Spontaneous dark formation of OH radicals at the interface of aqueous atmospheric droplets.

Hydroxyl radical (OH) is a key oxidant that triggers atmospheric oxidation chemistry in both gas and aqueous phases. The current understanding of its aqueous sources is mainly based on known bulk (photo)chemical processes, uptake from gaseous OH, or related to interfacial O3 and NO3 radical-driven chemistry. Here, we present experimental evidence that OH radicals are spontaneously produced at the air-water interface of aqueous droplets in the dark and the absence of known precursors, possibly due to the strong electric field that forms at such interfaces. The measured OH production rates in atmospherically relevant droplets are comparable to or significantly higher than those from known aqueous bulk sources, especially in the dark. As aqueous droplets are ubiquitous in the troposphere, this interfacial source of OH radicals should significantly impact atmospheric multiphase oxidation chemistry, with substantial implications on air quality, climate, and health.

Insights into the Formation Mechanism of Reactive Oxygen Species in the Interface Reaction of SO2 on Hematite.

The interplay between sulfur and iron holds significant importance in their atmospheric cycle, yet a complete understanding of their coupling mechanism remains elusive. This investigation delves comprehensively into the evolution of reactive oxygen species (ROS) during the interfacial reactions involving sulfur dioxide (SO2) and iron oxides under varying relative humidity conditions. Notably, the direct activation of water by iron oxide was observed to generate a surface hydroxyl radical (•OH). In comparison, the aging of SO2 was found to markedly augment the production of •OH radicals on the surface of α-Fe2O3 under humid conditions. This augmentation was ascribed to the generation of superoxide radicals (•O2-) stemming from the activation of O2 through the Fe(II)/Fe(III) cycle and its combination with the H+ ion to produce hydrogen peroxide (H2O2) on the acidic surface. Moreover, the identification of moderate relative humidity as a pivotal factor in sustaining the surface acidity of iron oxide during SO2 aging underscores its crucial role in the coupling of iron dissolution, ROS production, and SO2 oxidation. Consequently, the interfacial reactions between SO2 and iron oxides under humid conditions are elucidated as atmospheric processes that enhance oxidation capacity rather than deplete ROS. These revelations offer novel insights into the mechanisms underlying •OH radical generation and oxidative potential within atmospheric interfacial chemistry.

Photooxidation-Initiated Aqueous-Phase Formation of Organic Peroxides: Delving into Formation Mechanisms.

Formation of highly oxygenated molecules (HOMs) such as organic peroxides (ROOR, ROOH, and H2O2) is known to degrade food and organic matter. Gas-phase unimolecular autoxidation and bimolecular RO2 + HO2/RO2 reactions are prominently renowned mechanisms associated with the formation of peroxides. However, the reaction pathways and conditions favoring the generation of peroxides in the aqueous phase need to be evaluated. Here, we identified bulk aqueous-phase ROOHs in varying organic precursors, including a laboratory model compound and monoterpene oxidation products. Our results show that formation of ROOHs is suppressed at enhanced oxidant concentrations but exhibits complex trends at elevated precursor concentrations. Furthermore, we observed an exponential increase in the yield of ROOHs when UV light with longer wavelengths was used in the experiment, comparing UVA, UVB, and UVC. Water-soluble organic compounds represent a significant fraction of ambient cloud-water components (up to 500 µM). Thus, the reaction pathways facilitating the formation of HOMs (i.e., ROOHs) during the aqueous-phase oxidation of water-soluble species add to the climate and health burden of atmospheric particulate matter.

Green Emissive Molybdenum Nanoclusters for Selective and Sensitive Detection of Hydroxyl Radical in Water Samples.

In this work, Cassia tora (C. tora) have been used as a template to synthesize green fluorescent C. tora molybdenum nanoclusters (C. tora-MoNCs) through a green chemistry approach. These C. tora-MoNCs showed a quantum yield (QY) of 7.72% and exhibited a significant emission peak at 498 nm when excited at 380 nm. The as-prepared C. tora-MoNCs had an average size of 3.48 ± 0.80 nm and showed different surface functionality. The as-synthesized C. tora-MoNCs were successfully identified the hydroxyl radical (•OH) via a fluorescence quenching mechanism. Also, fluorescence lifetime and Stern-Volmer proved that after the addition of •OH radicals it was quenched the fluorescence intensity via a static quenching mechanism. The limit of detection is 9.13 nM, and this approach was successfully utilized for sensing •OH radicals in water samples with a good recovery rate.

Enhanced H2O2 Upcycling into Hydroxyl Radicals with GO/Ni:FeOOH-Coated Silicon Nanowire Photocatalysts for Wastewater Treatment.

There remains continued interest in improving the advanced water oxidation process [e.g., ultraviolet (UV)/hydrogen peroxide (H2O2)] for more efficient and environmentally friendly wastewater treatment. Here, we report the design, fabrication, and performance of graphene oxide (GO, on top)/nickel-doped iron oxyhydroxide (Ni:FeOOH, shell)/silicon nanowires (SiNWs, core) as a new multifunctional photocatalyst for the degradation of common pollutants like polystyrene and methylene blue through enhancing the hydroxyl radical (•OH) production rate of the UV/H2O2 system. The photocatalyst combines the advantages of a large surface area and light absorption characteristics of SiNWs with heterogeneous photo-Fenton active Ni:FeOOH and photocatalytically active/charge separator GO. In addition, the built-in electric field of GO/Ni:FeOOH/SiNWs facilitates the charge separation of electrons to GO and holes to Ni:FeOOH, thus boosting the photocatalytic performance. Our photocatalyst increases the •OH yield by 5.7 times compared with that of a blank H2O2 solution sample and also extends the light absorption spectrum to include visible light irradiation.

The Importance of Anharmonicity and Solvent Effects on the OH Radical Attack on Nucleobases.

Previous theoretical investigations of the reactions between an OH radical and a nucleobase have stated the most important pathways to be the C5-C6 addition for pyrimidines and the C8 addition for purines. Furthermore, the abstraction of a methyl hydrogen from thymine has also been proven an important pathway. The conclusions were based solely on gas-phase calculations and harmonic vibrational frequencies. In this paper, we supplement the calculations by applying solvent corrections through the polarizable continuum model (PCM) solvent model and applying anharmonicity in order to determine the importance of anharmonicity and solvent effects. Density functional theory (DFT) at the ωB97-D/6-311++G(2df,2pd) level with the Eckart tunneling correction is used. The total reaction rate constants are found to be 1.48 ×10-13 cm3 molecules-1s-1 for adenine, 1.02 ×10-11 cm3 molecules-1s-1 for guanine, 5.52 ×10-13 cm3 molecules-1s-1 for thymine, 1.47 ×10-13 cm3 molecules-1s-1 for cytosine and 7.59 ×10-14 cm3 molecules-1s-1 for uracil. These rates are found to be approximately two orders of magnitude larger than experimental values. We find that the tendencies observed for preferred pathways for reactions calculated in a solvent are comparable to the preferred pathways for reactions calculated in gas phase. We conclude that applying a solvent has a larger impact on more parameters compared to the inclusion of anharmonicity. For some reactions the inclusion of anharmonicity has no effect, whereas for others it does impact the energetics.

Ethanol Oxidation via 12-Electron Pathway on Spiky Au@AuPd Nanoparticles Assisted by Near-Infrared Light.

In this work, ethanol oxidation reaction (EOR) via 12-electron (C1-12e) pathway on spiky Au@AuPd nanoparticles (NPs) with ultrathin AuPd alloy shells is achieved in alkaline media with the assistance of the near-infrared (NIR) light. It is found that OH radicals can be produced from the OHads species adsorbed on the surfaces of Pd atoms led by surface plasmon resonance (SPR) effect of spiky Au@AuPd NPs under the irradiation of NIR light. Moreover, OH radicals play the key role for the achievement of EOR proceeded by the desirable C1-12e pathway because OH radicals can directly break the C-C bonds of ethanol. Accordingly, the electrocatalytic performance of spiky Au@AuPd NPs toward EOR under NIR light is greatly improved. For instance, their mass activity can be up to 33.2 A mgpd -1 in the 0.5 m KOH solution containing 0.5 m ethanol, which is about 158 times higher than that of commercial Pd/C catalysts (0.21 A mgpd -1 ) and is better than those of the state-of-the-art Pd-based catalysts reported in literature thus far, to the best of our knowledge. Moreover, their highest mass activity can be further improved to 118.3 A mgpd -1 in the 1.5 m KOH solution containing 1.25 m ethanol.

New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions.

Hexafluoropropylene oxide dimer acid (HFPO-DA) is widely used as a substitute for perfluorooctanoic acid (PFOA). HFPO-DA exhibits high water solubility and low adsorption potential, conferring significant fluidity in aquatic environments. Given that the toxicity of HFPO-DA is similar to PFOA, it is necessary to control its content in aquatic environments. Electrochemical and thermally-activated persulfates have been successfully used to degrade HFPO-DA, but UV-activated persulfates cannot degrade the compound. Given that research on degradation mechanisms is still incomplete and lacks kinetic research, the mechanism and kinetic calculations of oxidative degradation were studied in detail using DFT calculations. And the toxicity of HFPO-DA degradation intermediates and products was evaluated to reveal the feasibility of using advanced oxidation process (AOP) technology based on persulfate to degrade HFPO-DA in wastewater. The results showed that the committed step of HFPO-DA degradation was initiated by the electron transfer reaction of SO4•- radicals. This reaction is not spontaneous at room temperature and requires sufficient electrical or thermal energy to be absorbed from the external environment. The perfluoroalcohol produced during this reaction can subsequently undergo four possible reactions: H atom abstraction from alcohol groups by an OH radical; H atom abstraction by SO4•-; direct HF removal; and HF removal with water as the catalyst. The final degradation products of HFPO-DA mainly include CO2, CF3CF2COOH, CF3COOH, FCOOH and HF, which has been identified through previous experimental analysis. Ecotoxicity assessment indicates that degradation does not produce highly toxic intermediates, and that the final products are non-toxic, supporting the feasibility of persulfate-based AOP technologies.

A Theoretical Study of Hydrogen Abstraction Reactions in Guanosine and Uridine.

All practically possible hydrogen abstraction reactions for guanosine and uridine have been investigated through quantum chemical calculations of energy barriers and rate constants. This was done at the level of density functional theory (DFT) with the ωB97X-D functional and the 6-311++G(2df,2pd) Pople basis set. Transition state theory with the Eckart tunneling correction was used to calculate the rate constants. The results show that the reaction involving the hydrogen labelled C4' in the ribofuranose part has the largest rate constant for guanosine with the value 5.097×1010 L mol-1s-1 and the largest for uridine with the value 1.62×1010 L mol-1s-1. Based on the results for these two nucleosides, there is a noticeable similarity between the rate constants in the ribofuranose part of the molecule, even though they are bound to two entirely different nucleobases.

Heterogeneous kinetics of the OH-initiated degradation of fenthion and parathion.

Fenthion and parathion are two representative kinds of organophosphorus pesticides and widely used in agriculture. They are directly or indirectly released into the atmosphere by spraying or volatilization processes. However, their heterogeneous reactivity toward OH radicals has not yet been well understood. Therefore, this work investigated the heterogeneous kinetics of the OH-initiated degradation of surface-bound fenthion and parathion using a flow reactor. The results showed that OH radicals played an important role in the atmospheric degradation of fenthion and parathion. Their average rate constants were (7.20 ± 0.77) × 10-12 and (10.40 ± 0.60) × 10-12 cm3/(mol· sec) at a relative humidity (RH) and temperature of 35% and 20 °C, respectively, suggesting that they have relatively short lifetimes in the atmosphere. In addition, a negative RH dependence and a positive temperature dependence of the rate constants were observed. The Arrhenius expressions of fenthion and parathion were k2 = (1.34 ± 0.48) × 10-9exp[-(1432.59 ± 105.29)/T] and k2 = (1.96 ± 1.38) × 10-9exp[-(1619.98 ± 222.02)/T], respectively, and their overall activation energy was estimated to be (11.88 ± 0.87) and (13.48 ± 1.83) kJ/mol. The experimental results will update the kinetic data of fenthion and parathion in the atmosphere and be helpful to further understand their atmospheric transportation processes.

Exploring HONO formation and its role in driving secondary pollutants formation during winter in the North China Plain.

Daytime HONO photolysis is an important source of atmospheric hydroxyl radicals (OH). Knowledge of HONO formation chemistry under typical haze conditions, however, is still limited. In the Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain in 2018, we investigated the wintertime HONO formation and its atmospheric implications at a rural site Gucheng. Three different episodes based on atmospheric aerosol loading levels were classified: clean periods (CPs), moderately polluted periods (MPPs) and severely polluted periods (SPPs). Correlation analysis revealed that HONO formation via heterogeneous conversion of NO2 was more efficient on aerosol surfaces than on ground, highlighting the important role of aerosols in promoting HONO formation. Daytime HONO budget analysis indicated a large missing source (with an average production rate of 0.66 ± 0.26, 0.97 ± 0.47 and 1.45 ± 0.55 ppbV/hr for CPs, MPPs and SPPs, respectively), which strongly correlated with photo-enhanced reactions (NO2 heterogeneous reaction and particulate nitrate photolysis). Average OH formation derived from HONO photolysis reached up to (0.92 ± 0.71), (1.75 ± 1.26) and (1.82 ± 1.47) ppbV/hr in CPs, MPPs and SPPs respectively, much higher than that from O3 photolysis (i.e., (0.004 ± 0.004), (0.006 ± 0.007) and (0.0035 ± 0.0034) ppbV/hr). Such high OH production rates could markedly regulate the atmospheric oxidation capacity and hence promote the formation of secondary aerosols and pollutants.

Theoretical insights into the degradation mechanisms, kinetics and eco-toxicity of oxcarbazepine initiated by OH radicals in aqueous environments.

As an anticonvulsant, oxcarbazepine (OXC) has attracted considerable attention for its potential threat to aquatic organisms. Density functional theory has been used to study the mechanisms and kinetics of OXC degradation initiated by OH radicals in aqueous environment. A total of fourteen OH-addition pathways were investigated, and the addition to the C8 position of the right benzene ring was the most vulnerable pathway, resulting in the intermediate IM8. The H-abstraction reactions initiated by OH radicals were also explored, where the extraction site of the methylene group (C14) on the seven-member carbon heterocyclic ring was found to be the optimal path. The calculations show that the total rate constant of OXC with OH radicals is 9.47 × 109 (mol/L)-1sec-1, and the half-life time is 7.32 s at 298 K with the [·OH] of 10-11 mol/L. Moreover, the branch ratio values revealed that OH-addition (89.58%) shows more advantageous than H-abstraction (10.42%). To further understand the potential eco-toxicity of OXC and its transformation products to aquatic organisms, acute toxicity and chronic toxicity were evaluated using ECOSAR software. The toxicity assessment revealed that most degradation products such as OXC-2OH, OXC-4OH, OXC-1O-1OOH, and OXC-1OH' are innoxious to fish and daphnia. Conversely, green algae are more sensitive to these compounds. This study can provide an extensive investigation into the degradation of OXC by OH radicals and enrich the understanding of the aquatic oxidation processes of pharmaceuticals and personal care products (PPCPs).

The transformation mechanism and eco-toxicity evaluation of butylated hydroxyanisole in environment.

Butylated hydroxyanisole (BHA) is one of important phenolic antioxidants and its fate in the environment has attracted much attention in recent years. In this study, the initial reactions of BHA with OH radicals, including 8 abstraction reactions and 6 addition reactions, were calculated. The lowest energy barrier of 3.20 kcal mol-1 was found from the abstraction reaction on phenolic hydroxyl group. The reaction barriers of addition paths are in the range of 5.48-9.28 kcal mol-1, which are lower than those of the abstraction paths. The reaction rate constants were calculated by using transition state theory, and the rate constants are 8.12 × 107 M-1 s-1and 4.76 × 107 M-1 s-1 for the H-abstraction and OH-addition reactions, respectively. Through the calculation of the subsequent reactions of the abs-H0-TS1 and add-C4-M1 it was found that BHA would be further transformed into 2-tert-Butyl-1,4-benzoquinone (TBQ), tert-butylhydroquinone (TBHQ) etc. in the aqueous phase, and the eco-toxicities of these transformed products of BHA in the aqueous phase were significantly increased comparing with that of the BHA and they are toxic to aquatic organism.

Production of O Radicals from Cavitation Bubbles under Ultrasound.

In the present review, the production of O radicals (oxygen atoms) in acoustic cavitation is focused. According to numerical simulations of chemical reactions inside a bubble using an ODE model which has been validated through studies of single-bubble sonochemistry, not only OH radicals but also appreciable amounts of O radicals are generated inside a heated bubble at the violent collapse by thermal dissociation of water vapor and oxygen molecules. The main oxidant created inside an air bubble is O radicals when the bubble temperature is above about 6500 K for a gaseous bubble. However, the concentration and lifetime of O radicals in the liquid water around the cavitation bubbles are unknown at present. Whether O radicals play some role in sonochemical reactions in the liquid phase, which are usually thought to be dominated by OH radicals and H2O2, should be studied in the future.

Formation mechanisms of nitrous acid (HONO) during the haze and non-haze periods in Beijing, China.

As an important precursor of hydroxyl radical (OH), nitrous acid (HONO) plays a significant role in atmospheric chemistry. Here, an observation of HONO and relevant air pollutants in an urban site of Beijing from 14 to 28 April, 2017 was performed. Two distinct peaks of HONO concentrations occurred during the observation. In contrast, the concentration of particulate matter in the first period (period Ⅰ) was significantly higher than that in the second period (period Ⅱ). Comparing to HONO sources in the two periods, we found that the direct vehicle emission was an essential source of the ambient HONO during both periods at night, especially in period Ⅱ. The heterogeneous reaction of NO2 was the dominant source in period Ⅰ, while the homogeneous reaction of NO with OH was more critical source at night in period Ⅱ. In the daytime, the heterogeneous reaction of NO2 was a significant source and was confirmed by the good correlation coefficients (R2) between the unknown sources (Punknown) with NO2, PM2.5, NO2 × PM2.5 in period Ⅰ. Moreover, when solar radiation and OH radicals were considered to explore unknown sources in the daytime, the enhanced correlation of Punknown with photolysis rate of NO2 and OH ( [Formula: see text]  × OH) were 0.93 in period Ⅰ, 0.95 in period Ⅱ. These excellent correlation coefficients suggested that the unknown sources released HONO highly related to the solar radiation and the variation of OH radicals.

Clean and effective removal of Cl(-I) from strongly acidic wastewater by PbO2.

Recycling strongly acidic wastewater as diluted H2SO4 after contaminants contained being removed was previously proposed, however, Cl(-I), a kind of contaminant contained in strongly acidic wastewater, is difficult to remove, which severely degrades the quality of recycled H2SO4. In this study, the removal of Cl(-I) using PbO2 was investigated and the involved mechanisms were explored. The removal efficiency of Cl(-I) reached 93.38% at 50℃ when PbO2/Cl(-I) mole ratio reached 2:1. The identification of reaction products shows that Cl(-I) was oxidized to Cl2, and PbO2 was reduced to PbSO4. Cl2 was absorbed by NaOH to form NaClO, which was used for the regeneration of PbO2 from the generated PbSO4. Cl(-I) was removed through two pathways, i.e., surface oxidation and •OH radical oxidation. •OH generated by the reaction of PbO2 and OH- plays an important role in Cl(-I) removal. The regenerated PbO2 had excellent performance to remove Cl(-I) after six-time regeneration. This study provided an in-depth understanding on the effective removal of Cl(-I) by the oxidation method.

Generation and Release of OH Radicals from the Reaction of H2 O with O2 over Soot.

OH radicals in the air maintain the oxidizing power of the troposphere. A conventional view is that particulate matter (PM) in the atmosphere is a major sink of OH radicals, thereby lowering the oxidizing power of atmosphere in the event of high-level PM. By contrary, our joint experimental/theoretical study reveals a new mechanism for the generation of gaseous OH radicals by carbonaceous soot particles. We show that water and O2 react on carbonaceous surfaces and give rise to gaseous OH radicals under irradiation. With ample delocalized π electrons, carbonaceous surfaces enable the easy desorption of hydroxyl groups to produce gaseous OH radicals, evidenced by direct observation of the steady generation of OH radicals on a carbonaceous surface. Our results reveal a new chemical mechanism for the production of OH radicals.

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals.

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600-1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.

Development of wastewater treatment system based on cascade dielectric barrier discharge plasma atomizers.

A novel design for a cascade dielectric barrier discharge (DBD) atomizer was applied for treating samples of water containing biological and organic contaminants. Several experimental investigations were conducted on artificial samples and real sample (digested sludge collected from a wastewater treatment plant, WWTP). The artificial water samples were prepared by using different concentrations of E. coli for biological samples, whereas acetic acid was used to prepare the organic samples. The biological samples were subjected to the plasma effect for different treatment periods, and the growth curves of E. coli were generated for 24 h after treatment. Moreover, the viable cells were counted after each treatment period and the change in E. coli morphology was monitored. The results showed that a significant reduction in the viable cell number, by 3 orders of magnitude, occurred for an artificial biological sample after only 5-min treatment. The treatment of organic samples for 10 min showed a significant reduction in the concentration of acetic acid by 50%. In consequence, treatment of real wastewater sample for 10 min resulted in more than 70% reduction in BOD5 and 30% reduction in COD.

Photoluminescence shift in frustules of two pennate diatoms and nanostructural changes to their pores.

The diatom silicified cell wall (frustule) contains pore arrays at the micro- to nanometer scale that display efficient luminescence within the visible spectrum. Morphometric analysis of the size and arrangement of pores was conducted to observe whether any correlation exists with the photoluminescence (PL) of two diatom species of different ages. UV-excited PL displays four clearly defined peaks within the blue-region spectrum, on top of the broad PL characteristic of synthetic porous silicon dioxide, recorded for reference and where discrete lines are absent. A set of shifted emission lines was observed when diatom cultures reached adulthood. These discrete line shifts correlate with structural changes observed in adult frustules: reduction in pore diameter; appearance of pores within pores, 10 nm in size; an increase in the gap distance between stria; and the deposition of several girdle bands with a concomitant increase in the diatom waist length, as well as the appearance of pores on such bands. Destruction of the pores results in the disappearance of all discrete emission lines. The PL shifts are correlated with a substantial increment of Si-OH groups adsorbed on the frustule surface, as revealed by Fourier transform infrared spectroscopy.