Archean phosphorus recycling facilitated by ultraviolet radiation.

Of the six elements incorporated into the major polymers of life, phosphorus is the least abundant on a global scale [E. Anders, M. Ebihara, Geochim. Cosmochim. Acta 46, 2363-2380 (1982)] and has been described as the "ultimate limiting nutrient" [T. Tyrrell, Nature 400, 525-531 (1999)]. In the modern ocean, the supply of dissolved phosphorus is predominantly sustained by the oxidative remineralization/recycling of organic phosphorus in seawater. However, in the Archean Eon (4 to 2.5 Ga), surface waters were anoxic and reducing. Here, we conducted photochemical experiments to test whether photodegradation of ubiquitous dissolved organic phosphorus could facilitate phosphorus recycling under the simulated Archean conditions. Our results strongly suggest that organic phosphorus compounds, which were produced by marine biota (e.g., adenosine monophosphate and phosphatidylserine) or delivered by meteorites (e.g., methyl phosphonate) can undergo rapid photodegradation and release inorganic phosphate into solution under anoxic conditions. Our experimental results and theoretical calculations indicate that photodegradation of organic phosphorus could have been a significant source of bioavailable phosphorus in the early ocean and would have fueled primary production during the Archean eon.

Upconversion Phosphor-Driven Photodegradation of Plastics.

Plastic waste poses a profound threat to ecosystems and human health, necessitating novel strategies for effective degradation in nature. Here, we present a novel approach utilizing upconversion phosphors as additives to significantly accelerate plastic photodegradation in nature via enhancing ultraviolet (UV) radiation. Pr-doped Li2CaGeO4 (LCGO:Pr) upconversion phosphors readily converting blue light into deep-UV radiation, dramatically improve photodegradation rates for polyethylene (PE) and polyethylene terephthalate (PET) microplastics. In situ spectroscopic studies show that upconversion fluorescence initiates the photophysical cleavage of C-C and C-O bonds in the backbones of PE and PET, resulting in plastic degradation. Moreover, incorporating LCGO:Pr into polypropylene (PP) sheets realizes markedly enhanced photodamage, with the cracking area increasing by nearly 38-fold under simulated sunlight for 10 days. This underscores the potential of employing this approach for the construction of light-driven destructible polymers. Further optimization and exploration of material compatibility hold promise for developing sustainable photodegradable plastics.

Accelerated Solar-Driven Polyolefin Degradation via Self-Activated Hydroxy-Rich ZnIn2S4.

Degradation of polyolefin (PE) plastic by a traditional chemical method requires a high pressure and a high temperature but generates complex products. Here, sulfur vacancy-rich ZnIn2S4 and hydroxy-rich ZnIn2S4 were rationally fabricated to realize photocatalytic degradation of PE in an aqueous solution under mild conditions. The results reveal that the optimized photocatalyst could degrade PE into CO2 and CO, and PE had a weight loss of 84.5% after reaction for 60 h. Systematic experiments confirm that the synergetic effect of hydroxyl groups and S vacancies contributes to improve the photocatalytic degradation properties of plastic wastes. In-depth investigation illustrates that the active radicals attack (h+ and •OH) weak spots (C-H and C-C bonds) of the PE chain to form CO2, which is further selectively photoreduced to CO. Multimodule synergistic tandem catalysis can further improve the utilization value of plastic wastes; for example, product CO2/CO in the plastic degradation process can be converted in situ into HCOOH by coupling with electrocatalytic technology.

Full-Spectrum Utilization of ZIF-67/Ag NPs/NaYF4:Yb,Er Photocatalysts for Efficient Degradation of Sulfadiazine: Upconversion Mechanism and DFT Calculation.

In this work, novel ternary composite ZIF-67/Ag NPs/NaYF4:Yb,Er is synthesized by solvothermal method. The photocatalytic activity of the composite is evaluated by sulfadiazine (SDZ) degradation under simulated sunlight. High elimination efficiency of the composite is 95.4% in 180 min with good reusability and stability. The active species (h+, ·O2 - and ·OH) are identified. The attack sites and degradation process of SDZ are deeply investigated based on theoretical calculation and liquid chromatography-mass spectrometry analysis. The upconversion mechanism study shows that favorable photocatalytic effectiveness is attributed to the full utilization of sunlight through the energy transfer upconversion process and fluorescence resonance energy transfer. Additionally, the composite is endowed with outstanding light-absorbing qualities and effective photogenerated electron-hole pair separation thanks to the localized surface plasmon resonance effect of Ag nanoparticles. This work can motivate further design of novel photocatalysts with upconversion luminescence performance, which are applied to the removal of sulphonamide antibiotics in the environment.

Gd3+ Encapsulation on 2D-g-C3N4 Nanostructure for Spintronics and Ultrasound Assisted Photocatalytic Applications: First-Principles and Experimental Studies.

Atomically thin two-dimensional (2D) semiconductors have high potential in optoelectronics and magneto-optics appliances due to their tunable band structures and physicochemical stability. The work demonstrates that Gd3+ incorporated 2D-g-C3N4 nanosheet (Gd3+/2D-g-C3N4 NS) is synthesized through chemisorption methodology for defect enrichment. The material characterizations reveal that the ion decoration enhances the surface area and defect concentration of the 2D sheet. The experimental observations have been further corroborated with the help of density functional theory (DFT) simulation. Spin asymmetry polarizations near the Fermi level, obtained through the partial density of states (PDOS) analyses, reveal the magnetic nature of the synthesized material, validating the room temperature ferromagnetism obtained through a vibrating-sample magnetometer (VSM). Gd3+/2D-g-C3N4 NS shows significant enhancement in saturation magnetization (Ms) experimentally and computationally compared to the pristine one. The magnetic catalyst shows 98% remediation efficiency for ultrasound-assisted visible-light-driven photodegradation of methyl orange (MO). The synergistic approach of liquid chromatography-mass spectrometry (LC-MS) analyses and DFT studies elucidates reaction intermediates and unveils the degradation mechanism. Post-characterization studies assure the stability of the magnetic catalyst through optical, chemical, magnetic, and microscopic analyses. So, the synthesized material can be proficiently used as a magnetic nanocatalyst in wastewater treatments and spin-electronics applications.

Near UV and Visible Light Photodegradation in Solid Formulations: Generation of Carbon Dioxide Radical Anions from Citrate Buffer and Fe(III).

Near UV and visible light photodegradation can target therapeutic proteins during manufacturing and storage. While the underlying photodegradation pathways are frequently not well-understood, one important aspect of consideration is the formulation, specifically the formulation buffer. Citrate is a common buffer for biopharmaceutical formulations, which can complex with transition metals, such as Fe(III). In an aqueous solution, the exposure of such complexes to light leads to the formation of the carbon dioxide radical anion (•CO2-), a powerful reductant. However, few studies have characterized such processes in solid formulations. Here, we show that solid citrate formulations containing Fe(III) lead to the photochemical formation of •CO2-, identified through DMPO spin trapping and HPLC-MS/MS analysis. Factors such as buffers, the availability of oxygen, excipients, and manufacturing processes of solid formulations were evaluated for their effect on the formation of •CO2- and other radicals such as •OH.

Near UV Photodegradation Mechanisms of Amino Acid Excipients: Formation of the Carbon Dioxide Radical Anion from Aspartate and Fe(III).

Carbon dioxide radical anion (•CO2-) is a powerful reducing agent that can reduce protein disulfide bonds and convert molecular oxygen to superoxide. Therefore, the generation of •CO2- can be detrimental to pharmaceutical formulations. Iron is among the most prevalent impurities in formulations, where Fe(III) chelates of histidine (His) can produce •CO2- upon exposure to near-UV light (Zhang and Schöneich, Eur. J. Pharm. Biopharm. 2023, 190, 231-241). Here, we monitor by spin-trapping in combination with electron paramagnetic resonance spectroscopy and/or high-performance liquid chromatography-mass spectrometry analysis the photochemical formation of •CO2- for a series of common amino acid excipients, including arginine (Arg), methionine (Met), proline (Pro), glutamic acid (Glu), glycine (Gly), aspartic acid (Asp), and lysine (Lys). Our results indicate that in the presence of Fe(III), Asp, and Glu produce significant yields of •CO2- under photoirradiation with near-UV light. Notably, Asp demonstrates the highest efficiency of •CO2- generation compared with that of the other amino acid excipients. Stable isotope labeling indicates that •CO2- exclusively originates from the α-carboxyl group of Asp. Mechanistic studies reveal two possible pathways for •CO2- formation, which involve either a ß-carboxyl radical or an amino radical cation intermediate.

Near UV and Visible Light-Induced Degradation of Bovine Serum Albumin and a Monoclonal Antibody Mediated by Citrate Buffer and Fe(III): Reduction vs Oxidation Pathways.

Light exposure during manufacturing, storage, and administration can lead to the photodegradation of therapeutic proteins. This photodegradation can be promoted by pharmaceutical buffers or impurities. Our laboratory has previously demonstrated that citrate-Fe(III) complexes generate the •CO2- radical anion when photoirradiated under near UV (λ = 320-400 nm) and visible light (λ = 400-800 nm) [Subelzu, N.; Schöneich, C. Mol. Pharmaceutics 2020, 17 (11), 4163-4179; Zhang, Y. Mol. Pharmaceutics 2022, 19 (11), 4026-4042]. Here, we evaluated the impact of citrate-Fe(III) on the photostability and degradation mechanisms of disulfide-containing proteins (bovine serum albumin (BSA) and NISTmAb) under pharmaceutically relevant conditions. We monitored and localized competitive disulfide reduction and protein oxidation by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis depending on the reaction conditions. These competitive pathways were affected by multiple factors, including light dose, Fe(III) concentration, protein concentration, the presence of oxygen, and light intensity.

Photodegradation of tylosin tartrate by advanced oxidation processes.

Tylosin tartrate, a macrolide antibiotic, is one of a class of emerging contaminants that have been detected in natural bodies of water since they are not easily removed by conventional treatment processes. In this study, the direct and indirect photodegradation of tylosin tartrate was analyzed to understand the role of reactive oxygen species and organic matter that may be present in surface waters. While direct photolysis caused negligible degradation (k = (9.4 ± 1.8) × 10-5 s-1), the addition of 0.4 M hydrogen peroxide (k = (2.18 ± 0.01) × 10-4 s-1) or usage of the photo-Fenton process (k = (2.96 ± 0.02) × 10-4 s-1) resulted in greater degradation. The degradation was maximized by combining tylosin tartrate with an experimentally determined optimal concentration of humic acid (15 mg/L), which readily produced singlet oxygen and increased the overall degradation (k = 1.31 ± 0.05) × 10-3 s-1) by means of indirect photolysis. Absolute pseudo-first-order bimolecular reaction rate constants for tylosin tartrate were measured with singlet oxygen [(4.7936 ± 0.0001) × 105 M-1 s-1] and hydroxyl radical [(5.2693 ± 0.0002) × 109 M-1 s-1] using competition kinetics, and when combined with data on concentration of the reactive oxygen species, showed that the hydroxyl radical makes a contribution to the degradation that is approximately eleven orders of magnitude greater than singlet oxygen.

Cellulose acetate membranes loaded with WO3/g-C3N4: a synergistic approach for effective photocatalysis.

The objective of this study is to develop an efficient, easily recoverable membrane-based photocatalyst for removing organic pollutants from aqueous solutions. This study documents the effective synthesis of a novel composite photocatalyst comprising WO3/g-C3N4(WCN) loaded onto cellulose acetate (CA). The physicochemical properties of the synthesized nanocomposites were validated using a range of techniques, including Fourier transform infrared spectroscopy, x-ray diffraction, scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy, and UV-visible diffuse reflectance spectroscopy. SEM analysis revealed that the WCN particles exhibited a well-decorated arrangement on the CA surface in the form of spherical particles. The successfully synthesized film was utilized as a potential adsorbent for removing organic pollutants such as Rhodamine B (Rh-B) and Methylene blue (MB) from aqueous solutions under UV light illumination. The results showcased the significant potential of the WCN@CA nanocomposite, achieving a remarkable 83% and 85% efficiency in eliminating Rh-B and MB. The pseudo-first-order kinetic models were found to be appropriate for both dye adsorption onto the WCN@CA nanocomposite. The WCN@CA catalyst, capable of being reused five times without significant loss of efficiency, shows great potential for decomposing toxic organic pollutants. The novelty of this work lies in the innovative combination of WCN with CA, resulting in a highly efficient and reusable photocatalyst for environmental remediation.

Bovine Serum Albumin Bends Over Backward to Interact with Aged Plastics: A Model for Understanding Protein Attachment to Plastic Debris.

Plastic pollution, a major environmental crisis, has a variety of consequences for various organisms within aquatic systems. Beyond the direct toxicity, plastic pollution has the potential to absorb biological toxins and invasive microbial species. To better understand the capability of environmental plastic debris to adsorb these species, we investigated the binding of the model protein bovine serum albumin (BSA) to polyethylene (PE) films at various stages of photodegradation. Circular dichroism and fluorescence studies revealed that BSA undergoes structural rearrangement to accommodate changes to the polymer's surface characteristics (i.e., crystallinity and oxidation state) that occur as the result of photodegradation. To understand how protein structure may inform docking of whole organisms, we studied biofilm formation of bacteriaShewanella oneidensison the photodegraded PE. Interestingly, biofilms preferentially formed on the photodegraded PE that correlated with the state of weathering that induced the most significant structural rearrangement of BSA. Taken together, our work suggests that there are optimal physical and chemical properties of photodegraded polymers that predict which plastic debris will carry biochemical or microbial hitchhikers.

Dissolved Black Carbon Facilitates the Photodegradation of Microplastics via Molecular Weight-Dependent Generation of Reactive Intermediates.

Photodegradation of microplastics (MPs) induced by sunlight plays a crucial role in determining their transport, fate, and impacts in aquatic environments. Dissolved black carbon (DBC), originating from pyrolyzed carbon, can potentially mediate the photodegradation of MPs owing to its potent photosensitization capacity. This study examined the impact of pyrolyzed wood derived DBC (5 mg C/L) on the photodegradation of polystyrene (PS) MPs in aquatic solutions under UV radiation. It revealed that the photodegradation of PS MPs primarily occurred at the benzene ring rather than the aliphatic segments due to the fast attack of hydroxyl radical (•OH) and singlet oxygen (1O2) on the benzene ring. The photosensitivity of DBC accelerated the degradation of PS MPs, primarily attributed to the increased production of •OH, 1O2, and triplet-excited state DBC (3DBC*). Notably, DBC-mediated photodegradation was related to its molecular weight (MW) and chemical properties. Low MW DBC (<3 kDa) containing more carbonyl groups generated more •OH and 1O2, accelerating the photodegradation of MPs. Nevertheless, higher aromatic phenols in high MW DBC (>30 kDa) scavenged •OH and generated more O2•-, inhibiting the photodegradation of MPs. Overall, this study offered valuable insights into UV-induced photodegradation of MPs and highlighted potential impacts of DBC on the transformation of MPs.

Role of Direct and Sensitized Photolysis in the Photomineralization of Dissolved Organic Matter and Model Chromophores to Carbon Dioxide.

This study addresses the fundamental processes that drive the photomineralization of dissolved organic matter (DOM) to carbon dioxide (CO2), deconvoluting the role of direct and sensitized photolysis. Here, a suite of DOM isolates and model compounds were exposed to simulated sunlight in the presence of various physical and chemical quenchers to assess the magnitude, rate, and extent of direct and sensitized photomineralization to CO2. Results suggest that CO2 formation occurs in a biphasic kinetic system, with fast production occurring within the first 3 h, followed by slower production thereafter. Notably, phenol model chromophores were the highest CO2 formers and, when conjugated with carboxylic functional groups, exhibited a high efficiency for CO2 formation relative to absorbed light. Simple polycarboxylated aromatic compounds included in this study were shown to be resistant to photomineralization. Quencher results suggest that direct photolysis and excited triplet state sensitization may be largely responsible for CO2 photoproduction in DOM, while singlet oxygen and hydroxyl radical sensitization may play a limited role. After 3 h of irradiation, the CO2 formation rate significantly decreased, and the role of sensitized reactions in CO2 formation increased. Together, the results from this study advance the understanding of the fundamental reactions driving DOM photomineralization to CO2, which is an important part of the global carbon cycle.

Laboratory-Simulated Photoirradiation Reveals Strong Resistance of Primary Macroplastics to Weathering.

The photodegradation of macroplastics in the marine environment remains poorly understood. Here, we investigated the weathering of commercially available plastics (tabs 1.3 × 4.4 × 0.16 cm), including high-density polyethylene, low-density polyethylene, polypropylene, polystyrene, and polycarbonate, in seawater under laboratory-simulated ultraviolet A radiation for 3-9 months, equivalent to 25-75 years of natural sunlight exposure without considering other confounding factors. After the exposure, the physical integrity and thermal stability of the tabs remained relatively intact, suggesting that the bulk polymer chains were not severely altered despite strong irradiation, likely due to their low specific surface area. In contrast, the surface layer (∼1 µm) of the tabs was highly oxidized and eroded after 9 months of accelerated weathering. Several antioxidant additives were identified in the plastics through low temperature pyrolysis coupled with gas chromatography/mass spectrometry (Pyr-GC/MS) analysis. The Pyr-GC/MS results also revealed many new oxygen-containing compounds formed during photodegradation, and these compounds indicated the dominance of chain scission reactions during weathering. These findings highlight the strong resistance of industrial macroplastics to weathering, emphasizing the need for a broader range of plastics with varying properties and sizes to accurately estimate plastic degradation in the marine environment.

Heterogeneous Photodegradation Behavior of Liquid Crystal Monomers in Dust: Quantitative Structure-Activity Relationship and Product Identification.

The heterogeneous photodegradation behavior of liquid crystal monomers (LCMs) in standard dust (standard reference material, SRM 2583) and environmental dust was investigated. The measured photodegradation ratios for 23 LCMs in SRM and environmental dust in 12 h were 11.1 ± 1.8 to 23.2 ± 1.1% and 8.7 ± 0.5 to 24.0 ± 2.8%, respectively. The degradation behavior of different LCM compounds varied depending on their structural properties. A quantitative structure-activity relationship model for predicting the degradation ratio of LCMs in SRM dust was established, which revealed that the molecular descriptors related to molecular polarizability, electronegativity, and molecular mass were closely associated with LCMs' photodegradation. The photodegradation products of the LCM compound 4'-propoxy-4-biphenylcarbonitrile (PBIPHCN) in dust, including •OH oxidation, C-O bond cleavage, and ring-opening products, were identified by nontarget analysis, and the corresponding degradation pathways were suggested. Some of the identified products, such as 4'-hydroxyethoxy-4-biphenylcarbonitrile, showed predicted toxicity (with an oral rat lethal dose of 50%) comparable to that of PBIPHCN. The half-lives of the studied LCMs in SRM dust were estimated at 32.2-82.5 h by fitting an exponential decay curve to the observed photodegradation data. The photodegradation mechanisms of LCMs in dust were revealed for the first time, enhancing the understanding of LCMs' environmental behavior and risks.

Single-Particle Analysis of the Photodegradation of Submicron Polystyrene Particles Using Infrared Photothermal Heterodyne Imaging.

Sunlight irradiation is the predominant process for degrading plastics in the environment, but our current understanding of the degradation of smaller, submicron (<1000 nm) particles is limited due to prior analytical constraints. We used infrared photothermal heterodyne imaging (IR-PHI) to simultaneously analyze the chemical and morphological changes of single polystyrene (PS) particles (∼1000 nm) when exposed to ultraviolet (UV) irradiation (λ = 250-400 nm). Within 6 h of irradiation, infrared bands associated with the backbone of PS decreased, accompanied by a reduction in the particle size. Concurrently, the formation of several spectral features due to photooxidation was attributed to ketones, carboxylic acids, aldehydes, esters, and lactones. Spectral outcomes were used to present an updated reaction scheme for the photodegradation of PS. After 36 h, the average particle size was reduced to 478 ± 158 nm. The rates of size decrease and carbonyl band area increase were -24 ± 3.0 nm h-1 and 2.1 ± 0.6 cm-1 h-1, respectively. Using the size-related rate, we estimated that under peak terrestrial sunlight conditions, it would take less than 500 h for a 1000 nm PS particle to degrade to 1 nm.

Reactive Oxygen Species Generated in Situ During Carbamazepine Photodegradation at 222 nm Far-UVC: Unexpected Role of H2O Molecules.

When 222 nm far-UVC is used to drive AOPs, photolysis emerges as a critical pathway for the degradation of numerous organic micropollutants (OMPs). However, the photodegradation mechanisms of the asymmetrically polarized OMPs at 222 nm remain unclear, potentially posing a knowledge barrier to the applications of far-UVC. This study selected carbamazepine (CBZ), a prevalent aquatic antiepileptic drug that degrades negligibly at 254 nm, to investigate its photodegradation mechanisms at 222 nm. Accelerated CBZ treatment by 222 nm far-UVC was mainly attributed to in situ ROS generation via self-sensitized photodegradation of CBZ. By quenching experiments and EPR tests, •OH radicals were identified as the major contributor to the CBZ photodegradation, whereas O2•- played a minor role. By deoxygenation and solvent exchange experiments, the H2O molecules were demonstrated to play a crucial role in deactivating the excited singlet state of CBZ (1CBZ*) at 222 nm: generating •OH radicals via electron transfer interactions with 1CBZ*. In addition, 1CBZ* could also undergo a photoionization process. The transformation products and pathways of CBZ at 222 nm were proposed, and the toxicities of CBZ's products were predicted. These findings provide valuable insights into OMPs' photolysis with 222 nm far-UVC, revealing more mechanistic details for far-UVC-driven systems.

High-Resolution Mass Spectrometry Combined with Reactive Oxygen Species Reveals Differences in Photoreactivity of Dissolved Organic Matter from Microplastic Sources in Aqueous Environments.

Microplastics (MPs)-derived dissolved organic matter (MPs-DOM) is becoming a non-negligible source of DOM pools in aquatic systems, but there is limited understanding about the photoreactivity of different MPs-DOM. Herein, MPs-DOM from polystyrene (PS), polyethylene terephthalate (PET), poly(butylene adipate-co-terephthalate) (PBAT), PE, and polypropylene (PP), representing aromatic, biodegradable, and aliphatic plastics, were prepared to examine their photoreactivity. Spectral and high-resolution mass spectrometry analyses revealed that PS/PET/PBAT-DOM contained more unsaturated aromatic components, whereas PE/PP-DOM was richer in saturated aliphatic components. Photodegradation experiments observed that unsaturated aromatic molecules were prone to be degraded compared to saturated aliphatic molecules, leading to a higher degradation of PS/PET/PBAT-DOM than PE/PP-DOM. PS/PET/PBAT-DOM was mainly degraded by hydroxyl (•OH) via attacking unsaturated aromatic structures, whereas PE/PP-DOM by singlet oxygen (1O2) through oxidizing aliphatic side chains. The [•OH]ss was 1.21-1.60 × 10-4 M in PS/PET/PBAT-DOM and 0.97-1.14 × 10-4 M in PE/PP-DOM, while the [1O2]ss was 0.90-1.35 × 10-12 and 0.33-0.44 × 10-12 M, respectively. This contributes to the stronger photoreactivity of PS/PET/PBAT-DOM with a higher unsaturated aromatic degree than PE/PP-DOM. The photodegradation of MPs-DOM reflected a decreasing tendency from aromatic-unsaturated molecules to aliphatic-saturated molecules. Special attention should be paid to the photoreactivity and environmental impacts associated with MPs-DOM containing highly unsaturated aromatic compounds.

Effect of Dissolved Organic Matter on the Photodegradation of Decachlorobiphenyl (PCB-209) in Heterogeneous Systems: Experimental Analysis and Excited-State Theory Calculations.

Dissolved organic matter (DOM) can affect the transformation of pollutants through photosensitization, but most current research focuses on hydrophilic pollutants, making it such that less attention is paid to hydrophobic pollutants. In this paper, the effect and action mechanism of coexisting DOM on the photodegradation of decachlorobiphenyl (PCB-209) on suspended particles collected from the Yellow River were systematically investigated in a heterogeneous system using DOM standards and model compounds. Through molecular probe experiments, mass spectrometry analysis and theoretical calculations, we found that the excited triplet state of DOM (3DOM*) could excite PCB-209 to undergo dechlorination reaction. Due to the different modes of electron transition, the presence of carbonyl groups decreased the energy of 3DOM*, whereas the electron-donating groups made the energy of 3DOM* higher. DOM containing phenolic hydroxyl groups led to a higher steady-state concentration of •OH, and DOM containing phenyl ketone structures had a stronger ability to produce •O2-. Compared with aqueous •OH, •O2- produced from hydrophobic microregions could react more readily with PCB-209. This study deepens the understanding of the role of different functional groups of DOM in the photosensitized transformation of hydrophobic compounds.

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.