Precise carbon isotopic ratio analyses of micro amounts of carbonate and non-carbonate in basalt using continuous-flow isotope ratio mass spectrometry.

RATIONALE: Continuous-flow isotope ratio mass spectrometry (CF-IRMS) is a specialized technique used to quickly analyze very small amounts of sample. We have used CF-IRMS to assess the influences of sample weight and relative carbon content on the accuracy and precision of the δ13 C values of micro amounts of carbonate and non-carbonate in silicate rocks. METHODS: The analytical work was performed on a Gasbench II (GB) sample preparation device and on an Elemental Analyzer (EA), which were both interfaced to CF-IRMS instruments. Potential silicate matrix effects on the carbon isotopic analyses were investigated by measuring mixtures of calibrated carbon reference materials and quartz powder. The calibration lines, established by the measured raw values and the known values of three reference materials mixed with quartz powder, were used to calibrate the δ13 C values of basalt samples from eastern China. RESULTS: The δ13 C values measured by GB-CF-IRMS of one national carbonate reference material, GBW04416, deviate slightly from the known value for approximately 20-70 µg of carbonate contained in 4.5-mL vials; the smaller the sample size, the lower the measured δ13 C values. External precision better than 0.1‰ (1σ, n = 26) is achieved at a signal intensity for mass 44 of between 868 and 1614 mV, corresponding to a sample weight of 30.8-50.2 µg, whereas it is reduced to 0.27‰ (1σ, n = 34) at a signal intensity between 519 and 1614 mV, corresponding to a sample weight of 21.1-50.2 µg. In the EA-CF-IRMS experiments for non-carbonate carbon, at high carbon concentration (greater than 800 ppm) and at optimum sample weights, the accuracy and precision are both better than 0.2‰. For carbon concentrations less than 500 ppm, the measured δ13 C values deviate from the average by up to -1.2‰ and the precision is 0.74‰. CONCLUSIONS: The measured δ13 C values decrease substantially at lower carbon concentration and higher sample weights, and poorer precision is obtained. Suggestions are made to measure repeatedly the same carbon concentration of sample and reference materials in order to obtain not only reproducible, but also accurate carbon isotope ratios.

First finding of continental deep subduction in the Sesia Zone of the Western Alps and implications for subduction dynamics.

Continental deep subduction after the closure of large oceanic basins is commonly ascribed to the gravitational pull of the subducting oceanic slab. However, it is not clear how continental lithosphere adjacent to small oceanic basins was subducted to mantle depths. The Sesia Zone in the Western Alps provides an excellent target for exploration of subduction dynamics in such a tectonic setting. Here we report the first finding of coesite in a jadeite-bearing orthogneiss from the Sesia Zone, providing the first evidence for deep subduction of the continental crust to mantle depths for ultrahigh-pressure (UHP) metamorphism in this zone. Three coesite inclusions were identified by laser Raman spectroscopy in two garnet grains. Based on zircon U-Pb dating and trace element analysis, the UHP metamorphic age was constrained to be 76.0 ± 1.0 Ma. The phase equilibrium modeling yields peak metamorphic pressures of 2.8-3.3 GPa, demonstrating the continental deep subduction to mantle depths of >80 km. The subducted continental crust was a rifted hyperextended continental margin, which was converted to the passive continental margin during seafloor spreading and then deeply subducted during the oblique convergence between the Adria microplate and Eurasian plate in the Late Cretaceous. Because the slab pull could only play a limited role in closing small oceanic basins for continental collision, the distal push of either continental breakup or seafloor spreading is suggested as the major driving force for the deep subduction of continental crust in the Western Alps. Therefore, deep subduction of the continental crust bordering small oceanic basins would have been induced by the far-field stress of compression, whereas that bordering large oceanic basins was spontaneous due to the oceanic slab pull. This provides a new insight into the geodynamic mechanism of continental deep subduction.

Interplay between oceanic subduction and continental collision in building continental crust.

Generation of continental crust in collision zones reflect the interplay between oceanic subduction and continental collision. The Gangdese continental crust in southern Tibet developed during subduction of the Neo-Tethyan oceanic slab in the Mesozoic prior to reworking during the India-Asia collision in the Cenozoic. Here we show that continental arc magmatism started with fractional crystallization to form cumulates and associated medium-K calc-alkaline suites. This was followed by a period commencing at ~70 Ma dominated by remelting of pre-existing lower crust, producing more potassic compositions. The increased importance of remelting coincides with an acceleration in the convergence rate between India and Asia leading to higher basaltic flow into the Asian lithosphere, followed by convergence deceleration due to slab breakoff, enabling high heat flow and melting of the base of the arc. This two-stage process of accumulation and remelting leads to the chemical maturation of juvenile continental crust in collision zones, strengthening crustal stratification.

Novel 4-azasteroidal N-glycoside analogues bearing sugar-like D ring: synthesis and anticancer activities.

A series of novel N-glycoside analogues with 4-azasteroid moiety bearing sugar-like D ring were conveniently synthesized by constructing the core dihydropyran ring embedded in 4-azasteroidal skeleton which was prepared from 4-aza-5α-androst-3,17-dione 1 in four steps. The structure of 6b were unambiguously proved by the appropriate X-ray structural analysis. Anticancer activity was found for all of the analogues with purinyl moiety against breast cancer (MCF-7), human neuroblastoma (SK-N-SH), cervical cancer cell (HeLa) and prostatic cancer (PC-3), while the analogue 7 containing 1,2,4-triazole heterocycle as the nucleobase was inactive against all of the tested cancer cell lines. The biology results showed the purinyl moiety attached to the pyran ring of 6a-d, substituent at 6'-position of purine base and introduction of a halogen atom at 2'-position of 6'-chloropurine had obviously effect on the evaluated anticancer activity.

An online method combining a Gasbench II with continuous flow isotope ratio mass spectrometry to determine the content and isotopic compositions of minor amounts of carbonate in silicate rocks.

An online method using continuous flow isotope ratio mass spectrometry (CF-IRMS) interfaced with a Gasbench II device was established to analyze carbon and oxygen isotopic compositions and to estimate the content of minor amounts of carbonate in silicate rocks. The mixtures of standard materials and high-purity quartz are firstly used to calibrate different quantities of carbonate in silicates. The results suggest that the accuracy and precision of the online analysis are both better than those obtained using an offline method. There is a positive correlation between the carbonate weight and the Mass44 ion beam intensity (or peak area). When the weight of carbonate in the mixtures is greater than 70 microg (equal to approximately 1800 mV Mass44 ion beam intensity), the delta(13)C and delta(18)O values of samples usually have accuracy and precision of +/-0.1 per thousand and +/-0.2 per thousand (1sigma), respectively. If the weight is less than 70 microg, some limitations (e.g., not perfectly linear) are encountered that significantly reduce the accuracy and precision. The measured delta(18)O values are systematically lower than the true values by -0.3 to -0.7 per thousand; the lower the carbonate content, the lower the measured delta(18)O value. For samples with lower carbonate content, the required phosphoric acid doses are higher and more oxygen isotope exchanges with the water in the phosphoric acid. To guarantee accurate results with high precision, multiple analyses of in-house standards and an artificial MERCK sample with delta(13)C values from -35.58 to 1.61 per thousand and delta(18)O from 6.04 to 18.96 per thousand were analyzed simultaneously with the unknown sample. This enables correction of the measured raw data for the natural sample based on multiple-point normalization. The results indicate that the method can be successfully applied to a range of natural rocks.

Two styles of plate tectonics in Earth's history.

When plate tectonics started to occur on Earth and how it has evolved through time are two of the most fundamental questions in earth sciences. While gravity-driven subducting has been accepted as a critical condition for the operation of plate tectonics on Earth, it is intriguing how the dynamic regime and thermal state of subduction zones have affected the style of plate tectonics in Earth's history. The metamorphic rocks of regional distribution along convergent plate boundaries record reworking of crustal rocks through dehydration and melting at lithospheric depths. The property of regional metamorphism is determined by both dynamic regime and thermal state of plate margins. The two variables have secularly evolved in Earth's history, which is recorded by changes in the global distribution of metamorphic facies series through time. This results in two styles of plate tectonics. Modern-style plate tectonics has developed since the Neoproterozoic when plate margins were rigid enough for cold subducting, whereas ancient-style plate tectonics has developed since the Archean when plate margins were ductile enough for warm subducting. Such a difference is primarily dictated by higher mantle temperatures in the Archean than in the Phanerozoic. The development of plate subduction in both cold and warm realms is primarily dictated by the rheology of plate margins. This leads to a holistic model for the style of plate tectonics during different periods in Earth's history.

Enhanced weathering as a trigger for the rise of atmospheric O2 level from the late Ediacaran to the early Cambrian.

A shift toward a higher oxygen level in both ocean and atmosphere systems during the late Ediacaran to the early Cambrian has been suggested from multiple indirect proxies. However, the mechanism and magnitude of this oxidation remain unclear. To solve this issue, we measured carbon isotopes in both carbonate and organic matter as well as their trace element compositions for an Ediacaran-Cambrian sequence in the Lower Yangtze basin, South China. The δ13Corg and δ13Ccarb excursions of this sequence are coupled and can be compared with contemporaneous global carbon isotope curves. A 2‰ rise in Δ13Ccarb-org occurred from the late Ediacaran to the early Cambrian, suggesting a substantial increase in atmospheric oxygen level from 16% to 30% of the present atmospheric level (PAL). Furthermore, the distribution pattern of rare earth elements and the concentrations of water-insoluble elements in the carbonates indicate a sudden enhancement in chemical weathering of the continental crust during the early Cambrian, which may be a trigger for the rise of atmospheric O2 level. Both the supply of a large amount of nutrients due to the enhanced continental weathering and the contemporary increase of atmospheric oxygen concentrations may have promoted the appearance of large metazoans in the early Cambrian.

Author Correction: Zircon evidence for incorporation of terrigenous sediments into the magma source of continental basalts.

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Zircon evidence for incorporation of terrigenous sediments into the magma source of continental basalts.

Crustal components may be incorporated into continental basalts by either shallow contamination or deep mixing. While the former proceeds at crustal depths with common preservation of refractory minerals, the latter occurs at mantle depths with rare survival of relict minerals. Discrimination between the two mechanisms has great bearing to subcontinental mantle geochemistry. Here we report the occurrence of relict zircons in Cenozoic continental basalts from eastern China. A combined study of zircon U-Pb ages and geochemistry indicates that detrital zircons were carried by terrigenous sediments into a subcontinental subduction zone, where the zircon were transferred by fluids into the magma sources of continental basalts. The basalts were sampled from three petrotectonic units with distinct differences in their magmatic and metamorphic ages, making the crustal contamination discernible. The terrigenous sediments were carried by the subducting oceanic crust into the asthenospheric mantle, producing both soluble and insoluble materials at the slab-mantle interface. These materials were served as metasomatic agents to react with the overlying mantle wedge peridotite, generating a kind of ultramafic metasomatites that contain the relict zircons. Therefore, the occurrence of relict zircons in continental basalts indicates that this refractory mineral can survive extreme temperature-pressure conditions in the asthenospheric mantle.

Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange.

Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag3PO4 and BiPO4 are enriched in (18)O relative to AgPO4, and the three phosphates are consistently depleted in (18)O relative to Ba3[PO4]2; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of (18)O relative to hydroxyapatite. The valence, radii and coordination of metal cations play a quantitative role in dictating the (18)O/(16)O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag3PO4-H2O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag3PO4 has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite-water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate-water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates.

Oxygen isotope fractionation in double carbonates.

Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates.

Seeking a geochemical identifier for authigenic carbonate.

Authigenic carbonate was recently invoked as a third major global carbon sink in addition to primary marine carbonate and organic carbon. Distinguishing the two carbonate sinks is fundamental to our understanding of Earth's carbon cycle and its role in regulating the evolution of atmospheric oxygen. Here, using microscale geochemical measurements of carbonates in Early Triassic strata, we show that the growth of authigenic carbonate follows a different trajectory from primary marine carbonate in a cross-plot of uranium concentration and carbon isotope composition. Thus, a combination of the two geochemical variables is able to distinguish between the two carbonate sinks. The temporal distribution of authigenic carbonates in the Early Triassic strata suggests that the increase in the extent of carbonate authigenesis acted as a negative feedback to the elevated atmospheric CO2 concentration.

Synthesis and biological evaluation of novel C6-cyclo secondary amine substituted purine steroid-nucleosides analogues.

Novel C6-cyclo secondary amine substituted purine steroid-nucleoside analogues (2-9) were efficiently synthesized through displacement of the C6 chloro on the purine ring of series 1 with versatile cyclic secondary amines, including pyrrolidines, piperidine, morpholine, and piperazines. All the newly-synthesized compounds were evaluated for their anticancer activity in vitro against Hela, PC-3 and MCF-7 cell lines. Among them, compounds 5c and 6b exhibited significant cytotoxicity on PC-3 cell lines.

Synthesis and anticancer activity of novel C6-piperazine substituted purine steroid-nucleosides analogues.

Novel C6-piperazine substituted purine nucleoside analogues (2-9) bearing a modified pyranose-like D ring of the 4-azasteroid moiety were efficiently synthesized through nucleophilic substitution at C6 position of the steroid-nucleoside precursors (1) with versatile piperazines. All newly-synthesized compounds were evaluated for their anticancer activity in vitro against Hela, PC-3 and MCF-7 cell lines. Among them, compounds 8b and 9b exhibited significant cytotoxicity on PC-3 cell lines.

Postcollisional mafic igneous rocks record crust-mantle interaction during continental deep subduction.

Findings of coesite and microdiamond in metamorphic rocks of supracrustal protolith led to the recognition of continental subduction to mantle depths. The crust-mantle interaction is expected to take place during subduction of the continental crust beneath the subcontinental lithospheric mantle wedge. This is recorded by postcollisional mafic igneous rocks in the Dabie-Sulu orogenic belt and its adjacent continental margin in the North China Block. These rocks exhibit the geochemical inheritance of whole-rock trace elements and Sr-Nd-Pb isotopes as well as zircon U-Pb ages and Hf-O isotopes from felsic melts derived from the subducted continental crust. Reaction of such melts with the overlying wedge peridotite would transfer the crustal signatures to the mantle sources for postcollisional mafic magmatism. Therefore, postcollisonal mafic igneous rocks above continental subduction zones are an analog to arc volcanics above oceanic subduction zones, providing an additional laboratory for the study of crust-mantle interaction at convergent plate margins.

A novel [1,2,4] triazolo [1,5-a] pyrimidine-based phenyl-linked steroid dimer: synthesis and its cytotoxic activity.

A novel [1,2,4] triazolo [1,5-a] pyrimidine-based phenyl-linked steroid dimer was designed, synthesized and evaluated for its cytotoxic activity against five human cancer cell lines and the cytotoxicity against human normal liver cell L-02. Compound 3 showed excellent cytotoxic activity and good selectivity between cancer and normal cells. Further mechanistic studies revealed that treatment of EC109 cells with compound 3 caused an obvious G2/M arrest in a concentration- and time-dependent manner and induced apoptosis probably through the mitochondrial pathway accompanied with the decrease of mitochondrial membrane potential, activations of caspase-9/-3, cleavage of MDM2 as well as up-regulation of the expressions of p53 and Bax.

Isotopic evidence for continental ice sheet in mid-latitude region in the supergreenhouse Early Cretaceous.

Cretaceous represents one of the hottest greenhouse periods in the Earth's history, but some recent studies suggest that small ice caps might be present in non-polar regions during certain periods in the Early Cretaceous. Here we report extremely negative δ(18)O values of -18.12‰ to -13.19‰ for early Aptian hydrothermal zircon from an A-type granite at Baerzhe in northeastern China. Given that A-type granite is anhydrous and that magmatic zircon of the Baerzhe granite has δ(18)O value close to mantle values, the extremely negative δ(18)O values for hydrothermal zircon are attributed to addition of meteoric water with extremely low δ(18)O, mostly likely transported by glaciers. Considering the paleoaltitude of the region, continental glaciation is suggested to occur in the early Aptian, indicating much larger temperature fluctuations than previously thought during the supergreenhouse Cretaceous. This may have impact on the evolution of major organism in the Jehol Group during this period.

Synthesis and biological evaluation of novel steroidal[17,16-d][1,2,4]triazolo[1,5-a]pyrimidines.

The preparation of steroidal[17,16-d][1,2,4]triazolo[1,5-a]pyrimidines and their biological evaluation as potential anticancer agents are herein reported. These novel heterosteroids (2, 4) were prepared through the condensation reaction of 3-amino-1,2,4-triazole with 16-arylidene-17-ketosteroids (1, 3). All the synthesized compounds were evaluated for their anticancer activity in vitro against PC-3 (human prostatic carcinoma), MCF-7 (human breast carcinoma) and EC9706 (human esophageal carcinoma) cell lines. Among the screened compounds, 2i, 2n and 4f showed significant inhibitory activity against all the three human cell lines.

Synthesis of novel D-ring fused 7'-aryl-androstano[17,16-d][1,2,4] triazolo[1,5-a]pyrimidines.

The preparation of novel steroidal heterocycles containing the 7-aryl-substituted 1,2,4-triazolo[1,5-a]pyrimidine moiety fused to the 16,17-positions of the steroid nucleus is described. The Aldol reaction of 4-aza-androst-3,17-dione (1a) and dehydroepiandrosterone (DHEA, 1b) with aromatic aldehydes was catalyzed by KF/Al(2)O(3) to give the corresponding 3-oxo-4-aza-5α- and 3ß-hydroxy-5-en-16-arylidene-17-ketosteroids (2a-r). Subsequently, the intermediates 2a-r reacted with dinucleophilic 3-amino-1,2,4-triazole in presence of t-BuOK to afford the title compounds (3a-r). All the synthesized heterosteroids are new and are currently being evaluated for their biological activities.

An online method combining a thermal conversion elemental analyzer with isotope ratio mass spectrometry for the determination of hydrogen isotope composition and water concentration in geological samples.

An online continuous-flow method, combining a thermal conversion elemental analyzer (TC/EA) with isotope ratio mass spectrometry (MS), is evaluated for the determination of both the hydrogen isotope composition and the water concentration of hydrous and nominally anhydrous minerals. The technique involves reduction of hydrous minerals or nominally anhydrous minerals by reaction with glassy carbon at 1450 degrees C in a helium stream. The product gases, H2 and CO, are separated on a gas chromatographic column prior to analysis in the mass spectrometer. Calibration curves for the H concentration analysis were generated from a standard of benzoic acid (C7H6O2) that has an H concentration of 5.0 wt%; the analytical uncertainties were better than +/-0.05% in our runs. Two standards of material with given D values, polyethylene IAEA-CH-7 and biotite NBS-30, were tested for the purpose of calibrating a natural garnet 04BXL02 representing nominally anhydrous minerals. Preheating at 90 degrees C for 12 h was found to be suitable for removing adsorption water on the sample surface. This results in constant D values and total H2O contents for the garnet, with weighted means of -94 +/- 1 and 522 +/- 11 ppm (wt), respectively. The TC/EA-MS technique allows routine analysis of sample sizes as small as 0.01 microL H2O. For natural minerals, absolute reproducibilities for D values are +/-0.5 to +/-2 (1) and relative uncertainties for total H2O concentrations are at levels of +/-1% to +/-3% (1). Therefore, this online method can be used for the quantitative determination of H isotope composition and H2O concentration of either hydrous or anhydrous minerals.