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A new mechanism to simulate the formation of secondary organic aerosols (SOA) from reactive primary hydrocarbons is presented, together with comparisons with experimental smog chamber results and ambient measurements found in the literature. The SOA formation mechanism is based on an approach using calculated vapor pressures and a selection of species that can partition to the aerosol phase from a gas phase photochemical mechanism. The mechanism has been validated against smog chamber measurements using α-pinene, xylene and toluene as SOA precursors, and has an average error of 17%. Qualitative comparisons with smog chamber measurements using isoprene were also performed. A comparison against SOA production in the TORCH 2003 experiment (atmospheric measurements) had an average error of only 12%. This contrasts with previous efforts, in which it was necessary to increase partition coefficients by a factor of 500 in order to match the observed values. Calculations for rural and urban-influenced regions in the eastern U.S. suggest that most of the SOA is biogenic in origin, mainly originated from isoprene. A 0-dimensional calculation based on the New England Air Quality Study also showed good agreement with measured SOA, with about 40% of the total SOA from anthropogenic precursors. This mechanism can be implemented in a general circulation model (GCM) to estimate global SOA formation under ambient NOx and HOx levels.
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Fine particulate matter (PM<sub>2.5</sub>) samples were collected during a three week winter period in Fresno (CA). A composite sample was characterized by isolating several distinct fractions and characterizing them by infrared and nuclear magnetic resonance (NMR) spectroscopy. More than 80% of the organic matter in the aerosol samples was recovered and characterized. Only 35% of the organic matter was water soluble with another third soluble in dichloromethane and the remainder insoluble. Within the isolated water soluble material, hydrophobic acid and hydrophilic acids plus neutrals fractions contained the largest amounts of carbon. The hydrophobic acids fraction appears to contain significant amounts of lignin type structures, spectra of the hydrophilic acids plus neutrals fraction are indicative of carbohydrates and secondary organic material. The dichloromethane soluble fraction contains a variety of organic compound families typical of many previous studies of organic aerosol speciation, including alkanes, alkanols, alkanals and alkanoic acids. Finally the water and solvent insoluble fraction exhibits a strong aromaticity as one would expect from black or elemental carbon like material; however, these spectra also show a substantial amount of aliphaticity consistent with linear side chains on the aromatic structures.
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We present Multi AXis-Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of tropospheric BrO carried out on board the German research vessel Polarstern during the Antarctic winter 2006. Polarstern entered the area of first year sea ice around Antarctica on 24 June 2006 and stayed within this area until 15 August 2006. For the period when the ship cruised inside the first year sea ice belt, enhanced BrO concentrations were almost continuously observed. Outside the first year sea ice belt, typically low BrO concentrations were found. Based on back trajectory calculations we find a positive correlation between the observed BrO differential slant column densities (ΔSCDs) and the duration for which the air masses had been in contact with the sea ice surface prior to the measurement. While we can not completely rule out that in several cases the highest BrO concentrations might be located close to the ground, our observations indicate that the maximum BrO concentrations might typically exist in a (possibly extended) layer around the upper edge of the boundary layer. Besides the effect of a decreasing pH of sea salt aerosol with altitude and therefore an increase of BrO with height, this finding might be also related to vertical mixing of air from the free troposphere with the boundary layer, probably caused by convection over the warm ocean surface at polynyas and cracks in the ice. Strong vertical gradients of BrO and O<sub>3</sub> could also explain why we found enhanced BrO levels almost continuously for the observations within the sea ice. Based on our estimated BrO profiles we derive BrO mixing ratios of several ten ppt, which is slightly higher than many existing observations. Our observations indicate that enhanced BrO concentrations around Antarctica exist about one month earlier than observed by satellite instruments. From detailed radiative transfer simulations we find that MAX-DOAS observations are up to about one order of magnitude more sensitive to near-surface BrO than satellite observations. In contrast to satellite observations the MAX-DOAS sensitivity hardly decreases for large solar zenith angles and is almost independent from the ground albedo. Thus this technique is very well suited for observations in polar regions close to the solar terminator. For large periods of our measurements the solar elevation was very low or even below the horizon. For such conditions, most reactive Br-compounds might exist as Br<sub>2</sub> molecules and ozone destruction and the removal of reactive bromine compounds might be substantially reduced.
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The ground-based measurements of the Global Positioning System (GPS) allow estimation of the tropospheric delay along the slanted signal paths through the atmosphere. The meteorological exploitation of such slant delay (SD) observations relies on the hypothesis of azimuthal asymmetry of the information content. This article addresses the validity of the hypothesis. <br><br> A new concept of asymmetricity is introduced for studying the SD observations and their model counterparts. The asymmetricity is defined as the ratio of the absolute asymmetric delay component to total SD. The model counterparts are determined from 3-h forecasts of a numerical weather prediction (NWP) model, run with four different horizontal resolutions. The SD observations are compared with their model counterparts with emphasis on cases of high asymmetricity in order to see whether the observed asymmetry is a real atmospheric signature. <br><br> The asymmetricity is found to be of the order of a few parts per thousand. Thus, the asymmetric delay component barely exceeds the assumed standard deviation of the SD observation error. However, the observed asymmetric delay components show a statistically significant meteorological signal. Benefit of the asymmetric SD observations is therefore expected to be taken in future, when NWP systems will explicitly represent the small-scale atmospheric features revealed by the SD observations.
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Three independent single particle mass spectrometers measured Pb in individual aerosol particles. These data provide unprecedented sensitivity and statistical significance for the measurement of Pb in single particles. This paper explores the reasons for the frequency of Pb in fine particles now that most gasoline is unleaded. Trace amounts of Pb were found in 5 to 25% of 250 to 3000 nm diameter particles sampled by both aircraft and surface instruments in the eastern and western United States. Over 5% of particles at a mountain site in Switzerland contained Pb. Particles smaller than 100 nm with high Pb content were also observed by an instrument that was only operated in urban areas. Lead was found on all types of particles, including Pb present on biomass burning particles from remote fires. Less common particles with high Pb contents contributed a majority of the total amount of Pb. Single particles with high Pb content often also contained alkali metals, Zn, Cu, Sn, As, and Sb. The association of Pb with Zn and other metals is also found in IMPROVE network filter data from surface sites. Sources of airborne Pb in the United States are reviewed for consistency with these data. The frequent appearance of trace Pb is consistent with widespread emissions of fine Pb particles from combustion sources followed by coagulation with larger particles during long-range transport. Industrial sources that directly emit Pb-rich particles also contribute to the observations. Clean regions of the western United States show some transport of Pb from Asia but most Pb over the United States comes from North American sources. Resuspension of Pb from soil contaminated by the years of leaded gasoline was not directly apparent.
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The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument was launched aboard the environmental satellite ENVISAT into its sun-synchronous orbit on 1 March 2002. The short-lived species NO<sub>2</sub> is one of the key target products of MIPAS that are operationally retrieved from limb emission spectra measured in the stratosphere and mesosphere. Within the MIPAS validation activities, a large number of independent observations from balloons, satellites and ground-based stations have been compared to European Space Agency (ESA) version 4.61 operational NO<sub>2</sub> data comprising the time period from July 2002 until March 2004 where MIPAS measured with full spectral resolution. Comparisons between MIPAS and balloon-borne observations carried out in 2002 and 2003 in the Arctic, at mid-latitudes, and in the tropics show a very good agreement below 40 km altitude with a mean deviation of roughly 3%, virtually without any significant bias. The comparison to ACE satellite observations exhibits only a small negative bias of MIPAS which appears not to be significant. The independent satellite instruments HALOE, SAGE II, and POAM III confirm in common for the spring-summer time period a negative bias of MIPAS in the Arctic and a positive bias in the Antarctic middle and upper stratosphere exceeding frequently the combined systematic error limits. In contrast to the ESA operational processor, the IMK/IAA retrieval code allows accurate inference of NO<sub>2</sub> volume mixing ratios under consideration of all important non-LTE processes. Large differences between both retrieval results appear especially at higher altitudes, above about 50 to 55 km. These differences might be explained at least partly by non-LTE under polar winter conditions but not at mid-latitudes. Below this altitude region mean differences between both processors remain within 5% (during night) and up to 10% (during day) under undisturbed (September 2002) conditions and up to 40% under perturbed polar night conditions (February and March 2004). The intercomparison of ground-based NDACC observations shows no significant bias between the FTIR measurements in Kiruna (68° N) and MIPAS in summer 2003 but larger deviations in autumn and winter. The mean deviation over the whole comparison period remains within 10%. A mean negative bias of 15% for MIPAS daytime and 8% for nighttime observations has been determined for UV-vis comparisons over Harestua (60° N). Results of a pole-to-pole comparison of ground-based DOAS/UV-visible sunrise and MIPAS mid-morning column data has shown that the mean agreement in 2003 falls within the accuracy limit of the comparison method. Altogether, it can be indicated that MIPAS NO<sub>2</sub> profiles yield valuable information on the vertical distribution of NO<sub>2</sub> in the lower and middle stratosphere (below about 45 km) during day and night with an overall accuracy of about 10–20% and a precision of typically 5–15% such that the data are useful for scientific studies. In cases where extremely high NO<sub>2</sub> occurs in the mesosphere (polar winter) retrieval results in the lower and middle stratosphere are less accurate than under undisturbed atmospheric conditions.
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Hygroscopic properties of aerosol particles in the sub-micrometer and one-micrometer size ranges were measured during the ACE-Asia study (Aerosol Characterization Experiment-Asia) in spring 2001. The measurements took place off the coasts of Japan, Korea, and China. All instruments contributing to this study were deployed in a container on the forward deck of the NOAA Research Vessel Ronald H. Brown. Air masses with primarily marine influence and air masses from the Asian continent affected by both anthropogenic sources and by the transport of desert dust aerosol were encountered during the cruise. <br><br> Results showed very different hygroscopic behavior in the sub-micrometer size range compared to the one-micrometer size range. In general, for all continentally influenced air masses, the one-micrometer particle population was characterized by two different particle groups – a nearly hydrophobic fraction with growth factors around 1.0 representative of dust particles and a sea salt fraction with hygroscopic growth factors around 2.0. The number fraction of dust particles was generally about 60% independent of long-range air mass origin. <br><br> For sub-micrometer particles, a dominant, more hygroscopic particle fraction with growth factors between 1.5 and 1.9 (depending on dry particle size) consistent with ammonium sulfate or non-neutralized sulfates as major component was always found. In marine air masses and for larger sizes within the sub-micrometer range (<i>Dp</i>=250 and 350 nm), a sea salt fraction with growth factors between 2.0 and 2.1 was also observed. For all other air masses, the more hygroscopic particle fraction in the sub-micrometer size range was mostly accompanied by a less hygroscopic particle fraction with growth factors between 1.20 and 1.55 depending on both the continental sources and the dry particle size. Number fractions of this particle group varied between 4 and 39% depending on dry particle size and air mass type. Nearly hydrophobic particles indicating dust particles in the sub-micrometer size regime were only found for particles with <i>Dp</i>=250 and 350 nm during a time period when the aerosol was influenced by transport from Asian desert regions.
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We used a spectral radiative transfer model to compute the direct radiative effect (DRE) of natural plus anthropogenic aerosols in the solar near-infrared (IR), between 0.85–10 μm, namely, their effect on the outgoing near-IR radiation at the top of atmosphere (TOA, ΔF<sub>TOA</sub>), on the atmospheric absorption of near-IR radiation (ΔF<sub>atmab</sub>) and on the surface downward and absorbed near-IR radiation (ΔF<sub>surf</sub>, and ΔF<sub>surfnet</sub>, respectively). The computations were performed on a global scale (over land and ocean) under all-sky conditions, using detailed spectral aerosol optical properties taken from the Global Aerosol Data Set (GADS) supplemented by realistic data for the rest of surface and atmospheric parameters. The computed aerosol DRE, averaged over the 12-year period 1984–1995 for January and July, shows that on a global mean basis aerosols produce a planetary cooling by increasing the scattered near-IR radiation back to space by 0.48 W m<sup>−2</sup>, they warm the atmosphere by 0.37 W m<sup>−2</sup> and cool the surface by decreasing the downward and absorbed near-IR radiation at surface by 1.03 and 0.85 W m<sup>−2</sup>, respectively. The magnitude of the near-IR aerosol DRE is smaller than that of the combined ultraviolet (UV) and visible DRE, but it is still energetically important, since it contributes to the total shortwave (SW) DRE by 22–31%. The aerosol-produced near-IR surface cooling combined with the atmospheric warming, may affect the thermal dynamics of the Earth-atmosphere system, by increasing the atmospheric stability, decreasing thus cloud formation, and precipitation, especially over desertification threatened regions such as the Mediterranean basin. This, together with the fact that the sign of near-IR aerosol DRE is sometimes opposite to that of UV-visible DRE, demonstrates the importance of performing detailed spectral computations to provide estimates of the climatic role of aerosols for the Earth-atmosphere system. This was demonstrated by sensitivity tests revealing very large differences (up to 300%) between aerosol DREs computed using detailed spectral and spectrally-averaged aerosol optical properties. Our model results indicate thus that the aerosol direct radiative effect on the near-IR radiation is very sensitive to the treatment of the spectral dependence of aerosol optical properties and solar radiation.
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The impact of convection on the thermal structure of the Tropical Tropopause Layer (TTL) was investigated from a series of four daily radiosonde ascents and weather S-band radar observations carried out during the HIBISCUS campaign in the South Atlantic Convergence Zone in Southeast Brazil in February 2004. The temperature profiles display a large impact of convective activity on the thermal structure of the TTL. Compared to non-active periods, convection is observed to result in a cooling of 4.5°C to 7.5°C at the Lapse Rate Tropopause at 16 km, propagating up to 19 km or 440 K potential temperature levels in the stratosphere in most intense convective cases. Consistent with the diurnal cycle of echo top heights seen by a S-band weather radar, a systematic temperature diurnal cycle is observed in the layer, displaying a rapid cooling of 3.5°C on average (–9°, –2°C extremes) during the development phase of convection in the early afternoon during the most active period. Since the cooling occurs during daytime within a timescale of 6-h, its maximum amplitude is at the altitude of the Cold Point Tropopause at 390 K and temperature fluctuations associated to gravity waves do not display significant diurnal change, the afternoon cooling of the TTL cannot be attributed to radiation, advection, gravity waves or adiabatic lofting. It implies a fast insertion of adiabatically cooled air parcels by overshooting turrets followed by mixing with the warmer environment. During most intense convective days, the overshoot is shown to penetrate the stratosphere up to 450 K potential temperature level. Such fast updraft offers an explanation for the presence of ice crystals, and enhanced water vapour layers observed up to 18–19 km (410–430 K) in the same area by the HIBISCUS balloons and the TROCCINOX Geophysica aircraft, as well as high tropospheric chemical species concentrations in the TTL over land observed from space. Overall, injection of cold air by irreversible mixing of convective overshoots as proposed by Danielsen (1982) do not appear as episodic isolated features, but common and systematic events over a land convective area, that is a Stratospheric Fountain. Though the two-stages process proposed by Sherwood (2000) may also be operative, it offers a mechanism for producing the chemical, moisture and thermal properties observed in the stratosphere. The consistency between convective cooling of the TTL and weather radar echoes heights observed during the summer over South-East Brazil and the TRMM radar OPFs and LIS lightning events maximum frequencies, the latter showing also maximum events over Africa, South-East Asia, the Indonesian Islands and Northern Australia depending on the season (Liu and Zipser, 2005), suggests the existence of several "Stratospheric Fountains" over continents instead of the oceanic area of Micronesia as proposed by Newell and Gould-Stewart (1982), which appears a region of little overshoot.
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During the New England Air Quality Study (NEAQS) in the summer of 2004, airborne measurements were made of the major inorganic ions and the water-soluble organic carbon (WSOC) of the submicron (PM<sub>1.0</sub>) aerosol. These and ancillary data are used to describe the overall aerosol chemical characteristics encountered during the study. Fine particle mass was estimated from particle volume and a calculated density based on measured particle composition. Fine particle organic matter (OM) was estimated from WSOC and a mass balance analysis. The aerosol over the northeastern United States (U.S.) and Canada was predominantly sulfate and associated ammonium, and organic components, although in unique plumes additional ionic components were also periodically above detection limits. In power generation regions, and especially in the Ohio River Valley region, the aerosol tended to be predominantly sulfate (~60% μg μg<sup>−1</sup>) and apparently acidic, based on an excess of measured anions compared to cations. In all other regions where sulfate concentrations were lower and a smaller fraction of overall mass, the cations and anions were balanced suggesting a more neutral aerosol. In contrast, the WSOC and estimated OM were more spatially uniform and the fraction of OM relative to PM mass was largely influenced by sources of sulfate. The study median OM mass fraction was 40%. Throughout the study region, sulfate and organic aerosol mass were highest near the surface and decreased rapidly with increasing altitude. The relative fraction of organic mass to sulfate was similar throughout all altitudes within the boundary layer (altitude less than 2.5 km), but was significantly higher at altitude layers in the free troposphere (above 2.5 km). A number of distinct biomass burning plumes from fires in Alaska and the Yukon were periodically intercepted, mostly at altitudes between 3 and 4 km. These plumes were associated with highest aerosol concentrations of the study and were largely comprised of organic aerosol components (~60%).
