Effects of various meteorological conditions and spatial emissionresolutions on the ozone concentration and ROG/NO_x limitationin the Milan area (I)

The three-dimensional photochemical model UAM-V is used to investigate the effects of various meteorological conditions and of the coarseness of emission inventories on the ozone concentration and ROG/NO_x limitation of the ozone production in the Po Basin in the northern part of Italy. As a base case, the high ozone episode with up to 200ppb on 13 May 1998 was modelled and previously thoroughly evaluated with measurements gained during a large field experiment. Systematic variations in meteorology are applied to mixing height, air temperature, specific humidity and wind speed. Three coarser emission inventories are obtained by resampling from 3x3km² up to 54x54km² emission grids. The model results show that changes in meteorological input files strongly influence ozone in this area. For instance, temperature changes peak ozone by 10.1ppb/&degC and the ozone concentrations in Milan by 2.8ppb/&degC. The net ozone formation in northern Italy is more strongly temperature than humidity dependent, while the humidity is very important for the ROG/NO_x limitation of the ozone production. For all meteorological changes (e.g. doubling the mixing height), the modelled peak ozone remains ROG limited. A strong change towards NO_x sensitivity in the ROG limited areas is only found if much coarser emission inventories were applied. Increasing ROG limited areas with increasing wind speed are found, because the ROG limited ozone chemistry induced by point sources is spread over a larger area. Simulations without point sources tend to increase the NO_x limited areas

A Quantitative Comparison of SMC, LMC, and Milky Way UV to NIR Extinction Curves

We present an exhaustive, quantitative comparison of all of the known extinction curves in the Small and Large Magellanic Clouds (SMC and LMC) with our understanding of the general behavior of Milky Way extinction curves. The R_V dependent CCM relationship and the sample of extinction curves used to derive this relationship is used to describe the general behavior of Milky Way extinction curves. The ultraviolet portion of the SMC and LMC extinction curves are derived from archival IUE data, except for one new SMC extinction curve which was measured using HST/STIS observations. The optical extinction curves are derived from new (for the SMC) and literature UBVRI photometry (for the LMC). The near-infrared extinction curves are calculated mainly from 2MASS photometry supplemented with DENIS and new JHK photometry. For each extinction curve, we give R_V = A(V)/E(B-V) and N(HI) values which probe the same dust column as the extinction curve. We compare the properties of the SMC and LMC extinction curves with the CCM relationship three different ways: each curve by itself, the behavior of extinction at different wavelengths with R_V, and behavior of the extinction curve FM fit parameters with R_V. As has been found previously, we find that a small number of LMC extinction curves are consistent with the CCM relationship, but majority of the LMC and all of the SMC curves do not follow the CCM relationship. For the first time, we find that the CCM relationship seems to form a bound on the properties of all of the LMC and SMC extinction curves. This result strengthens the picture of dust extinction curves exhibit a continuum of properties between those found in the Milky Way and the SMC Bar. (abridged)Comment: 18 pages, 10 figures, ApJ in pres

Measurement of the ambient organic aerosol volatility distribution: application during the Finokalia Aerosol Measurement Experiment (FAME-2008)

A variable residence time thermodenuder (TD) was combined with an Aerodyne Aerosol Mass Spectrometer (AMS) and a Scanning Mobility Particle Sizer (SMPS) to measure the volatility distribution of aged organic aerosol in the Eastern Mediterranean during the Finokalia Aerosol Measurement Experiment in May of 2008 (FAME-2008). A new method for the quantification of the organic aerosol volatility distribution was developed combining measurements of all three instruments together with an aerosol dynamics model. <br><br> Challenges in the interpretation of ambient thermodenuder-AMS measurements include the potential resistances to mass transfer during particle evaporation, the effects of particle size on the evaporated mass fraction, the changes in the AMS collection efficiency and particle density as the particles evaporate partially in the TD, and finally potential losses inside the TD. Our proposed measurement and data analysis method accounts for all of these problems combining the AMS and SMPS measurements. <br><br> The AMS collection efficiency of the aerosol that passed through the TD was found to be approximately 10% lower than the collection efficiency of the aerosol that passed through the bypass. The organic aerosol measured at Finokalia is approximately 2 or more orders of magnitude less volatile than fresh laboratory-generated monoterpene (α-pinene, β-pinene and limonene under low NO<sub>x</sub> conditions) secondary organic aerosol. This low volatility is consistent with its highly oxygenated AMS mass spectrum. The results are found to be highly sensitive to the mass accommodation coefficient of the evaporating species. This analysis is based on the assumption that there were no significant reactions taking place inside the thermodenuder

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed

Aged organic aerosol in the Eastern Mediterranean: the Finokalia Aerosol Measurement Experiment – 2008

Aged organic aerosol (OA) was measured at a remote coastal site on the island of Crete, Greece during the Finokalia Aerosol Measurement Experiment-2008 (FAME-2008), which was part of the EUCAARI intensive campaign of May 2008. The site at Finokalia is influenced by air masses from different source regions, including long-range transport of pollution from continental Europe. A quadrupole aerosol mass spectrometer (Q-AMS) was employed to measure the size-resolved chemical composition of non-refractory submicron aerosol (NR-PM<sub>1</sub>), and to estimate the extent of oxidation of the organic aerosol. Factor analysis was used to gain insights into the processes and sources affecting the OA composition. The particles were internally mixed and liquid. The largest fraction of the dry NR-PM<sub>1</sub> sampled was ammonium sulfate and ammonium bisulfate, followed by organics and a small amount of nitrate. The variability in OA composition could be explained with two factors of oxygenated organic aerosol (OOA) with differing extents of oxidation but similar volatility. Hydrocarbon-like organic aerosol (HOA) was not detected. There was no statistically significant diurnal variation in the bulk composition of NR-PM<sub>1</sub> such as total sulfate or total organic aerosol concentrations. However, the OA composition exhibited statistically significant diurnal variation with more oxidized OA in the afternoon. The organic aerosol was highly oxidized, regardless of the source region. Total OA concentrations also varied little with source region, suggesting that local sources had only a small effect on OA concentrations measured at Finokalia. The aerosol was transported for about one day before arriving at the site, corresponding to an OH exposure of approximately 4×10<sup>11</sup> molecules cm<sup>−3</sup> s. The constant extent of oxidation suggests that atmospheric aging results in a highly oxidized OA at these OH exposures, regardless of the aerosol source

Near-Infrared Spectroscopy of Powerful Radio Galaxies at z=2.2-2.4

Near-infrared spectroscopy (rest-frame 3700-6800 Angstroms) of eight high redshift powerful radio galaxies (HzPRGs) at z = 2.2-2.6 is presented. Strong forbidden lines and H-alpha emission were detected in all sources; the data show evidence that the emission lines of the HzPRGs may contribute a substantial fraction (approx. 25-98%) of their total observed H - and/or K -band light. Diagnostic emission-line ratios for three of the eight HzPRGs are consistent with the presence of a Seyfert 2 nucleus; the [O III] 5007 / H-beta and [S II] 6716, 6731 / H-alpha ratios and/or limits of the remaining five galaxies are inconclusive. Furthermore, all six of the galaxies for which both H - and K -band spectra were obtained have observed [O III] 5007 / (H-alpha +[N II] 6548, 6583) ratios consistent with Seyfert 2 ionization...Comment: LaTex, 39 pages with 9 postscript figures and 2 gif figures, ApJ accepte

Spectropolarimetry of 3CR 68.1: A Highly Inclined Quasar

We present Keck spectropolarimetry of the highly polarized radio-loud quasar 3CR 68.1 (z=1.228, V=19). The polarization increases from 5 in the red (4000 A rest-frame) to >10% in the blue (1900 A rest-frame). The broad emission lines are polarized the same as the continuum, which shows that 3CR 68.1 is not a blazar as it has sometimes been regarded in the past. We also present measurements of the emission lines and a strong, blueshifted, associated absorption line system, as well as a detection at the emission-line redshift of Ca II K absorption, presumably from stars in the host galaxy. 3CR 68.1 belongs to an observationally rare class of highly polarized quasars that are neither blazars nor partially obscured radio-quiet QSOs. Taking into account 3CR 68.1's other unusual properties, such as its extremely red spectral energy distribution and its extreme lobe dominance, we explain our spectropolarimetric results in terms of unified models. We argue that we have a dusty, highly inclined view of 3CR 68.1, with reddened scattered (polarized) quasar light diluted by even more dust-reddened quasar light reaching us directly from the nucleus.Comment: 20 pages, includes 3 tables, 6 figures. Accepted by Ap

A Substantial Population of Red Galaxies at z > 2: Modeling of the Spectral Energy Distributions of an Extended Sample

We investigate the nature of the substantial population of high-z galaxies with Js-Ks>2.3 discovered as part of our FIRES survey. This colour cut efficiently isolates z>2 galaxies with red rest-frame optical colors ("Distant Red Galaxies" or DRGs). We select objects in the 2.5'x2.5' HDF-South (HDF-S) and 5'x5' field around the MS1054-03 cluster; the surface densities at Ks<21 are 1.6+-0.6 and 1.0+-0.2 arcmin^-2. We discuss the 34 DRGs at 2<z<3.5: 11 at Ks<22.5 in HDF-S and 23 at Ks<21.7 in the MS1054-03 field. We analyze the SEDs constructed from our deep near-infrared (NIR) and optical imaging from the ESO VLT and HST. We develop diagnostics involving I-Js, Js-H, and H-Ks to argue that the red NIR colors of DRGs cannot be attributed solely to extinction and require for many an evolved stellar population with prominent Balmer/4000A break. In the rest-frame, the optical colours of DRGs fall within the envelope of normal nearby galaxies and the UV colours suggest a wide range in star formation activity and/or extinction. This contrasts with the much bluer and more uniform SEDs of Lyman break galaxies (LBGs). From evolutionary synthesis models with constant star formation, solar metallicity, Salpeter IMF, and Calzetti et al. extinction law, we derive for the HDF-S (MS1054-03 field) DRGs median ages of 1.7(2.0) Gyr, A_V = 2.7(2.4) mag, stellar masses 0.8(1.6)x10^11 Msun, M/L_V = 1.2(2.3) Msun/LVsun, and SFR = 120(170) Msun/yr. Models assuming declining SFRs with e-folding timescales of 10Myr-1Gyr generally imply younger ages, lower A_V's and SFRs, but similar stellar masses within a factor of two. Compared to LBGs at similar redshifts and rest-frame L_V's, DRGs are older, more massive, and more obscured for any given star formation history. [ABRIDGED]Comment: Accepted for publication in the Astrophysical Journal. 27 pages, 14 b/w figure

Characterizing the impact of urban emissions on regional aerosol particles: airborne measurements during the MEGAPOLI experiment

The MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) experiment took place in July 2009. The aim of this campaign was to study the aging and reactions of aerosol and gas-phase emissions in the city of Paris. Three ground-based measurement sites and several mobile platforms including instrument equipped vehicles and the ATR-42 aircraft were involved. We present here the variations in particle- and gas-phase species over the city of Paris, using a combination of high-time resolution measurements aboard the ATR-42 aircraft. Particle chemical composition was measured using a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), giving detailed information on the non-refractory submicron aerosol species. The mass concentration of black carbon (BC), measured by a particle absorption soot photometer (PSAP), was used as a marker to identify the urban pollution plume boundaries. Aerosol mass concentrations and composition were affected by air-mass history, with air masses that spent longest time over land having highest fractions of organic aerosol and higher total mass concentrations. The Paris plume is mainly composed of organic aerosol (OA), BC, and nitrate aerosol, as well as high concentrations of anthropogenic gas-phase species such as toluene, benzene, and NO_x. Using BC and CO as tracers for air-mass dilution, we observe the ratio of ΔOA / ΔBC and ΔOA / ΔCO increase with increasing photochemical age (−log(NO_x / NO_y)). Plotting the equivalent ratios of different organic aerosol species (LV-OOA, SV-OOA, and HOA) illustrate that the increase in OA is a result of secondary organic aerosol (SOA) formation. Within Paris the changes in the ΔOA / &Delta;CO are similar to those observed during other studies in London, Mexico City, and in New England, USA. Using the measured SOA volatile organic compounds (VOCs) species together with organic aerosol formation yields, we were able to predict ~50% of the measured organics. These airborne measurements during the MEGAPOLI experiment show that urban emissions contribute to the formation of OA and have an impact on aerosol composition on a regional scale