Nonmetal doped carbon nitride nanosheet as photocatalyst for degradation of 4, 5-dichloroguaiacol.

Metal-free photocatalysts for high efficient photocatalytic degradation of pollutants have attracted growing concern in recent years. Herein, relying on density functional theory (DFT) calculations, boron and phosphorus doped C2N layers were explored for the potential of utilization as photocatalysts for 4, 5-dichloroguaiacol (4, 5-DCG) removal. Our computations revealed that the adsorption energy of 4, 5-DCG on B@N-doped C2N layers were 26.56 kcal mol-1, and the ΔG≠ of initial reactions of 4, 5-DCG with OH were also reduced onto the B@N-doped C2N substrates. The band gap of B@N-doped C2N was 2.27 eV. The obtained results showed that the doping of boron atom into C2N layer narrows bandgap, and retains well catalytic performance and adsorption properties. Hence, B@N-doped C2N layer is a promising photocatalyst for organic pollutants removal. Possible degradation pathways of 4, 5-DCG and aquatic toxicity assessment during degradation were also carried out. Products with higher toxicity would be formed and the transformation products were still toxic to three nutrient levels of aquatic organisms (green algae, fish, and daphnia).

Unravelling the effects of complexation of transition metal ions on the hydroxylation of catechol over the whole pH region.

Catechol pollutants (CATPs) serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes. Little information is available on the effects of complexation of metal ions on CATPs degradation. This work presents a systematical study of •OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes (AOPs). Results show that the pH-dependent complexation of metal ions (Zn2+, Cu2+, Ti4+ and Fe3+) promotes the deprotonation of catechol under neutral and even acidic conditions. The radical adduct formation (RAF) reactions are both thermodynamically and kinetically favorable for all dissociation and complexation species, and OH/O- group-containing C positions are more vulnerable to •OH attack. The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation. At pH 7, the apparent rate constant (kapp) values for different systems follow the order of catechol+Ti4+ ≈ catechol+Zn2+ > catechol+Cu2+ > catechol+Fe3+ > catechol. The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs. The toxicity assessment indicates that the •OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.

Ozonolysis of Permethrin in the Atmosphere: Mechanism, Kinetics, and Evaluation of Toxicity.

Pyrethroid, a pesticide widely used worldwide, could mimic, block, or synergize the effects of endogenous hormones in humans or mammals after entering into the atmosphere and after being sprayed and applied in large quantities. This research aims to study the mechanism, kinetics, and eco-toxicity evaluation of the ozonolysis of permethrin (PER)-one of the typical pyrethroid (type I) pesticides. Existing experimental studies only predicted that ozonolysis of PER could generate a cycloperoxy analogue of PER (IM13-1-11), and the reaction mechanism has not yet been completed. To make up for the lack of experimental results, the 13 primary reaction pathways of PER and ozone, as well as the subsequent reactions of Criegee intermediates with small molecules such as NOx, COx, SO2, and O2, have been studied to propose new reaction paths by quantum chemical calculations in this work. We calculated the total reaction rate constant of PER and ozone at 298 K and 1 atm based on the calculated thermodynamic data and the transition state theory (TST), which was compared with the experimental values to prove the reliability of our results. Based on the quantitative structure and activity relationship, we predicted the acute and chronic toxicity of PER and its products of ozonolysis to three representative organisms-fish, daphnia, and green algae to avoid animal experiments. The results show that ozonolysis products of PER are still extremely harmful to the environment and should be taken seriously, although the products have less toxicity than PER.

Theoretical Study of Ozonation of Methylparaben and Ethylparaben in Aqueous Solution.

Parabens are widely employed in toothpaste, cosmetics, textiles, beverages, and preservatives, causing a serious environmental concern because they are endocrine-disrupting compounds (EDCs). As one of the highly reactive oxidants, ozone has a great effect on EDC removal. To understand the degradation and transformation of parabens in the aquatic environment and their toxicity to aquatic organisms, the degradation reaction of parabens initiated by O3 was studied meticulously using quantum chemical calculations. The degradation process includes multiple initial reaction channels and consequent degradation pathways of the Criegee intermediates. Through thermodynamic data, the rate constants were computed using the transition state theory (TST). At a temperature of 298 K and a pressure of 1 atm, the calculated rate constants were 3.92 and 3.94 M-1 s-1 for methylparaben (MPB) and ethylparaben (EPB), respectively. The rate constants increased as the temperature increased or as the length of the alkyl chain on the benzene ring increased. Through the ecotoxicity assessment procedure, the ecotoxicity of parabens and the products in the degradation process can be assessed. Most degradation byproducts are either less toxic or nontoxic. Some byproducts are still harmful, such as oxalaldehyde (P2) and ethyl 2,3-dioxopropanoate (P10). Furthermore, the ecological toxicity of parabens increased with augmentation of the alkyl chain on the benzene ring. The effect of the alkyl chain length on the benzene ring in the compound cannot be ignored.

Ozonation of diclofenac in the aqueous solution: Mechanism, kinetics and ecotoxicity assessment.

The pharmaceutical and personal care products (PPCPs) in aquatic environment have aroused more interest recently. Many of them are hard to degrade by the typical biological treatments. Diclofenac (DCF), as a significant anti-inflammatory drug, is a typical PPCP and widely existed in water environment. It is reported that DCF has adverse effects on aquatic organisms. This work aims to investigate the mechanism, kinetics and ecotoxicity assessment of DCF transformation initiated by O3 in aqueous solution, and provide a solution to the degradation of DCF. The O3-initiated oxidative degradations of DCF were performed by quantum chemical calculations, including thirteen primary reaction pathways and subsequent reactions of the Criegee intermediates with H2O, NO and O3. Based on the thermodynamic data, the kinetic parameters were calculated by the transition state theory (TST). The total reaction rate constant of DCF initiated by O3 is 2.57 × 103 M-1 s-1 at 298 K and 1 atm. The results show that the reaction rate constants have a good correlation with temperature. The acute and chronic toxicities of DCF and its degradation products were evaluated at three different trophic levels by the ECOSAR program. Most products are converted into less toxic or harmless products. Oxalaldehyde (P3) and N-(2,6-dichlorophenyl)-2-oxoacetamide (P6) are still harmful to the three aquatic organisms, which should be paid more attention in the future.

Degradation of prosulfocarb by hydroxyl radicals in gas and aqueous phase: Mechanisms, kinetics and toxicity.

Prosulfocarb (PSC) is a thiocarbamate herbicide mainly used in winter cereals and a relevant aerosol precursor under OH radicals (OH) photooxidation conditions. We investigated the environmental risks, mechanisms, kinetics and products for the PSC withOH by employing theoretical chemical calculations. Two reaction types of H-abstraction andOH-addition reactions were taken into account. Whether in the atmosphere or aqueous particles, the most favorable pathway was the H-abstraction in the N-alkyl groups close to nitrogen atom. Subsequent reactions of primary intermediates were considered at different conditions. The total rate constants were determined as 2.62 × 10-10 cm3 molecule-1 s-1 and 4.96 × 10-11 cm3 molecule-1 s-1 at 298 K in atmosphere and aqueous particles, respectively. In natural water with theOH concentration of 10-15-10-18 mol l-1, the half-lives (t1/2) of PSC in theOH-initiated reactions were calculated as t1/2 = 2.40 × 104-2.40 × 107 s. With regard to the influence on human health and the ecosystem, oxidized products of PSC were estimated to be mutagenicity negative and had no obvious bioaccumulation potential. The aquatic toxicity of PSC and its degradation products was evaluated and the assessment results showed that the degradation of PSC was a toxicity-reduced process but they were still at toxic and harmful levels.

Theoretical investigation on the contribution of HO, SO4- and CO3- radicals to the degradation of phenacetin in water: Mechanisms, kinetics, and toxicity evaluation.

Indirect oxidation induced by reactive free radicals, such as hydroxyl radical (HO), sulfate radical (SO4-) and carbonate radical (CO3-), plays an important or even crucial role in the degradation of micropollutants. Thus, the coadjutant degradation of phenacetin (PNT) by HO, SO4- and CO3-, as well as the synergistic effect of O2 on HO and HO2 were studied through mechanism, kinetics and toxicity evaluation. The results showed that the degradation of PNT was mainly caused by radical adduct formation (RAF) reaction (69% for Г, the same as below) and H atom transfer (HAT) reaction (31%) of HO. For the two inorganic anionic radicals, SO4- initiated PNT degradation by sequential radical addition-elimination (SRAE; 55%), HAT (28%) and single electron transfer (SET; 17%) reactions, while only by HAT reaction for CO3-. The total initial reaction rate constants of PNT by three radicals were in the order: SO4- > HO > CO3-. The kinetics of PNT degradation simulated by Kintecus program showed that UV/persulfate could degrade target compound more effectively than UV/H2O2 in ultrapure water. In the subsequent reaction of PNT with O2, HO and HO2, the formation of mono/di/tri-hydroxyl substitutions and unsaturated aldehydes/ketones/alcohols were confirmed. The results of toxicity assessment showed that the acute and chronic toxicity of most products to fish increased and to daphnia decreased, and acute toxicity to green algae decreased while chronic toxicity increased.

Mechanisms and Kinetic Parameters for the Gas-Phase Reactions of 3-Methyl-3-buten-2-one and 3-Methyl-3-penten-2-one with Ozone.

Ozonolysis of unsaturated ketones is a common atmospheric chemical process that plays a significant role in controlling the atmospheric budget of OH and O3, organic acids, and secondary organic aerosols (SOA). In this work, the detailed reaction mechanism and rate coefficients for the reactions of O3 with two unsaturated ketones, 3-methyl-3-buten-2-one (MBO332) and 3-methyl-3-penten-2-one (MPO332), were investigated by using density functional theory (DFT) and Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results indicate that the major products are butanedione and formaldehyde for MBO332, and butanedione and acetaldehyde for MPO332. Possible reaction mechanism and thermodynamic parameters of some complex stable Criegee intermediates (SCIs) RR'COO were also be investigated in this study. Some organic peroxides can be regarded as the main products for the further reactions of SCIs. The rate constants calculated with O3 are 2.59 × 10-16 cm3 molecule-1 s-1 and 2.28 × 10-16 cm3 molecule-1 s-1 for MBO332 and MPO332 at 298 K and 1 atm. The total rate constant is negatively correlated with temperature (200-400 K) and positively correlated with pressure. The atmospheric half-lives of MBO332 and MPO332 based on O3 are estimated.

Design, Synthesis, and Herbicidal Activity of Pyrazole Amide Derivatives as Potential Transketolase Inhibitors.

The design and synthesis of new herbicidal active compounds based on a new target are of great significance for the development of new herbicides. Transketolase (TK) plays a key role in the Calvin cycle of plant photosynthesis and has been confirmed as a potential candidate target to develop and discover new herbicides. To obtain compounds with ultraefficient targeting of TK, a series of pyrazole amide derivatives were designed and synthesized through structural optimization for lead compound 4u based on TK as the new target. The bioassay results showed that compounds 6ba and 6bj displayed a highly inhibitory effect with the root inhibition of about 90% against Digitaria sanguinalis (DS) and 80% against Amaranthus retroflexus (AR) and Setaria viridis (SV) by the small cup method, which was better than the positive control mesotrione and nicosulfuron. Furthermore, compounds 6ba and 6bj exhibited an excellent inhibitory effect with the inhibition of about 80% (against DS) and over 80% (against SV) at the dosage of 150 g of active ingredient/ha by the foliar spray method. The TK enzyme activity inhibition test showed that the inhibition effect of target compounds against TK was consistent with the results of herbicidal activities. Also, molecular docking analysis showed that compounds 6ba and 6bj went deep into the active cavity of TK, bound to TK by a strong interaction, and might act on the enzyme TK. Above of all, compounds 6ba and 6bj are promising herbicide lead compounds targeting TK. Hence, they could be developed into more efficient herbicides by further structural optimization.

Discovery of Novel Pyrazole Acyl Thiourea Skeleton Analogue as Potential Herbicide Candidates.

To discover novel transketolase (TKL, EC 2.2.1.1) inhibitors with potential herbicidal applications, a series of pyrazole acyl thiourea derivatives were designed based on a previously obtained pyrazolamide acyl lead compound, employing a scaffold hopping strategy. The compounds were synthesized, their structures were characterized, and they were evaluated for herbicidal activities. The results indicate that 7a exhibited exceptional herbicidal activity against Digitaria sanguinalis and Amaranthus retroflexus at a dosage of 90 g ai/ha, using the foliar spray method in a greenhouse. This performance is comparable to that of commercial products, such as nicosulfuron and mesotrione. Moreover, 7a showed moderate growth inhibitory activity against the young root and stem of A. retroflexus at 200 mg/L in the small cup method, similar to that of nicosulfuron and mesotrione. Subsequent mode-of-action verification experiments revealed that 7a and 7e inhibited Setaria viridis TKL (SvTKL) enzyme activity, with IC50 values of 0.740 and 0.474 mg/L, respectively. Furthermore, they exhibited inhibitory effects on the Brassica napus acetohydroxyacid synthase enzyme activity. Molecular docking predicted potential interactions between these (7a and 7e) and SvTKL. A greenhouse experiment demonstrated that 7a exhibited favorable crop safety at 150 g ai/ha. Therefore, 7a is a promising herbicidal candidate that is worthy of further development.

Establishment of an indirect competitive immunoassay for the detection of dicamba based on a highly specific nanobody.

Dicamba, a traditional highly effective and low toxicity herbicide, has gained new life with the development of dicamba-tolerant transgenic crops in recent years. However, dicamba is highly volatile and therefore easy to cause drift damage to sensitive crops. The development of efficient and sensitive detection methods is essential for monitoring of trace dicamba in the environment. Nanobody-based immunoassay plays an important role in on-site detection of pesticides. However, now rapid and sensitive immunoassay methods based on nanobody for dicamba detection were lacking. In this study, the nanobodies specifically recognizing dicamba were successfully obtained by immunising camels and phage display library construction, and then an indirect competitive immunoassay based on Nb-242 was constructed with IC50 of 0.93 µg/mL and a linear range of 0.11-8.01 µg/mL. Nb-242 had good specificity with no cross-reactivities against the dicamba analogs other than 2,3,6-trichlorobenzoic acid and the developed immnoassay had a good correlation with the standard HPLC in the spike-recovery studies. Finally, the key amino acid Ala 123, Tyr 55, Tyr 59 and Arg 72 of Nb-242 that specifically recognizing and binding with dicamba were identified by homologous modeling and molecular docking, laying an important foundation for further structural modification of Nb-242. This study has important guiding significance for constructing immunoassay method of dicamba based on nanobody and provides a sensitive, specific, and reliable detection method that is suitable for the detection of dicamba in the environment.

Development of an immunoassay based on a specific antibody for the detection of diphenyl ether herbicide fomesafen.

Fomesafen belongs to the diphenyl ether herbicide, and is widely used in the control of broadleaf weeds in crop fields due to its high efficiency and good selectivity. The residual of fomesafen in soil has a toxic effect on subsequent sensitive crops and the microbial community structure because of its long residual period. Therefore, an efficient method for detecting fomesafen is critical to guide the correct and reasonable use of this herbicide. Rapid and sensitive immunoassay methods for fomesafen is unavailable due to the lack of specific antibody. In this study, a specific antibody for fomesafen was generated based on rational design of haptens and a sensitive immunoassay method was established. The half maximal inhibitory concentration (IC50) of the immunoassay was 39 ng/mL with a linear range (IC10-90) of 1.92-779.8 ng/mL. In addition, the developed assay had a good correlation with the standard UPLC-MS/MS both in the spike-recovery studies and in the detection of real soil samples. Overall, the developed indirect competitive enzyme immunoassay reported here is important for detecting and quantifying fomesafen contamination in soil and other environmental samples with good sensitivity and high reproducibility.

Synthesis of Novel Propionamide-Methylpyrazole Carboxylates as Herbicidal Candidates.

Transketolase (TKL; EC 2.2.1.1) is a highly promising potential target for herbicidal applications. To identify novel TKL inhibitors, we designed and synthesized a series of 3-oxopropionamide-1-methylpyrazole carboxylate analogues and assessed their herbicidal activities. Ethyl 3-((1-((2,4-dichlorophenyl)amino)-1-oxopropan-2-yl)oxy)-1-methyl-1H-pyrazole-5-carboxylate (D15) and ethyl 1-methyl-3-((1-oxo-1-((thiophen-2-ylmethyl)amino)propan-2-yl)oxy)-1H-pyrazole-5-carboxylate (D20) exhibited superior growth inhibition activities against both the root and stem of Amaranthus retroflexus (A. retroflexus) compared to nicosulfuron and mesotrione. Additionally, D15 achieved an inhibition rate of more than 90% against the roots and stems of Digitaria sanguinalis (D. sanguinalis), outperforming the four control agents at a concentration of 200 mg/L using the small cup method. In the pre-emergence herbicidal activity test, D15 effectively inhibited D. sanguinalis by more than 90% at 150 g ai/ha, surpassing the efficacy of the control, mesotrione. Conversely, in the postemergence herbicidal activity test, D20 exhibited efficient inhibition of A. retroflexus by more than 90% at 150 g ai/ha, outperforming the control agents nicosulfuron, mesotrione, and metamifop. The results of the TKL enzyme activity test showed that the IC50 values of compounds D15 and D20 were 0.384 and 0.655 mg/L, respectively, which were close to those of the control agents. Furthermore, molecular docking and molecular dynamics simulation studies revealed that D15 and D20 interacted favorably with the TKL of Setaria viridis. Such findings highlight the promising potential of D15 and D20 as lead TKL inhibitors for the optimization of new herbicides.

Discovery of novel Propionamide-Pyrazole-Carboxylates as Transketolase-inhibiting herbicidal candidates.

BACKGROUND: Transketolase (TKL, EC 2.2.1.1) is a key enzyme in the pentose phosphate pathway and Calvin cycle, and is expected to act as a herbicidal site-of-action. On the basis of TKL, we designed and synthesized a series of 1-oxy-propionamide-pyrazole-3-carboxylate analogues and evaluated their herbicidal activities. RESULTS: Methyl 1-methyl-5-((1-oxo-1-((4-(trifluoromethyl)phenyl)amino)propan-2-yl)oxy)-1H-pyrazole-3-carboxylate (C23) and methyl 1-methyl-5-((1-oxo-1-((perfluorophenyl)amino)propan-2-yl)oxy)-1H-pyrazole-3-carboxylate (C33) were found to provide better growth-inhibition activities against Digitaria sanguinalis root than those of nicosulfuron, mesotrione and pretilachlor at 200 mg L-1 using the small-cup method. These compounds were also identified as promising compounds in pre-emergence and postemergence herbicidal-activity experiments, with relatively good inhibitory effects toward Amaranthus retroflexus and D. sanguinalis at 150 g ai ha-1. In addition, enzyme inhibition assays and molecular docking studies revealed that C23 and C33 interact favourably with SvTKL (Setaria viridis TKL). CONCLUSION: C23 and C33 are promising lead TKL inhibitors for the optimization of new herbicides. © 2024 Society of Chemical Industry.

Ozone mechanism, kinetics, and toxicity studies of halophenols: Theoretical calculation combined with toxicity experiment.

Aromatic disinfection by-products (DBPs), which are generally more toxic than aliphatic DBPs, have attracted increasing attention. The toxicity of 13 typical halophenols on Scenedesmus obliquus was experimentally investigated, and the ozonation mechanism and kinetics of representative halophenols were further studied by quantum chemical calculations. The results showed that the EC50 values of halophenols ranged from 2.74 to 60.23 mg/L, and their toxicity ranked as follows: di-halogenated phenols > mono-halogenated phenols, mixed halogen-substituted phenols > single halogen-substituted phenols, and iodophenols > bromophenols > chlorophenols. The toxicity of halophenols was well described by the electronegativity index (ω) as lg(EC50)-1 = 6.228ω - 3.869, indicating halophenols capturing electrons as their potential toxicity mechanism. The reactions of O3 with halophenolate anions were dominated by three mechanisms: 1,3-dipolar cycloaddition, oxygen addition, and single electron transfer. The kinetic calculation indicated that O3 oxidized aqueous halophenols by reacting with halophenolate anions with the reaction rate constants as high as (0.91-3.47) × 1010 M-1 s-1. The number of halogen substituents affected the kO3, cal values of halophenolate anions, which are in the order of 2,4-dihalophenolate anions >4-halophenolate anions > 2,4,6-trihalophenolate anions. During the ozonation of 2,4,6-tribromophenol (246TBP), the toxic products (dimers and brominated benzoquinones) could be synergistically degraded by O3 and HO•. Thus, ozonation is feasible as a strategy to degrade aromatic DBPs.

Comparison of ribavirin degradation in the UV/H2O2 and UV/PDS systems: Reaction mechanism, operational parameter and toxicity evaluation.

Residues in surface water of ribavirin, which used extensively during the COVID-19 pandemic, have become an emerging issue due to its adverse impact on the environment and human health. UV/H2O2 and UV/peroxydisulfate (PDS) have different degradation effects on ribavirin, and the same operational parameter have different effects on the two processes. In this study, the reaction mechanism and degradation efficiency for ribavirin were studied to compare the differences under UV/H2O2 and UV/PDS processes. We calculated the total rate constants of ribavirin with HO• and SO4 •- in the liquid phase as 2.73 × 108 and 9.39 × 105 M-1s-1. The density functional theory (DFT) calculation results showed that HO• and SO4 •- react more readily with ribavirin via H-abstraction (HAA). The nitrogen-containing heterocyclic ring is difficult to undergo ring-opening degradation. The UV/PDS process was more stable and performed better than the UV/H2O2 for the ribavirin degradation when the same molar oxidant dosage was applied. HO• plays an extremely important role in the degradation of ribavirin by UV/PDS. The reason for this phenomenon is the combination of the higher yield of HO• produced in the UV/PDS process and the faster reaction rate of ribavirin with HO•. The UV/H2O2 process is more sensitive to pH than UV/PDS. Alkaline condition can significantly inhibit the ribavirin degradation. The effects of natural organic matter (NOM) and ribavirin concentration were also compared. Eventually, the toxicity prediction of the product showed that the opening-ring products were more toxic than the parent compound.

Citric acid modified ultrasmall copper peroxide nanozyme for in situ remediation of environmental sulfonylurea herbicide contamination.

Herbicide residues in the environment threaten high-quality agriculture and human health. Consequently, in situ remediation of herbicide contamination is vital. We synthesized a novel self-catalyzed nanozyme, ultrasmall (2-3 nm) copper peroxide nanodots modified by citric acid (CP@CA) for this purpose, which can break down into H2O2 and Cu2+ in water or soil. Ubiquitous glutathione reduces Cu2+ into Cu+, which promotes the decomposition of H2O2 into •OH through a Fenton-like reaction under mild acid conditions created by the presence of citric acid. The generated •OH efficiently degrade nicosulfuron in water and soil, and the maximum degradation efficiency could be achieved at 97.58% in water at 56 min. The possible degradation mechanisms of nicosulfuron were proposed through the 25 intermediates detected. The overall ecotoxicity of the nicosulfuron system was significantly reduced after CP@CA treatment. Furthermore, CP@CA had little impact on active components of soil bacterial community. Moreover, CP@CA nanozyme could effectively remove seven other sulfonylurea herbicides from the water. In this paper, a high-efficiency method for herbicide degradation was proposed, which provides a new reference for the in situ remediation of herbicide pollution.

Hydroxylation of some emerging disinfection byproducts (DBPs) in water environment: Halogenation induced strong pH-dependency.

In this work, the hydroxylation mechanisms and kinetics of some emerging disinfection byproducts (DBPs) have been systematically investigated through theoretical calculation methods. Five chlorophenols and eleven halogenated pyridinols were chosen as the model compounds to study their pH-dependent reaction laws in UV/H2O2 system. For the reactions of HO• with 37 different dissociation forms, radical adduct formation (RAF) was the main reaction pathway, and the reactivity decreased with the increase of halogenation degree. The kapp values (at 298 K) increased with the increase of pH from 0 to 10, and decreased with the increase of pH from 10 to 14. Compared with phenol, the larger the chlorination degree in chlorophenols was, the stronger the pH sensitivity of the kapp values; compared with chlorophenols, the pH sensitivity in halogenated pyridinols was further enhanced. As the pH increased from 2 to 10.5, the degradation efficiency increased at first and then decreased. With the increase of halogenation degree, the degradation efficiency range increased, the pH sensitivity increased, the optimal degradation efficiency slightly increased, and the optimal degradation pH value decreased. The ecotoxicity and bioaccumulation of most hydroxylated products were lower than their parental compounds. These findings provided meaningful insights into the strong pH-dependent hydroxylation of emerging DBPs on molecular level.

Simulation degradation of bromophenolic compounds in chlorine-based advanced oxidation processes: Mechanism, microscopic and apparent kinetics, and toxicity assessment.

Chlorine-based advanced oxidation processes (AOPs) have been extensively studied to remove contaminants through generating HO• and reactive chlorine species, including ClO• and Cl•. In this work, 2,4,6-tribromoanisole (246TBA) and 2,4,6-tribromophenol (246TBP) were selected as model to investigate the reaction mechanisms and micro-kinetics of brominated contaminants with HO•, ClO• and Cl• in chlorine-based AOPs. Also, the apparent degradation kinetics of two compounds were simulated at pH 3.0-9.5 under UV/H2O2, UV/chlorine and UV/NH2Cl. Calculated results showed that neutral 246TBA and 246TBP exhibited similar reactivity to HO• and ClO•, which was different from anionic 2,4,6-tribromophenolate (246TBPT): radical adduct formation (RAF) and H atom abstraction (HAA) were predominant mechanisms for the HO• and ClO• initiated reactions of 246TBA and 246TBP, while RAF and single electron transfer (SET) for 246TBPT; the reaction rate constants of 246TBA and 246TBP with HO• and ClO• were lower than 107 M-1 s-1, and such rate constants dramatically increased to 1010 M-1 s-1 once 246TBP was deprotonated to 246TBPT. The apparent degradation kinetics of 246TBA at pH 3.0-9.5 was simulated in the order of UV/NH2Cl > UV/chlorine > UV/H2O2, and UV/chlorine and UV/NH2Cl were more effective for the removal of 246TBP and 246TBPT than UV/H2O2. UV and/or Cl• dominated 246 TBA degradation under three AOPs. The main radicals mediating 246TBP and 246TBPT degradation are respectively HO• under UV/H2O2, ClO• under UV/chlorine, and HO• and Cl• under UV/NH2Cl. The transformation products of 246TBA, 246TBP and 246TBPT, especially methoxylated and hydroxylated polybrominated diphenyl ethers (MeO-PBDEs and HO-PBDEs), were still toxic pollutants.

The reaction laws and toxicity effects of phthalate acid esters (PAEs) ozonation degradation on the troposphere.

Low-molecular-weight (LMW) phthalate acid esters (PAEs) tend to enter the atmosphere, flying for several kilometers, so it is easy to endanger human health. This work is the first to use quantum chemistry calculations (Gaussian 16 program) and computational toxicology (ECOSAR, TEST, and Toxtree software) to comprehensively study the ozonolysis mechanism of six LMW PAEs (dimethyl phthalate (DMP), diethyl phthalate (DEP), dipropyl phthalate (DPP), diisopropyl phthalate (DIP), dibutyl phthalate (DBP), and diisobutyl phthalate (DIBP)) in the atmosphere and the toxicity of DMP (take DMP as an example) in the conversion process. The results show that the electron-donating effect of the ortho position of the LMW PAEs has the most obvious influence on the ozonolysis. We summarized the ozonation reaction law of LMW PAEs at the optimal reaction site. At 298 K, the law of initial ozonolysis total rate constant of the LMW PAEs is kDIP > kDPP > kDIBP > kDMP > kDEP > kDBP, and the range is 9.56 × 10-25 cm3 molecule-1 s-1 - 1.47 × 10-22 cm3 molecule-1 s-1. According to the results of toxicity assessment, the toxicity of products is lower than DMP for aquatic organisms after ozonolysis. But those products have mutagenicity, developmental toxicity, non-genotoxicity, carcinogenicity, and corrosiveness to the skin. The proposed ozonolysis mechanism promotes our understanding of the environmental risks of PAEs and provides new ideas for studying the degradation of PAEs in the tropospheric gas phase.