Mechanism of Hydrogen Peroxide Formation on Sprayed Water Microdroplets.

How is H2O2 formed in sprayed water is not well understood. It is believed to involve the association of HO• radicals spontaneously generated from HO- ions by internal electric fields on the surface of neutral microdroplets. Spraying water actually creates charged microdroplets carrying either excess OH- or H+ intrinsic ions that repel each other toward the very surface. The requisite electron transfer (ET) takes place between surface-bound ions: HOS- + HS+ = HOS• + HS•, during encounters between positive and negative microdroplets. The ET endothermicity in bulk water (ΔH = 448 kJ mol-1) is reversed in low-density surface water by the destabilization of the strongly hydrated reactant ions: ΔHhydration(H+ + OH-) = -1670 kJ mol-1, relative to neutral radical products: ΔHhydration(HO• + H•) = -58 kJ mol-1. The formation of H2O2 is driven by the energy supplied for spraying water, and caused by restricted hydration on microdroplet surfaces.

Comment on "Liquid-Gas Interface of Iron Aqueous Solutions and Fenton Reagents".

A recent Letter in this Journal (Gladich et al. J. Phys. Chem. Lett. 13, 2994-3001) reported that photoelectron spectroscopy could not detect any products on the surface of aqueous Fe2+ jets dosed with gaseous hydrogen peroxide. The Letter however concluded that Fe(aq)2+ ions react with H2O2(g) at the water-vapor interface to produce the same Fe3+ + HO• products as their reaction with H2O2(aq) in bulk water. We argue that this conclusion is untenable because nothing can be asserted about undetected species.

Role of Ferryl Ion Intermediates in Fast Fenton Chemistry on Aqueous Microdroplets.

In the aqueous environment, FeII ions enhance the oxidative potential of ozone and hydrogen peroxide by generating the reactive oxoiron species (ferryl ion, FeIVO2+) and hydroxyl radical (·OH) via Fenton chemistry. Herein, we investigate factors that control the pathways of these reactive intermediates in the oxidation of dimethyl sulfoxide (Me2SO) in FeII solutions reacting with O3 in both bulk-phase water and on the surfaces of aqueous microdroplets. Electrospray ionization mass spectrometry is used to quantify the formation of dimethyl sulfone (Me2SO2, from FeIVO2+ + Me2SO) and methanesulfonate (MeSO3-, from ·OH + Me2SO) over a wide range of FeII and O3 concentrations and pH. In addition, the role of environmentally relevant organic ligands on the reaction kinetics was also explored. The experimental results show that Fenton chemistry proceeds at a rate ∼104 times faster on microdroplets than that in bulk-phase water. Since the production of MeSO3- is initiated by ·OH radicals at diffusion-controlled rates, experimental ratios of Me2SO2/MeSO3- > 102 suggest that FeIVO2+ is the dominant intermediate under all conditions. Me2SO2 yields in the presence of ligands, L, vary as volcano-plot functions of E0(LFeIVO2++ O2/LFe2+ + O3) reduction potentials calculated by DFT with a maximum achieved in the case of L≡oxalate. Our findings underscore the key role of ferryl FeIVO2+ intermediates in Fenton chemistry taking place on aqueous microdroplets.

Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases.

The α-hydroxyalkyl-hydroperoxides [R-(H)C(-OH)(-OOH), α-HH] produced in the ozonolysis of unsaturated organic compounds may contribute to secondary organic aerosol (SOA) aging. α-HHs' inherent instability, however, hampers their detection and a positive assessment of their actual role. Here we report, for the first time, the rates and products of the decomposition of the α-HHs generated in the ozonolysis of atmospherically important monoterpenes α-pinene (α-P), d-limonene (d-L), γ-terpinene (γ-Tn), and α-terpineol (α-Tp) in water/acetonitrile (W/AN) mixtures. We detect α-HHs and multifunctional decomposition products as chloride adducts by online electrospray ionization mass spectrometry. Experiments involving D2O and H218O, instead of H216O, and an OH-radical scavenger show that α-HHs decompose into gem-diols + H2O2 rather than free radicals. α-HHs decay mono- or biexponentially depending on molecular structure and solvent composition. e-Fold times, τ1/e, in water-rich solvent mixtures range from τ1/e = 15-45 min for monoterpene-derived α-HHs to τ1/e > 103 min for the α-Tp-derived α-HH. All τ1/e's dramatically increase in <20% (v/v) water. Decay rates of the α-Tp-derived α-HH in pure water increase at lower pH (2.3 ≤ pH ≤ 3.3). The hydroperoxides detected in day-old SOA samples may reflect their increased stability in water-poor media and/or the slow decomposition of α-HHs from functionalized terpenes.

Comment on "The chemical reactions in electrosprays of water do not always correspond to those at the pristine air-water interface" by A. Gallo Jr, A. S. F. Farinha, M. Dinis, A.-H. Emwas, A. Santana, R. J. Nielsen, W. A. Goddard III and H. Mishra, Chem. Sci., 2019, 10, 2566.

Recently, Gallo et al. (Chem. Sci., 2019, 10, 2566) investigated whether the previously reported oligomerization of isoprene vapor on the surface of pH < 4 water in an electrospray ionization (ESI) mass spectrometer (J. Phys. Chem. A, 2012, 116, 6027 and Phys. Chem. Chem. Phys., 2018, 20, 15400) would also proceed in liquid isoprene-acidic water emulsions. Gallo et al. hypothesized that emulsified liquid isoprene would oligomerize on the surface of acidic water because, after all, isoprene, liquid or vapor, is always a hydrophobe. In their emulsion experiments, isoprene oligomers were to be detected by ex situ proton magnetic resonance (1H-NMR) spectrometry.

Vacuum-assisted headspace single-drop microextraction: Eliminating interfacial gas-phase limitations.

Gas-phase limitations have been neglected in headspace single-drop microextraction (HS-SDME) and rate control has been assumed to primarily reside in the liquid water and/or organic phases, but not in the headspace. Herein we demonstrate the presence of interfacial gas constraints and propose using reduced headspace pressures to remove them. To describe the pressure dependence of HS-SDME, the system was decoupled into two interfacial steps: (i) the evaporation step (water-headspace interface) formulated using the two-film theory and (ii) the analyte uptake by the microdrop (headspace-microdrop interface) formulated using the resistance model. Naphthalene, acenaphthene, and pyrene were chosen as model analytes for their large Henry's law solubility constants in n-octanol (HOA > 103 M atm-1), and their low to moderate Henry's law volatility constants in water as a solvent (KH). We have found that extraction times were significantly shortened for all analytes by sampling at pressures well below the 1 atm used in the standard HS-SDME procedure. The acceleration of naphthalene extraction, whose facile evaporation into the headspace had been assumed to be practically pressure independent, highlighted the role of mass transfer through the interfacial gas layer on the organic solvent drop. The larger accelerations observed for acenaphthene and (especially) pyrene upon reducing the sampling pressure, suggested that gas-sided constraints were important during both the evaporation and uptake steps. Model calculations incorporating mass transfers at the headspace-microdrop interface confirmed that gas-phase resistance is largely eliminated (>96%) when reducing the sampling pressure from 1 to 0.04 atm, an effect that is nearly independent of analyte molecular mass. The relative importance of the two interfacial steps and their gas- and liquid-phase limitations are discussed, next to the use of KH and HOA to predict the positive effect of vacuum on HS-SDME.

Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles.

α-Hydroxyalkyl-hydroperoxides (α-HHs), from the addition of water to Criegee intermediates in the ozonolysis of olefins, are reactive components of organic aerosols. Assessing the fate of α-HHs in such media requires information on the rates and products of their reactions in aqueous organic matrixes. This information, however, is unavailable due to the lack of analytical techniques for the detection and identification of labile α-HHs. Here, we report the mass spectrometric detection (as Cl- adducts) of the α-HH produced in the ozonolysis of a C15 diolefin in water (W):acetonitrile (AN) mixtures of variable composition containing inert NaCl. α-HH decays into a gem-diol + H2O2 within τ1/e ≈ 52 min in 50% (v:v) water, but persists longer than a day in ≤10% water mixtures. The strong nonlinear dependence of τ1/e on solvent composition reveals that water content is a major factor controlling the fate of α-HHs in atmospheric particles. It also suggests that α-HH decomposes while embedded in WnANm clusters rather than randomly dissolved in molecularly homogeneous W:AN mixtures.

Iodide Accelerates the Processing of Biogenic Monoterpene Emissions on Marine Aerosols.

Marine photosynthetic organisms emit organic gases, including the polyolefins isoprene (C5H8) and monoterpenes (MTPs, C10H16), into the boundary layer. Their atmospheric processing produces particles that influence cloud formation and growth and, as a result, the Earth's radiation balance. Here, we report that the heterogeneous ozonolysis of dissolved α-pinene by O3(g) on aqueous surfaces is dramatically accelerated by I-, an anion enriched in the ocean upper microlayer and sea spray aerosols (SSAs). In our experiments, liquid microjets of α-pinene solutions, with and without added I-, are dosed with O3(g) for τ < 10 µs and analyzed online by pneumatic ionization mass spectrometry. In the absence of I-, α-pinene does not detectably react with O3(g) under present conditions. In the presence of ≥ 0.01 mM I-, in contrast, new signals appear at m/z = 169 (C9H13O3 -), m/z = 183 (C10H15O3 -), m/z = 199 (C10H15O4 -), m/z = 311 (C10H16IO3 -), and m/z = 461 (C20H30IO4 -), plus m/z = 175 (IO3 -), and m/z = 381 (I3 -). Collisional fragmentation splits CO2 from C9H13O3 -, C10H15O3 - and C10H15O4 -, and I- plus IO- from C10H16IO3 - as expected from a trioxide IOOO•C10H16 - structure. We infer that the oxidative processing of α-pinene on aqueous surfaces is significantly accelerated by I- via the formation of IOOO- intermediates that are more reactive than O3. A mechanism in which IOOO- reacts with α-pinene (and likely with other unsaturated species) in competition with its isomerization to IO3 - accounts for present results and the fact that soluble iodine in SSA is mostly present as iodine-containing organic species rather than the thermodynamically more stable iodate. By this process, a significant fraction of biogenic MTPs and other unsaturated gases may be converted to water-soluble species rather than emitted to the atmosphere.

Chemical signatures of surface microheterogeneity on liquid mixtures.

Many chemical reactions in Nature, the laboratory, and chemical industry occur in solvent mixtures that bring together species of dissimilar solubilities. Solvent mixtures are visually homogeneous, but are not randomly mixed at the molecular scale. In the all-important binary water-hydrotrope mixtures, small-angle neutron and dynamic light scattering experiments reveal the existence of short-lived (<50 ps), short-ranged (∼1 nm) concentration fluctuations. The presence of hydrophobic solutes stabilizes and extends such fluctuations into persistent, mesoscopic (10-100 nm) inhomogeneities. While the existence of inhomogeneities is well established, their impacts on reactivity are not fully understood. Here, we search for chemical signatures of inhomogeneities on the surfaces of W:X mixtures (W = water; X = acetonitrile, tetrahydrofuran, or 1,4-dioxane) by studying the reactions of Criegee intermediates (CIs) generated in situ from O3(g) addition to a hydrophobic olefin (OL) solute. Once formed, CIs isomerize to functionalized carboxylic acids (FC) or add water to produce α-hydroxy-hydroperoxides (HH), as detected by surface-specific, online pneumatic ionization mass spectrometry. Since only the formation of HH requires the presence of water, the dependence of the R = HH/FC ratio on water molar fraction x w expresses the accessibility of water to CIs on the surfaces of mixtures. The finding that R increases quasi-exponentially with x w in all solvent mixtures is consistent with CIs being preferentially produced (from their OL hydrophobic precursor) in X-rich, long-lived OL:X m W n interfacial clusters, rather than randomly dispersed on W:X surfaces. R vs x w dependences therefore reflect the average ⟨m, n⟩ composition of OL:X m W n interfacial clusters, as weighted by cluster reorganization dynamics. Water in large, rigid clusters could be less accessible to CIs than in smaller but more flexible clusters of lower water content. Since mesoscale inhomogeneities are intrinsic to most solvent mixtures, these phenomena should be quite general.

OH-Radical Oxidation of Lung Surfactant Protein B on Aqueous Surfaces.

Air pollutants generate reactive oxygen species on lung surfaces. Here we report how hydroxyl radicals (·OH) injected on the surface of water react with SP-B1-25, a 25-residue polypeptide surrogate of human lung surfactant protein B. Our experiments consist of intersecting microjets of aqueous SP-B1-25 solutions with O3/O2/H2O/N2(g) gas streams that are photolyzed into ·OH(g) in situ by 266 nm laser nanosecond pulses. Surface-sensitive mass spectrometry enables us to monitor the prompt (<10 µs) and simultaneous formation of primary O n -containing products/intermediates (n≤5) triggered by the reaction of ·OH with interfacial SP-B1-25. We found that O-atoms from both O3 and ·OH are incorporated into the reactive cysteine Cys8 and Cys11 and tryptophan Trp9 components of the hydrophobic N-terminus of SP-B1-25 that lies at the topmost layers of the air-liquid interface. Remarkably, these processes are initiated by ·OH additions rather than by H-atom abstractions from S-H, C-H, or N-H groups. By increasing the hydrophilicity of the N-terminus region of SP-B1-25, these transformations will impair its role as a surfactant.

Reactivity of Monoterpene Criegee Intermediates at Gas-Liquid Interfaces.

Biogenic monoterpenes are major sources of Criegee intermediates (CIs) in the troposphere. Recent studies underscored the importance of their heterogeneous chemistry. The study of monoterpene CI reactions on liquid surfaces, however, is challenging due to the lack of suitable probes. Here, we report the first mass spectrometric detection of the intermediates and products, which include labile hydroperoxides, from reactions of CIs of representative monoterpenes (α-terpinene, γ-terpinene, terpinolene, d-limonene, α-pinene) with water, cis-pinonic acid (CPA) and octanoic acid (OA) on the surface of liquid microjets. Significantly, the relative yields of α-hydroxy-hydroperoxides production from CIs hydration at the gas-liquid interface-α-terpinene (1.00) ≫ d-limonene (0.18) > γ-terpinene (0.11) ∼ terpinolene (0.10) ≫ α-pinene (0.01)-do not track the rate constants of their gas-phase ozonolyses. Notably, in contrast with the inertness of the other CIs, the CIs derived from α-terpinene ozonolysis readily react with CPA and OA to produce C20 and C18 ester hydroperoxides, respectively. Present results reveal hitherto unknown structural effects on the reactivities of CIs at aqueous interfaces.

Enhanced Acidity of Acetic and Pyruvic Acids on the Surface of Water.

Understanding the acid-base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants p Ka = 4.6 and 2.4 in bulk water. These findings provide key insights into the relative Bronsted acidities of common carboxylic acids versus interfacial water. In addition, the work estimates the reactive uptake coefficient of gaseous pyruvic acid by water to be γPA = 0.06. This work is useful to interpret the interfacial behavior of pyruvic acid under low water activity conditions, typically found in haze aerosols, clouds, and fog waters.

Role of Nitrogen Dioxide in the Production of Sulfate during Chinese Haze-Aerosol Episodes.

Haze events in China megacities involve the rapid oxidation of SO2 to sulfate aerosol. Given the weak photochemistry that takes place in these optically thick hazes, it has been hypothesized that SO2 is mostly oxidized by NO2 emissions in the bulk of pH > 5.5 aerosols. Because NO2(g) dissolution in water is very slow and aerosols are more acidic, we decided to test such a hypothesis. Herein, we report that > 95% of NO2(g) disproportionates [2NO2(g) + H2O(l) = H+ + NO3-(aq) + HONO (R1)] upon hitting the surface of NaHSO3 aqueous microjets for < 50 µs, thereby giving rise to strong NO3- ( m/ z 62) signals detected by online electrospray mass spectrometry, rather than oxidizing HSO3- ( m/ z 81) to HSO4- ( m/ z 97) in the relevant pH 3-6 range. Because NO2(g) will be consumed via R1 on the surface of typical aerosols, the oxidation of S(IV) may in fact be driven by the HONO/NO2- generated therein. S(IV) heterogeneous oxidation rates are expected to primarily depend on the surface density and liquid water content of the aerosol, which are enhanced by fine aerosol and high humidity. Whether aerosol acidity affects the oxidation of S(IV) by HONO/NO2- remains to be elucidated.

Extensive H-atom abstraction from benzoate by OH-radicals at the air-water interface.

Much is known about OH-radical chemistry in the gas-phase and bulk water. Important atmospheric and biological processes, however, involve little investigated OH-radical reactions at aqueous interfaces with hydrophobic media. Here, we report the online mass-specific identification of the products and intermediates generated on the surface of aqueous (H2O, D2O) benzoate-h5 and -d5 microjets by ∼8 ns ˙OH(g) pulses in air at 1 atm. Isotopic labeling lets us unambiguously identify the phenylperoxyl radicals that ensue H-abstraction from the aromatic ring and establish a lower bound (>26%) to this process as it takes place in the interfacial water nanolayers probed by our experiments. The significant extent of H-abstraction vs. its negligible contribution both in the gas-phase and bulk water underscores the unique properties of the air-water interface as a reaction medium. The enhancement of H-atom abstraction in interfacial water is ascribed, in part, to the relative destabilization of a more polar transition state for OH-radical addition vs. H-abstraction due to incomplete hydration at the low water densities prevalent therein.

Lithium batteries: Improving solid-electrolyte interphases via underpotential solvent electropolymerization.

Understanding the mechanism of formation of solid-electrolyte interphases (SEI) is key to the prospects of lithium metal batteries (LMB). Here, we investigate via cyclic voltammetry, impedance spectroscopy and chronoamperometry the role of kinetics in controlling the properties of the SEI generated from the reduction of propylene carbonate (PC, a typical solvent in LMB). Our observations are consistent with the operation of a radical chain PC electropolymerization into polymer units whose complexity increases at lower initiation rates. As proof-of-concept, we show that slow initiation rates via one-electron PC reduction at underpotentials consistently yields compact, electronically insulating, Li+-conducting, PC-impermeable SEI films.

"Sizing" Heterogeneous Chemistry in the Conversion of Gaseous Dimethyl Sulfide to Atmospheric Particles.

The oxidation of biogenic dimethyl sulfide (DMS) emissions is a global source of cloud condensation nuclei. The amounts of the nucleating H2SO4(g) species produced in such process, however, remain uncertain. Hydrophobic DMS is mostly oxidized in the gas phase into H2SO4(g) + DMSO(g) (dimethyl sulfoxide), whereas water-soluble DMSO is oxidized into H2SO4(g) in the gas phase and into SO4(2-) + MeSO3(-) (methanesulfonate) on water surfaces. R = MeSO3(-)/(non-sea-salt SO4(2-)) ratios would therefore gauge both the strength of DMS sources and the extent of DMSO heterogeneous oxidation if Rhet = MeSO3(-)/SO4(2-) for DMSO(aq) + ·OH(g) were known. Here, we report that Rhet = 2.7, a value obtained from online electrospray mass spectra of DMSO(aq) + ·OH(g) reaction products that quantifies the MeSO3(-) produced in DMSO heterogeneous oxidation on aqueous aerosols for the first time. On this basis, the inverse R dependence on particle radius in size-segregated aerosol collected over Syowa station and Southern oceans is shown to be consistent with the competition between DMSO gas-phase oxidation and its mass accommodation followed by oxidation on aqueous droplets. Geographical R variations are thus associated with variable contributions of the heterogeneous pathway to DMSO atmospheric oxidation, which increase with the specific surface area of local aerosols.

Annealing kinetics of electrodeposited lithium dendrites.

The densifying kinetics of lithium dendrites is characterized with effective activation energy of Ea ≈ 6 - 7 kcal mol(-1) in our experiments and molecular dynamics computations. We show that heating lithium dendrites for 55 °C reduces the representative dendrites length λ¯(T,t) up to 36%. NVT reactive force field simulations on three-dimensional glass phase dendrites produced by our coarse grained Monte Carlo method reveal that for any given initial dendrite morphology, there is a unique stable atomic arrangement for a certain range of temperature, combined with rapid morphological transition (∼10 ps) within quasi-stable states involving concurrent bulk and surface diffusions. Our results are useful for predicting the inherent structural characteristics of lithium dendrites such as dominant coordination number.

Stepwise Oxidation of Aqueous Dicarboxylic Acids by Gas-Phase OH Radicals.

A leading source of uncertainty in predicting the climate and health effects of secondary organic aerosol (SOA) is how its composition changes over their atmospheric lifetimes. Because dicarboxylic acid (DCA) homologues are widespread in SOA, their distribution provides an ideal probe of both aerosol age and the oxidative power of the atmosphere along its trajectory. Here we report, for the first time, on the oxidation of DCA(aq) by ·OH(g) at the air-water interface. We found that exposure of aqueous HOOC-Rn-COOH (Rn = C2H4, C3H6, C4H8, C5H10, and C6H12) microjets to ∼10 ns ·OH(g) pulses from the 266 nm laser photolysis of O3(g)/O2(g)/H2O(g) mixtures yields the corresponding (n-1) species O═C(H)-Rn-1-COO(-)/HOOC-Rn-1-COO(-), in addition to an array of closed-shell HOOC-Rn(-H)(OOH)-COO(-), HOOC-Rn(-2H)(═O)-COO(-), HOOC-Rn(-H)(OH)-COO(-), and radical HOOC-Rn(-H)(OO·)-COO(-) species. Oxalic and malonic acids, which are shown to be significantly less hydrophobic and reactive than their higher homologues, will predictably accumulate in SOA, in accordance with field observations.

Thermal relaxation of lithium dendrites.

The average lengths λ̅ of lithium dendrites produced by charging symmetric Li(0) batteries at various temperatures are matched by Monte Carlo computations dealing both with Li(+) transport in the electrolyte and thermal relaxation of Li(0) electrodeposits. We found that experimental λ̅(T) variations cannot be solely accounted by the temperature dependence of Li(+) mobility in the solvent but require the involvement of competitive Li-atom transport from metastable dendrite tips to smoother domains over ΔE(++)(R) ∼ 20 kJ mol(-1) barriers. A transition state theory analysis of Li-atom diffusion in solids yields a negative entropy of activation for the relaxation process: ΔS(++)(R) ≈ -46 J mol(-1) K(-1) that is consistent with the transformation of amorphous into crystalline Li(0) electrodeposits. Significantly, our ΔE(++)(R) ∼ 20 kJ mol(-1) value compares favorably with the activation barriers recently derived from DFT calculations for self-diffusion on Li(0)(001) and (111) crystal surfaces. Our findings suggest a key role for the mobility of interfacial Li-atoms in determining the morphology of dendrites at temperatures above the onset of surface reconstruction: TSR ≈ 0.65 TMB (TMB = 453 K: the melting point of bulk Li(0)).