Shipping Remains a Globally Significant Source of Anthropogenic PN Emissions Even after 2020 Sulfur Regulation.

Shipping is the main source of anthropogenic particle emissions in large areas of the globe, influencing climate, air quality, and human health in open seas and coast lines. Here, we determined, by laboratory and on-board measurements of ship engine exhaust, fuel-specific particle number (PN) emissions for different fuels and desulfurization applied in shipping. The emission factors were compared to ship exhaust plume observations and, furthermore, exploited in the assessment of global PN emissions from shipping, utilizing the STEAM ship emission model. The results indicate that most particles in the fresh ship engine exhaust are in ultrafine particle size range. Shipping PN emissions are localized, especially close to coastal lines, but significant emissions also exist on open seas and oceans. The global annual PN produced by marine shipping was 1.2 × 1028 (±0.34 × 1028) particles in 2016, thus being of the same magnitude with total anthropogenic PN emissions in continental areas. The reduction potential of PN from shipping strongly depends on the adopted technology mix, and except wide adoption of natural gas or scrubbers, no significant decrease in global PN is expected if heavy fuel oil is mainly replaced by low sulfur residual fuels. The results imply that shipping remains as a significant source of anthropogenic PN emissions that should be considered in future climate and health impact models.

Concentrations and Adsorption Isotherms for Amphiphilic Surfactants in PM1 Aerosols from Different Regions of Europe.

Predicting the activation of submicrometer particles into cloud droplets in the atmosphere remains a challenge. The importance of surface tension, σ (mN m-1), in these processes has been evidenced by several works, but information on the "surfactants" lowering σ in actual atmospheric particles remains scarce. In this work, PM1 aerosols from urban, coastal, and remote regions of Europe (Lyon, France, Rogoznica, Croatia, and Pallas, Finland, respectively) were investigated and found to contain amphiphilic surfactants in concentrations up to 2.8 µg m-3 in the air and 1.3 M in the particle dry volume. In Pallas, correlations with the PM1 chemical composition showed that amphiphilic surfactants were present in the entire range of particle sizes, supporting recent works. This implied that they were present in hundreds to thousands of particles cm-3 and not only in a few large particles, as it has been hypothesized. Their adsorption isotherms and critical micelle concentration (CMC) were also determined. The low CMC obtained (3 × 10-5-9 × 10-3 M) implies that surface tension depression should be significant for all the particles containing these compounds, even at activation (growth factor ∼ 10). Amphiphilic surfactants are thus likely to enhance the CCN ability of submicrometer atmospheric particles.

A Predictive Model for Steady State Ozone Concentration at an Urban-Coastal Site.

Ground level ozone (O3) plays an important role in controlling the oxidation budget in the boundary layer and thus affects the environment and causes severe health disorders. Ozone gas, being one of the well-known greenhouse gases, although present in small quantities, contributes to global warming. In this study, we present a predictive model for the steady-state ozone concentrations during daytime (13:00⁻17:00) and nighttime (01:00⁻05:00) at an urban coastal site. The model is based on a modified approach of the null cycle of O3 and NOx and was evaluated against a one-year data-base of O3 and nitrogen oxides (NO and NO2) measured at an urban coastal site in Jeddah, on the west coast of Saudi Arabia. The model for daytime concentrations was found to be linearly dependent on the concentration ratio of NO2 to NO whereas that for the nighttime period was suggested to be inversely proportional to NO2 concentrations. Knowing that reactions involved in tropospheric O3 formation are very complex, this proposed model provides reasonable predictions for the daytime and nighttime concentrations. Since the current description of the model is solely based on the null cycle of O3 and NOx, other precursors could be considered in future development of this model. This study will serve as basis for future studies that might introduce informing strategies to control ground level O3 concentrations, as well as its precursors' emissions.

Characteristics of particle emissions and their atmospheric dilution during co-combustion of coal and wood pellets in a large combined heat and power plant.

Coal combustion is one of the most significant anthropogenic CO2 and air pollution sources globally. This paper studies the atmospheric emissions of a power plant fuelled with a mixture of industrial pellets (10.5%) and coal (89.5%). Based on the stack measurements, the solid particle number emission, which was dominated by sub-200 nm particles, was 3.4×1011 MJ-1 for the fuel mixture when electrostatic precipitator (ESP) was cleaning the flue gas. The emission factor was 50 mg MJ-1 for particulate mass and 11 740 ng MJ-1 for the black carbon with the ESP. In the normal operation situation of the power plant, i.e., including the flue-gas desulphurisation and fabric filters (FGD and FF), the particle number emission factor was 1.7×108 MJ-1, particulate mass emission factor 2 mg MJ-1 and black carbon emission factor 14 ng MJ-1. Transmission electron microscopy (TEM) analysis supported the particle number size distribution measurement in terms of particle size and the black carbon concentration. The TEM images of the particles showed variability of the particle sizes, morphologies and chemical compositions. The atmospheric measurements, conducted in the flue-gas plume, showed that the flue-gas dilutes closed to background concentrations in 200 sec. However, an increase in particle number concentration was observed when the flue gas aged. This increase in particle number concentration was interpret as formation of new particles in the atmosphere. In general, the study highlights the importance of detailed particle measurements when utilizing new fuels in existing power plants. Implications: CO2 emissions of energy production decrease when substituting coal with biofuels. The effects of fuels changes on particle emission characteristics have not been studied comprehensively. In this study conducted for a real-scale power plant, co-combustion of wood pellets and coal caused elevated black carbon emissions. However, it was beneficial from the total particle number and particulate mass emission point of view. Flue-gas cleaning can significantly decrease the pollutant concentrations but also changes the characteristics of emitted particles. Atmospheric measurements implicated that the new particle formation in the atmospheric flue-gas plume should be taken into account when evaluating all effects of fuel changes." Are implication statements part of the manuscript?

Homogenous nucleation rates of n-propanol measured in the Laminar Flow Diffusion Chamber at different total pressures.

Nucleation rates of n-propanol were investigated in the Laminar Flow Diffusion Chamber. Nucleation temperatures between 270 and 300 K and rates between 10(0) and 10(6) cm(-3) s(-1) were achieved. Since earlier measurements of n-butanol and n­pentanol suggest a dependence of nucleation rates on carrier gas pressure, similar conditions were adjusted for these measurements. The obtained data fit well to results available from literature. A small positive pressure effect was found which strengthen the assumption that this effect is attributed to the carbon chain length of the n-alcohol [D. Brus, A. P. Hyvärinen, J. Wedekind, Y. Viisanen, M. Kulmala, V. Zdímal, J. Smolík, and H. Lihavainen, J. Chem. Phys. 128, 134312 (2008)] and might be less intensive for substances in the homologous series with higher equilibrium vapor pressure. A comparison with the theoretical approach by Wedekind et al. [Phys. Rev. Lett. 101, 12 (2008)] shows that the effect goes in the same direction but that the intensity is much stronger in experiments than in theory.

Homogeneous water nucleation in a laminar flow diffusion chamber.

Homogeneous nucleation rates of water at temperatures between 240 and 270 K were measured in a laminar flow diffusion chamber at ambient pressure and helium as carrier gas. Being in the range of 10(2)-10(6) cm(-3) s(-1), the experimental results extend the nucleation rate data from literature consistently and fill a pre-existing gap. Using the macroscopic vapor pressure, density, and surface tension for water we calculate the nucleation rates predicted by classic nucleation theory (CNT) and by the empirical correction function of CNT by Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)]. As in the case of other systems (e.g., alcohols), CNT predicts a stronger temperature dependence than experimentally observed, whereas the agreement with the empirical correction function is good for all data sets. Furthermore, the isothermal nucleation rate curves allow us to determine the experimental critical cluster sizes by use of the nucleation theorem. A comparison with the critical cluster sizes calculated by use of the Gibbs-Thomson equation is remarkably good for small cluster sizes, for bigger ones the Gibbs-Thomson equation overestimates the cluster sizes.

The role of sulfuric acid in atmospheric nucleation.

Nucleation is a fundamental step in atmospheric new-particle formation. However, laboratory experiments on nucleation have systematically failed to demonstrate sulfuric acid particle formation rates as high as those necessary to account for ambient atmospheric concentrations, and the role of sulfuric acid in atmospheric nucleation has remained a mystery. Here, we report measurements of new particles (with diameters of approximately 1.5 nanometers) observed immediately after their formation at atmospherically relevant sulfuric acid concentrations. Furthermore, we show that correlations between measured nucleation rates and sulfuric acid concentrations suggest that freshly formed particles contain one to two sulfuric acid molecules, a number consistent with assumptions that are based on atmospheric observations. Incorporation of these findings into global models should improve the understanding of the impact of secondary particle formation on climate.

Adipic and malonic acid aqueous solutions: surface tensions and saturation vapor pressures.

The surface tension of adipic aqueous solutions was measured as a function of temperature (T=278-313 K) and adipic acid mole fraction (X=0.000-0.003) using the Wilhelmy plate method. A parametrization fitted to these data is presented. The evaporation rates of binary water-malonic and water-adipic acid droplets were measured with a TDMA technique at different temperatures (T=293-300 K) and relative humidities (58-80%), and the saturation vapor pressures of subcooled liquid malonic and adipic acids were derived from the data using a binary evaporation model. The temperature dependence of the vapor pressures was obtained as least-squares fits to the derived vapor pressures: ln(Psat,l) (Pa)=220.2389-22634.96/T (K)-26.66767 ln T (K) for malonic acid and ln(Psat,l) (Pa)=140.6704-18230.97/T (K)-15.48011 ln T (K) for adipic acid.

Nucleation simulations using the fluid dynamics software FLUENT with the fine particle model FPM.

This work is an assessment of the capabilities of the FLUENT-FPM software package to simulate actual nucleation experiments. In the first step, we verified the FPM condensation routine with the NEWALC code. Next, homogeneous nucleation of n-butanol, n-pentanol, and n-hexanol in a laminar flow diffusion chamber (LFDC) was simulated and the results were compared to experimental data and an earlier model, which was described by Lihavainen and Viisanen (2001) and will be called femtube2 in the following. Models based on classical nucleation theory typically give too small nucleation rates for alcohol vapors. Also, the FPM underestimates particle production by several orders of magnitude, the factor being a constant for each nucleation isotherm (i.e., at constant nucleation temperature). However, experimental observations beyond exact particle concentrations can be reproduced. We found a behavior similar to the experiment for the dependence of the concentration of nucleated particles N on the flow rate. After correcting the FPM nucleation rate by a constant factor, experimentally found vapor depletion effects could be simulated. Comparing the FPM and femtube2, we observed that the FPM systematically predicts lower saturation ratio values. Further investigation of vapor depletion showed significant differences between the FPM and the femtube2 model. Furthermore, FPM simulations confirm the earlier found carrier gas effect (Lihavainen and Viisanen, 2001).

The carrier gas pressure effect in a laminar flow diffusion chamber, homogeneous nucleation of n-butanol in helium.

Homogeneous nucleation rate isotherms of n-butanol+helium were measured in a laminar flow diffusion chamber at total pressures ranging from 50 to 210 kPa to investigate the effect of carrier gas pressure on nucleation. Nucleation temperatures ranged from 265 to 280 K and the measured nucleation rates were between 10(2) and 10(6) cm(-3) s(-1). The measured nucleation rates decreased as a function of increasing pressure. The pressure effect was strongest at pressures below 100 kPa. This negative carrier gas effect was also temperature dependent. At nucleation temperature of 280 K and at the same saturation ratio, the maximum deviation between nucleation rates measured at 50 and 210 kPa was about three orders of magnitude. At nucleation temperature of 265 K, the effect was negligible. Qualitatively the results resemble those measured in a thermal diffusion cloud chamber. Also the slopes of the isothermal nucleation rates as a function of saturation ratio were different as a function of total pressure, 50 kPa isotherms yielded the steepest slopes, and 210 kPa isotherms the shallowest slopes. Several sources of inaccuracies were considered in the interpretation of the results: uncertainties in the transport properties, nonideal behavior of the vapor-carrier gas mixture, and shortcomings of the used mathematical model. Operation characteristics of the laminar flow diffusion chamber at both under-and over-pressure were determined to verify a correct and stable operation of the device. We conclude that a negative carrier gas pressure effect is seen in the laminar flow diffusion chamber and it cannot be totally explained with the aforementioned reasons.

Homogeneous nucleation rate measurements of 1-butanol in helium: a comparative study of a thermal diffusion cloud chamber and a laminar flow diffusion chamber.

Isothermal homogeneous nucleation rates of 1-butanol were measured both in a thermal diffusion cloud chamber and in a laminar flow diffusion chamber built recently at the Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, Prague, Czech Republic. The chosen system 1-butanol-helium can be studied reasonably well in both devices, in the overlapping range of temperatures. The results were compared with those found in the literature and those measured by Lihavainen in a laminar flow diffusion chamber of a similar design. The same isotherms measured with the thermal diffusion cloud chamber occur at highest saturation ratios of the three devices. Isotherms measured with the two laminar flow diffusion chambers are reasonably close together; the measurements by Lihavainen occur at lowest saturation ratios. The temperature dependences observed were similar in all three devices. The molecular content of critical clusters was calculated using the nucleation theorem and compared with the Kelvin equation. Both laminar flow diffusion chambers provided very similar sizes slightly above the Kelvin equation, whereas the thermal diffusion cloud chamber suggests critical cluster sizes significantly smaller. The results found elsewhere in the literature were in reasonable agreement with our results.

Homogeneous nucleation rates of higher n-alcohols measured in a laminar flow diffusion chamber.

Nucleation rate isotherms of n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol were measured in a laminar flow diffusion chamber using helium as carrier gas. The measurements were made at 250-310 K, corresponding to reduced temperatures of 0.43-0.50, and at atmospheric pressure. Experimental nucleation rate range was from 10(3) to 10(7) cm(-3) s(-1). The expression and accuracy of thermodynamic parameters, in particular equilibrium vapor pressure, were found to have a significant effect on calculated nucleation rates. The results were compared to the classical nucleation theory (CNT), the self-consistency corrected classical theory (SCC) and the Hale's scaled model of the CNT. The average ratio between the experimental and theoretical nucleation rates for all alcohols used was 1.5x10(3) when the CNT was used, and 0.2x10(-1) when the SCC was used and 0.7x10(-1) when the Hale's scaled theory was used. The average values represent all the alcohols used at the same reduced temperatures. The average ratio was about the same throughout the temperature range, although J(exp)/J(the) calculated with the Hale's scaled theory increased slightly with increasing temperature. The saturation ratio dependency was predicted closest to experiment with the classical nucleation theory. The nucleation rates were compared to those found in the literature. The measurements were in reasonable agreement with each other. The molecular content of critical alcohol clusters was between 35 and 80 molecules. At a fixed reduced temperature, the number of molecules in a critical cluster decreased as a function of alcohol carbon chain length. The number of molecules in critical clusters was compared to those predicted by the Kelvin equation. The theory predicted the critical cluster sizes well.