Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of similar to 10(-11) cm(2) s(-1) for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance

Autofluorescence of atmospheric bioaerosols – fluorescent biomolecules and potential interferences

Primary biological aerosol particles (PBAP) are an important subset of air particulate matter with a substantial contribution to the organic aerosol fraction and potentially strong effects on public health and climate. Recent progress has been made in PBAP quantification by utilizing real-time bioaerosol detectors based on the principle that specific organic molecules of biological origin such as proteins, coenzymes, cell wall compounds and pigments exhibit intrinsic fluorescence. The properties of many fluorophores have been well documented, but it is unclear which are most relevant for detection of atmospheric PBAP. The present study provides a systematic synthesis of literature data on potentially relevant biological fluorophores. We analyze and discuss their relative importance for the detection of fluorescent biological aerosol particles (FBAP) by online instrumentation for atmospheric measurements such as the ultraviolet aerodynamic particle sizer (UV-APS) or the wide issue bioaerosol sensor (WIBS). <br><br> In addition, we provide new laboratory measurement data for selected compounds using bench-top fluorescence spectroscopy. Relevant biological materials were chosen for comparison with existing literature data and to fill in gaps of understanding. The excitation-emission matrices (EEM) exhibit pronounced peaks at excitation wavelengths of ~280 nm and ~360 nm, confirming the suitability of light sources used for online detection of FBAP. They also show, however, that valuable information is missed by instruments that do not record full emission spectra at multiple wavelengths of excitation, and co-occurrence of multiple fluorophores within a detected sample will likely confound detailed molecular analysis. Selected non-biological materials were also analyzed to assess their possible influence on FBAP detection and generally exhibit only low levels of background-corrected fluorescent emission. This study strengthens the hypothesis that ambient supermicron particle fluorescence in wavelength ranges used for most FBAP instruments is likely to be dominated by biological material and that such instrumentation is able to discriminate between FBAP and non-biological material in many situations. More detailed follow-up studies on single particle fluorescence are still required to reduce these uncertainties further, however

Relativistic Hartree-Bogoliubov description of ground-state properties of Ni and Sn isotopes

The Relativistic Hartree Bogoliubov (RHB) theory is applied in the description of ground-state properties of Ni and Sn isotopes. The NL3 parameter set is used for the effective mean-field Lagrangian, and pairing correlations are described by the pairing part of the finite range Gogny interaction D1S. Fully self-consistent RHB solutions are calculated for the Ni ($28\leq N\leq 50$) and Sn ($50\leq N\leq 82$) isotopes. Binding energies, neutron separation energies, and proton and neutron $rms$ radii are compared with experimental data. The model predicts a reduction of the spin-orbit potential with the increase of the number of neutrons. The resulting energy splittings between spin-orbit partners are discussed, as well as pairing properties calculated with the finite range effective interaction in the $pp$ channel.Comment: 11 pages, RevTex, 12 p.s figures, submitted to Phys. Rev.

Temperature and humidity dependence of secondary organic aerosol yield from the ozonolysis of ?-pinene

International audienceThe temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of ?-pinene was studied in a flow reactor at 263 K?303 K and 1007 hPa under dry and humid conditions (0% and 26%?68% relative humidity, respectively). The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.18?0.39 at high particle mass concentrations (Mo). Under dry conditions, however, the measurement data exhibited significant oscillatory deviations from the predicted linear increase with inverse temperature (up to 50% at high Mo). Under humid conditions the SOA yield exhibited a linear decrease with inverse temperature, which is opposite to modelled temperature dependence and implies that the model substantially overestimates the yield at low temperatures and underestimates it at high temperatures (deviations up to 80% at high Mo). For the atmospherically relevant concentration level of Mo=10 ?g m?3 and temperature range 263 K?293 K, the results from humid experiments in this study indicate that the SOA yield of ?-pinene ozonolysis may be well represented by an average value of 0.15 with an uncertainty estimate of ±0.05. When fitting the measurement data with a two-product model, both the partitioning coefficients (Kom,i) and the stoichiometric yields (?i) of the low-volatile and semi-volatile model species were found to vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are strongly dependent on temperature and the presence of water vapour. In fact, the oscillatory positive temperature dependence observed under dry conditions and the negative temperature dependence observed under humid conditions indicate that the SOA yield is governed much more by the temperature and humidity dependence of the involved chemical reactions than by vapour pressure temperature dependencies. We suggest that the elucidation and modelling of SOA formation need to take into account the effects of temperature and humidity on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products

Temperature dependence of secondary organic aerosol yield from the ozonolysis of ?-pinene

International audienceThe temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of ?-pinene was studied in a flow reactor at 263?303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22?0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (Kom,i) and the stoichiometric yields (?i) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products

Rural continental aerosol properties and processes observed during the Hohenpeissenberg Aerosol Characterization Experiment (HAZE2002)

International audienceDetailed investigations of the chemical and microphysical properties of rural continental aerosols were performed during the HAZE2002 experiment, which was conducted in May 2002 at the Meteorological Observatory Hohenpeissenberg (DWD) in Southern Germany. Online measurements included: Size-resolved chemical composition of submicron particles; total particle number concentrations and size distributions over the diameter range of 3 nm to 9 ?m; gas-phase concentration of monoterpenes, CO, O3, OH, and H2SO4. Filter sampling and offline analytical techniques were used to determine: Fine particle mass (PM2.5), organic, elemental and total carbon in PM2.5 (OC2.5, EC2.5, TC2.5), and selected organic compounds (dicarboxylic acids, polycyclic aromatic hydrocarbons, proteins). Overall, the non-refractory components of submicron particles detected by aerosol mass spectrometry (PM1, 6.6±5.4 ?g m?3, arithmetic mean and standard deviation) accounted for ~62% of PM2.5 determined by filter gravimetry (10.6±4.7 ?g m?3). The relative proportions of non-refractory submicron particle components were: (23±39)% ammonium nitrate, (27±23)% ammonium sulfate, and (50±40)% organics (OM1). OM1 was closely correlated with PM1 (r2=0.9) indicating a near-constant ratio of non-refractory organics and inorganics. The average ratio of OM1 to OC2.5 was 2.1±1.4, indicating a high proportion of heteroelements in the organic fraction of the sampled rural aerosol. This is consistent with the high ratio of oxygenated organic aerosol (OOA) over hydrocarbon-like organic aerosol (HOA) inferred from the AMS results (4:1), and also with the high abundance of proteins (~3%) indicating a high proportion of primary biological material (~30%) in PM2.5. This finding was confirmed by low abundance of PAHs (?3) and EC (?3) in PM2.5 and detection of several secondary organic aerosol compounds (dicarboxylic acids) and their precursors (monoterpenes). New particle formation was observed almost every day with particle number concentrations exceeding 104 cm?3 (nighttime background level 1000?2000 cm?3). Closer inspection of two major events indicated that the observed nucleation agrees with ternary H2SO4/H2O/NH3 nucleation and that condensation of both organic and inorganic species contributed to particle growth

Convergence rates in expectation for Tikhonov-type regularization of Inverse Problems with Poisson data

In this paper we study a Tikhonov-type method for ill-posed nonlinear operator equations \gdag = F( ag) where \gdag is an integrable, non-negative function. We assume that data are drawn from a Poisson process with density t\gdag where $t>0$ may be interpreted as an exposure time. Such problems occur in many photonic imaging applications including positron emission tomography, confocal fluorescence microscopy, astronomic observations, and phase retrieval problems in optics. Our approach uses a Kullback-Leibler-type data fidelity functional and allows for general convex penalty terms. We prove convergence rates of the expectation of the reconstruction error under a variational source condition as $t\to\infty$ both for an a priori and for a Lepski{\u\i}-type parameter choice rule

Relativistic Hartree-Bogoliubov description of the deformed ground-state proton emitters

Ground-state properties of deformed proton-rich odd-Z nuclei in the region $59 \leq Z \leq 69$ are described in the framework of Relativistic Hartree Bogoliubov (RHB) theory. One-proton separation energies and ground-state quadrupole deformations that result from fully self-consistent microscopic calculations are compared with available experimental data. The model predicts the location of the proton drip-line, the properties of proton emitters beyond the drip-line, and provides information about the deformed single-particle orbitals occupied by the odd valence proton.Comment: 9 pages, RevTeX, 3 PS figures, submitted Phys. Rev. Letter

Proton drip-line nuclei in Relativistic Hartree-Bogoliubov theory

Ground-state properties of spherical even-even nuclei $14\leq Z \leq 28$ and $N=18,20,22$ are described in the framework of Relativistic Hartree Bogoliubov (RHB) theory. The model uses the NL3 effective interaction in the mean-field Lagrangian, and describes pairing correlations by the pairing part of the finite range Gogny interaction D1S. Binding energies, two-proton separation energies, and proton $rms$ radii that result from fully self-consistent RHB solutions are compared with experimental data. The model predicts the location of the proton drip-line. The isospin dependence of the effective spin-orbit potential is discussed, as well as pairing properties that result from the finite range interaction in the $pp$ channel.Comment: 12 pages, RevTex, 10 p.s figures, submitted to Phys. Rev.

Exact, E=0, Solutions for General Power-Law Potentials. I. Classical Orbits

For zero energy, $E=0$, we derive exact, classical solutions for {\em all} power-law potentials, $V(r)=-\gamma/r^\nu$, with $\gamma>0$ and $-\infty <\nu<\infty$. When the angular momentum is non-zero, these solutions lead to the orbits $\r(t)= [\cos \mu (\th(t)-\th_0(t))]^{1/\mu}$, for all $\mu \equiv \nu/2-1 \ne 0$. When $\nu>2$, the orbits are bound and go through the origin. This leads to discrete discontinuities in the functional dependence of $\th(t)$ and $\th_0(t)$, as functions of $t$, as the orbits pass through the origin. We describe a procedure to connect different analytic solutions for successive orbits at the origin. We calculate the periods and precessions of these bound orbits, and graph a number of specific examples. Also, we explain why they all must violate the virial theorem. The unbound orbits are also discussed in detail. This includes the unusual orbits which have finite travel times to infinity and also the special $\nu = 2$ case.Comment: LaTeX, 27 pages with 12 figures available from the authors or can be generated from Mathematica instructions at end of the fil