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Recent work has shown that aqueous-phase reactions of phenolic compounds – phenol (C<sub>6</sub>H<sub>6</sub>O), guaiacol (C<sub>7</sub>H<sub>8</sub>O<sub>2</sub>), and syringol (C<sub>8</sub>H<sub>10</sub>O<sub>3</sub>) – can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatography system (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80–1.06 and carbon oxidation states (=2×O/C-H/C) between −0.14 and +0.47. The organic mass-to-carbon (OM/OC) ratios determined by the HR-AMS (=2.21–2.55) agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA). Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4−5.2% of the SOA mass, with generally higher yields in experiments with H<sub>2</sub>O<sub>2</sub> added as an OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C-C and C-O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, <i>m/z</i> 306 (C<sub>16</sub>H<sub>18</sub>O<sub>6</sub><sup>+</sup>) and <i>m/z</i> 246 (C<sub>14</sub>H<sub>14</sub>O<sub>4</sub><sup>+</sup>), respectively, are observed in ambient aerosols significantly influenced by wood combustion and fog processing. Our results indicate that cloud and fog processing of phenolic compounds, especially in areas with active biomass burning, might represent an important pathway for the formation of low-volatility and highly oxygenated organic species, which would remain in the particle phase after fog/cloud evaporation and affect the chemical and optical properties of atmospheric particles.
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Discrete in situ atmospheric measurements of molecular iodine (I<sub>2</sub>) were carried out at Mace Head and Mweenish Bay on the west coast of Ireland using diffusion denuders in combination with a gas chromatography-mass spectrometry (GC-MS) method. I<sub>2</sub>, IO and OIO were also measured by long-path differential optical absorption spectroscopy (LP-DOAS). The simultaneous denuder and LP-DOAS I<sub>2</sub> measurements were well correlated (<i>R</i><sup>2</sup>=0.80) but the denuder method recorded much higher concentrations. This can be attributed to the fact that the in situ measurements were made near to macroalgal sources of I<sub>2</sub> in the intertidal zone, whereas the LP-DOAS technique provides distance-averaged mixing ratios of an inhomogeneous distribution along the light-path. The observed mixing ratios of I<sub>2</sub> at Mweenish Bay were significantly higher than that at Mace Head, which is consistent with differences in local algal biomass density and algal species composition. Above algal beds, levels of I<sub>2</sub> were found to correlate inversely with tidal height and positively with the concentrations of O<sub>3</sub> in the surrounding air, indicating a role for O<sub>3</sub> in the production of I<sub>2</sub> from macroalgae, as has been previously suggested from laboratory studies. However, measurements made ~150 m away from the algal beds showed a negative correlation between O<sub>3</sub> and I<sub>2</sub> during both day and night. We interpret these results to indicate that the released I<sub>2</sub> can also lead to O<sub>3</sub> destruction via the reaction of O<sub>3</sub> with I atoms that are formed by the photolysis of I<sub>2</sub> during the day and via the reaction of I<sub>2</sub> with NO<sub>3</sub> radicals at night. The results show that the concentrations of daytime IO are correlated with the mixing ratios of I<sub>2</sub>, and suggest that the local algae sources dominate the inorganic iodine chemistry at Mace Head and Mweenish Bay.
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Ship-borne sunphotometer measurements obtained in the Arabian Sea (AS) in the pre-monsoon season (18 April–10 May 2006) during a cruise campaign (ICARB) have been used to retrieve the Aerosol Optical Depth (AOD; τ) and the Ångström wavelength exponent (α). The continents surrounding the AS produce natural and anthropogenic aerosols that have distinctive influences on α and its spectral distribution. The α values were estimated by means of the least-squares method over the spectral bands 340–1020 nm and 340–870 nm. The spectral distribution of AOD in logarithmic co-ordinates could be fit using a 2nd order polynomial with higher accuracy in the wavelength band 340–1020 nm than in the 340–870 nm band. A polynomial fit analytically parameterizes the observed wavelength dependencies of AOD with least errors in spectral variation of α and yields accurate estimates of the coefficients (<i>a</i><sub>1</sub> and <i>a</i><sub>2</sub>). The coarse-mode (positive curvature in the lnτ<sub>λ</sub> vs. lnλ) aerosols are mainly depicted in the Northern part of the AS closely associated with the nearby arid areas while fine-mode aerosols are mainly observed over the far and coastal AS regions. In the study period the mean AOD at 500 nm is 0.25±0.11 and the α<sub>340-1020</sub> is 0.90±0.19. The α<sub>340-870</sub> exhibits similar values (0.92±0.18), while significant differences revealed for the constant terms of the polynomial fit (<i>a</i><sub>1</sub> and <i>a</i><sub>2</sub>) proportionally to the wavelength band used for their determination. Observed day-to-day variability in the aerosol load and optical properties are direct consequence of the local winds and air-mass trajectories along with the position of the ship.
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Solid state vapour pressures of a selection of atmospherically important substituted dicarboxylic acids have been measured using Knudsen Effusion Mass Spectrometry (KEMS) over a range of 20 K (298–318 K). Enthalpies of fusion and melting points obtained using Differential Scanning Calorimetry (DSC) were used to obtain sub-cooled liquid vapour pressures. They have been compared to estimation methods used on the E-AIM website. These methods are shown to poorly represent – OH groups in combination with COOH groups. Partitioning calculations have been performed to illustrate the impact of the different estimation methods on organic aerosol mass compared to the use of experimental data.
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In an effort to understand and quantify the impact of local, regional, and far-distant atmospheric mercury sources to rainfall mercury deposition in the Pensacola, Florida watershed, a program of event-based rainfall sampling was started in late 2004. Modified Aerochem-Metrics wet/dry rainfall samplers were deployed at three sites in the region around the Crist coal-fired power plant and event-based samples were collected continuously for three years. Samples were analyzed for total Hg and a suite of trace elements including Al, As, Ba, Bi, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Sb, Se, Si, Sn, Sr, Th, U, V, and Zn. Nutrients (ammonia and nitrate) and major anions (chloride and sulfate) were also measured on each sample. Multivariate statistical methods were used to sort these tracers into factors that represent potential source categories contributing to the rainfall chemistry. As, Hg, Sb, Se, Sn, and non sea-salt sulfate were all significantly correlated (<i>R</i>>0.6) with one factor which we interpret as an anthropogenic source term reflecting input from coal combustion throughout the southeastern US. Using ratios of total Hg to volatile elements, we estimate that 22–33% of the rainfall Hg results from coal combustion in the southeastern US with the majority coming from the global background.
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An accurate but simple quantification of the fraction of aerosol particles that can act as cloud condensation nuclei (CCN) is needed for implementation in large-scale models. Data on aerosol size distribution, chemical composition, and CCN concentration from six different locations have been analyzed to explore the extent to which simple assumptions of composition and mixing state of the organic fraction can reproduce measured CCN number concentrations. <br><br> Fresher pollution aerosol as encountered in Riverside, CA, and the ship channel in Houston, TX, cannot be represented without knowledge of more complex (size-resolved) composition. For aerosol that has experienced processing (Mexico City, Holme Moss (UK), Point Reyes (CA), and Chebogue Point (Canada)), CCN can be predicted within a factor of two assuming either externally or internally mixed soluble organics although these simplified compositions/mixing states might not represent the actual properties of ambient aerosol populations, in agreement with many previous CCN studies in the literature. Under typical conditions, a factor of two uncertainty in CCN concentration due to composition assumptions translates to an uncertainty of ~15% in cloud drop concentration, which might be adequate for large-scale models given the much larger uncertainty in cloudiness.
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Parametric functions are currently used to represent droplet spectra in clouds and to develop bulk parameterizations of the microphysical processes and of their interactions with radiation. The most frequently used parametric functions are the Lognormal and the Generalized Gamma which have three and four independent parameters, respectively. In a bulk parameterization, two parameters are constrained by the total droplet number concentration and the liquid water content. In the Generalized Gamma function, one parameter is specified a priori, and the fourth one, like the third parameter of the Lognormal function, shall be tuned, for the parametric function to statistically best fit observed droplet spectra. <br><br> These parametric functions are evaluated here using droplet spectra collected in non-or slightly precipitating stratocumulus and shallow cumulus. Optimum values of the tuning parameters are derived by minimizing either the absolute or the relative error for successively the first, second, fifth, and sixth moments of the droplet size distribution. A trade-off value is also proposed that minimizes both absolute and relative errors for the four moments concomitantly. Finally, a parameterization is proposed in which the tuning parameter depends on the liquid water content. This approach significantly improves the fit for the smallest and largest values of the moments.
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The Preliminary VOCALS Model Assessment (PreVOCA) aims to assess contemporary atmospheric modeling of the subtropical South East Pacific, with a particular focus on the clouds and the marine boundary layer (MBL). Models results from fourteen modeling centers were collected including operational forecast models, regional models, and global climate models for the month of October 2006. Forecast models and global climate models produced daily forecasts, while most regional models were run continuously during the study period, initialized and forced at the boundaries with global model analyses. Results are compared in the region from 40° S to the equator and from 110° W to 70° W, corresponding to the Pacific coast of South America. Mean-monthly model surface winds agree well with QuikSCAT observed winds and models agree fairly well on mean weak large-scale subsidence in the region next to the coast. However they have greatly differing geographic patterns of mean cloud fraction with only a few models agreeing well with MODIS observations. Most models also underestimate the MBL depth by several hundred meters in the eastern part of the study region. The diurnal cycle of liquid water path is underestimated by most models at the 85° W 20° S stratus buoy site compared with satellite, consistent with previous modeling studies. The low cloud fraction is also underestimated during all parts of the diurnal cycle compared to surface-based climatologies. Most models qualitatively capture the MBL deepening around 15 October 2006 at the stratus buoy, associated with colder air at 700 hPa.
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We analyze the theoretical basis of three different methods to validate and intercompare satellite measurements of atmospheric composition, and apply them to tropospheric ozone retrievals from the Tropospheric Emission Spectrometer (TES) and the Ozone Monitoring Instrument (OMI). The first method (in situ method) uses in situ vertical profiles for absolute instrument validation; it is limited by the sparseness of in situ data. The second method (CTM method) uses a chemical transport model (CTM) as an intercomparison platform; it provides a globally complete intercomparison with relatively small noise from model error. The third method (averaging kernel smoothing method) involves smoothing the retrieved profile from one instrument with the averaging kernel matrix of the other; it also provides a global intercomparison but dampens the actual difference between instruments and adds noise from the a priori. We apply the three methods to a full year (2006) of TES and OMI data. Comparison with in situ data from ozonesondes shows mean positive biases of 5.3 parts per billion volume (ppbv) (10%) for TES and 2.8 ppbv (5%) for OMI at 500 hPa. We show that the CTM method (using the GEOS-Chem CTM) closely approximates results from the in situ method while providing global coverage. It reveals that differences between TES and OMI are generally less than 10 ppbv (18%), except at northern mid-latitudes in summer and over tropical continents. The CTM method further allows for CTM evaluation using both satellite observations. We thus find that GEOS-Chem underestimates tropospheric ozone in the tropics due to possible underestimates of biomass burning, soil, and lightning emissions. It overestimates ozone in the northern subtropics and southern mid-latitudes, likely because of excessive stratospheric influx of ozone.
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The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO<sub>3</sub>) and nitrogen dioxide (NO<sub>2</sub>) profiles and distributions of 1978/1979 are described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO<sub>3</sub> profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO<sub>2</sub> are accounted for better with V6. The accuracy of the retrieved V6 NO<sub>2</sub> is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO<sub>3</sub>/NO<sub>2</sub> ratio, day-to-night NO<sub>2</sub> ratio, and with estimates of the production of NO<sub>2</sub> in the mesosphere and its descent to the upper stratosphere during polar night. In particular, the findings for middle and upper stratospheric NO<sub>2</sub> should also be more compatible with those obtained from more recent satellite sensors because the effects of the spin-splitting of the NO<sub>2</sub> lines are accounted for now with the LIMS V6 algorithm. The improved precisions and more frequent retrievals of the LIMS profiles along their orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be studied quantitatively throughout the stratosphere with the LIMS V6 data.
