OH Production Research Articles

Multifunctional Nanoparticles for Enhanced Chemodynamic/Photodynamic Therapy through a Photothermal, H2O2-Elevation, and GSH-Consumption Strategy.

Chemodynamic therapy (CDT) has witnessed significant advancements in recent years due to its specific properties. Its association with photodynamic therapy (PDT) has also garnered increased attention due to its mutually reinforcing effects. However, achieving further enhancement of the CDT/PDT efficacy remains a major challenge. In this study, we have developed an integrated nanosystem comprising a Fenton catalyst and multifunctional photosensitizers to achieve triply enhanced CDT/PDT through photothermal effects, H2O2 elevation, and GSH consumption. We prepared nano-ZIF-8 vesicles as carriers to encapsulate ferrocene-(phenylboronic acid pinacol ester) conjugates (Fc-BE) and photosensitizers IR825. Subsequently, cinnamaldehyde-modified hyaluronic acid (HA-CA) was coated onto ZIF-8 through metal coordination interactions, resulting in the formation of active targeting nanoparticles (NPs@Fc-BE&IR825). Upon cellular internalization mediated by CD44 receptors, HA-CA elevated H2O2 levels, while released Fc-BE consumed GSH and catalyzed H2O2 to generate highly cytotoxic hydroxyl radicals (·OH). Furthermore, NIR irradiation led to increased ·OH production and the generation of singlet oxygen (1O2), accompanied by a greater GSH consumption. This accelerated and strengthened amplification of oxidative stress can be harnessed to develop highly effective CDT/PDT nanoagents.

Radical chemistry and ozone production at a UK coastal receptor site

Abstract. OH, HO2, total and partially speciated RO2, and OH reactivity (kOH′) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6–17 × 106, 0.75–4.2 × 108 and 2.3–8.0 × 108 molec. cm−3, respectively. kOH′ ranged from 1.7 to 17.6 s−1, with a median value of 4.7 s−1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW–SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW–SE air in the afternoon by a factor of ∼ 2–3, although slightly better agreement was found for HO2 in SW air (factor of ∼ 1.4–2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW–SE and SW air by factors of ∼ 8–9 on average. Measured radical and kOH′ levels and measurement–model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and kOH′ was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW–SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW–SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW–SE air by ∼ 35 %, whereas agreement (∼ 15 %) was found within instrumental uncertainty (∼ 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

Fluctuating redox conditions accelerate the electron storage and transfer in magnetite and production of dark hydroxyl radicals

Magnetite (Fe3O4), known as a geo-battery that can store and transfer electrons, often co-occurs with sulfide in subsurface environments with fluctuating redox conditions. However, little is known about how fluctuating redox conditions (e.g., sulfidation-oxidation) affect the electron storage and transfer in Fe3O4 that was associated with the production of dark hydroxyl radicals (⋅OH) and the oxidation of dissolved organic matter (DOM). This study revealed that Fe3O4 sulfidated by sulfide (S-Fe3O4) at neutral pH exhibited higher ⋅OH production upon oxygenation than Fe3O4, in which the cumulative ⋅OH concentration increased with increasing initial S/Fe ratio (≤ 0.50), sulfidation duration and number of sulfidation-oxidation cycle. X-ray photoelectron spectroscopy and wet-chemical analyses of Fe and S species of S-Fe3O4 showed that sulfidation enables electron storage in Fe3O4 by increasing both structural and surface Fe(II). Sulfide was converted into S0, acid volatile sulfur (AVS), and chromium-reducible sulfur (CRS) during Fe3O4 sulfidation. S-Fe3O4 with lower AVS/CRS ratio exhibited higher reactivity to produce ⋅OH, indicating the important role of CRS in transferring electrons from Fe(II) to O2. Based on quenching experiments and electron paramagnetic resonance analysis, a one-step two-electron transfer mechanism was proposed for O2 reduction during S-Fe3O4 oxygenation, and surface-bound rather than free ⋅OH were identified as the primary reactive oxygen species. The ⋅OH from S-Fe3O4 oxygenation was shown to be efficient in degradation of DOM. Overall, these results suggested that sulfidation-oxidation can accelerate the electron storage and transfer in Fe3O4 for dark ⋅OH production, having an important impact on the carbon cycling in subsurface environments.

Selective ozone catalyzation modulated by surface and bulk oxygen vacancies over MnO2 for superior water purification

The regulation behavior of oxygen vacancies (Vo) at different spatial positions (surface or bulk) in catalysts for selective O3 catalyzation, along with the reaction pathways evolution was well-investigated in α-MnO2−x/O3 systems. Combined characterization methods, systematic organic removal experiments, structure-activity relationship analysis, and theoretical calculations were employed to unveil O3 decomposition and electron transfer behaviors regulated by surface or bulk Vo. The contribution of electron transfer process (ETP) to atrazine (ATZ) removal was reinforced from 5.2 % to 34.8 % with the formation of bulk Vo, and Vo-rich α-MnO2−x-2/O3 system achieved ∼96.5 % ATZ removal along with improved TOC mineralization (∼38 % vs. ∼20 %). Surface Vo facilitated O3 adsorption, promoting its decomposition into •OH, while bulk Vo not only accelerated •OH production but also withdrew electrons from organics to build ETP. This study shed light on precise modification of metal-based catalysts with Vo to modulate •OH/ETP synergistic processes in catalytic ozonation for efficient water purification.

The significant contribution of nitrate to a severe haze event in the winter of Guangzhou, China

A severe haze pollution occurred in Guangzhou from January 14 to 16, 2021, during which the mass concentration of PM2.5 ranged from 76 to 243 μg m−3. This level of pollution was rarely observed in recent years considering the improved air quality in Guangzhou. Therefore, it is crucial to comprehensively study the formation mechanisms of this severe haze pollution to prevent its reoccurrence. During the haze period, the concentrations of NO and NO2 sharply increased by 7.4 and 3.8 times, respectively, and total volatile organic compounds (TVOCs) increased 7 times, suggesting enhanced primary emissions from vehicles due to stagnant meteorological conditions. Nitrate concentration (43 ± 20 μg m−3) increased 6.7 times and became the dominant species in PM2.5 during the haze period. Notably, gaseous NH3, HONO and HNO3 also exhibited a sharp increase, suggesting the important role of nitrate chemistry in the evolution of haze pollution. The simulation results from chemical box model revealed that the OH + NO2 reaction was the dominant formation pathway for nitrate production (82 %) during the haze period. The net production rate of ROx radicals (including OH, HO2 and RO2) was 4.4 times higher during the haze period (5.8 ppb h−1) compared to the pre-haze period (1.3 ppb h−1). This was mainly attributed to the enhanced HONO and OVOCs photolysis, which increased from 0.6 ppb h−1 to 3.1 ppb h−1 and 0.4 ppb h−1 to 2.1 ppb h−1, respectively. Furthermore, the sensitivity tests demonstrated the reductions in VOCs and NOx were both beneficial for controlling nitrate production by influencing OH production and N2O5 uptake rate. These findings provide insights into the formation mechanisms of nitrate production during severe haze pollution and suggest that joint mitigation of PM2.5 and O3 can be achieved through the control of VOCs emission.

Anchoring bimetallic PtAu nanoparticles on hierarchical zeolite as efficient electrocatalyst for the enhancement of ethanol electrooxidation

Zeolite materials as nanoreactor are promising candidates as catalysts for the oxidation of alcohol fuels. In the present work, the hierarchical zeolite was prepared via a hydrothermal technique. Then, the bimetallic Pt-Au-zeolite composite as electrocatalysts were synthesized by co-precipitation route. The surface morphology, composition and structure of the resulting composite were investigated by FE-SEM, EDS, XRD, XPS, BET&BJH and FT-IR. The catalytic performance of the composite has been examined in ethanol electrooxidation reactions under alkaline media. Pt-Au-zeolite exhibits superior selectivity for the electrooxidation of the ethanol, outperforming both conventional Au and Pt nanoparticles supported on zeolite crystals catalyst. The peak electrooxidation current of ethanol with Pt-Au-zeolite catalyst is 3.63 times that of Pt-zeolite with a scan rate of 50 mVs−1, which is due to the synergistic effect of Au and Pt in zeolite framework. It could be attributed to the incorporation of Au and Pt into zeolite framework, which was beneficial to the charge transferring the surface of Pt-Au-zeolite electrocatalyst and facilitated the ethanol oxidation. Besides, the significant electrochemical activity can be due to the production of OH–, which leads to the species present on the surface of the electrocatalysts during the activation process that controlled by the zeolite framework.

Ignition enhancement and NOx formation of NH3/air mixtures by non-equilibrium plasma discharge

This work computationally studies plasma assisted low temperature NH3/air ignition and NOx formation in a repetitively-pulsed nanosecond discharge at atmospheric pressure by using an experimentally-validated plasma-combustion kinetic model. The results show that plasma discharge significantly enhances low temperature NH3 ignition. Compared with thermal ignition, the ignition delay time is shortened by 2–5 orders of magnitude due to the kinetic enhancement of excited species and radicals. The radicals (NH2, NH, H and O) produced through electron impact dissociation and quenching of electronically excited N2*, O(1D) and N(2D) promote OH production and further accelerate NH3 oxidation. The results show that there exists a non-monotonic dependence of ignition delay time on the reduced electric field strength. The optimum ignition enhancement is achieved at 250 Td at which the production of electronically excited species and radicals is most efficient. The vibrationally excited species produced at lower electric fields (<100 Td) are less effective in enhancing ignition because they only induce gas heating through the fast vibrational-translational relaxation by NH3 and H2O. At a higher electric field, although the efficient production of NH2, NH, H, O and OH by plasma creates new low temperature reaction pathways in enhancing low temperature NH3 ignition, the ignition is inhibited through NH + NO = N2O + H and chain-termination reaction NH2 + HO2 = NH3 + O2. The ignition delay times at different equivalence ratios show that the ignition enhancement by plasma is more effective at fuel-lean conditions due to the faster generation of N2(B), O(1D) and O from air, leading to accelerated NH3 oxidation via O(1D) + NH3→ NH2 + OH, NH3 + O = NH2 + OH and NH2 + O = NH + OH. The sensitivity analysis shows that the reactions involving O and O(1D) production are more effective on NH3 ignition enhancement than the fuel dissociation by electrons. Moreover, the ignition is also enhanced by NOx formation in plasma via reactions NH2 + NO = NNH + OH and NO + HO2 = NO2 + OH. This work advances the understanding of non-equilibrium excitation and NOx formation by plasma discharge on low temperature NH3 ignition.

Redox property of coordinated iron ion enables activation of O2 via in-situ generated H2O2 and additionally added H2O2 in EDTA-chelated Fenton reaction

The Fenton system was a generation system of reactive oxygen species via the chain reactions, which employed H2O2 and O2 as radical precursors and Fe2+/Fe3+ as electron-donor/acceptor for triggering or terminating the generation of radicals. Recent work mainly emphasized the Fe2+- activated H2O2 and the application of in-situ generated •OH, while neglecting other side-reactions. In this work, EDTA (Ethylene diamine tetraacetic acid) was employed as a chelating agent of iron ions, which simultaneously changed the redox property of coordinated iron. The Fe2+-EDTA complexes in the presence of dissolved oxygen enabled the two-electron transfer from Fe2+ to O2 and the in-situ production of H2O2, which further activate H2O2 for yielding •OH. Meanwhile, coordinated Fe3+ exhibited non-negligible reactivity toward H2O2, which was higher than that of free Fe3+ in the traditional Fenton system. The complexation of EDTA with Fe3+ could enhance the Fe2+ generation reaction by the H2O2, accompanied by the O2•− formation. The enhancement of O2•− formation and Fe2+-EDTA regeneration induced the subsequent H2O2 activation by Fe2+-EDTA, thus accelerating the Fe3+-EDTA/Fe2+-EDTA cycle for simultaneously producing O2•− and •OH. To sum up, the EDTA-chelated Fenton system extended the applicable pH range to circumneutral/alkaline level and tuned the redox property of coordinated iron for diversifying the •OH production routes. The research reinterpreted the chain reactions in the Fenton system, revealing another way to enhance the radical production or other property of the Fenton/Fenton-like system.

Using compound-specific isotope analysis to identify the mechanism of acetochlor degradation during oxygenation of hyporheic zone sediment

Biodegradation is recognized as the main pathway for acetochlor attenuation in aquatic environments. However, the potential abiotic degradation of acetochlor by hydroxyl radicals (•OH) generated during oxygenation of hyporheic zone sediments has not been investigated. This study aims to examine the production of •OH during oxygenation of hyporheic zone sediments and its effects on acetochlor attenuation. A significant decrease of acetochlor, ranging from 77.9% to 100%, was observed in the water-sediment systems with extensive •OH production. The primary sources of •OH production were found to be the oxidation of Fe(II) and reduced humic acids. Furthermore, a •OH quenching experiment suggests that •OH driven oxidation is the dominant pathway for acetochlor attenuation. Carbon isotope fractionation of acetochlor degradation during oxygenation of sediments (εbulk,C ranged from −1.5‰ to −0.5 ± 0.3‰) was close to that during acetochlor degradation by •OH in a H2O2–Fe3O4 Fenton system (εbulk,C = −0.5 ± 0.1‰), but significantly smaller than that during acetochlor biodegradation (εbulk,C = −5.8 ± 0.9‰). Compound-specific isotope analysis (CSIA) further suggests that •OH produced by sediment oxygenation plays a critical role in acetochlor attenuation in aquatic environments. Results of calculated apparent kinetic isotope effect of carbon (AKIEC) and transformation products indicate that SN1 and SN2-type nucleophilic substitution are the first steps in acetochlor attenuation through •OH driven oxidation (AKIEC = 1.007 ± 0.001) and aerobic biodegradation (AKIEC = 1.088 ± 0.013), respectively. Our findings highlight the potential of CSIA to assess the acetochlor degradation in water-sediment system, which can help to elucidate the fate of herbicide in aquatic environments.

Accelerated Photolysis of H2O2 at the Air-Water Interface of a Microdroplet.

Photochemical homolysis of hydrogen peroxide (H2O2) occurs widely in nature and is a key source of hydroxyl radicals (·OH). The kinetics of H2O2 photolysis play a pivotal role in determining the efficiency of ·OH production, which is currently mainly investigated in bulk systems. Here, we report considerably accelerated H2O2 photolysis at the air-water interface of microdroplets, with a rate 1.9 × 103 times faster than that in bulk water. Our simulations show that due to the trans quasiplanar conformational preference of H2O2 at the air-water interface compared to the bulk or gas phase, the absorption peak in the spectrum of H2O2 is significantly redshifted by 45 nm, corresponding to greater absorbance of photons in the sunlight spectrum and faster photolysis of H2O2. This discovery has great potential to solve current problems associated with ·OH-centered heterogeneous photochemical processes in aerosols. For instance, we show that accelerated H2O2 photolysis in microdroplets could lead to markedly enhanced oxidation of SO2 and volatile organic compounds.

Enhanced degradation of refractory organics in ORR-EO system with a blue TiO2 nanotube array modified Ti-based Ni-Sb co-doped SnO2 anode

Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.

Bimetallic Au–Pd nanoparticles decorated electrospun spinel CoFe2O4 nanostructures as efficient electrocatalysts for ethanol fuel oxidation in alkaline media

Spinel-based materials are promising candidates as electro-catalysts for the oxidation of alcohol fuels. In the present study, electrospun CoFe2O4 spinel nanostructures were prepared by electrospinning technique and the subsequent thermal treatment processes. Then, the bimetallic Au–Pd–CoFe2O4 composite as electro-catalysts were synthesized by precipitation method. The surface morphology, composition and structure of the resulting composite nanostructures were studied by FE-SEM, EDS, TEM, XPS, XRD and FT-IR. The catalytic performance of resultant composite has been examined in ethanol electro-oxidation reactions under alkaline conditions. The effect of different Au:Pd ratios on the electrocatalytic performance of Au–Pd–CoFe2O4 composite nanostructures for ethanol oxidation was evaluated. The synthesized composite Au–Pd–CoFe2O4 (APCo22) illustrates a superior ethanol oxidation activity in comparison to other electrocalysts, and the peak current of this spinel-type electro-catalysts is 9.89 times that of Pd–CoFe2O4 with a scan rate of 50 mVs−1, which is due to the synergistic effect of Au and Pd on CoFe2O4. Furthermore, the remarkable electrochemical property can be due to the production of OH−, which leads to the species present on the surface of the electro-catalysts during the activation process.

Influence of natural cellulose on hydroxyl radical generation by abiotic oxidation of pyrite under acidic conditions

Natural cellulose is one of the most important substances coexisting on the surface of pyrite. Oxidation of pyrite produces hydroxyl radicals (•OH). In this study, a pyrite-cellulose binary system was constructed with natural cellulose to investigate the effect of cellulose on the mechanism of •OH generation via oxidation of pyrite, and the mechanism for abiotic oxidative •OH production by pyrite under the influence of cellulose was investigated with oxidation and quenching experiments and characterization techniques. It was demonstrated that cellulose was chemisorbed onto the pyrite surface and some of the Fe(II) on the pyrite surface was masked, thus inhibiting the reaction between pyrite and O2 and decreasing the •OH production level from 33.54 to 22.48 μM under oxic conditions. In addition, the cellulose caused SS bond breakage, resulting in defects on the pyrite surface, which oxidized H2O to produce •OH in anoxic conditions. Therefore, under anoxic conditions, cellulose promoted the production of •OH and increased the •OH content from 11.85 to 14.78 μM. In addition to •OH, pyrite oxidation also produced SO42−. The amount of SO42− produced by a single pyrite crystal was less than that produced in the pyrite-cellulose system in all cases, and the amount produced under oxic conditions was approximately 10 times greater than that produced under anoxic conditions. More sulfate production indicated more sulfur intermediates during the reaction, such as S2O32−, which may decompose to produce S0 or Sn2− adsorbed on pyrite and decrease the amount of •OH produced. During the oxidation of pyrite by H2O2, cellulose competed with pyrite to react with H2O2, which inhibited the reaction between pyrite and H2O2 and decreased •OH production. Therefore, natural cellulose influenced the abiotic oxidation of pyrite to produce •OH.

Efficient electrocatalytic H2O2 activation over nitrogen-doped carbon encapsulated Co3O4 for drinking water disinfection

Waterborne diseases claim a million lives each year in areas without adequate centralized water treatment. Electrocatalytic •OH production presents a promising avenue for decentralized water disinfection. However, existing catalysts are limited by low activity at neutral pH and the risk of metal leaching. We have developed a chainmail catalyst, N-doped carbon (NC) encapsulated Co3O4 (NC@Co3O4), for efficient electrocatalytic H2O2 activation. Co3O4 extracts electrons from NC, thus enhancing the affinity of O atom of H2O2 at the electron deficient carbon sites in NC and promoting the cleavage of O−O bonds. Consequently, the •OH generation rate catalyzed by NC@Co3O4 was 6.5 times of that by NC. Integrating the NC@Co3O4 into a flow-through electrochemical reactor as cathode, a voltage of only 2 V drove the device to achieve more than 6.8 logs (99.99998 %) of Escherichia coli inactivation in tap water. This work provides an energy-efficient, green, and safe solution for decentralized water disinfection.

An experimental and detailed kinetic modeling study of the auto-ignition of NH3/diesel mixtures: Part 2- Wide pressures up to 120bar

Ammonia (NH3) blending combustion strategy has been regarded as a high-efficient form of NH3 utilization. To understand the high-pressure gas-phase auto-ignition characteristics of NH3 blending with diesel, the ignition delay times of NH3/diesel mixtures with high NH3 energy fractions of 70%, 80% and 90% were measured in an ultrahigh-pressure rapid compression machine, at high pressures of 50–120 bar, temperatures of 755–996 K, and equivalence ratios of 0.5–1.5. As a consecutive study of Part 1 (Combust. Flame, 251 (2023), 112391), this study mainly focuses on the auto-ignition characteristics and oxidation mechanism of NH3/diesel mixtures at pressures higher than 50 bar. The ignition-promoting effect of increasing pressure from 50 to 120 bar was experimentally confirmed. Moreover, the increase of the diesel energy fraction, equivalence ratio, and oxygen concentration was found to decrease the ignition delay time of the NH3/diesel mixtures. The chemical reaction mechanism proposed in Part 1 was utilized to simulate the auto-ignition of the NH3/diesel mixtures. Simulation results show that the mechanism was able to quantitatively capture the ignition delay times of the NH3/diesel mixtures at the wide pressures. The cross-reactions between NH3 and diesel, especially reaction RH + NH2 = R + NH3, was found to play a key role in the correct prediction of auto-ignition at high pressure. In addition, it is revealed the effect of pressure is closely related to OH production reactions 2OH (+M) = H2O2 (+M) and NO + HO2 = NO2 + OH, the rate of which increase with rising pressure. The reaction H2NO + O2 = HNO + HO2 is an important pathway where oxygen concentration affects NH3/diesel mixture auto-ignition.

Dynamic Production of Hydroxyl Radicals during the Flooding-Drainage Process of Paddy Soil: An In Situ Column Study.

Frequent cycles of flooding and drainage in paddy soils lead to the reductive dissolution of iron (Fe) minerals and the reoxidation of Fe(II) species, all while generating a robust and consistent output of reactive oxygen species (ROS). In this study, we present a comprehensive assessment of the temporal and spatial variations in Fe species and ROS during the flooding-drainage process in a representative paddy soil. Our laboratory column experiments showed that a decrease in dissolved O2 concentration led to rapid Fe reduction below the water-soil interface, and aqueous Fe(II) was transformed into solid Fe(II) phases over an extended flooding time. As a result, the •OH production capacity of liquid phases was reduced while that of solid phases improved. The •OH production capacity of solid phases increased from 227-271 μmol kg-1 (within 1-11 cm depth) to 500-577 to 499-902 μmol kg-1 after 50 day, 3 month, and 1 year incubation, respectively. During drainage, dynamic •OH production was triggered by O2 consumption and Fe(II) oxidation. ROS-trapping film and in situ capture revealed that the soil surface was the active zone for intense H2O2 and •OH production, while limited ROS production was observed in the deeper soil layers (>5 cm) due to the limited oxygen penetration. These findings provide more insights into the complex interplay between dynamic Fe cycling and ROS production in the redox transition zones of paddy fields.

Synergistic effect triggered by Fe2O3 and oxygen-induced hydroxyl radical enhances formation of amino-phenolic humic-like substance

Metal oxides play a promising role in the transformation of polyphenols and amino acids involved in naturally occurring humification. The objective of this study was to explore the synergistic interactions between Fe2O3 and O2 in the formation of humic substances under a controlled O2 atmosphere (0%, 21% and 40% O2 levels). The results indicate that an O2 level of 21% with Fe2O3 was optimal for humic acid (HA) production. Hydroxyl radicals (∙OH) formed and promoted the formation of HA in the presence of O2, and O2 improved the enhancing capacity of Fe2O3 by oxidizing Fe(II) to Fe(III). Moreover, the combination of these processes resulted in a synergistic improvement in humification. The evolution of functional groups in HA suggested that O2 promoted the formation of oxygen-containing groups such as lipids, and Fe2O3 was conducive to the formation of dark-coloured polymers during the darkening process of humification. Furthermore, the O2 level of 40% inhibited the formation of HA by reducing the transformation from Fe(III) to Fe(II). The XRD results showed few changes in the composition of Fe2O3 before and after humification, which indicated that Fe2O3 was a catalyst and an oxidant. The heterospectral UV–Vis/FTIR results suggested that ∙OH attacked phenolic rings to form the aromatic ring skeleton of HA and benefit the ring-opening copolymerization of humic precursors. In addition, structural equation modelling demonstrated that dissolved Fe was the key parameter affecting the HA yield. These findings provide new insights into the synergism of O2-mediated ∙OH production associated with metal oxide-facilitated humification.

Numerical investigation of sonochemical production in a single bubble under dual-frequency acoustic excitation

A numerical computation study about sonochemical activity of an oxygen bubble oscillations in a dual-frequency acoustic field is presented in this paper. The variation of excitation frequency causes the change of magnitude and duration of pressure acting on the bubble, affecting the instantaneous bubble radius, internal bubble temperature as well as chemical reactions. The numerical results indicate the formation of O2, HO2 •, •OH, H•, O, H2 and H2O2 in an O2 bubble during oscillations. The main oxidant is •OH radical. The influence of several parameters (e.g. couples of frequencies, the total pressure amplitude and the ratio of pressure amplitudes of the two waves) on the molar yields of free radicals is analyzed. There is an optimum bubble collapse temperature (around 5648 K) for the •OH production. Moreover, the corresponding frequency intervals of enhanced effect and weakened effect under different coupled frequencies (i.e. 40, 140, 213, 355 and 515 kHz) are also investigated.

Indoor Air Quality Implications of Germicidal 222 nm Light.

One strategy for mitigating the indoor transmission of airborne pathogens, including the SARS-CoV-2 virus, is irradiation by germicidal UV light (GUV). A particularly promising approach is 222 nm light from KrCl excimer lamps (GUV222); this inactivates airborne pathogens and is thought to be relatively safe for human skin and eye exposure. However, the impact of GUV222 on the composition of indoor air has received little experimental study. Here, we conduct laboratory experiments in a 150 L Teflon chamber to examine the formation of secondary species by GUV222. We show that GUV222 generates ozone (O3) and hydroxyl radicals (OH), both of which can react with volatile organic compounds to form oxidized volatile organic compounds and secondary organic aerosol particles. Results are consistent with a box model based on the known photochemistry. We use this model to simulate GUV222 irradiation under more realistic indoor air scenarios and demonstrate that under some conditions, GUV222 irradiation can lead to levels of O3, OH, and secondary organic products that are substantially elevated relative to normal indoor conditions. The results suggest that GUV222 should be used at low intensities and in concert with ventilation, decreasing levels of airborne pathogens while mitigating the formation of air pollutants.

Insight into the relationship between the photostability and molecular structure of rhodamine dyes

It is still challenging to clarify the intrinsic relationship between the photostability and molecular structures of rhodamine dyes. Herein, we investigated the photostability of three rhodamine dyes RhB, Rh101, and Rh101-ME in water and 20%EtOH–H2O solutions under 525 nm LED light irradiation. The photostability of RhB is much higher than that of Rh 101 and Rh101-ME, indicating that forming rigid ring between the N-linked alkyl and xanthene can significantly decrease the photostability of rhodamine dyes, while the esterification of carboxyl on benzene ring can improve their photostability. The EPR analyses and radical trapping experiments proved that 1O2 is the most important reactive oxygen species responsible for dye degradation, and the Rh101 and Rh101-ME have higher 1O2 and •OH production rates than RhB. The cyclic voltammetry tests showed that forming rigid ring between the N-linked alkyls and xanthene can decrease the oxidation potential of RhB and consequently lower down its photostability. The theoretical calculations disclosed that the higher HOMO energy levels in ground states and lower singlet–triplet energy gaps of Rh101 and Rh101-ME are the main factor that results in their lower photostability when compared with RhB.