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Thermal treatment of perfluoroalkyl and polyfluoroalkyl substances (PFASs) presents a promising opportunity to halt the PFAS cycle. However, how co-occurring materials such as granular activated carbon (GAC) influence thermal decomposition products of PFASs, and underlying mechanisms remain unclear. We studied the pyrolysis of two potassium salts of perfluoroalkanesulfonates (PFSAs, C n F 2n+1 SO 3 K), perfluorobutanesulfonate (PFBS-K), and perfluorooctanesulfonate (PFOS-K), with or without GAC. PFBS-K is more stable than PFOS-K for pure standards, but when it is adsorbed onto GAC, its thermal stabilities and decomposition behaviors are similar. Temperatures and heating rates can significantly influence the decomposition mechanisms and products for pure standards, while these effects are less pronounced when PFSAs are adsorbed onto GAC. We further studied the underlying decomposition mechanisms. Pure standards of C n F 2n+1 SO 3 K can decompose directly in their condense phase by reactions: F(CF 2 ) n SO 3 K → F(CF 2 ) n-2 CF═CF 2 + KFSO 3 or F(CF 2 ) n SO 3 K → F(CF 2 ) n - + K + + SO 3 . GAC appears to facilitate breakage of the C-S bond to release SO 2 at temperatures as low as 280 °C. GAC promotes fluorine mineralization through functional reactive sites. SiO 2 is particularly important for the surface-mediated mineralization of PFASs into SiF 4 . These findings offer valuable insights into optimizing thermal treatment strategies for PFAS-contaminated waste.

The light absorption properties of brown carbon (BrC), which are linked to molecular chromophores, may play a significant role in the Earth's energy budget. While nitroaromatic compounds have been identified as strong chromophores in wildfire-driven BrC, other types of chromophores remain to be investigated. Given the electron-withdrawing nature of carbonyls ubiquitous in the atmosphere, we characterized carbonyl chromophores in BrC samples from the nighttime oxidation of furan and pyrrole derivatives, which are important but understudied precursors of secondary organic aerosols primarily found in wildfire emissions. Various carbonyl chromophores were characterized and quantified in BrC samples, and their ultraviolet-visible spectra were simulated by using time-dependent density functional theory. Our findings suggest that chromophores with carbonyls bonded to nitrogen (i.e., imides and amides) derived from N-containing heterocyclic precursors substantially contribute to BrC light absorption. The quantified N-containing carbonyl chromophores contributed to over 40% of the total light absorption at wavelengths below 350 nm and above 430 nm in pyrrole BrC. The contributions of chromophores to total light absorption differed significantly by wavelength, highlighting their divergent importance in different wavelength ranges. Overall, our findings highlight the significance of carbonyl chromophores in secondary BrC and underscore the need for further investigation.

Nitrogen-containing heterocyclic volatile organic compounds (VOCs) are important components of wildfire emissions that are readily reactive toward nitrate radicals (NO 3 ) during nighttime, but the oxidation mechanism and the potential formation of secondary organic aerosol (SOA) and brown carbon (BrC) are unclear. Here, NO 3 oxidation of three nitrogen-containing heterocyclic VOCs, pyrrole, 1-methylyrrole (1-MP), and 2-methylpyrrole (2-MP), was investigated in chamber experiments to determine the effect of precursor structures on SOA and BrC formation. The SOA chemical compositions and the optical properties were analyzed using a suite of online and offline instrumentation. Dinitro- and trinitro-products were found to be the dominant SOA constituents from pyrrole and 2-MP, but not observed from 1-MP. Furthermore, the SOA from 2-MP and pyrrole showed strong light absorption, while that from 1-MP were mostly scattering. From these results, we propose that NO 3 -initiated hydrogen abstraction from the 1-position in pyrrole and 2-MP followed by radical shift and NO 2 addition leads to light-absorbing nitroaromatic products. In the absence of a 1-position hydrogen, NO 3 addition likely dominates the 1-MP chemistry. We also estimate that the total SOA mass and light absorption from pyrrole and 2-MP are comparable to those from phenolic VOCs and toluene in biomass burning, underscoring the importance of considering nighttime oxidation of pyrrole and methylpyrroles in air quality and climate models.

The C-F bond is one of the strongest single bonds in nature. Although microbial reductive dehalogenation is well known for the other organohalides, no microbial reductive defluorination has been documented for perfluorinated compounds except for a single, nonreproducible study on trifluoroacetate. Here, we report on C-F bond cleavage in two C 6 per- and polyfluorinated compounds via reductive defluorination by an organohalide-respiring microbial community. The reductive defluorination was demonstrated by the release of F - and the formation of the corresponding product when lactate was the electron donor, and the fluorinated compound was the sole electron acceptor. The major dechlorinating species in the seed culture, Dehalococcoides , were not responsible for the defluorination as no growth of Dehalococcoides or active expression of Dehalococcoides- reductive dehalogenases was observed. It suggests that minor phylogenetic groups in the community might be responsible for the reductive defluorination. These findings expand our fundamental knowledge of microbial reductive dehalogenation and warrant further studies on the enrichment, identification, and isolation of responsible microorganisms and enzymes. Given the wide use and emerging concerns of fluorinated organics (e.g., per- and polyfluoroalkyl substances), particularly the perfluorinated ones, the discovery of microbial defluorination under common anaerobic conditions may provide valuable insights into the environmental fate and potential bioremediation strategies of these notorious contaminants.

Isoprene (C 5 H 8 ) is the main non-methane hydrocarbon emitted into the global atmosphere. Despite intense research, atmospheric transformations of isoprene leading to secondary organic aerosol (SOA) are still not fully understood, including its multiphase chemical reactions. Herein, we report on the detailed structural characterization of atmospherically relevant isoprene-derived organosulfates (OSs) with a molecular weight (MW) of 212 (C 5 H 8 SO 7 ), which are abundantly present in both ambient fine aerosol (PM 2.5 ) and laboratory-generated isoprene SOA. The results obtained from smog chamber-generated isoprene SOA and aqueous-phase laboratory experiments coupled to the S(IV)-autooxidation chemistry of isoprene, 3-methyl-2(5 H )-furanone, and 4-methyl-2(5 H )-furanone, allowed us for the first time to fully elucidate the isomeric structures of the MW 212 OSs. By applying liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry, we firmly confirmed six positional isomers of the MW 212 OSs in PM 2.5 collected from different sites in Europe and the United States. Our results also show that despite the low solubility of isoprene in water, aqueous-phase or multiphase chemistry can play an important role in the formation of OSs from isoprene. Possible formation mechanisms for the MW 212 OSs are also tentatively proposed.

Dimethyl selenide (DMSe) is one of the major volatile organoselenium compounds released from aquatic and terrestrial environments through microbial transformation and plant metabolism. The detailed processes of DMSe leading to secondary organic aerosol (SOA) formation and the pulmonary health effects induced by inhalation of DMSe-derived SOA remain largely unknown. In this study, we characterized the chemical composition and formation yields of SOA produced from the oxidation of DMSe with OH radicals and O 3 in controlled chamber experiments. Further, we profiled the transcriptome-wide gene expression changes in human airway epithelial cells (BEAS-2B) after exposure to DMSe-derived SOA. Our analyses indicated a significantly higher SOA yield resulting from the OH-initiated oxidation of DMSe. The oxidative potential of DMSe-derived SOA, as measured by the dithiothreitol (DTT) assay, suggested the presence of oxidizing moieties in DMSe-derived SOA at levels higher than typical ambient aerosols. Utilizing RNA sequencing (RNA-Seq) techniques, gene expression profiling followed by pathway enrichment analysis revealed several major biological pathways perturbed by DMSe-derived SOA, including elevated genotoxicity, DNA damage, and p53-mediated stress responses, as well as downregulated cholesterol biosynthesis, glycolysis, and interleukin IL-4/IL-13 signaling. This study highlights the significance of DMSe-derived SOA as a stressor in human airway epithelial cells.

Secondary organic aerosol (SOA) derived from the photochemical oxidation of isoprene contributes a substantial mass fraction to atmospheric fine particulate matter (PM 2.5 ). The formation of isoprene SOA is influenced largely by anthropogenic emissions through multiphase chemistry of its multigenerational oxidation products. Considering the abundance of isoprene SOA in the troposphere, understanding mechanisms of adverse health effects through inhalation exposure is critical to mitigating its potential impact on public health. In this study, we assessed the effects of isoprene SOA on gene expression in human airway epithelial cells (BEAS-2B) through an air-liquid interface exposure. Gene expression profiling of 84 oxidative stress and 249 inflammation-associated human genes was performed. Our results show that the expression levels of 29 genes were significantly altered upon isoprene SOA exposure under noncytotoxic conditions (p < 0.05), with the majority (22/29) of genes passing a false discovery rate threshold of 0.3. The most significantly affected genes belong to the nuclear factor (erythroid-derived 2)-like 2 (Nrf2) transcription factor network. The Nrf2 function is confirmed through a reporter cell line. Together with detailed characterization of SOA constituents, this study reveals the impact of isoprene SOA exposure on lung responses and highlights the importance of further understanding its potential health outcomes.

In the present study, formation of aromatic organosulfates (OSs) from the photo-oxidation of polycyclic aromatic hydrocarbons (PAHs) was investigated. Naphthalene (NAP) and 2-methylnaphthalene (2-MeNAP), two of the most abundant gas-phase PAHs and thought to represent "missing" sources of urban SOA, were photochemically oxidized in an outdoor smog chamber facility in the presence of nonacidified and acidified sulfate seed aerosol. Effects of seed aerosol composition, acidity and relative humidity on OS formation were examined. Chemical characterization of SOA extracts by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry revealed the formation of OSs and sulfonates from photo-oxidation in the presence of sulfate seed aerosol. Many of the organosulfur compounds identified in the smog chamber extracts were also measured in urban fine aerosol collected at Lahore, Pakistan, and Pasadena, USA, demonstrating that PAH photo-oxidation in the presence of sulfate aerosol is a hitherto unrecognized source of anthropogenic secondary organosulfur compounds, and providing new PAH SOA tracers.

Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

Isoprene significantly contributes to organic aerosol in the southeastern United States where biogenic hydrocarbons mix with anthropogenic emissions. In this work, the Community Multiscale Air Quality model is updated to predict isoprene aerosol from epoxides produced under both high- and low-NOx conditions. The new aqueous aerosol pathways allow for explicit predictions of two key isoprene-derived species, 2-methyltetrols and 2-methylglyceric acid, that are more consistent with observations than estimates based on semivolatile partitioning. The new mechanism represents a significant source of organic carbon in the lower 2 km of the atmosphere and captures the abundance of 2-methyltetrols relative to organosulfates during the simulation period. For the parametrization considered here, a 25% reduction in SOx emissions effectively reduces isoprene aerosol, while a similar reduction in NOx leads to small increases in isoprene aerosol.

We investigate the sources, chemical composition, and spectral properties of light-absorbing organic aerosol extracts (i.e., brown carbon, or BrC) in the Los Angeles (LA) Basin during the CalNex-2010 field campaign. Light absorption of PM2.5 water-soluble components at 365 nm (Abs365), used as a proxy for water-soluble BrC, was well correlated with water-soluble organic carbon (WSOC) (r(2) = 0.55-0.65), indicating secondary organic aerosol (SOA) formation from anthropogenic emissions was the major source of water-soluble BrC in this region. Normalizing Abs365 to WSOC mass yielded an average solution mass absorption efficiency (MAE365) of 0.71 m(2) g(-1) C. Detailed chemical speciation of filter extracts identified eight nitro-aromatic compounds that were correlated with Abs365. These compounds accounted for ∼4% of the overall water-soluble BrC absorption. Methanol-extracted BrC in LA was approximately 3 and 21 times higher than water-soluble BrC at 365 and 532 nm, respectively, and had a MAE365 of 1.58 m(2) g(-1) C (Abs365 normalized to organic carbon mass). The water-insoluble BrC was strongly correlated with ambient elemental carbon concentration, suggesting similar sources. Absorption Ångström exponent (Å(a)) (fitted between 300 and 600 nm wavelengths) was 3.2 (±1.2) for the PILS water-soluble BrC measurement, compared to 4.8 (±0.5) and 7.6 (±0.5) for methanol- and water-soluble BrC from filter extracts, respectively. These results show that fine particle BrC was prevalent in the LA basin during CalNex, yet many of its properties and potential impacts remain unknown.

Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NO(x) conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (>99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7-6.4% for β-IEPOX and 3.4-5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C(5)-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NO(x), isoprene-dominated regions influenced by the presence of acidic aerosols.