basins may be used to: 1) quantify geochemical processes that fractionate Mg-isotopes within these basins, such as dolomitization; and 2) complete the secular variations curve of the marine δ26Mg record using basins with well-established evaporitic sequences.

Magnesium isotopic composition of submarine vent fluids from arc and back-arc hydrothermal systems in the western Pacific

Seafloor hydrothermal systems are important sinks for Mg as their concentration in high-temperature hydrothermal vent fluids decreases to near zero through the formation of secondary minerals. However, the problem of mass balance still persists regarding the global sink for Mg via sub-seafloor high-temperature hydrothermal reactions. In this study, we measured isotopic compositions of Mg in high-temperature hydrothermal vent fluids from 5 arc and back-arc systems in the western Pacific. This was done to better understand Mg behavior during hydrothermal circulation and to quantify the oceanic Mg cycle. The samples with significantly low Mg concentrations showed 26Mg depletion due to Mg fractionation and Mg fixation during hydrothermal circulation. Addition of Mg to the permeable sub-seafloor during venting is the probable reason for the isotopic variation of Mg. The vent fluids (return flux) with lighter Mg isotopic compositions contain much smaller amounts of Mg than seawater. This confirms that the high-temperature hydrothermal sinks have a less significant effect on the oceanic Mg isotopic composition. Based on the simple steady state equations and low-temperature hydrothermal sinks of 26Mg (−0.25‰ to 0.00‰ of δ26Mg), 7–26% of the riverine Mg input is presumed to be removed through the high-temperature sink. This estimate is lower than that proposed by Mottl and Wheat (1994), which was 10–40%. Thus, other Mg sinks such as the low-temperature hydrothermal sink and/or the dolomite sink need to be considered.

Magnesium isotope evidence that accretional vapour loss shapes planetary compositions.

It has long been recognised that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and by inference the primordial disk from which they formed. An important question has been whether the notable volatile depletions of planetary bodies are a consequence of accretion1, or inherited from prior nebular fractionation2. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate3–6. Using a new analytical approach to address key issues of accuracy inherent in conventional methods, we show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour followed by vapour escape during accretionary growth of planetesimals generates appropriate residual compositions. Our modelling implies that the isotopic compositions of Mg, Si and Fe and the relative abundances of the major elements of Earth, and other planetary bodies, are a natural consequence of substantial (~40% by mass) vapour loss from growing planetesimals by this mechanism.

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite in the absence of growth rate effects

Calcite growth rate has been previously shown to be the dominating parameter controlling both Mg partitioning and Mg isotope fractionation during calcite growth. In natural calcite precipitation environments - characterized by abundant organic material - the presence of dissolved organic molecules may affect these two parameters. In order to assess the role of organic molecules, steady state calcite growth experiments have been performed at 25°C, 1bar pCO2 and constant, within analytical uncertainty growth rate (rp=10−7.4molm−2s−1) in the presence of aqueous Mg and six organic ligands in the concentration range from 0.01 to 10mM. The organic ligands used in this study are: (i) acetic acid, (ii) citric acid, (iii) glutamic acid, (iv) salycilic acid, (v) glycine, and (vi) ethylenediaminetetraacetic acid (EDTA). These contain one or more carboxyl- and amino-groups that are commonly present in natural organic substances found in lacustrine, fluvial, soil, cave, as well as in marine and earliest diagenetic porewater environments. Results shown here indicate that the presence of these carboxyl- and amino-groups promotes an increase in the partition coefficient of Mg in calcite DMg=(Mg/Ca)calcite(Mg/Ca)fluid that can be attributed to their adsorption onto the calcite surfaces and the subsequent reduction of the active sites of growth. This increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation: LogDMg=0.3694(±0.0329)×SIcalcite-1.9066(±0.0147)R2=0.92 In contrast, data shown here suggest that the presence of organic ligands, with exception of citric acid, does not significantly affect the Mg isotope fractionation factor between calcite and reactive fluid. Citric acid likely exhibits larger fractionation between the Mg-ligand complexes and free aqueous Mg, compared to the other organic ligands studied in this work, as evidenced from the smaller Δ26Mgcalcite-fluid values. The main result shown here is that in Earth’s surface precipitation environments the presence of organic ligands is not a major factor affecting the Mg content or Mg-isotope composition of inorganic calcite. But in the presence of higher contents of organic macromolecules from byproducts of metabolic activities, humid, and fulvic acids and/or exopolymeric substances and matrices, an impact on Mg content or Mg isotope composition of calcite cannot be ruled out.

Isotopic composition of Mg and Fe in garnet peridotites from the Kaapvaal and Siberian cratons

We present Mg and Fe isotopic data for whole rocks and separated minerals (olivine, clinopyroxene, orthopyroxene, garnet, and phlogopite) of garnet peridotites that equilibrated at depths of 134–186km beneath the Kaapvaal and Siberian cratons. There is no clear difference in δ26Mg and δ56Fe of garnet peridotites from these two cratons. δ26Mg of whole rocks varies from −0.243‰ to −0.204‰ with an average of −0.225±0.037‰ (2σ, n=19), and δ56Fe from −0.038‰ to 0.060‰ with an average of −0.003±0.068‰ (2σ, n=19). Both values are indistinguishable from the fertile upper mantle, indicating that there is no significant Mg-Fe isotopic difference between the shallow and deep upper mantle. The garnet peridotites from ancient cratons show δ26Mg similar to komatiites and basalts, further suggesting that there is no obvious Mg isotopic fractionation during different degrees of partial melting of deep mantle peridotites and komatiite formation.The precision of the Mg and Fe isotope data (⩽±0.05‰ for δ26Mg and δ56Fe, 2σ) allows us to distinguish inter-mineral isotopic fractionations. Olivines are in equilibrium with opx in terms of Mg and Fe isotopes. Garnets have the lowest δ26Mg and δ56Fe among the coexisting mantle minerals, suggesting the dominant control of crystal structure on the Mg-Fe isotopic compositions of garnets. Elemental compositions and mineralogy suggest that clinopyroxene and garnet were produced by later metasomatic processes as they are not in chemical equilibrium with olivine or orthopyroxene. This is consistent with the isotopic disequilibrium of Mg and Fe isotopes between orthopyroxene/olivine and garnet/clinopyroxene. Combined with one sample showing slightly heavy δ26Mg and much lighter δ56Fe, these disequilibrium features in the garnet peridotites reveal kinetic isotopic fractionation due to Fe-Mg inter-diffusion during reaction between peridotites and percolating melts in the Kaapvaal craton.

Using Mg isotope ratios to trace Cenozoic weathering changes: A case study from the Chinese Loess Plateau

The magnesium isotope system is a useful tracer of weathering processes due to its sensitivity to secondary mineral formation. We present elemental and isotopic data in bulk loess and paleosol sediments from the Luochuan profile in the Chinese Loess Plateau (CLP). Due to a relatively constant pre-weathering mineralogy, changes in the sediment chemistry with depth can be interpreted to reflect changes in weathering processes that are ultimately controlled by climate. We find that the Luochuan sediments are all enriched in light Mg relative to the upper continental crust (UCC: −0.22‰). The isotopically light signature is a result of three way mixing between Mg sourced from silicate, calcite and dolomite. Changes in δ26Mg between loess and paleosol reflect the higher weathering intensities during pedogenesis and corresponding loss of easily leachable calcite enriched in light Mg isotopes from the loess layers. This is confirmed by the results of a simple leaching procedure in which the leachate phase contains high Ca concentrations and isotopically light δ26Mg values of up to −2‰. Any isotopic fractionation of Mg imparted by isotopically heavy clay mineral formation appears to be insignificant, and is obscured by the presence of detrital dolomite that is resistant to acid leaching and is isotopically light. The isotopic composition of Mg at Luochuan broadly follows the magnetic susceptibility record in that loess layers are relatively isotopically light and have lower magnetic susceptibilities than their adjacent paleosol. As such, the changes in δ26Mg values with depth do correspond to changes in chemical weathering, however the driving factor behind these changing δ26Mg values is carbonate preservation which in itself is not a highly sensitive paleoclimate proxy.From a global perspective the δ26Mg value of Luochuan loess is similar to other loess sediments, which are often isotopically light relative to the UCC. We have recalculated the average δ26Mg value of global loess sediments to be −0.58±1.18‰. This reflects the fact that δ26Mg values in loess are highly heterogeneous, and are generally enriched in 24Mg compared to typical UCC rocks due to preservation of high amounts of isotopically light carbonate minerals. For this reason loess sediments cannot be used to approximate the isotopic composition of Mg in the Earth's crust.

Magnesium Isotope Fractionation During Arid Pedogenesis on the Island of Hawaii (USA)

We combines Mg isotopic analyses with soil characterization methods to determine Mg isotopic compositions of bulk soils, basalts, and carbonate fractions at an arid (∼30cm MAP) soil chronosequence on the Island of Hawaii. This chronosequence is developed on Pololu (350 ka) and Hawi (170 ka) lava flows. Both profiles contain pedogenic carbonates and secondary alumino- silicate and sequioxide phases. Bulk soil horizons at these sites range in δ26Mg from -0.21±0.31 ‰ to -1.75±0.22 ‰ for the Hawi and -0.01±0.31 ‰ to -0.21±0.31 ‰ for the Pololu. Basalts underlying the soil profiles have average δ26Mg values of - 0.25±0.06 ‰. Pedogenic carbonate δ26Mg values at these sites vary from -1.05±0.22‰ to -2.31±0.22‰. Integrating the soils as a whole yields bulk soil isotopic compositions of -1.35±0.16 ‰ for the Hawi and -0.12±0.12 ‰ for the Pololu. These differences in overall δ26Mg between total soils may be explained by the relative abundance of Mg in carbonate; in the Hawi soil 69±11% of Mg is hosted by carbonate phases, while in the Pololu soil 16±2% of Mg is in carbonate phases. Estimates of Mg input to the soils through time, through rainfall estimates as well as rock weathering estimates provided by the immobile index element Zr, allows the calculation of the δ26Mg of Mg exported from these systems. The isotopic composition Mg exported from the Hawi soil is not tightly constrained but must be significantly isotopically heavier than the basalt parent material. The Pololu soil is much better constrained and has exported Mg with a δ26Mg of -0.36±0.26 ‰, close to the weighted mean value of inputs to the soil from weathering and atmospheric deposition. The evolution of the soil mineralogy and morphology during progressive development of the weathering profile result in significant changes in the isotopic composition of Mg exported through time.

Investigating the behaviour of Mg isotopes during the formation of clay minerals

We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (−1.49‰ to −2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk clay minerals and can have an important influence over the bulk clay δ26Mg value. Modeling shows that in certain soils or sediments where the percentage of exchangeable Mg is >30% and the isotopic composition of the exchangeable Mg is around −2‰, the generation of bulk δ26Mg values of <−0.5‰ is likely. On a broader scale, Mg-rich minerals such as smectite and illite are likely to impart a stronger control over the Mg budget in clay rich sediments, and their high structural Mg component is likely to result in bulk sediment δ26Mg values that are closer in composition to the UCC. Despite this, results of modeling, together with experimental observation suggests that the uptake of exchangeable Mg into these clay rich sediments could cause a decrease in the bulk δ26Mg value by up to ∼0.3–0.4‰. This should be accounted for when assessing the δ26Mg value of sediments on a crustal scale.

The magnesium isotope record of cave carbonate archives

Abstract. Here we explore the potential of magnesium (δ26Mg) isotope time-series data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco), the warm-temperate (Germany), the equatorial-humid (Peru) and the cold-humid (Austria) climate zones. Changes in the calcite magnesium isotope signature with time are compared against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and disequilibrium processes governs the δ26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rainwater or snow as well as soil and host rock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean δ26Mg values (GDA: −4.26 ± 0.07‰ and HK3: −4.17 ± 0.15‰), and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value of all stalagmites (NC-A and NC-B δ26Mg: −3.96 ± 0.04‰) but only minor variations in Mg-isotope composition, which is consistent with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean δ26Mg: −4.01 ± 0.07‰; BU 4 mean δ26Mg: −4.20 ± 0.10‰) suggest changes in outside air temperature was the principal driver rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: −3.00 ± 0.73‰; SPA 59: −3.70 ± 0.43‰) are affected by glacial versus interglacial climate change with outside air temperature affecting soil zone activity and weathering balance. Several δ26Mg values of the Austrian and two δ26Mg values of the German speleothems are shifted to higher values due to sampling in detrital layers (Mg-bearing clay minerals) of the speleothems. The data and their interpretation shown here highlight the potential but also the limitations of the magnesium isotope proxy applied in continental climate research. An obvious potential lies in its sensitivity for even subtle changes in soil-zone parameters, a hitherto rather poorly understood but extremely important component in cave archive research. Limitations are most obvious in the low resolution and high sample amount needed for analysis. Future research should focus on experimental and conceptual aspects including quantitative and well-calibrated leaching and precipitation experiments.

Records of Neogene seawater chemistry and diagenesis in deep-sea carbonate sediments and pore fluids

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10–20Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from −0.78‰ near the sediment–water interface to −0.15‰ at 778mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average δ26Mg value of −4.72‰. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Iron, zinc, magnesium and uranium isotopic fractionation during continental crust differentiation: The tale from migmatites, granitoids, and pegmatites

The causes of some stable isotopic variations in felsic rocks are not well understood. In particular, the origin of the heavy Fe isotopic compositions (i.e., high δ56Fe values, deviation in ‰ of the 56Fe/54Fe ratio relative to IRMM-014) of granites with SiO2>70wt.% compared with less silicic rocks is still debated. It has been interpreted to reflect isotopic fractionation during late stage aqueous fluid exsolution, magma differentiation, partial melting, or Soret (thermal) diffusion. The present study addresses this issue by comparing the Fe isotopic compositions of a large range of differentiated crustal rocks (whole rocks of migmatites, granitoids, and pegmatites; mineral separates) with the isotopic compositions of Zn, Mg and U. The samples include granites, migmatites and pegmatites from the Black Hills, South Dakota (USA), as well as I-, S-, and A-type granitoids from Lachlan Fold Belt (Australia). The nature of the protolith (i.e., I- or S-type) does not influence the Fe isotopic composition of granitoids. Leucosomes (partial melts in migmatites) tend to have higher δ56Fe values than melanosomes (melt residues) indicating that partial melting of continental crust material can possibly fractionate Fe isotopes. No clear positive correlation is found between the isotopic compositions of Mg, U and Fe, which rules out the process of Soret diffusion in the systems studied here. Zinc isotopes were measured to trace fluid exsolution because Zn can easily be mobilized by aqueous fluids as chloride complexes. Pegmatites and some granitic rocks with high δ56Fe values also have high δ66Zn values. In addition, high-SiO2 granites show a large dispersion in the Zn/Fe ratio that cannot easily be explained by magma differentiation alone. These results suggest that fluid exsolution is responsible for some of the Fe isotopic fractionation documented in felsic rocks and in particular in pegmatites. However, some granites with high δ56Fe values have unfractionated δ66Zn values and were presumably poor in fluids (e.g., A-type). For these samples, iron isotopic fractionation during magma differentiation is a viable interpretation. Equilibrium Fe isotopic fractionation factors between silicic melts and minerals remain to be characterized to quantitatively assess the role of fractional crystallization on iron isotopes in granitoids.

EVIDENCE FOR MAGNESIUM ISOTOPE HETEROGENEITY IN THE SOLAR PROTOPLANETARY DISK

With a half-life of 0.73 Myr, the 26Al-to-26Mg decay system is the most widely used short-lived chronometer for understanding the formation and earliest evolution of the solar protoplanetary disk. However, the validity of 26Al-26Mg ages of meteorites and their components relies on the critical assumption that the canonical 26Al/27Al ratio of ~5 × 10–5 recorded by the oldest dated solids, calcium-aluminium-rich inclusions (CAIs), represents the initial abundance of 26Al for the solar system as a whole. Here, we report high-precision Mg-isotope measurements of inner solar system solids, asteroids, and planets demonstrating the existence of widespread heterogeneity in the mass-independent 26Mg composition (μ26Mg*) of bulk solar system reservoirs with solar or near-solar Al/Mg ratios. This variability may represent heterogeneity in the initial abundance of 26Al across the solar protoplanetary disk at the time of CAI formation and/or Mg-isotope heterogeneity. By comparing the U-Pb and 26Al-26Mg ages of pristine solar system materials, we infer that the bulk of the μ26Mg* variability reflects heterogeneity in the initial abundance of 26Al across the solar protoplanetary disk. We conclude that the canonical value of ~5 × 10–5 represents the average initial abundance of 26Al only in the CAI-forming region, and that large-scale heterogeneity—perhaps up to 80% of the canonical value—may have existed throughout the inner solar system. If correct, our interpretation of the Mg-isotope composition of inner solar system objects precludes the use of the 26Al-26Mg system as an accurate early solar system chronometer.

High-precision Mg-isotope measurements of terrestrial and extraterrestrial material by HR-MC-ICPMS—implications for the relative and absolute Mg-isotope composition of the bulk silicate Earth

We report novel methods for the chemical purification of Mg from silicate rocks by ion-exchange chromatography, and high-precision analysis of Mg-isotopes by high-resolution multiple collector inductively coupled plasma source mass spectrometry (HR-MC-ICPMS). Using these methods, we have measured the relative and absolute Mg-isotope composition of a number of terrestrial and extraterrestrial materials, including international reference rock standards as well as pure Mg standards, olivine crystals separated from a mantle-derived spinel lherzolite (J12 olivine), one enstatite chondrite, a martian shergottite and sea water samples. Repeated analyses of terrestrial and extraterrestrial samples demonstrate that it is possible to routinely measure the relative Mg-isotope composition of silicate materials with an external reproducibility of 2.5 and 20 ppm for the μ26Mg* and μ25Mg values, respectively (μ notation is the per 106 deviation from a reference material). Analyses of bulk mantle-derived rocks as well as a martian shergottite and an enstatite chondrite define a restricted range in μ25Mg of −120 ± 28 ppm (2sd) relative to the DSM-3 reference standard (μ25,26Mg = 0), suggesting that the Mg-isotope composition of inner solar system bulk planetary materials is uniform within the resolution of our analyses. We have determined the absolute Mg-isotope composition of the J12 olivine, two CI chondrites as well as the DSM-3 and Cambridge-1 reference standards using a mixed 26Mg-24Mg double-spike. The differences between the absolute 25Mg/24Mg ratios of the various materials analyzed relative to the DSM-3 standard are in excellent agreement with results obtained by the sample-standard bracketing method. Based on the averages obtained for the J12 olivine separates, we estimate the absolute Mg-isotope composition for Earth's mantle – and hence that of the bulk silicate Earth – to be 25Mg/24Mg = 0.126896 ± 0.000025 and 26Mg/24Mg = 0.139652 ± 0.000033. Given the restricted range of μ25Mg obtained for bulk planetary material by the sample-standard bracketing technique and the excellent agreement between the data obtained by the relative and absolute methods, we propose that these new values represent the absolute Mg-isotope composition of the bulk inner solar system. Using the absolute Mg-isotope composition of the J12 olivine, we calculate the isotopic abundances of Mg as 24Mg = 0.789548 ± 0.000026, 25Mg = 0.100190 ± 0.000018, and 26Mg = 0.110261 ± 0.000023. Based on this result, we have calculated an atomic weight for Mg of 24.305565 ± 0.000045, which is marginally heavier than previous estimates but a factor of 10 more precise.

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (∼50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ25Mg and δ26Mg values of the bulk flow are −0.138 ± 0.021‰ and −0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ56Fe and δ57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ56Fe and slightly heavy δ26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

Mg isotopic composition of carbonate: insight from speleothem formation

Simultaneous high-precision measurement of 24Mg, 25Mg and 26Mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry (MC-ICP-MS) relative to the international standard SRM980. Data are presented on low-Mg calcite speleothems and their associated host rocks and waters from four caves, one in the French Alps and three in Israel, covering various climate conditions. In addition, data are presented on three dolostones and three limestones from the Himalaya. The overall variation is 4.13‰ and 2.14‰ in δ 26Mg and δ 25Mg, respectively. This is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of Mg is not unique. Each speleothem shows a characteristic range of δ 26Mg values that are attributed to the isotopic composition of the local water. Differences between the isotopic composition of Mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to Mg isotopic fractionation during carbonate precipitation in the temperature range of 4–18°C. The low-Mg calcite is enriched in light isotopes by 1.35‰/AMU and the dependence on temperature has been found to be less than 0.02‰/AMU/°C. Despite various geological settings, the δ 26Mg of the studied dolostones is 2.0±1.2‰ higher than the δ 26Mg of the limestones. All together, these results suggest a strong mineralogical control and a weak temperature effect on the Mg isotopic composition of carbonate.

Formation of refractory inclusions by evaporation of condensate precursors

Berman’s (1983) activity-composition model for CaO-MgO-Al2O3-SiO2 liquids is used to calculate the change in bulk chemical and isotopic composition during simultaneous cooling, evaporation, and crystallization of droplets having the compositions of reasonable condensate precursors of Types A and B refractory inclusions in CV3 chondrites. The degree of evaporation of MgO and SiO2, calculated to be faithfully recorded in chemical and isotopic zoning of individual melilite crystals, is directly proportional to evaporation rate, which is a sensitive function of PH2, and inversely proportional to the droplet radius and cooling rate. When the precursors are partially melted in pure hydrogen at peak temperatures in the vicinity of the initial crystallization temperature of melilite, their bulk chemical compositions evolve into the composition fields of refractory inclusions, mass-fractionated isotopic compositions of Mg, Si, and O are produced that are in the range of the isotopic compositions of natural inclusions, and melilite zoning profiles result that are similar to those observed in real inclusions. For droplets of radius 0.25 cm evaporating at PH2 = 10−6 bar, precursors containing 8 to 13 wt.% MgO and 20 to 23% SiO2 evolve into objects similar to compact Type A inclusions at cooling rates of 2 to 12 K/h, depending on the precise starting composition. Precursors containing 13 to 14 wt.% MgO and 23 to 26% SiO2 evolve into objects with the characteristics of Type B1 inclusions at cooling rates of 1.5 to 3 K/h. The relatively SiO2-poor members of the Type B2 group can be produced from precursors containing 14 to 16 wt.% MgO and 27 to 33% SiO2 at cooling rates of <1 K/h. Type B2’s containing 27 to 35 wt.% SiO2 and <12% MgO require precursors with higher SiO2/MgO ratios at MgO > 15% than are found on any condensation curve. The characteristics of fluffy Type A inclusions, including their reversely zoned melilite, can only be understood in the context of this model if they contain relict melilite.

High-precision measurement of magnesium isotopes by multiple-collector inductively coupled plasma mass spectrometry

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of variations in the isotopic composition of Mg in a range of materials. The contributions of CC, CN, and MgH molecular species to the mass spectrum in the Mg mass region are minimised. Variations in sample 26Mg/24Mg and 25Mg/24Mg ratios are expressed as δ26Mg and δ25Mg units, which are deviations in parts per 103 from the same ratio in the SRM 980 Mg standard. The long-term repeatability of the 26Mg/24Mg and 25Mg/24Mg ratios of a sample Mg solution relative to the SRM 980 Mg isotope standard are 0.12‰ and 0.06‰, respectively, at 95% confidence. The addition of Na, Al, and Ca in a solution of Mg having a known isotopic composition induces 0.2‰–1‰ increase of δ26Mg. This chemical bias is a result of a mass-dependent process and is observed to be greater with Ca than Na. Isobaric interference from doubly charged 48Ca ions on mass 24 is observed to be significant when [Ca]/[Mg] ≥ 0.5. The results obtained on nine terrestrial material show a variation of Mg-isotopes of 4‰ in δ26Mg. When plotted in a three-isotope diagram, all the data fall on a single mass fractionation line. The excess of 26Mg has been determined by the deviation from that mass-dependent relationship, and its long-term repeatability is 0.06‰ at 95% confidence.

Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

Mg isotopic compositions of stony spherules from deep-sea sediments.

The isotopic compositions of Mg in 5 individual stony spherules from deep-sea sediments have been measured. The spherules are composed of olivine, glass, and magnetite, and considered to be of extraterrestrial origin. No significant mass fractionation of up to 2 per mil per amu was recognized. One sample showed a small but significant non-linear 26Mg isotopic effect (δ26Mg = +1.2 per mil) similar to that reported in interplanetary dust particles (IDPs). Based on Mg isotopic compositions of the spherules, we suggest that either vaporization mass loss of parent meteoroids of stony spherules was not so large, usually less than ∼20%, or ablative mass loss occurred effectively during entry into the Earth's atmosphere, and that physicochemical fractionations took place in parent meteoroids could be related to those of primitive IDPs. The processes responsible for the non-linear effect of 26Mg, however, remain undefined.