Avoiding Regrettable Replacements: Can the Introduction of Novel Functional Groups Move PFAS from Recalcitrant to Reactive?

Per- and polyfluoroalkyl substances (PFASs) are present in a range of commercial and consumer products. These chemicals are often high-performance surfactants or nonstick/water-repellant coatings due to their chemical stability; however, this stability leads to select PFAS being environmentally persistent. To facilitate degradation, new fluorosurfactant building blocks (F7C3-O-CHF-CF2-S-CH2-CH2-OH (FESOH), F3C-O-CHF-CF2-S-CH2-CH2-OH (MeFESOH), F7C3-O-CHF-CF2-O-CH2-CH2-OH (ProFdiEOH), F7C3-O-CHF-CF2-CH2-OH (ProFEOH), and F3C-O-CHF-CF2-O-CH2-CH2-OH (MeFdiEOH)) have been systematically developed with heteroatom linkages such as ethers, thioethers, and polyfluorinated carbons. The room temperature, gas-phase OH oxidation rate constants, and products of these chemicals were monitored in an atmospheric chamber to investigate their fate in the atmosphere. Analysis was performed using online high-resolution chemical ionization mass spectrometry (CIMS) using the iodide reagent ion and via offline UPLC-MS/MS. FESOH and MeFESOH, the thioether congeners, were observed to have the largest rate constants of kFESOH = 2.82 (±0.33) and kMeFESOH = 2.17 (±0.17) (×10-12 cm3 molecules-1 s-1, respectively). First-, second-, and third-generation products of OH oxidation were observed as a function of time, while product quantification yielded ultrashort perfluoropropionic acid (PFPrA) and short polyfluoroether acid species as the terminal products for FESOH and ProFdiEOH. There was evidence for MeFESOH being fully mineralized, demonstrating the potential benign chemical architecture.

Correction: Iodine emission from the reactive uptake of ozone to simulated seawater.

Correction for 'Iodine emission from the reactive uptake of ozone to simulated seawater' by Stephanie R. Schneider et al., Environ. Sci.: Processes Impacts, 2023, 25, 254-263, https://doi.org/10.1039/D2EM00111J.

Iodine emission from the reactive uptake of ozone to simulated seawater.

The heterogeneous reaction of ozone and iodide is both an important source of atmospheric iodine and dry deposition pathway of ozone in marine environments. While the iodine generated from this reaction is primarily in the form of HOI and I2, there is also evidence of volatile organoiodide compound emissions in the presence of organics without biological activity occuring [M. Martino, G. P. Mills, J. Woeltjen and P. S. Liss, A new source of volatile organoiodine compounds in surface seawater, Geophys. Res. Lett., 2009, 36, L01609, L. Tinel, T. J. Adams, L. D. J. Hollis, A. J. M. Bridger, R. J. Chance, M. W. Ward, S. M. Ball and L. J. Carpenter, Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions, Environ. Sci. Technol., 2020, 54, 13228-13237]. In this study, we evaluate our fundamental understanding of the ozonolysis of iodide which leads to gas-phase iodine emissions. To do this, we compare experimental measurements of ozone-driven gas-phase I2 formation in a flow tube to predictions made with the kinetic multilayer model for surface and bulk chemistry (KM-SUB). The KM-SUB model uses literature rate coefficients used in current atmospheric chemistry models to predict I2(g) formation in pH-buffered solutions of marine composition containing chloride, bromide, and iodide compared to solutions containing only iodide. Experimentally, I2(g) formation was found to be suppressed in solutions containing seawater levels of chloride compared to solutions containing only iodide, but the model does not predict this effect using literature rate constants. However, the model is able to predict this trend upon adjustment of two specific reaction rate constants. To more closely represent true oceanic conditions, we add an organic component to the proxy seawater solutions using material generated from Thalassiosira pseudonana phytoplankton cultures. Whereas the rate of ozone deposition is unaffected, the formation rate of I2(g) is strongly suppressed in the presence of biological organic material, indicative of a sink or reduction of reactive iodine formed during the oxidation process.

Air Quality Data Approach for Defining Wildfire Influence: Impacts on PM2.5, NO2, CO, and O3 in Western Canadian Cities.

As the climate warms, it is recognized that wildfires are increasing in size and frequency. The negative effects of wildfires on air quality are well documented, especially on commonly monitored atmospheric pollutants such as PM2.5, NO2, CO, and O3. However, it is not clear how frequently wildfires influence urban air quality and the size of that influence relative to traffic and industrial pollutants. To understand the impact of wildfires on air quality, we have established an automated method to identify wildfire-influenced ambient air measurements. The trajectory-fire interception method (TFIM) compares hybrid single-particle Lagrangian integrated trajectory (HYSPLIT) back-trajectories from an air quality monitoring station to satellite imagery of fire "hot-spots" to determine the number of trajectory-fire interceptions that occur. From the number of interceptions and local PM2.5 measurements, we have defined a wildfire-influenced period to occur if the interception count is ≥20. TFIM wildfire identification compares favorably with Environment and Climate Change Canada's smoke forecast, FireWork, and with the BlueSky trajectory-based forecast. Using TFIM, we studied the impact of wildfire-influenced periods on PM2.5, NO2, CO, and O3 from 2001 to 2019 in Western Canadian urban areas. We show that wildfire-influenced periods have elevated concentrations of PM2.5, NO2, and CO but not O3. We show that a decreasing urban baseline of CO and NO2 over time results in a relatively greater impact of wildfires on these pollutants, which emphasizes the changing relative importance of wildfires on air quality.

Reactive Uptake of Ozone to Simulated Seawater: Evidence for Iodide Depletion.

The reaction of ozone with iodide in the ocean is a major ozone dry deposition pathway, as well as an important source of reactive iodine to the marine troposphere. Few prior laboratory experiments have been conducted with environmentally relevant ozone mixing ratios and iodide concentrations, leading to uncertainties in the rate of the reaction under marine boundary layer conditions. As well, there remains disagreement in the literature assessment of the relative contributions of an interfacial reaction via ozone adsorbed to the ocean surface versus a bulk reaction with dissolved ozone. In this study, we measure the uptake coefficient of ozone over a buffered, pH 8 salt solution replicating the concentrations of iodide, bromide, and chloride in the ocean over an ozone mixing ratio of 60-500 ppb. Due to iodide depletion in the solution, the measured ozone uptake coefficient is dependent on the exposure time of the solution to ozone and its mixing ratio. A kinetic multilayer model confirms that iodide depletion is occurring not only within ozone's reactodiffusive depth, which is on the order of microns for environmental conditions, but also deeper into the solution as well. Best model-measurement agreement arises when some degree of nondiffusive mixing is occurring in the solution, transporting iodide from deeper in the solution to a thin, diffusively mixed upper layer. If such mixing occurs rapidly in the environment, iodide depletion is unlikely to reduce ozone dry deposition rates. Unrealistically high bulk-to-interface partitioning of iodide is required for the model to predict a substantial interfacial component to the reaction, indicating that the Langmuir-Hinshelwood mechanism is not dominant under environmental conditions.