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Plasmonic nanoparticles (NPs) hold considerable potential as photocatalysts owing to their robust light-matter interactions across diverse electromagnetic wavelengths, which significantly influence the photophysical characteristics of the adjacent molecular entities. Despite the widespread use of noble-metal NPs in surface-enhanced Raman scattering (SERS) applications, little is known about the kinetics of nanoparticle aggregation and how it affects their configurations. This study investigates the plasmon-driven photochemical conversion of 4-nitrobenzenethiol (NBT) to 4,4'-dimercaptoazobenzene (DMAB) on Au and Ag nanorods (NRs) through SERS. Significantly, photoconversion phenomena were observed on Ag NRs but not on Au NRs upon laser excitation at 633 nm. Finite-difference time-domain simulations revealed the presence of stronger electromagnetic fields on Ag NRs than on Au NRs. The aspect ratios and gaps between individual NPs in dimer configurations were determined to elucidate their effects on electromagnetic fields. The Ag NR dimer with an end-to-end configuration, an aspect ratio of 3.3, and a 1-nm gap exhibited the highest enhancement factor of 1.05 × 1012. Our results demonstrate that the primary contribution from diverse configurations in NR aggregates is the end-to-end configuration. The proposed NP design with adjustable parameters is expected to advance research in plasmonics, sensing, and wireless communications. These findings also contribute to the understanding of plasmon-driven photochemical processes in metallic nanostructures.

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A novel system for measuring net photochemical ozone production rates in the atmosphere based on cavity ring-down spectroscopy (OPR-CRDS) was developed. The system consists of two chambers (a reaction chamber and a reference chamber) and a dual-channel Ox-CRDS detector. To minimize the wall loss of Ox in the chambers, the inner surfaces of both chambers are coated with Teflon film. The performance of the OPR-CRDS system was characterized. It was found that even though the photolysis frequency (J value) decreased by 10%, the decrease in the P(O3) caused by the ultraviolet-blocking film coating was less than 3%. The two chambers had a good consistency in the mean residence time and the measurement of NO2 and Ox under the condition of no sunlight. The detection limit of the OPR-CRDS was determined to be 0.20 ppbv/hr. To further verify the accuracy of the system, the direct measurement values of the OPR-CRDS system were compared with the calculation results based on radical (OH, HO2, and RO2) reactions, and a good correlation was obtained between the measured and calculated values. Finally, the developed instrument was applied to obtain the comprehensive field observations at an urban site in the Yangtze River Delta (China) for 40 days, the time series and change characteristics of the P(O3) were obtained directly, and the good environmental adaptability and stability of the OPR-CRDS system were demonstrated. It is expected that the new instrument will be beneficial to investigations of the relationship between P(O3) and its precursors.

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Coastal dunes are characterised by strong gradients of abiotic stress, typically increasing in severity from inland areas towards the shoreline. Thus, dune gradients represent unique opportunities to study intraspecific responses to environmental changes and to investigate which factors drive community change. This study aims to examine functional trait variation in two coexisting species in response to environmental changes along a dune gradient in NW Spain. Trait convergence was also investigated and compared between both ends of the gradient. We measured functional leaf traits related to plant efficiency in the use of light, water and nutrients, also possible stressors (salt content and pH) and availability of limiting resources (water and nutrients) in the soil. Most soil variables showed changes following a non-directional gradient. Differences in soil variables were site specific and depended on growth of the study species. Structural and functional traits depended on species and/or plant position on the gradient, except for effective quantum yield of PSII and leaf δ15N. The pattern of variation was mostly directional for reflectance indices related to leaf physiology. Multivariate analyses showed significant interspecific differences in the set of traits they exhibited along positions in the gradient. Species also differed in the combination of traits selected under given environmental conditions. Coexisting species display a specific set of traits that reflects different strategies to environmental stress. Our study highlights the overly simplistic nature of some previous studies that assume dune gradients are monotonically directional, without considering that these gradients may be differentially modified by species activity.

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Correlating damage outcomes to a retinal laser exposure is critical for diagnosis and choosing appropriate treatment modalities. Therefore, it is important to understand the causal relationships between laser parameters, such as wavelength, power density, and length of exposure, and any resulting injury. Differentiating photothermal from photochemical processes in an in vitro retinal model using cultured retinal pigment epithelial cells would be a first step in achieving this goal. The first-order rate constant of Arrhenius has been used for decades to approximate cellular thermal damage. A modification of this equation, called the damage integral (Ω), has been used extensively to predict the accumulation of laser damage from photothermal inactivation of critical cellular proteins. Damage from photochemical processes is less well studied and most models have not been verified because they require quantification of one or more uncharacterized chemical species. Additionally, few reports on photochemical damage report temperature history, measured or simulated. We used simulated threshold temperatures from a previous in vitro study to distinguish between photothermal and photochemical processes. Assuming purely photochemical processes also inactivate critical cellular proteins, we report the use of a photothermal Ω and a photochemical Ω that work in tandem to indicate overall damage accumulation. The combined damage integral (ΩCDI) applies a mathematical switch designed to describe photochemical damage relative to wavelength and rate of photon delivery. Although only tested in an in vitro model, this approach may transition to predict damage at the mammalian retina.

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Femtosecond transient absorption spectroscopy was used to study the dynamics of the excited primary electron donor in the reaction centers of the purple bacterium Rhodobacter sphaeroides. Using global analysis and the interval method, we found a correlation between the vibrational coherence damping of the excited primary electron donor and the lifetime of the charge-separated state P+BA-, indicating the reversibility of electron transfer to the primary electron acceptor, the BA molecule. In the reaction centers, the signs of superposition of two electronic states of P were found for a delay time of less than 200 fs. It is suggested that the admixture value of the charge transfer state PA+PB- with the excited primary electron donor P* is about 24%. The results obtained are discussed in terms of the two-step electron transfer mechanism.

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Antibiotics are currently recognized as environmental pollutants. In this work, the methods involved in the degradation of a ß-lactam antibiotic (i.e., DXC) by treatments based on inorganic peroxides and UVC (e.g., UVC alone, UV-C/H2O2, UVC/peroxymonosulfate, and UVC/peroxydisulfate) are presented. The methodology of computational calculations to obtain frontier orbitals and Fukui indices for DXC, and elucidate the reactive moieties on the target substance is also shown. Finally, the direct oxidation by peroxides and UV-C/H2O2 action to treat DXC in simulated pharmaceutical wastewater are depicted. The chromatographic and theoretical analyses allowed for determining the degrading performance of inorganic peroxides and UVC-based treatments toward the target pollutant in aqueous samples.•Treatments based on inorganic peroxides and UVC as useful methods for degrading the ß-lactam antibiotic dicloxacillin.•Persulfates and UV-C/H2O2 showed high degrading action on the target pharmaceutical.•Methodologies based on theoretical calculations for the identification of reactive moieties on the DXC susceptible to radical attacks are presented.

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The escalating contamination caused by lead ions (Pb2⁺) and its harmful effects on all life forms has raised global concerns. Certain microalgae thrive in metal mining sites characterized by low pH and high concentrations of Pb2⁺, which are usually prohibitive for many microorganisms. Little is known about the mechanisms underlying the adaptation of such microalgae to these hostile conditions. In this study, we elucidated the adaptive strategies of the green microalga Micractinium belenophorum strain AUMW, isolated from a lead mining site, and its application for the removal of Pb+2. Results revealed that strain AUMW can efficiently tolerate up to 200 ppm of Pb+2 in an F/2 medium. Further experimental variables were optimized through response surface methodology (RSM), and 99.6 % removal of Pb2⁺ was achieved. Novel adaptive responses of strain AUMW to high levels of Pb2⁺ include: (i) activation of metal-protective response by modulation of quantum yield (F v /F m ) and non-photochemical quenching (NPQ) of photosystem II; (ii) extracellular silicification encapsulated cells of strain AUMW and altered cell morphology from oval to hexagonal; (iii) silicification prevented intracellular translocation of Pb+2; (iv) silicification boosted adsorption of Pb+2, thus enhanced its removal. This study offers new insights into the protective role of silicification in green microalgae and its potential for the removal of metals from metal-polluted sites, waste from energy storage battery industries, and spent batteries. It also provides a solid base to explore the genetic and metabolic pathways involved in the adaptation of strain AUMW to elevated levels of Pb+2.

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Acid mine drainage (AMD) raises a global environmental concern impacting the iron cycle. Although the formation of Fe(III) minerals in AMD-impacted waters has previously been reported to be regulated by biological processes, the role of abiotic processes remains largely unknown. This study first reported that a photochemical reaction coupled with O2 significantly accelerated the formation of Fe(III) flocculates (i.e., schwertmannite) in the AMD, as evidenced by the comparison of samples from contaminated sites across different natural conditions at latitudes 24-29° N. Combined with experimental and modeling results, it is further discovered that the intramolecular oxidation of photogenerated Fe(II) with a five-coordinative pyramidal configuration (i.e., [(H2O)5Fe]2+) by O2 was the key in enhancing the photooxidation of Fe(II) in the simulated AMD. The in situ attenuated total reflectance-Fourier transform infrared spectrometry (ATR-FTIR), UV-vis spectroscopy, solvent substitution, and quantum yield analyses indicated that, acting as a precursor for flocculation, [(H2O)5Fe]2+ likely originated from both the dissolved and colloidal forms of Fe(III) through homogeneous and surface ligand-to-metal charge transfers. Density functional theory calculations and X-ray absorption spectroscopy results further suggested that the specific oxidation pathways of Fe(II) produced the highly reactive iron species and triggered the hydrolysis and formation of transient dihydroxo dimers. The proposed new pathways of Fe cycle are crucial in controlling the mobility of heavy metal anions in acidic waters and enhance the understanding of complicated iron biochemistry that is related to the fate of contaminants and nutrients.

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In this study, a self-healing epoxy asphalt material was developed by incorporating coumarin groups. This material achieved microcrack self-repair under UV irradiation at 50 °C. Fluorescence microscopy observations and mechanical performance tests demonstrated significant advantages in crack filling and mechanical property recovery after repair, with the fracture toughness of the repaired epoxy asphalt reaching 69% of that in its original state. Furthermore, the synergistic effect of temperature and UV irradiation in the self-healing process enhanced the material's durability and service life. This research offers new insights and methods for developing more durable and long-lasting self-healing asphalt materials, showcasing the great potential of smart materials in infrastructure applications.

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In many regions, nitrogen (N) deficiency limits pepper cultivation, presenting significant cultivation challenges. This study investigates the impact of N deficiency and silicon (Si) supplementation on physiological responses and antioxidant modulation in pepper plants, focusing particularly on the homeostasis of carbon (C), nitrogen, and phosphorus (P), and their effects on growth and biomass production. Conducted in a factorial design, the experiment examined pepper plants under conditions of N sufficiency and deficiency, with and without Si supplementation (0.0 mM and 2.0 mM). Results showed that N deficiency sensitizes pepper plants, leading to increased electrolyte leakage (39.59%) and disrupted C, N, and P homeostasis. This disruption manifests as reductions in photosynthetic pigments (-64.53%), photochemical efficiency (-14.92%), and the synthesis of key metabolites such as total free amino acids (-86.97%), sucrose (-53.88%), and soluble sugars (-39.96%), ultimately impairing plant growth. However, Si supplementation was found to alleviate these stresses. It modulated the antioxidant system, enhanced the synthesis of ascorbic acid (+30.23), phenolic compounds (+33.19%), and flavonoids (+7.52%), and reduced cellular electrolyte leakage (-25.02%). Moreover, Si helped establish a new homeostasis of C, N, and P, optimizing photosynthetic and nutritional efficiency by improving the utilization of C (+17.46%) and N (+13.20%). These Si-induced modifications in plant physiology led to increased synthesis of amino acids (+362.20%), soluble sugars (+51.34%), and sucrose (77.42%), thereby supporting enhanced growth of pepper plants. These findings elucidate the multifaceted biological roles of Si in mitigating N deficiency effects, offering valuable insights for more sustainable horticultural practices.

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Dearomative cycloadditions offer rapid access to complex 3D molecular architectures, commonly via a sp2-to-sp3 rehybridization of two atoms of an aromatic ring. Here we report that the 6e π-system of a benzenoid aromatic pendant could be exhaustively depleted within a single photochemical cascade. An implementation of this approach involves the initial dearomative [4+2] cycloaddition of the Exited State Intramolecular Proton Transfer (ESIPT)-generated azaxylylene, followed by two consecutive [2+2] cycloadditions of auxiliary π moieties strategically positioned in the photoprecursor. Such photochemical cascade fully dearomatizes the benzenoid aromatic ring, saturating all six sp2 atoms to yield a complex sp3-rich scaffold with high control of its 3D molecular shape, rendering it a robust platform for rapid systematic mapping of underexplored chemical space. Significant growth of molecular complexity - starting with a modular synthesis of photoprecursors from readily available building blocks - is quantified by Böttcher score calculations.

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-Action potential (AP) of excitable plant cells is an important signaling event that can differentially alter physicochemical and physiological processes in various parts of the same cell. In giant cells of characean algae, the AP propagation has minor effect on photosynthetic electron transport in areas with high activity of plasmalemmal H+-pump but inhibits linear electron flow in regions featuring high passive H+/OH- conductance of the plasma membrane (PM). Uneven spatial distributions of local periplasmic and cytoplasmic pH facilitate the operation of distinct (CO2-dependent and O2-mediated) pathways of photoinduced electron flow, which presumably accounts for differential influence of AP on photosynthesis. The excitation of Chara australis cell in the presence of methyl viologen (MV), a redox mediator with the prooxidant action, provides a convenient model system to clarify the influence of voltage-dependent ion fluxes across PM on photosynthetic activity of chloroplasts. This study shows that permeation of MV to their target sites in chloroplasts is restricted by PM in resting cells, but MV easily passes through ionic channels opened during the PM depolarization. This gated permeation of MV gives rise to strong non-photochemical quenching, decrease in the effective quantum yield of linear electron flow, apparent O2 uptake, and, finally, the enhanced ROS production, as detected by the fluorescent probe dichlorofluorescein. Taken together, the results indicate that the AP generation in the presence of MV acts as trigger for instant redirection of photosynthetic linear electron flow from CO2-dependent route to the path of O2 reduction with the eventual formation of H2O2 as a dominant and most stable ROS form.

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Microplastics, particularly microfibers (MFs), pose a significant threat to the environment. Despite their widespread presence, the photochemical reactivity, weathering products, and environmental fate of MFs remain poorly understood. To address this knowledge gap, photodegradation experiments were conducted on three prevalent MFs: polyester (POL), nylon (NYL), and acrylic (ACR), to elucidate their degradation pathways, changes in surface morphology and polymer structure, and chemical and colloidal characterization of weathering products during photochemical degradation of MFs. The results showed that concentrations of dissolved organic carbon, chromophoric dissolved organic matter (DOM), and fluorescent components consistently increased during weathering, exhibiting a continuous release of DOM. Scanning electron microscopy and Raman spectroscopy revealed changes in the surface morphology and polymer spectra of the MFs. During the weathering experiments, DOM aromaticity (SUVA254) decreased, while spectral slope increased, indicating concurrent DOM release and degradation of aromatic components. The released DOM or nanoplastics were negatively charged with sizes between 128 and 374 nm. The production rate constants of DOM or the photochemical reactivity of MFs followed the order ACR > NYL ≥ POL, consistent with their differences in chemical structures. These findings provide an improved understanding of the photochemical reactivity, degradation pathways, weathering products, and environmental fate of microfibers in the environment.

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The global challenge of feeding an ever-increasing population to maintain food security requires novel approaches to increase crop yields. Photosynthesis, the fundamental energy and material basis for plant life on Earth, is highly responsive to environmental conditions. Evaluating the operational status of the photosynthetic mechanism provides insights into plants' capacity to adapt to their surroundings. Despite immense effort, photosynthesis still falls short of its theoretical maximum efficiency, indicating significant potential for improvement. In this review, we provide background information on the various genetic aspects of photosynthesis, explain its complexity, and survey relevant genetic engineering approaches employed to improve the efficiency of photosynthesis. We discuss the latest success stories of gene-editing tools like CRISPR-Cas9 and synthetic biology in achieving precise refinements in targeted photosynthesis pathways, such as the Calvin-Benson cycle, electron transport chain, and photorespiration. We also discuss the genetic markers crucial for mitigating the impact of rapidly changing environmental conditions, such as extreme temperatures or drought, on photosynthesis and growth. This review aims to pinpoint optimization opportunities for photosynthesis, discuss recent advancements, and address the challenges in improving this critical process, fostering a globally food-secure future through sustainable food crop production.

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Ozone (O3) pollution is a severe environmental problem in China. The incomplete understanding of atmospheric photochemical reaction mechanisms prevents us from accurately understanding the chemistry of O3 production. Here, we used an improved dual-channel reaction chamber technique to measure net photochemical O3 production rate (P(O3)net) directly in Dongguan, a typical industrial city in China. The maximum P(O3)net was 46.3 ppbv h-1 during the observation period, which is at a relatively high level compared to previous observations under different environment worldwide. We employed an observation-based box model coupled with the state-of-the-art atmospheric chemical mechanism (MCM v3.3.1) to investigate the chemistry of O3 production. Under the base scenario, the modelling underestimates P(O3)net by ~30 %. Additionally considering HO2 uptake by ambient aerosols, inorganic deposition, and Cl chemistry only caused a small change (< 13 %) in the simulation of P(O3)net. Further analysis indicates that unmeasured reactive volatile organic compounds (VOCs), such as oxygenated VOCs and branched alkenes are potential contributors to the underestimation of P(O3)net. This study underscores the underestimation of P(O3)net in conventional atmospheric modelling setups, providing a crucial scientific foundation for further investigation aimed at promoting our understanding of photochemical O3 formation.

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Temperature-dependent rate coefficients for the reactions of 2-methyl tetrahydrofuran (MTHF) with Cl atoms in the temperature range of 268-343 K at atmospheric pressure were measured using the relative-rate method. Ethylene and propane were used as reference compounds. Quantitative analysis of the post-photolysis reaction mixture was conducted using a gas chromatograph paired with a flame ionization detector (GC-FID). A gas chromatograph connected to a mass spectrometer (GC-MS) was employed for the purpose of qualitative analysis. In the experimental temperature range, the derived Arrhenius expression for the title reaction is represented by the equation k M T H F + C l Expt 268 - 343 K = ( 1.48 ± 0.13 ) × 10 - 12 × e x p 1474.51 ± 25.16 T cm3 molecule-1 s-1. In addition to our experimental findings, we conducted computational calculations employing the CCSD(T)//BHandHLYP/6-31 + G(d,p) level of theory to complement our study. The canonical transition state theory (CTST) was utilized to compute the rate coefficients at 250-400 K and 760 Torr. The Arrhenius expression for the theoretically calculated "k" values is found to be k M T H F + C l Theory 250 - 400 K = ( 1.51 ± 0.10 ) × 10 - 12 × e x p 1544.97 ± 22.14 T cm3 molecule-1 s-1. The local reactivity parameters, such as Fukui functions ( f r 0 ), local softness ( s r 0 ), and global softness ( S ) were also calculated theoretically to understand the site-specific reactivity trend of MTHF towards Cl atoms. The atmospheric implications, branching ratios, degradation mechanism, and feasibility of the reaction are discussed in this study.

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Accounting for the dynamic responses of photosynthesis and photoprotection to naturally fluctuating irradiance can improve predictions of plant performance in the field, but the variation of these dynamics within crop canopies is poorly understood. We conducted a detailed study of dynamic and steady-state photosynthesis, photoprotection, leaf pigmentation, and stomatal anatomy in four leaf layers (100, 150, 200 and 250 cm from the floor) of a fully-grown tomato canopy in the greenhouse. We found that leaves at the top of the canopy exhibited higher photosynthetic capacity and slightly faster photosynthetic induction compared to lower-canopy leaves, accompanied by higher stomatal conductance and a faster activation of carboxylation and linear electron transport capacities. In upper-canopy leaves, non-photochemical quenching showed faster induction and relaxation after in- and decreases in irradiance, allowing for more effective photoprotection in these leaves. Despite these observed differences in transient responses between leaf layers, steady-state rather than dynamic photosynthesis traits were more influential for predicting photosynthesis under fluctuating irradiance. Also, a model analysis revealed that time-averaged photosynthesis under fluctuating irradiance could be accurately predicted by one set of Rubisco activation/deactivation parameters across all four leaf layers, thereby greatly simplifying future modelling efforts of whole-canopy photosynthesis.

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A flow photochemical reaction system for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence was developed, which utilizes in situ-generated 2-benzopyrylium intermediates as the photoredox catalyst and electrophilic substrates. The key 2-benzopyrylium intermediates were generated in the flow reaction system through the intramolecular cyclization of ortho-carbonyl alkynylbenzene derivatives by the π-Lewis acidic metal catalyst AgNTf2 and the subsequent proto-demetalation with trifluoroacetic acid. The 2-benzopyrylium intermediates underwent further photoreactions with benzyltrimethylsilane derivatives as the donor molecule in the flow photoreactor to provide 1H-isochromene derivatives in higher yields in most cases than the batch reaction system.

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Given the prevalence of pyridine motifs in FDA-approved drugs, selective fluoroalkylation of pyridines and quinolines is essential for preparing diverse bioisosteres. However, conventional Minisci reactions often face challenges in achieving precise regioselectivity due to competing reaction sites of pyridine and the limited availability of fluoroalkyl radical sources. Herein, we present a light-driven, C4-selective fluoroalkylation of azines utilizing N-aminopyridinium salts and readily available sulfinates. Our approach employs electron donor-acceptor complexes, achieving highly C4-selective fluoroalkylation under mild conditions without an external photocatalyst. This practical method not only enables the installation of CF2H groups but also allows for the incorporation of CF2-alkyl groups with diverse functional entities, surpassing the limitations of previous methods. The versatility of the radical pathway is further demonstrated through straightforward three-component reactions involving alkenes and [1.1.1]propellane. Detailed experimental and computational studies have elucidated the origins of regioselectivity, providing profound insights into the mechanistic aspects.

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The surface photochemical activity of goethite, which occurs widely in surface soils and sediments, plays a crucial role in the environmental transformation of various pollutants and natural organic matter. This study systemically investigated the mechanism of different types of surface hydroxyl groups on goethite in generating reactive oxygen species (ROSs) and Fe(III) reduction under sunlight irradiation. Surface hydroxyl groups were found to induce photoreductive dissolution of Fe(III) at the goethite-water interface to produce Fe2+(aq), while promoting the production of ROSs. Substitution of the surface hydroxyl groups on goethite by fluoride significantly inhibited the photochemical activity of goethite, demonstrating their important role in photochemical activation of goethite. The results showed that the surface hydroxyl groups (especially the terminating hydroxyl groups, ≡FeOH) led to the formation of Fe(III)-hydroxyl complexes via ligand-metal charge transfer on the goethite surface upon photoexcitation, facilitating the production of Fe2+(aq) and •OH. The bridging hydroxyl groups (≡Fe2OH) were shown to mainly catalyze the production of H2O2, leading to the subsequent light-driven Fenton reaction to produce •OH. These findings provide important insights into the activation of molecular oxygen on the goethite surface driven by sunlight in the environment, and the corresponding degradation of anthropogenic and natural organic compounds caused by the generated ROSs.

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