Experimental and density functional theory investigation of surface-modified biopolymer for improved adsorption of mixtures of per- and polyfluoroalkyl substances in water.

Glutaraldehyde (GTH) cross-linked chitosan (CTN) biopolymer-based and polyethyleneimine (PEI) functionalized (GTHCTNPEI) aerogels were proven promising for removing mixtures of long- and short chain per- and polyfluoroalkyl substances (PFAS) in water. In this study, to further improve the performance of the aerogel for short-chain PFAS and undecafluoro-2-methyl-3-oxahexanoic acid (GenX) removal, GTHCTNPEI aerogel chunks with an average size of 13.4 mm were turned into flakes with an average size of 9.1 mm. The GTHCTNPEI flakes achieved >99 % removal of all target PFAS, including long- and short-chain PFAS and >97 % for GenX after 10 h. In addition, the flakes can be regenerated and reused for at least four cycles. When added to tap water spiked with PFAS at initial concentrations of 30, 70, or 100 ng/L, the flakes removed almost 100 % of all tested PFAS. Mechanistic investigations using density functional theory (DFT) revealed strong stabilizing hydrophobic and electrostatic interactions between the aerogels and PFAS, with GTHCTNPEI to PFAS binding energies ranging between -24.0 - -30.1 kcal/mol for PFOA; -41.3 - -48.5 kcal/mol for PFOS; and -40.5 - -47.3 kcal/mol for PFBS. These results demonstrate the great potential of the flakes for removing PFAS from drinking water, surface water, and groundwater.

Theoretical Insights into the Gas-Phase Oxidation of 3-Methyl-2-butene-1-thiol by the OH Radical: Thermochemical and Kinetic Analysis.

3-Methyl-2-butene-1-thiol ((CH3)2C═CH-CH2-SH; MBT) is a recently identified volatile organosulfur compound emitted from Cannabis sativa and is purported to contribute to its skunky odor. To understand its environmental fate, hydroxyl radical (•OH)-mediated oxidation of MBT was conducted using high-level quantum chemical and theoretical kinetic calculations. Three stable conformers were identified for the title molecule. Abstraction and addition pathways are possible for the MBT + OH radical reaction, and thus, potential energy surfaces involving H-abstraction and •OH addition were computed at the CCSD(T)/aug-cc-pV(T+d)Z//M06-2X/aug-cc-pV(T+d)Z level of theory. The barrier height for the addition of the OH radical to a C atom of the alkene moiety, leading to the formation of a C-centered MBT-OH radical, was computed to be -4.1 kcal mol-1 below the energy of the starting MBT + OH radical-separated reactants. This reaction was found to be dominant compared to other site-specific H-abstraction and addition paths. The kinetics of all the site-specific abstraction and addition reactions associated with the most stable MBT + OH radical reaction were assessed using the MESMER kinetic code between 200 and 320 K. Further, we considered the contributions from two other conformers of MBT to the overall reaction of MBT + OH radical. The estimated global rate coefficient for the oxidation of MBT with respect to its reactions with the OH radical was found to be 6.1 × 10-11 cm3 molecule-1 s-1 at 298 K and 1 atm pressure. The thermodynamic parameters and atmospheric implications of the MBT + OH reaction are discussed.

Theoretical Study of the Atmospheric Chemistry of Methane Sulfonamide Initiated by OH Radicals and the CH3S(O)2N•H + 3O2 Reaction.

In the present work, we have revisited the reaction mechanism of the atmospheric oxidation of methane sulfonamide (CH3S(═O)2NH2; MSAM) initiated by hydroxyl (OH) radicals in the gas phase. The present reaction has been studied for the first time using quantum calculations combined with chemical kinetic modeling. The abstraction of an H-atom from the -NH2 group of MSAM by OH radical to form the products CH3S(═O)2N•H + H2O was found to be a major path with a barrier height of ∼2.3 kcal mol-1 relative to the energy of the separated MSAM + •OH starting reactants. This study is the first to identify the reaction of MSAM with •OH as exclusively generating N-centered MSAM radicals. The chemical kinetic calculations for various paths associated with the MSAM + •OH reaction were performed under pre-equilibrium approximation conditions using canonical variational transition state theory, employing the small curvature tunneling method in the temperature range of 200-400 K. A recent experimental study reported that OH radical-mediated degradation of MSAM proceeds via the formation of the C-centered MSAM radical (•CH2S(═O)2NH2) product. However, the energetics and rate coefficient calculations in the present work suggest that the formation of the N-centered MSAM radical is a major path compared to that which proceeds via the C-centered MSAM radical. The overall rate coefficient for the MSAM + •OH reaction was calculated in the 200-400 K temperature range. The overall rate coefficient for the MSAM + •OH reaction was estimated to be k = 1.2 × 10-13 cm3 molecule-1 s-1 at 298 K. This rate coefficient at 298 K agrees well with the reported experimental value (1.4 × 10-13 cm3 molecule-1 s-1) at the same temperature. We also provide branching ratios for each path associated with the MSAM + •OH reaction. In addition, the atmospheric implications for the title reactions are discussed. The oxidation mechanism of the MSAM + •OH reaction suggests that the formed CH3S(═O)2N•H further reacts with atmospheric oxygen (3O2) to form the corresponding RO2 radical adduct. The downstream products of the CH3S(═O)2N•H + 3O2 reaction in the present work indicate that sulfur dioxide (SO2), carbon monoxide (CO), carbon dioxide (CO2), nitric acid (HNO3), nitrous oxide (N2O), and formic acid [HC(O)OH] are formed as final products.

Thermochemistry and Kinetics of the Atmospheric Oxidation Reactions of Propanesulfinyl Chloride Initiated by OH Radicals: A Computational Approach.

The thermochemistry and kinetics of the atmospheric oxidation mechanism for propanesulfinyl chloride (CH3-CH2-CH2-S(═O)Cl; PSICl) initiated by the hydroxyl (OH) radical were investigated with high level quantum chemistry calculations and the Master equation solver for multi-energy well reaction (Mesmer) kinetic code. The mechanism for the oxidation of PSICl in the presence of OH radical can proceed via H-abstraction and substitution pathways. The CCSD(T)/aug-cc-pV(T+d)Z//MP2/aug-cc-pV(T+d)Z level calculated energies revealed addition of the OH radical to the S-atom of the sulfinyl (-S(═O)) moiety, followed by cleavage of the Cl-S(═O) single bond, leading to formation of propanesulfinic acid (PSIA) and the Cl radical to be the major pathway when compared to all other possible channels. The transition state barrier height for this reaction was found to be -3.0 kcal mol-1 relative to the energy of the starting PSICl + OH radical reactants. The rate coefficients were calculated for all possible paths in the atmospherically relevant temperature range of 200-320 K and at 1 atm. The rate coefficient for the formation of the PSIA + Cl radical from the PSICl + OH radical reaction was found to be 8.2 × 10-12 cm3 molecule-1 s-1 at 298 K and a pressure of 1 atm. From branching ratio calculations, it was revealed that the reaction resulting in the formation of the PSIA + Cl radical contributed ∼52% to the total reaction. The overall rate coefficient for the PSICl + OH reaction was also calculated and found to be 1.6 × 10-11 cm3 molecule-1 s-1 at 298 K and a pressure of 1 atm. In the aggregate, the results indicate the atmospheric lifetime of PSICl to be ∼12-20 h in the temperature range between 200 and 320 K, which suggests that its contribution to global warming is negligible. However, the degradation products revealed to be formed in its interactions with the OH radical, which include that SO2, Cl radical, HO2 radical, and propylene have significant effects on the formation of acid rain, secondary organic aerosols, the ozone layer, and global warming.

Atmospheric Ring-Closure and Dehydration Reactions of 1,4-Hydroxycarbonyls in the Gas Phase: The Impact of Catalysts.

1,4-Hydroxycarbonyls can potentially undergo sequential reactions involving cyclization followed by dehydration to form dihydrofurans. As dihydrofurans contain a double bond, they are highly reactive toward atmospheric oxidants such as OH, O3, and NO3. In the present study, we use ab initio calculations to examine the impact of various atmospheric catalysts on the energetics and kinetics of the gas-phase cyclization and dehydration reaction steps associated with 4-hydroxybutanal, a prototypical 1,4-hydroxycarbonyl molecule. The cyclization step transforms 4-hydroxybutanal into 2-hydroxytetrahydrofuran, which can subsequently undergo dehydration to form 2,3-dihydrofuran. As the barriers associated with the cyclization and dehydration steps for 4-hydroxybutanal are, respectively, 34.8 and 63.0 kcal/mol in the absence of a catalyst, both reaction steps are inaccessible under atmospheric conditions in the gas phase. However, the presence of a suitable catalyst can significantly reduce the reaction barriers, and we have examined the impact of a single molecule of H2O, HO2 radical, HC(O)OH, HNO3, and H2SO4 on these reactions. We find that H2SO4 reduces the reaction barriers the greatest, with the barrier for the cyclization step being reduced to -13.1 kcal/mol and that for the dehydration step going down to 9.2 kcal/mol, measured relative to their respective separated starting reactants. Interestingly, our kinetic study shows that HNO3 gives the fastest rate due to the combined effects of a larger atmospheric concentration and a reduced barrier. Thus, our study suggests that, with acid catalysis, the cyclization reaction step can readily occur for 1,4-hydroxycarbonyls in the gas phase. Because the dehydration step exhibits a significant barrier even with acid catalysis, the 2-hydroxytetrahydrofuran products, once formed, are likely lost through their reaction with OH radicals in the atmosphere. We have investigated the reaction pathways and the rate constant for this bimolecular reaction in the presence of excess molecular oxygen (3O2), as it would occur under tropospheric conditions, using computational chemistry over the 200-300 K temperature range. We find that the main products from these OH-initiated oxidation reactions are succinaldehyde + HO2 and 2,3-dihydro-2-furanol + HO2.

Thermal Decomposition of 2-Methyltetrahydrofuran behind Reflected Shock Waves over the Temperature Range of 1179-1361 K.

The thermal unimolecular decomposition of 2-methyltetrahydrofuran (2-MTHF) was studied behind reflected shock waves in a single-pulse shock tube over the temperature range of 1179-1361 K and pressure range of 9-17 atm. Methane, ethylene, ethane, 1,3-butadiene, propylene, acetaldehyde, and acetylene were identified as products in the decomposition of 2-MTHF. A reaction scheme was proposed to explain the mechanism for the observed products. The experimentally determined rate coefficients were best fit to an Arrhenius expression for the overall decomposition and is represented as ktotalexp(1179-1361 K) = (3.23 ± 0.59) × 1011 s-1 exp(-51.3 ± 1.4 kcal mol-1/RT). Quantum chemistry methods were used to calculate the energetics and kinetics of various possible unimolecular dissociation pathways involved in the thermal decomposition of 2-MTHF. The initial decomposition of 2-MTHF occurs predominantly via ring-methyl (C-CH3) single bond fission, leading to the formation of tetrahydrofuran (C4H7O) radical, and methyl radical was found to be the major reaction compared to all the possible initial bond fission, ring opening, and molecular elimination channels. The temperature-dependent rate coefficients for the unimolecular dissociation of 2-MTHF were calculated using the RRKM (Rice-Ramsperger-Kassel-Marcus) theory in combination with the CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of electronic structure calculations over the temperature range of 800-1500 K. The computed high-pressure limiting rate coefficients for the initial decomposition of 2-MTHF through C-CH3 single bond fission channel were found to be ∼2 times higher in the temperatures between 800 and 900 K, and above this temperature, they agree well with the values reported in the literature.

Catalytic effect of water and formic acid on the reaction of carbonyl sulfide with dimethyl amine under tropospheric conditions.

CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ calculations were performed on the addition of amines [i.e. ammonia (NH3), methyl amine (MA), and dimethyl amine (DMA)] to carbonyl sulfide (OCS), followed by transfer of the amine H-atom to either the S-atom or O-atom of OCS, assisted by a single water (H2O) or a formic acid (FA) molecule, leading to the formation of the corresponding carbamothioic S- or O acids. For the OCS + NH3 and OCS + MA reactions with or without the H2O or FA, very high barriers were observed, making these reactions unfeasible. Interestingly, the barrier heights for the OCS + DMA reaction, involving H-atom transfer to either the S-atom or O-atom of OCS and assisted by a FA, were found to be -4.2 kcal mol-1 and -3.9 kcal mol-1, respectively, relative to those of the separated reactants. The barrier height values suggest that FA lowers the reaction barriers by ∼28.4 kcal mol-1 and ∼35.9 kcal mol-1 compared to the OCS + DMA reaction without the catalyst. Rate coefficient calculations were performed on the OCS + DMA reaction both without a catalyst, and assisted by a H2O and a FA molecule using canonical variational transition state theory and small curvature tunneling at the temperatures between 200 and 300 K. The rate data show that the OCS + DMA + FA reaction proceeds through H-atom transfer to the S-atom of OCS, which was found to be ∼103-1011 and 103-1010 times faster than the OCS + DMA and OCS + DMA + H2O reactions, respectively, in the studied temperature range. For the same temperature range, the rate of the OCS + DMA + FA reaction was found to be ∼108-1016 and 103-1012 times faster than the OCS + DMA and OCS + DMA + H2O reactions in which H-atom transfer to the O-atom of OCS occurred. This suggests that the OCS + DMA reaction that is assisted by FA is more efficient than the H2O assisted reaction. In addition, the rate of the OCS + DMA + FA reaction was found to be ∼1010 times slower than the OCS + ˙OH reaction at 298 K. This clarifies that the OCS + DMA + FA reaction may be feasible for the atmospheric removal of OCS under night-time forest fire conditions when the OCS and DMA concentrations are high and the ˙OH concentration is low.

Computational Study Investigating the Atmospheric Oxidation Mechanism and Kinetics of Dipropyl Thiosulfinate Initiated by OH Radicals and the Fate of Propanethiyl Radical.

The OH radical-initiated atmospheric oxidation mechanism of dipropyl thiosulfinate (CH3CH2CH2-S(O)S-CH2CH2CH3, DPTS), a volatile released by Allium genus plants, has been investigated using ab initio/DFT electronic structure calculations. The DPTS + •OH reaction can proceed through (1) abstraction and (2) substitution pathways. The present calculations show that addition of •OH to the sulfur atom of the sulfinyl (-S(═O)) group, followed by simultaneous cleavage of the S-S single bond, leading to the formation of propanethiyl radical (PTR) and propanesulfinic acid, is the major pathway when compared to the other possible abstraction and substitution reactions. The barrier height for this reaction was computed to be -5.4 kcal mol-1 relative to that of the separated DPTS + •OH reactants. The rate coefficients for all the possible pathways for DPTS + •OH were explored by RRKM-ME calculations using the MESMER kinetic code in the atmospherically relevant temperatures T = 200-300 K and the pressure range of 0.1-10 atm. The calculated total rate coefficient for the DPTS + •OH reaction was found to be 1.7 × 10-10 cm3 molecule-1 s-1 at T = 300 K and P = 1 atm. The branching ratios and atmospheric lifetime of DPTS + •OH were also determined in the studied temperature range. In addition, electronic structure calculations on the multichannel reactions of PTR with atmospheric oxygen (3O2) were investigated using the same level of theory. The calculations showed that unimolecular elimination of hydroperoxyl radical (HO2) from the RO2 adduct through formation of propanethial is a major reaction under atmospherically relevant conditions. The overall results suggest that the atmospheric removal of DPTS is mainly due to reactions with •OH and 3O2, resulting in formation of propanesulfinic acid, propanethial, HO2, and sulfur dioxide (SO2) as the major products. The atmospheric lifetime of DPTS was estimated to be less than 2 h in the studied temperature range. Estimations of the global warming potential of DPTS and the products of its reaction with •OH reveal that while the contribution made by DPTS to global warming is negligible, the various products formed as a consequence of its interaction with OH radical may make substantial contributions to global warming, acid rain, and formation of secondary organic aerosols.

Reaction mechanism, energetics, and kinetics of the water-assisted thioformaldehyde + ˙OH reaction and the fate of its product radical under tropospheric conditions.

The reactions of thioformaldehyde (H2CS) with OH radicals and assisted by a single water molecule have been investigated using high level ab initio quantum chemistry calculations. The H2CS + ˙OH reaction can in principle proceed through: (1) abstraction, and (2) addition pathways. The barrier height for the addition reaction in the absence of a catalyst was found to be -0.8 kcal mol-1, relative to the separated reactants, which has a ∼1.0 kcal mol-1 lower barrier than the abstraction channel. The H2CS + ˙OH reaction assisted by a single water molecule reduces the barrier heights significantly for both the addition and abstraction channels, to -5.5 and -6.7 kcal mol-1 respectively, compared to the un-catalyzed H2CS + ˙OH reaction. These values suggest that water lowers the barriers by ∼6.0 kcal mol-1 for both reaction paths. The rate constants for the H2CSH2O + ˙OH and OHH2O + H2CS bimolecular reaction channels were calculated using Canonical Variational Transition state theory (CVT) in conjunction with the Small Curvature Tunneling (SCT) method over the atmospherically relevant temperatures between 200 and 400 K. Rate constants for the H2CS + ˙OH reaction paths for comparison with the H2CS + ˙OH + H2O reaction in the same temperature range were also computed. The results suggest that the rate of the H2CS + ˙OH + H2O reaction is slower than that of the H2CS + ˙OH reaction by ∼1-4 orders of magnitude in the temperatures between 200 and 400 K. For example, at 300 K, the rates of the H2CS + ˙OH + H2O and H2CS + ˙OH reactions were found to be 2.2 × 10-8 s-1 and 6.4 × 10-6 s-1, respectively, calculated using [OH] = 1.0 × 106 molecules cm-3, and [H2O] = 8.2 × 1017 molecules cm-3 (300 K, RH 100%) atmospheric conditions. Electronic structure calculations on the H2C(OH)S˙ product in the presence of 3O2 were also performed. The results show that H2CS is removed from the atmosphere primarily by reacting with ˙OH and O2 to form thioformic acid, HO2, formaldehyde, and SO2 as the main end products.

Theoretical Studies of the Gas-Phase Reactions of S-Methyl Methanesulfinothioate (Dimethyl Thiosulfinate) with OH and Cl Radicals: Reaction Mechanisms, Energetics, and Kinetics.

The mechanisms, energetics, and kinetics of the gas-phase reactions of terrestrial plant-derived dimethyl thiosulfinate (DMTS) with the atmospheric oxidants OH and Cl radicals were investigated using high-level ab initio calculations. The results show that the addition of OH and Cl radicals to the sulfinyl [-S(═O)] of DMTS, followed by S(═O)-S single bond cleavage to form methanesulfinic acid + CH3S• and methanesulfinyl chloride + CH3S•, respectively, are the more dominant reactions. The barrier heights for the reactions with OH and Cl radicals were found to be -5.6 and -12.7 kcal/mol relative to the energies of the starting reactants, respectively, when computed at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311++G(3df,3pd) level of theory. The rate constants for all possible pathways of DMTS + •OH/•Cl reactions were investigated using the MESMER kinetics code over the temperature range between 200 and 300 K. The calculated global rate constants for the DMTS + •OH and DMTS + •Cl reactions at 300 K were found to be 1.42 × 10-11 and 3.72 × 10-11 cm3 molecule-1 s-1, respectively. In addition, the thermochemistry of all possible paths and branching ratios was determined. The atmospheric chemistry implications of the DMTS + •OH/•Cl reactions are discussed.