Calibration of oxygen 1s ionization energies. Accurate energies for CO2, H2O, CO, and O2

Access to accurate reference data is a prerequisite in order to translate chemical shifts to an absolute scale for inner-shell ionization energies. Calibration standards for oxygen 1s (O 1s) ionization energies are less well established than, for instance, for carbon 1s. To improve upon this situation, adiabatic and vertical O 1s ionization energies for gaseous carbon dioxide (CO2) are critically reviewed and used to establish the most accurate values currently available: 541.085(17) and 541.253(17) eV, respectively. Combining these with new precise measurements of shifts in O 1s ionization energies for H2O, CO, and O2 allows us to establish equally accurate absolute ionization energies for these molecules as for CO2. The resulting adiabatic and vertical energies are 539.728(17) and 539.827(17) eV for H2O, 542.439(17) and 542.495(17) eV for CO, 543.285(17) and 543.294(17) eV for O2 (4Σ final state), and 544.338(17) and 544.423(17) eV for O2 (2Σ final state). It is proposed that O 1s in CO2 be adopted as a standard of higher precedence, and that H2O, CO, and O2 be used also. The O 1s ionization energies in these molecules occur in the range 540–543 eV. These proposed standards should provide optimal internal calibration for a wide range of oxygen-containing compounds.publishedVersio

Noble Gases Identify the Mechanisms of Fugitive Gas Contamination in Drinking-Water Wells Overlying the Marcellus and Barnett Shales

Horizontal drilling and hydraulic fracturing have enhanced energy production but raised concerns about drinking-water contamination and other environmental impacts. Identifying the sources and mechanisms of contamination can help improve the environmental and economic sustainability of shale-gas extraction. We analyzed 113 and 20 samples from drinking-water wells overlying the Marcellus and Barnett Shales, respectively, examining hydrocarbon abundance and isotopic compositions (e.g., C2H6/CH4, δ13C-CH4) and providing, to our knowledge, the first comprehensive analyses of noble gases and their isotopes (e.g., 4He, 20Ne, 36Ar) in groundwater near shale-gas wells. We addressed two questions. (i) Are elevated levels of hydrocarbon gases in drinking-water aquifers near gas wells natural or anthropogenic? (ii) If fugitive gas contamination exists, what mechanisms cause it? Against a backdrop of naturally occurring salt- and gas-rich groundwater, we identified eight discrete clusters of fugitive gas contamination, seven in Pennsylvania and one in Texas that showed increased contamination through time. Where fugitive gas contamination occurred, the relative proportions of thermogenic hydrocarbon gas (e.g., CH4, 4He) were significantly higher (P \u3c 0.01) and the proportions of atmospheric gases (air-saturated water; e.g., N2, 36Ar) were significantly lower (P \u3c 0.01) relative to background groundwater. Noble gas isotope and hydrocarbon data link four contamination clusters to gas leakage from intermediate-depth strata through failures of annulus cement, three to target production gases that seem to implicate faulty production casings, and one to an underground gas well failure. Noble gas data appear to rule out gas contamination by upward migration from depth through overlying geological strata triggered by horizontal drilling or hydraulic fracturing

Tubulin Polymerization Promoting Protein Affects the Circadian Timing System in C57Bl/6 Mice

The circadian timing system (CTS) is a complex set of cyclic cellular mechanisms which serve to synchronize discrete cell groups across multiple organ systems to adapt the body’s physiology to a (roughly) 24-hour clock. Many genes and hormones have been shown to be strongly associated with the CTS, some of which include the genes 'Bmal1, Period1, Period2, Cryptochrome1', and 'Cryptochrome2', and the hormone melatonin. Previous data suggest that microtubule dynamics play an important role in melatonin function as it relates to the CTS in vitro, though this relationship has never been explored in vivo. The purpose of this study was to determine whether disruption of microtubule regulation in C57Bl/6 mice results in measurable changes to the CTS. To study the potential effects of microtubule dynamics on the CTS in vivo, we utilized a mouse model of microtubule instability, knocked out for the tubulin polymerization promoting protein gene ('Tppp' -/-), comparing them to their wild type (WT) littermates in three categories: locomotor activity (in light/dark and dark/dark photoperiods), serial clock gene expression, and serial serum melatonin concentration. These comparisons showed differences in all three categories, including significant differences in locomotor characteristics under dark/dark conditions. Our findings support and extend previous reports that microtubule dynamics are a modulator of circadian rhythm regulation likely through a mechanism involving melatonin induced phase shifting

The Campo de Calatrava Volcanic Field (central Spain): Fluid geochemistry in a CO2-rich area.

The Campo de Calatrava Volcanic Field (CCVF) located in central-southern Spain (along with Selva-Emporda in Catalonia, NE Spain) is regarded as one of the most important CO emitting zones in Peninsular Spain. Here, we report and evaluate new molecular and isotopic geochemistry of thermal waters and COrich gas discharges from the CCVF. Locally, these CO-rich fluid emissions represent the remnants of the past volcanic activity that affected this area from the late Miocene through the Quaternary, with the most recent events occurring in the Holocene. The locations of discharging fluids and previous volcanic centers appear to be aligned along well-defined NW-SE and NNW-SSE lineaments, with subordinate trends in the ENE-WSW direction. The chemical and isotopic composition of the thermal waters suggests a meteoric origin, dominated by three distinct geochemical facies: 1) HCO-Mg(Ca) type waters, associated with a relatively shallow aquifer and related to the interaction of meteoric waters with CO-rich gases, alkaline volcanic products, and sedimentary formations, 2) SO(Cl)-Ca(Mg) type waters, which stems from the two rivers (Guadiana and Jabalón) that drain Triassic evaporitic rocks before entering the study area, and 3) HCO-Na type waters, hosted in deep geopressurized CO-rich reservoirs within the Ordovician basement rocks. The Sr/Sr isotopic compositions (ranging between 0.70415 and 0.71623) and δS-SO values (+10.7 to +18.3‰ vs. CDT) of CO-rich fluids are consistent with interactions between water and either the Paleozoic basement, Triassic evaporites, Quaternary volcanic rocks, or a combination thereof. Dissolution of a CO-rich gas phase into the aquifer produces low pH values (down to 5.4) and enhances water-rock interactions causing relatively high salinity (Total Ionic Salinity: up to ∼185 meq/L). Carbon dioxide is by far the most abundant gas constituent (up to 992 mmol/mol) and is dominated by mantle-derived sources as indicated by the combination of relatively high helium isotopic ratios (up to 2.7 R/Ra), high isotopic ratios of carbon in CO (ranging between −6.8 and −3.2‰ V-PDB), and the carbon isotopic signature of TDIC (from −6.8 to +2.2‰ vs. VPDB). In the last two decades, numerous (CO-rich) gas blowouts have occurred in the area during well drillings, suggesting the presence of a geopressurized gas reservoir at relatively shallow depth.The Municipality of Almagro is gratefully acknowledged for the help provided during the sampling activities. We would like to thank Dr. Luis Perez del Villar for his help during the first sampling fieldwork at CCVF. We wish to thank D. Melero Cabañas who accompanied us in the field to collect the water samples during the first survey. Many thanks are also due to the personnel of Amphos21 (J. Bruno, A. Cedez, F. Grandia) and Ciudad de la Energia (D. Angel) and F. Capecchiacci (Dept. Earth Science of Florence) for their help during the second survey. We would like to acknowledge the comments and suggestions provided by two reviewers, who greatly improved an early version of the manuscript. This work was partially funded by Ciudad de la Energia (Resp. OV; Grant contract: ALM-08-006) and the Laboratory of Stable Isotopes and Fluid Geochemistry of the Department of Earth Sciences (University of Florence)

Epidemiology of injuries from fire, heat and hot substances: global, regional and national morbidity and mortality estimates from the Global Burden of Disease 2017 study

Background Past research has shown how fires, heat and hot substances are important causes of health loss globally. Detailed estimates of the morbidity and mortality from these injuries could help drive preventative measures and improved access to care. Methods We used the Global Burden of Disease 2017 framework to produce three main results. First, we produced results on incidence, prevalence, years lived with disability, deaths, years of life lost and disability-adjusted life years from 1990 to 2017 for 195 countries and territories. Second, we analysed these results to measure mortality-to-incidence ratios by location. Third, we reported the measures above in terms of the cause of fire, heat and hot substances and the types of bodily injuries that result. Results Globally, there were 8 991 468 (7 481 218 to 10 740 897) new fire, heat and hot substance injuries in 2017 with 120 632 (101 630 to 129 383) deaths. At the global level, the age-standardised mortality caused by fire, heat and hot substances significantly declined from 1990 to 2017, but regionally there was variability in age-standardised incidence with some regions experiencing an increase (eg, Southern Latin America) and others experiencing a significant decrease (eg, High-income North America). Conclusions The incidence and mortality of injuries that result from fire, heat and hot substances affect every region of the world but are most concentrated in middle and lower income areas. More resources should be invested in measuring these injuries as well as in improving infrastructure, advancing safety measures and ensuring access to care. This is an open access article distributed in accordance with the Creative Commons Attribution 4.0 Unported (CC BY 4.0) license, which permits others to copy, redistribute, remix, transform and build upon this work for any purpose, provided the original work is properly cited, a link to the licence is given, and indication of whether changes were made

Electronic Properties of Chlorine, Methyl, and Chloromethyl as Substituents to the Ethylene Group-Viewed from the Core of Carbon

“Substituent effects” is an important and useful concept in organic chemistry. Although there are many approaches to parametrizing the electronic and steric effects of substituents, the physical basis for the parameters is often unclear. The purpose of the present work is to explore the properties of chemical shifts in carbon 1s energies as a well-defined basis for characterizing substituents to an ethylene C═C moiety. To this end, high-resolution carbon 1s photoelectron spectra of six chloro-substituted ethenes and seven chloro-substituted propenes have been measured in the gas phase. Site-specific adiabatic ionization energies have been determined from the spectra using theoretical ab initio calculations to predict the vibrational structures. For two molecules, 3-chloropropene and 2,3-dichloropropene, the spectral analyses give quantitative results for the conformer populations. The observed shifts have been analyzed in terms of initial-state (potential) and relaxation effects, and charge relaxation has also been analyzed by means of natural resonance theory. On the basis of core-level spectroscopy and models, chlorine, methyl, and chloromethyl have been characterized in terms of their effect on the carbon to which they are attached (α site) as well as the neighboring sp² carbon (β site). The derived spectroscopic substituent parameters are characterized by both inductive (electronegativity) effects and the ability of each substituent to engage in electron delocalization via the π system. Moreover, the adopted approach is extended to include substituent–substituent interaction parameters

Cytotoxic polyfunctionality maturation of cytomegalovirus-pp65-specific CD4 + and CD8 + T-cell responses in older adults positively correlates with response size

Cytomegalovirus (CMV) infection is one of the most common persistent viral infections in humans worldwide and is epidemiologically associated with many adverse health consequences during aging. Previous studies yielded conflicting results regarding whether large, CMV-specific T-cell expansions maintain their function during human aging. In the current study, we examined the in vitro CMV-pp65-reactive T-cell response by comprehensively studying five effector functions (i.e., interleukin-2, tumor necrosis factor-α, interferon-γ, perforin, and CD107a expression) in 76 seropositive individuals aged 70 years or older. Two data-driven, polyfunctionality panels (IL-2-associated and cytotoxicity-associated) derived from effector function co-expression patterns were used to analyze the results. We found that, CMV-pp65-reactive CD8 + and CD4 + T cells contained similar polyfunctional subsets, and the level of polyfunctionality was related to the size of antigen-specific response. In both CD8 + and CD4 + cells, polyfunctional cells with high cytotoxic potential accounted for a larger proportion of the total response as the total response size increased. Notably, a higher serum CMV-IgG level was positively associated with a larger T-cell response size and a higher level of cytotoxic polyfunctionality. These findings indicate that CMV-pp65-specific CD4 + and CD8 + T cell undergo simultaneous cytotoxic polyfunctionality maturation during aging

T Cells Specific for a Mycobacterial Glycolipid Expand after Intravenous Bacillus Calmette-Guérin Vaccination

Intradermal vaccination with Mycobacterium bovis bacillus Calmette-Guérin (BCG) protects infants from disseminated tuberculosis, and i.v. BCG protects nonhuman primates (NHP) against pulmonary and extrapulmonary tuberculosis. In humans and NHP, protection is thought to be mediated by T cells, which typically recognize bacterial peptide Ags bound to MHC proteins. However, during vertebrate evolution, T cells acquired the capacity to recognize lipid Ags bound to CD1a, CD1b, and CD1c proteins expressed on APCs. It is unknown whether BCG induces T cell immunity to mycobacterial lipids and whether CD1-restricted T cells are resident in the lung. In this study, we developed and validated Macaca mulatta (Mamu) CD1b and CD1c tetramers to probe ex vivo phenotypes and functions of T cells specific for glucose monomycolate (GMM), an immunodominant mycobacterial lipid Ag. We discovered that CD1b and CD1c present GMM to T cells in both humans and NHP. We show that GMM-specific T cells are expanded in rhesus macaque blood 4 wk after i.v. BCG, which has been shown to protect NHP with near-sterilizing efficacy upon M. tuberculosis challenge. After vaccination, these T cells are detected at high frequency within bronchoalveolar fluid and express CD69 and CD103, markers associated with resident memory T cells. Thus, our data expand the repertoire of T cells known to be induced by whole cell mycobacterial vaccines, such as BCG, and show that lipid Ag-specific T cells are resident in the lungs, where they may contribute to protective immunity