Search Results (33)

Environmental persistent free radicals (EPFRs) represent a class of long-lived, redox-active species with half lives spanning minutes to months. Emerging as critical environmental pollutants, EPFRs pose significant risks due to their persistence, potential for bioaccumulation, and adverse effects on ecosystems and human health. This review critically synthesizes recent advancements in understanding EPFR formation mechanisms, analytical detection methodologies, environmental distribution patterns, and toxicological impacts. While progress has been made in characterization techniques, challenges persist—particularly in overcoming limitations of electron paramagnetic resonance (EPR) spectroscopy and spin-trapping methods in complex environmental matrices. Key knowledge gaps remain, including molecular-level dynamics of EPFR formation, long-term environmental fate under varying geochemical conditions, and quantitative relationships between chronic EPFR exposure and health outcomes. Future research priorities could focus on: (1) atomic-scale mechanistic investigations using advanced computational modeling to resolve formation pathways; (2) development of next-generation detection tools to improve sensitivity and spatial resolution; and (3) integration of EPFR data into region-specific air-quality indices to enhance risk assessment and inform mitigation strategies. Addressing these gaps will advance our capacity to mitigate EPFR persistence and safeguard environmental and public health. Full article

Tetracycline (TC) is widely used in medicine and livestock farming. TC is difficult to degrade and tends to persist and accumulate in aquatic environments, and it has gradually become an emerging pollutant. Biochar (BC) has strong potential for removing TC from water. This potential arises from its excellent surface properties, low-cost raw materials, and renewable nature. However, raw biomass materials are highly diverse, and their preparation conditions vary significantly. Modification methods differ in specificity and the application scenarios are complex. These factors collectively cause unstable TC removal efficiency by biochar. The chemical activation process using KOH/H₃PO₄ significantly enhanced porosity and surface functionality, transforming raw biochar into an activated carbon material with targeted adsorption capacity. Adjusting the application dosage and environmental factors (particularly pH) further enhanced the removal performance. Solution pH critically governs the adsorption efficiency: optimal conditions (pH 5–7) increased removal by 35–40% through strengthened electrostatic attraction, whereas acidic/alkaline extremes disrupted ionizable functional groups. The dominant adsorption mechanisms of biochar involved π–π interactions, pore filling, hydrophobic interactions, hydrogen bonding, electrostatic interactions, and surface complexation. In addition, the main challenges currently hindering the large-scale application of biochar for the removal of TC from water are highlighted: (i) secondary pollution risks of biochar application from heavy metals, persistent free radicals, and toxic organic leaching; (ii) economic–environmental conflicts due to high preparation/modification costs; and (iii) performance gaps between laboratory studies and real water applications. Full article

Sludge-derived biochar (SDB) synthesized by the pyrolysis of sludge is gaining enormous interest as a sustainable solution to wastewater treatment and sludge disposal. Despite the proliferation of general biochar reviews, a focused synthesis on SDB-specific advances, particularly covering the recent surge in multifunctional wastewater treatment applications (2020–2025), receives little emphasis. In particular, a critical analysis of recent trends, application challenges, and future research directions for SDB is still limited. Unlike broader biochar reviews, this mini-review highlights the comparative advantages and limitations of SDB, identifies emerging integration strategies (e.g., bio-electrochemical systems, catalytic membranes), and outlines future research priorities toward enhancing the durability and environmental safety of SDB applications. Specifically, this review summarized the advances from 2020 to 2025, focusing exclusively on functional modifications, and practical applications of SDB across diverse wastewater treatment technologies involved in adsorption, catalytic oxidation, membrane integration, electrochemical processes and bio-treatment systems. Quantitative comparisons of adsorption capacities (e.g., >99% Cd2+ removal, >150 mg/g tetracycline adsorption) and catalytic degradation efficiencies are provided to illustrate recent improvements. The potential of SDB in evaluating traditional and emerging contaminant degradation among the Fenton-like, persulfate, and peracetic acid activation systems was emphasized. Integration with membrane technologies reduces fouling, while electrochemical applications, including microbial fuel cells, yield higher power densities. To improve the functionality of SDB-based systems in targeting contamination removal, modification strategies, i.e., thermal activation, heteroatom doping (N, S, P), and metal loading, played crucial roles. Emerging trends highlight hybrid systems and persistent free radicals for non-radical pathways. Despite progress, critical challenges persist in scalability, long-term stability, lifecycle assessments, and scale-up implementation. The targeted synthesis of this review offers valuable insights to guide the development and practical deployment of SDB in sustainable wastewater management. Full article

The growing diversity and prevalence of contaminants of emerging concern (CECs) in aquatic environments present significant risks to human health and ecosystems, necessitating the development of effective remediation strategies. Advanced oxidation processes (AOPs) have emerged as a promising solution due to their ability to produce highly reactive species that efficiently degrade persistent contaminants. Among the various oxidizing agents, peracetic acid (PAA) has attracted significant attention in the field of water treatment for its powerful oxidative properties, environmentally safe decomposition, and ease of use. This article is designed to offer a comprehensive overview of the latest trends in PAA-based AOPs. The discussion begins with an overview of the intrinsic performance of PAA, emphasizing its oxidation potential and degradation mechanisms. Subsequently, the effectiveness of PAA-based AOPs in remediating CECs is explored, focusing on transition metal-mediated activation (Fe, Co, Mn), UV irradiation, and carbon-based catalysts, all of which enhance the generation of reactive species (RS). Next, the determination of RS in PAA-based AOPs is examined, distinguishing between free radical (organic and inorganic) and non-radical (singlet oxygen and high-valent metal) mechanisms that govern pollutant degradation. Then, key factors affecting the removal of CECs in PAA-based AOPs, including initial PAA concentration, catalyst dosage, and pH, are also addressed. Following that, the potential by-products and hazard assessments associated with PAA oxidation are discussed. Finally, current challenges and future research directions are proposed to facilitate the large-scale application of PAA-based AOPs in water remediation. Full article

Persistent free radicals (PFRs) in humic substances (HSs) are relatively stable free radicals with a longer lifespan compared to transient free radicals. These PFRs are abundant in the ecological environment, such as in soil and water. The formation of PFRs in HSs occurs primarily through the humification of biological residues, electron transfer between quinone and phenolic groups in HSs, and interactions among microorganisms, HSs, and mineral particles. Mineral particles contribute significantly to the stability of these radicals. Conditions such as prolonged exposure to light and redox changes further influence their formation and stability. PFRs in HSs have been applied in the treatment and remediation of environmental pollution due to their ability to adsorb, degrade, and undergo redox reactions with soil pollutants. The formation mechanisms of PFRs (including semiquinone free radicals) in soil HSs are reviewed, and the factors affecting their stability are explored. Additionally, the interaction between PFRs and soil pollutants, and their effects on pollutant migration and transformation, and soil microbial communities, are discussed. Lastly, perspectives for future research aimed at improving innovation in understanding the impact of PFRs on pollutant migration and transformation, soil microbial communities, and the environmental behavior of PFRs are provided. Full article

We hypothesize that predictable variations in environmental conditions caused by night/day cycles created opportunities and hazards that initiated information dynamics central to life’s origin. Increased daytime temperatures accelerated key chemical reactions but also caused the separation of double-stranded polynucleotides, leading to hydrolysis, particularly of single-stranded RNA. Daytime solar UV radiation promoted the synthesis of organic molecules but caused broad damage to protocell macromolecules. We hypothesize that inter-related simultaneous adaptations to these hazards produced molecular dynamics necessary to store and use information. Self-replicating RNA heritably reduced the hydrolysis of single strands after separation during warmer daytime periods by promoting sequences that formed hairpin loops, generating precursors to transfer RNA (tRNA), and initiating tRNA-directed evolutionary dynamics. Protocell survival during daytime promoted sequences in self-replicating RNA within protocells that formed RNA–peptide hybrids capable of scavenging UV-induced free radicals or catalyzing melanin synthesis from tyrosine. The RNA–peptide hybrids are precursors to ribosomes and the triplet codes for RNA-directed protein synthesis. The protective effects of melanin production persist as melanosomes are found throughout the tree of life. Similarly, adaptations mitigating UV damage led to the replacement of Na⁺ by K⁺ as the dominant mobile cytoplasmic cation to promote diel vertical migration and selected for homochirality. We conclude that information dynamics emerged in early life through adaptations to predictably fluctuating opportunities and hazards during night/day cycles, and its legacy remains observable in extant life. Full article

Wildfires significantly alter watershed functions, particularly the mobilization of organic carbon (OC). This study investigated OC mobility and the physicochemical characteristics of wildfire-impacted soils and ashes from the northern California and Nevada fires (Dixie, Beckworth, Caldor). Organic carbon in wildfire-derived ashes (9.2–57.3 mg/g) generally exceeded levels in the background soils (4.3–24.4 mg/g), except at the Dixie fire sites. The mobile OC fraction varied from 0.0093 to 0.029 in ashes and 0.010 to 0.065 in soils, though no consistent trend was observed between the ashes and soils. Notably, the ash samples displayed lower OC mobility compared with the soils beneath them. A negative correlation was found between the mobile OC fraction and bulk OC content. Wildfire increased the total amount of mobile OC substantially by 5.2–574% compared to the background soils. Electron paramagnetic resonance (EPR) spectra confirmed the presence of environmentally persistent free radicals (EPFRs), which correlated with observed redox reactivity. Additionally, X-ray absorption near edge structure (XANES) and X-ray fluorescence (XRF) imaging revealed that Fe(II) oxidation in soils beneath the ashes may have enhanced the OC mobility, likely driven by pyrogenic carbon and free radicals. These findings enhance our understanding of post-wildfire OC mobilization and the impact of ash–soil physicochemical properties on watershed health. Full article

Environmentally persistent free radicals (EPFRs) are a new class of pollutants that have been identified as potential environmental contaminants due to their persistence and ability to generate reactive oxygen species (ROS) that cause oxidative stress in living organisms. This study investigates the formation and behavior of EPFRs during the photodegradation of organic pollutants, emphasizing the role of metal ions, precursor concentration, and environmental conditions. Results show that light exposure significantly enhances pollutant degradation rates, EPFR yield, and formation speed, though it simultaneously shortens EPFR lifespan due to reactive oxygen species (ROS) generation. In dark conditions, EPFR formation is slower but results in more stable radicals. Metal ions play a pivotal role, with Cu(II) exhibiting the highest EPFR generation capacity due to its strong electron-accepting properties, surpassing Zn(II) and Na(I), highlighting that metal ions with greater oxidizing potential enhance EPFR formation. The precursor, as both reaction product and reactant, plays a dual role in EPFR formation. Individual compounds like anthracene (ANT) yield stable carbon-centered radicals, while mixtures of polycyclic aromatic hydrocarbons (PAHs) produce more complex radical spectra. The study of the influencing factors and transformation mechanisms of EPFR generation in soil can provide a more comprehensive understanding of the environmental behavior of new pollutants, provide a scientific basis for sustainable development, and be of great significance for the assessment and management of environmental risks and the protection of the ecological environment. Full article

Environmental persistent free radicals (EPFRs) are a type of environmental risk substances existing in atmospheric particulate matter, which pose a challenge to human survival and sustainable development. The current understanding is that the formation mechanism of EPFRs is generally related to metallic materials. However, this study analyzed the PM_2.5 generated from cellulose combustion and found that EPFRs could be generated even without the metallic materials. Therefore, this paper explores the emission characteristics of non-metal-induced EPFRs, aiming to reveal the influencing factors, distribution, and decay characteristics of non-metal-induced EPFRs generated from cellulose combustion. The results show that combustion conditions such as combustion temperature and oxygen concentration have a significant impact on the emission concentration of non-metal-induced EPFRs in PM_2.5 from cellulose combustion. The emission concentrations of non-metal-induced EPFRs in PM_2.5 are at the order of magnitude of 10¹⁴ spins/m³ and over 50% is distributed in the inextricable substances. Their g-factor are in the range from 2.0015 to 2.0022, indicating that these EPFRs are carbon-centered radicals. Furthermore, non-metal-induced EPFRs in PM_2.5 from cellulose combustion have a half-life of several years or even longer, which exhibit distinct characteristics different from metal-induced EPFRs. Full article

Studies on particulate air pollution indicate that a new type of pollutant should be considered from mainly fossil fuel combustion and automobile exhaust emissions, i.e., environmentally persistent free radicals. These radicals, ubiquitous in the environment, have a long life span and are capable of producing harmful reactive oxygen species. Samples of dandelion were collected in 2020 and 2021 in spring and late summer. Roots, leaves, flower stalks, and inflorescences of Taraxacum sp. were collected from six sites with three plants each, along with monitoring of particulate matter air pollution. Four sites were located at streets with heavy traffic and two were control sites in the rural part of the city. The free radical content in each part of the plant was measured by electron paramagnetic resonance. The leaf was selected as the most appropriate part of the plant for the measurement of carbon-derived free radicals. The g_eff value and the total number of spins were calculated. Relationships were found between location, season, and measurements. The electron paramagnetic resonance spectrum consists of at least two components, which can be attributed to C-type radicals and mixed C + O radicals. Their increase in numbers in the fall seasons, compared to the spring seasons, is also noticeable. It has also been observed that leaves collected in autumn have a higher g_eff value, which is probably related to the higher amount of oxygen- and carbon-derived free radicals. Full article

Environmentally persistent free radicals (EPFRs) generated on particles under irradiation in water have attracted particular attention, and their formation mechanisms are not well understood. This study investigated the photoformation of EPFRs on both actual samples collected from an oil production plant in Panjin, Liaoning, China, and simulated Fe(III)-montmorillonite samples in water. The EPFRs detected on actual samples were not easily generated compared with those in the soil or in the air, based on the concentrations of identified PAHs. EPR signals in the range of 10¹⁷ to 10¹⁸ spin/g were detected on the simulated Fe(III)-montmorillonite samples. Their g factors were smaller than 2.0030, which indicated the generation of carbon-centered EPFRs. The primary byproducts were identified by chromatography–mass spectrometry (GC-MS), and a possible EPFR formation pathway during PAH degradation was proposed. Hydrogenation of PAHs during the photoformation of EPFRs was observed and might be due to the catalysis of the simulated particles and the interaction of the intermediates. Meanwhile, the effects of the typical anions (NO₂⁻ and Cl⁻) and the surfactant (TWEEN^® 80 and sodium dodecyl sulfate) were investigated and indicated that the phototransformation process and adsorption process would affect the formation of EPFRs. Overall, our study provided useful information to understand the photoformation of EPFRs in aqueous environments. Full article

This study developed a new system for removing antibiotics using UV/ZIF-67 (Co)-activated peroxymonosulfate. The presence of antibiotic organic pollutants in urban sewage presents a substantial challenge for sewage treatment technologies. Due to the persistent chemical stability of antibiotics, their low environmental concentrations, and their resistance to degradation, effectively removing residual antibiotics remains a significant issue in urban wastewater treatment. This study introduces an eco-friendly photocatalytic technology designed to enhance the removal of oxytetracycline (OTC) from municipal wastewater using a UV/ZIF-67 (Co)/PMS system. The results showed that compared with UV, UV/PMS, ZIF-67 (Co), ZIF-67 (Co)/PMS, and UV/ZIF-67 (Co) systems, the UV/ZIF-67 (Co)/PMS system had the highest OTC removal rate. When 10 mg ZIF-67 (Co) and 1 mM PMS were applied to 100 mL 30 mg/L OTC solution, the degradation efficiency reached 87.73% under 400 W ultraviolet light. Increasing the dosage of ZIF-67 (Co) and PMS can improve the removal rate of OTC, but the marginal benefit of additional dosage is reduced. The highest degradation efficiency was observed at weakly acidic pH, which may be due to potential damage to the internal structure of the catalyst and reduced performance under extreme pH conditions. The influence of chloride ions and nitrate ions on the reaction system is minimal, while bicarbonate ions exhibit a significant inhibitory effect on the removal of OTC. The UV/ZIF-67 (Co)/PMS system exhibits adaptability to various water sources, including tap water, Guitang River water, and pure water. The results of free radical identification indicate the presence of hydroxyl and sulfate groups in the UV/ZIF-67 (Co)/PMS system, both of which play important roles in the degradation of OTC. This study offers valuable insights and technical support for the green, efficient, and environmentally friendly removal of antibiotics from urban wastewater. Full article

The formation of environmentally persistent free radicals (EPFRs) is mediated by the particulate matter's surface, especially transition metal oxide surfaces. In the context of current atmospheric complex pollution, various atmospheric components, such as key atmospheric oxidants ·OH and O₃, are often absorbed on particulate matter surfaces, forming particulate matter surfaces containing ·OH and O₃. This, in turn, influences EPFRs formation. Here, density functional theory (DFT) calculations were used to explore the formation mechanism of EPFRs by C₆H₅OH on α-Fe₂O₃(0001) surface containing the ·OH and O₃, and compare it with that on clean surface. The results show that, compared to EPFRs formation with an energy barrier on a clean surface, EPFRs can be rapidly formed through a barrierless process on these surfaces. Moreover, during the hydrogen abstraction mechanism leading to EPFRs formation, the hydrogen acceptor shifts from a surface O atom on a clean surface to an O atom of ·OH or O₃ on these surfaces. However, the detailed hydrogen abstraction process differs on surfaces containing oxidants: on surfaces containing ·OH, it occurs directly through a one-step mechanism, while, on surfaces containing O₃, it occurs through a two-step mechanism. But, in both types of surfaces, the essence of this promotional effect mainly lies in increasing the electron transfer amounts during the reaction process. This research provides new insights into EPFRs formation on particle surfaces within the context of atmospheric composite pollution. Full article

Biochar (BC) is a carbonaceous material obtained by pyrolysis at 200–1000 °C in the limited presence of O₂ from different vegetable and animal biomass feedstocks. BC has demonstrated great potential, mainly in environmental applications, due to its high sorption ability and persistent free radicals (PFRs) content. These characteristics enable BC to carry out the direct and PFRs-mediated removal/degradation of environmental organic and inorganic contaminants. The types of PFRs that are possibly present in BC depend mainly on the pyrolysis temperature and the kind of pristine biomass. Since they can also cause ecological and human damage, a systematic evaluation of the environmental behavior, risks, or management techniques of BC-derived PFRs is urgent. PFRs generally consist of a mixture of carbon- and oxygen-centered radicals and of oxygenated carbon-centered radicals, depending on the pyrolytic conditions. Here, to promote the more productive and beneficial use of BC and the related PFRs and to stimulate further studies to make them environmentally safer and less hazardous to humans, we have first reviewed the most common methods used to produce BC, its main environmental applications, and the primary mechanisms by which BC remove xenobiotics, as well as the reported mechanisms for PFR formation in BC. Secondly, we have discussed the environmental migration and transformation of PFRs; we have reported the main PFR-mediated application of BC to degrade inorganic and organic pollutants, the potential correlated environmental risks, and the possible strategies to limit them. Full article

Biochar (BC), also referred to as “black gold”, is a carbon heterogeneous material rich in aromatic systems and minerals, preparable by the thermal decomposition of vegetable and animal biomasses in controlled conditions and with clean technology. Due to its adsorption ability and presence of persistent free radicals (PFRs), BC has demonstrated, among other uses, great potential in the removal of environmental organic and inorganic xenobiotics. Bamboo is an evergreen perennial flowering plant characterized by a short five-year growth period, fast harvesting, and large production in many tropical and subtropical countries worldwide, thus representing an attractive, low-cost, eco-friendly, and renewable bioresource for producing BC. Due to their large surface area and increased porosity, the pyrolyzed derivatives of bamboo, including bamboo biochar (BBC) or activated BBC (ABBC), are considered great bio-adsorbent materials for removing heavy metals, as well as organic and inorganic contaminants from wastewater and soil, thus improving plant growth and production yield. Nowadays, the increasing technological applications of BBC and ABBC also include their employment as energy sources, to catalyze chemical reactions, to develop thermoelectrical devices, as 3D solar vapor-generation devices for water desalination, and as efficient photothermal-conversion devices. Anyway, although it has great potential as an alternative biomass to wood to produce BC, thus paving the way for new bio- and circular economy solutions, the study of bamboo-derived biomasses is still in its infancy. In this context, the main scope of this review was to support an increasing production of BBC and ABBC and to stimulate further studies about their possible applications, thus enlarging the current knowledge about these materials and allowing their more rational, safer, and optimized application. To this end, after having provided background concerning BC, its production methods, and its main applications, we have reviewed and discussed the main studies on BBC and ABBC and their applications reported in recent years. Full article