Application of several activity coefficient models to water-organic-electrolyte aerosols of atmospheric interest

In this work, existing and modified activity coefficient models are examined in order to assess their capabilities to describe the properties of aqueous solution droplets relevant in the atmosphere. Five different water-organic-electrolyte activity coefficient models were first selected from the literature. Only one of these models included organics and electrolytes which are common in atmospheric aerosol particles. In the other models, organic species were solvents such as alcohols, and important atmospheric ions like NH₄⁺ could be missing. The predictions of these models were compared to experimental activity and solubility data in aqueous single electrolyte solutions with 31 different electrolytes. <P style='line-height: 20px;'> Based on the deviations from experimental data and on the capabilities of the models, four predictive models were selected for fitting of new parameters for binary and ternary solutions of common atmospheric electrolytes and organics. New electrolytes (H⁺, NH₄⁺, Na⁺, Cl^-, NO₃^- and SO₄^2-) and organics (dicarboxylic and some hydroxy acids) were added and some modifications were made to the models if it was found useful. All new and most of the existing parameters were fitted to experimental single electrolyte data as well as data for aqueous organics and aqueous organic-electrolyte solutions. Unfortunately, there are very few data available for organic activities in binary solutions and for organic and electrolyte activities in aqueous organic-electrolyte solutions. This reduces model capabilities in predicting solubilities. <P style='line-height: 20px;'> After the parameters were fitted, deviations from measurement data were calculated for all fitted models, and for different data types. These deviations and the calculated property values were compared with those from other non-electrolyte and organic-electrolyte models found in the literature. Finally, hygroscopic growth factors were calculated for four 100 nm organic-electrolyte particles and these predictions were compared to experimental data and to predictions from other models. <P style='line-height: 20px;'> All of the newly fitted models show good agreement with experimental water activity data in binary and ternary solutions. One of the models is for activities of non-electrolytes only, but the other three models show quite small deviations from measured electrolyte activities. Because there were not enough experimental data for organic and electrolyte activities, some models show bigger deviation for mutual deliquescence relative humidities of organic-electrolyte particles, but calculated growth factors for liquid droplets are quite close to the experimental data. Even in cases with somewhat bigger deviations, the results can be considered satisfactory, because they were calculated based mainly on the predictive properties of the models

The role of surfactants in Köhler theory reconsidered

International audienceAtmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is in the organic compounds that are surface active i.e. they concentrate on droplet surface and decrease droplet surface tension. Gibbsian surface thermodynamics were used to find out how partitioning in binary and ternary aqueous solutions affects the droplet surface tension and the droplet bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate was used as a model compound together with sodium chloride to find out the effect the correct evaluation of surfactant partitioning has on the solute effect (Raoult effect). While the partitioning is known to lead to higher surface tension compared to a case in which partitioning is neglected, the present results show that the partitioning also alters the solute effect, and that the change is large enough to further increase the critical supersaturation and hence decrease the droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solution was studied in order to relate the partitioning to more realistic atmospheric situation and to find out the combined effects of dissolution and partitioning behaviour. The results show that correct partitioning consideration alters the shape of the Köhler curve when compared to a situation in which the partitioning is neglected either completely or in the Raoult effect

A method for detecting the presence of organic fraction in nucleation mode sized particles

New particle formation and growth has a very important role in many climate processes. However, the overall knowlegde of the chemical composition of atmospheric nucleation mode (particle diameter, d<20 nm) and the lower end of Aitken mode particles (d&#x2264;50 nm) is still insufficient. In this work, we have applied the UFO-TDMA (ultrafine organic tandem differential mobility analyzer) method to shed light on the presence of an organic fraction in the nucleation mode size class in different atmospheric environments. The basic principle of the organic fraction detection is based on our laboratory UFO-TDMA measurements with organic and inorganic compounds. Our laboratory measurements indicate that the usefulness of the UFO-TDMA in the field experiments would arise especially from the fact that atmospherically the most relevant inorganic compounds do not grow in subsaturated ethanol vapor, when particle size is 10 nm in diameter and saturation ratio is about 86% or below it. Furthermore, internally mixed particles composed of ammonium bisulfate and sulfuric acid with sulfuric acid mass fraction &#x2264;33% show no growth at 85% saturation ratio. In contrast, 10 nm particles composed of various oxidized organic compounds of atmospheric relevance are able to grow in those conditions. These discoveries indicate that it is possible to detect the presence of organics in atmospheric nucleation mode sized particles using the UFO-TDMA method. In the future, the UFO-TDMA is expected to be an important aid to describe the composition of atmospheric newly-formed particles

Hygroscopic properties of ultrafine aerosol particles in the boreal forest: diurnal variation, solubility and the influence of sulfuric acid

International audienceThe hygroscopic growth of aerosol particles present in a boreal forest was measured at a relative humidity of 88%. Simultaneously the gas phase concentration of sulfuric acid, a very hygroscopic compound, was monitored. The focus was mainly on days with new particle formation by nucleation. The measured hygroscopic growth factors (GF) correlated positively with the gaseous phase sulfuric acid concentrations. The smaller the particles, the stronger the correlation, with r=0.20 for 50 nm and r=0.50 for 10 nm particles. The increase in GF due to condensing sulfuric acid is expected to be larger for particles with initially smaller masses. During new particle formation, the changes in solubility of the new particles were calculated during their growth to Aitken mode sizes. As the modal diameter increased, the solubility of the particles decreased. This indicated that the initial particle growth was due to more hygroscopic compounds, whereas the later growth during the evening and night was mainly caused by less hygroscopic or even hydrophobic compounds. For all the measured sizes, a diurnal variation in GF was observed both during days with and without particle formation. The GF was lowest at around midnight, with a mean value of 1.12?1.24 depending on particle size and if new particle formation occurred during the day, and increased to 1.25?1.34 around noon. This can be tentatively explained by day- and nighttime gas-phase chemistry; different vapors will be present depending on the time of day, and through condensation these compounds will alter the hygroscopic properties of the particles in different ways

One in Three of Pediatric Tibia Shaft Fractures is Currently Treated Operatively : A 6-Year Epidemiological Study in two University Hospitals in Finland Treatment of Pediatric Tibia Shaft Fractures

Background: Internal fixation of pediatric tibia shaft fractures has become increasingly popular despite the fact that non-operative treatment results in satisfactory outcome with few exceptions. Indications for surgery and benefits of internal fixation are however still debatable. Materials and Methods: All 296 less than 16-year-old patients treated for a tibia shaft fracture between 2010 and 2015 in two of the five university hospitals in Finland were included in the study. Patient data were analyzed in three treatment groups: cast immobilization in emergency department, manipulation under anesthesia, and operative treatment. Incidence of operative treatment of pediatric tibia shaft fractures was calculated in the cities of Helsinki and Kuopio. Results: A total of 143 (47.3%) children's tibia shaft fractures were treated with casting in emergency department, 71 (22.3%) with manipulation under anesthesia, and 82 (30.4%) with surgery. Mean age of the patients in these treatment groups was 6.2, 8.7, and 12.7 years. Fibula was intact in 89%, 51%, and 27% of the patients, respectively. All 6 patients with multiple fractures and 16 of 18 patients with open fractures were treated operatively. In eight patients, primary non-operative treatment was converted to internal fixation. Operatively treated patients with isolated closed fractures were more likely to have a fibula fracture (46/66 vs 52/214, p <0.001), be older in age (13.08 2.4 vs 6.4 +/- 3.7, p <0.001), and have more primary angulation (6.9 +/- 5.8 vs 0.48 +/- 3.1, p <0.001). Re-operations were done to eight and corrective osteotomy to two operatively treated children. Conclusion: Operative treatment of a pediatric tibia shaft fracture is currently nearly a rule in patients with open or multiple fractures. Surgical treatment of closed tibia shaft fractures is based on surgeon's personal preference, type of fracture and age of the patient.Peer reviewe

The role of surfactants in Köhler theory reconsidered

International audienceAtmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is the organic compounds that are surface active i.e. tend to concentrate on droplet surface and decrease the surface tension. Gibbsian surface thermodynamics was used to find out how partitioning between droplet surface and the bulk of the droplet affects the surface tension and the surfactant bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate (SDS) was used together with sodium chloride to investigate the effect of surfactant partitioning on the Raoult effect (solute effect). While accounting for the surface to bulk partitioning is known to lead to lowered bulk surfactant concentration and thereby to increased surface tension compared to a case in which the partitioning is neglected, the present results show that the partitioning also alters the Raoult effect, and that the change is large enough to further increase the critical supersaturation and hence decrease cloud droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solutions were studied in order to study the partitioning with compounds found in the atmosphere and to find out the combined effects of dissolution and partitioning behavior. The results show that the partitioning consideration presented in this paper alters the shape of the Köhler curve when compared to calculations in which the partitioning is neglected either completely or in the Raoult effect. In addition, critical supersaturation was measured for SDS particles with dry radii of 25-60nm using a static parallel plate Cloud Condensation Nucleus Counter. The experimentally determined critical supersaturations agree very well with theoretical calculations taking the surface to bulk partitioning fully into account and are much higher than those calculated neglecting the partitioning

Commentary on cloud modelling and the mass accommodation coefficient of water

International audienceThe mass accommodation coefficient of water is a quantity for which different experimental techniques have yielded conflicting values in the range 0.04-1. From the viewpoint of cloud modelling, this is an unfortunate situation, since the value of the mass accommodation coefficient affects the model results, e.g. the number concentration of activated cloud droplets. In this commentary we note that in cloud modelling, the primary quantity of interest is the droplet growth rate rather than the mass accommodation coefficient, and that experimental investigations of droplet growth rates provide more direct verification of cloud models than do measurements of the mass accommodation coefficient. Furthermore, we argue that the droplet growth rates calculated in cloud model studies are consistent with experimental results obtained so far only if a mass accommodation coefficient of unity is applied

Technical note: Analytical formulae for the critical supersaturations and droplet diameters of CCN containing insoluble material

International audienceIn this paper, we consider the cloud drop activation of aerosol particles consisting of water soluble material and an insoluble core. Based on the Köhler theory, we derive analytical equations for the critical diameters and supersaturations of such particles. We demonstrate the use of the equations by comparing the critical supersaturations of particles composed of ammonium sulfate and insoluble substances with those of model organic particles with varying molecular sizes