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Environmental DNA (eDNA), i.e., DNA found in the environment, can interact with various geochemical surfaces, yet little is known about these interactions. Mineral surfaces may alter the structure, stability, and reactivity of eDNA, impacting the cycling of genetic information and the reliability of eDNA-based detection tools. Understanding how eDNA interacts with surfaces is crucial for predicting its fate in the environment. In this study, we examined the surface interaction and stability of herring testes DNA, a model system for eDNA, on two common iron oxide phases present in the environment: α-FeOOH (goethite) and α-Fe 2 O 3 (hematite). Utilizing spectroscopic probes, including attenuated total reflection Fourier-transform infrared (ATR-FTIR) and UV-vis spectroscopy, we quantified the DNA adsorption capacity at pH 5 and determined its secondary structure. DNA adsorbed irreversibly at pH 5 and 25 °C, primarily through its phosphate groups, and retained the solution-phase B-form structure. However, the infrared data also indicated some distortion of the B-form likely due to additional interactions between nitrogenous bases when adsorbed on the α-Fe 2 O 3 particle surfaces. The distortion in the double helical structure of adsorbed DNA on α-Fe 2 O 3 led to a lower melting temperature ( T m ) of 60 °C compared to 70 °C for DNA in solution. In contrast, DNA adsorbed on α-FeOOH melted at higher temperatures relative to solution-phase DNA and in two distinct phases. Upon testing adsorbed DNA stability at higher pH values, there were distinct differences between the two iron oxide phases. For α-FeOOH, nearly 50% of the DNA desorbed from the surface when the solution pH changed from 5 to 8, while less than 5% desorbed from α-Fe 2 O 3 under the same conditions. Overall, these findings underscore the importance of mineral-specific eDNA-surface interactions and their role in adsorbed eDNA stability, in terms of DNA melting and the impact of solution-phase pH changes.

As wildfire events become more frequent, there is a need to better understand the impact of smoke on the environment and human health. Smoke, or biomass burning aerosol (BBA), can undergo atmospheric processing changing its chemical and optical properties. We examined the interactions between four lignin pyrolysis products (catechol, syringol, syringic acid, and vanillic acid) and three BBA-relevant iron oxide mineral phases (hematite, maghemite, and magnetite) using attenuated total reflectance-Fourier transform infrared spectroscopy and dissolved iron measurements to better understand how atmospheric processing changes concentrations of soluble iron, iron oxidation state, and brown carbon abundance. Reductive dissolution was the primary dissolution mechanism for catechol and syringol, which led to a substantial amount of iron release ( p < 0.05), whereas syringic and vanillic acids had little impact on dissolution. Comparisons with other BBA relevant compounds highlight the importance of both steric and electronic structures in the reductive dissolution process. The maghemite and magnetite phases, which are more likely to be present in BBA, released significantly more dissolved iron than hematite ( p < 0.05), emphasizing the need to use BBA relevant iron oxide proxies in laboratory studies. This work provides insight into observations of iron dissolution and transformation of organics in BBA., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Although aqueous microdroplets have been shown to exhibit enhanced chemical reactivity compared to bulk solutions, mechanisms for these enhancements are not completely understood. Here we combine experimental measurements and kinetic modeling to show the strong coupling of interfacial reactions and gas/droplet partitioning in the condensation reaction of pyruvic acid (PA) to yield zymonic acid (ZA) in acidic aqueous microdroplets. Experimental analysis of single microdroplets reveals the substantial influence of evaporation of PA and partitioning of water on the size-, relative humidity (RH)- and temperature-dependent sigmoidal reaction kinetics for the condensation reaction. A newly developed diffusion-reaction-partitioning model is used to simulate the complex kinetics observed in the microdroplets. The model can quantitatively predict the size and compositional changes as the reaction proceeds under different environmental conditions, and provides insights into how microdroplet reactivity is controlled by coupled interfacial reactions and the gas-phase partitioning of PA and water. Importantly, the kinetic model best fits the data when an autocatalytic step is included in the mechanism, i.e. a reaction step where the product, ZA, catalyzes the interfacial condensation reaction. Overall, the dynamic nature of aqueous microdroplet chemistry and the coupling of interfacial chemistry with gas-phase partitioning are demonstrated. Furthermore, autocatalysis of small organic molecules at the air-water interface for aqueous microdroplets, shown here for the first time, has implications for several fields including prebiotic chemistry, atmospheric chemistry and chemical synthesis., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Variable wind speeds over the ocean can have a significant impact on the formation mechanism and physical-chemical properties of sea spray aerosols (SSA), which in turn influence their climate-relevant impacts. Herein, for the first time, we investigate the effects of wind speed on size-dependent morphology and composition of individual nascent SSA generated from wind-wave interactions of natural seawater within a wind-wave channel as a function of size and their particle-to-particle variability. Filter-based thermal optical analysis, atomic force microscopy (AFM), AFM infrared spectroscopy (AFM-IR), and scanning electron microscopy (SEM) were employed in this regard. This study focuses on SSA with sizes within 0.04-1.8 μm generated at two wind speeds: 10 m/s, representing a wind lull scenario over the ocean, and 19 m/s, indicative of the wind speeds encountered in stormy conditions. Filter-based measurements revealed a reduction of the organic mass fraction as the wind speed increases. AFM imaging at 20% relative humidity of individual SSA identified six main morphologies: prism-like, rounded, core-shell, rod, rod inclusion core-shell, and aggregates. At 10 m/s, most SSA were rounded, while at 19 m/s, core-shells became predominant. Based on AFM-IR, rounded SSA at both wind speeds had similar composition, mainly composed of aliphatic and oxygenated species, whereas the shells of core-shells displayed more oxygenated organics at 19 m/s and more aliphatic organics at 10 m/s. Collectively, our observations can be attributed to the disruption of the sea surface microlayer film structure at higher wind speeds. The findings reveal a significant impact of wind speed on morphology and composition of SSA, which should be accounted for accurate assessment of their climate effects., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The Chemical Assessment of Surfaces and Air (CASA) study aimed to understand how chemicals transform in the indoor environment using perturbations ( e.g. , cooking, cleaning) or additions of indoor and outdoor pollutants in a well-controlled test house. Chemical additions ranged from individual compounds ( e.g. , gaseous ammonia or ozone) to more complex mixtures ( e.g. , a wildfire smoke proxy and a commercial pesticide). Physical perturbations included varying temperature, ventilation rates, and relative humidity. The objectives for CASA included understanding (i) how outdoor air pollution impacts indoor air chemistry, (ii) how wildfire smoke transports and transforms indoors, (iii) how gases and particles interact with building surfaces, and (iv) how indoor environmental conditions impact indoor chemistry. Further, the combined measurements under unperturbed and experimental conditions enable investigation of mitigation strategies following outdoor and indoor air pollution events. A comprehensive suite of instruments measured different chemical components in the gas, particle, and surface phases throughout the study. We provide an overview of the test house, instrumentation, experimental design, and initial observations - including the role of humidity in controlling the air concentrations of many semi-volatile organic compounds, the potential for ozone to generate indoor nitrogen pentoxide (N 2 O 5 ), the differences in microbial composition between the test house and other occupied buildings, and the complexity of deposited particles and gases on different indoor surfaces.

Solid-water interfaces are crucial for clean water, conventional and renewable energy, and effective nuclear waste management. However, reflecting the complexity of reactive interfaces in continuum-scale models is a challenge, leading to oversimplified representations that often fail to predict real-world behavior. This is because these models use fixed parameters derived by averaging across a wide physicochemical range observed at the molecular scale. Recent studies have revealed the stochastic nature of molecular-level surface sites that define a variety of reaction mechanisms, rates, and products even across a single surface. To bridge the molecular knowledge and predictive continuum-scale models, we propose to represent surface properties with probability distributions rather than with discrete constant values derived by averaging across a heterogeneous surface. This conceptual shift in continuum-scale modeling requires exponentially rising computational power. By incorporating our molecular-scale understanding of solid-water interfaces into continuum-scale models we can pave the way for next generation critical technologies and novel environmental solutions., (© 2024. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

Nitrous acid (HONO) is a key molecule in the reactive nitrogen cycle. However, sources and sinks for HONO are not fully understood. Particulate nitrate photochemistry has been suggested to play a role in the formation of HONO in the marine boundary layer (MBL). Here we investigate the impact of marine relevant organic compounds on HONO formation from aqueous nitrate photochemistry. In particular, steady-state, gas-phase HONO yields were measured from irradiated nitrate solutions at low pH containing marine-dissolved organic matter (m-DOM). m-DOM induces a nonlinear increase in HONO yield across all concentrations compared to that for pure nitrate solutions, with rates of HONO formation increasing by up to 3-fold when m-DOM is present. Furthermore, to understand the potential synergistic effects that may occur within complex samples such as m-DOM, mixtures of chromophoric (light-absorbing) and aliphatic (non-light-absorbing) molecular proxies were utilized. In particular, mixtures of 4-benzoylbenzoic acid (4-BBA) and ethylene glycol (EG) in acidic aqueous solutions containing nitrate showed more HONO upon irradiation compared to solutions containing only one of the molecular proxies. This suggests that synergistic effects in the HONO formation can occur in complex organic samples. Atmospheric implications of the results presented here are discussed., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Dibasic esters (DBEs) have recently become emerging indoor air pollutants due to their usage as a solvent for mixtures of paints and coatings. In this study, we explored the adsorption/desorption kinetics, heterogeneous interactions, and chemical transformations of dimethyl succinate (DMS, C 6 H 10 O 4 ), a component of commercial dibasic ester solvent mixtures, on indoor relevant surfaces using transmission Fourier-transform infrared (FTIR) spectroscopy and high-resolution mass spectrometry (HRMS). Silica (SiO 2 ) and rutile (TiO 2 ) were used as proxies for window glass, and an active component in paint and self-cleaning surfaces, respectively. FTIR spectroscopy of these surfaces shows that DMS can interact with SiO 2 and TiO 2 through hydrogen bonding between the carbonyl oxygen and surface hydroxyl groups. The kinetics show fast adsorption of DMS onto these surfaces followed by slow desorption. Furthermore, new products formed observed on TiO 2 surfaces in addition to molecularly adsorbed DMS. In particular, succinate (C 5 H 7 O) was observed binding to the surface in a bidentate chelating coordination mode as indicated by the appearance of ν as (COO - ) and ν s (COO - ) bands in the FTIR spectra. These absorption bands grow in intensity over time and the resulting product remains strongly adsorbed on the surface. The formation of adsorbed succinate is a result of a reaction with DMS on Lewis acid sites of the TiO 2 surface. Overall, the slow desorption of these adsorbed species indicates that indoor surfaces can become long term reservoirs for dibasic esters and their surface products. Moreover, in the presence of ∼50% relative humidity, water displaces outer layers of adsorbed DMS on SiO 2 and TiO 2 , while having no impact on the more strongly bound surface species.

Phenol, a common semi-volatile compound associated with different emissions including from plants and biomass burning, as well as anthropogenic emissions and its derivatives, are important components of secondary organic aerosols (SOAs). Gas and aqueous phase reactions of phenol, in the presence of photochemical drivers, are fairly well understood. However, despite observations showing aromatic content within SOA size and mass increases during dust episodes, the heterogeneous reactions of phenol with mineral dusts are poorly understood. In the current study, surface reactions of phenol at the gas/solid interface with different components of mineral dust including SiO 2 , α-Fe 2 O 3 , and TiO 2 have been investigated. Whereas reversible surface adsorption of phenol occurs on SiO 2 surfaces, for both α-Fe 2 O 3 and TiO 2 surfaces, phenol reacts to form a wide range of OH substituted aromatic products. For α-Fe 2 O 3 surfaces that have been nitrated by gas-phase reactions of nitric acid prior to exposure to phenol, unique compounds form on the surface including nitro-phenolic compounds. Moreover, additional surface chemistry was observed when adsorbed nitro-phenolic products were exposed to gas-phase SO 2 as a result of the formation of adsorbed nitrite from nitrate redox chemistry with adsorbed SO 2 . Overall, this study reveals the extensive chemistry as well as the complexity of reactions of prevalent organic compounds leading to the formation of SOA on mineral surfaces., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The use of household bleach cleaning products results in emissions of highly oxidative gaseous species, such as hypochlorous acid (HOCl) and chlorine (Cl 2 ). 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/Cl 2 with limonene in the gas phase and on indoor relevant surfaces were investigated. Using an environmental Teflon chamber, we show that silica (SiO 2 ), a proxy for window glass, and rutile (TiO 2 ), a component of paint and self-cleaning surfaces, act as a reservoir for adsorption of gas-phase products formed between HOCl/Cl 2 and limonene. Furthermore, high-resolution mass spectrometry (HRMS) shows that the gas-phase reaction products of HOCl/Cl 2 and limonene readily adsorb on both SiO 2 and TiO 2 . 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 SiO 2 and TiO 2 surfaces for days, providing potential sources of human exposure and sinks for additional heterogeneous reactions.

In-situ Raman spectroscopy of single levitated charged aqueous microdroplets irradiated by dual-beam (266 and 532 nm) lasers demonstrates that the nitrate anion (NO 3 - ) can be depleted in the droplet through an energy transfer mechanism following excitation of sulfanilic acid (SA), a UV-absorbing aromatic organic compound. Upon 266 nm irradiation, a fast decrease of the NO 3 - concentration was observed when SA is present in the droplet. This photoinduced reaction occurs without the direct photolysis of NO 3 - . Instead, the rate of NO 3 - depletion was found to depend on the initial concentration of SA and the pH of the droplet. Based on absorption-emission spectral analysis and excited-state energy calculations, triplet-triplet energy transfer between SA and NO 3 - is proposed as the underlying mechanism for the depletion of NO 3 - in aqueous microdroplets. These results suggest that energy transfer mechanisms initiated by light-absorbing organic molecules may play a significant role in NO 3 - photochemistry.

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 ( R 2 ), 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.

Wildfires are increasing in frequency, raising concerns that smoke can permeate indoor environments and expose people to chemical air contaminants. To study smoke transformations in indoor environments and evaluate mitigation strategies, we added smoke to a test house. Many volatile organic compounds (VOCs) persisted days following the smoke injection, providing a longer-term exposure pathway for humans. Two time scales control smoke VOC partitioning: a faster one (1.0 to 5.2 hours) that describes the time to reach equilibrium between adsorption and desorption processes and a slower one (4.8 to 21.2 hours) that describes the time for indoor ventilation to overtake adsorption-desorption equilibria in controlling the air concentration. These rates imply that vapor pressure controls partitioning behavior and that house ventilation plays a minor role in removing smoke VOCs. However, surface cleaning activities (vacuuming, mopping, and dusting) physically removed surface reservoirs and thus reduced indoor smoke VOC concentrations more effectively than portable air cleaners and more persistently than window opening.

Minerals play a critical role in the chemistry occurring along the interface of different environmental systems, including the atmosphere/geosphere and hydrosphere/geosphere. In the past few decades, vibrational spectroscopy has been used as a probe for studying interfacial geochemistry. Here, we compare four different vibrational methods for probing physical and chemical features across different mineral samples and length scales, from the macroscale to nanoscale. These methods include Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR), Optical Photothermal Infrared (O-PTIR), Atomic Force Microscopy-Infrared (AFM-IR) and micro-Raman spectroscopy. The emergence of these micro-spectroscopic probes has offered new insights into heterogeneities within geochemical thin films and particles. These developments represent an important step forward for analyzing environmental interfaces and thin films as often these are assumed to be physically and chemically homogeneous. By comparing and integrating data across these measurement techniques, new insights into sample differences and heterogeneities can be gained. For example, interrogation of the various mineral samples at smaller length scales is shown to be particularly informative in highlighting unique chemical environments, including for chemically complex, multicomponent samples such as Arizona Test Dust (AZTD), as well as differences due to crystal orientation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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.

Organic acids are prevalent in the environment and their acidity and the corresponding dissociation constants can change under varying environmental conditions. The impact of nanoconfinement (when acids are confined within nanometer-scale domains) on physicochemical properties of chemical species is poorly understood and is an emerging field of study. By combining infrared and Raman spectroscopies with molecular dynamics (MD) simulations, we quantified the effect of nanoconfinement in silica nanopores on one of the fundamental chemical reactions-the dissociation of organic acids. The p K a of formic and acetic acids confined within cylindrical silica nanopores with 4 nm diameters were measured. MD models were constructed to calculate the shifts in the p K a values of acetic acid nanoconfined within 1, 2, 3, and 4 nm silica slit pores. Both experiments and MD models indicate a decrease in the apparent acid dissociation constants ( i.e. , increase in the p K a values) when organic acids are nanoconfined. Therefore, nanoconfinement stabilizes the protonated species. We attribute this observation to (1) a decrease in the average dielectric response of nanoconfined aqueous solutions where charge screening may be decreased; or (2) an increase in proton concentration inside nanopores, which would shift the equilibrium towards the protonated form. Overall, the results of this study provide the first quantification of the p K a values for nanoconfined formic and acetic acids and pave the way for a unifying theory predicting the impact of nanoconfinement on acid-base chemistry., Competing Interests: All authors declare no competing financial or non-financial interests., (This journal is © The Royal Society of Chemistry.)

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, 1 H-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 C 6 H 5 COC 6 H 4 COOH·(H 2 O) 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 p K a 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.

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.

Sea spray aerosol (SSA) ejected through bursting bubbles at the ocean surface is a complex mixture of salts and organic species. Submicrometer SSA particles have long atmospheric lifetimes and play a critical role in the climate system. Composition impacts their ability to form marine clouds, yet their cloud-forming potential is difficult to study due to their small size. Here, we use large-scale molecular dynamics (MD) simulations as a "computational microscope" to provide never-before-seen views of 40 nm model aerosol particles and their molecular morphologies. We investigate how increasing chemical complexity impacts the distribution of organic material throughout individual particles for a range of organic constituents with varying chemical properties. Our simulations show that common organic marine surfactants readily partition between both the surface and interior of the aerosol, indicating that nascent SSA may be more heterogeneous than traditional morphological models suggest. We support our computational observations of SSA surface heterogeneity with Brewster angle microscopy on model interfaces. These observations indicate that increased chemical complexity in submicrometer SSA leads to a reduced surface coverage by marine organics, which may facilitate water uptake in the atmosphere. Our work thus establishes large-scale MD simulations as a novel technique for interrogating aerosols at the single-particle level., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The hygroscopicity and pH of aqueous microdroplets and smaller aerosols control their impacts on human health and the climate. Nitrate depletion and chloride depletion through the partitioning of HNO 3 and HCl into the gas phase are processes that are enhanced in micron-sized and smaller aqueous droplets and this depletion influences both hygroscopicity and pH. Despite a number of studies, uncertainties remain about these processes. While acid evaporation and the loss of HCl or HNO 3 have been observed during dehydration, there is a question as to the rate of acid evaporation and whether this can occur in fully hydrated droplets at higher relative humidity (RH). To directly elucidate the kinetics of nitrate and chloride depletion through evaporation of HNO 3 and HCl, respectively at high RH, single levitated microdroplets are probed with cavity-enhanced Raman spectroscopy. Using glycine as a novel in situ pH probe, we are able to simultaneously measure changes in microdroplet composition and pH over timescales of hours. We find that the loss of chloride from the microdroplet is faster than that of nitrate, and the calculated rate constants infer that depletion is limited by the formation of HCl or HNO 3 at the air-water interface and subsequent partitioning into the gas phase., Competing Interests: The authors have no competing interests to declare., (This journal is © The Royal Society of Chemistry.)

Minerals in groundwater interact with various chemical and biological species including organic matter, proteins, and prevalent oxyanions, resulting in surface coatings and thin films of these different components. Surface interactions and the surface adsorption of these components on both oxide and oxyhydroxide iron surfaces have been widely investigated using a variety of spectroscopic methods. Despite these numerous studies, there still remains uncertainty with respect to interactions between these individual components, as well as heterogeneities and phase segregations within these thin films. In this study, we investigate mixtures containing Fe-containing minerals, proteins, and oxyanions to better understand surface interactions and phase segregation using Atomic Force Microscopy PhotoThermal Infrared (AFM-PTIR) spectroscopy. The results of this study show that AFM-PTIR spectroscopy can identify both nano- and microscale heterogeneities present within these thin films that are difficult to discern with other more conventional techniques such as ATR-FTIR spectroscopy due to phase segregation and mineral surface interactions. Overall, AFM-PTIR spectroscopy provides insights into multi-component environmental films that are difficult to uncover using other methodologies. This method has the potential to differentiate between bound and unbound toxic species as well as biological components, including environmental DNA, which can be used to assess the fate and transport of these species in the environment.

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, SiO 2 , a model for a glass window, and TiO 2 , 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 SiO 2 surface shows that relative humidity does not impact surface adsorption and adsorbed water does not displace 6-MHO from the hydroxylated SiO 2 surface. Additionally, the desorption kinetics of 6-MHO from the hydroxylated SiO 2 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 TiO 2 surface compared to the SiO 2 surface. This study suggests that skin oil ozonolysis products can partition to indoor surfaces leading to the formation of organic films.

Organonitrates (ON) and nitroxy-organosulfates (NOS) are important components of secondary organic aerosols (SOAs). Gas-phase reactions of α-pinene (C 10 H 16 ), a primary precursor for several ON compounds, are fairly well understood although formation pathways for NOS largely remain unknown. NOS formation may occur via reactions of ON and organic peroxides with sulfates as well as through radical-initiated photochemical processes. Despite the fact that organosulfates (OS) represent a significant portion of the organic aerosol mass, ON and NOS formation from OS is less understood, especially through nighttime heterogeneous and multiphase chemistry pathways. In the current study, surface reactions of adsorbed α-pinene-derived OS with nitrogen oxides on hematite and kaolinite surfaces, common components of mineral dust, have been investigated. α-Pinene reacts with sulfated mineral surfaces, forming a range of OS compounds on the surface. These OS compounds when adsorbed on mineral surfaces can further react with HNO 3 and NO 2 , producing several ON and NOS compounds as well as several oxidation products. Overall, this study reveals the complexity of reactions of prevalent organic compounds leading to the formation of OS, ON, and NOS via heterogeneous and multiphase reaction pathways on mineral surfaces. It is also shown that this chemistry is mineralogy-specific., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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 TiO 2 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 TiO 2 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.

The effects of atmospheric aging on single-particle nascent sea spray aerosol (nSSA) physicochemical properties, such as morphology, composition, phase state, and water uptake, are important to understanding their impacts on the Earth's climate. The present study investigates these properties by focusing on the aged SSA (size range of 0.1-0.6 μm) and comparing with a similar size range nSSA, both generated at a peak of a phytoplankton bloom during a mesocosm study. The aged SSAs were generated by exposing nSSA to OH radicals with exposures equivalent to 4-5 days of atmospheric aging. Complementary filter-based thermal optical analysis, atomic force microscopy (AFM), and AFM photothermal infrared spectroscopy were utilized. Both nSSA and aged SSA showed an increase in the organic mass fraction with decreasing particle sizes. In addition, aging results in a further increase of the organic mass fraction, which can be attributed to new particle formation and oxidation of volatile organic compounds followed by condensation on pre-existing particles. The results are consistent with single-particle measurements that showed a relative increase in the abundance of aged SSA core-shells with significantly higher organic coating thickness, relative to nSSA. Increased hygroscopicity was observed for aged SSA core-shells, which had more oxygenated organic species. Rounded nSSA and aged SSA had similar hygroscopicity and no apparent changes in the composition. The observed changes in aged SSA physicochemical properties showed a significant size-dependence and particle-to-particle variability. Overall, results showed that the atmospheric aging can significantly influence the nSSA physicochemical properties, thus altering the SSA effects on the climate., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Marine chromophoric dissolved organic matter (m-CDOM) mediates many vital photochemical processes at the ocean's surface. Isolating m-CDOM within the chemical complexity of marine dissolved organic matter has remained an analytical challenge. The SeaSCAPE campaign, a large-scale mesocosm experiment, provided a unique opportunity to probe the in situ production of m-CDOM across phytoplankton and microbial blooms. Results from mass spectrometry coupled with UV-VIS spectroscopy reveal production of a chemodiverse set of compounds well-correlated with increases in absorbance after a bacterial bloom, indicative of autochthonous m-CDOM production. Notably, many of the absorbing compounds were found to be enriched in nitrogen, which may be essential to chromophore function. From these results, quinoids, porphyrins, flavones, and amide-like compounds were identified via structural analysis and may serve as important photosensitizers in the marine boundary layer. Overall, this study demonstrates a step forward in identifying and characterizing m-CDOM using temporal mesocosm data and integrated UV-VIS spectroscopy and mass spectrometry analyses.

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 TiO 2 , 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 TiO 2 surface and that carvone adsorbs on the TiO 2 surface through a variety of molecular interactions including through carbonyl oxygen atoms with Ti 4+ 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 TiO 2 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 TiO 2 and the impact of relative humidity on these interactions.

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 NO 2 , in the presence and absence of light, and nitrate (NO 3 - ) 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 NO 2 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.

Organonitrates (ON) are important components of secondary organic aerosols (SOAs). α-Pinene (C 10 H 16 ), 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 (NO 2 , NO 3 ) 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-Fe 2 O 3 ) and kaolinite (SiO 2 Al 2 O 3 (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.

Chemical contaminants are becoming an increasingly greater concern for water quality and it is well known that interactions with geochemical interfaces impact the fate and transport of these contaminants in the environment. In this study, we investigated the interactions of one such chemical contaminant, monoethanolamine (MEA), with oxide surfaces, particularly titanium dioxide (TiO 2 ) and iron oxide (α-Fe 2 O 3 ). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to probe the adsorption behavior of MEA on titanium dioxide (TiO 2 ) and iron oxide (α-Fe 2 O 3 ) nanoparticles as a function of pH and other environmental conditions including concentration and ionic strength. Both the extent and initial rates of adsorption of MEA on these oxide surfaces increases with increasing pH. Adsorption on these oxide surfaces increases with solution concentration until saturation occurs and MEA adsorbs more readily at higher pH. Furthermore, adsorption decreases with increasing ionic strength, demonstrating the importance of electrostatic interactions to this process. Based on these results, a mechanistic picture emerges for the interaction of MEA with titanium dioxide and iron oxide across a range of pH values. Overall, this study provides important insights into the surface chemistry and interactions between an alkanolamine and geochemical oxide interfaces., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Plasmonic gold nanorods (AuNRs) are often employed as photoacoustic (PA) contrast agents due to their ease of synthesis, functionalization, and biocompatibility. These materials can produce activatable signals in response to a change in optical absorbance intensity or absorbance wavelength. Here, we report a surprising finding: Ag 2 S/Se-coated AuNRs have a ~40-fold PA enhancement upon addition of an oxidant but with no change in absorption spectra. We then study the mechanism underlying this enhancement. Electron micrographs and absorption spectra show good colloidal stability and retention of the core-shell structure after potassium hexacyanoferrate(III) (HCF) addition, ruling out aggregation and morphology-induced PA enhancement. X-ray diffraction data showed no changes, ruling out crystallographic phase changes upon HCF addition, thus leading to induced PA enhancement. Attenuated total reflectance-Fourier transform infrared spectroscopy and zeta potential analysis suggest that PA enhancement is driven by the irreversible displacement of hexadecyltrimethylammonium bromide with HCF. This is further confirmed using elemental mapping with energy-dispersive X-ray analysis. PA characterization after HCF addition showed a four-fold increase in the Grüneisen parameter (Γ), thus resulting in PA enhancement. The PA enhancement is not seen in uncoated AuNRs or spherical particles. Two possible mechanisms for PA enhancement are proposed: first, the photo-induced redox heating at the Ag 2 S/Se shell-HCF interface, resulting in an increase in temperature-dependent Γ, and second, an enhanced electrostriction response due to HCF adsorption on a layered plasmonic nanoparticle surface, resulting in a high thermal expansion coefficient ( β ) that is directly proportional to Γ., Competing Interests: The authors declare no competing financial interest.

Amino acids (AAs), the building blocks of proteins, are enriched by several orders of magnitude in sea spray aerosols compared to ocean waters. This suggests that AAs may reside at the air-water interface and be highly surface active. Using surface tension measurements, infrared reflection-absorption spectroscopy, and molecular dynamics simulations, we show that AAs are surface active and that salts and low-pH environments are drivers of surface activity. At typical sea spray salt concentrations and pH values, we determine that the surface coverage of hydrophobic AAs increases by approximately 1 order of magnitude. Additionally, divalent cations such as Ca 2+ and Mg 2+ can further increase AA surface propensity, particularly at neutral pH. Overall, these results indicate that AAs are likely to be found at increased concentrations at the surface of sea spray aerosols, where they can impact the cloud activation properties of the aerosol and enhance peptide formation under certain conditions.

Marine aerosols strongly influence climate through their interactions with solar radiation and clouds. However, significant questions remain regarding the influences of biological activity and seawater chemistry on the flux, chemical composition, and climate-relevant properties of marine aerosols and gases. Wave channels, a traditional tool of physical oceanography, have been adapted for large-scale ocean-atmosphere mesocosm experiments in the laboratory. These experiments enable the study of aerosols under controlled conditions which isolate the marine system from atmospheric anthropogenic and terrestrial influences. Here, we present an overview of the 2019 Sea Spray Chemistry and Particle Evolution (SeaSCAPE) study, which was conducted in an 11 800 L wave channel which was modified to facilitate atmospheric measurements. The SeaSCAPE campaign sought to determine the influence of biological activity in seawater on the production of primary sea spray aerosols, volatile organic compounds (VOCs), and secondary marine aerosols. Notably, the SeaSCAPE experiment also focused on understanding how photooxidative aging processes transform the composition of marine aerosols. In addition to a broad range of aerosol, gas, and seawater measurements, we present key results which highlight the experimental capabilities during the campaign, including the phytoplankton bloom dynamics, VOC production, and the effects of photochemical aging on aerosol production, morphology, and chemical composition. Additionally, we discuss the modifications made to the wave channel to improve aerosol production and reduce background contamination, as well as subsequent characterization experiments. The SeaSCAPE experiment provides unique insight into the connections between marine biology, atmospheric chemistry, and climate-relevant aerosol properties, and demonstrates how an ocean-atmosphere-interaction facility can be used to isolate and study reactions in the marine atmosphere in the laboratory under more controlled conditions.

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.

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.

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.

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 SO 2 , making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

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.

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 (SO 3 2- /HSO 3 - ), 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 SO 2 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.

Surface chemistry affects the physiochemical properties of nanoparticles in a variety of ways. Therefore, there is great interest in understanding how nanoparticle surfaces evolve under different environmental conditions of pH and temperature. Here, we discuss the use of vibrational spectroscopy as a tool that allows for in situ observations of oxide nanoparticle surfaces and their evolution due to different surface processes. We highlight oxide nanoparticle surface chemistry, either engineered anthropogenic or naturally occurring geochemical nanoparticles, in complex media, with a focus on the impact of ( a ) pH on adsorption, intermolecular interactions, and conformational changes; ( b ) surface coatings and coadsorbates on protein adsorption kinetics and protein conformation; ( c ) surface adsorption on the temperature dependence of protein structure phase changes; and ( d ) the use of two-dimensional correlation spectroscopy to analyze spectroscopic results for complex systems. An outlook of the field and remaining challenges is also presented.

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 NO 2 and gaseous HNO 3 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. NO 2 and HNO 3 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 NO 2 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 NO 2 is predicted to be the dominant HONO generation channel, where NO 2 is produced through the photolysis of surface-adsorbed nitrates. This hydrolysis reaction predominantly occurs in the first layer of surface-adsorbed water.

Lipopolysaccharides (LPS) in sea spray aerosol (SSA) particles have recently been shown to undergo heterogeneous reactions with HNO 3 in the atmosphere. Here, we integrate theory and experiment to further investigate how the most abundant sea salt cations, Na + , Mg 2+ , and Ca 2+ , impact HNO 3 reactions with LPS-containing SSA particles. Aerosol reaction flow tube studies show that heterogeneous reactions of SSA particles with divalent cation (Mg 2+ and Ca 2+ ) and LPS signatures were less reactive with HNO 3 than those dominated by monovalent cations (Na + ). All-atom molecular dynamics simulations of model LPS aggregates suggest that divalent cations cross-link the oligosaccharide chains to increase molecular aggregation and rigidity, which changes the particle phase and morphology, decreases water diffusion, and consequently decreases the reactive uptake of HNO 3 . This study provides new insight into how complex chemical interactions between ocean-derived salts and biogenic organic species can impact the heterogeneous reactivity of SSA particles.

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 SiO 2 ) by combining vibrational spectroscopy with ab initio molecular dynamics simulations. The adsorption of these compounds on the SiO 2 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.

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.

Organic films on indoor surfaces serve as a medium for reactions and for partitioning of semi-volatile organic compounds and thus play an important role in indoor chemistry. However, the chemical and physical properties of these films are poorly characterized. Here, we investigate the chemical composition of an organic film collected during the HOMEChem campaign, over three cumulative weeks in the kitchen, using both Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) and offline Aerosol Mass Spectrometry (AMS). We also characterize the viscosity of this film using a model based on molecular formulas as well as poke-flow measurements. We find that the film contains organic material similar to cooking organic aerosol (COA) measured during the campaign using on-line AMS. However, the average molecular formula observed using FT-ICR MS is ∼C50H90O11, which is larger and more oxidized than fresh COA. Solvent extracted film material is a low viscous semisolid, with a measured viscosity <104 Pa s. This is much lower than the viscosity model predicts, which is parametrized with atmospherically relevant organic molecules, but sensitivity tests demonstrate that including unsaturation can explain the differences. The presence of unsaturation is supported by reactions of film material with ozone. In contrast to the solvent extract, manually removed material appears to be highly viscous, highlighting the need for continued work understanding both viscosity measurements as well as parameterizations for modeled viscosity of indoor organic films.