Aqueous Particles Research Articles

Triple-Bioinspired Burying/Crosslinking Interfacial Coassembly Strategy for Layer-by-Layer Construction of Robust Functional Bioceramic Self-Coatings for Osteointegration Applications.

Coating bioceramics of inherent bioactivity onto biometallic implants is a straightforward yet promising solution to address poor osteointegration of the latter. One step further, it would be a nontrivial accomplishment to develop a mild, cheap, and universal route to firmly stabilizing, in principle, any ceramics onto any implant substrate, while imparting expectedly versatile biofunctional performances. Herein, we describe a triple-bioinspired burying/cross-linking interfacial coassembly strategy for enabling such ceramic coatings, which ingeniously fuses bioinspiration from sea rocks (burying assisted particle immobilization), marine mussels (universal adhesion and versatile chemical reactivity), and reef-building oysters (cross-linking rendered cohesion). Specifically, surface functionalized, aqueous dispersed ceramic particles were buried within an substrate-anchored organic matrix of polyelectrolyte multilayers (i.e., (poly(ether imide) (PEI)/poly(sodium-p-styrenesulfonate) (PSS)) n), through a new inorganic-organic hybrid layer-by-layer (LBL) coassembly scheme wherein mussel (oyster) inspired adhesive (cohesive) chemistries were exquisitely orchestrated. As a conceptual demonstration, bioactive baghdadite (Ca3ZrSi2O9) was synthesized as model ceramics, with which we constructed on medical titanium robust, biomimetic, and cross-linkable LBL self-assemblies harnessing the said strategy. Intimate substrate contacts and well-defined buried inorganic-organic interfaces were evidently seen, together with good structural and chemical stabilities, especially after cross-linking. Sustained bioactive ion releasing and appreciable biomineralization activity were confirmed in vitro. Subsequently, biological performances of the assemblies were systematically investigated with respect to surface hydrophilicity, protein adsorption, and osteoblast functions. Additionally, nanosilver deposition, which imparted the surfaces with added antibacterial potencies, was used to exemplify the strategy's versatility in allowing multifunctionality. What's more, the flexibility of our approach was testified through modifying clinically relevant complicated 3D porous scaffolds. Overall, our strategy basically met the design expectations, boding well for future medical adoption. This study offers the promise of an alternative broadly useful avenue to bioactive and functional surface design of bone implants. It may also provide insights into other multiple-bioinspired materials/interfaces for biological and other applications.

A kinetic model for ozone uptake by solutions and aqueous particles containing I- and Br-, including seawater and sea-salt aerosol.

The heterogeneous interactions of gaseous ozone (O3) with seawater and with sea-salt aerosols are known to generate volatile halogen species, which, in turn, lead to further destruction of O3. Here, a kinetic model for the interaction of ozone (O3) with Br- and I- solutions and aqueous particles has been proposed that satisfactorily explains previous literature studies about this process. Apart from the aqueous-phase reactions X- + O3 (X = I, Br), the interaction also involves the surface reactions X- + O3 that occur via O3 adsorption on the aqueous surface. In single salt solutions and aerosols, the partial order in ozone and the total order of the surface reactions are one, but the apparent total order is second order because the number of ozone sites where reaction can occur is equal to the surficial concentration of X- ([X-]surf). In the presence of Cl-, the surface reactions are enhanced by a factor equal to , where and . Therefore, we have inferred that Cl- acts as a catalyst in the surface reactions X- + O3. The model has been applied to estimate ozone uptake by the reaction with these halides in/on seawater and in/on sea-salt aerosol, where it has been concluded that the Cl--catalyzed surface reaction is important relative to total ozone uptake and should therefore be considered to model Y/YO (Y = I, Br, Cl) levels in the troposphere.

Establishing a model organic film of low volatile compound mixture on aqueous aerosol surface

Long chain fatty acids and alcohols are low volatile species in continental and marine aerosols. We established a surface film model by Langmuir trough to investigate the interfacial properties of sea salts droplets coated by surface active molecules—stearic acid (SA), oleic acid (OA), 1-octadecanol (C18OH) and their mixtures. The aim of this work was to verify the impact of the head group, saturation degree, mixing ratio of different surfactants on miscibility and stability between these compounds in monolayers at the air–water interface. Compared to the organic-coated water droplets, the surface properties of mixed fatty acid and alcohol-coated aqueous sea salt particles are substantially different. Mixed SA/C18OH monolayers are less stable than pure SA or C18OH monolayer at high surface pressure. From the point of view of the geometry, steric hindrance of unsaturated chain is the crucial factor in loose packing of OA monolayer. The negative values of excess mixing areas (ΔAex) for OA/C18OH monolayer on artificial seawater result from the attractive interaction between tail groups. The maximum negative value of excess Gibbs free energies (ΔGex) appears at the equimolecular OA and C18OH. Surface pressure−area (π–A) isotherm combined with equilibrium spreading pressure (ESP) confirms that the tightly packed monolayer formed by C18OH molecules can minimize water evaporation rate of the potential droplet. Different surface properties of organic films coated on aqueous aerosol must have a significant impact on interaction droplet growth. The interactions between fatty acid and alcohol at the air-water interface provide an insight into the nucleation and growth mechanism of droplets covered by film-forming species.

Vibration of fresh concrete understood through the paradigm of granular physics

Fresh concrete is often cited as an example of a yield-stress fluid, typically being modeled as a Bingham material. We describe how this is an incomplete understanding to rationalize simple but important flow behaviors. As a motivating phenomenon, we consider the practice of vibrating fresh concrete during placement to induce flow and remove air voids. It is demonstrated that a simple yield-stress fluid (an aqueous polymer microgel particle suspension, Carbopol) cannot recreate the phenomenon, falsifying the hypothesis that traditional yield-stress fluid models embody the key physics. However, a granular hard-particle suspension (millimetric glass beads in silicone oil) does recreate the phenomenon. We use shear rheology to further show that concrete displays noticeable granular physics as indicated by vibration-induced loss of the yield stress, consistent with the granular constitutive model of Hanotin et al. (2015). These results have implications for understanding the unseen phenomenon of air bubbles rising in concrete.

Ozonation of 3-methylcatechol and 4-methylcatechol in the atmosphere and aqueous particles: Mechanism, kinetics and ecotoxicity assessment

Lignin pyrolysis products that generated by biomass burning can conduce to the formation of secondary organic aerosols (SOA), especially in municipal environments. 3-Methylcatechol (3-MC) and 4-Methylcatechol (4-MC) were selected as a representative congener of lignin pyrolysis product to investigate its fate both in the atmosphere and in aqueous particles. This work aims to summarize the reaction rules of this kind of compound, evaluate the contribution of such previously unconsidered reactions to the SOA formation from methylcatechols, and to provide a solution for the optimization of the water environment of such pollutants. We performed quantum chemical calculations for the O3-initiated oxidative degradation of methylcatechols, including six addition reaction pathways and the further reactions of the Criegee intermediates (generated during the primary reaction) with NO (only in the gas phase), H2O and O2. Using kinetic simulation, the calculated total rate constant (at 298 K and 1 atm) of O3-initiated reactions of 3-MC and 4-MC are 7.89 × 10−17 and 1.11 × 10−17 cm3 molecule−1 s−1. For the lignin pyrolysis products in this work and our previous studies, atmospheric lifetime comparison shows that the reactivity of these compounds takes the order 3-methylcatechol > 4-methylcatechol > catechol > methoxybenzene, which is consistent with experimental results. The ecotoxicity assessment shows majority of the toxic intermediates and intermediate products are converted into harmless compounds after ozone addition reactions.

Determining the size and refractive index of single aerosol particles using angular light scattering and Mie resonances

Optical trapping allows for high precision studies of many microphysical and chemical processes as it enables measurements on the single-particle level. This has been a tremendous benefit to fundamental aerosol research. In the vast majority of these experiments, trapped particles are characterized using light scattering – most often angular light scattering (phase functions) or Mie resonance spectroscopy. In this report, we compare the radii and refractive indices of best-fit found with these two light scattering methods by trapping single aerosol particles in a relative humidity-controlled cell where we can simultaneously measure both phase functions and Mie resonances, the latter of which are found using cavity-enhanced Raman scattering. Additionally, we compare best-fits found using both one- and two-dimensional phase functions. The application of Mie theory to these light scattering problems is thoroughly reviewed. Both the accuracy and uncertainty of the best-fits that these light scattering techniques produce are investigated using a model aqueous inorganic aerosol particle.

Direct Determination of Aerosol pH: Size-Resolved Measurements of Submicrometer and Supermicrometer Aqueous Particles.

Measuring the acidity of atmospheric aerosols is critical, as many key multiphase chemical reactions involving aerosols are highly pH-dependent. These reactions impact processes, such as secondary organic aerosol (SOA) formation, that impact climate and health. However, determining the pH of atmospheric particles, which have minute volumes (10-23-10-18 L), is an analytical challenge due to the nonconservative nature of the hydronium ion, particularly as most chemical aerosol measurements are made offline or under vacuum, where water can be lost and acid-base equilibria shifted. Because of these challenges, there have been no direct methods to probe atmospheric aerosol acidity, and pH has typically been determined by proxy/indirect methods, such as ion balance, or thermodynamic models. Herein, we present a novel and facile method for direct measurement of size-resolved aerosol acidity from pH 0 to 4.5 using quantitative colorimetric image processing of cellular phone images of (NH4)2SO4-H2SO4 aqueous aerosol particles impacted onto pH-indicator paper. A trend of increasing aerosol acidity with decreasing particle size was observed that is consistent with spectroscopic measurements of individual particle pH. These results indicate the potential for direct measurements of size-resolved atmospheric aerosol acidity, which is needed to improve fundamental understanding of pH-dependent atmospheric processes, such as SOA formation.

Zwitterion Functionalized Silica Nanoparticle Coatings: The Effect of Particle Size on Protein, Bacteria, and Fungal Spore Adhesion.

The negative impacts that arise from biological fouling of surfaces have driven the development of coatings with unique physical and chemical properties that are able to prevent interactions with fouling species. Here, we report on low-fouling hydrophilic coatings presenting nanoscaled features prepared from different size silica nanoparticles (SiNPs) functionalized with zwitterionic chemistries. Zwitterionic sulfobetaine siloxane (SB) was reacted to SiNPs ranging in size from 7 to 75 nm. Particle stability and grafting density were confirmed using dynamic light scattering and thermogravimetric analysis. Thin coatings of nanoparticles were prepared by spin-coating aqueous particle suspensions. The resulting coatings were characterized using scanning electron microscopy, atomic force microscopy, and contact angle goniometry. SB functionalized particle coatings displayed increased hydrophilicity compared to unmodified particle coating controls while increasing particle size correlated with increased coating roughness and increased surface area. Coatings of zwitterated particles demonstrated a high degree of nonspecific protein resistance, as measured by quartz crystal microgravimetry. Adsorption of bovine serum albumin and hydrophobin proteins were reduced by up to 91 and 94%, respectively. Adhesion of bacteria ( Escherichia coli) to zwitterion modified particle coatings were also significantly reduced over both short and long-term assays. Maximum reductions of 97% and 94% were achieved over 2 and 24 h assay periods, respectively. For unmodified particle coatings, protein adsorption and bacterial adhesion were generally reduced with increasing particle size. Adhesion of fungal spores to SB modified SiNP coatings was also reduced, however no clear trends in relation to particle size were demonstrated.

Functional Microgels: Recent Advances in Their Biomedical Applications

Here, a spotlight is shown on aqueous microgel particles which exhibit a great potential for various biomedical applications such as drug delivery, cell imaging, and tissue engineering. Herein, different synthetic methods to develop microgels with desirable functionality and properties along with degradable strategies to ensure their renal clearance are briefly presented. A special focus is given on the ability of microgels to respond to various stimuli such as temperature, pH, redox potential, magnetic field, light, etc., which helps not only to adjust their physical and chemical properties, and degradability on demand, but also the release of encapsulated bioactive molecules and thus making them suitable for drug delivery. Furthermore, recent developments in using the functional microgels for cell imaging and tissue regeneration are reviewed. The results reviewed here encourage the development of a new class of microgels which are able to intelligently perform in a complex biological environment. Finally, various challenges and possibilities are discussed in order to achieve their successful clinical use in future.

Particle acidity and sulfate production during severe haze events in China cannot be reliably inferred by assuming a mixture of inorganic salts

Abstract. Atmospheric measurements showed rapid sulfate formation during severe haze episodes in China, with fine particulate matter (PM) consisting of a multi-component mixture that is dominated by organic species. Several recent studies using the thermodynamic model estimated the particle acidity and sulfate production rate, by treating the PM exclusively as a mixture of inorganic salts dominated by ammonium sulfate and neglecting the effects of organic compounds. Noticeably, the estimated pH and sulfate formation rate during pollution periods in China were highly conflicting among the previous studies. Here we show that a particle mixture of inorganic salts adopted by the previous studies does not represent a suitable model system and that the acidity and sulfate formation cannot be reliably inferred without accounting for the effects of multi-aerosol compositions during severe haze events in China. Our laboratory experiments show that SO2 oxidation by NO2 with NH3 neutralization on fine aerosols is dependent on the particle hygroscopicity, phase-state, and acidity. Ammonium sulfate and oxalic acid seed particles exposed to vapors of SO2, NO2, and NH3 at high relative humidity (RH) exhibit distinct size growth and sulfate formation. Aqueous ammonium sulfate particles exhibit little sulfate production, in contrast to aqueous oxalic acid particles with significant sulfate production. Our field measurements demonstrate significant contribution of water-soluble organic matter to fine PM in China and indicate that the use of oxalic acid in laboratory experiments is representative of ambient organic dominant aerosols. While the particle acidity cannot be accurately determined from field measurements or calculated using the thermodynamic model, our results reveal that the pH value of ambient organics-dominated aerosols is sufficiently high to promote efficient SO2 oxidation by NO2 with NH3 neutralization under polluted conditions in China.

Influence of Particle Physical State on the Uptake of Medium-Sized Organic Molecules.

The uptake of medium-sized levoglucosan and 2,4-dinitrophenol to organic particles produced by α-pinene ozonolysis and to ammonium sulfate particles was studied from 10% to >95% relative humidity (RH). For aqueous sulfate particles, the water-normalized gas-particle partitioning coefficient of levoglucosan decreased from (1.0 ± 0.1) × 10-3 to (0.2 ± 0.1) × 10-3 (ng μg-1)particle/(ng m-3)gas from 40% to >95% RH, suggestive of a salting-in mechanism between levoglucosan and ionic ammonium sulfate solutions. For the organic particles, the levoglucosan partitioning coefficient increased from 10% to 40% RH and became invariant at (2.0 ± 0.4) × 10-3 (ng μg-1)/(ng m-3) above 40% RH. A kinetic limitation on uptake below 40% RH was implied, compared to a thermodynamic regime above 40% RH. The estimated diffusivity was 10-19±0.05 m2 s-1 at 40% RH. By comparison, the uptake of 2,4-dinitrophenol onto the organic particles was below detection limit, implying an upper limit on the partitioning coefficient of 6.8 × 10-6 (ng μg-1)/(ng m-3) at 80% RH. The results highlight that the molecular uptake of gases onto particles can be regulated by both kinetic and thermodynamic factors, either of which can limit the uptake of medium-sized organic molecules by atmospherically relevant particles.

Technical note: Updated parameterization of the reactive uptake of glyoxal and methylglyoxal by atmospheric aerosols and cloud droplets

Abstract. We present updated recommendations for the reactive uptake coefficients for glyoxal and methylglyoxal uptake to aqueous aerosol particles and cloud droplets. The particle and droplet types considered were based on definitions in GEOS-Chem v11, but the approach is general. Liquid maritime and continental cloud droplets were considered. Aerosol types include sea salt (fine and coarse), with varying relative humidity and particle size, and sulfate/nitrate/ammonium as a function of relative humidity and particle composition. We take into account salting effects, aerosol thermodynamics, mass transfer, and irreversible reaction of the organic species with OH in the aqueous phase. The new recommended values for the reactive uptake coefficients in most cases are lower than those currently used in large-scale models, such as GEOS-Chem. We expect application of these parameterizations will result in improved representation of aqueous secondary organic aerosol formation in atmospheric chemistry models.

Dynamic Aggregation of Poly-N-Isopropylacrylamide Characterized Using Second-Order Scattering.

A second-order scattering (SOS) method is presented for the characterization of aqueous particle suspensions undergoing aggregation. Scattering intensities are measured at 90° by a standard fluorimeter and referenced against dynamic light scattering (DLS) measurements to determine particle size increase in a metal-promoted aggregation process for 0.05 mg/mL aqueous poly-N-isopropylacrylamide (PNIPAm), MW ∼10 k g/mol. Particle size increases monotonically from 30 nm to 210 nm at temperature 308 K. A further validation of the SOS method was performed using monodisperse polystyrene reference particles sized at 52 nm, 101 nm, 151 nm, and 206 nm, which demonstrated the technique's accuracy to within 6% and its versatility with respect to sample composition. The technique is ideal for monitoring colloidal stability and macromolecular assembly and it can be performed at lower concentrations than are typically used in DLS.

Reactive Uptake of Glyoxal by Ammonium-Containing Salt Particles as a Function of Relative Humidity.

Reactions between dissolved ammonia and carbonyls, which form light-absorbing species in atmospheric particles, can be accelerated by actively removing water from the reaction system. Here, we examine the effects of relative humidity (RH) on the reactive uptake of glyoxal (Gly) by aqueous particles of ammonium sulfate (AS), ammonium bisulfate, sodium sulfate, magnesium sulfate, ammonium nitrate (AN), and sodium nitrate. In situ Raman analysis was used to quantify particle-phase Gly and a colored product, 2,2'-biimidazole (BI), as a function of uptake time. Overall, the Gly uptake rate increases with decreasing RH, reflecting the "salting-in" effect. The BI formation rate increases significantly with decreasing RH or aerosol liquid water (ALW). Compared to that at 75% RH, the BI formation rate is enhanced by factors of 29 at 60% RH and 330 at 45% RH for AS particles and 65 at 60% RH, 210 at 45% RH, and 460 at 30% RH for AN particles. These enhancement factors are much larger than those estimated from increased reactant concentrations due to decreases in RH and ALW alone. We postulate that the reduction in ALW at low RH increases the Gly uptake rate via the "salting-in" effect and the BI formation rate by facilitating dehydration reactions.

Determination of the refractive index of insoluble organic extracts from atmospheric aerosol over the visible wavelength range using optical tweezers

Abstract. Optical trapping combined with Mie spectroscopy is a new technique used to record the refractive index of insoluble organic material extracted from atmospheric aerosol samples over a wide wavelength range. The refractive index of the insoluble organic extracts was shown to follow a Cauchy equation between 460 and 700 nm for organic aerosol extracts collected from urban (London) and remote (Antarctica) locations. Cauchy coefficients for the remote sample were for the Austral summer and gave the Cauchy coefficients of A = 1.467 and B = 1000 nm2 with a real refractive index of 1.489 at a wavelength of 589 nm. Cauchy coefficients for the urban samples varied with season, with extracts collected during summer having Cauchy coefficients of A=1.465±0.005 and B=4625±1200 nm2 with a representative real refractive index of 1.478 at a wavelength of 589 nm, whilst samples extracted during autumn had larger Cauchy coefficients of A = 1.505 and B = 600 nm2 with a representative real refractive index of 1.522 at a wavelength of 589 nm. The refractive index of absorbing aerosol was also recorded. The absorption Ångström exponent was determined for woodsmoke and humic acid aerosol extract. Typical values of the Cauchy coefficient for the woodsmoke aerosol extract were A=1.541±0.03 and B=14800±2900 nm2, resulting in a real refractive index of 1.584 ± 0.007 at a wavelength of 589 nm and an absorption Ångström exponent of 8.0. The measured values of refractive index compare well with previous monochromatic or very small wavelength range measurements of refractive index. In general, the real component of the refractive index increases from remote to urban to woodsmoke. A one-dimensional radiative-transfer calculation of the top-of-the-atmosphere albedo was applied to model an atmosphere containing a 3 km thick layer of aerosol comprising pure water, pure insoluble organic aerosol, or an aerosol consisting of an aqueous core with an insoluble organic shell. The calculation demonstrated that the top-of-the-atmosphere albedo increases by 0.01 to 0.04 for pure organic particles relative to water particles of the same size and that the top-of-the-atmosphere albedo increases by 0.03 for aqueous core-shell particles as volume fraction of the shell material increases to 25 %.

Model Behavior: Characterization of Hydroxyacetone at the Air-Water Interface Using Experimental and Computational Vibrational Sum Frequency Spectroscopy.

Small atmospheric aldehydes and ketones are known to play a significant role in the formation of secondary organic aerosols (SOA). However, many of them are difficult to experimentally isolate, as they tend to form hydration and oligomer species. Hydroxyacetone (HA) is unusual in this class as it contributes to SOA while existing predominantly in its unhydrated monomeric form. This allows HA to serve as a valuable model system for similar secondary organic carbonyls. In this paper the surface behavior of HA at the air-water interface has been investigated using vibrational sum frequency (VSF) spectroscopy and Wilhelmy plate surface tensiometry in combination with computational molecular dynamics simulations and density functional theory calculations. The experimental results demonstrate that HA has a high degree of surface activity and is ordered at the interface. Furthermore, oriented water is observed at the interface, even at high HA concentrations. Spectral features also reveal the presence of both cis and trans HA conformers at the interface, in differing orientations. Molecular dynamics results indicate conformer dependent shifts in HA orientation between the subsurface (∼5 Å deep) and surface. Together, these results provide a picture of a highly dynamic, but statistically ordered, interface composed of multiple HA conformers with solvated water. These results have implications for HA's behavior in aqueous particles, which may affect its role in the atmosphere and SOA formation.

Aqueous Polymeric Hollow Particles as an Opacifier by Emulsion Polymerization Using Macro-RAFT Amphiphiles.

A robust polymerization technique that enables the surfactant-free aqueous synthesis of a high solid content latex containing polymeric hollow particles is presented. Uniquely designed amphiphilic macro-reversible addition fragmentation chain transfer (RAFT) copolymers were used as sole stabilizers for monomer emulsification as well as for free-radical emulsion polymerization. The polymerization was found to be under RAFT control, generating various morphologies from spherical particles, wormlike structures to polymer vesicles. The final particles were dominantly polymeric vesicles which had a substantially uniform and continuous polymer layer around a single aqueous filled void. They produced hollow particles once dried and were successfully used as opacifiers to impart opacity into polymer paint films. This method is simple, can be performed in a controllable and reproducible manner, and may be performed using diverse procedures.

Multiphase oxidation of SO<sub>2</sub> by NO<sub>2</sub> on CaCO<sub>3</sub> particles

Abstract. Heterogeneous/multiphase oxidation of SO2 by NO2 on solid or aqueous particles is thought to be a potentially important source of sulfate in the atmosphere, for example, during heavily polluted episodes (haze), but the reaction mechanism and rate are uncertain. In this study, in order to assess the importance of the direct oxidation of SO2 by NO2 we investigated the heterogeneous/multiphase reaction of SO2 with NO2 on individual CaCO3 particles in N2 using Micro-Raman spectroscopy. In the SO2 ∕ NO2 ∕ H2O ∕ N2 gas mixture, the CaCO3 solid particle was first converted to the Ca(NO3)2 droplet by the reaction with NO2 and the deliquescence of Ca(NO3)2, and then NO2 oxidized SO2 in the Ca(NO3)2 droplet forming CaSO4, which appeared as needle-shaped crystals. Sulfate was mainly formed after the complete conversion of CaCO3 to Ca(NO3)2, that is, during the multiphase oxidation of SO2 by NO2. The precipitation of CaSO4 from the droplet solution promoted sulfate formation. The reactive uptake coefficient of SO2 for sulfate formation is on the order of 10−8, and RH enhanced the uptake coefficient. We estimate that the direct multiphase oxidation of SO2 by NO2 is not an important source of sulfate in the ambient atmosphere compared with the SO2 oxidation by OH in the gas phase and is not as important as other aqueous-phase pathways, such as the reactions of SO2 with H2O2, O3, and O2, with or without transition metals.

Coupling colloidal forces with yield stress of charged inorganic particle suspension: A review.

This paper aims to summarize the series of investigations on coupling suspension yield stress and DLVO (Derjaguin-Landau-Verwey-Overbeek) forces, i.e. van der Waals and electrical double layer forces. This summary provides a better understanding of the basic phenomena associated, historical development and current status of this useful coupling, and also discusses the applicability and limitations/variations of such coupling applied to different types of concentrated aqueous particle suspensions. Aqueous suspensions discussed are composed of charged inorganic fine particles, including metal oxide colloidal particles, mineral fine particles, and clays. The research gaps are identified and specific future perspectives are discussed to further enhance the use of this unique and useful coupling, and to aim for the transition from the modelling of similar particle suspension systems to its dissimilar/mix particle suspension systems that fit more with the current and future industry needs in particle processing.

The effects of isoprene and NO x on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water.

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11h after isoprene concentrations, with maxima at a time lag of 9h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NO x /isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NO x oxidation products may be responsible for these effects. The observed relationships with NO x and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NO x levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.