-
A scheme for introducing mountain wave-induced temperature pertubations in a microphysical PSC model has been developed. A data set of temperature fluctuations attributable to mountain waves as computed by the Mountain Wave Forecast Model (MWFM-2) has been used for the study. The PSC model has variable microphysics, enabling different nucleation mechanisms for nitric acid trihydrate, NAT, to be employed. In particular, the difference between the formation of NAT and ice particles in a scenario where NAT formation is not dependent on preexisting ice particles, allowing NAT to form at temperatures above the ice frost point, <i>T<sub>ice</sub></i>, and a scenario, where NAT nucleation is dependent on preexisting ice particles, is examined. The performance of the microphysical model in the different microphysical scenarios and a number of temperature scenarios with and without the influence of mountain waves is tested through comparisons with lidar measurements of PSCs made from the NASA DC-8 on 23 and 25 January during the SOLVE/THESEO 2000 campaign in the 1999-2000 winter and the effect of mountain waves on local PSC production is evaluated in the different microphysical scenarios. Mountain waves are seen to have a pronounced effect on the amount of ice particles formed in the simulations. Quantitative comparisons of the amount of solids seen in the observations and the amount of solids produced in the simulations show the best correspondence when NAT formation is allowed to take place at temperatures above <i>T<sub>ice</sub></i>. Mountain wave-induced temperature fluctuations are introduced in vortex-covering model runs, extending the full 1999-2000 winter season, and the effect of mountain waves on large-scale PSC production is estimated in the different microphysical scenarios. It is seen that regardless of the choice of microphysics ice particles only form as a consequence of mountain waves whereas NAT particles form readily as a consequence of the synoptic conditions alone if NAT nucleation above <i>T<sub>ice</sub></i> is included in the simulations. Regardless of the choice of microphysics, the inclusion of mountain waves increases the amount of NAT particles by as much as 10%. For a given temperature scenario the choice of NAT nucleation mechanism may alter the amount of NAT substantially; three-fold increases are easily found when switching from the scenario which requires pre-existing ice particles in order for NAT to form to the scenario where NAT forms independently of ice.
-
Particles from biomass burning and regional haze were sampled in Rondônia, Brazil, during dry, transition and wet periods from September to November 2002, as part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall, and Climate) field campaign. Water soluble organic and inorganic compounds in bulk (High Volume and Stacked Filter Unit sampler) and size-resolved (Micro Orifice Uniform Deposit Impactor – MOUDI) smoke samples were determined by ion chromatography. It was found that low molecular weight polar organic acids account for a significant fraction of the water soluble organic carbon (WSOC) in biomass burning aerosols (C<sub>2</sub>-C<sub>6</sub> dicarboxylic acids reached up to 3.7% and one-ring aromatic acids reached up to 2% of fine fraction WSOC during burning period). Short dicarboxylic (C<sub>2</sub>-C<sub>6</sub>) acids are dominated by oxalic acid followed by malonic and succinic acids. The largest ionic species is ammonium sulfate (60–70% of ionic mass). It was found that most of the ionic mass is concentrated in submicrometer-sized particles. Based on the size distribution and correlations with K<sup>+</sup>, a known biomass burning tracer, it is suggested that many of the organic acids are directly emitted by vegetation fires. Concentrations of dicarboxylic acids in the front and back filters of high volume sampler were determined. Based on these measurements, it was concluded that in the neutral or slightly basic smoke particles typical of this region, dicarboxylic acids are mostly confined to the particulate phase. Finally, it is shown that the distribution of water soluble species shifts to larger aerosols sizes as the aerosol population ages and mixes with other aerosol types in the atmosphere.
-
Hygroscopicity (i.e. water vapour affinity) of atmospheric aerosol particles is one of the key factors in defining their impacts on climate. Condensation of sulphuric acid onto less hygroscopic particles is expected to increase their hygrocopicity and hence their cloud condensation nuclei formation potential. In this study, differences in the hygroscopic and ethanol uptake properties of ultrafine aerosol particles in the Arctic air masses with a different exposure to anthropogenic sulfur pollution were examined. The main discovery was that Aitken mode particles having been exposed to polluted air were more hygroscopic and less soluble to ethanol than after transport in clean air. This aging process was attributed to sulphur dioxide oxidation and subsequent condensation during the transport of these particle to our measurement site. The hygroscopicity of nucleation mode aerosol particles, on the other hand, was approximately the same in all the cases, being indicative of a relatively similar chemical composition despite the differences in air mass transport routes. These particles had also been produced closer to the observation site typically 3–8 h prior to sampling. Apparently, these particles did not have an opportunity to accumulate sulphuric acid on their way to the site, but instead their chemical composition (hygroscopicity and ethanol solubility) resembled that of particles produced in the local or semi-regional ambient conditions.
-
The last decade has seen tremendous advances in atmospheric aerosol particle research that is often performed in the context of climate and global change science. Biomass burning, one of the largest sources of accumulation mode particles globally, has been closely studied for its radiative, geochemical, and dynamic impacts. These studies have taken many forms including laboratory burns, in situ experiments, remote sensing, and modeling. While the differing perspectives of these studies have ultimately improved our qualitative understanding of biomass-burning issues, the varied nature of the work make inter-comparisons and resolutions of some specific issues difficult. In short, the literature base has become a milieu of small pieces of the biomass-burning puzzle. This manuscript, the second part of four, examines the properties of biomass-burning particle emissions. Here we review and discuss the literature concerning the measurement of smoke particle size, chemistry, thermodynamic properties, and emission factors. Where appropriate, critiques of measurement techniques are presented. We show that very large differences in measured particle properties have appeared in the literature, in particular with regards to particle carbon budgets. We investigate emissions uncertainties using scale analyses, which shows that while emission factors for grass and brush are relatively well known, very large uncertainties still exist in emission factors of boreal, temperate and some tropical forests. Based on an uncertainty analysis of the community data set of biomass burning measurements, we present simplified models for particle size and emission factors. We close this review paper with a discussion of the community experimental data, point to lapses in the data set, and prioritize future research topics.
-
Because of its wide coverage over much of the globe, biomass burning has been widely studied in the context of direct radiative forcing. Such study is warranted as smoke particles scatter and at times absorb solar radiation efficiently. Further, as much of what is known about smoke transport and impacts is based on remote sensing measurements, the optical properties of smoke particles have far reaching effects into numerous aspects of biomass burning studies. Global estimates of direct forcing have been widely varying, ranging from near zero to −1 W m<sup>-2</sup>. A significant part of this difference can be traced to varying assumptions on the optical properties of smoke. This manuscript is the third part of four examining biomass-burning emissions. Here we review and discuss the literature concerning measurement and modeling of optical properties of biomass-burning particles. These include available data from published sensitivity studies, field campaigns, and inversions from the Aerosol Robotic Network (AERONET) of Sun photometer sites. As a whole, optical properties reported in the literature are varied, reflecting both the dynamic nature of fires, variations in smoke aging processes and differences in measurement technique. We find that forward modeling or 'internal closure' studies ultimately are of little help in resolving outstanding measurement issues due to the high degree of degeneracy in solutions when using 'reasonable' input parameters. This is particularly notable with respect to index of refraction and the treatment of black carbon. Consequently, previous claims of column closure may in fact be more ambiguous. Differences between in situ and retrieved ω<sub><i>o</i></sub> values have implications for estimates of mass scattering and mass absorption efficiencies. In this manuscript we review and discuss this community dataset. Strengths and lapses are pointed out, future research topics are prioritized, and best estimates and uncertainties of key smoke particle parameters are provided.
-
Recent in situ measurements at tropical tropopause temperatures as low as 187 K indicate supersaturations with respect to ice exceeding 100% with little or no ice present. In contrast, models used to simulate cloud formation near the tropopause assume a supersaturation threshold for ice nucleation of about 65% based on laboratory measurements of aqueous aerosol freezing. The high supersaturations reported here, along with cloud simulations assuming a plausible range of temperature histories in the sampled air mass, indicate that the vast majority of aerosols in the air sampled on this flight must have had supersaturation thresholds for ice nucleation exceeding 100% (i.e. near liquid water saturation at these temperatures). Possible explanations for this high threshold are that (1) the expressions used for calculating vapor pressure over supercooled water at low temperatures give values are at least 20% too low, (2) organic films on the aerosol surfaces reduce their accommodation coefficient for uptake of water, resulting in aerosols with more concentrated solutions when moderate-rapid cooling occurs and correspondingly inhibited homogeneous freezing, and (3) if surface freezing dominates, organic coatings may increase the surface energy of the ice embryo/vapor interface resulting in suppressed ice nucleation. Simulations of in situ cloud formation in the tropical tropopause layer (TTL) throughout the tropics indicate that if decreased accommodation coefficients and resulting high thresholds for ice nucleation prevailed throughout the tropics, then the calculated occurrence frequency and areal coverage of TTL cirrus would be significantly suppressed. However, the simulations also show that even if in situ TTL cirrus form only over a very small fraction of the tropics in the western Pacific, enough air passes through them due to rapid horizontal transport such that they can still effectively freeze-dry air entering the stratosphere. The TTL cirrus simulations show that even if very large supersaturations are required for ice nucleation, these large supersaturations should occur very rarely.
-
In this paper we present a parameterization of the nitric acid effect on cloud droplet formation. The new parameterization is intended to be used in large scale models in order to obtain regional and global estimates of the effect of nitric acid on cloud drop concentrations and the radiative balance. The parameterization is based on numerical air parcel model simulations and can be applied for unimodal and bimodal lognormal aerosol particle size distributions in a large variety of different conditions. In addition to the aerosol particle distribution and gas-phase HNO<sub>3</sub> concentration, the parameterization requires temperature, total pressure, updraft velocity, and the number concentration of cloud droplets formed at zero nitric acid concentration, as input parameters. The parameterization is also suitable for describing the effect of hydrochloric acid on the cloud drop concentrations, and in practice, the HNO<sub>3</sub> and HCl concentrations can be summed up to yield the total effect. The comparison between the parameterization and the results from numerical air parcel model simulations show good consistency.
-
Sulphuric acid concentrations were measured and calculated based on pseudo steady state model with corresponding measurements of CO, NO<sub>x</sub>, O<sub>3</sub>, SO<sub>2</sub>, methane and non-methane hydrocarbon (NMHC) concentrations as well as solar spectral irradiance and particle number concentrations with size distributions. The measurements were performed as a part of the EU project QUEST (Quantification of Aerosol Nucleation in the European Boundary layer) during an intensive field campaign, which was conducted in Hyytiälä, Finland in March–April 2003. In this paper, the closure between measured and calculated H<sub>2</sub>SO<sub>4</sub> concentrations is investigated. Besides that, also the contribution of sulphuric acid to nucleation mode particle growth rates is studied. Hydroxyl and hydroperoxy radical concentrations were determined using a pseudo steady state box model including photo stationary states. The maximum midday OH concentrations ranged between 4.1×10<sup>5</sup> to 1.8×10<sup>6</sup> molecules cm<sup>-3</sup> and the corresponding values for HO<sub>2</sub> were 1.0×10<sup>7</sup> to 1.5×10<sup>8</sup> molecules cm<sup>-3</sup>. The dominant source term for hydroxyl radicals is the reaction of NO with HO<sub>2</sub> (56%) and the reaction of CO with OH covers around 41% of the sinks. The sulphuric acid source term is the reaction SO<sub>2</sub> with OH and the sink term is condensation of sulphuric acid. The closure between measured and calculated sulphuric acid concentrations is achieved with a high agreement to the measured values. In sensitivity studies, we used different values for the non-methane hydrocarbons, the peroxy radicals and nitrogen dioxide. The best fits between calculated and measured values were found by decreasing the NO<sub>2</sub> concentration when it exceeded values of 1.5 ppb and doubling the non-methane hydrocarbon concentrations. The ratio, standard deviation and correlation coefficient between measured and calculated sulphuric acid concentrations are 0.99, 0.412 and 0.645, respectively. The maximum midday sulphuric acid concentrations varied between 3×10<sup>5</sup> to 1.9×10<sup>7</sup> molecules cm<sup>-3</sup> for the measurements and 3×10<sup>5</sup> to 1.4×10<sup>7</sup> molecules cm<sup>-3</sup> for the calculations, respectively. An average participation of sulphuric acid to the nucleation mode particle growth rates is 8.8%. Classifying the days into two groups – 'polluted' days with air masses originated over Central Europe or UK, and 'cleaner' days with air masses originated over the Northern Atlantic or the Polar regions – reflects an equal sulphuric acid contribution to the aerosol growth in both air mass classes.
-
This study examines two key parameters of the hydrological cycle, water vapor (WV) and precipitation rates (PR), as modelled by the chemistry transport model MATCH (Model of Atmospheric Transport and Chemistry) driven by National Centers for Environmental Prediction (NCEP) reanalysis data (NRA). For model output evaluation we primarily employ WV total column data from the Global Ozone Monitoring Experiment (GOME) on ERS-2, which is the only instrument capable measuring WV on a global scale and over all surface types with a substantial data record from 1995 to the present. We find that MATCH and NRA WV and PR distributions are closely related, but that significant regional differences in both parameters exist in magnitude and distribution patterns when compared to the observations. We also find that WV residual patterns between model and observations show remarkable similarities to residuals observed in the PR when comparing MATCH and NRA output to observations comprised by the Global Precipitation Climatology Project (GPCP). We conclude that deficiencies in model parameters shared by MATCH and NRA, like in the surface evaporation rates and regional transport patterns, are likely to lead to the observed differences. Monthly average regional differences between MATCH modelled WV columns and the observations can be as large as 2 cm, based on the analysis of three years. Differences in the global mean WV values are, however, below 0.1 cm. Regional differences in the PR between MATCH and GPCP can be above 0.5 cm per day and MATCH computes on average a higher PR than what has been observed. The lower water vapor content of MATCH is related to shorter model WV residence times by up to 1 day as compared to the observations. We find that MATCH has problems in modelling the WV content in regions of strong upward convection like, for example, along the Inter Tropical Convergence Zone, where it appears to be generally too dry as compared to the observations. We discuss possible causes for this bias and demonstrate the value of the GOME WV record for model evaluation.
-
On 21–22 August 2001, NO, NO<sub>2</sub> and HNO<sub>3</sub> mixing ratio profiles were measured at high latitudes during sunset and sunrise using the Limb Profile Monitor of the Atmosphere (LPMA) and the DOAS experiments under stratospheric balloon. Photochemical simulations using the chemistry module of the Reprobus Chemistry Transport Model (CTM) that are constrained by ozone and total NO<sub>y</sub> balloon observations reproduce well the partitioning of NO<sub>x</sub> and NO<sub>y</sub> when model results are calculated at the exact time and location of the measurement for each tangent altitude. Taking the recently recommended reaction rate coefficients for the NO<sub>y</sub> partitioning (JPL-2003) and using realistic aerosol surface area in order to initialise the model leads to an agreement between calculations and measurements better than 10% all over the covered altitude range.
