This study investigates reaction pathways for the formation of pre-PXDD/F intermediates via a radical/molecule mechanism. Thermodynamic and kinetic parameters for the combination reactions of 2-bromophenol (2-BP) and 2-chlorophenol (2-CP) precursors with key radical species including the phenoxy radicals, the phenyl radicals and the phenoxyl diradicals were calculated in detail. The couplings of phenoxy radicals with 2-B(C)P tend to produce pre-PXDD intermediates of halogenated o-phenoxyphenol. The combinations of phenyl and phenoxyl diradicals with 2-B(C)P produce two types of structures, i.e., dihydroxybiphenyl and o-phenoxyphenyl, which exclusively act as prestructures of PXDFs. These condensation reactions, especially those involving the phenyl C atom sites in phenyl and phenoxyl diradicals, are proven to be both thermodynamically and kinetically favorable and are nearly comparable with the corresponding steps involved in the radical/radical reactions. Most importantly, reactions of phenyl and phenoxyl diradicals with halogenated phenols solely lead to the formation of PXDFs, which to some extent provides a plausible explanation for the high PXDF-to-PXDD ratios in the real environment. Therefore, our study reveals the pivotal role of the radical/molecule mechanism in homogeneous gas-phase PXDD/F formation, especially in PXDF formation. The present results fill in a knowledge gap that has hitherto existed regarding dioxin formation and improve our understanding of PXDD/F formation characteristics in the environment.

Advanced oxidation processes (AOPs) based on formation of free radicals at ambient temperature and pressure are effective for treating endocrine disrupting chemicals (EDCs) in waters. In this study, we systematically investigated the degradation kinetics of bisphenol A (BPA), a representative EDC by hydroxyl radical (OH) with a combination of experimental and theoretical approaches. The second–order rate constant (k) of BPA with OH was experimentally determined to be 7.2 ± 0.34 × 109 M−1 s−1 at pH 7.55. We also calculated the thermodynamic and kinetic behaviors for the bimolecular reactions by density functional theory (DFT) using the M05–2X method with 6–311++G** basis set and solvation model based on density (SMD). The results revealed that H–abstraction on the phenol group is the most favorable pathway for OH. The theoretical k value corrected by the Collins–Kimball approach was determined to be 1.03 × 1010 M−1 s−1, which is in reasonable agreement with the experimental observation. These results are of fundamental and practical importance in understanding the chemical interactions between OH and BPA, and aid further AOPs design in treating EDCs during wastewater treatment processes.

This study investigated the factors that regulated the degradation of perfluorooctanoic acid (PFOA) in laccase-catalyzed oxidative humification reactions with 1-hydroxybenzotriazole (HBT) as a mediator. The reaction rates were examined under conditions with key factors varied, including initial PFOA concentrations, laccase and HBT dosages, and the ionic contents of the reaction solutions. The PFOA degradation followed pseudo-first order kinetics, and the rate constants (k) were similar for the high (100 μmol L⁻¹) and low (1.00 μmol L⁻¹) initial PFOA concentrations, respectively at 0.0040 day⁻¹ (r² = 0.98) and 0.0042 day⁻¹ (r² = 0.86) under an optimum reaction condition tested in this study. The metal ions contained in the reaction solution appeared to have a strong impact on PFOA degradation. Differential UV-Vis spectrometry revealed that Cu²⁺ can complex with PFOA, which plays an essential role to enable PFOA degradation, probably by bridging the negatively charged PFOA and laccase, so that the free radicals of HBT that are released from laccase can reach and react with PFOA. It was also found that Fe³⁺ plays a similar role as Cu²⁺ to enable PFOA degradation in the laccase-HBT reaction system. In contrast, Mg²⁺ and Mn²⁺ cannot complex with PFOA under the investigated conditions, and do not enable PFOA degradation in the laccase-HBT system. Fluoride and partially fluorinated compounds were detected as PFOA degradation products using ion chromatography and high resolution mass spectrometry. The structures of the products suggest the reaction pathways involving free-radical initiated decarboxylation, rearrangement, and cross-coupling.

Solid digestate, a by-product of anaerobic digestion systems, has led to a range of environmental issues. In the present study, a novel composite based on a solid digestate-biochar-Cu NP composite was synthesized for tetracycline removal from an aqueous medium. The removal efficiency values for tetracycline (200 mg L⁻¹) were 31.5% and 97.8%, respectively, by the biochar-Cu NP composite (0.5 g L⁻¹) in the absence and presence of hydrogen peroxide (H2O2, 20 mM) within 6 h of reaction time. The possible degradation pathway of tetracycline was investigated using liquid chromatography-mass spectrometry. The desorption experiment results suggested that no significant concentration of tetracycline was detected on the composite after the reaction, but a small amount of intermediates in terms of total organic carbon (TOC) accounting for 3.1%, and 23.3% of the end-product NH4⁺ was adsorbed onto the biochar sheets. The dispersive Cu NPs on the biochar resulted in an increase in the surface area and pore volume of the biochar-Cu NP composite, which enhanced tetracycline adsorption as well as the degradation efficiency. Relative tetracycline removal mechanisms were dominantly ascribed to ·OH generation from the Cu(II)/Cu(I) redox reaction with H2O2 and the electron-transfer process of free radicals (FRs) in biochar. The proposed approach serves dual purposes of waste digestate reuse and treatment of antibiotic pollutants.This study highlights the activation of H2O2 by the dispersive Cu NPs coupling with biochar derived from a waste solid digestate for tetracycline treatment.

Extensive studies have been conducted on the environmental degradation of multiwall carbon nanotubes (MWCNTs), but primarily focused on the extent and rate of MWCNTs mineralization. Few studies have explored possible structural changes that may occur to MWCNTs during natural or engineered processes. We systematically examined MWCNTs in oxidative coupling reactions in the presence of a common contaminant tetrabromobisphenol A (TBBPA). MWCNTs was modified by the radicals of TBBPA resulting from peroxidase-mediated coupling reaction. Interactions between TBBPA radicals and MWCNTs were definitely confirmed by analyzing the characteristic mass spectrometry response of bromine in TBBPA and the structures of MWCNTs. After reaction with TBBPA radicals for 60 min, the content of bromine contained in MWCNTs was 6.84(±0.12)%, a quantity equivalent to a 501.65(±2.19) mg loading of TBBPA per gram MWCNTs. Modified MWCNTs had better stability and smaller sizes than that of MWCNTs and TBBPA-adsorbed MWCNTs. Assessment using zebrafish embryos revealed that the modified MWCNTs passed through the chorion and entered the embryo inducing acute toxicity, while the MWCNTs/TBBPA-adsorbed MWCNTs was trapped by chorion. These findings indicated that MWCNTs was modified in peroxidase-mediated coupling reactions, and suggested that such modifications may have an influence on the ecological risks of MWCNTs.

Membrane photocatalytic ozonization coupled with wet absorption offers potential for elemental mercury (Hg0) removal. This study reports on a novel FeTiO2-coated polyvinylidene fluoride (PVDF) wet photocatalytic membrane reactor (WPCMR) for mercury removal in flue gas. Hg0 removal efficiency in the WPCMR reached up to 93.3%. Ozone could enhance mercury oxidation in WPCMR. Wet absorption helps to increases mercury removal efficiency. FeTiO2 catalyst was synthesized by sol-gel method and characterized by XRD, FTIR, UV–Vis, XPS and SEM. XPS analysis confirmed Hg0 oxidation to divalent mercury (Hg (II)). Elemental mercury was oxidized to mercuric oxide followed by wet absorption in the presence of OH free radical and ozone. Wet photocatalytic membrane reactor and photocatalytic membrane reactor (PCMR) of elemental mercury reaction with the FeTiO2/PVDF catalyst all follow Langmuir-Hinshelwood kinetics.

The ultraviolet (UV)-based advanced oxidation process (AOP) is a powerful technology commonly utilised in recent potable water reuse (PR) schemes. The AOP involves the generation of highly reactive free radicals (e.g. hydroxyl, HO•) and is primarily applied for the removal of two target trace organic chemicals—N-nitrosodimethylamine (NDMA) and 1,4-dioxane — in the PR schemes. Both of these organics are not well removed by the reverse osmosis (RO) process. NDMA is a probable carcinogen and is often present in reclaimed water at concentrations higher than the guidelines established for PR. This review aimed to provide an understanding of the current UV-based advanced oxidation technologies for NDMA removal in PR, their limitations and the future of advanced technologies for their removal. NDMA is readily photolysed by direct UV irradiation, while an AOP such as UV/H₂O₂ process is necessary for the destruction of 1,4-dioxane. Unfortunately, the generation of hydroxyl radicals through UV photolysis of H₂O₂ is largely inefficient with conversion on the order of 20% under normal plant operations and the addition of H₂O₂ (e.g. 3 mg/L) provides only a negligible improvement in NDMA destruction. However, AOP can also be achieved without continuous chemical addition through the application of UV irradiation to heterogeneous photocatalysts (e.g. TiO₂). The UV/TiO₂ process generates hydroxyl radicals and singlet oxygen molecules, both of which degrade NDMA into by-products (e.g. methylamine or dimethylamine). Recent studies revealed that modification of the surface morphology of TiO₂ can not only enhance NDMA destruction but also alter the composition of the degradation by-products.

In situ chemical oxidation using persulfate is one alternative to remediate polycyclic aromatic hydrocarbon-contaminated soil; however, oxidation can lead to the formation of toxic and persistent by-products, and treatment efficiency can be dependent on environmental conditions. Temperature and soil matrix properties can dictate reaction rates and pathways, promoting oxidant activation or scavenging the free radicals generated. This research investigated the ability of persulfate to degrade anthracene in tropical environmental conditions. Batch tests were conducted for various persulfate systems (naturally and chelated-iron-activated), with an Oxisol contaminated with anthracene. Electron paramagnetic resonance (EPR) was used to identify free radicals formed. Naturally activated persulfate degraded more than 96% of the anthracene and its by-product anthraquinone after 90 days, considered more toxic and persistent, while the chelated-iron-activated persulfate system used was able to remove 70% of the anthracene. EPR measurements showed the coexistence of SO₄·⁻ and ·OH radicals. Sulfate radicals were formed by thermal activation at ambient temperatures (mean of 23.7 °C), and ·OH was formed by propagation reactions and hydrolysis in acidic conditions that lead to peroxide formation. In the naturally activated system, anthracene degradation was observed and SO₄·⁻ radicals were abundant, indicating that this treatment system can be effective in a typical tropical soil environment.

The role of different operational parameters related to Fenton reactions (pH, concentration of Fe²⁺ and H₂O₂, and reaction time) and of Cl⁻ and SO ₄ ⁻ was investigated in the degradation of the azo dye Direct Red 81, expressed in terms of its decolorization. The factorial design and Pareto’s charts showed that only Fe²⁺ concentration and pH influence the decolorization under the conditions evaluated. So, only these parameters were optimized using the response surface model. Under the best experimental conditions (initial pH 2.5, 11 mg L⁻¹ Fe²⁺, 78 mg L⁻¹ H₂O₂, and 20 min of reaction), 94 % of decolorization was achieved. However, even under the these conditions, but in the presence of Cl⁻ and SO ₄ ⁻ , a striking loss of efficiency was observed as the concentration of these ions was increased, due the formation of chloride- and sulfate-iron complexes and less reactive inorganic radicals (Cl₂ •– and SO₄ •–). The results show that the presence of Cl⁻ is more deleterious, since sulfate-iron complexes are more reactive towards H₂O₂, and the SO₄ •– turns out to favor the degradation. On the other hand, the negative effect of Cl⁻ can be compensated by increasing the chloride concentration up to 300 mmol L⁻¹. In addition, although a high degradation level has been obtained by monitoring the dye absorbance and by HPLC-UV, a low mineralization occurred, being generated degradation products of higher ecotoxicity to Vibrio fischeri, showing the need of subsequent studies to identify these compounds as well as the application of additional treatments aiming the complete mineralization of the dye.

The toxicity of levofloxacin to yellow lupin plants was evaluated in this study. Recommended indexes of plant (roots and shoots) growth were determined and new indexes were proposed which better characterise the phytotoxicity of levofloxacin. These were, in particular, the activity of antioxidative enzymes, the content of free radicals, as well as the root protein content and the root protein profile. The results showed that levofloxacin considerably affected EC₅₀, measured as the activity of catalase in roots, and leaves (1.05 and 0.069 mM, respectively). The activity of peroxidase in the roots and the dry weight of seedlings were the least sensitive parameters (EC₅₀ was 1.8 and 1.76 mM, respectively). Units of toxicity clearly showed that the activity of catalase is a better measure of toxicity for low concentrations of the drug, and it is a better index of plant physiological state than the morphological parameters of seedlings. Moreover, levofloxacin changed the location of free radicals and the protein profile in plants. The changes in location of reactive oxygen species in roots were an important symptom of the drug toxicity to lupin seedlings. Our results have shown that the toxicity of levofloxacin was manifested mainly by changes in the protein profile. The content of the glyceraldehyde-3-phosphate dehydrogenase, 14-3-3-like protein A, expansin-B3-like precursor, fructose-bisphosphate aldolase, lipoxygenase, nucleotide-binding subunit of vacuolar ATPase and pyruvate dehydrogenase were found to decrease. On the other hand, plant exposure to levofloxacin resulted in an increase in the content of enolase, protein LlR18A, class III chitinase, ascorbate peroxidase, aspartate aminotransferase, alcohol dehydrogenase 1, leghemoglobin reductase-like 17 and heat shock cognate protein 80-like.