Comments on "was hydrogen peroxide present before the arrival of oxygenic photosynthesis? The important role of iron(II) in the archean ocean".

Recent research has hypothesized that hydrogen peroxide (H2O2) may have emerged from abiotic geochemical processes during the Archean eon (4.0-2.5 Ga), stimulating the evolution of an enzymatic antioxidant system in early life. This eventually led to the evolution of cyanobacteria, and in turn, the accumulation of oxygen on Earth. In the latest issue of Redox Biology, Koppenol and Sies (vol. 29, no. 103012, 2024) argued against this hypothesis and suggested instead that early organisms would not have been exposed to H2O2 due to its short half-life in the ferruginous oceans of the Archean. We find these arguments to be factually incomplete because they do not consider that freshwater or some coastal marine environments during the Archean could indeed have led to H2O2 generation and accumulation. In these environments, abiotic oxidants could have interacted with early life, thus steering its evolutionary course.

Kinetics of Oriented Attachment of Mica Crystals.

Oriented attachment (OA), that is, the coalescence of crystals through attachment on coaligned crystal faces, is a nonclassical crystal growth process. Before attachment, a mesocrystal consisting of coaligned parallel crystals but with liquid separating them was observed. Fundamental questions such as why OA is kinetically favored and whether a mesocrystal stage is a prerequisite for OA are raised. Through combining brute-force molecular dynamics simulations and path samplings based on extensive umbrella simulations, we address these questions with a case study on the OA of a mica nanocrystal onto a mica crystal substrate in water. Brute-force simulations show that if two mica crystals are attached but largely misaligned, coalignment hardly appears. Thus, if OA is possible, then coalignment must appear before the attachment between crystals. Electrophoresis of the nanocrystal toward the substrate surface is spontaneous, but mesocrystal formation is occasional, also shown by brute-force simulations. Free energies along different pathways show that OA is spontaneous and kinetically favored over non-OA, and a mesocrystal formation is just a bifurcation in the pathway. OA is through a pathway in which the nanocrystal is tilted with respect to the substrate. Part of the nanocrystal is attached to the substrate first, and then, OA is gradually completed. Once a mesocrystal is occasionally formed, then a jump event is needed for the nanocrystal to get back to the OA pathway. The sampling technique here can hopefully guide the design of nanostructured materials facilitated by OA.

Effect of virtual reality training to enhance laparoscopic assistance skills.

BACKGROUND: While laparoscopic assistance is often entrusted to less experienced individuals, such as residents, medical students, and operating room nurses, it is important to note that they typically receive little to no formal laparoscopic training. This deficiency can lead to poor visibility during minimally invasive surgery, thus increasing the risk of errors. Moreover, operating room nurses and medical students are currently not included as key users in structured laparoscopic training programs. OBJECTIVES: The aim of this study is to evaluate the laparoscopic skills of OR nurses, clinical medical postgraduate students, and residents before and after undergoing virtual reality training. Additionally, it aimed to compare the differences in the laparoscopic skills among different groups (OR nurses/Students/Residents) both before and after virtual reality training. METHODS: Operating room nurses, clinical medical postgraduate students and residents from a tertiary Grade A hospital in China in March 2022 were selected as participants. All participants were required to complete a laparoscopic simulation training course in 6 consecutive weeks. One task from each of the four training modules was selected as an evaluation indicator. A before-and-after self-control study was used to compare the basic laparoscopic skills of participants, and laparoscopic skill competency was compared between the groups of operating room nurses, clinical medical postgraduate students, and residents. RESULTS: Twenty-seven operating room nurses, 31 clinical medical postgraduate students, and 16 residents were included. The training course scores for the navigation training module, task training module, coordination training module, and surgical skills training module between different groups (operating room nurses/clinical medical postgraduate/residents) before laparoscopic simulation training was statistically significant (p < 0.05). After laparoscopic simulation training, there was no statistically significant difference in the training course scores between the different groups. The surgical level scores before and after the training course were compared between the operating room nurses, clinical medical postgraduate students, and residents and showed significant increases (p < 0.05). CONCLUSION: Our findings show a significant improvement in laparoscopic skills following virtual surgery simulation training across all participant groups. The integration of virtual surgery simulation technology in surgical training holds promise for bridging the gap in laparoscopic skill development among health care professionals.

Engineering an injectable gellan gum-based hydrogel with osteogenesis and angiogenesis for bone regeneration.

Injectable hydrogels are currently a topic of great interest in bone tissue engineering, which could fill irregular bone defects in a short time and avoid traditional major surgery. Herein, we developed an injectable gellan gum (GG)-based hydrogel for bone defect repair by blending nano-hydroxyapatite (nHA) and magnesium sulfate (MgSO4). In order to acquire an injectable GG-based hydrogel with superior osteogenesis, nHA were blended into GG solution with an optimized proportion. For the aim of endowing this hydrogel capable of angiogenesis, MgSO4 was also incorporated. Physicochemical evaluation revealed that GG-based hydrogel containing 5% nHA (w/v) and 2.5 mM MgSO4 (GG/5%nHA/MgSO4) had appropriate sol-gel transition time, showed a porosity-like structure, and could release magnesium ions for at least 14 days. Rheological studies showed that the GG/5%nHA/MgSO4 hydrogel had a stable structure and repeatable self-healing properties. In-vitro results determined that GG/5%nHA/MgSO4 hydrogel presented superior ability on stimulating bone marrow mesenchymal stem cells (BMSCs) to differentiate into osteogenic linage and human umbilical vein endothelial cells (HUVECs) to generate vascularization. In-vivo, GG/5%nHA/MgSO4 hydrogel was evaluated via a rat cranial defect model, as shown by better new bone formation and more neovascularization invasion. Therefore, the study demonstrated that the new injectable hydrogel, is a favorable bioactive GG-based hydrogel, and provides potential strategies for robust therapeutic interventions to improve the repair of bone defect.

Mechanochemical reduction of clay minerals to porous silicon nanoflakes for high-performance lithium-ion battery anodes.

Hierarchically porous silicon nanoflakes were synthesized from natural talc via a mechanochemical reduction method, which showed great potential in the scalable production of silicon nanoflakes due to the abundant precursor and facile strategy. The unique layered structure and chemical composition of talc enabled the formation of two-dimensional nanostructured silicon without any additional templates. As lithium-ion battery anodes, the silicon nanoflakes showed excellent electrochemical properties.

Accumulation, translocation, and fractionation of rare earth elements (REEs) in fern species of hyperaccumulators and non-hyperaccumulators growing in urban areas.

The issue of ion-adsorption type rare earth deposits (IADs) in urban areas of South China has garnered significant attention due to its environmental implications. Hyperaccumulator-based phytoremediation is a potentially effective solution for reducing the environmental impact of IADs in urban areas, particularly using ferns as they are known to be REE hyperaccumulators. However, the ability of different fern species to accumulate REEs in urban areas remains unknown. In this study, four fern species, including known hyperaccumulators (Dicranopteris linearis and Blechnum orientale) and other ferns (Pteris ensiformis and Cibotium barometz), were studied to investigate their REE accumulation abilities in the Guangzhou urban area. The aboveground parts of Dicranopteris linearis (848.7 µg g-1) and Blechum orientale (1046.8 µg g-1) have been found to accumulate high concentrations of REEs, demonstrating they probably can be applied for phytoremediation in the natural environments. Despite having lower REE concentrations than REE hyperaccumulators, Pteris ensiformis and Cibotium barometz still probably have the function as phytostabilizers in urban areas, as REEs can be enriched in their roots beyond the normal levels of plants. The enrichment of REEs in ferns is influenced by the availability of various nutrients (K, Ca, Fe, and P), which probably can be associated with different growth processes. The four fern species show LREE enrichment, moderate Eu anomalies and different Ce anomalies. It is difficult to absorb and transfer Ce to the aboveground parts of Blechnum orientale and Cibotium barometz. The study also identified selective enrichment of Ce in Pteris ensiformis, which has potential for comprehensive extraction of REEs when combined with other REE hyperaccumulators. REE fractionations are probably determined by the specific characteristics of different fern parts. Overall, these findings provide insights for addressing potential environmental problems related to IADs and offer guidelines for phytoremediation technology in addressing high REE levels in urban areas.

Metabolome, Plant Hormone, and Transcriptome Analyses Reveal the Mechanism of Spatial Accumulation Pattern of Anthocyanins in Peach Flesh.

Anthocyanins are important secondary metabolites in fruits, and anthocyanin accumulation in the flesh of peach exhibits a spatial pattern, but the relevant mechanism is still unknown. In this study, the yellow-fleshed peach, cv. 'Jinxiu', with anthocyanin accumulation in the mesocarp around the stone was used as the experimental material. Red flesh (RF) and yellow flesh (YF) were sampled separately for flavonoid metabolite (mainly anthocyanins), plant hormone, and transcriptome analyses. The results showed that the red coloration in the mesocarp was due to the accumulation of cyanidin-3-O-glucoside, with an up-regulation of anthocyanin biosynthetic genes (F3H, F3'H, DFR, and ANS), transportation gene GST, and regulatory genes (MYB10.1 and bHLH3). Eleven ERFs, nine WRKYs, and eight NACs were also defined as the candidate regulators of anthocyanin biosynthesis in peach via RNA-seq. Auxin, cytokinin, abscisic acid (ABA), salicylic acid (SA), and 1-aminocyclopropane-1-carboxylic acid (ACC, ethylene precursor) were enriched in the peach flesh, with auxin, cytokinin, ACC, and SA being highly accumulated in the RF, but ABA was mainly distributed in the YF. The activators and repressors in the auxin and cytokinin signaling transduction pathways were mostly up-regulated and down-regulated, respectively. Our results provide new insights into the regulation of spatial accumulation pattern of anthocyanins in peach flesh.

Histone mRNA polyadenylation-mediated inflammation underlies various virus infections and cancers.

The mechanistic understanding of virus infection and inflammation in many diseases is incomplete. Normally, messenger RNA (mRNA) tails of replication-dependent histones (RDH) that safeguard naked nuclear DNAs are protected by a specialized stem-loop instead of polyadenylation. Here, we showed that infection by various RNA viruses (including severe acute respiratory syndrome coronavirus 2) induced aberrant polyadenylation of RDH mRNAs (pARDH) that resulted in inflammation or cellular senescence, based on which we constructed a pARDH inflammation score (pARIS). We further investigated pARIS elevation in various disease conditions, including different types of virus infection, cancer, and cellular senescence. Notably, we found that pARIS was positively correlated with coronavirus disease 2019 severity in specific immune cell types. We also detected a subset of HIV-1 elite controllers characterized by pARDH "flipping" potentially mediated by HuR. Importantly, pARIS was positively associated with transcription of endogenous retrovirus but negatively associated with most immune cell infiltration in tumors of various cancer types. Finally, we identified and experimentally verified two pARIS regulators, ADAR1 and ZKSCAN1, which was first linked to inflammation. The ZKSCAN1 was known as a transcription factor but instead was shown to regulate pARIS as a novel RNA binding protein. Both regulators were upregulated under most infection and inflammation conditions. In conclusion, we unraveled a potential antiviral mechanism underlying various types of virus infections and cancers.

A mineral-based origin of Earth's initial hydrogen peroxide and molecular oxygen.

Terrestrial reactive oxygen species (ROS) may have played a central role in the formation of oxic environments and evolution of early life. The abiotic origin of ROS on the Archean Earth has been heavily studied, and ROS are conventionally thought to have originated from H2O/CO2 dissociation. Here, we report experiments that lead to a mineral-based source of oxygen, rather than water alone. The mechanism involves ROS generation at abraded mineral-water interfaces in various geodynamic processes (e.g., water currents and earthquakes) which are active where free electrons are created via open-shell electrons and point defects, high pressure, water/ice interactions, and combinations of these processes. The experiments reported here show that quartz or silicate minerals may produce reactive oxygen-containing sites (≡SiO•, ≡SiOO•) that initially emerge in cleaving Si-O bonds in silicates and generate ROS during contact with water. Experimental isotope-labeling experiments show that the hydroxylation of the peroxy radical (≡SiOO•) is the predominant pathway for H2O2 generation. This heterogeneous ROS production chemistry allows the transfer of oxygen atoms between water and rocks and alters their isotopic compositions. This process may be pervasive in the natural environment, and mineral-based production of H2O2 and accompanying O2 could occur on Earth and potentially on other terrestrial planets, providing initial oxidants and free oxygen, and be a component in the evolution of life and planetary habitability.

Three-step closed reduction and percutaneous screw fixation: A reliable and reproducible protocol in managing displaced intra-articular calcaneal fractures.

BACKGROUND: For displaced intra-articular calcaneal fractures (DIACFs), the less invasive surgical techniques vary widely. Herein, the study is to introduce a novel, reliable and reproducible protocol of three-step closed reduction (distracting, elevating, and clamping) and percutaneous screw fixation for DIACFs. METHODS: This retrospective study included 32 patients with 33 DIACFs treated by the abovementioned surgical procedures with an average follow-up of 17.7 months. Postoperative outcomes were evaluated by complications, radiographs, and functional scores. RESULTS: There were no incision complications. Postoperative Böhler's angle, height, and width were significantly recovered with p < 0.001. Especially, mean postoperative subtalar incongruity was 0.5 ± 0.5 mm. The average values of Maryland Foot Score (MFS) and American Orthopaedic Foot and Ankle Society (AOFAS) ankle hindfoot score were 93.6 ± 5.9, 91.7 ± 6.7, respectively. The average scores of short form-36 (SF-36) and visual analog scale (VAS) were 89.9 ± 10.4 and 3.1 ± 1.6, respectively. Further subgroup analysis showed that the functional scores were comparable among different fracture types according to either Sanders or Essex-Lopresti classification. CONCLUSION: We consider the three-step reduction (distracting, elevating and clamping) and percutaneous screw fixation to be a reliable and reproducible protocol for the treatment of DIACFs.

Effect of ozonated water, mancozeb, and thiophanate-methyl on the phyllosphere microbial diversity of strawberry.

Phyllosphere microorganisms are closely linked to plant health. This study investigated the effect of ozonated water, mancozeb, and thiophanate-methyl on phyllosphere microorganisms in strawberry plants of the "Hongyan" variety. Sequencing analysis of the phyllosphere bacterial and fungal communities was performed using 16S rRNA gene fragment and ITS1 region high-throughput sequencing after spraying ozonated water, mancozeb, thiophanate-methyl, and clear water. Proteobacteria, Actinobacteria, and Firmicutes were the dominant bacterial phyla in strawberry. The relative abundance of Proteobacteria (82.71%) was higher in the ozonated water treatment group than in the other treatment groups, while the relative abundance of Actinobacteria (9.38%) was lower than in the other treatment groups. The strawberry phyllosphere fungal communities were mainly found in the phyla Basidiomycota and Ascomycota. The relative abundance of Basidiomycota was highest in the ozonated water treatment group (81.13%), followed by the mancozeb treatment group (76.01%), while the CK group only had an abundance of 43.38%. The relative abundance of Ascomycota was lowest in the ozonated water treatment group (17.98%), 23.12% in the mancozeb treatment group, 43.39% in the thiophanate-methyl treatment group, and 55.47% in the CK group. Pseudomonas, Halomonas, and Nesterenkonia were the dominant bacterial genera on strawberry surfaces, while Moesziomyces, Aspergillus, and Dirkmeia were the dominant fungal genera. Ozonated water was able to significantly increase the richness of bacteria and fungi and decrease fungal diversity. However, bacterial diversity was not significantly altered. Ozonated water effectively reduced the relative abundance of harmful fungi, such as Aspergillus, and Penicillium, and enriched beneficial bacteria, such as Pseudomonas and Actinomycetospora, more effectively than mancozeb and thiophanate-methyl. The results of the study show that ozonated water has potential as a biocide and may be able to replace traditional agents in the future to reduce environmental pollution.

Characterization of volatile constituents and odorous compounds in peach (Prunus persica L) fruits of different varieties by gas chromatography-ion mobility spectrometry, gas chromatography-mass spectrometry, and relative odor activity value.

The aim of this study is to acquire information for future breeding efforts aimed at improving fruit quality via effects on aroma by comparing the diversity of Chinese local peach cultivars across 10 samples of three varieties (honey peach, yellow peach, and flat peach). The volatile components of peach fruits were analyzed and identified by gas chromatography-ion mobility spectrometry (GC-IMS) combined with gas chromatography-mass spectrometry (GC-MS), and the main flavor components of peach fruit were determined by relative odor activity value (ROAV) and principal component analysis (PCA). A total number of 57 volatile components were detected by GC-IMS, including eight aldehydes, nine alcohols, eight ketones, 22 esters, two acids, two phenols, two pyrazines, one thiophene, one benzene, and two furans. The proportion of esters was up to 38.6%. A total of 88 volatile components were detected by GC-MS, among which 40 were key aroma compounds, with an ROAV ≥ 1. The analysis results showed that alcohols, ketones, esters, and aldehydes contributed the most to the aroma of peach fruit. PCA demonstrated that (E,E)-2, 6-non-adienal, γ-decalactone, ß-ionone, and hexyl hexanoate were the key contributors to the fruit aroma. A reference for future directional cultivation and breeding could be provided by this study through evaluating the aroma quality of the peach at the cultivar level. The possible reasonable application of these peach fruits pulp will be guided through these research.

Microorganisms Accelerate REE Mineralization in Supergene Environments.

Exogenic deposits are an important source of rare earth elements (REEs), especially heavy REEs (HREEs). It is generally accepted that microorganisms are able to dissolve minerals and mobilize elements in supergene environments. However, little is known about the roles of microorganisms in the formation of exogenic deposits such as regolith-hosted REE deposits that are of HREE enrichment and provide over 90% of global HREE demand. In this study, we characterized the microbial community composition and diversity along a complete weathering profile drilled from a regolith-hosted REE deposit in Southeastern China and report the striking contributions of microorganisms to the enrichment of REEs and fractionation between HREEs and light REEs (LREEs). Our results provide evidence that the variations in REE contents are correlated with microbial community along the profile. Both fungi and bacteria contributed to the accumulation of REEs, whereas bacteria played a key role in the fractionation between HREEs and LREEs. Taking advantage of bacteria strains isolated from the profile, Gram-positive bacteria affiliated with Bacillus and Micrococcus preferentially adsorbed HREEs, and teichoic acids in the cell wall served as the main sites for HREE adsorption, leading to an enrichment of HREEs in the deposit. The present study provides the first database of microbial community in regolith-hosted REE deposits. These findings not only elucidate the crucial contribution of fungi and bacteria in the supergene REE mineralization but also provide insights into efficient utilization of mineral resources via a biological pathway. IMPORTANCE Understanding the role of microorganisms in the formation of regolith-hosted rare earth element (REE) deposits is beneficial for improving the metallogenic theory and deposit exploitation, given that such deposits absolutely exist in subtropical regions with strong microbial activities. Little is known of the microbial community composition and its contribution to REE mineralization in this kind of deposit. Using a combination of high-throughput sequencing, batch adsorption experiments, and spectroscopic characterization, the functional microorganisms contributing to REE enrichment and fractionation are disclosed. For bacteria, the surface carboxyl and phosphate groups are active sites for REE adsorption, while teichoic acids in the cell walls of G+ bacteria lead to REE fractionation. The above-mentioned findings not only unravel the importance of microorganisms in the formation of supergene REE deposits but also provide experimental evidence for the bioutilization of REE resources.

Effect of electron structure on the catalytic activity of LaCoO3 perovskite towards toluene oxidation.

LaCoO3 perovskites with different spin states of Co3+ were prepared by calcination at 600-1000 °C. LaCoO3 with electron filling in the eg orbital at 1 exhibited a moderate interaction between the surface oxygen, resulting in the best catalytic activity. This was verified by the O p-band center.

Oxalate regulate the redox cycle of iron in heterogeneous UV-Fenton system with Fe3O4 nanoparticles as catalyst: Critical role of homogeneous reaction.

The redox cycle of iron is a well-known rate-determining step for hydroxyl radical generation in photo-Fenton system. In this study, oxalate was employed as regulator to enhance the degradation of Orange II in Fe3O4 magnetic nanoparticles (NPs)-catalyzed heterogeneous UV-Fenton system. Results showed that the oxalate could interact with the surface ≡FeIII species of catalyst, which weakened the bond of ≡FeIII-O and promoted the leaching of iron ions. Then the redox cycle of iron and generation of HO· would be accelerated via the homogeneous UV-Fenton reaction. The degradation rate constant of Orange II reached 0.220 min-1 when additional oxalate concentration was 0.4 mM, which was 2.5 times as high as that without oxalate in heterogeneous UV-Fenton system. In this case, the removal efficiencies of color and TOC were 99.3% and 92.0% after 30 and 120 min treatment, respectively. In addition, based on the results of XRD and XPS characterization, it could be deduced that the crystal structure and elemental configuration of Fe3O4 magnetic nanoparticles could be maintained after reaction. Besides, the results of FTIR and magnetization characterization indicated that the C2O42- on surface of catalyst could be degraded and the catalyst could be easily separated from aqueous by applying an external magnetic field. The Fe3O4 magnetic nanoparticles showed high catalytic stability and reusability under the regulation of oxalate due to the fact that the leached iron ions could be re-adsorbed on the catalyst after treatment.

Environmental risk assessment of the potential "Chemical Time Bomb" of ion-adsorption type rare earth elements in urban areas.

Ion-adsorption type rare earth elements (REEs) located in tropical and subtropical zones have abundant movable and bioavailable ion-exchangeable REEs and could be an environmental hazard. However, our understanding of their environmental risk in urban areas is limited. We aimed to determine whether ion-adsorption type REEs in Guangzhou represent a kind of potential "Chemical Time Bomb" (CTB) and assess the environmental risk. We conducted a comprehensive survey of REEs in 181 samples including regolith (n = 70), surface water (n = 55), sediment (n = 25), vegetables (n = 22) and rhizosphere soil (n = 9), collected from five regions around Guangzhou, as a representative city of ion-adsorption type REEs in tropical and subtropical zones. The existing environmental risk was assessed by calculating the estimated daily intake (EDI) of REEs through vegetable consumption, and leaching simulation experiments were used to discuss the factors affecting the long-term stability of REEs. The average REEs concentrations (ΣREEs) in the regolith and sediment were 458.5 and 218.6 µg·g-1, respectively, which were higher than the background values of regolith (197.3 µg·g-1) and sediment (173.3 µg·g-1), and large proportions of ion-exchangeable REEs were observed in regolith and sediment, indicating that ion-adsorption type REEs in Guangzhou are a kind of potential CTB. The average ΣREEs in surface water (3.9 µg·L-1), rhizosphere soil (466.9 µg·g-1) and vegetables (25.0 µg·g-1·dw) suggest that REEs have migrated to the supergene environment even organisms. The average EDI (55.4 µg·kg-1·d-1) close to the safety limitation (70 µg·kg-1·d-1) suggests that the existing health risk is very worrisome. Human factors, including acid rain, mining and farming, probably ignite the CTB, causing the release of REEs to the urban environment on a large scale. This prospective study demonstrated that REEs exposure problems in urban areas of ion-adsorption type REEs should not be ignored.

Assessing environmental fate of hexavalent chromium as influenced by fractionation of ferrihydrite with dissolved organic matter.

The dynamic interactions among iron (Fe) oxides, dissolved organic matter (DOM) and toxic trace metals play crucial roles in risk assessment and environmental remediation. Although the inhibitory effects of DOM on the iron oxides transformation process have been studied previously, there is still a lack of mechanistic and quantitative understanding on the kinetics of Cr(VI) and ferrihydrite transformation in the present of DOM. In this study, we investigated the fractionation process of DOM on ferrihydrite and its influence on the fate of Cr(VI) and transformation of ferrihydrite. The result of three-dimension excitation emission matrix (3D-EEM), Q-Exactive LC-MS/MS, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) indicated that fulvic acid-like compounds of DOM were the mainly fractionated compounds on the surface of ferrihydrite, which further inhibited the transformation of ferrihydrite. Besides, bracewellite (CrO(OH)) generated as an accompanied mineral during the transformation of ferrihydrite in the present of Cr(VI). Based on the DFT theoretical calculation, we concluded that Cr(VI) mainly in the form of HCr O4- was more inclined to be adsorbed on iron-oxide tetrahedron by inner-sphere monodentate mononuclear configurations. The findings on the dynamic coupling among Fe oxide transformation and Cr(VI) sequestration under the effect of DOM provided the basis for accurately predicting the fate of trace elements and iron mineral.

Hydrothermal carbons/ferrihydrite heterogeneous Fenton catalysts with low H2O2 consumption and the effect of graphitization degrees.

As the heterogeneous Fenton reactions are always restricted by the unsatisfied reduction efficiency of Fe(III) and ineffective consumption of H2O2, many strategies have been developed. In this work, we prepared hydrothermal carbons (HTC) with different graphitization degrees using glucose under different hydrothermal times, and then they were combined with ferrihydrite (Fh). Interestingly, although 30%HTC/Fh has much better BPA degradation efficiency than Fh (26 times larger of calculated degradation rate constants), the decomposition rate of H2O2 in the former system is lower. The generated Fe(II) of HTC/Fh is much higher than that of Fh during the heterogeneous Fenton reactions, and the degradation of BPA is almost unaffected by p-benzoquinone (scavenger of superoxide radicals (O2•-)) while greatly inhibited by isopropanol (scavenger of hydroxyl radicals (HO•)). These results indicate that HTC act as electron donors due to the abundant carbon-centered persistent free radicals (PFRs) to directly reduce Fe(III) to Fe(II) and therefore decrease the H2O2 consumption by Fe(III), which subsequently inhibits the generation of less active O2•- and promote the utilization efficiency of H2O2. HTC with a low graphitization degree contain more PFRs for Fe(III) reducing, significantly enhancing the Fenton catalytic activity of Fh.

An abiotic source of Archean hydrogen peroxide and oxygen that pre-dates oxygenic photosynthesis.

The evolution of oxygenic photosynthesis is a pivotal event in Earth's history because the O2 released fundamentally changed the planet's redox state and facilitated the emergence of multicellular life. An intriguing hypothesis proposes that hydrogen peroxide (H2O2) once acted as the electron donor prior to the evolution of oxygenic photosynthesis, but its abundance during the Archean would have been limited. Here, we report a previously unrecognized abiotic pathway for Archean H2O2 production that involves the abrasion of quartz surfaces and the subsequent generation of surface-bound radicals that can efficiently oxidize H2O to H2O2 and O2. We propose that in turbulent subaqueous environments, such as rivers, estuaries and deltas, this process could have provided a sufficient H2O2 source that led to the generation of biogenic O2, creating an evolutionary impetus for the origin of oxygenic photosynthesis.