Seasonal Aerosol Acidity, Liquid Water Content and Their Impact on Fine Urban Aerosol in SE Canada

This study explores the drivers of aerosol pH and their impact on the inorganic fraction and mass of aerosol in the S.E. Canadian urban environments of Hamilton and Toronto, Ontario. We find that inter-seasonal pH variability is mostly driven by temperature changes, which cause variations of up to one pH unit. Wintertime acidity is reduced, compared to summertime values. Because of this, the response of aerosol to precursors fundamentally changes between seasons, with a strong sensitivity of aerosol mass to levels of HNO3 in the wintertime. Liquid water content (LWC) fundamentally influences the aerosol sensitivity to NH3 and HNO3 levels. In the summertime, organic aerosol is mostly responsible for the LWC at Toronto, and ammonium sulfate for Hamilton; in the winter, LWC was mostly associated with ammonium nitrate at both sites. The combination of pH and LWC in the two sites also affects N dry deposition flux; NO3 fluxes were comparable between the two sites, but NH3 deposition flux at Toronto is almost twice what was seen in Hamilton; from November to March N deposition flux slows down leading to an accumulation of N as NO3 in the particle phase and an increase in PM2.5 levels. Given the higher aerosol pH in Toronto, aerosol masses at this site are more sensitive to the emission of HNO3 precursors compared to Hamilton. For both sites, NOx emissions should be better regulated to improve air quality during winter; this is specifically important for the Toronto site as it is thermodynamically more sensitive to the emissions of HNO3 precursors.

Dry and ambient aerosol properties at the Jungfraujoch

Remo Nessler

Atmospheric aerosol is defined as a suspension of solid or liquid particles in air. The major concerns about aerosol particles are their adverse health effects and their role in the Earth's climate system. Atmospheric particles influence the Earth's radiation budget in two ways: either directly by scattering and absorbing incoming solar radiation (and to a far less extent longwave radiation emitted from the Earth) or indirectly by their ability to act as cloud condensation nuclei (CCN). With increasing particle concentrations, caused by, e.g., anthropogenic emissions, more CCN are available to form cloud droplets. For a fixed water content in the atmosphere this leads to more but smaller droplets and therefore to enhanced cloud albedos as well as to rain suppression. Both effects have been recognized in recent years to be of great importance for understanding the observed climate change. Nevertheless, they remain poorly understood and quantified. The Jungfraujoch (JFJ, 3580 m asl; 46.548°N, 7.984°E) High Alpine Research Station is equipped with instruments that have for decades performed important Global Climate Observations. A major part of the aerosol instruments perform in-situ measurements. However, due to the harsh weather conditions, they usually cannot be run outdoors. The ambient air has to be inducted into a housing, such that the aerosol is sampled at a temperature (T) and relative humidity (RH) different from the ambient values. Therefore, the measured aerosol properties may considerably differ from the ambient — the climate-relevant — ones. During the first Cloud and Aerosol Characterization Experiment (CLACE) at the JFJ in-situ aerosol size distributions were measured simultaneously indoor at dry conditions (T ≈ 25 °C and RH < 10%) and, for the first time in such an exposed place, outdoor at ambient conditions (T < –5 °C) by means of two scanning mobility particle sizers (SMPS). The data set was completed by measurements of hygroscopic growth factors using a hygroscopicity tandem differential mobility analyzer (H-TDMA). A comparison of dry and ambient size distributions shows two main features: First, the dry total number concentration is often considerably smaller (on average 28%) than the ambient total number concentration. This is most likely due to the evaporation of volatile material at the higher indoor temperature. These particle losses mainly concern small particles (dry diameter Ddry ≤ 100 nm), and therefore have only a minimal affect on the surface and volume concentrations. Second, the dry number size distribution is shifted towards smaller particles, reflecting the hygroscopic behavior of the aerosols. This shift was modeled using a modified Köhler equation adapted to the measured hygroscopic growth factors. The corrected dry surface and volume concentrations are in good agreement with the ambient measurements for the whole RH range, but the correction works best for RH < 80%. The results indicate that size distribution data measured at indoor conditions (i.e. dry and warm) may be successfully corrected to reflect ambient conditions. By combining these results with earlier JFJ aerosol measurements (e.g. chemical composition), it was possible to model dry and ambient optical aerosol properties for a summer and a winter case. The model calculations were based on a total of 496 size distributions representative for the JFJ aerosol, hygroscopic growth parameterizations and the following simplified aerosol structures: The fine mode (Ddry ≤ 1 µm) aerosol was assumed to consist of a water-insoluble spherical core concentrically encased by a coating comprising all water-soluble compounds, and the coarse mode (Ddry > 1 µm) particles were assumed to be water-insoluble homogeneous spheres. Ambient scattering coefficients σsca(RH) were found to be considerably different from the dry scattering coefficients σsca(RH = 0). The scattering enhancement factors ξ(RH) = σsca(RH)/σsca(RH = 0) strongly depend on the particle size. At RH = 85% they vary for example between ≈ 1.2 and ≈ 3.8. It was possible to establish a parameterization of ξ(RH) with the dry Ångström exponent å (based on scattering only). Since å follows directly from the dry scattering measurements, the parameterization allows to derive ambient scattering coefficients from the dry scattering coefficients without the need of any additional measurement other than ambient RH. RH also affects the absorption coefficient σabs. Depending on particle size and wavelength (investigated between 370 nm and 950 nm) absorption enhancement factors χ(RH) = σabs(RH)/σabs(RH = 0) were found to range from 0.84 to 1.78. However, it was possible to demonstrate that, even though the humidity effect on absorption is substantial, its contribution to the humidity effect on extinction and the single scattering albedo is negligible at the JFJ. The EPFL Raman lidar installed at the JFJ provides profiles of extinction and backscattering coefficients at the wavelengths 355 nm, 532 nm and 1064 nm for altitudes between typically 4 km and 15 km asl. These measurements are ambient but afflicted with more uncertainties than the dry in-situ measurements. A method was developed to derive microphysical aerosol properties from optical lidar data. This is a so-called ill-posed problem, i.e., small errors in the lidar data lead to huge errors in the inverted microphysical properties, unless special mathematical tools are applied. Therefore the method makes use of regularization techniques. It is shown that microphysical parameters can be inverted with acceptable accuracy from an optical dataset as it is provided by a lidar of e.g. the EPFL type.

EPFL2004

Chemistry and climate interactions

Luca Pozzoli

Atmospheric trace gases and aerosols and climate interact in many ways. A quantitative assessment of the influence of trace gases and aerosols on climate can only be achieved if the interactions and feedbacks among these three major components are accounted for. The goal of this thesis was to develop, evaluate and apply the ECHAM5-HAMMOZ chemistry-aerosol-climate model. The model includes fully interactive simulations of the NOx-Ox-hydrocarbons chemistry and of the aerosol chemistry and microphysics, the two simulations being embedded into the well established ECHAM5 climate model. In particular, on-line calculation of the photolysis rates (that accounts for aerosols and clouds) and heterogeneous reactions of trace gases on aerosols are accounted for in the model. In addition, the aerosol simulation provides a prognostic representation of the mixing state of the aerosol components, a feature that is particularly important to examine the effect of the SO2 uptake and subsequent sulfate formation on aerosols. A thorough model evaluation of the model was performed using observations from the Transport and Chemical Evolution over the Pacific (TRACE-P) aircraft campaign. We also used ground based measurements from the European network EMEP (SO2 and sulfate), from the north American network IMPROVE (sulfate, black carbon and organic carbon), and from AERONET (aerosol optical depth). The coupled model is able to reproduce fairly well many of the observations over the TRACE-P region, even though some improvements are still needed. For example, we find a mean absolute bias of 20 ppbv (30%) and 40 ppbv (13%) for the simulated O3 and CO, respectively. Sulfate concentrations are represented fairly well, for all the regions considered, while SO2 is overestimated by a factor of 2 in general. Black carbon concentrations are underestimated over the TRACE-P region (mean absolute bias of 80%), most probably because of too low emissions, but well reproduced over north America. The aerosol optical depths compare well with observations at many sites in general, both in terms of annual means and seasonal variations. We show the results from a series of sensitivity simulations which goals are to assess the impact of heterogeneous reactions, photolysis reactions and sulfur chemistry on the regional and global trace gas distribution, and aerosol distribution, composition and optical properties. We found that heterogeneous reactions result in a reduction of 7% in the global O3 burden, and by up to 15% in surface O3 over regions rich in mineral dust. OH burden decreases by 10%, NO and NO2 by 20% and 29%, respectively while CO burden increases by 7%. Our numbers fall in general within the range of previous studies. We find that the effect of aerosols through the modifications of photolysis rates do not affect significantly the trace gas distributions and global burdens, while previous studies suggested larger effect. Heterogeneous reactions reduce the global mean SO2 surface concentration by 14%, while the global burden remains unchanged. This reflects the effect of competing processes. In particular, the depletion in SO2 by direct uptake on sea salt and dust is counterbalanced by the decrease in SO2 oxidation that is associated with the decrease in OH. The balance between the two competing effects differs depending on the regions (SO2 increases by more than +10% over north Africa and Indian Ocean and decreases by up to -20% at high latitudes). These processes, in turn, affect the sulfate formation. We find in general an increase (by up to 4%) in sulfate burden over the oceans because of sea salt uptake of SO2, and a decrease by up to 6% over Sahara and India, where SO2 increases. Our global burden of SO2 and sulfate amount to 0.77 and 0.87 (Tg(S)), respectively, which fall in the range of previous estimates. We find that SO2 uptake on sea salt contributes to the production of 3.69 Tg(S) yr-1 of sulfate (5% of total sulfate production) in good agreement with recent observation-based estimates. Uptake of SO2 on dust only contributes to the production of 0.55 Tg(S) yr-1 (< 1%) of sulfate, but it is an important process as it is responsible for the coating of mineral dust particles. A total of 300 Tg yr-1 of dust are transferred from the insoluble to the soluble mixed modes (56% of total emissions) because of this later process. The total burden of black carbon does not change significantly because of the heterogeneous reactions, but it is redistributed between insoluble/soluble modes. The changes in the mixing state of aerosols produce significant regional variations in aerosol optical depth and absorption. The aerosol optical depth and aerosol absorption increase by 10 to 30% and by 15%, respectively, during winter in the main polluted regions of the north hemisphere because of enhancing absorption efficiency of black carbon mixed with sulfate. On the contrary aerosol absorption decreases by up to 20% over the Atlantic ocean because of enhancing black carbon removal by wet scavenging. ECHAM5-HAMMOZ is a fully coupled model which includes many of the trace gas-aerosol and chemistry-climate interactions, and is thus a tool that allows an integrated assessment of the impact of the major short-life species that contribute to climate change and air quality.

EPFL2007

Effectiveness of ammonia reduction on control of fine particle nitrate

Hairun Guo, Athanasios Nenes

In some regions, reducing aerosol ammonium nitrate (NH4NO3) concentrations may substantially improve air quality. This can be accomplished by reductions in precursor emissions, such as nitrogen oxides (NO) to lower nitric acid (HNO3) that partitions to the aerosol, or reductions in ammonia (NH3) to lower particle pH and keep HNO3 in the gas phase. Using the ISORROPIA-II thermodynamic aerosol model and detailed observational data sets, we explore the sensitivity of aerosol NH4NO3 to gas-phase NH3 and NOx controls for a number of contrasting locations, including Europe, the United States, and China. NOx control is always effective, whereas the aerosol response to NH3 control is highly nonlinear and only becomes effective at a thermodynamic sweet spot. The analysis provides a conceptual framework and fundamental evaluation on the relative value of NOx versus NH3 control and demonstrates the relevance of pH as an air quality parameter. We find that, regardless of the locations examined, it is only when ambient particle pH drops below an approximate critical value of 3 (slightly higher in warm and slightly lower in cold seasons) that NH3 reduction leads to an effective response in PM2.5 mass. The required amount of NH3 reduction to reach the critical pH and efficiently decrease NH4NO3 at different sites is assessed. Owing to the linkage between NH3 emissions and agricultural productivity, the substantial NH3 reduction required in some locations may not be feasible. Finally, controlling NH3 emissions to increase aerosol acidity and evaporate NH4NO3 will have other effects, beyond reduction of PM2.5 NH4NO3, such as increasing aerosol toxicity and potentially altering the deposition patterns of nitrogen and trace nutrients. © 2018 Author(s).