Eddy covariance measurements and parameterisation of traffic related particle emissions in an urban environment

Urban aerosol sources are important due to the health effects of particles and their potential impact on climate. Our aim has been to quantify and parameterise the urban aerosol source number flux <i>F</i> (particles m^&minus;2 s^&minus;1), in order to help improve how this source is represented in air quality and climate models. We applied an aerosol eddy covariance flux system 118.0 m above the city of Stockholm. This allowed us to measure the aerosol number flux for particles with diameters >11 nm. Upward source fluxes dominated completely over deposition fluxes in the collected dataset. Therefore, the measured fluxes were regarded as a good approximation of the aerosol surface sources. Upward fluxes were parameterised using a traffic activity (<I>TA</I>) database, which is based on traffic intensity measurements. <P style='line-height: 20px;'> The footprint (area on the surface from which sources and sinks affect flux measurements, located at one point in space) of the eddy system covered road and building construction areas, forests and residential areas, as well as roads with high traffic density and smaller streets. We found pronounced diurnal cycles in the particle flux data, which were well correlated with the diurnal cycles in traffic activities, strongly supporting the conclusion that the major part of the aerosol fluxes was due to traffic emissions. <P style='line-height: 20px;'> The emission factor for the fleet mix in the measurement area <I>EF</I>_<i>fm</i>=1.4&plusmn;0.1&times;10¹⁴ veh^&minus;1 km^&minus;1 was deduced. This agrees fairly well with other studies, although this study has an advantage of representing the actual effective emission from a mixed vehicle fleet. Emission from other sources, not traffic related, account for a <I>F</I>₀=15&plusmn;18&times;10⁶ m^&minus;2 s^&minus;1. The urban aerosol source flux can then be written as <I>F=EF</I>_<i>fm</i><I>TA+F</I>₀. In a second attempt to find a parameterisation, the friction velocity <i>U</i>_* normalised with the average friction velocity <!-- MATH $overline{U_ast}$ --> <IMG WIDTH='21' HEIGHT='36' ALIGN='MIDDLE' BORDER='0' src='http://www.atmos-chem-phys.net/6/769/2006/acp-6-769-img15.gif' ALT='$overline{U_ast}$'> has been included, <I>F=EF</I><!-- MATH $_{fm }TAleft({frac{U_ast }{overline{U_ast}}} ight)^{0.4}{+}F_{0}$ --> <IMG WIDTH='136' HEIGHT='51' ALIGN='MIDDLE' BORDER='0' src='http://www.atmos-chem-phys.net/6/769/2006/acp-6-769-img16.gif' ALT='$_{fm }TAleft({frac{U_ast }{overline{U_ast}}}right)^{0.4}{+}F_{0}$'>. This parameterisation results in a somewhat reduced emission factor, 1.3&times;10¹⁴ veh^&minus;1 km^&minus;1. When multiple linear regression have been used, two emission factors are found, one for light duty vehicles <I>EF</I>_LDV=0.3&plusmn;0.3&times;10¹⁴ veh^&minus;1 km^&minus;1 and one for heavy-duty vehicles, <I>EF</I>_HDV=19.8&plusmn;4.0&times;10¹⁴ veh^&minus;1 km^&minus;1, and <i>F</I>₀=19&plusmn;16&times;10⁶ m^&minus;2 s^&minus;1. The results show that during weekdays ~70&ndash;80% of the emissions came from HDV

Depletion of density of states near Fermi energy induced by disorder and electron correlation in alloys

We have performed high resolution photoemission study of substitutionally disordered alloys Cu-Pt, Cu-Pd, Cu-Ni, and Pd-Pt. The ratios between alloy spectra and pure metal spectra are found to have dips at the Fermi level when the residual resistivity is high and when rather strong repulsive electron-electron interaction is expected. This is in accordance with Altshuler and Aronov's model which predicts depletion of density of states at the Fermi level when both disorder and electron correlation are present.Comment: 1 tex file and 4 ps file

Eddy covariance measurements and parameterisation of traffic related particle emissions in an urban environment

International audienceUrban aerosol sources are important due to the health effects of particles and their potential impact on climate. Our aim has been to quantify and parameterise the urban aerosol source number flux F (particles m-2 s-1), in order to help improve how this source is represented in air quality and climate models. We applied an aerosol eddy covariance flux system 118.0 m above the city of Stockholm. This allowed us to measure the aerosol number flux for particles with diameters >11 nm. Upward source fluxes dominated completely over deposition fluxes in the collected dataset. Therefore, the measured fluxes were regarded as a good approximation of the aerosol surface sources. Upward fluxes were parameterised using a traffic activity (TA) database, which is based on traffic intensity measurement. The footprint (area on the surface from which sources and sinks affect flux measurements, located at one point in space) of the eddy system covered road and building construction areas, forests and residential areas, as well as roads with high traffic density and smaller streets. We found pronounced diurnal cycles in the particle flux data, which were well correlated with the diurnal cycles in traffic activities, strongly supporting the conclusion that the major part of the aerosol fluxes was due to traffic emissions. The emission factor for the fleet mix in the measurement area EFfm=1.4±0.1×1014 veh-1 km-1 was deduced. This agrees fairly well with other studies, although this study has an advantage of representing the actual effective emission from a mixed vehicle fleet. Emission from other sources, not traffic related, account for a F0=14±18×106 m-2 s-1. The urban aerosol source flux can then be written as F=EFfmTA+F0. In a second attempt to find a parameterisation, the friction velocity U* normalised with the average friction velocity has been included, F=EF. This parameterisation results in a somewhat reduced emission factor, 1.3×1014 veh-1 km-1. When multiple linear regression have been used, two emission factors are found, one for light duty vehicles EFLDV=0.3±0.3×1014 veh-1 km-1 and one for heavy-duty vehicles, EFHDV=19.8±4.0×1014 veh-1 km-1, and F0=18±16×106 m-2 s-1. The results show that during weekdays ~70?80% of the emissions came from HDV

Resonant Auger spectroscopy at the L2,3 shake-up thresholds as a probe of electron correlation effects in nickel

The excitation energy dependence of the three-hole satellites in the L3-M4,5M4,5 and L2-M4,5M4,5 Auger spectra of nickel metal has been measured using synchrotron radiation. The satellite behavior in the non-radiative emission spectra at the L3 and L2 thresholds is compared and the influence of the Coster-Kronig channel explored. The three-hole satellite intensity at the L3 Auger emission line reveals a peak structure at 5 eV above the L3 threshold attributed to resonant processes at the 2p53d9 shake-up threshold. This is discussed in connection with the 6-eV feature in the x-ray absorption spectrum.Comment: 8 pages, 4 figures; http://prb.aps.org/abstract/PRB/v58/i7/p3677_

Isotope shift in the electron affinity of chlorine

The specific mass shift in the electron affinity between ^{35}Cl and ^{37}Cl has been determined by tunable laser photodetachment spectroscopy to be -0.51(14) GHz. The isotope shift was observed as a difference in the onset of the photodetachment process for the two isotopes. In addition, the electron affinity of Cl was found to be 29138.59(22) cm^{-1}, giving a factor of 2 improvement in the accuracy over earlier measurements. Many-body calculations including lowest-order correlation effects demonstrates the sensitivity of the specific mass shift and show that the inclusion of higher-order correlation effects would be necessary for a quantitative description.Comment: 16 pages, 6 figures, LaTeX2e, amsmat

Primary marine aerosol emissions: size resolved eddy covariance measurements with estimates of the sea salt and organic carbon fractions

International audiencePrimary marine aerosol fluxes were measured using eddy covariance (EC), a condensation particle counter (CPC) and an optical particle counter (OPC) with a heated inlet. The later was used to discriminate between sea salt and total aerosol. Measurements were made from the 25 m tower at the research station Mace Head at the Irish west coast, May to September 2002. The aerosol fluxes were dominated by upward fluxes, sea spray from bubble bursting at the ocean surface. The sea salt aerosol number emissions increased two orders of magnitude with declining diameter from 1 to 0.1 ?m where it peaked at values of 105 to 107 particles m?2s?1. The sea salt emissions increased at all sizes in the wind range 4 to 22 ms?1, in consistency with a power function of the wind speed. The sea salt emission data were compared to three recent sub micrometer sea salt source parameterisations. The best agreement was with Mårtensson et al. (2003), which appear to apply from 0.1 to 1.1 ?m diameters in temperate water (12°C) as well as tropical water (25°C). The total aerosol emissions were independent of the wind speed below 10 ms?1, but increased with the wind above 10 ms?1. The aerosol volume emissions were larger for the total aerosol than for the sea salt at all wind speeds, while the sea salt number emissions approached the total number emissions at 15 ms?1. It is speculated that this is caused by organic carbon in the surface water that is depleted at high wind speeds. The data are consistent with an internal aerosol mixture of sea salt, organic carbon and water. Using the aerosol model by Ellison et al. (1999) (a mono-layer of organic carbon surrounding a water-sea-salt brine) we show that the total and sea salt aerosol emissions are consistent. This predict that the organic carbon fraction increase with decreasing diameter from a few % at 1 ?m over 50% at about 0.5 ?m to about 90% at 0.1 ?m, in consistency with simultaneous chemical data by Cavalli et al. (2004). The combined models of Mårtensson et al. (2003) and Ellison et al. (1999) reproduce the observed total aerosol emissions and offer an approach to model the organic sea spray fraction

Exploring Biorthonormal Transformations of Pair-Correlation Functions in Atomic Structure Variational Calculations

Multiconfiguration expansions frequently target valence correlation and correlation between valence electrons and the outermost core electrons. Correlation within the core is often neglected. A large orbital basis is needed to saturate both the valence and core-valence correlation effects. This in turn leads to huge numbers of CSFs, many of which are unimportant. To avoid the problems inherent to the use of a single common orthonormal orbital basis for all correlation effects in the MCHF method, we propose to optimize independent MCHF pair-correlation functions (PCFs), bringing their own orthonormal one-electron basis. Each PCF is generated by allowing single- and double- excitations from a multireference (MR) function. This computational scheme has the advantage of using targeted and optimally localized orbital sets for each PCF. These pair-correlation functions are coupled together and with each component of the MR space through a low dimension generalized eigenvalue problem. Nonorthogonal orbital sets being involved, the interaction and overlap matrices are built using biorthonormal transformation of the coupled basis sets followed by a counter-transformation of the PCF expansions. Applied to the ground state of beryllium, the new method gives total energies that are lower than the ones from traditional CAS-MCHF calculations using large orbital active sets. It is fair to say that we now have the possibility to account for, in a balanced way, correlation deep down in the atomic core in variational calculations

Isotope shift calculations for atoms with one valence electron

This work presents a method for the ab initio calculation of isotope shift in atoms and ions with one valence electron above closed shells. As a zero approximation we use relativistic Hartree-Fock and then calculate correlation corrections. The main motivation for developing the method comes from the need to analyse whether different isotope abundances in early universe can contribute to the observed anomalies in quasar absorption spectra. The current best explanation for these anomalies is the assumption that the fine structure constant, alpha, was smaller at early epoch. We test the isotope shift method by comparing the calculated and experimental isotope shift for the alkali and alkali-like atoms Na, MgII, K, CaII and BaII. The agreement is found to be good. We then calculate the isotope shift for some astronomically relevant transitions in SiII and SiIV, MgII, ZnII and GeII.Comment: 11 page

Temporal trends of molecular markers associated with artemether- lumefantrine tolerance/resistance in Bagamoyo district, Tanzania

Background: Development and spread of Plasmodium falciparum resistance to artemisinin-based combination therapy (ACT) constitutes a major threat to recent global malaria control achievements. Surveillance of molecular markers could act as an early warning system of ACT-resistance before clinical treatment failures are apparent. The aim of this study was to analyse temporal trends of established genotypes associated with artemether-lumefantrine tolerance/resistance before and after its deployment as first-line treatment for uncomplicated malaria in Tanzania 2006. Methods: Single nucleotide polymorphisms in the P. falciparum multidrug resistance gene 1 (pfmdr1) N86Y, Y184F, D1246Y and P. falciparum chloroquine transporter gene (pfcrt) K76T were analysed from dried blood spots collected during six consecutive studies from children with uncomplicated P. falciparum malaria in Fukayosi village, Bagamoyo District, Tanzania, between 2004-2011. Results: There was a statistically significant yearly increase of pfmdr1 N86, 184F, D1246 and pfcrt K76 between 2006-2011 from 14% to 61% (yearly OR = 1.38 [95% CI 1.25-1.52] p \u3c 0.0001), 14% to 35% (OR = 1.17 [95% CI 1.07-1.30] p = 0.001), 54% to 85% (OR = 1.21 [95% CI 1.03-1.42] p = 0.016) and 49% to 85% (OR = 1.33 [95% CI 1.17-1.51] p \u3c 0.0001), respectively. Unlike for the pfmdr1 SNP, a significant increase of pfcrt K76 was observed already between 2004-2006, from 26% to 49% (OR = 1.68 [95% CI 1.17-2.40] p = 0.005). From 2006 to 2011 the pfmdr1 NFD haplotype increased from 10% to 37% (OR = 1.25 [95% CI 1.12-1.39] p \u3c 0.0001), whereas the YYY haplotype decreased from 31% to 6% (OR = 0.73 [95% CI 0.56-0.98] p = 0.018). All 390 successfully analysed samples had one copy of the pfmdr1 gene. Conclusion: The temporal selection of molecular markers associated with artemether-lumefantrine tolerance/resistance may represent an early warning sign of impaired future drug efficacy. This calls for stringent surveillance of artemether-lumefantrine efficacy in Tanzania and emphasizes the importance of molecular surveillance as a complement to standard in vivo trials. © 2013 Malmberg et al.; licensee BioMed Central Ltd

High accuracy calculation of 6s -> 7s parity nonconserving amplitude in Cs

We calculated the parity nonconserving (PNC) 6s -> 7s amplitude in Cs. In the Dirac-Coulomb approximation our result is in a good agreement with other calculations. Breit corrections to the PNC amplitude and to the Stark-induced amplitude $\beta$ are found to be -0.4% and -1% respectively. The weak charge of $^{133}$Cs is $Q_W=-72.5 \pm 0.7$ in agreement with the standard model.Comment: 4 pages, LaTeX2e, uses revtex4.cls, submitted to PR