Sensitivity of modelled sulphate and nitrate aerosol to cloud,pH and ammonia emissions

A Lagrangian dispersion model has been used to predict daily sulphate aerosol in 2006 at five UK rural measurement sites and hourly nitrate aerosol in April 2003 at Harwell (UK). The sensitivity of aqueous phase sulphate production to the meteorological input has been investigated. Large differences were found between cloud fraction and cloud liquid water output from the regional and mesoscale Met Office Unified Model. The impact on the sulphate aerosol was relatively small, with the mesoscale meteorology giving better results.Sulphate aerosol production in the aqueous phase was found to be very sensitive to modelled cloud pH. As the cloud becomes acidic sulphate production is greatly limited, conversely if the cloud is basic large amounts of sulphate aerosol are produced. A fixed model pH of 5.8 was found to produce better results than allowing the model to calculate pH which resulted in large over-predictions of measured sulphate aerosol in some episodes.Nitrate aerosol was not sensitive to cloud variables or pH, but showed a slight increase with 30% more ammonia emissions, and a slight decrease with 30% less ammonia.Sulphate production in model runs with fixed pH was not sensitive to changing ammonia emissions, however the sulphate production with modelled pH was very sensitive to plus or minus 30% ammonia. This work suggests that good modelling of ammonia is essential to correct estimation of aqueous phase sulphate aerosol if cloud pH is modelled. It is concluded that modelling to estimate the effect of reduced ammonia emission scenarios on future ambient aerosol levels should also take into account the neutralising effect of ammonia in cloud and hence the effect on aqueous phase production of sulphate.     

Halogen production from aqueous tropospheric particles

Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values.For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986.It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations.The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea-salt aerosols shows that the particle phase can act as a main source of halogen containing molecules (Cl(2), BrCl, Br(2)) which are photolysed in the gas phase to yield halogen atoms (about 70% of all Cl sources and more than 99% for Br).     

Observations and modelling of aerosol growth in marine stratocumulus—case study

Airborne measurements of the growth of the marine accumulation mode after multiple cycles through stratocumulus cloud are presented. The nss-sulphate cloud residual mode was log-normal in spectral shape and it’s mode radius was observed to progressively increase in size from 0.78 to 0.94 μm over 155 min of air parcel evolution through the cloudy marine boundary layer. The primary reason for this observed growth was thought to result from aqueous phase oxidation of SO₂ to aerosol sulphate in activated cloud drops. An aqueous phase aerosol–cloud-chemistry model was used to simulate this case study of aerosol growth and was able to closely reproduce the observed growth. The model simulations illustrate that aqueous phase oxidation of SO₂ in cloud droplets was able to provide enough additional sulphate mass to increase the size of activated aerosol. During a typical cloud cycle simulation, ≈4.6 nmoles kg^-1_air (0.44 μg m^-3) of sulphate mass was produced with ≈70% of sulphate production occurring in cloud droplets activated upon sea-salt nuclei and ≈30% occurring upon nss-sulphate nuclei, even though sea-salt nuclei contributed less than 15% to the activated droplet population. The high fraction of nss-sulphate mass internally mixed with sea-salt aerosol suggests that aqueous phase oxidation of SO₂ in cloud droplets activated upon sea-salt nuclei is the dominant nss-sulphate formation mechanism and that sea-salt aerosol provides the primary chemical sink for SO₂ in the cloudy marine boundary layer.     

Air parcel model simulations of a convective cloud: Bacteria acting as immersion ice nuclei

The effects of bacteria acting as immersion ice nuclei were investigated in numerical sensitivity studies and compared to the efforts of other ice nuclei such as mineral dust and soot particles. An adiabatic air parcel model was employed simulating convective situations with different initial aerosol particle distributions. The maximum fractions of active ice nuclei were based on field measurements of the proportioning of atmospheric aerosol particle types in continental and marine air masses. Recent field measurements of bacteria concentrations in cloud water and in snow samples were used. From the concentrations in bulk samples the concentration in mean sized cloud droplets was estimated. Immersion freezing was described based on laboratory measurements to constrain the freezing fraction versus temperature. The results indicated that the effects of diminutive amounts of bacteria on ice formation in convective clouds, while being significantly less than the effects of mineral dust particles, might be comparable to the expected effects of soot particles acting as ice nuclei. It can be predicted that bacterial ice nuclei would have to be enriched by at least 10⁴ times reported concentrations in cloud water in order to equate to the impact of mineral dust ice nuclei present in 20–25% of all cloud droplets.     

Nomogram for Relating Particle and Particle Cloud Parameters

Three concentration units, i.e., mass density, number density, and surface area, often are alternatively used to describe an aerosol cloud. While most aerosol clouds are composed of poly-disperse particles, the nomogram based upon monodisperse spherical particles (Figure 1) has been found useful for relating these different concentration values.     

Analysis of organic and inorganic species on the surface of atmospheric aerosol using time-of-flight secondary ion mass spectrometry (TOF-SIMS)

This work explores the utility of time-of-flight static secondary-ion mass spectrometry (TOF-SIMS) for the analysis of the surface organic layer on individual atmospheric aerosol particles. The surface sensitivity and minimal fragmentation available with TOF-SIMS suggest that it can be a powerful tool for the examination of the organic and inorganic species on the surface of individual particles. Cascade impactors were used to collect aerosol from summer 2000 Montana forest fires, winter snowmobile samples in Yellowstone National Park, Hawaiian lava and sea salt, from an Asian Dust event reaching Salt Lake City, Utah in April 2001 and from Salt Lake Valley summer urban aerosol. TOF-SIMS analysis and multivariate statistical techniques combined gave chemical and morphological information about the particles. Surfaces of the aerosol from forest fires, snowmobile exhaust, and sea salt were all dominated by aliphatic hydrocarbons and their amphiphilic derivatives. Each source showed a different organic chemical signature. The extent and composition of the organics layer which typically covers the surface of atmospheric particles are expected to effect all of the surface related aerosol properties such as health effects, the ability of the particle to activate and form cloud droplets, and the aggregation of particles as well as reactions between the particle and gas phase species.     

Dissolution and solubility of trace metals from natural and anthropogenic aerosol particulate matter

An open flow reactor is used to simulate the dissolution process of mineral aerosol particles in atmospheric water droplets. Data on dissolution kinetic and solubility are provided for the major trace metals from two kinds of matrix: alumino-silicated and carbonaceous sample. The results emphasise that the metals contained in the carbonaceous aerosols are easier dissolved than in the alumino-silicated particles. The released concentrations are not related to the total metal composition or the origin of particles, but are directly associated with the type of liaisons whereby the metals are bound in the solid matrix. Thus, the metals coming from carbonaceous particles are adsorbed impurities or salts and hence are very soluble and with a dissolution hardly dependent on pH, whereas the metals dissolved from alumino-silicated particles are less soluble, notably the ones constitutive of the matrix network (Fe, Mn), and with a dissolution highly influenced by pH. Consequently, in the regions with an anthropogenic influence, the dissolved concentrations of metals found in the atmospheric waters are mainly governed by the elemental carbon content. Moreover, it appears that the dissolution kinetic of metals is not constant as a function of time. The dissolution rates are very rapid in the first 20 min of leaching and then they are stabilised to lower values in comparison to initial rates. By consequence, the total dissolved metal content is provided after the first 20 min of the droplet lifetime. For this reason, the effects of trace metals on the atmospheric aqueous chemistry and as atmospheric wet input to the marine biota are maximal for "aged" droplets.     

Effect of biomass burning and regional background aerosols on CCN activity derived from airborne in-situ measurements

Airborne in-situ measurements were analyzed to investigate the effects of biomass burning and regional background aerosols on cloud condensation nuclei (CCN) activity in the Pacific Dust Experiment (PACDEX) during April and May 2007. Airmass trajectories with both horizontal and vertical motions were provided to identify the aerosol sources. In the biomass burning cases, the elevated aerosol layers were clearly observed at dry conditions because of the convection of airmass in the source region. The relative aging of aerosols was supported by the ratios of BC to particles with size ranging from 0.1 to 1.0 μm (N_0.1–1.0) and BC to carbon monoxide. Compared to aerosols in the precedent plume of biomass burning, aged particles in the latter plume were more activated to CCN at 0.4% (CCN_0.4%) than 0.1% supersaturation (CCN_0.1%) due to aerosols chemical modification during the aging process. On the other hand, significant difference of CCN_0.4% and CCN_0.1% at regional background aerosols over the Pacific Ocean was due to the activated particles below 1 μm in diameter. Although higher concentrations of aged particles were observed over the eastern Pacific Ocean, activated aerosols to cloud droplet was comparatively similar in the western Pacific Ocean because of the similar concentrations of N_0.1–1.0 in both cases.     

Mercury and photochemistry in the marine boundary layer-modelling studies suggest the in situ production of reactive gas phase mercury

Following a modelling investigation of the role of the ambient aerosol in the cycling—that is the transport, transformation and deposition—of mercury in the atmosphere, the precise part played by the sea salt component of the marine aerosol in the remote marine boundary layer has been studied using a combination of models to describe the photolytic, gas phase and aqueous phase and heterogeneous chemistry of the marine boundary layer, in conjunction with inter phase mass transport and mercury chemistry. The role of the ocean in the emission of elemental mercury is, as yet, not entirely understood, but certainly the speciation of mercury deposited to the ocean surface is important as regards its re-emission. Models of mercury chemistry to date have tended to focus on cloud chemistry, and with good reason, as precipitation accounts for a large part of the global mercury deposition pattern; however, the composition of the marine aerosol is entirely different from that of cloud or fog droplets and the modelling studies here show that it plays a more local role being partially responsible for the gas phase speciation of mercury. The role of photochemical processes is investigated and particular attention is paid to halogen chemistry, as the chloride ion has been shown previously to have a notable effect on the concentration of oxidised mercury associated with particles, or better, solution droplets. The role of the sea salt component of the marine aerosol in the production of gas phase oxidised mercury species is described qualitatively and quantitatively.     

Dissolution of trace metals from lava ash: influence on the composition of rainwater in the Mount Etna volcanic area

Dissolution of trace metals from lava ash of the Mount Etna volcano in aqueous suspensions is studied as a function of solution pH and aerosol mass loading. The rate of dissolution and the final concentration increase with decreasing pH. Leaching experiments are found to be consistent with the observations of these metals in rainwater of the volcanic area. Elements such as Fe and Mn are important in the aqueous oxidation of SO(2) which increases the acidity of the rainwater. Leaching of Na, Ca, K, Fe and Mg may have a buffering effect in reacting with cloud and aerosol droplets.     

Estimating fine particulate matter component concentrations and size distributions using satellite-retrieved fractional aerosol optical depth: part 2--a case study

We use the fractional aerosol optical depth (AOD) values derived from Multiangle Imaging Spectroradiometer (MISR) aerosol component measurements, along with aerosol transport model constraints, to estimate ground-level concentrations of fine particulate matter (PM2.5) mass and its major constituents in the continental United States. Regression models using fractional AODs predict PM2.5 mass and sulfate (SO4) concentrations in both the eastern and western United States, and nitrate (NO3) concentrations in the western United States reasonably well, compared with the available ground-level U.S. Environment Protection Agency (EPA) measurements. These models show substantially improved predictive power when compared with similar models using total-column AOD as a single predictor, especially in the western United States. The relative contributions of the MISR aerosol components in these regression models are used to estimate size distributions of EPA PM2.5 species. This method captures the overall shapes of the size distributions of PM2.5 mass and SO4 particles in the east and west, and NO3 particles in the west. However, the estimated PM2.5 and SO4 mode diameters are smaller than those previously reported by monitoring studies conducted at ground level. This is likely due to the satellite sampling bias caused by the inability to retrieve aerosols through cloud cover, and the impact of particle hygroscopicity on measured particle size distributions at ground level.     

Organosulfates from glycolaldehyde in aqueous aerosols and clouds: Laboratory studies

Secondary organic aerosol (SOA) formation is enhanced on acidic seed particles; SOA also forms during cloud processing reactions where acidic sulfate is prevalent. Recently several studies have focused on the identification of organosulfates in atmospheric aerosols or smog chamber experiments, and upon the mechanism of formation for these products. We identify several organosulfate products formed during the laboratory OH radical oxidation of dilute aqueous glycolaldehyde in the presence of sulfuric acid. We propose a radical–radical reaction mechanism as being consistent with formation of these products under our experimental conditions. Using a kinetics model we estimate that organosulfates account for less than 1% of organic matter formed from these precursors during cloud processing. However, in wet acidic aerosols, where precursors are highly concentrated and acidic sulfate makes up close to half of the aerosol mass, this radical–radical reaction could account for significant organosulfate production.     

Deposition rates on smooth surfaces and coagulation of aerosol particles inside a test chamber

Because aerosol particle deposition is an important factor in indoor air quality, many empirical and theoretical studies have attempted to understand the process. In this study, we estimated the deposition rate of aerosol particles on smooth aluminum surfaces inside a test chamber. We investigated the influence of turbulent intensity due to ventilation and fan operation. We also investigated two important processes in particle deposition: turbophoresis, which is significant for micron particles, and coagulation, which is relevant to ultrafine particles (UFP diameter <0.1 μm) at high particle concentrations. Our analysis included semi-empirical estimates of the deposition rates that were compared to available deposition models and verified with simulations of an aerosol dynamics model. In agreement with previous studies, this study found that induced turbulent intensity greatly enhanced deposition rates of fine particles (FP diameter <1 μm). The deposition rate of FP was proportional to the ventilation rate, and it increased monotonically with fan speed. With our setup, turbophoresis was very important for coarse particles larger than 5 μm. The coagulation of aerosol particles was insignificant when the particle concentration was less than 10⁴ cm^?3 during fan operation. The model simulation results verified that the aerosol dynamics module incorporated in our Multi-Compartment and Size-Resolved Indoor Aerosol Model (MC-SIAM) was valid. The behavior of aerosol particles inside our chamber was similar to that found in real-life conditions with the same ventilation rates (0.018–0.39 h^?1) and similar air mixing modes. Therefore, our findings provide insight into indoor particle behavior.     

Interaction of radiation fog with tall vegetation

A one-dimensional radiation fog model is presented. It is coupled with a second model to include the effects of tall vegetation. The fog model describes in detail the dynamics, thermodynamics, and microphysical structure of a fog, as well as the interactions with the atmospheric radiative transfer. A two-dimensional joint size distribution for the aerosol particles and activated fog droplets is used, the activation of aerosol particles is explicitly modeled.The implications of the presence of tall vegetation on the state of the atmosphere and on the evolution of radiation fog are stated. It is shown that the existence of tall vegetation impedes the evolution of radiation fog. The life cycle of radiation fog is discussed. The input of fog water and associated aerosol particles onto the vegetation surfaces via fog water interception processes is assessed.     

Splitting error estimation for micro-physical–multiphase chemical systems in meso-scale air quality models

Operator splitting applied to cloud micro-physical and multiphase chemical process causes the so-called operator splitting errors in addition to other numerical errors when used in numerical models. Operator splitting is mainly used due to limited computer resources or for historical reasons. Unfortunately, it is impossible so far to theoretically estimate either the order of magnitude or the tendency of the splitting errors in complex non-linear systems such as mutually interacting cloud chemical and micro-physical processes.The present study systematically investigates the splitting error mentioned above, by numerical means to define valid ranges of the applicability of the method of operator splitting to those systems. Results of the current study show that de-coupling intervals larger than 100 s cause an underestimation of the total liquid water content as well as the particle radius of the order of 10% for simulation periods of 1000 s. The maximum overprediction of the total content of dissolved material in the particles is of the order of about 20% for de-coupling intervals of 10–15 min. The error in the sulphate production contributes about 50% to the discrepancy in total aerosol content. Since the de-coupling intervals between dynamical, micro-physical, and chemical processes in most recent air quality models are considerably longer than 15 min, the consequences of the application of operator splitting requires further investigation with respect to predicted aerosol formation, cloud water content, deposition rates, photo-chemistry, cloud optical properties, etc.     

The Evolution of Visibility Deterioration and Aerosol Spectra in the St. Louis Urban Plume

Under the auspices of Project METROMEX, studies of visibility de-teoration downwind of St. Louis were conducted during July-August 1974-1975. Estimates of horizontal visual range, standard meteorological data, and aerosol characteristics within the mixing layer were acquired upwind, over, and downwind of the metropolitan area by means of airborne transects. Aerosol number, surface, and volume distributions for particles between 0.025-2.5 µm were generated from the airborne measurement of Aitken nucleus concentrations, cloud condensation nuclei, and aerosols detected in situ with optical probes. Visibility reduction amounting to 50% of prevailing regional upwind visibilities consistently occurs at a distance corresponding to 2-3 hours travel time downwind for an air parcel moving with the mean transport wind. The regions of visibility minimum do not coincide with locations of maximum Aitken nucleus concentrations, but rather correspond in space and time to increased values of cloud condensation nuclei and increased numbers of particles in the 0.1-2.5 µm diameter range. Comparisons of observed aerosol evolution with similar laboratory studies suggest that most of the light scattering aerosols are of secondary origin.     

Mineral dust is a sink for chlorine in the marine boundary layer

Dust particles affect the budgets of important traces gases by providing a surface on which heterogeneous reactions can occur. The uptake of soluble species on dust alters the physical, chemical, and optical properties and the overall ability of dust to act as cloud condensation and ice nuclei. It is commonly assumed that all measured chloride in particulate filter samples is associated with sea-salt particles and any chloride in dust occurs as the result of internal mixtures of sea-salt and dust particles, formed by cloud processing. Here we show high temporal resolution data demonstrating the direct uptake of chlorine by dust via heterogeneous reaction with HCl(g). This reaction added significant amounts of chlorine to the dust particles during a major dust storm, representing 4–9% of the individual dust particle mass. Up to 65±4% of the dust particles contained chlorine due to this heterogeneous reaction during the dust front. Ignoring this process leads to an overestimation of sea-salt concentrations from bulk measurements, and an underestimation of the degree of sea-salt aging. The uptake of chloride will change the pH and hygroscopic properties of the dust and thus can influence the budgets of other reactive gases. Including this heterogeneous process in atmospheric measurements and chemical transport models will improve our ability to predict the atmosphere's composition and radiation budget with greater accuracy.     

Ion balances of size-resolved tropospheric aerosol samples: implications for the acidity and atmospheric processing of aerosols

A large set of size-resolved aerosol samples was inspected with regard to their ion balance to shed light on how the aerosol acidity changes with particle size in the lower troposphere and what implications this might have for the atmospheric processing of aerosols. Quite different behaviour between the remote and more polluted environments could be observed. At the remote sites, practically the whole accumulation mode had cation-to-anion ratios clearly below unity, indicating that these particles were quite acidic. The supermicron size range was considerably less acidic and may in some cases have been close to neutral or even alkaline. An interesting feature common to the remote sites was a clear jump in the cation-to-anion ratio when going from the accumulation to the Aitken mode. The most likely reason for this was cloud processing which, via in-cloud sulphate production, makes the smallest accumulation-mode particles more acidic than the non-activated Aitken-mode particles. A direct consequence of the less acidic nature of the Aitken mode is that it can take up semi-volatile, water-soluble gases much easier than the accumulation mode. This feature may have significant implications for atmospheric cloud condensation nuclei production in remote environments. In rural and urban locations, the cation-to-anion ratio was close to unity over most of the accumulation mode, but increased significantly when going to either larger or smaller particle sizes. The high cation-to-anion ratios in the supermicron size range were ascribed to carbonate associated with mineral dust. The ubiquitous presence of carbonate in these particles indicates that they were neutral or alkaline, making them good sites for heterogeneous reactions involving acidic trace gases. The high cation-to-anion ratios in the Aitken mode suggest that these particles contained some water-soluble anions not detected by our chemical analysis. This is worth keeping in mind when investigating the hygroscopic properties or potential health effects of ultrafine particles in polluted environments.