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We describe the large-scale meteorological conditions that affected atmospheric chemistry over Mexico during March 2006 when several field campaigns were conducted in the region. In-situ and remote-sensing instrumentation was deployed to obtain measurements of wind, temperature, and humidity profiles in the boundary layer and free atmosphere at four primary sampling sites in central Mexico. Several models were run operationally during the field campaign to provide forecasts of the local, regional, and synoptic meteorology as well as the predicted location of the Mexico City pollutant plume for aircraft flight planning purposes. Field campaign measurements and large-scale analyses are used to define three regimes that characterize the overall meteorological conditions: the first regime prior to 14 March, the second regime between 14 and 23 March, and the third regime after 23 March. Mostly sunny and dry conditions with periods of cirrus and marine stratus along the coast occurred during the first regime. The beginning of the second regime was characterized by a sharp increase in humidity over the central plateau and the development of late afternoon convection associated with the passage of a weak cold surge on 14 March. Over the next several days, the atmosphere over the central plateau became drier so that deep convection gradually diminished. The third regime began with the passage of a strong cold surge that lead to humidity, afternoon convection, and precipitation over the central plateau that was higher than during the second regime. The frequency and intensity of fires, as determined by satellite measurements, also diminished significantly after the third cold surge. The synoptic-scale flow patterns that govern the transport of pollutants in the region are described and compared to previous March periods to put the transport into a climatological context. The complex terrain surrounding Mexico City produces local and regional circulations that govern short-range transport; however, the mean synoptic conditions modulate the thermally-driven circulations and on several days the near-surface flow is coupled to the ambient winds aloft.
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A solar eclipse is a rare but spectacular natural phenomenon and furthermore it is a challenge for radiative transfer modelling. Whereas a simple one-dimensional radiative transfer model with reduced solar irradiance at the top of the atmosphere can be used to calculate the brightness during partial eclipses a much more sophisticated model is required to calculate the brightness (i.e. the diffuse radiation) during the total eclipse. The reason is that radiation reaching a detector in the shadow gets there exclusively by horizontal transport of photons in a spherical shell atmosphere, which requires a three-dimensional radiative transfer model. In this study the first fully three-dimensional simulations for a solar eclipse are presented exemplified by the solar eclipse at 29 March 2006. Using a backward Monte Carlo model we calculated the diffuse radiation in the umbra and simulated the changing colours of the sky. Radiance and irradiance are decreased by 3 to 4 orders of magnitude, depending on wavelength. We found that aerosol has a comparatively small impact on the radiation in the umbra. We also estimated the contribution of the solar corona to the radiation under the umbra and found that it is negligible compared to the diffuse solar radiation in the wavelength region from 310 to 500 nm.
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The concentrations of peroxyacetyl nitrate (PAN) in ambient air can be a good indicator of air quality and the effectiveness of control strategies for reducing ozone levels in urban areas. As PAN is formed by the oxidation of reactive hydrocarbons in the presence of nitrogen dioxide (NO<sub>2</sub>), it is a direct measure of the peroxyacyl radical levels produced from reactive organic emissions in the urban air shed. Carbon soot, known as black carbon (BC) or elemental carbon (EC), is a primary atmospheric aerosol species and is a good indicator of the levels of combustion emissions, particularly from diesel engines, in major cities. Mexico City is the second largest megacity in the world and has long suffered from poor air quality. Reported here are atmospheric measurements of PAN and BC obtained in Mexico City during the Mexico Megacity 2003 field study. These results are compared with measurements obtained earlier during the <i>Investigación sobre Materia Particulada y Deterioro Atmosférico – Aerosol and Visibility Research</i> (IMADA-AVER) campaign in 1997 to obtain an estimate of the changes in emissions in Mexico City and the effectiveness of control strategies adopted during that time. Concentrations of PAN in 1997 reached a maximum of 34 ppb with an average daily maximum of 15 ppb. The PAN levels recorded in 2003 were quite different, with an average daily maximum of 3 ppb. This dramatic reduction in PAN levels observed in 2003 indicate that reactive hydrocarbon emissions have been reduced in the city due to controls on olefins in liquefied petroleum gas (LPG) and also due to the significant number of newer vehicles with catalytic converters that have replaced older higher emission vehicles. In contrast, black/elemental carbon levels were similar in 1997 and 2003 indicating little improvement likely due to the lack of controls on diesel vehicles in the city. Thus, while air quality and ozone production have improved, Mexico City and other megacities continue to be a major source of black carbon aerosols, which can be an important species in determining regional radiative balance and climate.
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In this study, we measured the mobility distributions of cluster and intermediate ions with an ion spectrometer near a waterfall. We observed that the concentration of negative 1.5–10 nm ions was one-hundred fold higher than a reference point 100 m away from the waterfall. Also, the concentration of positive intermediate ions was found to be higher than that at the reference point by a factor of ten. This difference was observed only at the smallest sizes; above 10 nm the difference was insignificant.
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We investigate the issue of "dangerous human-made interference with climate" using simulations with GISS modelE driven by measured or estimated forcings for 1880–2003 and extended to 2100 for IPCC greenhouse gas scenarios as well as the "alternative" scenario of Hansen and Sato (2004). Identification of "dangerous" effects is partly subjective, but we find evidence that added global warming of more than 1°C above the level in 2000 has effects that may be highly disruptive. The alternative scenario, with peak added forcing ~1.5 W/m<sup>2</sup> in 2100, keeps further global warming under 1°C if climate sensitivity is ~3°C or less for doubled CO<sub>2</sub>. The alternative scenario keeps mean regional seasonal warming within 2σ (standard deviations) of 20th century variability, but other scenarios yield regional changes of 5–10σ, i.e. mean conditions outside the range of local experience. We conclude that a CO<sub>2</sub> level exceeding about 450 ppm is "dangerous", but reduction of non-CO<sub>2</sub> forcings can provide modest relief on the CO<sub>2</sub> constraint. We discuss three specific sub-global topics: Arctic climate change, tropical storm intensification, and ice sheet stability. We suggest that Arctic climate change has been driven as much by pollutants (O<sub>3</sub>, its precursor CH<sub>4</sub>, and soot) as by CO<sub>2</sub>, offering hope that dual efforts to reduce pollutants and slow CO<sub>2</sub> growth could minimize Arctic change. Simulated recent ocean warming in the region of Atlantic hurricane formation is comparable to observations, suggesting that greenhouse gases (GHGs) may have contributed to a trend toward greater hurricane intensities. Increasing GHGs cause significant warming in our model in submarine regions of ice shelves and shallow methane hydrates, raising concern about the potential for accelerating sea level rise and future positive feedback from methane release. Growth of non-CO<sub>2</sub> forcings has slowed in recent years, but CO<sub>2</sub> emissions are now surging well above the alternative scenario. Prompt actions to slow CO<sub>2</sub> emissions and decrease non-CO<sub>2</sub> forcings are required to achieve the low forcing of the alternative scenario.
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Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NO<sub>x</sub> with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R<sub>3</sub>NH<sup>+</sup>) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.
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We present an intercomparison of several aerosol modules, sectional and modal, in a global 2-D model in order to differentiate their behavior for tropospheric and stratospheric applications. We model only binary sulfuric acid-water aerosols in this study. Three versions of the sectional model and three versions of the modal model are used to test the sensitivity of background aerosol mass and size distribution to the number of bins or modes and to the prescribed width of the largest mode. We find modest sensitivity to the number of bins (40 vs. 150) used in the sectional model. Aerosol mass is found to be reduced in a modal model if care is not taken in selecting the width of the largest lognormal mode, reflecting differences in sedimentation in the middle stratosphere. The size distributions calculated by the sectional model can be better matched by a modal model with four modes rather than three modes in most but not all situations. A simulation of aerosol decay following the 1991 eruption of Mt. Pinatubo shows that the representation of the size distribution can have a signficant impact on model-calculated aerosol decay rates in the stratosphere. Between 1991 and 1995, aerosol extinction and surface area density calculated by two versions of the modal model adequately match results from the sectional model. Calculated effective radius for the same time period shows more intermodel variability, with a 20-bin sectional model performing much better than any of the modal models.
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We have used an off-line three-dimensional (3-D) chemical transport model (CTM) to study long-term changes in stratospheric O<sub>3</sub>. The model was run from 1977–2004 and forced by ECMWF ERA-40 and operational analyses. Model runs were performed to examine the impact of increasing halogens and additional stratospheric bromine from short-lived source gases. The analyses capture much of the observed interannual variability in column ozone, but there are also unrealistic features. In particular the ERA-40 analyses cause a large positive anomaly in northern hemisphere (NH) column O<sub>3</sub> in the late 1980s. Also, the change from ERA-40 to operational winds at the start of 2002 introduces abrupt changes in some model fields (e.g. temperature, ozone) which affect analysis of trends. The model reproduces the observed column increase in NH mid-latitudes from the mid 1990s. Analysis of a run with fixed halogens shows that this increase is not due to a significant decrease in halogen-induced loss, i.e. is not an indication of recovery. The model predicts only a small decrease in halogen-induced loss after 1999. In the upper stratosphere, despite the modelled turnover of chlorine around 1999, O<sub>3</sub> does not increase because of the effects of increasing ECMWF temperatures, decreasing modelled CH<sub>4</sub> at this altitude, and abrupt changes in the SH temperatures at the end of the ERA-40 period. The impact of an additional 5 pptv stratospheric bromine from short-lived species decreases mid-latitude column O<sub>3</sub> by about 10 DU. However, the impact on the modelled relative O<sub>3</sub> anomaly is generally small except during periods of large volcanic loading.
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In order to predict the physical properties of aerosol particles, it is necessary to adequately capture the behaviour of the ubiquitous complex organic components. One of the key properties which may affect this behaviour is the contribution of the organic components to the surface tension of aqueous particles in the moist atmosphere. Whilst the qualitative effect of organic compounds on solution surface tensions has been widely reported, our quantitative understanding on mixed organic and mixed inorganic/organic systems is limited. Furthermore, it is unclear whether models that exist in the literature can reproduce the surface tension variability for binary and higher order multi-component organic and mixed inorganic/organic systems of atmospheric significance. The current study aims to resolve both issues to some extent. Surface tensions of single and multiple solute aqueous solutions were measured and compared with predictions from a number of model treatments. On comparison with binary organic systems, two predictive models found in the literature provided a range of values resulting from sensitivity to calculations of pure component surface tensions. Results indicate that a fitted model can capture the variability of the measured data very well, producing the lowest average percentage deviation for all compounds studied. The performance of the other models varies with compound and choice of model parameters. The behaviour of ternary mixed inorganic/organic systems was unreliably captured by using a predictive scheme and this was dependent on the composition of the solutes present. For more atmospherically representative higher order systems, entirely predictive schemes performed poorly. It was found that use of the binary data in a relatively simple mixing rule, or modification of an existing thermodynamic model with parameters derived from binary data, was able to accurately capture the surface tension variation with concentration. Thus, it would appear that in order to model multi-component surface tensions involving compounds used in this study one requires the use of appropriate binary data. However, results indicate that the use of theoretical frameworks which contain parameters derived from binary data may predict unphysical behaviour when taken beyond the concentration ranges used to fit such parameters. The effect of deviations between predicted and measured surface tensions on predicted critical saturation ratios was quantified, by incorporating the surface tension models into an existing thermodynamic framework whilst firstly neglecting bulk to surface partitioning. Critical saturation ratios as a function of dry size for all of the multi-component systems were computed and it was found that deviations between predictions increased with decreasing particle dry size. As expected, use of the surface tension of pure water, rather than calculate the influence of the solutes explicitly, led to a consistently higher value of the critical saturation ratio indicating that neglect of the compositional effects will lead to significant differences in predicted activation behaviour even at large particle dry sizes. Following this two case studies were used to study the possible effect of bulk to surface partitioning on critical saturation ratios. By employing various assumptions it was possible to perform calculations not only for a binary system but also for a mixed organic system. In both cases this effect lead to a significant increase in the predicted critical supersaturation ratio compared to the above treatment. Further analysis of this effect will form the focus of future work.
