Persistent Free Radical Research Articles

Influence of aeration-induced air–water interfaces on pollutant degradation in water treatment: A theoretical and experimental study

Advanced oxidation processes (AOPs) based on hydroxyl radicals (OH)-dominant pathway are the most important technologies for the removal of bio-recalcitrant organic pollutants in industrial wastewater. Air–water interface formed by aeration is one of the factors that affect the removal efficiency of pollutants in AOPs. In this work, the mechanistic and kinetic insights into the roles of air–water interface on the hydroxylation of three chlorophenols (CPs) in UV/H2O2 process have been investigated via theoretical calculation and experimental methods. Results show that CPs is more prone to accumulate at the air–water interface as the number of chlorine substituents increases. Consequently, the hydration reaction of CPs occurring at the interfacial influence the electron transfer associated with OH, leading to the non-oxidative consumption of OH. This interfacial reaction diminishes degradation efficiency, resulting in the formation of persistent organic pollutants. Herein, in UV/H2O2 degradation of 2,4,6-TCPs, persistent free radical (PFRs), as well as 1,3,7,9-TCDD and 2,3,6-Trichloro-4-(2,4,6-trichlorophenoxy)phenol, were identified using EPR spectroscopy and LC-Q-TOF-MS mass spectrometry, respectively. Altogether, this work provides a comprehensive understanding of the roles of aeration on OH-initiated degradation behavior of chlorinated phenol pollutants.

Distribution and Biotoxicity of Endogenous Pollutants in Pennisetum sp. Biochar from Different Polluted Areas

Due to the wide sources of biomass raw materials and the lack of limits for the endogenous pollutants in biochar and their dosage, some biochar with high endogenous pollutants may be used for environmental remediation, which results in potential environmental risks. In this study, three biochars were prepared from the straws of Pennisetum sp. grown in clean, moderately polluted and highly polluted soils, respectively. The total endogenous copper (Cu) and cadmium (Cd), acid-soluble fraction, and persistent free radical (PFRs) distribution in biochars were investigated, and their biotoxicities were evaluated based on wheat root elongation inhibition rate and antioxidant enzyme activity. The results indicated that total Cu in Jiuniu biochar from the highly polluted soil and total Cd in Shuiquan biochar from the moderately-polluted soil were 3.73 and 4.43 times higher than that in Hongrang biochar from the clean soil, respectively. Moreover, acid-soluble Cu in Jiuniu biochar was 3.32 and 2.84 times higher than that in Shuiquan and Hongrang biochar, respectively, and acid-soluble Cd in Shuiquan and Jiuniu biochar was 7.95 and 5.11 times higher than that in Hongrang biochar, respectively. All three biochars had PFRs with adjacent oxygen atoms centered on carbon and followed the order of Hongrang>Jiuniu>Shuiquan. Three biochar leaching solutions significantly inhibited wheat root elongation but enhanced the enzyme activities of SOD, POD, and CAT for the wheat seedlings compared with that in the control. In particular, the highest inhibition rate (27.7%) was found in Jiuniu biochar. This study indicated that the interaction of endogenous heavy metals and PFRs in biochar exhibited significant biotoxicity to wheat seedlings. In the future, more attention should be paid to the potential environmental toxicity of endogenous pollutants from biochar to avoid new environmental pollution problems.

Enhanced removal of sulfamethoxazole in soil by ball-milled Fe0-FeS@BC activated persulfate process

A heterogeneous combination of different materials is a viable way to prompt persulfate (PS) activation in the removal of organic compounds in soil. In this study, the hybrids of Fe0, FeS and biochar (Fe0-FeS@BC) was synthesized by ball milling method to activate PS in soil-water suspension environment to degrade sulfamethoxazole (SMX) which remains a high detection rate in soil and may have serious eco-system and health risks. Fe0-FeS@BC performed the highest SMX removal efficiency among the tested materials (BC, FeS, Fe0, ball milled Fe0-FeS, and Fe0-FeS@BC). The interference and involvement of mineral fraction (MF) and soil organic matter (SOM) complicated the removal process of SMX in soil/Fe0-FeS@BC/SMX/PS system. The coexistence of 1O2, O2•-, •OH, SO4• - and persistent free radical (PFR) was proposed to explicate the removal of SMX in soil/Fe0-FeS@BC/SMX/PS system. In addition, several influencing factors incorporating Fe0-FeS@BC dosage, Fe0-FeS/BC mass ratio, initial pH, PS dosage and soil-water ratio were investigated to demonstrate the applicability of the Fe0-FeS@BC/PS system in soil remediation. Prevailing reducing condition possessed high Fe3+/Fe2+ cycle that resulted in the continuous SMX degradation. Correspondingly, intermediates and possible degradation pathways of SMX were also proposed. In general, the Fe0-FeS@BC/PS system performed prompting efficiency on the removal of SMX in soil and showed great potential for soil remediation.

Nitrogen-rich magnetic biochar prepared by urea was used as an efficient catalyst to activate persulfate to degrade organic pollutants

In order to fully exploit the potential of magnetic biochar-based persulfate (PS) systems, N was utilized to modify the magnetic biochar-based catalysts through impregnation-pyrolysis method. A typical antifungal drug, metronidazole (MNZ), is selected as the target pollutant to score the reactivity of as-synthetic nitrogen-rich magnetic biochar (NMBC) catalysts. In the modified system, 99.6% of MNZ was removed, 13.6 times of that in the unmodified system. Active radical verification experiments showed that 1O2 was the key active radical. Various characterization showed that the nitrogen-rich significantly improved the persistent free radical, defect degree, content of oxygen-containing groups, electrochemical conductivity and other catalytic activity related properties. Physicochemical characterization, Fe(II) semi-quantitative analysis and masking experiments confirmed that the doping of magnetic biochar with nitrogen increased its Fe(II) content (23.79 mg/g), approximately 2.6 times higher than that of pristine magnetic biochar. Moreover, N induces strong electron accretion of Fe atom through coordination bond, which leads to the increase of electron density on the Fe atom, which increases the content of Fe (II) in the material, thus improving the ability of the material to activate PS to generate 1O2, and promoting the degradation reaction of MNZ. This paper provides a method to improve the activation performance of magnetic biochar.

Microbial resistance stability of rice straw biochar with vermiculite modification: A novel insight into persistent free radicals and pore structure

Biochar is considered a promising material for carbon sequestration owing to its high stability. However, the effects of biochar properties, especially pore structure and persistent free radical (PFR) content, on its microbial resistance stability (MRS) remain unclear. Incubation experiments were conducted to investigate the anaerobic and aerobic MRS of rice straw biochar produced at 300–700 °C, with and without vermiculite modification, and to evaluate the relationship between key biochar properties and MRS. The results showed that PFR signal intensity in biochar was much higher under anaerobic conditions than that under aerobic conditions, increasing with production temperatures of 300–600 °C, but sharply decreasing at 700 °C. Anaerobic MRS of biochar produced at 700 °C was lower than that of biochar produced at 300–600 °C, as indicated by higher CH4 emission. Redundancy analysis revealed a negative correlation between PFR concentration and cumulative CH4 emission with a correlation coefficient of –0.467, and a positive correlation between cumulative CH4 emission and pore volume and specific surface area with correlation coefficients of 0.405 and 0.281, respectively. Biochar dissolved organic carbon content and pH were the two most important factors affecting aerobic MRS as reflected by their high correlation coefficients (0.933 and –0.848) with cumulative CO2 emission. Vermiculite modification enhanced MRS and accordingly lowered the global warming potential of biochar produced at low temperature (300–500 °C) by 4.59–20.2 % and 15.3–42.9 % under anaerobic and aerobic conditions, respectively. However, it had a contrasting effect on biochar produced at 700 °C. Biochar would be more effective at mitigating global warming in paddy fields than in dry lands.

Persistent Free Radicals in Petroleum

The persistent free radical content in petroleum is of the order 1018 spins/g (1 μmol/g), with higher and lower values found depending on origin and in different distillation fractions. The field of persistent free radicals in petroleum was reviewed with the aim of addressing and explaining apparent inconsistencies between free radical persistence and reactivity. The macroscopic average free radical concentration in petroleum is persistent over geological time, but individual free radical species in petroleum are short-lived and reactive. The persistent free radical concentration in petroleum can be explained in terms of a dynamic reaction equilibrium of free radical dissociation and association that causes a finite number of species at any given time to be present as free radicals. Evidence to support this description are observed changes in free radical concentration related to change in Gibbs free energy when the bulk liquid properties are changed and responsiveness of free radical concentration to dynamic changes in temperature. Cage effects, solvent effects, steric protection, and radical stabilization affect free radical reaction rate but do not explain the persistent free radical concentration in petroleum. The difference between persistent free radicals in straight-run petroleum and converted petroleum is that straight-run petroleum is an equilibrated mixture, but converted petroleum is not at equilibrium and the free radical concentration can change over time. Based on the limited data available, free radicals in straight-run petroleum appear to be part of the compositional continuum proposed by Altgelt and Boduszynski. Persistent free radical species are partitioned during solvent classification of whole oil, with the asphaltenes (n-alkane insoluble) fraction having a higher concentration of persistent free radicals than maltenes (n-alkane soluble) fraction. Attempts to relate persistent free radical concentration to petroleum composition were inconclusive.

Cyanocobalamin (VB12) Bionic Enzyme-Assisted Photocatalytic Chain-Growth Polymerization for Detection of Lung Cancer Biomarkers.

Cobalt-mediated radical polymerization is noted for its great level of control over the polymerization of acrylic and vinyl esters monomers, even at high molar mass. Vitamin B12, a natural bionic enzyme cobalt complex, involves the conversion of organic halides to olefins through chain-growth polymerization. In this work, the notion of R-Co(III) free radical persistent free radical effect and vitamin B12 circulation were first reported for the perception of ultralow abundance of microRNA-21, a lung cancer biomarker. Indeed, most Co-containing catalytic reactions can occur under mild conditions due to their minimal bond dissociation of the C-Co bond, with blue light irradiation. Based on the intrinsic stability of the vitamin B12 framework and recycling of the catalyst, it is evident that this natural catalytic scheme has potential applications in medicinal chemistry and biomaterials. In addition, this strategy, combined with highly specific recognition probes and vitamin B12 circulation-mediated chain-growth polymerization, has a detection limit as low as 910 aM. Furthermore, it is sensitive for sensing in serum samples containing biomarkers and shows great potential for RNA selection and amplification sensing in clinical samples.

Outdoor Health Risk of Atmospheric Particulate Matter at Night in Xi'an, Northwestern China.

The deterioration of air quality via anthropogenic activities during the night period has been deemed a serious concern among the scientific community. Thereby, we explored the outdoor particulate matter (PM) concentration and the contributions from various sources during the day and night in winter and spring 2021 in a megacity, northwestern China. The results revealed that the changes in chemical compositions of PM and sources (motor vehicles, industrial emissions, coal combustion) at night lead to substantial PM toxicity, oxidative potential (OP), and OP/PM per unit mass, indicating high oxidative toxicity and exposure risk at nighttime. Furthermore, higher environmentally persistent free radical (EPFR) concentration and its significant correlation with OP were observed, suggesting that EPFRs cause reactive oxygen species (ROS) formation. Moreover, the noncarcinogenic and carcinogenic risks were systematically explained and spatialized to children and adults, highlighting intensified hotspots to epidemiological researchers. This better understanding of day-night-based PM formation pathways and their hazardous impact will assist to guide measures to diminish the toxicity of PM and reduce the disease led by air pollution.

Sulfur-Containing Persistent Free Radicals and Reactive Species on Photoaged Microplastics: Identification and the Formation Mechanism.

The elemental composition may affect the persistent free radical (PFR) and reactive species (RS) formation associated with photoaging microplastics; however, a relevant study is still lacking. This study systematically investigated the formation, evolution, and types of PFRs and RS on sulfur-containing microplastics (S-MPs) under simulated sunlight. Electron paramagnetic resonance detection and power saturation curve analysis isolated three different PFRs on each photoaging poly(phenylene sulfide) (PPS) and polysulfone (PSF). Combining the results of characterization and density functional theory calculation, these observed PFRs on the irradiated S-MPs were classified as oxygen-centered radicals with an adjacent S atom (namely, thio-oxygen radicals), oxygen-centered and sulfur-centered radicals, where the thio-oxygen radicals on PPS were benzenethiol-like radicals, and oxygen-centered radicals and sulfur-centered radicals on PSF that were identified as benzenesulfonic-like radicals and phenyl sulfonyl-like radicals, respectively. Moreover, potential precursor molecule fragments of PFRs on the photoaging S-MPs, including p-toluenesulfinic acid and benzenesulfonic acid, were detected by pyrolysis-gas chromatography/mass spectrometry and liquid chromatography-mass spectrometry. Interestingly, reactive sulfur species (SO3•-) was also observed on irradiated S-MPs in addition to reactive oxygen species, which was mainly derived from the reaction of •OH and sulfonyl radicals. These results have implications for assessing the potential risks of atmospheric S-MPs.

Expandable polystyrene waste modified iron sludge-based biochar activating multiple free radicals for deep wastewater treatment

Fe-containing sludge can be converted to functional biochar as a promising resource recycle pathway. However, activating properties of Fe sludge-based biochar are always limited by low specific surface area and weak carbon center for persistent free radical(PFRs). In the current study, waste expandable polystyrene particles were simultaneously used to improve the biochar catalytic performance. The co-prepared biochar achieved a high micromesoporous ratio(98.4%) with specific surface area (345.3 m²/g), improved by 20.1% and 105.2% than unimproved biochar. The improved micromesoporous properties performed better iron active sites and oxygen-containing functional groups for PFRs functioning in wastewater. The co-prepared biochar showed an efficient catalytic degradation through persulfate activating multiple free radicals of 1O2, O2˙ˉ, ˙OH and SO4˙ˉ, which removed 95.4% sulfamethoxazole with mineralizing ratio of 74% within 60 min. The recycling of waste iron sludge and waste polystyrene foam material can achieve functional biochar to apply in deep treatment of refractory organic wastewater.

Pyrrolic N and persistent free radical synergistically promote catalytic degradation of dyes via Fe2O3/activated biochar derived from Taihu blue algae

Fe-based activated biochar composites are promising catalysts for environmental remediation. However, the limited efficiency of Fe(III)/Fe(II) cycling reaction of commercial Fe2O3 at neutral conditions still impeded the catalytic performance of the heterogeneous Fenton-like catalysts. In this work, high-performance Fe2O3/activated biochar Fenton-like catalysts with Taihu blue algae (hazardous algae to aquatic ecosystems) as carbon precursors were synthesized and used for the degradation of methylene blue (MB). The physicochemical properties of Fe2O3/activated biochar composites including pore structure, the generated N species, and persistent free radicals (PFRs) were effectively tailored by activation temperatures. ACK-7-Fe (prepared under the activation temperature, 700 °C) showed a stronger adsorption ability while ACK-8-Fe (800 °C) exhibited superior MB degradation performance (∼99.97% in 30 min at neutral pH). The former was ascribed to the formation of more mesopores with suitable size which was beneficial for MB adsorption. The latter is due to the promoting effect of pyrrolic N and PFRs on the Fe(III)/Fe(II) cycle, responsible for the high catalytic efficiency of ACK-8-Fe. The hydroxyl radicals were the dominant active radicals evidenced by scavenging experiments and electron spin resonance. Moreover, the. The ACK-8-Fe exhibited superior reusability, which was crucial for its practical applications.

Environmentally persistent free radicals enhance SARS-CoV-2 replication in respiratory epithelium.

Epidemiological evidence links lower air quality with increased incidence and severity of COVID-19; however, mechanistic data have yet to be published. We hypothesized air pollution-induced oxidative stress in the nasal epithelium increased viral replication and inflammation. Nasal epithelial cells (NECs), collected from healthy adults, were grown into a fully differentiated epithelium. NECs were infected with the ancestral strain of SARS-CoV-2. An oxidant combustion by-product found in air pollution, the environmentally persistent free radical (EPFR) DCB230, was used to mimic pollution exposure four hours prior to infection. Some wells were pretreated with antioxidant, astaxanthin, for 24 hours prior to EPFR-DCB230 exposure and/or SARS-CoV-2 infection. Outcomes included viral replication, epithelial integrity, surface receptor expression (ACE2, TMPRSS2), cytokine mRNA expression (TNF-α, IFN-β), intracellular signaling pathways, and oxidative defense enzymes. SARS-CoV-2 infection induced a mild phenotype in NECs, with some cell death, upregulation of the antiviral cytokine IFN-β, but had little effect on intracellular pathways or oxidative defense enzymes. Prior exposure to EPFR-DCB230 increased SARS-CoV-2 replication, upregulated TMPRSS2 expression, increased secretion of the proinflammatory cytokine TNF-α, inhibited expression of the mucus producing MUC5AC gene, upregulated expression of p21 (apoptosis pathway), PINK1 (mitophagy pathway), and reduced levels of antioxidant enzymes. Pretreatment with astaxanthin reduced SARS-CoV-2 replication, downregulated ACE2 expression, and prevented most, but not all EPFR-DCB230 effects. Our data suggest that oxidant damage to the respiratory epithelium may underly the link between poor air quality and increased COVID-19. The apparent protection by antioxidants warrants further research.

Transformation of phosphorus species during phosphoric acid-assisted pyrolysis of lignocellulose

Phosphoric acid-assisted pyrolysis (PAAP) is a pyrolysis technique with potential for the engineered and environmental application. Nevertheless, the volatilisation, immobilisation, and dissolution of phosphorus (P) species have been neglected during PAAP of lignocellulose. Therefore, we compared the transformation of P species with direct-pyrolysis and PAAP system, using multiple techniques including gas chromatography tandem mass spectrometry (GCMS) and 31P nuclear magnetic resonance (NMR). It was also investigated that the properties of pyrogenic and modified carbons obtained from lignocellulose pyrolysis at 200–650 °C. As the temperature increased, volatile P species evolved into gas-phase during PAAP, inhibiting the formation of the macromolecular volatile components. Compared with pyrogenic carbons, modified carbons with more aromatic structures experienced a higher degree of dehydration and cyclisation via catalytic crosslinking reaction. PAAP system facilitated more generation of persistent free radical (PFR) below 500 °C and the attenuation of PFR signals was observed at 500–650 °C, which may be associated with the sequestration and elimination of P species between carbon matrix. Notably, three configurations of C3PO, CPO, and COP were the major combinations of P and C elements on modified carbons. Increased gaseous P and decreased soluble P were observed with elevated temperatures in PAAP system. The species proportion of immobilised P clearly demonstrated the transformation of partial P species from inorganic to organic through pyrolysis. The immobilised P could serve as a potential sustained-release source participating in P biogeochemical cycles. These findings are fundamental for the technical design of lignocellulose pyrolysis.

Rapid Simulation of Decade-Scale Charcoal Aging in Soil: Changes in Physicochemical Properties and Their Environmental Implications.

In situ aging can change biochar properties, influencing their ecosystem benefits or risks over time. However, there is a lack of field verification of laboratory methods that attempt simulation of long-term natural aging of biochar. We exploited a decade-scale natural charcoal (a proxy for biochar) aging event to determine which lab-aging methods best mimicked field aging. We oxidized charcoal by ultraviolet A radiation (UVA), H2O2, or monochloramine (NH2Cl), and compared it to 10-year field-aged charcoal. We considered seven selected charcoal properties related to surface chemistry and organic matter release, and found that oxidation with 30% H2O2 most representatively simulated 10-year field aging for six out of seven properties. UVA aging failed to approximate oxidation levels while showing a distinctive dissolved organic carbon (DOC) release pattern. NH2Cl-aged charcoal was the most different, showing an increased persistent free radical (PFR) concentration and lower hydrophilicity. All lab oxidation techniques overpredicted polycyclic aromatic hydrocarbon release. The O/C ratio was well-correlated with DOC release, PFR concentration, surface charge, and charcoal pH, indicating the possibility to accurately predict biochar aging with a reduced suite of physicochemical properties. Overall, our rapid and verified lab-aging methods facilitate research toward derisking and enhancing long-term benefits of biochar application.

Role of persistent free radicals and lewis acid sites in visible-light-driven wet peroxide activation by solid acid biochar catalysts – A mechanistic study

We report the synthesis of H2SO4-modified biochars (SBCs) as solid-acid catalysts to activate H2O2 at circumneutral pH under visible light radiation. Spent coffee grinds were pyrolyzed with TiO2 at 300, 500 and 600 °C followed by steeping in 5 M H2SO4 and were used for the Fenton-like degradation of methyl orange (MO). The catalytic activity of SBC depended on the pyrolysis temperature and correlated well with the surface acidity and persistent free radical (PFR) concentration. Results showed that a complete MO removal and a TOC reduction of 70.2% can be achieved with SBC500 under photo-Fenton conditions. However, poisoning of the Lewis acid sites on SBC by PO43- led to a dramatic decrease in the removal of MO with inhibition effects more pronounced than with radical scavengers, suggesting the key role played by acid-sites on the activation of H2O2. Finally, electron paramagnetic resonance (EPR) studies identified •OH as the key transient in the degradation followed by •O2- and 1O2. These findings suggest that H2O2 was likely adsorbed on the surface oxygenated functional groups before being decomposed by accepting electrons from the PFRs on the SBC surface.

Environmentally Persistent Free Radical Promotes Lung Cancer Progression by Regulating the Expression Profile of miRNAs.

Background: Environmentally persistent free radicals (EPFRs) are generated in the combustion processes of solid waste and can cause adverse influences on human health, especially lung diseases. Lung cancer is one of the most serious malignancies in recent years, which the global deaths rate is about 1.6 million every year. Methods and Results: In this study, we verified that ZnO/MCB EPFRs promote cell proliferation and migration, impedes cell apoptosis in lung cancer. Furthermore, we found that ZnO/MCB could influence the expression of miRNAs (miR-18a and miR-34a). In vivo, ZnO/MCB and ZnO EPFRs can reduce the weight and survival rate of BALB/c male mice more than that of BALB/c female mice. In the ZnO/MCB exposed group, male mice lung became even smaller, while the female mice the lung increased significantly. Taken together, our results provide evidence for assessing the potential health risks of persistent free radicals on fine particles. Conclusions: This study linked toxicity of EPFRs with miRNAs revealed the potential health hazard to human lung cancer.

Effect of Solvents on Persistent Free Radical Content in the Absence of Reactions

Effect of Solvents on Persistent Free Radical Content in the Absence of Reactions

Distribution, influence factors, and biotoxicity of environmentally persistent free radical in soil at a typical coking plant

Environmentally persistent free radicals (EPFRs) are emerging pollutants in contaminated soils and have attracted significant attention. Chinese coke production making a great contribution to the globe is increasingly identified as the non-ignorable source of EPFRs. However, the distribution level, influence factors, and biotoxicity of EPFRs at coking sites remain poorly understood. Herein, a typical coking plant in Tangshan, China, featuring two functional regions (the reconstructed project (RP) and elimination engineering (EE)) was used to study the existence of EPFRs. The spin density of the EPFRs in coking soils was 3.20 × 1020–3.11 × 1021 spins/g with g-factor values of 2.0020–2.0036. The EPFRs presented higher concentrations and g-factor values in RP region than in EE region, and a mixture of carbon-centered radicals and carbon-centered radicals with adjacent oxygen atoms as well as carbon-centered radical was ascertained in the former and the latter, respectively. Correlation analysis and FT-ICR-MS results indicated that polycyclic aromatic hydrocarbons (PAH) together with other unsaturated hydrocarbons and condensed aromatic contaminants, might contribute to the EPFRs formation in the soils of RP region, whereas PAHs were the main source of EPFRs in EE region. Soil components were determined to investigate the influence factors in EPFRs formation. Cu and Fe2O3 were recognized as the markedly positive influence factors, while TOC had a negative impact on EPFR formation. Visible light irradiation can induce the transformation and generation of EPFRs. As representative contaminants, both toluene and 2-chlorophenol can create EPFRs in coking soil under visible light irradiation. The potential biotoxicity tests of Photobacterium phosphoreum T3 spp. showed that EPFRs from the soils diminished bacterial luminescence. Such effect was proven to be induced by the OH based on the quenching experiment. Understanding the influence factors of EPFRs formation and their biotoxicity in coking soils is critical for developing risk assessments and prevention strategies.

Functional Biochar and Its Balanced Design.

Biochar has attracted increasing research attention. Various modification methods have been proposed to enhance a certain biochar function. However, these modifications may also result in an unstable structure, additional energy consumption, secondary pollution, and/or extra cost. Balanced consideration of different aspects will ensure the sustainable development of biochar technology. This review first summarizes the most commonly used methods for biochar modification. These methods are categorized according to the purposes of modification, such as surface area enlargement, persistent free radical manipulation, magnetism introduction, and redox potential enhancement. More importantly, a systematic analysis and discussion are provided regarding the balanced consideration of biochar designs, such as the balance between effectiveness and stability, functions and risks, as well as effectiveness and cost. Then, perspectives regarding biochar modification are presented. This review calls for attention that biochar modifications should not be evaluated for their functions only. A balanced design of biochars will ensure both the practicability and the effectiveness of this technology.

Low-temperature oxidation of monobromobenzene: Bromine transformation and yields of phenolic species

Brominated benzenes and phenols constitute direct precursors in the formation of bromine-bearing pollutants; most notably PBDD/Fs and other dioxin-type compounds. Elucidating accurate mechanisms and constructing robust kinetic models for the oxidative transformation of bromobenzenes and bromophenols into notorious Br-toxicants entail a comprehensive understanding of their initial oxidation steps. However, pertinent mechanistic studies, based on quantum chemical calculations, have only focused on secondary condensation reactions into PBDD/Fs and PBDEs. Literature provide kinetic parameters for these significant reactions, nonetheless, without attempting to compile the acquired Arrhenius coefficients into kinetic models. To fill in this gap, this study sets out to illustrate primary chemical phenomena underpinning the low-temperature combustion of a monobromobenzene molecule (MBZ) based on a detail chemical kinetic model. The main aim is to map out temperature-dependent profiles for major intermediates and products. The constructed kinetic model encompasses several sub-mechanisms (i.e, HBr and benzene oxidation, bromination of phenoxy radicals, and initial reaction of oxygen molecules with MBZ). In light of germane experimental observations, the formulated kinetic model herein offers an insight into bromine speciation, conversion profile of MBZ, and formation of higher brominated congeners of benzene and phenol. For instance, the model satisfactorily accounts for the yields of dibromophenols from oxidation of a 2-bromophenol (2-MBP) molecule, in reference to analogous experimental measurements. From an environmental perspective, the model reflects the accumulation of appreciable loads of 2-bromophenoxy radicals at intermediate temperatures (i.e., a bromine-containing environmental persistent free radical, EPFR) from combustion of MBZ and 2-MBP molecules. Acquired mechanistic/kinetic parameters shall be useful in comprehending the complex bromine transformation chemistry in real scenarios, most notably those prevailing in thermal recycling of brominated flame retardants (BFRs).