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Particle mass yield in secondary organic aerosol formed by the dark ozonolysis of α-pinene

The yield of particle mass in secondary organic aerosol (SOA) formed by dark ozonolysis was measured for 0.3–22.8 ppbv of reacted α-pinene. Most experiments were conducted using a continuous-flow chamber, allowing nearly constant SOA concentration and chemical composition for several days. For comparison, some experiments were also conducted in batch mode. Reaction conditions were 25°C, 40% RH, dry (NH4)SO4 seed particles, and excess 1-butanol. The organic particle loading was independently measured by an aerosol mass spectrometer and a scanning mobility particle sizer, and the two measurements agreed well. The observations showed that SOA formation occurred for even the lowest reacted α-pinene concentration of 0.3 ppbv. The particle mass yield was 0.09 at 0.15 μg m−3, increasing to 0.27 at 40 μg m−3. Compared to some results reported in the literature, the yields were 80 to 100% larger for loadings above 2 μg m−3. At lower loadings, the yields had an offset of approximately +0.07 from those reported in the literature. To as low as 0.15 μm−3, the yield curve had no inflection point toward null yield, implying the formation of one or several products having vapor pressures below this value. These observations of increased yields, especially for low loadings, are potentially important for accurate prediction by chemical transport models of organic particle concentrations in the ambient atmosphere.
Summertime stratospheric processes at northern mid-latitudes: comparisons between MANTRA balloon measurements and the Canadian Middle Atmosphere Model

In this paper we report on a study conducted using the Middle Atmospheric Nitrogen TRend Assessment (MANTRA) balloon measurements of stratospheric constituents and temperature and the Canadian Middle Atmosphere Model (CMAM). Three different kinds of data are used to assess the inter-consistency of the combined dataset: single profiles of long-lived species from MANTRA 1998, sparse climatologies from the ozonesonde measurements during the four MANTRA campaigns and from HALOE satellite measurements, and the CMAM climatology. In doing so, we evaluate the ability of the model to reproduce the measured fields and to thereby test our ability to describe mid-latitude summertime stratospheric processes. The MANTRA campaigns were conducted at Vanscoy, Saskatchewan, Canada (52° N, 107° W) in late August and early September of 1998, 2000, 2002 and 2004. During late summer at mid-latitudes, the stratosphere is close to photochemical control, providing an ideal scenario for the study reported here. From this analysis we find that: (1) reducing the value for the vertical diffusion coefficient in CMAM to a more physically reasonable value results in the model better reproducing the measured profiles of long-lived species; (2) the existence of compact correlations among the constituents, as expected from independent measurements in the literature and from models, confirms the self-consistency of the MANTRA measurements; and (3) the 1998 measurements show structures in the chemical species profiles that can be associated with transport, adding to the growing evidence that the summertime stratosphere can be much more disturbed than anticipated. The mechanisms responsible for such disturbances need to be understood in order to assess the representativeness of the measurements and to isolate long-term trends.
Global anthropogenic aerosol effects on convective clouds in ECHAM5-HAM

Aerosols affect the climate system by changing cloud characteristics in many ways. They act as cloud condensation and ice nuclei and may have an influence on the hydrological cycle. Here we investigate aerosol effects on convective clouds by extending the double-moment cloud microphysics scheme developed for stratiform clouds, which is coupled to the HAM double-moment aerosol scheme, to convective clouds in the ECHAM5 general circulation model. This enables us to investigate whether more, and smaller cloud droplets suppress the warm rain formation in the lower parts of convective clouds and thus release more latent heat upon freezing, which would then result in more vigorous convection and more precipitation. In ECHAM5, including aerosol effects in large-scale and convective clouds (simulation ECHAM5-conv) reduces the sensitivity of the liquid water path increase with increasing aerosol optical depth in better agreement with observations and large-eddy simulation studies. In simulation ECHAM5-conv with increases in greenhouse gas and aerosol emissions since pre-industrial times, the geographical distribution of the changes in precipitation better matches the observed increase in precipitation than neglecting microphysics in convective clouds. In this simulation the convective precipitation increases the most suggesting that the convection has indeed become more vigorous.
Air pollution during the 2003 European heat wave as seen by MOZAIC airliners

This study presents an analysis of both MOZAIC profiles above Frankfurt and Lagrangian dispersion model simulations for the 2003 European heat wave. The comparison of MOZAIC measurements in summer 2003 with the 11-year MOZAIC climatology reflects strong temperature anomalies (exceeding 4°C) throughout the lower troposphere. Higher positive anomalies of temperature and negative anomalies of both wind speed and relative humidity are found for the period defined here as the heat wave (2–14 August 2003), compared to the periods before (16–31 July 2003) and after (16–31 August 2003) the heat wave. In addition, Lagrangian model simulations in backward mode indicate the suppressed long-range transport in the mid- to lower troposphere and the enhanced southern origin of air masses for all tropospheric levels during the heat wave. Ozone and carbon monoxide also present strong anomalies (both ~+40 ppbv) during the heat wave, with a maximum vertical extension reaching 6 km altitude around 11 August 2003. Pollution in the planetary boundary layer (PBL) is enhanced during the day, with ozone mixing ratios two times higher than climatological values. This is due to a combination of factors, such as high temperature and radiation, stagnation of air masses and weak dry deposition, which favour the accumulation of ozone precursors and the build-up of ozone. A negligible role of a stratospheric-origin ozone tracer has been found for the lower troposphere in this study. From 29 July to 15 August 2003 forest fires burnt around 0.3×106 ha in Portugal and added to atmospheric pollution in Europe. Layers with enhanced CO and NOy mixing ratios, advected from Portugal, were crossed by the MOZAIC aircraft in the free troposphere over Frankfurt. A series of forward and backward Lagrangian model simulations have been performed to investigate the origin of anomalies during the whole heat wave. European anthropogenic emissions present the strongest contribution to the measured CO levels in the lower troposphere (near 30%). This source is followed by Portuguese forest fires which affect the lower troposphere after 6 August 2003 and even the PBL around 10 August 2003. The averaged biomass burning contribution reaches 35% during the affected period. Anthropogenic CO of North American origin only marginally influences CO levels over Europe during that period.
MIPAS: an instrument for atmospheric and climate research

MIPAS, the Michelson Interferometer for Passive Atmospheric Sounding, is a mid-infrared emission spectrometer which is part of the core payload of ENVISAT. It is a limb sounder, i.e. it scans across the horizon detecting atmospheric spectral radiances which are inverted to vertical temperature, trace species and cloud distributions. These data can be used for scientific investigations in various research fields including dynamics and chemistry in the altitude region between upper troposphere and lower thermosphere. The instrument is a well calibrated and characterized Fourier transform spectrometer which is able to detect many trace constituents simultaneously. The different concepts of retrieval methods are described including multi-target and two-dimensional retrievals. Operationally generated data sets consist of temperature, H2O, O3, CH4, N2O, HNO3, and NO2 profiles. Measurement errors are investigated in detail and random and systematic errors are specified. The results are validated by independent instrumentation which has been operated at ground stations or aboard balloon gondolas and aircraft. Intercomparisons of MIPAS measurements with other satellite data have been carried out, too. As a result, it has been proven that the MIPAS data are of good quality. MIPAS can be operated in different measurement modes in order to optimize the scientific output. Due to the wealth of information in the MIPAS spectra, many scientific results have already been published. They include intercomparisons of temperature distributions with ECMWF data, the derivation of the whole NOy family, the study of atmospheric processes during the Antarctic vortex split in September~2002, the determination of properties of Polar Stratospheric Clouds, the downward transport of NOx in the middle atmosphere, the stratosphere-troposphere exchange, the influence of solar variability on the middle atmosphere, and the observation of Non-LTE effects in the mesosphere.
The chemistry influencing ODEs in the Polar Boundary Layer in spring: a model study

Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic cycles involving reactive halogens are now recognized to be of main importance for Ozone Depletion Events (ODEs) in the Polar Boundary Layer (PBL). We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br2, BrCl, or Cl2 to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H2O2, DMS, Cl2, C2H4, C2H6, HONO, NO2, and RONO2 was investigated. Cases with elevated mixing ratios of HCHO, H2O2, DMS, Cl2, and HONO induced a shift in bromine speciation from Br/BrO to HOBr/HBr, while high mixing ratios of C2H6 induced a shift from HOBr/HBr to Br/BrO. Cases with elevated mixing ratios of HONO, NO2, and RONO2 induced a shift to BrNO2/BrONO2. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). These shifts to HOBr/HBr also hindered the BrO self-reaction. In these cases, the ozone depletion was slowed down, where increases in H2O2 and HONO had the greatest effect. The tests with increased mixing ratios of C2H4 highlighted the decrease in HOx which reduced the production of HOBr from bromine radicals. In addition, the direct reaction of C2H4 with bromine atoms led to less available reactive bromine. The aerosol debromination was therefore strongly reduced. Ozone levels were highly affected by the chemistry of C2H4. Cl2-induced ozone depletions were found unrealistic compared to field measurements due to the rapid production of CH3O2, HOx, and ROOH which rapidly convert reactive chlorine to HCl in a "chlorine counter-cycle". This counter-cycle efficiently reduces the concentration of reactive halogens in the boundary layer. Depending on the relative bromine and chlorine mixing ratios, the production of CH3O2, HOx, and ROOH from the counter-cycle can significantly affect the bromine chemistry. Therefore, the presence of both bromine and chlorine in the air may unexpectedly lead to a slow down in ozone destruction. For all NOy species studied (HONO, NO2, RONO2) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NOx. The production of HNO3 led to the acid displacement of HCl, and the release of chlorine out of salt aerosols (Cl2 or BrCl) increased.
Technical Note: Intercomparison of formaldehyde measurements at the atmosphere simulation chamber SAPHIR

The atmosphere simulation chamber SAPHIR at the Research Centre Jülich was used to test the suitability of state-of-the-art analytical instruments for the measurement of gas-phase formaldehyde (HCHO) in air. Five analyzers based on four different sensing principles were deployed: a differential optical absorption spectrometer (DOAS), cartridges for 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by off-line high pressure liquid chromatography (HPLC) analysis, two different types of commercially available wet chemical sensors based on Hantzsch fluorimetry, and a proton-transfer-reaction mass spectrometer (PTR-MS). A new optimized mode of operation was used for the PTR-MS instrument which significantly enhanced its performance for online HCHO detection at low absolute humidities. The instruments were challenged with typical ambient levels of HCHO ranging from zero to several ppb. Synthetic air of high purity and particulate-filtered ambient air were used as sample matrices in the atmosphere simulation chamber onto which HCHO was spiked under varying levels of humidity and ozone. Measurements were compared to mixing ratios calculated from the chamber volume and the known amount of HCHO injected into the chamber; measurements were also compared between the different instruments. The formal and blind intercomparison exercise was conducted under the control of an independent referee. A number of analytical problems associated with the experimental set-up and with individual instruments were identified, the overall agreement between the methods was fair.
Technical Note: Continuity of MIPAS-ENVISAT operational ozone data quality from full- to reduced-spectral-resolution operation mode

MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) is operating on the ENVIronmental SATellite (ENVISAT) since March 2002. After two years of nearly continuous limb scanning measurements, at the end of March 2004, the instrument was stopped due to problems with the mirror drive of the interferometer. Operations with reduced maximum path difference, corresponding to both a reduced-spectral-resolution and a shorter measurement time, were resumed on January 2005. In order to exploit the reduction in measurement time, the measurement scenario was changed adopting a finer vertical limb scanning. The change of spectral resolution and of measurement scenario entailed an update of the data processing strategy. The aim of this paper is the assessment of the differences in the quality of the MIPAS ozone data acquired before and after the stop of the operations. Two sets of MIPAS ozone profiles acquired in 2003–2004 (full-resolution measurements) and in 2005–2006 (reduced-resolution measurements) are compared with collocated ozone profiles obtained by GOMOS (Global Ozone Monitoring by Occultation of Stars), itself also onboard ENVISAT. The continuity of the GOMOS data quality allows to assess a possible discontinuity of the MIPAS performances. The relative bias and precision of MIPAS ozone profiles with respect to the GOMOS ones have been compared for the measurements acquired before and after the stop of the MIPAS operations. The results of the comparison show that, in general, the quality of the MIPAS ozone profiles retrieved from reduced-resolution measurements is comparable or better than that obtained from the full-resolution dataset. The only significant change in MIPAS performances is observed at pressures around 2 hPa, where the relative bias of the instruments increases by a factor of 2 from the 2003–2004 to 2005–2006 measurements.
Evaluation of the tropospheric flows to a major Southern Hemisphere stratospheric warming event using NCEP/NCAR Reanalysis data with a PSU/NCAR nudging MM5V3 model

Previous studies of the exceptional 2002 Southern Hemisphere (SH) stratospheric warming event lead to some uncertainty, namely the question of whether excessive heat fluxes in the upper troposphere and lower stratosphere are a symptom or cause of the 2002 SH warming event. In this work, we use a hemispheric version of the MM5 model with nudging capability and we devised a novel approach to separately test the significance of the stratosphere and troposphere for this year. We paired the flow conditions from 2002 in the stratosphere and troposphere, respectively, against the conditions in 1998 (a year with displaced polar vortex) and in 1948 (a year with strong polar vortex that coincided with the geographical South Pole). Our experiments show that the flow conditions from below determine the stratospheric flow features over the polar region. Regardless of the initial stratospheric conditions in 1998 or 1948, when we simulated these past stratospheres with the troposphere/lower stratosphere conditions constrained to 2002 levels, the simulated middle stratospheres resemble those observed in 2002 stratosphere over the polar region. On the other hand, when the 2002 stratosphere was integrated with the troposphere/lower stratosphere conductions constrained to 1948 and 1998, respectively, the simulated middle stratospheric conditions over the polar region shift toward those of 1948 and 1998. Thus, our experiments further support the wave-forcing theory as the cause of the 2002 SH warming event.
The Comparative Reactivity Method – a new tool to measure total OH Reactivity in ambient air

Hydroxyl (OH) radicals play a vital role in maintaining the oxidizing capacity of the atmosphere. To understand variations in OH radicals both source and sink terms must be understood. Currently the overall sink term, or the total atmospheric reactivity to OH, is poorly constrained. Here, we present a new on-line method to directly measure the total OH reactivity (i.e.~total loss rate of OH radicals) in a sampled air mass. In this method, a reactive molecule (X), not normally present in air, is passed through a glass reactor and its concentration is monitored with a suitable detector. OH radicals are then introduced in the glass reactor at a constant rate to react with X, first in the presence of zero air and then in the presence of ambient air containing VOCs and other OH reactive species. Comparing the amount of X exiting the reactor with and without the ambient air allows the air reactivity to be determined. In our existing set up, X is pyrrole and the detector used is a proton transfer reaction mass spectrometer. The present dynamic range for ambient air reactivity is about 6 to 300 s−1, with an overall maximum uncertainty of 25% above 8 s−1 and up to 50% between 6–8 s−1. The system has been tested and calibrated with different single and mixed hydrocarbon standards showing excellent linearity and accountability with the reactivity of the standards. Potential interferences such as high NO in ambient air, varying relative humidity and photolysis of pyrrole within the setup have also been investigated. While interferences due changing humidity and photolysis of pyrrole are easily overcome by ensuring that humidity in the set up does not change drastically and the photolytic loss of pyrrole is measured and taken into account, respectively, NO>10 ppb in ambient air remains a significant interference for the current configuration of the instrument. Field tests in the tropical rainforest of Suriname (~53 s<sup-1) and the urban atmosphere of Mainz (~10 s-1) Germany, show the promise of the new method and indicate that a significant fraction of OH reactive species in the tropical forests is likely missed by current measurements. Suggestions for improvements to the technique and future applications are discussed.