Ligand bound structure of a 6-hydroxynicotinic acid 3-monooxygenase provides mechanistic insights.

6-Hydroxynicotinic acid 3-monooxygenase (NicC) is a bacterial enzyme involved in the degradation of nicotinic acid. This enzyme is a Class A flavin-dependent monooxygenase that catalyzes a unique decarboxylative hydroxylation. The unliganded structure of this enzyme has previously been reported and studied using steady- and transient-state kinetics to support a comprehensive kinetic mechanism. Here we report the crystal structure of the H47Q NicC variant in both a ligand-bound (solved to 2.17 Å resolution) and unliganded (1.51 Å resolution) form. Interestingly, in the liganded form, H47Q NicC is bound to 2-mercaptopyridine (2-MP), a contaminant present in the commercial stock of 6-mercaptopyridine-3-carboxylic acid(6-MNA), a substrate analogue. 2-MP binds weakly to H47Q NicC and is not a substrate for the enzyme. Based on kinetic and thermodynamic characterization, we have fortuitously captured a catalytically inactive H47Q NicC•2-MP complex in our crystal structure. This complex reveals interesting mechanistic details about the reaction catalyzed by 6-hydroxynicotinic acid 3-monooxygenase.

PFAS on atmospheric aerosol particles: a review.

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants of concern to human health. These synthetic chemicals are in widespread use for consumer products, firefighting foams, and industrial applications. They have been detected all over the globe, including at remote locations distant from any possible point sources. One mechanism for long-range transport of PFAS is through sorption to aerosol particles in the atmosphere. PFAS can be transferred from the sea surface to sea spray aerosol particles through wave breaking and bubble bursting, and PFAS emitted to the atmosphere in the gas phase can sorb to particulate matter through gas-particle partitioning. Here we present a comprehensive review of global measurements of PFAS on ambient particulate matter dating back to the first reports from the early 2000s. We summarize findings for the historically important C8 species, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), including detection of isomers and size-segregated measurements, as well as studies of newer and emerging PFAS. We conclude that long-term monitoring of PFAS on particulate matter should be expanded to include more measurement sites in under-sampled regions of the world and that further non-targeted work to identify novel PFAS structures is needed as PFAS manufacturing and regulations continue to evolve.

Non-targeted identification and semi-quantitation of emerging per- and polyfluoroalkyl substances (PFAS) in US rainwater.

High-resolution mass spectrometry was used to screen for emerging per- and polyfluorinated alkyl substances (PFAS) in precipitation samples collected in summer 2019 at seven sites in the United States. We previously quantified the concentration of ten PFAS in the rainwater samples using the method of isotopic dilution (Pike et al., 2021). Nine of these targeted analytes belonged to the U.S. Environmental Protection Agency Regional Screening Level list, herein referred to as EPA-monitored analytes. In this new work, we identify emerging PFAS compounds by liquid chromatography quadrupole time-of-flight mass spectrometry. Several emerging PFAS were detected across all samples, with the most prevalent compounds being C3-C8 hydrogen-substituted perfluorocarboxylic acids (H-PFCAs) and fluorotelomer carboxylic acids (FTCAs). Concentrations of emerging PFAS were in the 10-1000 ng L-1 range (approximately 1-2 orders of magnitude greater than EPA-monitored PFAS) at all sites except Wooster, OH, where concentrations were even higher, with a maximum estimated ΣPFAS of 16 400 ng L-1. The elevated levels of emerging PFAS in the Wooster samples were predominantly even and odd chain-length H-PFCAs and FTCAs comprised of complex mixtures of branched isomers. This unique composition did not match any known manufactured PFAS formulation reported to date, but it could represent thermally transformed by-products emitted by a local point source. Overall, the results indicate that PFAS outside of the standard analyte lists make up a significant and previously unappreciated fraction of contaminants in rainwater collected within the central U.S.-and potentially world-wide-especially in proximity to localized point sources.

Correlation Analysis of Perfluoroalkyl Substances in Regional U.S. Precipitation Events.

Per- and polyfluoroalkyl substances (PFAS) are transported in the atmosphere, leading to both wet and dry deposition to the surface. The concentrations of 15 PFAS were measured at six locations in the Ohio-Indiana region of the U.S. during the summer of 2019 and compared to samples collected at a distant site in NW Wyoming. ΣPFAS concentrations ranged from 50-850 ng L-1, with trifluoroacetic acid (TFA) being the dominant compound (~90%). Concentrations of perfluorooctanoic acid (PFOA) and perfluorosulfonic acid (PFOS) were similar to amounts observed over the past 20 years, indicating persistence in the atmosphere despite regulatory action, and the newer species HFPO-DA (GenX) was also widely detected in rainwater. ANOVA modeling and correlation matrices were used to determine association of PFAS concentrations, location, and functional group and chain length. Statistically significant differences (p < 0.05) in PFAS profiles across sites separated by 10-100 km indicate that local point sources strongly contribute to wet deposition. This work introduces correlation plots for PFAS that allow rapid visual comparison of multi-analyte and multi-site data sets.

Organic Surfactants Protect Dissolved Aerosol Components against Heterogeneous Oxidation.

Oxidative aging alters the composition of organic aerosols over time, in turn affecting the ability of aerosols to seed cloud formation and scatter solar radiation. Here we explore the heterogeneous photooxidation of model organic particles with and without a soluble surfactant coating. Tricarballylic acid (TCA), a proxy for α-pinene oxidation products, serves as a representative small organic solute. Sodium dodecyl sulfate (SDS) was selected as the representative soluble surfactant because its surface properties have been extensively characterized. A flow reactor and aerosol mass spectrometer were used to determine the second-order reaction rate constant ( k = (1.9 ± 0.1) × 10-11 cm3 molecule-1 s-1) and reactive uptake coefficient (γ = 3.0) for the heterogeneous photooxidation of uncoated TCA particles by gas-phase OH radicals; such a high uptake coefficient implicates radical chain reactions in the oxidation mechanism. SDS dramatically slows the disappearance of TCA: when the SDS concentration approaches monolayer coverage, the rate of reaction of TCA with OH decreases by ∼60% relative to the rate in the absence of SDS. These results indicate that small concentrations of surface-active molecules on atmospheric particles can protect organic solutes in the bulk from oxidative aging. This effect extends the environmental lifetime of dissolved pollutants.

Role of Aerosol Liquid Water in Secondary Organic Aerosol Formation from Volatile Organic Compounds.

A key mechanism for atmospheric secondary organic aerosol (SOA) formation occurs when oxidation products of volatile organic compounds condense onto pre-existing particles. Here, we examine effects of aerosol liquid water (ALW) on relative SOA yield and composition from α-pinene ozonolysis and the photooxidation of toluene and acetylene by OH. Reactions were conducted in a room-temperature flow tube under low-NOx conditions in the presence of equivalent loadings of deliquesced (∼20 µg m-3 ALW) or effloresced (∼0.2 µg m-3 ALW) ammonium sulfate seeds at exactly the same relative humidity (RH = 70%) and state of wall conditioning. We found 13% and 19% enhancements in relative SOA yield for the α-pinene and toluene systems, respectively, when seeds were deliquesced rather than effloresced. The relative yield doubled in the acetylene system, and this enhancement was partially reversible upon drying the prepared SOA, which reduced the yield by 40% within a time scale of seconds. We attribute the high relative yield of acetylene SOA on deliquesced seeds to aqueous partitioning and particle-phase reactions of the photooxidation product glyoxal. The observed range of relative yields for α-pinene, toluene, and acetylene SOA on deliquesced and effloresced seeds suggests that ALW plays a complicated, system-dependent role in SOA formation.

Microjets and coated wheels: versatile tools for exploring collisions and reactions at gas-liquid interfaces.

This tutorial review describes experimental aspects of two techniques for investigating collisions and reactions at the surfaces of liquids in vacuum. These gas-liquid scattering experiments provide insights into the dynamics of interfacial processes while minimizing interference from vapor-phase collisions. We begin with a historical survey and then compare attributes of the microjet and coated-wheel techniques, developed by Manfred Faubel and John Fenn, respectively, for studies of high- and low-vapor pressure liquids in vacuum. Our objective is to highlight the strengths and shortcomings of each technique and summarize lessons we have learned in using them for scattering and evaporation experiments. We conclude by describing recent microjet studies of energy transfer between O2 and liquid hydrocarbons, HCl dissociation in salty water, and super-Maxwellian helium evaporation.

Gas-Microjet Reactive Scattering: Collisions of HCl and DCl with Cool Salty Water.

Liquid microjets provide a powerful means to investigate reactions of gases with salty water in vacuum while minimizing gas-vapor collisions. We use this technique to explore the fate of gaseous HCl and DCl molecules impinging on 8 molal LiCl and LiBr solutions at 238 K. The experiments reveal that HCl or DCl evaporate infrequently if they become thermally accommodated at the surface of either solution. In particular, we observe minimal thermal desorption of HCl following HCl collisions and no distinct evidence for rapid, interfacial DCl→HCl exchange following DCl collisions. These results imply that surface thermal motions are not generally strong enough to propel momentarily trapped HCl or DCl back into the gas phase before they ionize and disappear into solution. Instead, only HCl and DCl molecules that scatter directly from the surface escape entry. These recoiling molecules transfer less energy upon collision to LiBr/H2O than to LiCl/H2O, reflecting the heavier mass of Br(-) than of Cl(-) in the interfacial region.

Super-Maxwellian helium evaporation from pure and salty water.

Helium atoms evaporate from pure water and salty solutions in super-Maxwellian speed distributions, as observed experimentally and modeled theoretically. The experiments are performed by monitoring the velocities of dissolved He atoms that evaporate from microjets of pure water at 252 K and 4-8.5 molal LiCl and LiBr at 232-252 K. The average He atom energies exceed the flux-weighted Maxwell-Boltzmann average of 2RT by 30% for pure water and 70% for 8.5m LiBr. Classical molecular dynamics simulations closely reproduce the observed speed distributions and provide microscopic insight into the forces that eject the He atoms from solution. Comparisons of the density profile and He kinetic energies across the water-vacuum interface indicate that the He atoms are accelerated by He-water collisions within the top 1-2 layers of the liquid. We also find that the average He atom kinetic energy scales with the free energy of solvation of this sparingly soluble gas. This free-energy difference reflects the steeply decreasing potential of mean force on the He atoms in the interfacial region, whose gradient is the repulsive force that tends to expel the atoms. The accompanying sharp decrease in water density suppresses the He-water collisions that would otherwise maintain a Maxwell-Boltzmann distribution, allowing the He atom to escape at high energies. Helium is especially affected by this reduction in collisions because its weak interactions make energy transfer inefficient.

Ballistic Evaporation and Solvation of Helium Atoms at the Surfaces of Protic and Hydrocarbon Liquids.

Atomic and molecular solutes evaporate and dissolve by traversing an atomically thin boundary separating liquid and gas. Most solutes spend only short times in this interfacial region, making them difficult to observe. Experiments that monitor the velocities of evaporating species, however, can capture their final interactions with surface solvent molecules. We find that polarizable gases such as N2 and Ar evaporate from protic and hydrocarbon liquids with Maxwell-Boltzmann speed distributions. Surprisingly, the weakly interacting helium atom emerges from these liquids at high kinetic energies, exceeding the expected energy of evaporation from salty water by 70%. This super-Maxwellian evaporation implies in reverse that He atoms preferentially dissolve when they strike the surface at high energies, as if ballistically penetrating into the solvent. The evaporation energies increase with solvent surface tension, suggesting that He atoms require extra kinetic energy to navigate increasingly tortuous paths between surface molecules.

Surfactant-promoted reactions of Cl2 and Br2 with Br- in glycerol.

Gas-liquid scattering experiments are used to explore reactions of gaseous Cl2 and Br2 with a 0.03 M solution of the surfactant tetrahexylammonium bromide (THABr) dissolved in glycerol. At thermal collision energies, 79 ± 2% of incident Cl2 molecules react with Br(-) to form Cl2Br(-) in the interfacial region. This reaction probability is three times greater than the reactivity of Cl2 with 3 M NaBr-glycerol, even though the interfacial Br(-) concentrations are similar in each solution. We attribute the high 79% uptake to the presence of surface THA(+) ions that stabilize the Cl2Br(-) intermediate as it is formed in the charged, hydrophobic pocket created by the hexyl chains. Cl2Br(-) generates the single exchange product BrCl in a 1% yield close to the surface, while the remaining 99% desorbs as the double exchange product Br2 over >0.1 s after diffusing deeply into the bulk. When NaCl is added to the surfactant solution in a 20:1 Cl(-)/Br(-) ratio, the Cl2 reaction probability drops from 79% to 46 ± 1%, indicating that Cl(-) in the interfacial region only partially blocks reaction with Br(-). In parallel, we observe that gaseous Br2 molecules dissolve in 0.03 M THABr for 10(4) times longer than in 3 M NaBr. We attribute this change to formation of stabilizing interfacial and bulk-phase THA(+)Br3(-) ion pairs, in analogy with the capture of Cl2 and formation of THA(+)Cl2Br(-) pairs. The THA(+) ion appears to be a powerful interfacial catalyst for promoting reaction of Cl2 and Br2 with Br(-) and for ferrying the resultant ions into solution.

Near-interfacial halogen atom exchange in collisions of Cl2 with 2.7 M NaBr-glycerol.

Gas-liquid scattering experiments are used to investigate reactions of Cl(2) with a 2.7 M NaBr-glycerol solution at 291 K. Only the single and double halogen exchange products, BrCl and Br(2), are observed to desorb from solution. When Cl(2) molecules strike the surface at thermal collision energies, 76% desorb as Cl(2) before reacting, 1% react to form BrCl, and 23% react to form Br(2). Residence time measurements, modeled by mass-transfer equations for absorption, diffusion, reaction, and evaporation, were used to determine the time and depth scales for Cl(2) escape and BrCl and Br(2) production. This modeling indicates that Cl(2) molecules desorb from the interfacial region in less than 1 µs or are attacked within this time by Br(-) ions and irreversibly captured as Cl(2)Br(-). The products BrCl and Br(2) are created primarily within the top few monolayers of the solution and then evaporate on average 12 and 28 µs after Cl(2) initially reacts with Br(-). Notably, Br(2) is not generated from BrCl via Cl(2)Br(-) → BrCl + Cl(-) and BrCl + Br(-) → Br(2)Cl(-) but from the parallel reaction Cl(2)Br(-) + Br(-) → Br(2)Cl(-)+ Cl(-) that bypasses the BrCl intermediate. Br(2) is then likely released through two pathways, Br(2)Cl(-) → Br(2) + Cl(-) and Br(2)Cl(-) + Br(-) → Br(3)(-) + Cl(-), followed by Br(3)(-) ↔ Br(2) + Br(-). The experiments demonstrate that single and double halogen exchange reactions can occur rapidly and close to the surface even when the products are created by multiple sequential reactions.