Observed NO/NO2 Ratios in the Upper Troposphere Imply Errors in NO-NO2-O3 Cycling Kinetics or an Unaccounted NOx Reservoir

Observations from the SEAC4RS aircraft campaign over the southeast United States in August-September 2013 show NO/NO2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NOx reservoir species, presumably organic, decomposing thermally to NO2 in the instrument. The NO2 instrument corrects for this artifact from known labile HNO4 and CH3O2NO2 NOx reservoirs. To bridge the gap between measured and simulated NO2, additional unaccounted labile NOx reservoir species would have to be present at a mean concentration of ~40 ppt for the SEAC4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low-temperature rate constant for the NO + O3 reaction (30% 1-σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO2 photolysis (20% 1-σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO2 columns

Observed NO/NO_2 Ratios in the Upper Troposphere Imply Errors in NO-NO_2-O_3 Cycling Kinetics or an Unaccounted NO_x Reservoir

Observations from the SEAC^4RS aircraft campaign over the southeast United States in August–September 2013 show NO/NO_2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NO_x reservoir species, presumably organic, decomposing thermally to NO_2 in the instrument. The NO_2 instrument corrects for this artifact from known labile HNO_4 and CH_3O_2NO_2 NO_x reservoirs. To bridge the gap between measured and simulated NO_2, additional unaccounted labile NO_x reservoir species would have to be present at a mean concentration of ~40 ppt for the SEAC^4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low‐temperature rate constant for the NO + O_3 reaction (30% 1‐σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO_2 photolysis (20% 1‐σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO_2 columns

Cellular and developmental control of O2 homeostasis by hypoxia-inducible factor 1 alpha.

Hypoxia is an essential developmental and physiological stimulus that plays a key role in the pathophysiology of cancer, heart attack, stroke, and other major causes of mortality. Hypoxia-inducible factor 1 (HIF-1) is the only known mammalian transcription factor expressed uniquely in response to physiologically relevant levels of hypoxia. We now report that in Hif1a-/- embryonic stem cells that did not express the O2-regulated HIF-1alpha subunit, levels of mRNAs encoding glucose transporters and glycolytic enzymes were reduced, and cellular proliferation was impaired. Vascular endothelial growth factor mRNA expression was also markedly decreased in hypoxic Hif1a-/- embryonic stem cells and cystic embryoid bodies. Complete deficiency of HIF-1alpha resulted in developmental arrest and lethality by E11 of Hif1a-/- embryos that manifested neural tube defects, cardiovascular malformations, and marked cell death within the cephalic mesenchyme. In Hif1a+/+ embryos, HIF-1alpha expression increased between E8.5 and E9.5, coincident with the onset of developmental defects and cell death in Hif1a-/- embryos. These results demonstrate that HIF-1alpha is a master regulator of cellular and developmental O2 homeostasis

Why do models overestimate surface ozone in the Southeast United States

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx  ≡  NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°  ×  0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer

Expression of the RNA helicase DDX3 and the hypoxia response in breast cancer

<p>Aims: DDX3 is an RNA helicase that has antiapoptotic properties, and promotes proliferation and transformation. In addition, DDX3 was shown to be a direct downstream target of HIF-1α (the master regulatory of the hypoxia response) in breast cancer cell lines. However, the relation between DDX3 and hypoxia has not been addressed in human tumors. In this paper, we studied the relation between DDX3 and the hypoxic responsive proteins in human breast cancer.</p> <p>Methods and Results: DDX3 expression was investigated by immunohistochemistry in breast cancer in comparison with hypoxia related proteins HIF-1α, GLUT1, CAIX, EGFR, HER2, Akt1, FOXO4, p53, ERα, COMMD1, FER kinase, PIN1, E-cadherin, p21, p27, Transferrin receptor, FOXO3A, c-Met and Notch1. DDX3 was overexpressed in 127 of 366 breast cancer patients, and was correlated with overexpression of HIF-1α and its downstream genes CAIX and GLUT1. Moreover, DDX3 expression correlated with hypoxia-related proteins EGFR, HER2, FOXO4, ERα and c-Met in a HIF-1α dependent fashion, and with COMMD1, FER kinase, Akt1, E-cadherin, TfR and FOXO3A independent of HIF-1α.</p> <p>Conclusions: In invasive breast cancer, expression of DDX3 was correlated with overexpression of HIF-1α and many other hypoxia related proteins, pointing to a distinct role for DDX3 under hypoxic conditions and supporting the oncogenic role of DDX3 which could have clinical implication for current development of DDX3 inhibitors.</p&gt

Retrieval of atmospheric CO2 vertical profiles from ground-based near-infrared spectra

We evaluate vertical profile retrievals of CO2 from 0.02&thinsp;cm&minus;1 resolution ground-based near-infrared solar absorption spectra with the GFIT2 algorithm, using improved spectroscopic line lists and line shapes. With these improvements, CO2 profiles were obtained from sequential retrievals in five spectral windows with different vertical sensitivities using synthetic and real spectra. A sensitivity study using synthetic spectra shows that the leading source of uncertainty in the retrieved CO2 profiles is the error in the a priori temperature profile, even with 3-hourly reanalysis a priori profiles. A 2&thinsp;∘C error in the temperature profile in the lower troposphere between 0.6 and 0.85&thinsp;atm causes deviations in the retrieved CO2 profiles that are larger than the typical vertical variations of CO2. To distinguish the effect of errors in the a priori meteorology and trace gas concentration profiles from those in the instrument alignment and spectroscopic parameters, we retrieve CO2 profiles from atmospheric spectra while using an a priori profile built from coincident AirCore, radiosonde, and surface in situ measurements at the Lamont, Oklahoma (USA), Total Carbon Column Observing Network station. In those cases, the deviations in retrieved CO2 profiles are also larger than typical vertical variations of CO2, suggesting that remaining errors in the forward model limit the accuracy of the retrieved profiles. Implementing a temperature retrieval or correction and quantifying and modeling an imperfect instrument alignment are critical to improve CO2 profile retrievals. Without significant advances in modeling imperfect instrument alignment, and improvements in the accuracy of the temperature profile, the CO2 profile retrieval with GFIT2 presents no clear advantage over scaling retrievals for the purpose of ascertaining the total column. &nbsp;</p

Lightning NO_x Emissions: Reconciling Measured and Modeled Estimates With Updated NO_x Chemistry

Lightning is one of the most important sources of upper tropospheric NO_x; however, there is a large spread in estimates of the global emission rates (2–8 Tg N yr^(−1)). We combine upper tropospheric in situ observations from the Deep Convective Clouds and Chemistry (DC3) experiment and global satellite-retrieved NO_2 tropospheric column densities to constrain mean lightning NO_x (LNO_x) emissions per flash. Insights from DC3 indicate that the NO_x lifetime is ~3 h in the region of outflow of thunderstorms, mainly due to production of methyl peroxy nitrate and alkyl and multifunctional nitrates. The lifetime then increases farther downwind from the region of outflow. Reinterpreting previous analyses using the 3 h lifetime reduces the spread among various methods that have been used to calculate mean LNO_x emissions per flash and indicates a global LNO_x emission rate of ~9 Tg N yr^(−1), a flux larger than the high end of recent estimates

Why do models overestimate surface ozone in the Southeast United States?

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx  ≡  NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°  ×  0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer

Observed NO/NO_2 Ratios in the Upper Troposphere Imply Errors in NO-NO_2-O_3 Cycling Kinetics or an Unaccounted NO_x Reservoir

Observations from the SEAC^4RS aircraft campaign over the southeast United States in August–September 2013 show NO/NO_2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NO_x reservoir species, presumably organic, decomposing thermally to NO_2 in the instrument. The NO_2 instrument corrects for this artifact from known labile HNO_4 and CH_3O_2NO_2 NO_x reservoirs. To bridge the gap between measured and simulated NO_2, additional unaccounted labile NO_x reservoir species would have to be present at a mean concentration of ~40 ppt for the SEAC^4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low‐temperature rate constant for the NO + O_3 reaction (30% 1‐σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO_2 photolysis (20% 1‐σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO_2 columns