Deliquescent Particles Research Articles

Dynamics and Viability of Airborne Respiratory Syncytial Virus under Various Indoor Air Conditions.

The factors governing the viability of airborne viruses embedded within respiratory particles are not well understood. This study aimed to investigate the relative humidity (RH)-dependent viability of airborne respiratory syncytial virus (RSV) in simulated respiratory particles suspended in various indoor air conditions. We tested airborne RSV viability in three static indoor air conditions, including sub-hysteresis (RH < 39%), hysteresis (39% < RH < 65%), and super-hysteresis (RH > 65%) air as well as in three dynamic indoor air conditions, including the transitions between the static conditions. The dynamic conditions were hysteresis → super-hysteresis → hysteresis, sub-hysteresis → hysteresis, and super-hysteresis → hysteresis. We found that after 45 min of particle aging in static conditions, the viability of RSV in sub-hysteresis, hysteresis, and super-hysteresis air was 0.72% ± 0.06%, 0.03% ± 0.006%, and 0.27% ± 0.008%, respectively. After 45 min of aging in dynamic conditions, the RSV viability decreased for particles that remained in a liquid (deliquesced) state during aging when compared with particles in a solid (effloresced) state. The decreased viability of airborne RSV for deliquesced particles is consistent with prolonged exposure to elevated aqueous solutes. These results represent the first measurements of the survival of airborne RSV over particle aging time, with equal viability in low, intermediate, and high RHs at 5 and 15 min and a V-shaped curve after 45 min.

Factors Influencing the Formation of Nitrous Acid from Photolysis of Particulate Nitrate.

Enhanced photolysis of particulate nitrate (pNO3) to form photolabile species, such as gas-phase nitrous acid (HONO), has been proposed as a potential mechanism to recycle nitrogen oxides (NOx) in the remote boundary layer ("renoxification"). This article presents a series of laboratory experiments aimed at investigating the parameters that control the photolysis of pNO3 and the efficiency of HONO production. Filters on which artificial or ambient particles had been sampled were exposed to the light of a solar simulator, and the formation of HONO was monitored under controlled laboratory conditions. The results indicate that the photolysis of pNO3 is enhanced, compared to the photolysis of gas-phase HNO3, at low pNO3 levels, with the enhancement factor reducing at higher pNO3 levels. The presence of cations (Na+) and halides (Cl-) and photosensitive organic compounds (imidazole) also enhance pNO3 photolysis, but other organic compounds such as oxalate and succinic acid have the opposite effect. The precise role of humidity in pNO3 photolysis remains unclear. While the efficiency of photolysis is enhanced in deliquescent particles compared to dry particles, some of the experimental results suggest that this may not be the case for supersaturated particles. These experiments suggest that both the composition and the humidity of particles control the enhancement of particulate nitrate photolysis, potentially explaining the variability in results among previous laboratory and field studies. HONO observations in the remote marine boundary layer can be explained by a simple box-model that includes the photolysis of pNO3, in line with the results presented here, although more experimental work is needed in order to derive a comprehensive parametrization of this process.

Kinetics of hypochlorous acid reactions with organic and chloride-containing tropospheric aerosol.

Chlorine plays an important role in tropospheric oxidation processes, in both marine and continental environments. Although modeling studies have explored the importance of halogen chemistry, uncertainty remains in associated chemical mechanisms and fundamental kinetics parameters. Prior kinetics measurements of multiphase halogen recycling reactions have been largely performed with dilute, bulk solutions, leaving unexplored more realistic chemical systems which have high solute concentrations and are internally mixed with both halide and organic components. Here, we address the multiphase kinetics of gaseous HOCl using an aerosol flow tube and aerosol mass spectrometer to study its reactions with particulate chloride, using atmospherically relevant particle acidity, solute concentrations, and ionic strength. We also investigate the chemistry that results when biomass burning (BB) aerosol components and chloride are internally mixed. Using pH-buffered deliquesced particles, we show that the rate constant for reaction of dissolved HOCl with H+ and Cl- at high relative humidity (RH) (80-85%) is within a factor of two of the literature value for bulk phase conditions. However, at lower RH values (60-70%) where the particles are considerably more concentrated, the rate constant for chloride loss from the particles is an order of magnitude higher. For pure organic compounds commonly found in biomass burning (BB) aerosol, such as coniferaldehyde, salicylic acid and furfural, an increase in the aerosol chlorine content occurs with HOCl exposure, indicating the formation of organochlorine species. Together, these independent findings explain results for internally mixed aerosol particles with both chloride and BB components present where we observed behavior consistent with both chloride loss and organochlorine formation occurring simultaneously upon HOCl exposure. Our results indicate that chlorine recycling via HOCl uptake by chloride-containing particles will occur in the atmosphere efficiently over a wide range of RH conditions, even when reactive organic compounds are present in the same particles as chloride. Simultaneously, formation of organochlorine compounds, which are commonly toxic, is likely occurring when reactive organic components are present.

Oxidation of sulfur dioxide by nitrogen dioxide accelerated at the interface of deliquesced aerosol particles.

Although the multiphase chemistry of SO2 in aerosol particles is of great importance to air quality under polluted haze conditions, a fundamental understanding of the pertinent mechanisms and kinetics is lacking. In particular, there is considerable debate on the importance of NO2 in the oxidation of SO2 in aerosol particles. Here experiments with atmospherically relevant deliquesced particles at buffered pH values of 4-5 show that the effective rate constant for the reaction of NO2 with SO32- ((1.4 ± 0.5) × 1010 M-1 s-1) is more than three orders of magnitude larger than the value in dilute solutions. An interfacial reaction at the surface of aerosol particles probably drives the very fast kinetics. Our results indicate that oxidation of SO2 by NO2 at aerosol surfaces may be an important source of sulfate aerosols under polluted haze conditions.

Secondary aerosol formation from dimethyl sulfide – improved mechanistic understanding based on smog chamber experiments and modelling

Abstract. Dimethyl sulfide (DMS) is the dominant biogenic sulfur compound in the ambient marine atmosphere. Low-volatility acids from DMS oxidation promote the formation and growth of sulfur aerosols and ultimately alter cloud properties and Earth's climate. We studied the OH-initiated oxidation of DMS in the Aarhus University Research on Aerosol (AURA) smog chamber and the marine boundary layer (MBL) with the aerosol dynamics and gas- and particle-phase chemistry kinetic multilayer model ADCHAM. Our work involved the development of a revised and comprehensive multiphase DMS oxidation mechanism, capable of both reproducing smog chamber and atmospheric relevant conditions. The secondary aerosol mass yield in the AURA chamber was found to have a strong dependence on the reaction of methyl sulfinic acid (MSIA) and OH, causing a 82.8 % increase in the total PM at low relative humidity (RH), while the autoxidation of the intermediate radical CH3SCH2OO forming hydroperoxymethyl thioformate (HPMTF) proved important at high temperature and RH, decreasing the total PM by 55.8 %. The observations and modelling strongly support the finding that a liquid water film existed on the Teflon surface of the chamber bag, which enhanced the wall loss of water-soluble intermediates and oxidants dimethyl sulfoxide (DMSO), MSIA, HPMTF, SO2, methanesulfonic acid (MSA), sulfuric acid (SA) and H2O2. The effect caused a 64.8 % and 91.7 % decrease in the secondary aerosol mass yield obtained at both dry (0 % RH–12 % RH) and humid (50 % RH–80 % RH) conditions, respectively. Model runs reproducing the ambient marine atmosphere indicate that OH comprises a strong sink of DMS in the MBL (accounting for 31.1 % of the total sink flux of DMS) although less important than the combined effect of halogen species Cl and BrO (accounting for 24.3 % and 38.7 %, respectively). Cloudy conditions promote the production of SO42- particular mass (PM) from SO2 accumulated in the gas phase, while cloud-free periods facilitate MSA formation in the deliquesced particles. The exclusion of aqueous-phase chemistry lowers the DMS sink as no halogens are activated in the sea spray particles and underestimates the secondary aerosol mass yield by neglecting SO42- and MSA PM production in the particle phase. Overall, this study demonstrated that the current DMS oxidation mechanisms reported in literature are inadequate in reproducing the results obtained in the AURA chamber, whereas the revised chemistry captured the formation, growth and chemical composition of the formed aerosol particles well. Furthermore, we emphasize the importance of OH-initiated oxidation of DMS in the ambient marine atmosphere during conditions with low sea spray emissions.

Aqueous-phase oxidation of syringic acid emitted from biomass burning: Formation of light-absorbing compounds

Syringic acid is a methoxyphenol model compound derived from biomass burning, and its photooxidation processes have important effects on atmospheric chemistry. However, its aqueous-phase photochemistry remains unclear. In this study, we systematically report the photooxidation of syringic acid induced by OH radicals in the aqueous phase. Employing the relative rate technique, the bimolecular rate constant for syringic acid reaction with OH radicals was acquired to be (1.1 ± 0.3) × 1010 M−1 s−1. Notably, colored products were formed as the reaction progressed. Furthermore, the UV–vis and fluorescence spectra confirmed the formation of light-absorbing organic species, and the results agreed well with previous results on atmospheric and natural humic-like substances (HULIS). The photooxidation products were detected by high performance liquid chromatography mass spectrometry (HPLC/MS), and a possible reaction mechanism was proposed. The aqueous-phase reaction of syringic acid would undergo functionalization process forming a hydroxylation product that enhances the degree of oxidation of aqueous secondary organic aerosol (aqSOA), and goes through dimerization process by C-C or C-O coupling of phenoxy radicals which may conduce to the formation of HULIS. These findings suggest that the photooxidation of syringic acid is an important pathway for highly oxygenated phenolic aqSOA formation, providing a secondary source for HULIS in a liquid phase or in deliquescent particles surrounded by a layer of water.

Ionic strength effect on the formation of organonitrate compounds through photochemical degradation of vanillin in liquid water of aerosols

The ionic strength can affect the photochemical reactions occurring in the liquid core of the aerosol deliquescent particles. Yet, the investigations related to ionic strength effect on aqueous-phase reactions are limited. Here we assess the photochemical degradation of a typical lignin-derived compound, vanillin (VL), upon addition of either sodium nitrate (NaNO3) or sodium sulfate (Na2SO4). The UV-VIS absorption spectra of VL exhibits a hyperchromic effect and a bathochromic shift of the n→π* absorption band, in going from λmax = 310 nm in the dilute aqueous phase to λmax = 346 nm at I = 0.3 M adjusted by Na2SO4. A hypsochromic shift of the n→π* absorption band of VL, in going from λmax = 310 nm in the dilute liquid water to λmax = 303 nm at Ieff = 0.124 M is observed when the ionic strength was adjusted with NaNO3.At fixed pH ≈ 4, representing both the cloud droplets and the liquid core of the aerosol particles, the pseudo-first-order rate constant, k1st (Ieff.→0) = (1.5 ± 0.2) x 10−5 s−1, in dilute aqueous solution (Ieff = 0 M, NaNO3), linearly decreases to (k1st = (3.7 ± 0.2) x 10−6 s−1), at Ieff = 0.124 M (NaNO3) with kinetic salting coefficient b = -(4.8 ± 0.2) L mol−1. The very subtle pH change of the absorption spectra of irradiated VL is observed due to the formation of carboxylic acids, hydroxylated compounds and oligomers which presence was confirmed by FT-ICR MS analysis. Most likely aliphatic like CHO compounds are formed upon photodegradation of VL in dilute aqueous phase while the condensed aromatic CHO and CHON compounds are produced in presence of nitrate ions (Ieff = 0.124 M). These results suggest that inorganic ions present in the liquid water of aerosols alters the kinetics and the product formation of photochemical degradation of organic compounds which in turn can affect the light absorption properties of aerosols.

Ionic Strength Effect Alters the Heterogeneous Ozone Oxidation of Methoxyphenols in Going from Cloud Droplets to Aerosol Deliquescent Particles.

Methoxyphenols are one of the most abundant classes of biomarker tracers for atmospheric wood smoke pollution. The reactions of atmospheric oxidants (ozone, OH) with methoxyphenols can contribute to the formation of secondary organic aerosols (SOA). Here, for the first time, we use the well-established vertical wetted wall flow tube (VWWFT) reactor to assess the effect of ionic strength (I), pH, temperature, and ozone concentration on the reaction kinetics of ozone with acetosyringone (ACS), as a representative methoxyphenol compound. At fixed pH 3, typical for acidic atmospheric deliquescent particles, and at I = 0.9 M adjusted by Na2SO4, the uptake coefficient (γ) of O3 increases by 2 orders of magnitude from γ = (5.0 ± 0.8) × 10-8 on neat salt solution (Na2SO4) to γ = (6.0 ± 0.01) × 10-6 on a mixture of ACS and Na2SO4. The comparison of the uptake coefficients of O3 at different pH values indicates that the reaction kinetics strongly depends on the acidity of the phenolic group of ACS. The observed different reactivity of gas-phase ozone with ACS has implications for ozone uptake by the dilute aqueous phase of cloud droplets and by aerosol deliquescent particles loaded with inorganic salts, and it can affect the formation of SOA in the atmosphere.

Treatment of non-ideality in the SPACCIM multiphase model – Part 2: Impacts on the multiphase chemical processing in deliquesced aerosol particles

Abstract. Tropospheric deliquesced particles are characterised by concentrated non-ideal solutions (“aerosol liquid water” or ALW) that can affect the occurring multiphase chemistry. However, such non-ideal solution effects have generally not yet been considered in and investigated by current complex multiphase chemistry models in an adequate way. Therefore, the present study aims at accessing the impact of non-ideality on multiphase chemical processing in concentrated aqueous aerosols. Simulations with the multiphase chemistry model (SPACCIM-SpactMod) are performed under different environmental and microphysical conditions with and without a treatment of non-ideal solutions in order to assess its impact on aqueous-phase chemical processing. The present study shows that activity coefficients of inorganic ions are often below unity under 90 % RH-deliquesced aerosol conditions and that most uncharged organic compounds exhibit activity coefficient values of around or even above unity. Due to this behaviour, model studies have revealed that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), oxidants, and related chemical subsystems such as organic chemistry. In detail, both the chemical formation and oxidation rates of Fe(II) are substantially lowered by a factor of 2.8 in the non-ideal base case compared to the ideal case. The reduced Fe(II) processing in the non-ideal base case, including lowered chemical rates of the Fenton reaction (−70 %), leads to a reduced processing of HOx∕HOy under deliquesced aerosol conditions. Consequently, higher multiphase H2O2 concentrations (larger by a factor of 3.1) and lower aqueous-phase OH concentrations (lower by a factor of ≈4) are modelled during non-cloud periods. For H2O2, a comparison of the chemical reaction rates reveals that the most important sink, the reaction with HSO3-, contributes with a 40 % higher rate in the non-ideal base case than in the ideal case, leading to more efficient sulfate formation. On the other hand, the chemical formation rates of the OH radical are about 50 % lower in the non-ideal base case than in the ideal case, leading to lower degradation rates of organic aerosol components. Thus, considering non-ideality influences the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For example, the reduced oxidation budget under deliquesced particle conditions leads to both increased and decreased concentration levels, e.g. of important C2∕C3 carboxylic acids. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations than observed under ambient highly polluted conditions. Furthermore, the simulations imply that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes.

Ionic strength effects on heterogeneous and multiphase chemistry: Clouds versus aerosol particles

The ionic strength effect can influence the kinetics and products distribution within the liquid water content (LWC) of aerosol deliquescent particles. The heterogeneous reactions of atmospheric oxidants (O3, SO2, and NO2, among others) with liquid core of aerosols can be also influenced by ionic strength, which in turn can impact important atmospheric processes such as haze formation. However, the ionic strength effects on liquid phase reactions and on heterogeneous reactions of atmospheric relevance have been barely studied in the past. Finally, the gas-liquid equilibrium can be affected by ionic strength of the liquid water. Here we highlight the importance of ionic strength effects on chemical processes in the aerosol deliquescent particles. We give the future directions on this topic emphasizing that ionic strength can affect the absorption and/or scattering properties of aerosol particles and cloud droplets which in turn is crucial for accurate estimates of radiative forcing of clouds and aerosols.

The Giant Nucleus Impactor (GNI)—A System for the Impaction and Automated Optical Sizing of Giant Aerosol Particles with Emphasis on Sea Salt. Part I: Basic Instrument and Algorithms

AbstractSize distributions of giant aerosol particles (dry radius larger than 0.5μm, sometimes referred to as coarse-mode aerosol particles) are not well characterized in the atmosphere. Measurements are problematic for these particles because they (i) occur in low concentrations, (ii) have difficulty in passing through air inlets, (iii) may be dry or deliquesced particles, and (iv) if sampled by impaction, typically require labor-intensive methods. In this study, a simple, high-volume impaction system called the Giant Nucleus Impactor (GNI), based on free-stream exposure of polycarbonate slides from aircraft, is described along with an automated optical microscope–based system for analysis of the impacted particles. The impaction slides are analyzed in a humidity-controlled chamber (typically 90% relative humidity) that ensures deliquescence of soluble (typically sea salt) particles. A computer-controlled optical microscope with two digital cameras is used to acquire and analyze images of the aerosol particles. At relative humidities above deliquescence (74% RH for sea salt), such particles will form near-spherical cap solution drops on the polycarbonate slides. The sea-salt mass in each giant aerosol particle is then calculated using simple geometry and published water activity measurements. The system has a sample volume of about 10 L s−1at aircraft speeds of 105 m s−1. For salt particles, the measurement range is from about 0.7μm dry radius to at least 16μm dry radius, with a size-bin resolution of 0.2μm dry radius. The sizing accuracy was tested using polystyrene latex (PSL) beads of known size.

Correction to: A conceptual model to understand the soluble and insoluble Cr species in deliquesced particles

The original version of this article unfortunately contained a mistake. The authors missed to include following statement as Acknowledgment.

Formation of highly oxygenated multifunctional compounds from cross-reactions of carbonyl compounds in the atmospheric aqueous phase

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but this chemistry is currently not adequately represented in atmospheric models due to the missing information on most products. The main focus of this study is to provide molecular-level insight into the photosensitized reaction mechanism of pyruvic acid (PA) alone in the atmospheric aqueous phase, and of mixtures of PA with glyoxal (GL), a typical and widely occurring carbonyl compound. With two ultrahigh resolution mass spectrometers, ORBITRAP and FT-ICR-MS, a broad and complex spectrum of organic products were unambiguously identified. The detected formation of organic compounds illustrates the progression from C3 to C20 molecules through direct PA photolysis and irradiation of PA + GL. The performed ab-initio calculations indicate that cross-reactions (i.e., PA + GL) are more likely than self-reactions (i.e., PA alone) in clouds and aerosol deliquescent particles. Hence, this result implies that photosensitizers like PA can initiate the transformation of common organic cloud constituents like GL into highly oxygenated multifunctional compounds. These high-molecular- weight compounds that are formed in significant amount could potentially impact optical and cloud-forming properties of aerosols, especially if they partition to the aerosol surface.

A conceptual model to understand the soluble and insoluble Cr species in deliquesced particles

Trivalent chromium is a trace nutrient essential to human beings while hexavalent chromium is a known carcinogen and was among the 18 core hazardous air pollutants defined in 2004 by the US EPA. A new conceptual model of Cr speciation in deliquesced particles (pH 4) has been developed. The model provides new information on the soluble and insoluble forms of Cr in atmospheric PM. The dominant form of Cr(VI) in the solution was found to be Cr2O72−. CrO42− was produced by the dissolution of Na2CrO4(s) and K2CrO4(s) available in the solid core, but a considerable portion of the CrO42− precipitated as (NH4)2CrO4(s), CaCrO4(s), BaCrO4(s), and PbCrO4(s). Cr(OH)3 was found to be soluble, and the insoluble form of Cr(III) was Cr2(SO4)3. Conversion of Cr(VI) to Cr(III) was higher than the conversion of Cr(III) to Cr(VI). The simulation results agree with the field measurements near Cr industries.

Ionic strength effects on the photochemical degradation of acetosyringone in atmospheric deliquescent aerosol particles

A number of laboratory experimental investigations, field campaigns, and modeling results have emphasized the role of aqueous-phase photochemical reactions in the formation of secondary organic aerosols (SOA). However, investigations focused on aqueous-phase reactions under high ionic-strength conditions are scarce. Here we study the photochemical behavior of a lignin-derived compound, acetosyringone (AcS), upon addition of an inert salt (NaClO4). The increase in the ionic strength modifies the acidic constant of AcS, enhancing its deprotonation. As a consequence, the UV-VIS absorption spectra of AcS undergo modifications due to red shifts at high ionic strength of the electronic transitions n → π* (from λmax = 297 nm to λmax = 354 nm) and π → π* (from λmax = 214 nm to λmax = 247 nm). At fixed pH = 4, representative of moderately acidic atmospheric aerosol deliquescent particles, the pseudo-first-order rate constants (k1st) of AcS increased by ∼6 times from a dilute aqueous phase to a solution with an effective ionic strength Ieff. = 0.46 M. The rate constant then followed a saturation trend at elevated ionic strength up to Ieff. = 3.1 M. A similar saturation effect of the observed rate constants with ionic strength was observed in presence of NaCl and Na2SO4. Differential absorption spectroscopy (DAS) methodology was applied to examine the changes in absorption spectra of AcS upon prolonged light irradiation. The very subtle pH-induced changes of the absorption spectra of irradiated AcS are due to the formation of acidic compounds emerged upon photochemical transformation of AcS.

Exploring the ionic strength effects on the photochemical degradation of pyruvic acid in atmospheric deliquescent aerosol particles

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.

Further Laboratory Experiments on Aerosol Scavenging in Mixed Clouds to Assess the Role of Phoretic Forces and Particle Solubility

Scavenging experiments have been performed in a cloud chamber inside a cold room with different aerosol particles: Paraffin particles, NaCl particles, Magnesium oxide particles, Carbon particles, Sahara dust particles. Essentially the experimental tests were carried on following the sequence of operations: the generation of the aerosol particles, their injection in the lower part of the cloud chamber, injection of water droplets in the whole chamber volume, nucleation of ice crystals, collection of ice crystals and their examination as for resulting scavenging efficiency. Evidence is given of the peculiar behaviour of soluble particles, individual and eventually inside mixed particles, leading to very much important scavenging efficiency, probably to be ascribed to aerodynamic capture. The evident peculiar behaviour of deliquescent particles can be oriented towards applications to an efficient abatement of specific effluents, on one side, and to weather modification experiments, both rain enhancement and hail prevention experiments.

Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H2O2 with Fe2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H2O2 and Fe2+. In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

Treatment of non-ideality in the SPACCIM multiphase model – Part 1: Model development

Abstract. Ambient tropospheric deliquesced particles generally comprise a complex mixture of electrolytes, organic compounds, and water. Dynamic modeling of physical and chemical processes in this complex matrix is challenging. Thus, up-to-date multiphase chemistry models generally do not consider non-ideal solution effects. Therefore, the present study was aimed at presenting further development of the SPACCIM (Spectral Aerosol Cloud Chemistry Interaction Model) through treatment of solution non-ideality, which has not been considered before. The present paper firstly describes the model developments including (i) the implementation of solution non-ideality in aqueous-phase reaction kinetics in the SPACCIM framework, (ii) the advancements in the coupling scheme of microphysics and multiphase chemistry and (iii) the required adjustments of the numerical schemes, especially in the sparse linear solver and the calculation of the Jacobian. Secondly, results of sensitivity investigations are outlined, aiming at the evaluation of different activity coefficient modules and the examination of the contributions of different intermolecular forces to the overall activity coefficients. Finally, first results obtained with the new model framework are presented. The SPACCIM parcel model was developed and, so far, applied for the description of aerosol–cloud interactions. To advance SPACCIM also for modeling physical and chemical processes in deliquesced particles, the solution non-ideality has to be taken into account by utilizing activities in reaction terms instead of aqueous concentrations. The main goal of the extended approach was to provide appropriate activity coefficients for solved species. Therefore, an activity coefficient module was incorporated into the kinetic model framework of SPACCIM. Based on an intercomparison of different activity coefficient models and the comparison with experimental data, the AIOMFAC approach was implemented and extended by additional interaction parameters from the literature for mixed organic–inorganic systems. Moreover, the performance and the capability of the applied activity coefficient module were evaluated by means of water activity measurements, literature data and results of other activity coefficient models. Comprehensive comparison studies showed that the SpactMod (SPACCIM activity coefficient module) is valuable for predicting the thermodynamic behavior of complex mixtures of multicomponent atmospheric aerosol particles. First simulations with a detailed chemical mechanism have demonstrated the applicability of SPACCIM-SpactMod. The simulations indicate that the treatment of solution non-ideality might be needed for modeling multiphase chemistry processes in deliquesced particles. The modeled activity coefficients imply that chemical reaction fluxes of chemical processes in deliquesced particles can be both decreased and increased depending on the particular species involved in the reactions. For key ions, activity coefficients on the order of 0.1–0.8 and a strong dependency on the charge state as well as the RH conditions are modeled, implying a lowered chemical processing of ions in concentrated solutions. In contrast, modeled activity coefficients of organic compounds are in some cases larger than 1 under deliquesced particle conditions and suggest the possibility of an increased chemical processing of organic compounds. Moreover, the model runs have shown noticeable differences in the pH values calculated with and without consideration of solution non-ideality. On average, the predicted pH values of the simulations considering solution non-ideality are −0.27 and −0.44 pH units lower under 90 and 70 % RH conditions, respectively. More comprehensive results of detailed SPACCIM-SpactMod studies on the multiphase processing in organic–inorganic mixtures of deliquesced particles are described in a companion paper.

Humidity-dependent surface tension measurements of individual inorganic and organic submicrometre liquid particles.

Surface tension, an important property of liquids, is easily measured for bulk samples. However, for droplets smaller than one micron in size, there are currently no reported measurements. In this study, atomic force microscopy (AFM) and force spectroscopy have been utilized to measure surface tension of individual submicron sized droplets at ambient pressure and controlled relative humidity (RH). Since the surface tension of atmospheric aerosols is a key factor in understanding aerosol climate effects, three atmospherically relevant systems (NaCl, malonic and glutaric acids) were studied. Single particle AFM measurements were successfully implemented in measuring the surface tension of deliquesced particles on the order of 200 to 500 nm in diameter. Deliquesced particles continuously uptake water at high RH, which changes the concentration and surface tension of the droplets. Therefore, surface tension as a function of RH was measured. AFM based surface tension measurements are close to predicted values based on bulk measurements and activities of these three chemical systems. Non-ideal behaviour in concentrated organic acid droplets is thought to be important and the reason for differences observed between bulk solution predictions and AFM data. Consequently, these measurements are crucial in order to improve atmospheric climate models as direct measurements hitherto have been previously inaccessible due to instrument limitations.