High-precision zinc isotope measurement of chemically different geostandards by multicollector inductively coupled plasma mass spectrometry.

RATIONALE: Zinc isotopes are becoming increasingly applicable in high-temperature geochemistry, for example in crust-mantle interaction and volatilization-related processes. The published zinc isotope data for some commonly used reference materials, however, show large interlaboratory offsets. In addition, there is still limited data for zinc isotope compositions of many widely used geological reference materials. METHODS: For precise and accurate zinc isotopic ratio analysis of chemically diverse geostandards, including ultramafic to felsic igneous rocks, carbonatites, sediments and soils, an improved procedure for chemical purification of zinc was introduced in this study. The factors potentially affecting zinc isotopic ratio measurement were assessed. The accuracy and long-term reproducibility were obtained by measurements on both synthetic solutions and well-characterized geostandards. RESULTS: Purification of geologic samples with different zinc concentrations and matrix compositions yields consistent elution curves with nearly 100% recovery. Acidity and concentration mismatches and the presence of some matrix elements (e.g., Mg, Ti and Cr) have significant impacts on the precision and accuracy of zinc isotopic ratio measurement. The zinc isotope compositions of a suite of reference materials were measured using this method. CONCLUSIONS: The present study describes methods for the chemical purification of zinc and high-precision and accurate zinc isotopic ratio measurements using multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The long-term external reproducibility for δ66 Zn values is ±0.04‰ (2SD). High-quality zinc isotope data of chemically different geostandards were reported to stimulate future interlaboratory calibrations.

Development of three chalcopyrites and one copper metal as potential reference materials for copper isotopic analysis by LA-MC-ICP-MS.

RATIONALE: Laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) has become a powerful technique for in situ Cu isotopic analysis in natural geological samples. Cu isotopic compositions in natural chalcopyrites have been used to reveal aspects of the mineralization processes directly. However, internationally or commercially available matrix-matched chalcopyrite reference materials for mass fractionation correction or quality control purposes are still lacking for in situ Cu isotopic analysis using LA-MC-ICP-MS. METHODS: Three natural chalcopyrites 14ZJ12-1, JGZ-29 and JGZ-78, and one copper metal GBW02141 with different Cu isotopic compositions were investigated as potential microanalytical reference materials by LA-MC-ICP-MS. Ga element was used as an internal standard to correct the mass fractionation of Cu isotopes during LA-MC-ICP-MS analysis. RESULTS: A large number of Cu isotope ratio measurements using femtosecond LA-MC-ICP-MS were conducted and produced good intermediate precision of δ65 CuNIST976 (0.07-0.08‰, 2 standard deviations), demonstrating the homogeneous Cu isotopic distribution in the recommended samples. The mean δ65 CuNIST976 values of -0.21 ± 0.04‰, 0.46 ± 0.04‰, -0.06 ± 0.04‰ and 0.11 ± 0.05‰ (2 standard deviations) in 14ZJ12-1, JGZ-29, JGZ-78 and GBW02141, respectively, were obtained using solution-MC-ICP-MS in the four recommended samples. CONCLUSIONS: Here, we describe three natural chalcopyrites 14ZJ12-1, JGZ-29, JGZ-78, and one copper metal GBW02141 as the potential Cu isotopic reference materials for LA-MC-ICP-MS analysis. Our analyses demonstrate that these recommended materials have a high degree of elemental and isotopic homogeneity, indicating that they are suitable for microanalysis techniques for data quality assurance or interlaboratory calibration.

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.

Probing recycled carbonate in the lower mantle.

Whether surficial carbonates can be carried into the Earth's lower mantle is key to global deep carbon cycles but remains poorly understood. New clues from magnesium and zinc isotopic systematics on rocks from deep-rooted mantle plumes are presented and discussed in this Perspective.

Linking deep CO2 outgassing to cratonic destruction.

Outgassing of carbon dioxide from the Earth's interior regulates the surface climate through deep time. Here we examine the role of cratonic destruction in mantle CO2 outgassing via collating and presenting new data for Paleozoic kimberlites, Mesozoic basaltic rocks and their mantle xenoliths from the eastern North China Craton (NCC), which underwent extensive destruction in the early Cretaceous. High Ca/Al and low Ti/Eu and δ 26Mg are widely observed in lamprophyres and mantle xenoliths, which demonstrates that the cratonic lithospheric mantle (CLM) was pervasively metasomatized by recycled carbonates. Raman analysis of bubble-bearing melt inclusions shows that redox melting of the C-rich CLM produced carbonated silicate melts with high CO2 content. The enormous quantities of CO2 in these magmas, together with substantial CO2 degassing from the carbonated melt-CLM reaction and crustal heating, indicate that destruction of the eastern NCC resulted in rapid and extensive mantle CO2 emission, which partly contributed to the early Cretaceous greenhouse climate episode.

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.

Fingerprinting the Cretaceous-Paleogene boundary impact with Zn isotopes.

Numerous geochemical anomalies exist at the K-Pg boundary that indicate the addition of extraterrestrial materials; however, none fingerprint volatilization, a key process that occurs during large bolide impacts. Stable Zn isotopes are an exceptional indicator of volatility-related processes, where partial vaporization of Zn leaves the residuum enriched in its heavy isotopes. Here, we present Zn isotope data for sedimentary rock layers of the K-Pg boundary, which display heavier Zn isotope compositions and lower Zn concentrations relative to surrounding sedimentary rocks, the carbonate platform at the impact site, and most carbonaceous chondrites. Neither volcanic events nor secondary alteration during weathering and diagenesis can explain the Zn concentration and isotope signatures present. The systematically higher Zn isotope values within the boundary layer sediments provide an isotopic fingerprint of partially evaporated material within the K-Pg boundary layer, thus earmarking Zn volatilization during impact and subsequent ejecta transport associated with an impact at the K-Pg.

Felsic volcanism as a factor driving the end-Permian mass extinction.

The Siberian Traps large igneous province (STLIP) is commonly invoked as the primary driver of global environmental changes that triggered the end-Permian mass extinction (EPME). Here, we explore the contributions of coeval felsic volcanism to end-Permian environmental changes. We report evidence of extreme Cu enrichment in the EPME interval in South China. The enrichment is associated with an increase in the light Cu isotope, melt inclusions rich in copper and sulfides, and Hg concentration spikes. The Cu and Hg elemental and isotopic signatures can be linked to S-rich vapor produced by felsic volcanism. We use these previously unknown geochemical data to estimate volcanic SO2 injections and argue that this volcanism would have produced several degrees of rapid cooling before or coincident with the more protracted global warming. Large-scale eruptions near the South China block synchronous with the EPME strengthen the case that the STLIP may not have been the sole trigger.

Magmatic record of India-Asia collision.

New geochronological and geochemical data on magmatic activity from the India-Asia collision zone enables recognition of a distinct magmatic flare-up event that we ascribe to slab breakoff. This tie-point in the collisional record can be used to back-date to the time of initial impingement of the Indian continent with the Asian margin. Continental arc magmatism in southern Tibet during 80-40 Ma migrated from south to north and then back to south with significant mantle input at 70-43 Ma. A pronounced flare up in magmatic intensity (including ignimbrite and mafic rock) at ca. 52-51 Ma corresponds to a sudden decrease in the India-Asia convergence rate. Geological and geochemical data are consistent with mantle input controlled by slab rollback from ca. 70 Ma and slab breakoff at ca. 53 Ma. We propose that the slowdown of the Indian plate at ca. 51 Ma is largely the consequence of slab breakoff of the subducting Neo-Tethyan oceanic lithosphere, rather than the onset of the India-Asia collision as traditionally interpreted, implying that the initial India-Asia collision commenced earlier, likely at ca. 55 Ma.

Enhanced recombinant protein productivity by genome reduction in Bacillus subtilis.

The emerging field of synthetic genomics is expected to facilitate the generation of microorganisms with the potential to achieve a sustainable society. One approach towards this goal is the reduction of microbial genomes by rationally designed deletions to create simplified cells with predictable behavior that act as a platform to build in various genetic systems for specific purposes. We report a novel Bacillus subtilis strain, MBG874, depleted of 874 kb (20%) of the genomic sequence. When compared with wild-type cells, the regulatory network of gene expression of the mutant strain is reorganized after entry into the transition state due to the synergistic effect of multiple deletions, and productivity of extracellular cellulase and protease from transformed plasmids harboring the corresponding genes is remarkably enhanced. To our knowledge, this is the first report demonstrating that genome reduction actually contributes to the creation of bacterial cells with a practical application in industry. Further systematic analysis of changes in the transcriptional regulatory network of MGB874 cells in relation to protein productivity should facilitate the generation of improved B. subtilis cells as hosts of industrial protein production.