Oxide- and Silicate-Water Interfaces and Their Roles in Technology and the Environment.

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

Acidity across the interface from the ocean surface to sea spray aerosol.

Aerosols impact climate, human health, and the chemistry of the atmosphere, and aerosol pH plays a major role in the physicochemical properties of the aerosol. However, there remains uncertainty as to whether aerosols are acidic, neutral, or basic. In this research, we show that the pH of freshly emitted (nascent) sea spray aerosols is significantly lower than that of sea water (approximately four pH units, with pH being a log scale value) and that smaller aerosol particles below 1 µm in diameter have pH values that are even lower. These measurements of nascent sea spray aerosol pH, performed in a unique ocean-atmosphere facility, provide convincing data to show that acidification occurs "across the interface" within minutes, when aerosols formed from ocean surface waters become airborne. We also show there is a correlation between aerosol acidity and dissolved carbon dioxide but no correlation with marine biology within the seawater. We discuss the mechanisms and contributing factors to this acidity and its implications on atmospheric chemistry.

Size-Dependent Sigmoidal Reaction Kinetics for Pyruvic Acid Condensation at the Air-Water Interface in Aqueous Microdroplets.

The chemistry of pyruvic acid (PA) under thermal dark conditions is limited in bulk solutions, but in microdroplets it is shown to readily occur. Utilizing in situ micro-Raman spectroscopy as a probe, we investigated the chemistry of PA within aqueous microdroplets in a relative humidity- and temperature-controlled environmental cell. We found that PA undergoes a condensation reaction to yield mostly zymonic acid. Interestingly, the reaction follows a size-dependent sigmoidal kinetic profile, i.e., an induction period followed by reaction and then completion. The induction time is linearly proportional to the surface area (R2), and the maximum apparent reaction rate is proportional to the surface-to-volume ratio (1/R), showing that both the induction and reaction occur at the air-water interface. Furthermore, the droplet size is shown to be dynamic due to changes in droplet composition and re-equilibration with the relative humidity within the environmental cell as the reaction proceeds. Overall, the size-dependent sigmoidal kinetics, shown for the first time in microdroplets, demonstrates the complexity of the reaction mechanism and the importance of the air-water interface in the pyruvic acid condensation reaction.

Gas-Phase and Surface-Initiated Reactions of Household Bleach and Terpene-Containing Cleaning Products Yield Chlorination and Oxidation Products Adsorbed onto Indoor Relevant Surfaces.

The use of household bleach cleaning products results in emissions of highly oxidative gaseous species, such as hypochlorous acid (HOCl) and chlorine (Cl2). These species readily react with volatile organic compounds (VOCs), such as limonene, one of the most abundant compounds found in indoor enviroments. In this study, reactions of HOCl/Cl2 with limonene in the gas phase and on indoor relevant surfaces were investigated. Using an environmental Teflon chamber, we show that silica (SiO2), a proxy for window glass, and rutile (TiO2), a component of paint and self-cleaning surfaces, act as a reservoir for adsorption of gas-phase products formed between HOCl/Cl2 and limonene. Furthermore, high-resolution mass spectrometry (HRMS) shows that the gas-phase reaction products of HOCl/Cl2 and limonene readily adsorb on both SiO2 and TiO2. Surface-mediated reactions can also occur, leading to the formation of new chlorine- and oxygen-containing products. Transmission Fourier-transform infrared (FTIR) spectroscopy of adsorption and desorption of bleach and terpene oxidation products indicates that these chlorine- and oxygen-containing products strongly adsorb on both SiO2 and TiO2 surfaces for days, providing potential sources of human exposure and sinks for additional heterogeneous reactions.

Adsorption of 6-MHO on two indoor relevant surface materials: SiO2 and TiO2.

The compound 6-methyl-5-hepten-2-one (6-MHO) is a product of skin oil ozonolysis and is of significance in understanding the role of human occupants in the indoor environment. We present a joint computational and experimental study investigating the adsorption of 6-MHO on two model indoor relevant surfaces, SiO2, a model for a glass window, and TiO2, a component of paint and self-cleaning surfaces. Our classical force field-based molecular dynamics, ab initio molecular dynamics simulations, and FTIR absorption spectra indicate 6-MHO can adsorb on to both of these surfaces via hydrogen and π-hydrogen bonds and is quite stable due to the linear geometry of 6-MHO. Detailed analysis of 6-MHO on the SiO2 surface shows that relative humidity does not impact surface adsorption and adsorbed water does not displace 6-MHO from the hydroxylated SiO2 surface. Additionally, the desorption kinetics of 6-MHO from the hydroxylated SiO2 surface is compared to other compounds found in indoor environments and 6-MHO is shown to desorb with a first order rate constant that is approximately four times slower than that of limonene, but six times faster than that of carvone. In addition, our joint results indicate 6-MHO forms a stronger interaction with the TiO2 surface compared to the SiO2 surface. This study suggests that skin oil ozonolysis products can partition to indoor surfaces leading to the formation of organic films.

Distinguishing different surface interactions for nucleotides adsorbed onto hematite and goethite particle surfaces through ATR-FTIR spectroscopy and DFT calculations.

Geochemical interfaces can impact the fate and transport of aqueous species in the environment including biomolecules. In this study, we investigate the surface chemistry of adsorbed nucleotides on two different minerals, hematite and goethite, using infrared spectroscopy and density functional theory (DFT) calculations. Attenuated total reflectance-Fourier transform infrared spectroscopy is used to probe the adsorption of deoxyadenosine monophosphate (dAMP), deoxyguanosine monophosphate (dGMP), deoxycytidine monophosphate (dCMP), and deoxythymidine monophosphate (dTMP) onto either hematite or goethite particle surfaces. The results show preferential adsorption of the phosphate group to either surface. Remarkably, surface adsorption of the four nucleotides onto either hematite or goethite have nearly identical experimental spectra in the phosphate region (900 to 1200 cm-1) for each mineral surface yet are distinctly different between the two minerals, suggesting differences in binding of these nucleotides to the two mineral surfaces. The experimental absorption frequencies in the phosphate region were compared to DFT calculations for nucleotides adsorbed through the phosphate group to binuclear clusters in either a monodentate or bidentate bridging coordination. Although the quality of the fits suggests that both binding modes may be present, the relative amounts differ on the two surfaces with preferential bonding suggested to be monodentate coordination on hematite and bidentate bridging on goethite. Possible reasons for these differences are discussed.

pH Dependence of the speciation and optical properties of 4-benzoylbenzoic acid.

Organic chromophores initiate much of daytime aqueous phase chemistry in the environment. Thus, studying the absorption spectra of commonly used organic photosensitizers is paramount to fully understand their relevance in environmental processes. In this work, we combined UV-Vis spectroscopy, 1H-NMR spectroscopy, quantum chemical calculations, and molecular dynamics simulations to investigate the absorption spectra of 4-benzoyl benzoic acid (4BBA), a widely used photosensitizer and a common proxy of environmentally relevant chromophores. Solutions of 4BBA at different pH values show that protonated and deprotonated species have an effect on its absorbance spectra. Theoretical calculations of these species in water clusters provide physical and chemical insights into the spectra. Quantum chemical calculations were conducted to analyze the UV-Vis absorbance spectra of 4BBA species using various cluster sizes, such as C6H5COC6H4COOH·(H2O)n, where n = 8 for relatively small clusters and n = 30 for larger clusters. While relatively small clusters have been successfully used for smaller chromophores, our results indicate that simulations of protonated species of 4BBA require relatively larger clusters of n = 30. A comparison between the experimental and theoretical results shows good agreement in the pH-dependent spectral shift between the hydrated cluster model and the experimental data. Overall, the theoretical and empirical results indicate that the experimental optical spectra of aqueous phase 4BBA can be represented by the acid-base equilibrium of the keto-forms, with a spectroscopically measured pKa of 3.41 ± 0.04. The results summarized here contribute to a molecular-level understanding of solvated organic molecules through calculations restricted to cluster models, and thereby, broader insight into environmentally relevant chromophores.

Differential Surface Interactions and Surface Templating of Nucleotides (dGMP, dCMP, dAMP, and dTMP) on Oxide Particle Surfaces.

The fate of biomolecules in the environment depends in part on understanding the surface chemistry occurring at the biological-geochemical (bio-geo) interface. Little is known about how environmental DNA (eDNA) or smaller components, like nucleotides and oligonucleotides, persist in aquatic environments and the role of surface interactions. This study aims to probe surface interactions and adsorption behavior of nucleotides on oxide surfaces. We have investigated the interactions of individual nucleotides (dGMP, dCMP, dAMP, and dTMP) on TiO2 particle surfaces as a function of pH and in the presence of complementary and noncomplementary base pairs. Using attenuated total reflectance-Fourier transform infrared spectroscopy, there is an increased number of adsorbed nucleotides at lower pH with a preferential interaction of the phosphate group with the oxide surface. Additionally, differential adsorption behavior is seen where purine nucleotides are preferentially adsorbed, with higher surface saturation coverage, over their pyrimidine derivatives. These differences may be a result of intermolecular interactions between coadsorbed nucleotides. When the TiO2 surface was exposed to two-component solutions of nucleotides, there was preferential adsorption of dGMP compared to dCMP and dTMP, and dAMP compared to dTMP and dCMP. Complementary nucleotide base pairs showed hydrogen-bond interactions between a strongly adsorbed purine nucleotide layer and a weaker interacting hydrogen-bonded pyrimidine second layer. Noncomplementary base pairs did not form a second layer. These results highlight several important findings: (i) there is differential adsorption of nucleotides; (ii) complementary coadsorbed nucleotides show base pairing with a second layer, and the stability depends on the strength of the hydrogen bonding interactions and; (iii) the first layer coverage strongly depends on pH. Overall, the importance of surface interactions in the adsorption of nucleotides and the templating of specific interactions between nucleotides are discussed.

Gas-Phase Nitrous Acid (HONO) Is Controlled by Surface Interactions of Adsorbed Nitrite (NO2-) on Common Indoor Material Surfaces.

Nitrous acid (HONO) is a household pollutant exhibiting adverse health effects and a major source of indoor OH radicals under a variety of lighting conditions. The present study focuses on gas-phase HONO and condensed-phase nitrite and nitrate formation on indoor surface thin films following heterogeneous hydrolysis of NO2, in the presence and absence of light, and nitrate (NO3-) photochemistry. These thin films are composed of common building materials including zeolite, kaolinite, painted walls, and cement. Gas-phase HONO is measured using an incoherent broadband cavity-enhanced ultraviolet absorption spectrometer (IBBCEAS), whereby condensed-phase products, adsorbed nitrite and nitrate, are quantified using ion chromatography. All of the surface materials used in this study can store nitrogen oxides as nitrate, but only thin films of zeolite and cement can act as condensed-phase nitrite reservoirs. For both the photo-enhanced heterogeneous hydrolysis of NO2 and nitrate photochemistry, the amount of HONO produced depends on the material surface. For zeolite and cement, little HONO is produced, whereas HONO is the major product from kaolinite and painted wall surfaces. An important result of this study is that surface interactions of adsorbed nitrite are key to HONO formation, and the stronger the interaction of nitrite with the surface, the less gas-phase HONO produced.

Nanoscopic Study of Water Uptake on Glass Surfaces with Organic Thin Films and Particles from Exposure to Indoor Cooking Activities: Comparison to Model Systems.

Water uptake by thin organic films and organic particles on glass substrates at 80% relative humidity was investigated using atomic force microscopy-infrared (AFM-IR) spectroscopy. Glass surfaces exposed to kitchen cooking activities show a wide variability of coverages from organic particles and organic thin films. Water uptake, as measured by changes in the volume of the films and particles, was also quite variable. A comparison of glass surfaces exposed to kitchen activities to model systems shows that they can be largely represented by oxidized oleic acid and carboxylate groups on long and medium hydrocarbon chains (i.e., fatty acids). Overall, we demonstrate that organic particles and thin films that cover glass surfaces can take up water under indoor-relevant conditions but that the water content is not uniform. The spatial heterogeneity of the changes in these aged glass surfaces under dry (5%) and wet (80%) conditions is quite marked, highlighting the need for studies at the nano- and microscale.

Interactions of limonene and carvone on titanium dioxide surfaces.

Limonene, a monoterpene, found in cleaning products and air fresheners can interact with a variety of surfaces in indoor environments. An oxidation product of limonene, carvone, has been reported to cause contact allergens. In this study, we have investigated the interactions of limonene and carvone with TiO2, a component of paint and self-cleaning surfaces, at 297 ± 1 K with FTIR spectroscopy and force field-based molecular dynamics and ab initio simulations. The IR absorption spectra and computational methods show that limonene forms π-hydrogen bonds with the surface O-H groups on the TiO2 surface and that carvone adsorbs on the TiO2 surface through a variety of molecular interactions including through carbonyl oxygen atoms with Ti4+ surface atoms, O-H hydrogen bonding (carbonyl O⋯HO) and π-hydrogen bonds with surface O-H groups. Furthermore, we investigated the effects of relative humidity (RH) on the adsorption of limonene and carvone on the TiO2 surface. The spectroscopic results show that the adsorbed limonene can be completely displaced by water at a relative humidity of ca. 50% RH (∼2 MLs of water) and that 25% of carvone is displaced at ca. 67% RH, which agrees with the calculated free energies of adsorption which show carvone more strongly adsorbs on the surface relative to limonene and thus would be harder to displace from the surface. Overall, this study shows how a monoterpene and its oxidation product interact with TiO2 and the impact of relative humidity on these interactions.

Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products.

Organonitrates (ON) are important components of secondary organic aerosols (SOAs). α-Pinene (C10H16), the most abundant monoterpene in the troposphere, is a precursor for the formation of several of these compounds. ON from α-pinene can be produced in the gas phase via photochemical processes and/or following reactions with oxidizers including hydroxyl radical and ozone. Gas-phase nitrogen oxides (NO2, NO3) are N sources for ON formation. Although gas-phase reactions of α-pinene that yield ON are fairly well understood, little is known about their formation through heterogeneous and multiphase pathways. In the current study, surface reactions of α-pinene with nitrogen oxides on hematite (α-Fe2O3) and kaolinite (SiO2Al2O3(OH)4) surfaces, common components of mineral dust, have been investigated. α-Pinene oxidizes upon adsorption on kaolinite, forming pinonaldehyde, which then dimerizes on the surface. Furthermore, α-pinene is shown to react with adsorbed nitrate species on these mineral surfaces producing multiple ON and other oxidation products. Additionally, gas-phase oxidation products of α-pinene on mineral surfaces are shown to more strongly adsorb on the surface compared to α-pinene. Overall, this study reveals the complexity of reactions of prevalent organic compounds such as α-pinene with adsorbed nitrate and nitrogen dioxide, revealing new heterogeneous reaction pathways for SOA formation that is mineralogy specific.

Absorption Spectra and the Electronic Structure of Gallic Acid in Water at Different pH: Experimental Data and Theoretical Cluster Models.

Gallic acid (GA) has been characterized in terms of its optical properties in aqueous solutions at varying pH in experiments and in theoretical calculations by analyzing the protonated and deprotonated forms of GA. This work is part of a series of studies of the optical properties of different carboxylic acids in aqueous media. The experimental electronic spectra of GA exhibit two strong well-separated absorption peaks (B- and C-bands), which agree with previous studies. However, in the current study, an additional well-defined low-energy shoulder band (A-band) in the optical spectra of GA was identified. It is likely that the A-band occurs for other carboxylic acids in solution, but because it can overlap with the B-band, it is difficult to discern. The theoretical calculations based on density functional theory were used to simulate the optical absorption spectra of GA in water at different pH to prove the existence of this newly found shoulder band and to describe and characterize the full experimental optical spectra of GA. Different cluster models were tested: (i) all water molecules are coordinated near the carboxy-group and (ii) additional water molecules near the hydroxy-groups of the phenyl ring were included. In this study, we found that both the polarizable continuum model (dielectric property of a medium) and neighboring water molecules (hydrogen-bonding) play significant roles in the optical spectrum. The results showed that only an extended cluster model with water molecules near carboxy- and hydroxy-groups together with the polarizable continuum model allowed us to fully reproduce the experimental data and capture all three absorption bands (A, B, and C). The oscillator strengths of the absorption bands were obtained from the experimental data and compared with theoretical results. Additionally, our work provides a detailed interpretation of the pH effects observed in the experimental absorption spectra.

Enhanced Rates of Transition-Metal-Ion-Catalyzed Oxidation of S(IV) in Aqueous Aerosols: Insights into Sulfate Aerosol Formation in the Atmosphere.

The oxidation of S(IV) is a critical step in the fate of sulfur dioxide emissions that determines the amount of sulfate aerosol in the atmosphere. Herein, we measured accelerated S(IV) oxidation rates in micron-sized aqueous aerosols compared to bulk solutions. We have investigated both buffered and unbuffered systems across a range of pH values in the presence of atmospherically relevant transition-metal ions and salts and consistently found the oxidation rate to be accelerated by ca. 1-2 orders of magnitude in the aerosol. This enhancement is greater than can be explained by the enrichment of species in the aerosol compared to the bulk and indicates that surface effects and potentially aerosol pH gradients play important roles in the S(IV) oxidation process in the aqueous aerosol. In addition, our experiments were performed with dissolved S(IV) ions (SO32-/HSO3-), allowing us to demonstrate that acceleration occurs in the condensed phase showing that enhanced sulfate formation is not exclusively due to gas-aerosol partitioning or interfacial SO2 oxidation. Our findings are an important step forward in understanding larger than expected sulfate concentrations observed in the atmosphere and show that inorganic oxidation processes can be accelerated in micron-sized aqueous droplets compared to the bulk solution.

HONO Production from Gypsum Surfaces Following Exposure to NO2 and HNO3: Roles of Relative Humidity and Light Source.

Nitrous acid (HONO) is a toxic household pollutant and a major source of indoor OH radicals. The high surface-to-volume ratio and diverse lighting conditions make the indoor photochemistry of HONO complex. This study demonstrates surface uptake of NO2 and gaseous HNO3 followed by gas-phase HONO generation on gypsum surfaces, model system for drywall, under reaction conditions appropriate for an indoor air environment. Tens of parts per billion of steady-state HONO are detected under these experimental conditions. Mechanistic insight into this heterogeneous photochemistry is obtained by exploring the roles of material compositions, relative humidities, and light sources. NO2 and HNO3 are adsorbed onto drywall surfaces, which can generate HONO under illumination and under dark conditions. Photoenhanced HONO generation is observed for illumination with a solar simulator as well as with the common indoor light sources such as compact fluorescence light and incandescent light bulbs. Incandescent light sources release more HONO and NO2 near the light source compared to the solar radiation. Overall, HONO production on the gypsum surface increases with the increase of RH up to 70% relative humidity; above that, the gaseous HONO level decreases due to surface loss. Heterogeneous hydrolysis of NO2 is predicted to be the dominant HONO generation channel, where NO2 is produced through the photolysis of surface-adsorbed nitrates. This hydrolysis reaction predominantly occurs in the first layer of surface-adsorbed water.

Heterogeneous Interactions of Prevalent Indoor Oxygenated Organic Compounds on Hydroxylated SiO2 Surfaces.

Oxygenated organic compounds (OOCs) are widely found in indoor environments and come from either the direct emissions from indoor activities or the subsequent oxidation of nonoxygenated OCs. Adsorption and partitioning of OCs on surfaces are significant processes in indoor chemistry, yet these interactions specifically involving OOCs are still poorly understood. In this study, we investigate the interactions of three prevalent indoor OOCs (dihydromyrcenol, α-terpineol, and linalool) on an indoor surface proxy (hydroxylated SiO2) by combining vibrational spectroscopy with ab initio molecular dynamics simulations. The adsorption of these compounds on the SiO2 surface is driven by π hydrogen bonding and O-H hydrogen bonding interactions, with O-H hydrogen bonding interactions being stronger. The results of kinetic measurements suggest that indoor surfaces play a significant role in the removal of these OOCs, especially under moderate and low air exchange. Additionally, indoor surfaces can also serve as a reservoir of OOCs due to their much slower desorption kinetics when compared to other indoor relevant organic compounds such as limonene. Overall, the results gleaned by experiment and theoretical simulations provide a molecular representation of the interaction of OOCs on indoor relevant surfaces as well as implications of these interactions for indoor air chemistry.

Atmospheric Benzothiazoles in a Coastal Marine Environment.

Organic emissions from coastal waters play an important but poorly understood role in atmospheric chemistry in coastal regions. A mesocosm experiment focusing on facilitated biological blooms in coastal seawater, SeaSCAPE (Sea Spray Chemistry and Particle Evolution), was performed to study emission of volatile gases, primary sea spray aerosol, and formation of secondary marine aerosol as a function of ocean biological and chemical processes. Here, we report observations of aerosol-phase benzothiazoles in a marine atmospheric context with complementary measurements of dissolved-phase benzothiazoles. Though previously reported dissolved in polluted coastal waters, we report the first direct evidence of the transfer of these molecules from seawater into the atmosphere. We also report the first gas-phase observations of benzothiazole in the environment absent a direct industrial, urban, or rubber-based source. From the identities and temporal dynamics of the dissolved and aerosol species, we conclude that the presence of benzothiazoles in the coastal water (and thereby their emissions into the atmosphere) is primarily attributable to anthropogenic sources. Oxidation experiments to explore the atmospheric fate of gas-phase benzothiazole show that it produces secondary aerosol and gas-phase SO2, making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

Toward a microscopic model of light absorbing dissolved organic compounds in aqueous environments: theoretical and experimental study.

Water systems often contain complex macromolecular systems that absorb light. In marine environments, these light absorbing components are often at the air-water interface and can participate in the chemistry of the atmosphere in ways that are poorly understood. Understanding the photochemistry and photophysics of these systems represents a major challenge since their composition and structures are not unique. In this study, we present a successful microscopic model of this light absorbing macromolecular species termed "marine derived chromophoric dissolved organic matter" or "m-CDOM" in water. The approach taken involves molecular dynamics simulations in the ground state using on the fly Density Functional Tight-Binding (DFTB) electronic structure theory; Time Dependent DFTB (TD-DFTB) calculations of excited states, and experimental measurements of the optical absorption spectra in aqueous solution. The theoretical hydrated model shows key features seen in the experimental data for a collected m-CDOM sample. As will be discussed, insights from the model are: (i) the low-energy A-band (at 410 nm) is due to the carbon chains combined with the diol- and the oxy-groups present in the structure; (ii) the weak B-band (at 320-360 nm) appears due to the contribution of the ionized speciated form of m-CDOM; and (iii) the higher-energy C-band (at 280 nm) is due to the two fused ring system. Thus, this is a two-speciated formed model. Although a relatively simple system, these calculations represent an important step in understanding light absorbing compounds found in nature and the search for other microscopic models of related materials remains of major interest.

Low-Temperature Water Uptake of Individual Marine and Biologically Relevant Atmospheric Particles Using Micro-Raman Spectroscopy.

The interaction of water vapor and the water uptake behavior of atmospheric particles are often investigated as a function of relative humidity (0-100% RH) at ambient temperature. However, lower temperature studies are important to understand how atmospheric particles nucleate ice through various mechanisms including immersion freezing. Immersion freezing requires the formation of a condensed water droplet at lower temperatures prior to freezing. To better understand low-temperature water uptake behavior of marine and biologically relevant atmospheric particles, we have investigated water uptake of single atmospheric particles using a micro-Raman spectrometer coupled to an environmental cell for measurements at lower temperatures and as a function of relative humidity. These particles include sodium chloride, sucrose, Snomax, lipopolysaccharide, and laminarin. Particles range in size from 2 to 3 µm in diameter and can be monitored by using optical microscopy and Raman spectroscopy as a function of relative humidity at temperatures between 253 and 298 K. From the Raman spectra collected, we can determine a Raman growth factor defined as an increase in the intensity of the O-H stretch as a measure of the integrated water content of a particle compared to the dry particle. These data show that for lipopolysaccharide, laminarin, and Snomax, unlike simple saccharides such as sucrose and other soluble organics, as temperature decreases, water uptake begins at lower relative humidity and does not follow a solubility temperature dependence. This suggests that at lower temperatures the particles are adsorbing water on the surface rather than dissolving and absorbing water. Furthermore, repeated water uptake cycles cause a change in the morphology of some of these particles, which is shown to promote water uptake at lower relative humidity. These results give new insights into water uptake of these different marine and biologically relevant particles at low temperature at subsaturation relative humidity prior to droplet formation and immersion freezing.

Temperature-Dependent Liquid Water Structure for Individual Micron-Sized, Supercooled Aqueous Droplets with Inclusions.

Herein, we measure the water structure for individual micron-sized droplets of water, salt water, and water containing biologically and marine relevant atmospheric inclusions as a function of temperature. Individual droplets, formed on a hydrophobic substrate, are analyzed with micro-Raman spectroscopy. Analysis of the Raman spectra in the O-H stretching region shows that the equilibrium of partially and fully hydrogen-bonding water interactions change as temperature decreases up until there is a phase transition to form ice. Using these temperature-dependent measurements, the thermodynamic parameters for the interchange between partially and fully hydrogen-bonded water (PHW ⇄ FHW) for different supercooled droplets (water, salt water, and water containing biologically and marine relevant atmospheric inclusions) have been determined.