Fast and precise boron isotopic analysis of carbonates and seawater using Nu Plasma II multi-collector inductively coupled plasma mass spectrometry and a simple sample introduction system.

RATIONALE: The boron (B) isotopic composition in marine carbonates provides important insights into paleoclimate reconstruction and biomineralization. However, precise and accurate measurements of B isotopes using plasma-based mass spectrometry is difficult due to the volatile nature of B, which typically requires complex and more specialized sample introduction systems. Existing analytical protocols have mostly been based on Thermo Scientific Neptune Plus multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) instruments, whereas methods based on Nu Plasma mass spectrometers are scarce. METHODS: We have developed a simplified analytical protocol using Nu Plasma II MC-ICPMS with standard glass sample introduction systems. Boron extraction and purification were conducted using a two-stage column chemistry with cation-exchange and Amberlite IRA 743 B-specific resin. A sample drying step was avoided, which allows for direct isotopic analysis after column chemistry. A wet plasma mode with a standard glass cyclonic spray chamber and a glass nebulizer was used instead of a more specialized perfluoroalkoxy (PFA) sample introduction system. Low residual B signals were achieved with a relatively short period of wash-out with 0.5 N HNO3 . RESULTS: The external precision is better than 0.30‰ (2SD) calculated from the long-term bracketing standard, NIST SRM 951a. The overall robustness of the method was demonstrated by measurements of the international carbonate standard JCp-1 (δ11 B = +24.49 ± 0.36‰, 2SD) and seawater (δ11 B = +39.98 ± 0.35‰), which are consistent with reported values. CONCLUSIONS: Our method provides an alternative approach for B isotope analysis using a routine wet plasma MC-ICPMS setup that can facilitate geochemical and environmental application of B isotopes.

Magnesium isotope geochemistry in arc volcanism.

Incorporation of subducted slab in arc volcanism plays an important role in producing the geochemical and isotopic variations in arc lavas. The mechanism and process by which the slab materials are incorporated, however, are still uncertain. Here, we report, to our knowledge, the first set of Mg isotopic data for a suite of arc lava samples from Martinique Island in the Lesser Antilles arc, which displays one of the most extreme geochemical and isotopic ranges, although the origin of this variability is still highly debated. We find the δ(26)Mg of the Martinique Island lavas varies from -0.25 to -0.10, in contrast to the narrow range that characterizes the mantle (-0.25 ± 0.04, 2 SD). These high δ(26)Mg values suggest the incorporation of isotopically heavy Mg from the subducted slab. The large contrast in MgO content between peridotite, basalt, and sediment makes direct mixing between sediment and peridotite, or assimilation by arc crust sediment, unlikely to be the main mechanism to modify Mg isotopes. Instead, the heavy Mg isotopic signature of the Martinique arc lavas requires that the overall composition of the mantle wedge is buffered and modified by the preferential addition of heavy Mg isotopes from fluids released from the altered subducted slab during fluid-mantle interaction. This, in turn, suggests transfer of a large amount of fluid-mobile elements from the subducting slab to the mantle wedge and makes Mg isotopes an excellent tracer of deep fluid migration.

Episode of intense chemical weathering during the termination of the 635 Ma Marinoan glaciation.

Cryogenian (∼720-635 Ma) global glaciations (the snowball Earth) represent the most extreme ice ages in Earth's history. The termination of these snowball Earth glaciations is marked by the global precipitation of cap carbonates, which are interpreted to have been driven by intense chemical weathering on continents. However, direct geochemical evidence for the intense chemical weathering in the aftermath of snowball glaciations is lacking. Here, we report Mg isotopic data from the terminal Cryogenian or Marinoan-age Nantuo Formation and the overlying cap carbonate of the basal Doushantuo Formation in South China. A positive excursion of extremely high δ26Mg values (+0.56 to +0.95)-indicative of an episode of intense chemical weathering-occurs in the top Nantuo Formation, whereas the siliciclastic component of the overlying Doushantuo cap carbonate has significantly lower δ26Mg values (<+0.40), suggesting moderate to low intensity of chemical weathering during cap carbonate deposition. These observations suggest that cap carbonate deposition postdates the climax of chemical weathering, probably because of the suppression of carbonate precipitation in an acidified ocean when atmospheric CO2 concentration was high. Cap carbonate deposition did not occur until chemical weathering had consumed substantial amounts of atmospheric CO2 and accumulated high levels of oceanic alkalinity. Our finding confirms intense chemical weathering at the onset of deglaciation but indicates that the maximum weathering predated cap carbonate deposition.

Magnesium isotopic homogeneity of San Carlos olivine: a potential standard for Mg isotopic analysis by multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Previous analyses on San Carlos olivine from Arizona (USA) have shown inter-laboratory δ(26) Mg differences of up to 0.67‰, while mantle olivine samples worldwide are homogeneous at a current analytical uncertainty of ~0.1‰. The differing measurements on San Carlos olivine may be attributable to analytical artifacts or sample heterogeneity. The latter must be ruled out before using it as a standard for Mg isotopic analysis. METHODS: To examine sample homogeneity, two different batches of San Carlos olivine from a lherzolite and four batches from a harzburgite have been analyzed together with coexisting harzburgitic pyroxene. In addition, the effect of acid purity on resin performance and the reusability of AG50W-X8 resin for Mg separation have been evaluated by processing another batch of lherzolitic San Carlos olivine and Hawaiian seawater through both new and used resins cleaned with different acids. RESULTS: Six different batches of olivine grains from two San Carlos peridotite xenoliths show homogeneous δ(26) Mg values to within 0.03‰, and all the mineral phases in the harzburgite are in Mg isotope equilibrium. Furthermore, there is no resolvable δ(26) Mg shift in either lherzolitic San Carlos olivine or Hawaiian seawater by using either new or used resins that were cleaned with single-distilled or double-distilled acids. CONCLUSIONS: The new data are consistent with the narrow δ(26) Mg range of mantle olivine worldwide, while they stand in contrast to the wide range measured on the same San Carlos olivine powder in different laboratories. Therefore, previous inter-laboratory discrepancies reflect analytical artifacts instead of sample heterogeneity, and San Carlos olivine is a suitable standard for Mg isotopic analysis. Copyright © 2016 John Wiley & Sons, Ltd.

Comparison of factors affecting the accuracy of high-precision magnesium isotope analysis by multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: High accuracy is the prerequisite for high-precision isotopic analysis. METHODS: Here we evaluate how the presence of matrix elements, and mismatch between samples and standards in Mg concentration and acid molarity affect the accuracy of stable Mg isotopic analysis on Nu Plasma and IsoProbe multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) instruments. RESULTS: Our results show that these factors can lead to large (>1‰) deviation in the high-precision analysis of Mg isotopes. The degree and direction of these accuracy offsets can vary for different instruments, instrumental settings and different laboratories. CONCLUSIONS: Detailed tests and tight controls on these effects are thus needed for high-precision high-accuracy stable Mg isotopic analysis.

Copper isotope evidence for sulfide fractionation and lower crustal foundering in making continental crust.

The continental crust is strongly depleted in copper compared with its building blocks-primary arc magmas-and this depletion is intrinsically associated with continental crust formation. However, the process by which Cu removal occurs remains enigmatic. Here we show, using Cu isotopes, that subduction-zone processes and mantle melting produce limited fractionation of Cu isotopes in arc magmas, and, instead, the heterogeneous Cu isotopic compositions of lower crustal rocks, which negatively correlate with Cu contents, suggest segregation or accumulation of isotopically light sulfides during intracrustal differentiation of arc magmas. This is supported by the extremely light Cu isotopic compositions of lower crustal mafic cumulates and heavy Cu isotopic compositions of differentiated magmas in thick continental arcs. Intracrustal differentiation of mantle-derived magmas and subsequent foundering of sulfide-rich mafic cumulates preferentially removes isotopically light Cu, leaving a Cu-depleted and isotopically heavy continental crust.

Extensive crystal fractionation of high-silica magmas revealed by K isotopes.

Fractional crystallization plays a critical role in generating the differentiated continental crust on Earth. However, whether efficient crystal-melt separation can occur in viscous felsic magmas remains a long-standing debate because of the difficulty in discriminating between differentiated melts and complementary cumulates. Here, we found large (~1 per mil) potassium isotopic variation in 54 strongly peraluminous high-silica (silicon dioxide >70 weight %) leucogranites from the Himalayan orogen, with potassium isotopes correlated with trace elemental proxies (e.g., strontium, rubidium/strontium, and europium anomaly) for plagioclase crystallization. Quantitative modeling requires up to ~60 to 90% fractional crystallization to account for the progressively light potassium isotopic composition of the fractionated leucogranites, while plagioclase accumulation results in enrichment of heavy potassium isotopes in cumulate leucogranites. Our findings strongly support fractional crystallization of high-silica magmas and highlight the great potential of potassium isotopes in studying felsic magma differentiation.

Homogeneous magnesium isotopic composition of seawater: an excellent geostandard for Mg isotope analysis.

The magnesium (Mg) isotopic compositions of 40 seawater samples from the Gulf of Mexico and of one seawater sample from the southwest Hawaii area were determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) to investigate the homogeneity of Mg isotopes in seawater. The results indicate that the Mg isotopic composition of seawater from the Gulf of Mexico is homogeneous, both vertically and horizontally, with average values for δ(26)Mg = -0.832 ± 0.068 and δ(25)Mg = -0.432 ± 0.053 (n = 40, 2SD)--identical to those of seawater from Hawaii (average δ(26)Mg = -0.829 ± 0.037 and δ(25)Mg = -0.427 ± 0.033) and to the average literature values of seawater worldwide (δ(26)Mg = -0.83 ± 0.11 and δ(25)Mg = -0.43 ± 0.06, n = 49, 2SD). Collectively, global seawater has a homogeneous Mg isotopic composition with δ(26)Mg = -0.83 ± 0.09 and δ(25) Mg = -0.43 ± 0.06 (2SD, n = 90). The magnesium isotopic composition of seawater is principally controlled by river water input, carbonate precipitation and oceanic hydrothermal interactions. The homogeneous Mg isotopic composition of seawater indicates a steady-state budget in terms of Mg isotopes in oceans, consistent with a long Mg residence time (~13 Ma). Considering that seawater is homogeneous, readily available in large amounts, can be easily accessed and processed for isotopic analysis, and has an isotopic composition near the middle of the natural range of variation, it is an excellent geostandard for accuracy assessment to rule out analytical artifacts during high-precision Mg isotopic analysis.

Imprint of chondrule formation on the K and Rb isotopic compositions of carbonaceous meteorites.

Chondrites display isotopic variations for moderately volatile elements, the origin of which is uncertain and could have involved evaporation/condensation processes in the protoplanetary disk, incomplete mixing of the products of stellar nucleosynthesis, or aqueous alteration on parent bodies. Here, we report high-precision K and Rb isotopic data of carbonaceous chondrites, providing new insights into the cause of these isotopic variations. We find that the K and Rb isotopic compositions of carbonaceous chondrites correlate with their abundance depletions, the fractions of matrix material, and previously measured Te and Zn isotopic compositions. These correlations are best explained by the variable contribution of chondrules that experienced incomplete condensation from a supersaturated medium. From the data, we calculate an average chondrule cooling rate of ~560 ± 180 K/hour, which agrees with values constrained from chondrule textures and could be produced in shocks induced by nebular gravitational instability or motion of large planetesimals through the nebula.

Nickel isotopic evidence for late-stage accretion of Mercury-like differentiated planetary embryos.

Earth's habitability is closely tied to its late-stage accretion, during which impactors delivered the majority of life-essential volatiles. However, the nature of these final building blocks remains poorly constrained. Nickel (Ni) can be a useful tracer in characterizing this accretion as most Ni in the bulk silicate Earth (BSE) comes from the late-stage impactors. Here, we apply Ni stable isotope analysis to a large number of meteorites and terrestrial rocks, and find that the BSE has a lighter Ni isotopic composition compared to chondrites. Using first-principles calculations based on density functional theory, we show that core-mantle differentiation cannot produce the observed light Ni isotopic composition of the BSE. Rather, the sub-chondritic Ni isotopic signature was established during Earth's late-stage accretion, probably through the Moon-forming giant impact. We propose that a highly reduced sulfide-rich, Mercury-like body, whose mantle is characterized by light Ni isotopic composition, collided with and merged into the proto-Earth during the Moon-forming giant impact, producing the sub-chondritic Ni isotopic signature of the BSE, while delivering sulfur and probably other volatiles to the Earth.

Potassium isotopic heterogeneity in subducting oceanic plates.

Oceanic crust and sediments are the primary K sinks for seawater, and they deliver considerable amounts of K to the mantle via subduction. Historically, these crustal components were not studied for K isotopes because of the lack of analytical precision to differentiate terrestrial variations. Here, we report a high-precision dataset that reveals substantial variability in oceanic plates and provides further insights into the oceanic K cycle. Sixty-nine sediments worldwide yield a broad δ41K range from -1.3 to -0.02‰. The unusually low values are indicative of release of heavy K during continental weathering and uptake of light K during submarine diagenetic alteration. Twenty samples of altered western Pacific crust from ODP Site 801 display δ41K from -0.60 to -0.05‰, averaging at -0.32‰. Our results indicate that submarine alteration of oceanic plates is essential for generating the high-δ41K signature of seawater. These regionally varying subducting components are heterogeneous K inputs to the mantle.

Magnesium isotope fractionation during microbially enhanced forsterite dissolution.

Bacillus subtilis endospore-mediated forsterite dissolution experiments were performed to assess the effects of cell surface reactivity on Mg isotope fractionation during chemical weathering. Endospores present a unique opportunity to study the isolated impact of cell surface reactivity because they exhibit extremely low metabolic activity. In abiotic control assays, 24 Mg was preferentially released into solution during forsterite dissolution, producing an isotopically light liquid phase (δ26 Mg = -0.39 ± 0.06 to -0.26 ± 0.09‰) relative to the initial mineral composition (δ26 Mg = -0.24 ± 0.03‰). The presence of endospores did not have an apparent effect on Mg isotope fractionation associated with the release of Mg from the solid into the aqueous phase. However, the endospore surfaces preferentially adsorbed 24 Mg from the dissolution products, which resulted in relatively heavy aqueous Mg isotope compositions. These aqueous Mg isotope compositions increased proportional to the fraction of dissolved Mg that was adsorbed, with the highest measured δ26 Mg (-0.08 ± 0.07‰) corresponding to the highest degree of adsorption (~76%). The Mg isotope composition of the adsorbed fraction was correspondingly light, at an average δ26 Mg of -0.49‰. Secondary mineral precipitation and Mg adsorption onto secondary minerals had a minimal effect on Mg isotopes at these experimental conditions. Results demonstrate the isolated effects of cell surface reactivity on Mg isotope fractionation separate from other common biological processes, such as metabolism and organic acid production. With further study, Mg isotopes could be used to elucidate the role of the biosphere on Mg cycling in the environment.

The role of marine sediment diagenesis in the modern oceanic magnesium cycle.

The oceanic magnesium cycle is largely controlled by continental weathering and marine authigenic mineral formation, which are intimately linked to long-term climate. Uncertainties in the magnesium cycle propagate into other chemical budgets, and into interpretations of paleo-oceanographic reconstructions of seawater δ26Mg and Mg/Ca ratios. Here, we produce a detailed global map of the flux of dissolved magnesium from the ocean into deeper marine sediments (greater than ∼1 meter below seafloor), and quantify the global flux and associated isotopic fractionation. We find that this flux accounts for 15-20% of the output of magnesium from the ocean, with a flux-weighted fractionation factor of ∼0.9994 acting to increase the magnesium isotopic ratio in the ocean. Our analysis provides the best constraints to date on the sources and sinks that define the oceanic magnesium cycle, including new constraints on the output flux of magnesium and isotopic fractionation during low-temperature ridge flank hydrothermal circulation.

Chromite-induced magnesium isotope fractionation during mafic magma differentiation.

To better understand the mechanism of Mg isotopic variation in magma systems, here we report high precision Mg isotopic data of 17 bulk rock samples including dunite, clinopyroxenite, hornblendite and gabbro and 10 pairs of dunite-hosted olivine and chromite separates from the well-characterized Alaskan-type Xiadong intrusion in NW China, which formed by continuous and high degree of lithological differentiation from mafic magmas. Chromite separates have highly variable δ26Mg values from -0.10‰ to 0.40‰, and are consistently heavier than coexisting olivine separates (-0.39‰ to -0.15‰). Both mineral δ26Mg values and the degrees of inter-mineral fractionation are well correlated with geochemical indicators of magma differentiation, indicating that these inter-sample and inter-mineral Mg isotope fractionations are caused by magma evolution. The δ26Mg values range from -0.20‰ to -0.02‰ in the dunite, -0.43‰ in the clinopyroxenite, -0.43‰ to -0.28‰ in the hornblendite, 0.18‰ in the chromite-bearing hornblendite, and -0.56‰ to -0.16‰ in the gabbro. The Mg isotopic variations in different types of rocks are closely related to fractional crystallization and accumulation of different proportions of oxides vs. silicates. Chromite crystallization and accumulation is the most important factor in controlling Mg isotope fractionation during the formation of the Xiadong intrusion. Compared to basaltic and granitic magmas, differentiation of the Alaskan-type intrusions occurs at a relatively high oxygen fugacity, which favors chromite crystallization and consequently significant Mg isotope fractionations at both mineral and whole-rock scales. Therefore, Mg isotope systematics can be used to trace the degree of magma differentiation and related-mineralization.

Tracing carbonate-silicate interaction during subduction using magnesium and oxygen isotopes.

Subduction of carbonates and carbonated eclogites into the mantle plays an important role in transporting carbon into deep Earth. However, to what degree isotopic exchanges occur between carbonate and silicate during subduction remains unclear. Here we report Mg and O isotopic compositions for ultrahigh pressure metamorphic marbles and enclosed carbonated eclogites from China. These marbles include both calcite- and dolomite-rich examples and display similar O but distinct Mg isotopic signatures to their protoliths. Their δ(26)Mg values vary from -2.508 to -0.531‰, and negatively correlate with MgO/CaO ratios, unforeseen in sedimentary carbonates. Carbonated eclogites have extremely heavy δ(18)O (up to +21.1‰) and light δ(26)Mg values (down to -1.928‰ in garnet and -0.980‰ in pyroxene) compared with their protoliths. These unique Mg-O isotopic characteristics reflect differential isotopic exchange between eclogites and carbonates during subduction, making coupled Mg and O isotopic studies potential tools for tracing deep carbon recycling.

Iron isotope fractionation during magmatic differentiation in Kilauea Iki lava lake.

Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stagemeltveins are 0.2 permil (per thousand) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2 per thousand lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.