Development of the adjoint of GEOS-Chem

We present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate – ammonium – nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The adjoint model is extensively validated by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances; most sets of comparisons have a nearly 1:1 correlation and R2>0.9. We explore the robustness of these results, noting how insufficient observations or nonlinearities in the advection routine can degrade the adjoint model performance. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework through a series of tests using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors

Inverse modeling and mapping US air quality influences of inorganic PM_(2.5) precursor emissions using the adjoint of GEOS-Chem

Influences of specific sources of inorganic PM_(2.5) on peak and ambient aerosol concentrations in the US are evaluated using a combination of inverse modeling and sensitivity analysis. First, sulfate and nitrate aerosol measurements from the IMPROVE network are assimilated using the four-dimensional variational (4D-Var) method into the GEOS-Chem chemical transport model in order to constrain emissions estimates in four separate month-long inversions (one per season). Of the precursor emissions, these observations primarily constrain ammonia (NH_3). While the net result is a decrease in estimated US~NH_3 emissions relative to the original inventory, there is considerable variability in adjustments made to NH_3 emissions in different locations, seasons and source sectors, such as focused decreases in the midwest during July, broad decreases throughout the US~in January, increases in eastern coastal areas in April, and an effective redistribution of emissions from natural to anthropogenic sources. Implementing these constrained emissions, the adjoint model is applied to quantify the influences of emissions on representative PM_(2.5) air quality metrics within the US. The resulting sensitivity maps display a wide range of spatial, sectoral and seasonal variability in the susceptibility of the air quality metrics to absolute emissions changes and the effectiveness of incremental emissions controls of specific source sectors. NH_3 emissions near sources of sulfur oxides (SO_x) are estimated to most influence peak inorganic PM_(2.5) levels in the East; thus, the most effective controls of NH_3 emissions are often disjoint from locations of peak NH_3 emissions. Controls of emissions from industrial sectors of SO_x and NO_x are estimated to be more effective than surface emissions, and changes to NH_3 emissions in regions dominated by natural sources are disproportionately more effective than regions dominated by anthropogenic sources. NOx controls are most effective in northern states in October; in January, SO_x controls may be counterproductive. When considering ambient inorganic PM_(2.5) concentrations, intercontinental influences are small, though transboundary influences within North America are significant, with SO_x emissions from surface sources in Mexico contributing almost a fourth of the total influence from this sector

Impact of the isoprene photochemical cascade on tropical ozone

Tropical tropospheric ozone affects Earth's radiative forcing and the oxidative capacity of the atmosphere. Considerable work has been devoted to the study of the processes controlling its budget. Yet, large discrepancies between simulated and observed tropical tropospheric ozone remain. Here, we characterize some of the mechanisms by which the photochemistry of isoprene impacts the budget of tropical ozone. At the regional scale, we use forward sensitivity simulation to explore the sensitivity to the representation of isoprene nitrates. We find that isoprene nitrates can account for up to 70% of the local NO_x = NO+NO_2 sink. The resulting modulation of ozone can be well characterized by their net modulation of NO_x. We use adjoint sensitivity simulations to demonstrate that the oxidation of isoprene can affect ozone outside of continental regions through the transport of NO_x over near-shore regions (e.g., South Atlantic) and the oxidation of isoprene outside of the boundary layer far from its emissions regions. The latter mechanism is promoted by the simulated low boundary-layer oxidative conditions. In our simulation, ~20% of the isoprene is oxidized above the boundary layer in the tropics. Changes in the interplay between regional and global effect are discussed in light of the forecasted increase in anthropogenic emissions in tropical regions

Testing normality in any dimension by Fourier methods in a multivariate Stein equation

We study a novel class of affine-invariant and consistent tests for multivariate normality. The tests are based on a characterization of the standard d-variate normal distribution by way of the unique solution of an initial value problem connected to a partial differential equation, which is motivated by a multivariate Stein equation. The test criterion is a suitably weighted L2-statistic. We derive the limit distribution of the test statistic under the null hypothesis as well as under contiguous and fixed alternatives to normality. A consistent estimator of the limiting variance under fixed alternatives, as well as an asymptotic confidence interval of the distance of an underlying alternative with respect to the multivariate normal law, is derived. In simulation studies, we show that the tests are strong in comparison with prominent competitors and that the empirical coverage rate of the asymptotic confidence interval converges to the nominal level. We present a real data example and also outline topics for further research

Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs low-yield pathways

Formation of SOA from the aromatic species toluene, xylene, and, for the first time, benzene, is added to a global chemical transport model. A simple mechanism is presented that accounts for competition between low and high-yield pathways of SOA formation, wherein secondary gas-phase products react further with either nitrogen oxide (NO) or hydroperoxy radical (HO2) to yield semi- or non-volatile products, respectively. Aromatic species yield more SOA when they react with OH in regions where the [NO]/[HO2] ratios are lower. The SOA yield thus depends upon the distribution of aromatic emissions, with biomass burning emissions being in areas with lower [NO]/[HO2] ratios, and the reactivity of the aromatic with respect to OH, as a lower initial reactivity allows transport away from industrial source regions, where [NO]/[HO2] ratios are higher, to more remote regions, where this ratio is lower and, hence, the ultimate yield of SOA is higher. As a result, benzene is estimated to be the most important aromatic species with regards to formation of SOA, with a total production nearly equal that of toluene and xylene combined. In total, while only 39% percent of the aromatic species react via the low-NOx pathway, 72% of the aromatic SOA is formed via this mechanism. Predicted SOA concentrations from aromatics in the Eastern United States and Eastern Europe are actually largest during the summer, when the [NO]/[HO2] ratio is lower. Global production of SOA from aromatic sources is estimated at 3.5 Tg/yr, resulting in a global burden of 0.08 Tg, twice as large as previous estimates. The contribution of these largely anthropogenic sources to global SOA is still small relative to biogenic sources, which are estimated to comprise 90% of the global SOA burden, about half of which comes from isoprene. Compared to recent observations, it would appear there are additional pathways beyond those accounted for here for production of anthropogenic SOA. However, owing to differences in spatial distributions of sources and seasons of peak production, there are still regions in which aromatic SOA produced via the mechanisms identified here are predicted to contribute substantially to, and even dominate, the local SOA concentrations, such as outflow regions from North America and South East Asia during the wintertime, though total SOA concentrations there are small (~0.1 μg/m^³)

X-ray monitoring of classical novae in the central region of M31. III. Autumn and winter 2009/10, 2010/11 and 2011/12

[Abridged] Classical novae (CNe) represent the major class of supersoft X-ray sources (SSSs) in the central region of our neighbouring galaxy M31. We performed a dedicated monitoring of the M31 central region, aimed to detect SSS counterparts of CNe, with XMM-Newton and Chandra between Nov and Mar of the years 2009/10, 2010/11 and 2011/12. In total we detected 24 novae in X-rays. Seven of these sources were known from previous observations, including the M31 nova with the longest SSS phase, M31N~1996-08b, which was found to fade below our X-ray detection limit 13.8 yr after outburst. Of the new discoveries several novae exhibit significant variability in their short-term X-ray light curves with one object showing a suspected period of about 1.3 h. We studied the SSS state of the most recent outburst of a recurrent nova which had previously shown the shortest time ever observed between two outbursts (about 5 yr). The total number of M31 novae with X-ray counterpart was increased to 79 and we subjected this extended catalogue to detailed statistical studies. Four previously indicated correlations between optical and X-ray parameters could be confirmed and improved. We found indications that the multi-dimensional parameter space of nova properties might be dominated by a single physical parameter. We discuss evidence for a different X-ray behaviour of novae in the M31 bulge and disk. Exploration of the multi-wavelength parameter space of optical and X-ray measurements is shown to be a powerful tool for examining properties of extragalactic nova populations. While there are hints that the different stellar populations of M31 (bulge vs disk) produce dissimilar nova outbursts, there is also growing evidence that the overall behaviour of an average nova might be understood in surprisingly simple terms.Comment: 39 pages (half of them for 9 tables), 14 figures, accepted for publication in A&A; updated after language editing stag

Development of the adjoint of GEOS-Chem

International audienceWe present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate ? ammonium ? nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The accuracy of the adjoint model is extensively verified by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances. We explore the robustness of these results, noting how discontinuities in the advection routine hinder, but do not entirely preclude, the use of such comparisons for validation of the adjoint model. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors

Intraossäre Infusion: Eine wichtige Technik auch für die Kinderanästhesie

Zusammenfassung: Die zeitgerechte Etablierung eines venösen Zugangs kann insbesondere bei Säuglingen und Kleinkindern eine große Herausforderung sein. Hier hat sich die intraossäre Infusionstechnik seit den 1940er Jahren als schnelle, effiziente und sichere Alternativmethode zur Schaffung eines Gefäßzugangs bewährt, um einem vitalgefährdeten Kind dringend benötigte Medikamente und Flüssigkeiten zu applizieren. Während in den internationalen Leitlinien zur pädiatrischen Notfallmedizin der intraossären Infusion eine hohe Priorität eingeräumt wird, greifen die meisten Anästhesisten nur sehr zögerlich auf diese langjährig bewährte Punktionstechnik zurück. Die vorliegende Arbeit beschreibt die intraossäre Infusionstechnik, stellt zwei unterschiedliche Kanülierungssysteme vor und diskutiert, basierend auf den aktuellen notfallmedizinischen Leitlinien sowie anhand von eigenen Fallbeispielen, potenzielle Indikationen für die Kinderanästhesie. Demnach sollten insbesondere akut vital-gefährdete Kinder mit Kreislaufstillstand, Laryngospasmus, akuter Atemwegsblutung, hypovolämischem Schock oder Hypothermie bei ausgedehnten Verbrennungen ohne liegenden bzw. rasch anzulegenden venösen Zugang mit einer intraossären Kanüle versorgt werden. Inwieweit die intraossäre Infusion auch beim nichtakut vital-gefährdeten Kind mit schwierigem oder unmöglichem peripheren Venenzugang in der Anästhesie überbrückend und zeitlich begrenzt eingesetzt werden sollte, wird die zukünftige Diskussion zeigen. Die erfolgreiche Anwendung der intraossären Infusionstechnik in der Kinderanästhesie verlangt die unmittelbare Verfügbarkeit der entsprechenden Ausrüstung, die umfassende Schulung und das regelmäßige Training sowie eine klare Regelung für ihre Anwendung innerhalb der Anästhesieabteilun

CXOM31 J004253.1+411422: The first ultra-luminous X-ray transient in M 31

We seek clarification of the nature of X-ray sources detected in M 31. Here we focus on CXOM31 J004253.1+411422, the brightness of which suggests that it belongs to the class of ultraluminous X-ray sources. We determine the X-ray properties of sources detected in the XMM-Newton Chandra monitoring program. We investigate spectral properties and search for periodic or quasi-periodic oscillations. A multi-component model is applied to the spectra obtained from XMM-Newton data to evaluate the relative contributions from thermal and non-thermal emission. The time dependence of this ratio is evaluated over a period of forty days. We simultaneously fit data from XMM-Newton EPIC-pn, MOS1 and MOS2 detectors with (non-thermal) powerlaw and (thermal) multicolored blackbody. The X-ray spectrum is best fit by the combination of a thermal component with kT ~ 1 keV and a powerlaw component with photon index approximately 2.6. From combined analysis of Chandra, Swift and XMM-Newton data, the unabsorbed total luminosity of this source decreases from ~ 3.8 x 10^{39} erg s^{-1} in the first observation to ~ 0.5 x 10^{39} ergs s^{-1} over a period of three months. The decay closely follows an exponential decline with a time constant of 32 days. The source spectrum evolves significantly, exhibiting a faster decline of the thermal component. We do not find evidence of any significant temporal features in the power density spectrum. The presence of a thermal component at kT ~ 1 keV in conjunction with a non-thermal high energy tail, is also consistent with spectral properties of other ULXs in the "high state". Our analysis indicates that the underlying source of this first ULX in M~31 is a black hole of mass, M > 13 M_{sun}, accreting near the Eddington limit, that underwent a transient outburst followed by an exponential decay reminiscent of transients associated with galactic X-ray novae.Comment: Accepted by Astronomy and Astrophysics. 6 pages, 8 figure