Global atmospheric oxygen variations recorded by Th/U systematics of igneous rocks

Atmospheric oxygen has evolved from negligible levels in the Archean to the current level of about 21% through 2 major step rises: The Great Oxidation Event (GOE) in the early Proterozoic and the Neoproterozoic Oxygenation Event (NOE) during the late Proterozoic. However, most previous methods for constraining the time of atmospheric oxygenation have relied on evidence from sedimentary rocks. Here, we investigate the temporal variations of the Th/U of arc igneous rocks since 3.0 billion y ago (Ga) and show that 2 major Th/U decreases are recorded at ca. 2.35 Ga and ca. 0.75 Ga, coincident with the beginning of the GOE and NOE. The decoupling of U from Th is predominantly caused by the significant rise of atmospheric oxygen. Under an increasingly oxidized atmosphere condition, more uranium in the surface environment became oxidized from the water-insoluble U4+ to the water-soluble U6+ valance and incorporated in the sea water and altered oceanic crust. Eventually, the subduction of this altered oceanic crust produced the low-Th/U signature of arc igneous rocks. Therefore, the sharp decrease of Th/U in global arc igneous rocks may provide strong evidence for the rise of atmospheric oxygen. We suggest that the secular Th/U evolution of arc igneous rocks could be an effective geochemical indicator recording the global-scale atmospheric oxygen variation.This study was supported by Strategic Priority Research Program of the Chinese Academy of Sciences (CAS) Grant XDB18020102 and National Key R & D Program of China Grant 2016YFC0600408 (to W.-d.S.). T.R.I. acknowledges a CAS President visiting fellowshi

Impacts of Mid-Level Biofuel Content In Gasoline on SIDI Engine-Out and Tailpipe Particulate Matter Emissions

In this work, the influences of ethanol and iso-butanol blended with gasoline on engine-out and post three-way catalyst (TWC) particle size distribution and number concentration were studied using a General Motors (GM) 2.0L turbocharged spark ignition direct injection (SIDI) engine. The engine was operated using the production engine control unit (ECU) with a dynamometer controlling the engine speed and the accelerator pedal position controlling the engine load. A TSI Fast Mobility Particle Sizer (FMPS) spectrometer was used to measure the particle size distribution in the range from 5.6 to 560 nm with a sampling rate of 1 Hz. U.S. federal certification gasoline (E0), two ethanol-blended fuels (E10 and E20), and 11.7% iso-butanol blended fuel (BU12) were tested. Measurements were conducted at 10 selected steady-state engine operation conditions. Bi-modal particle size distributions were observed for all operating conditions with peak values at particle sizes of 10 nm and 70 nm. Idle and low-speed / low-load conditions emitted higher total particle numbers than other operating conditions. At idle, the engine-out particulate matter (PM) emissions were dominated by nucleation mode particles, and the production TWC reduced these nucleation mode particles by more than 50%, while leaving the accumulation mode particle distribution unchanged. At an engine load higher than 6 bar net mean effective pressure (NMEP), accumulation mode particles dominated the engine-out particle emissions, and the TWC had little effect. Compared to the baseline gasoline (E0), E10 does not significantly change PM emissions, while E20 and BU12 both reduce PM emissions under the conditions studied. Iso-butanol was observed to impact PM emissions more than ethanol, with up to 50% reductions at some conditions. In this paper, issues related to PM measurement using the FMPS are also discussed. While some uncertainties are due to engine variation, the FMPS must be carefully maintained in order to achieve repeatable measurement results

Switching the stereochemical outcome of 6-endo-trig cyclizations; Synthesis of 2,6-Cis-6-substituted 4-oxopipecolic acids

A base-mediated 6-endo-trig cyclization of readily accessible enone-derived α-amino acids has been developed for the direct synthesis of novel 2,6-cis-6- substituted-4-oxo-L-pipecolic acids. A range of aliphatic and aryl side chains were tolerated by this mild procedure to give the target compounds in good overall yields. Molecular modeling of the 6-endo-trig cyclization allowed some insight as to how these compounds were formed, with the enolate intermediate generated via an equilibrium process, followed by irreversible tautomerization/neutralization providing the driving force for product formation. Stereoselective reduction and deprotection of the resulting 2,6-cis-6-substituted 4-oxo-L-pipecolic acids to the corresponding 4-hydroxy-L-pipecolic acids was also performed

Chemical heterogeneity of the Emeishan mantle plume: Evidence from highly siderophile element abundances in picrites

Highly magnesian lavas or picrites have the potential to preserve important information about the origin and thermochemical state of the mantle source(s) of large igneous provinces. We have conducted a comprehensive study of highly siderophile element (HSE) concentrations in picrites from the ca. 260 Ma Emeishan large igneous province. We show that HSE abundances in the Emeishan picrites are greater than those in mid-ocean ridge basalts (MORBs) and parental melts of Hawaiian picrites, but are similar to those in komatiites. The picrites have two types of C1-normalized HSE patterns: (a) type 1, as represented by the Muli picrites is similar to that of the primitive upper mantle; (b) type 2, as represented by the Dali picrites resembles East Greenland and Iceland picrites. Pt/Ir and Pd/Ir ratios in the type 2 picrites are higher than those in type 1 picrites. The primary melt compositions of the studied samples have been estimated by back-addition of equilibrium olivine. The calculated HSE abundances of the parental liquids of the Dali and Muli picrites are higher than those of the parental melts to Hawaiian picrites. Along with previously published isotopic data, our study provides further evidence for chemical heterogeneity of the Emeishan mantle plume

Acute WNT signalling activation perturbs differentiation within the adult stomach and rapidly leads to tumour formation

A role for WNT signalling in gastric carcinogenesis has been suggested due to two major observations. First, patients with germline mutations in adenomatous polyposis coli (APC) are susceptible to stomach polyps and second, in gastric cancer, WNT activation confers a poor prognosis. However, the functional significance of deregulated WNT signalling in gastric homoeostasis and cancer is still unclear. In this study we have addressed this by investigating the immediate effects of WNT signalling activation within the stomach epithelium. We have specifically activated the WNT signalling pathway within the mouse adult gastric epithelium via deletion of either glycogen synthase kinase 3 (GSK3) or APC or via expression of a constitutively active β-catenin protein. WNT pathway deregulation dramatically affects stomach homoeostasis at very short latencies. In the corpus, there is rapid loss of parietal cells with fundic gland polyp (FGP) formation and adenomatous change, which are similar to those observed in familial adenomatous polyposis. In the antrum, adenomas occur from 4 days post-WNT activation. Taken together, these data show a pivotal role for WNT signalling in gastric homoeostasis, FGP formation and adenomagenesis. Loss of the parietal cell population and corresponding FGP formation, an early event in gastric carcinogenesis, as well as antral adenoma formation are immediate effects of nuclear β-catenin translocation and WNT target gene expression. Furthermore, our inducible murine model will permit a better understanding of the molecular changes required to drive tumourigenesis in the stomach

Time- and Dose-Dependent Induction of HSP70 in Lemna minor Exposed to Different Environmental Stressors

The objective of this study was to examine the influence of different stressors, including cadmium (heavy metal), anthracene (polycyclic aromatic hydrocarbon—PAH) and chloridazon (herbicide), on population growth and biosynthesis of cytoplasmic HSP70 in Lemna minor (duckweed) in short (4 h)- and long (7 days)-term tests. A heat shock response was confirmed in Lemna exposed to high temperature: 35, 37.5, 40, or 42.5°C in short-term (4 h) treatments. The chemicals tested stimulated the biosynthesis of the cytoplasmic HSP70 protein in a concentration-dependent way (0.5–5 μM), higher in fronds exposed to lower doses of stressors. Additionally, production of HSP70 was greater after 4 h of incubation than after 7 days. The results suggest that HSP70 could be applied as a non-specific and sensitive detector of stress induced by different chemicals at concentrations below those that produce the type of response observed in classical cytotoxicity tests, such as growth inhibition

Postoperative pain management in children: Guidance from the pain committee of the European Society for Paediatric Anaesthesiology (ESPA Pain Management Ladder Initiative)

The main remit of the European Society for Paediatric Anaesthesiology (ESPA) Pain Committee is to improve the quality of pain management in children. The ESPA Pain Management Ladder is a clinical practice advisory based upon expert consensus to help to ensure a basic standard of perioperative pain management for all children. Further steps are suggested to improve pain management once a basic standard has been achieved. The guidance is grouped by the type of surgical procedure and layered to suggest basic, intermediate, and advanced pain management methods. The committee members are aware that there are marked differences in financial and personal resources in different institutions and countries and also considerable variations in the availability of analgesic drugs across Europe. We recommend that the guidance should be used as a framework to guide best practice

Evaluation of Pyridoacridine Alkaloids in a Zebrafish Phenotypic Assay

Three new minor components, the pyridoacridine alkaloids 1-hydroxy-deoxyamphimedine (1), 3-hydroxy-deoxyamphimedine (2), debromopetrosamine (3), and three known compounds, amphimedine (4), neoamphimedine (5) and deoxyamphimedine (6), have been isolated from the sponge Xestospongia cf. carbonaria, collected in Palau. Structures were assigned on the basis of extensive 1D and 2D NMR studies as well as analysis by HRESIMS. Compounds 1–6 were evaluated in a zebrafish phenotype-based assay. Amphimedine (4) was the only compound that caused a phenotype in zebrafish embryos at 30 μM. No phenotype other than death was observed for compounds 1–3, 5, 6

Dust and molecular shells in asymptotic giant branch stars - Mid-infrared interferometric observations of R Aql, R Aqr, R Hya, W Hya and V Hya

Mid-IR (8 - 13 micron) interferometric data of four oxygen-rich AGB stars (R Aql, R Aqr, R Hya, and W Hya) and one carbon-rich AGB star (V Hya) were obtained with MIDI/VLTI between April 2007 and September 2009. The spectrally dispersed visibility data are analyzed by fitting a circular fully limb-darkened disk (FDD). Results. The FDD diameter as function of wavelength is similar for all oxygen-rich stars. The apparent size is almost constant between 8 and 10 micron and gradually increases at wavelengths longer than 10 micron. The apparent FDD diameter in the carbon-rich star V Hya essentially decreases from 8 to 12 micron. The FDD diameters are about 2.2 times larger than the photospheric diameters estimated from K-band observations found in the literature. The silicate dust shells of R Aql, R Hya and W Hya are located fairly far away from the star, while the silicate dust shell of R Aqr and the amorphous carbon (AMC) and SiC dust shell of V Hya are found to be closer to the star at around 8 photospheric radii. Phase-to-phase variations of the diameters of the oxygen-rich stars could be measured and are on the order of 15% but with large uncertainties. From a comparison of the diameter trend with the trends in RR Sco and S Ori it can be concluded that in oxygen-rich stars the overall larger diameter originates from a warm molecular layer of H2O, and the gradual increase longward of 10 micron can be most likely attributed to the contribution of a close Al2O3 dust shell. The chromatic trend of the Gaussian FWHM in V Hya can be explained with the presence of AMC and SiC dust. The observations suggest that the formation of amorphous Al2O3 in oxygen- rich stars occurs mainly around or after visual minimum. However, no firm conclusions can be drawn concerning the mass-loss mechanism.Comment: 32 pages (including 7 pages appendix), 10 figure