Quantifying the Viscosity of Individual Submicrometer Semisolid Particles Using Atomic Force Microscopy.

Atmospheric aerosols' viscosities can vary significantly depending on their composition, mixing states, relative humidity (RH) and temperature. The diffusion time scale of atmospheric gases into an aerosol is largely governed by its viscosity, which in turn influences heterogeneous chemistry and climate-relevant aerosol effects. Quantifying the viscosity of aerosols in the semisolid phase state is particularly important as they are prevalent in the atmosphere and have a wide range of viscosities. Currently, direct viscosity measurements of submicrometer individual atmospheric aerosols are limited, largely due to the inherent size limitations of existing experimental techniques. Herein, we present a method that utilizes atomic force microscopy (AFM) to directly quantify the viscosity of substrate-deposited individual submicrometer semisolid aerosol particles as a function of RH. The method is based on AFM force spectroscopy measurements coupled with the Kelvin-Voigt viscoelastic model. Using glucose, sucrose, and raffinose as model systems, we demonstrate the accuracy of the AFM method within the viscosity range of ∼104-107 Pa s. The method is applicable to individual particles with sizes ranging from tens of nanometers to several micrometers. Furthermore, the method does not require prior knowledge on the composition of studied particles. We anticipate future measurements utilizing the AFM method on atmospheric aerosols at various RH to aid in our understanding of the range of aerosols' viscosities, the extent of particle-to-particle viscosity variability, and how these contribute to the particle diversity observable in the atmosphere.

Atomic Force Microscopy: An Emerging Tool in Measuring the Phase State and Surface Tension of Individual Aerosol Particles.

Atmospheric aerosols are suspended particulate matter of varying composition, size, and mixing state. Challenges remain in understanding the impact of aerosols on the climate, atmosphere, and human health. The effect of aerosols depends on their physicochemical properties, such as their hygroscopicity, phase state, and surface tension. These properties are dynamic with respect to the highly variable relative humidity and temperature of the atmosphere. Thus, experimental approaches that permit the measurement of these dynamic properties are required. Such measurements also need to be performed on individual, submicrometer-, and supermicrometer-sized aerosol particles, as individual atmospheric particles from the same source can exhibit great variability in their form and function. In this context, this review focuses on the recent emergence of atomic force microscopy as an experimental tool in physical, analytical, and atmospheric chemistry that enables such measurements. Remaining challenges are noted and suggestions for future studies are offered.

Isotopic Insights into Organic Composition Differences between Supermicron and Submicron Sea Spray Aerosol.

To elucidate the seawater biological and physicochemical factors driving differences in organic composition between supermicron and submicron sea spray aerosol (SSAsuper and SSAsub), carbon isotopic composition (δ13C) measurements were performed on size-segregated, nascent SSA collected during a phytoplankton bloom mesocosm experiment. The δ13C measurements indicate that SSAsuper contains a mixture of particulate and dissolved organic material in the bulk seawater. After phytoplankton growth, a greater amount of freshly produced carbon was observed in SSAsuper with the proportional contribution being modulated by bacterial activity, emphasizing the importance of the microbial loop in controlling the organic composition of SSAsuper. Conversely, SSAsub exhibited no apparent relationship with biological activity but tracked closely with surface tension measurements probing the topmost ∼0.2-1.5 µm of the sea surface microlayer. This probing depth is similar to a bubble's film thickness at the ocean surface, suggesting that SSAsub organic composition may be influenced by the presence of surfactants at the air-sea interface that are transferred into SSAsub by bubble bursting. Our findings illustrate the substantial impact of seawater dynamics on the pronounced organic compositional differences between SSAsuper and SSAsub and demonstrate that these two SSA populations should be considered separately when assessing their contribution to marine aerosols and climate.

Surface Tension Measurements of Aqueous Liquid-Air Interfaces Probed with Microscopic Indentation.

To elucidate the intricate role that the sea surface microlayer (SML) and sea spray aerosols (SSAs) play in climate, understanding the chemical complexity of the SML and how it affects the physical-chemical properties of the microlayer and SSA are important to investigate. While the surface tension of the SML has been studied previously using conventional experimental tools, accurate measurements must be localized to the thickness of the air-liquid interface of the SML. Here we explore the atomic force microscopy (AFM) capabilities to quantify the surface tension of aqueous solution droplets with (sub)micrometer indentation depths into the interface. Sample droplets of hexanoic acid at molar concentrations ranging from 0.1 to 80 mM and SML from a recent wave flume study were investigated. A constant-radius AFM nanoneedle was used to probe ca. 200 µL droplets with 0.3-1.2 µm indentation depths. As a comparison, the surface tension of bulk samples was also measured using a conventional force tensiometer. The data for the hexanoic acid show an excellent overlap between the AFM and force tensiometer surface tension measurements. For the surface tension measurements of the SML, however, the measured values from the AFM were 2.5 mN/m lower than that from the force tensiometer, which was attributed to the structural and chemical complexity of the SML, differences in the probing depth for each method, and the time scale required for the surface film to restructure as the needle is retracted away from the liquid surface. Overall, the study confirmed the accuracy of the AFM method in quantifying the surface tension of aqueous solutions over a wide range of concentrations for surface-active organic compounds. The methodology can be further used to reveal small, yet important, differences in the surface tension of complex air-liquid interfaces such as liquid systems where the type and concentration of surfactants vary with the distance from the air-liquid interface. For such complex systems, AFM measurements of the surface tension as a function of the probing depth and pulling rate may reveal a sublayer film structure of the liquid interface.

Mechanical Properties and Photomechanical Fatigue of Macro- and Nanodimensional Diarylethene Molecular Crystals.

The diarylethene derivative, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene, undergoes a reversible photoisomerization between its ring-open and ring-closed forms in the solid-state and has applications as a photomechanical material. Mechanical properties of macrocrystals, nanowire single crystals, and amorphous films as a function of multiple sequential UV and visible light exposures have been quantified using atomic force microscopy nanoindentation. The isomerization reaction has no effect on the elastic modulus of each solid. But going from the macro- to the nanowire crystal results in a remarkable over 3-fold decrease in the elastic modulus. The macrocrystal and amorphous solids are highly resistant to photomechanical fatigue, while nanowire crystals show clear evidence of photomechanical fatigue attributed to a transition from crystal to amorphous forms. This study provides first experimental evidence of size-dependent photomechanical fatigue in photoreactive molecular crystalline solids and suggests crystal morphology and size must be considered for future photomechanical applications.

Platelet-derived Growth Factor-α and Neuropilin-1 Mediate Lung Fibroblast Response to Rigid Collagen Fibers.

During pulmonary secondary alveolar septation, the rudimentary distal saccule subdivides by extending tissue sheets into the saccular air space, creating alveoli, which open into the alveolar duct. The sheets originate from saccular mesenchymal cells, which contain α-SMA (αSMA [ACTA2]) and abut elastic fibers (myofibroblasts [MF]), characteristics that are shared by cells that subsequently occupy the secondary septal tips. During elongation, collagen fibers are positioned to provide a scaffold for translocating septal mesenchymal cells. We hypothesized that collagen fibers direct the migration, orientation, and location of MFs during septal elongation. To address this hypothesis, we examined how electrospun collagen fibers direct the migration of fibroblasts bearing targeted deletions of PDGFRα (platelet-derived growth factor receptor-α) or Nrp1 (neuropilin-1), after their isolation from lungs that exhibit reduced secondary septation. We observed that deletion of either gene reduced Rac1 activation and the speed of migration of lung fibroblasts (LF) along electrospun fibers. The deletions did not reduce the proportion of LF that displayed collagen-binding integrins and increased the proportion of LF bearing activated ß1-integrin. LF bearing the PDGFRα deletion failed to localize focal adhesions over electrospun fibers, suggesting that they may not appropriately sense and respond to regionally increased stiffness near the fibers. In lungs of mice bearing the PDGFRα deletion, collagen fibers are delocalized from ACTA2-containing MF, and their orientation deviated from the plane of the alveolar walls. Diminished PDGFRα or Nrp1 reduces LF localization to stiffer regions of fibrillar collagen substrates, suggesting that signaling through these receptors enables responsiveness to regional differences in extracellular matrix rigidity.

Rigid Double-Stranded DNA Linkers for Single Molecule Enzyme-Drug Interaction Measurements Using Molecular Recognition Force Spectroscopy.

Single-molecule studies can reveal the distribution of states and interactions between ligand-enzyme complexes not accessible for most studies that measure a large ensemble average response of many molecules. Furthermore, in some biological applications, the information regarding the outliers, not the average of measured properties, can be more important. The high spatial and force resolution provided by atomic force microscopy (AFM) under physiological conditions has been utilized in this study to quantify the force-distance relations of enzyme-drug interactions. Different immobilization techniques of the protein to a surface and the drug to AFM tip were quantitatively compared to improve the accuracy and precision of the measurement. Protein that is directly bound to the surface, forming a monolayer, was compared to enzyme molecules bound to the surface with rigid double-stranded (ds) DNA spacers. These surfaces immobilization techniques were studied with the drug bound directly to the AFM tip and drug bound via flexible poly(ethylene glycol) and rigid dsDNA linkers. The activity of the enzyme was found to be not significantly altered by immobilization methods relative to its activity in solution. The findings indicate that the approach for studying drug-enzyme interaction based on rigid dsDNA linker on the surface and either flexible or rigid linker on the tip affords straightforward, highly specific, reproducible, and accurate force measurements with a potential for single-molecule level studies. The method could facilitate in-depth examination of a broad spectrum of biological targets and potential drugs.

Size-Dependent Mechanical Properties of a Metal-Organic Framework: Increase in Flexibility of ZIF-8 by Crystal Downsizing.

Size engineering is an emerging strategy to modulate the mechanical properties of crystalline materials. Herein, micro- and nanodimensional single crystals of the prototypical metal-organic framework (MOF) ZIF-8 are generated using solvothermal and solution methods, respectively. Atomic force microscopy-based nanoindentation technique was used to measure the Young's modulus values of micro- and nanodimensional individual ZIF-8 crystals. We demonstrate that crystal downsizing to nanoscale dimensions results in a 40% reduction in crystal stiffness. The change is attributed to a greater contribution of surface effects to the physical properties of nanocrystalline ZIF-8. The observed change in the mechanical properties may be used to explain reported size-dependent changes in gas adsorption of ZIF-8, thought to be a result of differences in framework flexibility at the nanoscale. Our work provides an important example on how downsizing of crystalline metal-organic materials can give rise to specific and tunable physical properties.

Correlating 3D Morphology, Phase State, and Viscoelastic Properties of Individual Substrate-Deposited Particles.

Depending on the source and relative humidity, aerosols can have different compositional, morphological, and viscoelastic properties. Aerosol studies determining the relationship between these properties and their combined effect on the climate and environment are important. This work aims to correlate the 3D morphology, phase state, and viscoelastic properties of selected single-component chemical systems found in sea spray aerosol (SSA) that were substrate-deposited on a solid surface, studied with atomic force microscopy (AFM). Specifically, two inorganic salts (NaCl and MgSO4), four organic acids (malonic, glutaric, azelaic, and palmitic acids), three saccharides (glucose, sucrose, and raffinose), and lipopolysaccharide from Escherichia coli were studied. Furthermore, three inorganic-organic binary chemical mixtures (NaCl-malonic acid, NaCl-glucose, and MgSO4-glucose) at 1:3 and 3:1 mass ratio were studied. AFM imaging and force spectroscopy at 20% relative humidity were performed to record 3D height images of individual particles and measure force-distance plots, respectively. First, by utilizing combined relative indentation depth (RID) and viscoelastic response distance (VRD) data obtained from the force-distance plots, we establish quantitative framework toward differentiation of the solid, semisolid and liquid phase states of individual particles without prior knowledge of their chemical identity. Second, we show that the single particle aspect ratio (AR) of a wide range of compounds relevant to SSA is a measure of the extent of the particle spreading as a result of impaction with the solid substrate, which can be directly related to the RID and VRD results. Thus, we demonstrate that a quick height imaging and determination of a single particle AR can be used to assess the phase state. Therefore, we introduce the ability to semiquantitatively assess the phase states of individual substrate deposited particles of SSA-relevant compounds, irrespective of the microscopy technique used, which can subsequently be further validated by more quantitative AFM force spectroscopy.

Lab on a tip: atomic force microscopy - photothermal infrared spectroscopy of atmospherically relevant organic/inorganic aerosol particles in the nanometer to micrometer size range.

New developments in nanoscale analytical techniques have paved the way for detailed spectroscopic and microscopic measurements of substrate-deposited aerosol particles on a single particle basis. Atomic force microscopy based photothermal infrared (AFM-PTIR) spectroscopy is a technique that combines the nanometer spatial resolution of AFM with the chemical analysis capabilities of vibrational IR spectroscopy. Herein we demonstrate the capability of AFM-PTIR to investigate single and multi-component systems comprised of inorganic salts and organic compounds relevant to the atmosphere. Chemical and microscopic characterization of individual particles as small as 50 nm in diameter is shown. Moreover, single particle spectro-microscopic characterization as a function of relative humidity using this technique is shown for the first time. These new measurements as a function of relative humidity allow for the simultaneous and independent acquisition of photothermal IR spectra, contact resonance frequency shifts, and water uptake growth factors, providing insight on changes in the composition, stiffness, and size of the particles, respectively. These results lay the foundation for more detailed AFM-PTIR studies of multicomponent aerosol particles under a range of environmental conditions.

Solid, Semisolid, and Liquid Phase States of Individual Submicrometer Particles Directly Probed Using Atomic Force Microscopy.

Currently, the impact of various phase states of aerosols on the climate is not well understood, especially for submicrometer sized aerosol particles that typically have extended lifetime in the atmosphere. This is largely due to the inherent size limitations present in current experimental techniques that aim to directly assess the phase states of fine aerosol particles. Herein we present a technique that uses atomic force microscopy to probe directly for the phase states of individual, submicrometer particles by using nanoindentation and nano-Wilhelmy methodologies as a function of relative humidity (RH) and ambient temperature conditions. When using these methodologies for substrate deposited individual sucrose particles, Young's modulus and surface tension can be quantified as a function of RH. We show that the force profiles collected to measure Young's modulus and surface tension can also provide both qualitative and quantitative assessments of phase states that accompany solid, semisolid, and liquid particle phases. Specifically, we introduce direct measurements of relative indentation depth and viscoelastic response distance on a single particle basis at a given applied force to quantitatively probe for the phase state as a function of RH and corresponding viscosity. Thus, we show that the three phase states and phase state transitions of sucrose can be identified and ultimately propose that this technique may also be used to study other atmospherically relevant systems.

Core and surface microgel mechanics are differentially sensitive to alternative crosslinking concentrations.

Microgel mechanics are central to the swelling of stimuli-responsive materials and furthermore have recently emerged as a novel design space for tuning the uptake of nanotherapeutics. Despite this importance, the techniques available to assess mechanics, at the sub-micron scale, remain limited. In this report, all mechanical moduli for a series of air-dried, polystyrene-co-poly(N-isopropylacrylamide) (pS-co-NIPAM) microgels of varying composition in monomer and crosslinker (N,N'-methylene-bisacrylamide (BIS)) mol% have been determined using Brillouin light scattering (BLS) and AFM nanoindentation. These techniques sample the material through distinct means and provide complementary nanomechanical data. An initial demonstration of this combined approach is used to evaluate size-dependent nanomechanics in pS particles of varying diameter. For the pS-co-NIPAM series, our BLS results demonstrate an increase in Young's (E) and shear moduli with increasing NIPAM and/or BIS mol%, while the Poisson's ratio decreased. The same rank order in E was observed from AFM and the two techniques correlate well. However, at low BIS crosslinking, an inverted particle structure persists and small increases in BIS yield a higher increase in E from AFM relative to BLS, consistent with a higher density at the particle surface. At higher BIS incorporation, the microgel reverts to a typical, dense-core structure and further increasing BIS yields changes to core-particle mechanics reflected in BLS. Lastly, at 75 mol% NIPAM, the microgels displayed a broad volume phase transition and increased crosslinking resulted in a minor, yet unexpected, increase in swelling ratio. This complementary approach offers new insight into nanomechanics critical for microgel design and application.

Linking hygroscopicity and the surface microstructure of model inorganic salts, simple and complex carbohydrates, and authentic sea spray aerosol particles.

Individual airborne sea spray aerosol (SSA) particles show diversity in their morphologies and water uptake properties that are highly dependent on the biological, chemical, and physical processes within the sea subsurface and the sea surface microlayer. In this study, hygroscopicity data for model systems of organic compounds of marine origin mixed with NaCl are compared to data for authentic SSA samples collected in an ocean-atmosphere facility providing insights into the SSA particle growth, phase transitions and interactions with water vapor in the atmosphere. In particular, we combine single particle morphology analyses using atomic force microscopy (AFM) with hygroscopic growth measurements in order to provide important insights into particle hygroscopicity and the surface microstructure. For model systems, a range of simple and complex carbohydrates were studied including glucose, maltose, sucrose, laminarin, sodium alginate, and lipopolysaccharides. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM). It is shown here that the E-AIM model describes well the deliquescence transition and hygroscopic growth at low mass ratios but not as well for high ratios, most likely due to a high organic volume fraction. AFM imaging reveals that the equilibrium morphology of these single-component organic particles is amorphous. When NaCl is mixed with the organics, the particles adopt a core-shell morphology with a cubic NaCl core and the organics forming a shell similar to what is observed for the authentic SSA samples. The observation of such core-shell morphologies is found to be highly dependent on the salt to organic ratio and varies depending on the nature and solubility of the organic component. Additionally, single particle organic volume fraction AFM analysis of NaCl : glucose and NaCl : laminarin mixtures shows that the ratio of salt to organics in solution does not correspond exactly for individual particles - showing diversity within the ensemble of particles produced even for a simple two component system.

Direct Surface Tension Measurements of Individual Sub-Micrometer Particles Using Atomic Force Microscopy.

Understanding the role of sea spray aerosol (SSA) on climate and the environment is of great interest due to their high number concentration throughout the Earth's atmosphere. Despite being of fundamental importance, direct surface tension measurements of SSA relevant sub-micrometer particles are rare, largely due to their extremely small volumes. Herein, atomic force microscopy (AFM) is used to directly measure the surface tension of individual sub-micrometer SSA particle mimics at ambient temperature and varying relative humidity (RH). Specifically, we probed both atmospherically relevant and fundamentally important model systems including electrolyte salts, dicarboxylic acids, and saccharides as single components and mixtures. Our results show that the single particle surface tension depends on RH or solute mole percentage and chemical composition. Moreover, for liquid droplets at and below 100 Pa s in viscosity, or at corresponding RH, we show good agreement between the AFM single particle and the bulk solution surface tension measurements at overlapping concentration ranges. Thus, direct surface tension measurements of individual particles using AFM is shown over a wide range of chemical systems as a function of RH, solute mole percentage, and viscosity than previously reported.

Quantifying the Hygroscopic Growth of Individual Submicrometer Particles with Atomic Force Microscopy.

The water uptake behavior of atmospheric aerosol dictates their climate effects. In many studies, aerosol particles are deposited onto solid substrates to measure water uptake; however, the effects of the substrate are not well understood. Furthermore, in some cases, methods used to analyze and quantify water uptake of substrate deposited particles use a two-dimensional (2D) analysis to monitor growth by following changes in the particle diameter with relative humidity (RH). However, this 2D analysis assumes that the droplet grows equally in all directions. If particle growth is not isotropic in height and diameter, this assumption can cause inaccuracies when quantifying hygroscopic growth factors (GFs), where GF for a for a spherical particle is defined as the ratio of the particle diameter at a particular relative humidity divided by the dry particle diameter (typically about 5% RH). However, as shown here, anisotropic growth can occur in some cases. In these cases, a three-dimensional (3D) analysis of the growth is needed. This study introduces a way to quantify the hygroscopic growth of substrate deposited particles composed of model systems relevant to atmospheric aerosols using atomic force microscopy (AFM), which gives information on both the particle height and area and thus a three-dimensional view of each particle. In this study, we compare GFs of submicrometer sized particles composed of single component sodium chloride (NaCl) and malonic acid (MA), as well as binary mixtures of NaCl and MA, and NaCl and nonanoic acid (NA) determined by AFM using area (2D) equivalent diameters, similar to conventional microscopy methods, to GFs determined using volume (3D) equivalent diameter. We also compare these values to GFs determined by a hygroscopic tandem differential mobility analyzer (HTDMA; substrate free, 3D method). It was found that utilizing volume equivalent diameter for quantifying GFs with AFM agreed well with those determined by substrate-free HTDMA method, regardless of particle composition but area equivalent derived GFs varied for different chemical systems. Furthermore, the NaCl and MA mixture was substrate-deposited both wet and dry, revealing that the hydration state of the particle at the time of impaction influences how the particle grows on the substrate upon water uptake. Most importantly, for the binary mixtures it is shown here that different populations of particles can be distinguished with AFM, an individual particle method, whereas HTDMA sees the ensemble average. Overall, this study establishes the methodology of using AFM to accurately quantify the water uptake of individual submicrometer particles at ambient conditions over a wide range of RH values. Furthermore, the importance of single particle AFM analysis is demonstrated.

Enrichment of Saccharides and Divalent Cations in Sea Spray Aerosol During Two Phytoplankton Blooms.

Sea spray aerosol (SSA) is a globally important source of particulate matter. A mesocosm study was performed to determine the relative enrichment of saccharides and inorganic ions in nascent fine (PM2.5) and coarse (PM10-2.5) SSA and the sea surface microlayer (SSML) relative to bulk seawater. Saccharides comprise a significant fraction of organic matter in fine and coarse SSA (11 and 27%, respectively). Relative to sodium, individual saccharides were enriched 14-1314-fold in fine SSA, 3-138-fold in coarse SSA, but only up to 1.0-16.2-fold in SSML. Enrichments in SSML were attributed to rising bubbles that scavenge surface-active species from seawater, while further enrichment in fine SSA likely derives from bubble films. Mean enrichment factors for major ions demonstrated significant enrichment in fine SSA for potassium (1.3), magnesium (1.4), and calcium (1.7), likely because of their interactions with organic matter. Consequently, fine SSA develops a salt profile significantly different from that of seawater. Maximal enrichments of saccharides and ions coincided with the second of two phytoplankton blooms, signifying the influence of ocean biology on selective mass transfer across the ocean-air interface.

Mechanical Properties of a Series of Macro- and Nanodimensional Organic Cocrystals Correlate with Atomic Polarizability.

A correlation between Young's modulus, as determined by using nanoindentation atomic force microscopy (AFM), and atomic polarizability is observed for members of a series of cocrystals based on systematic changes to one cocrystal component. Time domain spectroscopy over terahertz frequencies (THz-TDS) is used for the first time to directly measure the polarizability of macro- and nanosized organic solids. Cocrystals of both macro- and nanodimensions with highly polarizable atoms result in softer solids and correspondingly higher polarizabilities.

Determination of concentration and activity of immobilized enzymes.

Methods that directly measure the concentration of surface-immobilized biomolecules are scarce. More commonly, the concentration of the soluble molecule is measured before and after immobilization, and the bound concentration is assessed by elimination, assuming that all bound molecules are active. An assay was developed for measuring the active site concentration, activity, and thereby the catalytic turnover rate (kcat) of an immobilized dihydrofolate reductase as a model system. The new method yielded a similar first-order rate constant, kcat, to that of the same enzyme in solution. The findings indicate that the activity of the immobilized enzyme, when separated from the surface by the DNA spacers, has not been altered. In addition, a new immobilization method that leads to solution-like activity of the enzyme on the surface is described. The approaches developed here for immobilization and for determining the concentration of an immobilized enzyme are general and can be extended to other enzymes, receptors, and antibodies.

Substrate-Deposited Sea Spray Aerosol Particles: Influence of Analytical Method, Substrate, and Storage Conditions on Particle Size, Phase, and Morphology.

Atmospheric aerosols are often collected on substrates and analyzed weeks or months after the initial collection. We investigated how the selection of substrate and microscopy method influence the measured size, phase, and morphology of sea spray aerosol (SSA) particles and how sample storage conditions affect individual particles using three common microscopy techniques: optical microscopy, atomic force microscopy, and scanning electron microscopy. Micro-Raman spectroscopy was used to determine changes in the water content of stored particles. The results show that microscopy techniques operating under ambient conditions provide the most relevant and robust measurement of particle size. Samples stored in a desiccator and at ambient conditions leads to similar sizes and morphologies, while storage that involves freezing and thawing leads to irreversible changes due to phase changes and water condensation. Typically, SSA particles are deposited wet and, if possible, samples used for single-particle analysis should be stored at or near conditions at which they were collected in order to avoid dehydration. However, if samples need to be dry, as is often the case, then this study found that storing SSA particles at ambient laboratory conditions (17-23% RH and 19-21 °C) was effective at preserving them and reducing changes that would alter samples and subsequent data interpretation.

Size matters in the water uptake and hygroscopic growth of atmospherically relevant multicomponent aerosol particles.

Understanding the interactions of water with atmospheric aerosols is crucial for determining the size, physical state, reactivity, and climate impacts of this important component of the Earth's atmosphere. Here we show that water uptake and hygroscopic growth of multicomponent, atmospherically relevant particles can be size dependent when comparing 100 nm versus ca. 6 µm sized particles. It was determined that particles composed of ammonium sulfate with succinic acid and of a mixture of chlorides typical of the marine environment show size-dependent hygroscopic behavior. Microscopic analysis of the distribution of components within the aerosol particles show that the size dependence is due to differences in the mixing state, that is, whether particles are homogeneously mixed or phase separated, for different sized particles. This morphology-dependent hygroscopicity has consequences for heterogeneous atmospheric chemistry as well as aerosol interactions with electromagnetic radiation and clouds.