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The accumulation of atrazine in soils can create environmental challenges, potentially posing risks to human health. Superabsorbent hydrogel (SH)-based formulations offer an eco-friendly approach to accelerate herbicide degradation. However, the impact of SHs on soil microbial community structure, and thus on the fate of atrazine, remains uncertain. In this study, a radioactive tracer was employed to investigate the influence of SHs on microbial communities and atrazine transformation in soils. The results revealed that the mineralization of atrazine in active soils was considerably greater than that in sterilized soils. Atrazine degradation proceeded rapidly under SH treatment, indicating the potential of SH to accelerate atrazine degradation. Furthermore, SH addition did not alter the atrazine degradation pathway in soils, which included dealkylation, dechlorination and hydroxylation. The relative abundance of dominant microbial population was influenced by the presence of SHs in the soil. Additionally, SH application led to an increased relative abundance of Lysobacter, suggesting its potential involvement in atrazine degradation. These findings reveal the significance of soil microorganisms and SH in atrazine degradation, offering crucial insights for the development of effective strategies for atrazine remediation and environmental sustainability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In an attempt to create economically feasible and sustainable wastewater treatment "green" techniques, Malva parviflora leaf water extract was used for biosynthesizing silver nanoparticles (Malva-AgNPs). Fourier transform infrared, ultraviolet-visible (UV-Vis), scanning electron microscopy, and dynamic light scattering (DLS) were used for the characterization of Malva-AgNPs. UV-Vis and DLS analysis revealed the stability of the Malva-AgNPs at a wavelength of 420 nm and an average size of 100 nm ± 1 nm. A zeta potential of - 26.4 mV provides additional support for the stability of the material. The removal studies were conducted using atrazine and methylene blue (MB) in a single or mixed liquid state. The adsorbent dose, pH, incubation time, and pollutant concentration in the adsorption process were investigated. The optimal removal for 500 mg L -1 of atrazine and MB at the adsorbent dosage of 450 mg, when incubated for 5 min, was found to be 99.5% and 82.03% for atrazine and MB, respectively. Also, Malva-AgNPs eliminated more than 95% and 50% of the atrazine and MB mixture, respectively, in 5 min. The kinetics study showed that the pseudo-second-order kinetics model was a better fit for explaining the experimental adsorption experiments for atrazine and MB. The obtained equilibrium adsorption data were examined using the Langmuir and Freundlich isotherm models, which indicate that atrazine and MB have maximum adsorption capacities of 434.78 mg g -1 and 400 mg g -1 , respectively., Competing Interests: Declarations Ethics approval All authors have read, understood, and have complied as applicable with the statement on “Ethical responsibilities of Authors” as found in the “Instructions for Authors.” Competing interests The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Environmental microplastics (MPs) are complex mixtures of plastic polymers and sorbed chemical pollutants with high degrees of heterogeneity, particularly in terms of particle size, morphology and degree of weathering. Currently, limitations exist in sampling sufficient amounts of environmental particles for laboratory studies to assess toxicity endpoints with statistical rigor and to examine chemical pollutant interactions. This study seeks to bridge this gap by investigating environmental plastic particle mimetics and pollutant-polymer interactions by mixing polymer particles with persistent organic pollutants (POPs) at set concentrations over time. Solutions containing combinations of polymers including polystyrene (PS), polypropylene (PP), polyethylene terephthalate (PET), and polyamide (PA) and POPs including 2,3,7,8 -Tetrachlorodibenzo-p-dioxin (TCDD), bisphenol A (BPA), and atrazine, were stirred for up to 19 weeks and monitored using assays to test for aryl hydrocarbon (AhR) and estrogen receptor (ER) activity which are cell signaling pathways impacted by environmental pollutants. TCDD induced AhR activity decreased over time in the presence of PS in a surface area dependent manner. BPA and atrazine also exhibited AhR antagonist activity in the presence of TCDD. The addition of BPA slowed the loss of activity but atrazine did not, suggesting that polymer chemistry impacts interactions with POPs. We also observed potential differences in TCDD sorption with different plastic polymers and that higher concentrations of PS particles may inhibit BPA-induced estrogen receptor activation. These results emphasize the need for additional understanding of how POPs and polymer chemistry impact their interaction and toxicity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

As the rapidly growing number of waste lithium-ion batteries (LIBs), the recycling and reutilization of anode graphite is of increasing interest. Converting waste anode graphite into functional materials may be a sensible option. Herein, a series of carbonaceous catalysts (TG) were successfully prepared using spent anode graphite calcined at various temperatures and applied for activating peroxymonosulfate (PMS) to degrade atrazine (ATZ). The catalyst obtained at 800 °C (TG-800) showed the optimum performance for ATZ removal (99.2% in 6 min). Various experimental conditions were explored to achieve the optimum efficiency of the system. In the TG-800/PMS system, free radicals (e.g., SO 4 ·- , HO·), singlet oxygen ( 1 O 2 ), together with a direct electron transfer pathway all participated in ATZ degradation, and the ketonic (CO) group was proved as the leading catalytic site for PMS activation. The potential degradation routes of ATZ have also been presented. According to the toxicity assessment experiments, the toxicity of the intermediate products decreased. The reusability and universal applicability of the TG-800 were also confirmed. This research not only provides an efficient PMS activator for pollutant degradation, but also offers a meaningful reference for the recovery of waste anode graphite to develop environmentally functional materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Triazine pesticide (atrazine and its derivatives) detection sensors have been developed to thoroughly check for the presence of these chemicals and ultimately prevent their exposure to humans. Sensitive coatings were designed by utilizing molecular imprinting technology, which aims to create artificial receptors for the detection of chlorotriazine pesticides with gravimetric transducers. Initially, imprinted polymers were developed, using acrylate and methacrylate monomers containing hydrophilic and hydrophobic side chains, specifically for atrazine, which shares a basic heterocyclic triazine structure with its structural analogs. By adjusting the ratio of the acid to the cross-linker and introducing acrylate ester as a copolymer, optimal non-covalent interactions were achieved with the hydrophobic core of triazine molecules and their amino groups. A maximum sensor response of 546 Hz (frequency shift/layer height equal to 87.36) was observed for a sensitive coating composed of 46% methacrylic acid and 54% ethylene glycol dimethacrylate, with a demonstrated layer height of 250 nm (6.25 kHz). The molecularly imprinted copolymer demonstrated fully reversible sensor responses, not only for atrazine but also for its metabolites, like des-ethyl atrazine, and structural analogs, such as propazine and terbuthylazine. The efficiency of modified molecularly imprinted polymers for targeted analytes was tested by combining them with a universally applicable quartz crystal microbalance transducer. The stable selectivity pattern of the developed sensor provides an excellent basis for a pattern recognition procedure.

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 μA mM -1 cm -2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

In the conventional drinking water treatment process (CDWTP), powdered activated carbon (PAC) is commonly used for removing organic pesticides, or other organic contaminants. However, the hydraulic retention time (HRT) in CDWTP is insufficient for fulfilling PAC adsorption equilibrium to realize its full capacity. This study examined the adsorption kinetics, adsorption thermal dynamics, and removal efficiency for six organic pesticides using the ball-milled PAC (BPAC) with varying particle sizes in CDWTP. Based on the experiments with the pesticides of atrazine, diazinon, dimethoate, fenitrothion, isoproturon and thiometon, the results indicated that as the particle size reduced from around 38 μm for the commercial PAC to 1 μm for the BPAC, the adsorption rates for hydrophobic pesticides increased up to twentyfold. Diffusional adsorption from the bulk solution to the external PAC surface is the most likely predominant mechanism. This could allow a sufficient pesticides' adsorption within the limited HRT and to achieve a great depth removal of these toxic compounds. However, the addition of BPAC with a diameter of 1 μm was observed to significantly increase residual particles in treated water after the conventional treatment process. With a further systematic evaluation of both adsorption rate and particle penetration, a particle size of around 6 μm BPAC was considered a practical compromise between the adsorption rate and particle penetration for real application. Results from five surface waters of different water quality indicated that, compared to commercial PAC, application of 6 μm BPAC could achieve up to a 75% reduction in adsorbent dosage while maintaining around the same pesticide removal efficiencies. Additionally, thermodynamic analyses suggest that adsorption of these pesticides could be enthalpically or entropically driven depending on the degree of pesticide hydrophobicity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

An efficient perovskite-based heterogeneous catalyst is highly desired to activate peroxymonosulfate (PMS) for removing organic pollutants in water. A high surface area PMS-activator was fabricated by loading LaCoO 3 on SBA-15 to degrade atrazine (ATR) in water. The LaCoO 3 /SBA-15 depicted better textural properties and higher catalytic activity than LaCoO 3 . In 6.0 min, atrazine (ATZ) degradation in the selected LaCoO 3 /SBA-15/PMS system, LaCoO 3 , adsorption by LaCoO 3 /SBA-15, sole PMS processes reached approximately 100%, 55.15%, 12.80%, and 16.65 % respectively. Furthermore, 0.04 mg L -1 Co was leached from LaCoO 3 /SBA-15 during PMS activation by LaCoO 3 /SBA-15. The LaCoO 3 /SBA-15 showed stable catalytic activity after reuse. The use of radical scavengers and electron paramagnetic resonance spectroscopy (EPR) demonstrated that ROS such as 1 O 2 , O 2 •- , • OH, and SO 4 •- were generated by PMS activated by LaCoO 3 /SBA-15 owing to redox reactions [Co 2+ /Co 3+ , and O 2- /O 2 ]. EPR, XPS, ATR-FTIR, EIS, LSV, and chronoamperometric measurements were used to explain the catalytic mechanism for PMS activation. Excellent atrazine degradation was due to high surface area, porous nature, diffusion-friendly structure, and ROS. Our investigation proposes that perovskites with different A and B metals and modified perovskites can be loaded on high surface area materials to activate PMS into ROS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The degradation kinetics and mechanism of atrazine (ATZ) via an enzyme-based Fenton reaction were investigated at various substrate concentrations and pH values. Toxicological assessment was conducted on ATZ and its degradation products, and the associated reaction pathway was examined. The in situ production of hydrogen peroxide (H 2 O 2 ) was monitored within the range of 3-15 mM, depending on the increase in glucose concentration, while decreasing the pH to 3.2-5.1 (initial pH of 5.8) or 6.5-7.4 (initial pH of 7.7). The degradation efficiency of ATZ was approximately 2-3 times higher at an initial pH of 5.8 with lower glucose concentrations than at an initial pH of 7.7 with higher substrate concentrations during the enzyme-based Fenton reaction. The apparent pseudo-first-order rate constant for H 2 O 2 decomposition under various conditions in the presence of ferric citrate was 1.9-6.3 × 10 -5 s -1 . The •OH concentration ([•OH] ss ) during the enzyme-based Fenton reaction was 0.5-4.1 × 10 -14  M, and the second-order rate constant for ATZ degradation was 1.5-3.3 × 10 9  M -1  s -1 . ATZ intrinsically hinders the growth and development of Arabidopsis thaliana, and its inhibitory effect is marginal, depending on the reaction time of the enzyme-based Fenton process. The ATZ transformation during this process occurs through dealkylation, hydroxylation, and dechlorination via •OH-mediated reactions. The degradation kinetics, mechanism, and toxicological assessment in the present study could contribute to the development and application of enzyme-based Fenton reactions for in situ pollutant abatement. Moreover, the enzyme-based Fenton reaction could be an environmentally benign and applicable approach for eliminating persistent organic matter, such as herbicides, using diverse H 2 O 2 -producing microbes and ubiquitous ferric iron with organic complexes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

The competition impact and feedstock type on the removal of water pesticides using biochar have not yet been sufficiently investigated. Therefore, here we investigated the potentiality of three different biochars (BCs) derived from rice husk (RHB), date pit (DPB), and sugarcane bagasse (SBB) biowastes for the simultaneous removal of ten pesticides from water in a competitive adsorption system. The BCs structural characterization and morphology were investigated by XRD, FTIR spectroscopy and SEM analysis. The potential adsorption mechanisms have been investigated using various isothermal and kinetic models. RHB showed the highest removal percentages (61% for atrazine/dimethoate and 97.6% for diuron/chlorfenvinphos) followed by DPB (56% for atrazine/dimethoate and 95.4% for diuron/chlorpyrifos) and then SBB (60.8% for atrazine/dimethoate and 90.8% for chlorpyrifos/malathion). The higher adsorption capacity of RHB and DPB than SBB can be due to their high total pore volume and specific surface area (SSA). Langmuir model described well the sorption data (R 2  = 0.99). Adsorption equilibrium was achieved after 60 min for RHB, and 120 min for both DPB and SBB. The optimum adsorbent dose (g/L) was 10 for RHB and 4 for DPB and SBB. The removal efficiency of pesticides was enhanced by decreasing pH from 9 to 5 by RHB and to 3 by DPB and SBB. XRD and FTIR spectroscopy confirmed that BCs contain some active adsorption groups and metal oxides such as MgO, SiO, Al 2 O 3 , CaO, and TiO 2 that can play an effective role in the pesticides sorption. BET-N 2 adsorption analysis demonstrated that the BC pore size contributes significantly to pesticide adsorption. These findings indicate that RHB, DPB, and SBB have ability for adsorption of water pesticides even under acidic conditions. Therefore, the rice husk, date pit, and sugarcane bagasse biowastes could be pyrolyzed and reused as effective and low-cost sorbents for elimination of hazardous substances such as pesticides in the aqueous environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Long-term input of agricultural chemicals such as pesticides into the soil can increase soil pollution, thereby affecting the productivity and quality of black soil. Triazine herbicide atrazine has been shown to have long-lasting residual effects in black soil. The atrazine residues affected soil biochemical properties, further leading to microbial metabolism restriction. It is necessary to explore the strategies to mitigate the limitations on microbial metabolism in atrazine-contaminated soils. Here, we evaluated the effect of the atrazine on microbial nutrient acquisition strategies as indicated by extracellular enzyme stoichiometry (EES) in four black soils. Atrazine degradation in soil followed the first-order kinetics model across various concentrations ranging from 10 to 100 mg kg -1 . We found that the atrazine was negatively correlated with the EES for C-, N-, and P-acquisition. Vector lengths and angles decreased and increased significantly with an increase of atrazine concentration in tested black soils except for Lishu soils. Moreover, the vector angles were >45° for tested four black soils, indicating that atrazine residue had the greatest P-limitation on soil microorganisms. Interestingly, microbial C- and P-limitations with different atrazine concentrations showed a strong linear relationship, especially in Qiqihar and Nongan soils. Atrazine treatment significantly negatively affected microbial metabolic limitation. Soil properties and EES interaction explained up to 88.2% for microbial C-/P-limitation. In conclusion, this study confirms the EES as a useful method in evaluating the effects of pesticides on microbial metabolic limitations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In sulfate radical-based advanced oxidation processes (SR-AOPs), high-efficiency and perdurable materials have drawn considerable interest for use as cathodes, which can effectively degrade refractory organic contaminants through the synergistic electro-activation and transition metal activation of persulfate (PS). Here, the FeCuO@C modified composite cathode (FeCuO@C/AGF) was synthesized via the solvothermal and thermal treatment method based on the CuFe-MOF-74 structure, and the electro-activation PS process (EC/FeCuO@C/AGF/PS) was developed to effectively remove atrazine (ATZ). The surface morphology, electrochemical characteristics, chemical composition, crystal structure, and electrode surface wettability of FeCuO@C/AGF were investigated. It was found that the proposed EC/FeCuO@C/AGF/PS process can successfully remove 100% of ATZ in 20 min at a low current density (2 mA cm -2 ) and a low PS concentration (0.4 mM), and PS is successfully activated by combining the electrical and transition metal synergistic activation. The FeCuO@C/AGF cathode exhibits outstanding catalytic functionality over a broad pH range (2-9) and remains stable over five successive cycles. Additionally, the active species involved in the reaction as well as the potential ATZ degradation reaction mechanisms and pathways are discussed. Electrochemical oxidation is a process in which both radicals (SO 4 ·- , ·OH, and O 2 ·- ) and non-radical ( 1 O 2 ) participate in the degradation of ATZ. The intermediates of the ATZ degradation process were studied upon the toxicity changing, and the toxicity of the intermediates was found to be reduced during degradation. These results present a novel approach toward the establishment of an effective and reliable electrode in SR-AOPs that can efficiently treat pesticide wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Agrobacterium rhizogenes AT13, a novel bacterial strain that was isolated from contaminated soil, could utilize atrazine as the sole nitrogen, thereby degrading it. Optimization of the degradation reaction using a Box-Behnken design resulted in 99.94% atrazine degradation at pH 8.57, with an inoculum size of 3.10 × 10 9  CFU/mL and a concentration of 50 mg/L atrazine. Ultra-high performance liquid chromatography-electrospray ionization-high resolution mass spectrometry (UPLC-ESI-HRMS), liquid chromatography tandem mass spectrometry (LC-MS/MS) and high performance liquid chromatography (HPLC) analyses identified and quantified six reported metabolites and a novel metabolite (2-hydroxypropazine) from atrazine degradation by AT13. On the basis of these metabolites, we propose an atrazine degradation pathway that includes dichlorination, hydroxylation, deamination, dealkylation and methylation reactions. The toxicity of the degradation products was evaluated by Toxicity Estimation Software Tool (T.E.S.T). Bioaugmentation of atrazine-polluted soils/water with strain AT13 significantly improved the atrazine removal rate. Thus, AT13 has potential applications in bioremediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Efficient degradation technologies are urgent to be developed to avoid the ecological and healthy hazards brought from atrazine (ATZ). LaCoO 3-δ /peroxymonosulfate (PMS) system was proved to have strong degradation capabilities to contaminants. In this work, we intended to investigate the effect of the synthesis method on LaCoO 3-δ . However, the hydrothermal method yielded a new material (H-Co) with better catalytic performance than LaCoO 3-δ , which showed stable catalytic ability at pH 3.0-9.0 and 5 consecutive cycles. The coexistence of inorganic Cl - , SO 4 2- , NO 3 - , H 2 PO 4 - , HCO 3 - and organic humic acids exerted little influences on the H-Co/PMS system. In addition, the actual livestock and poultry breeding wastewater could be well degraded and mineralized by the H-Co/PMS system. Free radical burst experiments and EPR characterization were performed to verify the synergistic effects of free radicals and non-free radicals during ATZ degradation. Based on SEM, XRD, O 2 -TPD, FTIR, XPS, and electrochemistry characterizations, the efficient catalytic ability of H-Co could be attributed to the abundant oxygen vacancies, surface hydroxyl groups, zero-valent cobalt sites and high electronic conductivity. The degradation pathways were proposed based on the detection of degradation intermediates of ATZ by UPLC-MS. Moreover, the toxic of ATZ during the oxidation was evaluated by TEXT and E. coli inhibition assay. This work comprehensively analyzed the catalytic reaction mechanism of the H-Co/PMS system and provided a feasible pathway for the treatment of the actual livestock and poultry breeding wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The presence of herbicides like Atrazine (ATZ) in groundwater from non-target runoff of the agriculture industry becomes a big concern due to its potential negative impacts on the environment and human health. The use of advanced oxidative processes (AOP) to remove harmful contaminants has been shown to be effective for wastewater treatment. Herein, we report on an advanced photoelectrochemical (PEC) approach based on electrochemically modified nanoporous TiO 2 electrode for efficient degradation of ATZ. The electrochemical treated TiO 2 electrodes were shown to have a six-fold increase in the photo-current density over the untreated ones. This increase in PEC activity was attributed to the increase in Ti 3+ sites after the electrochemical modification, which was corroborated by low-temperature electron paramagnetic resonance (EPR) studies. The removal of ATZ by the PEC process resulted in a rate constant of 1.91 × 10 -3 s -1 , compared to 3.12 × 10 -4 s -1 obtained by a strictly photocatalytic process. Liquid-Chromatography Mass-Spectrometric measurements showed the modified TiO 2 electrodes highly effective at removing ATZ, with 96.1% removed after 10 h. Monitoring of the common degradation products desethyl atrazine (DEA), desisopropyl atrazine (DIA) and desethyl desisopropyl atrazine (DDA) revealed very low concentrations throughout the degradation process, indicating that further degradation was achieved. Quantum mechanical-based test for overall free radical scavenging activity (QM-ORSA) computational studies were performed and a mechanism for the N-dealkylation processes of ATZ has been proposed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Quinones are potential pollutants and redox active compounds widely distributed in environmental media. In this study, methyl-p-benzoquinone (MBQ) was introduced into Fe(III)/peroxydisulfate system (Fe(III)/PDS) to expedite the conversion of Fe(III) to Fe(II) and the degradation of atrazine (ATZ), ultimately establishing an environmentally friendly system of "treating pollution with pollution". MBQ/Fe(III)/PDS system showed superior performance to traditional Fe(II)/PDS system in pH range of 2-7. Sulfate radical (SO 4 •- ) and hydroxyl radical ( • OH) were confirmed to exist in MBQ/Fe(III)/PDS system according to alcohol quenching experiments and ESR tests. Meanwhile, stable 80% of η[PMSO 2 ] (i.e., the molar ratio of PMSO 2 generation to PMSO consumption) was achieved and manifested that highly reactive substance Fe(IV) also participated in MBQ/Fe(III)/PDS system. The spontaneous transformation of MBQ and methyl-hydroquinone (MHQ) drove Fe(III)/Fe(II) cycle, during which MHQ induced Fe(III) reduction and Fe(II) regeneration. Transformation pathways of ATZ were proposed based on HPLC-MS detection and DFT calculation and ATZ degradation could be initiated by lateral chain oxidation and dechlorination-hydroxylation. The acute toxicity, bioaccumulation factor, developmental toxicity and mutagenicity of ATZ and its degradation intermediates were evaluated by Toxicity Estimation Software Tool, and the luminescent bacteria test was conducted to investigate the acute toxicity variation of the reaction solution. Cl - obviously inhibited ATZ degradation and three main by-products generation, while humic acid (HA) had little effect on them probably due to the established balance between inhibition (some components in HA competed to consume reactive species) and acceleration (quinone units in HA also facilitated Fe(III)/Fe(II) cycle)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Soil organic matter (SOM) and its heterogeneous nature constitutes the main factor determining the fate and transformation of organic chemicals (OCs). Thus, the aim of thus research was to analyze the influence of the molecular chemodiversity of a stable SOM (S-SOM) on the sorption potential of different groups of OCs (organochloride pesticides—OCPs, and non-chlorinated pesticides—NCPs, polycyclic aromatic hydrocarbons—PAHs). The research was conducted as a batch experiment. For this purpose, a S-SOM was separated from six soils (TOC = 15.0−58.7 gkg−1; TN = 1.4−6.6 gkg−1, pH in KCl = 6.4−7.4 and WRB taxonomy: fluvisols, luviosols, leptosols) by alkaline urea and dimethylsulphoxide with sulfuric acid. Isolated S-SOM fraction was evaluated by UV−VIS, FT-IR and EEM spectroscopy to describe molecular diversity, which allowed the assessment of its potential sorption properties regarding OCs. In order to directly evaluate the sorption affinity of individual OCs to S-SOM, the mixture of the 3 deuterated contaminants: chrysene (PAHs), 4,4′DDT (OCPs) atrazine (NCPs) were applied. The sorption experiment was carried out according to the 106 OECD Guidelines. The OCs concentration was analyzed by gas chromatography triple mass spectrometry (GC-MS/MS). OCs were characterized by different sorption rates to S-SOM fractions according to the overall trend: atrazine (87.5−99.9%) > 4,4′DDT (64−81.6%) > chrysene (35.2−79.8%). Moreover, atrazine exhibited the highest saturation dynamic with fast bounding time amounting to 6 h of contact with S-SOM. Proportionally, the chrysene showed the slowest binding time achieving an average of 55% sorption after 78 h. Therefore, S-SOM isolated from different soils demonstrated varying binding capacity to OCs (CoV = 21%, 27% and 33% for atrazine, DDT and chrysene, respectively). Results indicate that each sample contains S-SOM with different degrees of transformation and sorption properties that affect the OCs availability in soil. Spectroscopic analyses have shown that the main component of S-SOM are biopolymers at various stages of transformation that contain numerous aromatic−aliphatic groups with mostly hydrophilic substituents.

The catalytic ozonation-based advanced oxidation process (AOP) is applied to remove nondegradable chemical oxygen demand (COD), while the application in industry is limited by the economics and activity of catalysts. In this study, we demonstrate that by taking atrazine (ATZ) as a model pollutant, the removal rates of catalytic ozonation were negatively correlated with the interlayer water content of metal-modified montmorillonite (M x @MMT), instead of the loadings metals. Among the modified MMT, Zn 0.1 @MMT achieved 83.2% degradation of ATZ within 15 min, and corresponding removal rates of COD and total organic carbon (TOC) reached 40.3% and 46.5%, respectively. Detailed EPR and quenching experiments identified that hydroxyl radicals (HO•) were the main reactive oxygen species and QTOF/MS/MS analysis helped to propose a possible degradation pathway of ATZ. Moreover, the catalytic performance of Zn 0.1 @MMT under different conditions was also systematically evaluated., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

High resolution mass spectrometry (HRMS) was coupled with ultra-high-performance liquid chromatography (uHPLC) to monitor atrazine (ATZ) degradation process of Fenton/ultrasound (US) treatment in real time. Samples were automatically taken through a peristaltic pump, and then analysed by HPLC-HRMS. The injection in the mass spectrometer was performed every 4 min for 2 h. ATZ and its degradation metabolites were sampled and identified. Online Fenton experiments in different equivalents of Fenton reagents, online US experiments with/without Fe 2+ and offline Fenton experiments were conducted. Higher equivalents of Fenton reagents promoted the degradation rate of ATZ and the generation of the late-products such as Ammeline (AM). Besides, adding Fe 2+ accelerated ATZ degradation in US treatment. In offline Fenton, the degradation rate of ATZ was higher than that of online Fenton, suggesting the offline samples were still reacting in the vial. The online analysis precisely controls the effect of reagents over time through automatic sampling and rapid detection, which greatly improves the measurement accuracy. The experimental set up proposed here both prevents the degradation of potentially unstable metabolites and provides a good way to track each metabolite.

The inclusion of warm-season grasses, such as switchgrass (Panicum virgatum) and eastern gamagrass (EG) (Tripsacum dactyloides), in vegetated buffer strips has been shown to mitigate herbicide contamination in runoff and increase herbicide degradation in soil. The mode of action by which buffer strip rhizospheres enhance herbicide degradation remains unclear, but microorganisms and phytochemicals are believed to facilitate degradation processes. The objectives of this study were to: 1) screen root extracts from seven switchgrass cultivars for the ability to degrade the herbicide atrazine (ATZ) in solution; 2) determine sorption coefficients (K d ) of the ATZ-degrading phytochemical 2-β-D-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one (DBG) to soil and Ca-montmorillonite, and investigate if DBG or ATZ sorption alters degradation processes; and 3) quantify ATZ degradation rates and soil microbial response to ATZ application in mesocosms containing soil and select warm-season grasses. Phytochemicals extracted from the roots of switchgrass cultivars degraded 44-85% of ATZ in 16-h laboratory assays, demonstrating that some switchgrass cultivars could rapidly degrade ATZ under laboratory conditions. However, attempts to isolate ATZ-degrading phytochemicals from plant roots were unsuccessful. Sorption studies revealed that DBG was strongly sorbed to soil (K d  = 87.2 L kg -1 ) and Ca-montmorillonite (K d  = 31.7 L kg -1 ), and DBG driven hydrolysis of ATZ was entirely inhibited when either ATZ or DBG were sorbed to Ca-montmorillonite. Atrazine degradation rates in mesocosm soils were rapid (t 0.5  = 8.2-11.2 d), but not significantly different between soils collected from the two switchgrass cultivar mesocosms, the eastern gamagrass cultivar mesocosm, and the unvegetated mesocosm (control). Significant changes in three phospholipid fatty acid biomarkers were observed among the treatments. These changes indicated that different ATZ-degrading microbial consortia resulted in equivalent ATZ degradation rates between treatments. Results demonstrated that soil microbial response was the dominant mechanism controlling ATZ degradation in the soil studied, rather than root phytochemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)

This work reports the radicals detected and identified during the degradation of atrazine in methanol medium in the presence and absence of different proportions of water (0%, 5%, and 10%). The determination of these radicals is an important step to understand the electrolysis processes in methanol medium and contribute to clarify the degradation mechanism. Furthermore, the parameters for the successful removal of the contaminant were optimized and the results showed that the application of the technique led to the removal of nearly 99.8% of atrazine after 1 h of electrolysis. The oxidation kinetics was found to be very fast and most of the atrazine molecule in the medium was degraded in the first hour of electrolysis. The results obtained from a thorough analysis conducted with a view to evaluating the effects of different current densities and initial pH values on atrazine degradation showed that the application of higher current densities resulted in lower energy consumption, as this led to faster removal of atrazine. Additionally, the initial pH of the solution was found to favor the formation of different species of active chlorine. The radicals formed during the electro-oxidation process were detected by electron paramagnetic resonance spectroscopy and include hydroxyl, methoxy and hydroxymethyl. The use of methanol for the degradation of pollutants is a highly promising technique and this work shows that the identification of the different radicals formed in the process can be the key to understanding the degradation mechanism., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Artur de Jesus Motheo reports financial support was provided by State of Sao Paulo Reuter Foundation. William Santacruz reports financial support was provided by Coordination of Higher Education Personnel Improvement. Isabela Fiori reports financial support was provided by Coordination of Higher Education Personnel Improvement. Rodrigo de Mello reports financial support was provided of Sao Paulo Reuter Foundation., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Atrazine residue in soil is one of the serious environmental problems and continues to risk ecosystem and human health. To address the environmental behaviors and dissipation of atrazine and better manage the application of atrazine in reality, we comprehensively investigated the adsorption and desorption, migration ability, and vanishing of atrazine in three distinct soils in China including Jiangxi (JX, pH 5.45, TOC 0.54%), Nanjing (NJ, pH 6.15, TOC 2.13%), and Yancheng (YC, pH 8.60, TOC 0.58%) soils. The atrazine adsorptive capacity to the soils was arranged in the order of NJ > YC > JX. The leaching assay with profiles of the soils showed strong migration, suggesting it had a high bioavailability to weeds and potential for underground water contamination. We further investigated the effects of environmental factors such as soil moisture, microbial activity and photolysis on atrazine degradation and showed that the degradation of atrazine in the soil mainly underwent the abiotic process, most likely through hydrolysis and photolysis-mediated mechanisms, and to less extend through soil microbial catabolism. Using HRLC-Q-TOF-MS/MS and by comparing the measured and theoretical m/z values and fragmentation data, ten metabolites comprising eight degraded products and two conjugates were characterized. Atrazine existing in the soils and sprayed coordinately blocked the growth of three common weeds, which prompted us to use the minimal atrazine in practice to control the waste of the pesticide and its impact on the environment. Overall, our work provided an insight into the mechanisms for the degradation of atrazine residues in the soils and contributed to the environmental risk assessment of the pesticide and management in its application control in the crop rotation and safe production., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Developing low-cost, high-efficiency catalysts for advanced oxidation processes remain a key issue for the degradation of organic pollutants. In this study, a novel FeCo 2 O 4 /rectorite composite was synthesized via a facile combustion process and employed to activate peroxymonosulfate (PMS) for dealing with atrazine (ATZ). The addition of rectorite could result in higher specific surface area, smaller pore size and more hydroxyl groups, which were beneficial to enrich pollutants to the adsorption sites and provide sufficient reactive sites. After meticulous evaluation, the degradation efficiency of FeCo 2 O 4 /rectorite composite towards ATZ exhibited improved PMS activation efficiency which was about 2.6 times than that of pure FeCo 2 O 4 . Based on the characterization results, the sulfate radicals and hydroxyl radicals were considered to be the main free radicals which were involved into the circulation of Co(II)-Co(III)-Co(II) as well as the oxidation of ≡Fe(II), which was responsible for the remarkable catalytic efficiency. In addition, the chemical stability and superior catalytic performance of FeCo 2 O 4 /rectorite should also be attributed to the chemical combination between metal ions and the surface hydroxyl groups of rectorite. Overall, these findings are beneficial for understanding the mechanism of PMS activation by natural mineral-based catalysts and contributing to the practical application of sulfate-based technology for organic wastewater treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In Brazil, the atrazine has been applied frequently to join with glyphosate to control resistant biotypes and weed tolerant species to glyphosate. However, there are no studies about atrazine's behavior in soil when applied in admixture with glyphosate. Knowledge of atrazine's sorption and desorption mixed with glyphosate is necessary because the lower sorption and higher desorption may increase the leaching and runoff of pesticides, reaching groundwaters and rivers. Thereby, the objective of this study was to evaluate the adsorption mechanisms of atrazine when isolated and mixed with glyphosate formulations in a Red-Yellow Latosol. The maximum adsorbed amount of atrazine in equilibrium (qe) was not altered due to glyphosate formulations. The time to reach equilibrium was shortest when atrazine was mixed with the Roundup Ready® (te = 4.3 hours) due to the higher adsorption velocity (k2 = 2.3 mg min-1) in the soil. The highest sorption of atrazine occurred when mixed with the Roundup WG®, with the Freundlich sorption coefficient (Kf) equal to 2.51 and 2.43 for both formulation concentrations. However, other glyphosate formulations did not affect the sorption of atrazine. The desorption of atrazine was high for all treatments, with values close to 80% of the initial adsorbed amount, without differences among isolated and mixed treatments. The change in the velocity and capacity of sorption for the atrazine mixed with some glyphosate formulations indicates that further studies should be conducted to identify the mechanisms involved in this process., Competing Interests: The authors have declared that no competing interests exist.

Declining rate of productivity and environmental sustainability is forcing growers to use organic manures as a source of nutrient supplement in maize farming. However, weed is a major constraint to maize production. A field study was carried out over two seasons to evaluate various integrated nutrient and weed management practices in hybrid maize. The treatment combinations comprised of supplementation of inorganic fertilizer (25% nitrogen) through bulky (Farmyard manure and vermicompost) and concentrated ( Brassicaceous seed meal (BSM) and neem cake (NC)) organic manures and different mode of weed management practices like chemical (atrazine 1000 g ha -1 ) and integrated approach (atrazine 1000 g ha -1 followed by mechanical weeding). Repeated supplementation of nitrogen through concentrated organic manures reduced the density and biomass accumulation of most dominant weed species, Anagalis arvensis by releasing allelochemicals into the soil. But organic manures had no significant impact on restricting the growth of bold seeded weeds like Vicia hirsuta and weed propagated through tubers i.e., Cyperus rotundus in maize. By restricting the weed growth and nutrient removal by most dominating weeds, application of BSM enhanced the growth and yield of maize crop. Repeated addition of organic manures (BSM) enhanced the maize grain yield by 19% over sole chemical fertilizer in the second year of study. Application of atrazine as pre-emergence (PRE) herbicide significantly reduced the density of A . arvensis , whereas integration of mechanical weeding following herbicide controlled those weeds which were not usually controlled with the application of atrazine. As a result, atrazine at PRE followed by mechanical weeding produced the highest maize grain yield 6.81 and 7.10 t/ha in the first year and second year of study, respectively.

In order to improve the catalytic activity and recycling performance of heterogeneous Fenton catalyst, a heterogeneous Fenton catalyst Fe/TiO 2 based on TiO 2 supported visible light response was prepared by a simple method using TiO 2 synthesized by sol-gel method as carrier and ferric nitrate as Fe source. It was characterized by SEM, EDX, XRD, UV-vis instruments. The influencing factors of catalytic degradation of atrazine by visible light heterogeneous Fenton of Fe/TiO 2 were studied and the reaction kinetics were fitted. The mineralization degree of atrazine was reflected by the removal rate of TOC. The intermediate products by the degradation of the catalytic system was analyzed and the reaction mechanism of Fe/TiO 2 -H 2 O 2 visible light system was discussed. The XRD results showed that Fe was highly dispersed on the surface of TiO 2 in the form of α-Fe 2 O 3 . The Fe/TiO 2 catalyst with heterogeneous Fenton and visible light photocatalytic activity was successfully optimized, forbidden bandwidth of Fe/TiO 2 after Fe supported was narrower, the scope of light absorption red-shifted, the electron-hole pairs were more generated, and there was a significant synergistic effect between the carrier TiO 2 and the supported Fe, which exhibited good oxidation capacity for degradation of 10 mg L -1 atrazine in pH of 3, the concentration of H 2 O 2 was 1.6 mM, and the catalyst was added at 1 g L -1 , achieving over 95% removal efficiency within 30 min, and, in the range of pH 3-7, the degradation rate of the reaction for 30 min can be maintained above 75%, which greatly broadened the range of pH application and had good recycling performance. The degradation process conformed to the quasi-first-order kinetic model. Through LC-MS analyzed, 12 intermediate products were formed during the degradation of atrazine, the final products were all cyanuric acid, and then the triazine ring was mineralized into inorganic substances such as CO 2 , H 2 O and NO 3 - by oxidation of ·OH, and the possible degradation pathways were inferred., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Herein, the potential of bimetallic MOFs in catalytic ozonation was investigated for the first time. Three novel ozonation catalysts, i.e. cobalt-based, nickel-based and cobalt/nickel-based metal-organic frameworks (Co-MOF, Ni-MOF and Co/Ni-MOF), were synthesized, characterized by XRD, SEM, N 2 sorption-desorption isotherms, FTIR and XPS, and applied in catalytic ozonation for atrazine removal. It was found that the catalysts showed outstanding performance in the catalytic ozonation, especially Co/Ni-MOF which was attributed to multiple metal sites, higher coordination unsaturation, metal centers with larger electron density, and better efficiency in electron transfer than its single-metal counterparts. Under specific experimental conditions, 47.8%, 67.0%, 75.5%, and 93.9% of atrazine were removed after adsorption and degradation in the ozonation system without catalyst, and the catalytic ozonation systems with Co-MOF, Ni-MOF and Co/Ni-MOF, respectively. Higher removal rates could be achieved by growing initial pH, increasing oxidant dosage and reducing pollutant concentration, while an excess of Co/Ni-MOF was not favorable for the catalytic ozonation. Surface hydroxyl groups and acid sites were considered as the critical catalytic sites on Co/Ni-MOF. From the results of EPR tests, O 2 · - , 1 O 2 and ·OH were ascertained as the main reactive species in the degradation. It was suspected that O 2 · - and H 2 O 2 played important roles in the formation of ·OH and the cycle of Co(II)/Co(III) and Ni(II)/Ni(III). Additionally, Co/Ni-MOF displayed good stability and reusability in cycling experiments, ascribed to the enhancement of the porosity and pore hydrophobicity. Finally, based on MS/MS analysis at different reaction times, major degradation pathways for atrazine were proposed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Persulfate (PS) is widely used for environmental remediation, but its organic contaminant removal performance strongly depends on its activation. In this study, we demonstrate that pyrite (FeS 2 ) can more effectively activate PS than the commonly used FeSO 4 for atrazine degradation. When 3.0 mM of PS and 4.2 mM of iron salts were used, the atrazine degradation efficiency of FeS 2 /PS was 1.4 times that of FeSO 4 /PS, while the amount of consumed PS in case of FeS 2 was only 53% of that by FeSO 4 . The better PS activation performance of FeS 2 could be attributed to its slow and sustainable release of dissolved Fe(II), inhibiting the quenching reaction between •SO 4 - /•OH and Fe(II) ions, and thus producing more reactive oxygen species for the atrazine degradation. More importantly, the surface bound Fe(II) of FeS 2 could activate molecular oxygen to generate superoxide radical (•O 2 - ), which could further promote the effective decomposition of PS by accelerating the Fe(III)/Fe(II) redox cycle. This study unravels the roles of dissolved Fe(II) and surface bound Fe(II) on the persulfate activation, and provides a promising heterogeneous persulfate activator for pollutant control and environmental remediation., Competing Interests: Declaration of competing interest None., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Atrazine is a kind of triazine herbicide that is widely used for weed control due to its good weeding effect and low price. The study of atrazine removal from the environment is of great significance due to the stable structure, difficult degradation, long residence time in environment, and toxicity on the organism and human beings. Therefore, a number of processing technologies are developed and widely employed for atrazine degradation, such as adsorption, photochemical catalysis, biodegradation, etc. In this article, with our previous research work, the progresses of researches about the treatment technology of atrazine are systematically reviewed, which includes the four main aspects of physicochemical, chemical, biological, and material-microbial-integrated aspects. The advantages and disadvantages of various methods are summarized and the degradation mechanisms are also evaluated. Specially, recent advanced technologies, both plant-microbial remediation and the material-microbial-integrated method, have been highlighted on atrazine degradation. Among them, the plant-microbial remediation is based on the combined system of soil-plant-microbes, and the material-microbial-integrated method is based on the synergistic effect of materials and microorganisms. Additionally, future research needs to focus on the excellent removal effect and low environmental impact of functional materials, and the coordination processing of two or more technologies for atrazine removal is also highlighted.

Microbial communities are pivotal in the biodegradation of xenobiotics including pesticides. In the case of atrazine, multiple studies have shown that its degradation involved a consortia rather than a single species, but little is known about how interdependency between the species composing the consortium is set up. The Black Queen Hypothesis (BQH) formalized theoretically the conditions leading to the evolution of dependency between species: members of the community called 'helpers' provide publicly common goods obtained from the costly degradation of a compound, while others called 'beneficiaries' take advantage of the public goods, but lose access to the primary resource through adaptive degrading gene loss. Here, we test whether liquid media supplemented with the herbicide atrazine could support coexistence of bacterial species through BQH mechanisms. We observed the establishment of dependencies between species through atrazine degrading gene loss. Labour sharing between members of the consortium led to coexistence of multiple species on a single resource and improved atrazine degradation potential. Until now, pesticide degradation has not been approached from an evolutionary perspective under the BQH framework. We provide here an evolutionary explanation that might invite researchers to consider microbial consortia, rather than single isolated species, as an optimal strategy for isolation of xenobiotics degraders.

Biochar is an adsorbent widely used to remove contaminants from polluted water. A series of biochar from corn straw, corncob and corn starch was prepared through one-step pyrolysis. The biochar was characterized, and the capacity for triazine pesticide (TRZ) removal from water was compared. P doped biochar from corn straw (CSWP) was able to remove six TRZs (>96%) from water after shaking five times. The removal was more rapid than that by four other commonly used adsorbents. The physicochemical properties of CSWP were characterized systematically, and carboxyl and metaphosphates on CSWP were found to provide adsorption sites. The experimental data were best fitted by a pseudo-second-order kinetic model and the Freundlich model. Adsorption equilibrium of atrazine on CSWP occurred within 20 min, and the maximum adsorption capacity reached up to 79.6 mg g -1  at 25 °C. The adsorption mechanism of CSWP for atrazine includes Van der Waals' forces, hydrogen bonding, electrostatic interactions and pore filling. CSWP can be reused at least five times and shows strong potential as a candidate for the rapid and efficient removal of TRZs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Traditional extraction methods (soil solution and solvent extraction) are simple to use and conventionally employed to assess pesticide chemical form and bioavailability in soils. However, whilst convenient for regulatory testing, it has been suggested that these approaches may be too crude or are poor predictors of bioavailability, due to their arbitrary original development to detect 'total' concentration using exhaustive extraction. The diffusive gradients in thin films (DGT) technique has been widely used to measure chemical speciation in situ and shown to reliably predict bioavailability of a range of contaminants (e.g. heavy metals, radionuclides, nutrients) in soil systems, because it dynamically samples contaminants from/re-supplied to the soil solution phase. Experiments were therefore conducted with 5 soils of different properties to compare DGT and the two conventional extraction approaches for sampling atrazine (ATR) and its metabolites from soils and for predicting their uptake by maize tissues. After 23 days aging, a large proportion of total ATR was still available for solvent (acetonitrile) extraction and the major constituent in soils was parent ATR. The best correlations of total ATR concentrations in maize and total ATR measured in soil were with DGT and soil solution measurements. This is encouraging, in jointly supporting one of the established methodologies traditionally used in pesticide testing (i.e. soil solution) and a widely used method (i.e. DGT), which has been validated previously for a range of contaminants. The poorer performance of solvent extraction (a procedure widely used for pesticide testing) is perhaps to be expected, given that solvents will not truly mimic the conditions encountered in soil-plant systems., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Exploring adaptive strategies by which microorganisms function and survive in low-energy natural environments remains a grand goal of microbiology, and may help address a prime challenge of the 21st century: degradation of man-made chemicals at low concentrations ("micropollutants"). Here we explore physiological adaptation and maintenance energy requirements of a herbicide (atrazine)-degrading microorganism (Arthrobacter aurescens TC1) while concomitantly observing mass transfer limitations directly by compound-specific isotope fractionation analysis. Chemostat-based growth triggered the onset of mass transfer limitation at residual concentrations of 30 μg L -1 of atrazine with a bacterial population doubling time (t d ) of 14 days, whereas exacerbated energy limitation was induced by retentostat-based near-zero growth (t d  = 265 days) at 12 ± 3 μg L -1 residual concentration. Retentostat cultivation resulted in (i) complete mass transfer limitation evidenced by the disappearance of isotope fractionation (ε 13 C = -0.45‰ ± 0.36‰) and (ii) a twofold decrease in maintenance energy requirement compared with chemostat cultivation. Proteomics revealed that retentostat and chemostat cultivation under mass transfer limitation share low protein turnover and expression of stress-related proteins. Mass transfer limitation effectuated slow-down of metabolism in retentostats and a transition from growth phase to maintenance phase indicating a limit of ≈10 μg L -1 for long-term atrazine degradation. Further studies on other ecosystem-relevant microorganisms will substantiate the general applicability of our finding that mass transfer limitation serves as a trigger for physiological adaptation, which subsequently defines a lower limit of biodegradation.

Atrazine is a widely used pesticide which acts as an endocrine disruptor in various organisms. The aim of this study was to investigate adverse effects of atrazine on life parameters, oxidative stress, and ecdysteroid biosynthetic pathway in the marine copepod Tigriopus japonicus. In T. japonicus, no mortality was shown in response to atrazine up to 20 mg/L in acute toxicity assessment. In nauplii, retardation in the growth and prolonged molting and metamorphosis resulted under chronic exposure of atrazine at 20 mg/L. In addition, body sizes of T. japonicus nauplii were significantly decreased (P < 0.01 in length and P < 0.001 in width) in response to 20 mg/L of atrazine. Furthermore, atrazine induced oxidative stress by the generation of reactive oxygen species at all concentrations compared to the control in the nauplii. Also, significant increase in glutathione-S transferase activity was observed in adult T. japonicus at low concentration of atrazine. To understand effects of atrazine on ecdysteroid biosynthetic pathway-involved genes (e.g., neverland, CYP307E1, CYP306A1, CYP302A1, CYP3022A1 [CYP315A1], CYP314A1, and CYP18D1) were examined with mRNA expressions of ecdysone receptor (EcR) and ultraspiracle (USP) in response to 20 mg/L atrazine in nauplii and adults. In the nauplii, these genes were significantly downregulated (P < 0.05) in response to atrazine, compared to the control but not in the adult T. japonicus. These results suggest that atrazine can interfere in vivo life parameters by oxidative stress-induced retrogression and ecdysteroid biosynthetic pathway in this species., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Bacterial strain FH-1 with high efficiency of degrading Atrazine is separated by means of enrichment culture from the soil applied with Atrazine for many years. FH-1, recognized as Klebsiella variicola based on phylogenetic analysis of 16S rDNA sequences, can grow with Atrazine which is the sole nitrogen source. In fluid inorganic salt medium, the optimal degradation temperature, pH value, and initial concentration of Atrazine are 25°C, 9.0, and 50 mg L -1 , respectively, and the degradation rate of Atrazine by strain FH-1 reached 81.5% in 11 d of culture. The degrading process conforms to the kinetics equation of pesticide degradation. Among the metal ions tested, Zn 2+ (0.2 mM) has the most significant effect of facilitation on the degradation of Atrazine. In the fluid medium with Zn 2+ , the degradation rate of Atrazine is increased to 72.5%, while the Cu 2+ (0.2 mM) inhibits the degradation of Atrazine. The degradation products of Atrazine by strain FH-1 were identified as HEIT (2-hydroxyl-4-ethylamino-6-isopropylamino-1,3,5-triazine), MEET (2-hydroxyl-4,6-bis(ethylamino)-1,3,5-triazine), and AEEO (4,6-bis(ethylamino)-1,3,5-triazin-2(1H)-one) by HPLC-MS/MS. Three genes ( atzC , trzN , and trzD ) encoding for Atrazine degrading enzymes were identified by PCR and sequencing in strain FH-1. This study provides additional theoretical support for the application of strain FH-1 in bioremediation of fields polluted by Atrazine., Competing Interests: The authors declare that they have no conflicts of interest.

Drinking water treatment residuals (WTRs) have been applied in organic pollutants degradation in water by generating reactive oxygen species from peroxymonosulfate (PMS), however, the slow transformation of Fe(III) to Fe(II) may limit its widespread application. Hydroxylamine (HA) was introduced into the system to enhance the degradation efficiency of atrazine (ATZ) and several key reaction parameters (HA concentration, PMS concentration, pH and temperature) were concerned to study their influence on ATZ degradation. The results revealed that ATZ degradation efficiency was enhanced in the HA/WTRs/PMS system. Effects of some basic inorganic ions (Cl - , SO 4 2- and NO 3 - ) and natural organic matter on ATZ degradation were investigated and results showed that both have an inhibitory effect on ATZ removal. In addition to the reduction role, HA can also react directly with PMS to produce free radicals that helpful for ATZ degradation. Sulfate radical and hydroxyl radicals were generated and sulfate radical was identified as primary radicals in the HA/WTRs/PMS system by alcohol quenching experiments. Moreover, the HA/WTRs/PMS system also showed good performance for ATZ degradation in authentic water like surface water and groundwater. Introduction of hydroxylamine into the system may promote organic pollutant degradation and use of WTRs as an iron source for PMS activation provides new ideas for sludge treatment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The degradation effect, degradation mechanism, oxidation kinetics, and degradation products of Atrazine (ATZ) by Ultrasound/Peroxymonosulfate (US/PMS) in phosphate buffer (PB) under different conditions were studied. It turned out that the degradation rate of US/PMS to ATZ was 45.85% when the temperature of the reaction system, concentration of PMS, concentration of ATZ, ultrasonic intensity, and reaction time were 20 °C, 200 μmol/L, 1.25 μmol/L, 0.88 W/mL, and 60 min, respectively. Mechanism analysis showed that PB alone had no degradation effect on ATZ while PMS alone had extremely weak degradation effect on ATZ. HO• and SO 4 - • coexist in the US/PMS system, and the degradation of ATZ at pH7 is dominated by free radical degradation. Inorganic anion experiments revealed that Cl - , HCO 3 - , and NO 3 - showed inhibitory effects on the degradation of ATZ by US/PMS, with Cl - contributing the strongest inhibitory effect while NO 3 - showed the weakest suppression effect. According to the kinetic analysis, the degradation kinetics of ATZ by US/PMS was in line with the quasi-first-order reaction kinetics. ETA with concentration of 1 mmol/L reduced the degradation rate of ATZ by US/PMS to 10.91%. Product analysis indicated that the degradation of ATZ by US/PMS was mainly achieved by dealkylation, dichlorination, and hydroxylation, but the triazine ring was not degraded. A total of 10 kinds of ATZ degradation intermediates were found in this experiment.

Microbial communities play a vital role in biogeochemical cycles, allowing the biodegradation of a wide range of pollutants. The composition of the community and the interactions between its members affect degradation rate and determine the identity of the final products. Here, we demonstrate the application of sequencing technologies and metabolic modeling approaches towards enhancing biodegradation of atrazine-a herbicide causing environmental pollution. Treatment of agriculture soil with atrazine is shown to induce significant changes in community structure and functional performances. Genome-scale metabolic models were constructed for Arthrobacter, the atrazine degrader, and four other non-atrazine degrading species whose relative abundance in soil was changed following exposure to the herbicide. By modeling community function we show that consortia including the direct degrader and non-degrader differentially abundant species perform better than Arthrobacter alone. Simulations predict that growth/degradation enhancement is derived by metabolic exchanges between community members. Based on simulations we designed endogenous consortia optimized for enhanced degradation whose performances were validated in vitro and biostimulation strategies that were tested in pot experiments. Overall, our analysis demonstrates that understanding community function in its wider context, beyond the single direct degrader perspective, promotes the design of biostimulation strategies.

The photocatalytic degradation of atrazine by activated carbon/graphitic carbon nitride composites with peroxymonosulfate (PMS) was investigated under visible light irradiation. The photocatalysts were prepared at different activated carbon (AC) loaded percentages and characterized by XRD, FT-IR, BET surface area, SEM, UV-Vis absorbance, photocurrent response and EIS. Several parameters which might influence the degradation efficiency were studied including PMS concentration, solution pH, catalyst dosage, initial atrazine concentration as well as water matrix effect. The results indicated that incorporation of AC contributes effectively in suppressing the recombination of electron-holes pairs and enhancing the photocatalytic performance of graphitic carbon nitride. More significantly, the degradation efficiency of atrazine showed remarkable improvement with PMS addition under visible light irradiation. The reaction rate constant of the 10% AC/g-C 3 N 4 /Vis/PMS system (0.0376 min -1 ) was approximately 2.9 times higher than that of g-C 3 N 4 /Vis/PMS system (0.0128 min -1 ). Results from quenching tests revealed that both sulfate and hydroxyl radicals were involved in the degradation of atrazine, while the latter is the main contributor. This paper constitutes an insight for the metal-free catalyst activation of PMS by photocatalysis for environmental remediation., (Copyright © 2018. Published by Elsevier Ltd.)

Nanosized BaFe 1-x Cu x O 3 powders were prepared using the Pechini method. To limit grain growth and agglomeration, the temperature of calcination was limited to 800 °C. For all samples, the cubic form of BaFeO 2.75 was predominant with minor additional phases. Cu doping was found to have a remarkable effect on the structural cubic unit cell parameter as the Cu concentration increased. As shown by XRD,the samples were in the nanometer size range (17-63 nm). However, as the Cu concentration increases, the agglomeration increases with the highest surface area for the BaFe 0.95 Cu 0.05 O 3 composition, which also displays the highest photocatalytic atrazine degradation. For this sample, more than 90% degradation of atrazine was obtained at the optimum conditions (120 min irradiation under visible light at pH 11 using 0.75 mg of the catalyst). The Atrazine degradation was found to follow the pseudo-order kinetics. GC/MS was used to detect the intermediates and the reaction pathways. All the prepared samples and produced waters at the end of the experiment were found to be nontoxic., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Plant activities might alter the environmental behavior of organic pollutants in rhizosphere soil during phytoremediation. To further illustrate the mechanisms underlying the varying adsorption about the different adsorbing abilities of rhizosphere soil (RS) and non-rhizosphere soil (NRS) for the same pollutant, atrazine was selected to investigate the adsorption traits in the NRS and RS of Pennisetum americanum (L.) K. Schum (P. americanum), a potential phytoremediator of atrazine pollution. Furthermore, the different fluorescence spectral properties of the dissolved organic matter (DOM) extracted from RS and NRS when binding with atrazine were also investigated. RS exhibited a higher atrazine adsorption capacity than NRS, although the kinetic and isothermal properties of atrazine adsorption onto the two kinds soil were described by a pseudo second-order model and the Freundlich model. The DOM extracted from RS showed a stronger atrazine-binding ability than that extracted from NRS, as proven by the much more obvious decrease in fluorescence intensity when binding with atrazine. Although synchronous fluorescence spectra analysis suggested that both DOM types bind atrazine using a static fluorescence quenching mechanism, Fourier transform infrared spectroscopy showed that some distinct functional groups, which might liable to combine with atrazine, were found in only the DOM extracted from RS. Considering the findings mentioned above and the fact that the typical chemical characteristics of RS were different from those of NRS, we concluded that the P. americanum enhances the atrazine adsorption ability of RS by regulating the chemical characteristics and atrazine-binding ability of DOM in RS., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) is a commonly used agricultural herbicide that, as a result, is frequently detected in surface and ground water. In this study, we provide evidence of the photo-oxidation of atrazine under environmentally relevant conditions, specifically, in the presence of natural montmorillonite clay and the ubiquitous phytohormone indole-3-acetic acid (IAA). The reaction is initiated by the generation of hydrated electrons from the photo-ionization of IAA. These electrons react with protons and dissolved oxygen to form hydroxyl radicals, which promote the further degradation of atrazine. Montmorillonite strongly enhances the yield of hydrated electrons and prolongs their lifetime, by stabilizing radical cations through electrostatic attraction by the negative charges embedded in the clay. Moreover, by providing a confined space, montmorillonite markedly increases the probability of contact between atrazine and the active radicals. Other factors strongly influencing the degradation process are the solution pH, the type of exchangeable cations present in the clay interlayer, and the hydration status of montmorillonite. Since both IAA and montmorillonite clay are widely distributed in the environment, the proposed reaction is predicted to play an important role in the degradation of atrazine and perhaps other potentially persistent organic contaminants., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Biochars that were produced from pig manure at two different temperatures were incubated with three different minerals to examine the effects of soil minerals on biochar properties and sorption capacities. Biochars freshly mixed with minerals showed dramatic decreases in the sorption of atrazine (maximum decrease by 70.9% at C e  = 0.5 S w ) and phenanthrene (maximum decrease by 69.5% at C e  = 0.5 S w ) compared to unmixed biochars. Following the incubation, minerals were tightly attached to the biochar surface and insert into inner pores, thus changing the elemental composition and surface area of biochars in a manner dependent on the types of biochars and minerals involved. The changes in biochar properties in turn affected biochar sorption capacities. The sorption of both atrazine and phenanthrene by the pig manure biochar produced at 300 °C (BC300) decreased after aging due to an increase in surface hydrophilicity. In contrast, the sorption of atrazine and phenanthrene by BC700 increased after aging with minerals, which could be attributed to the increase in surface area caused by the minerals. However, the sorption capacities of the aged BC700 were still lower than those of the fresh BC700., (Copyright © 2018. Published by Elsevier Ltd.)

Saccharomyces cerevisiae and nanoparticles of iron oxide (Fe 3 O 4 ) which were linked with chitosan (CS) through epichlorohydrin (ECH) were encapsulated in calcium alginate to prepare a novel type of bionanocomposites. Characterization results showed that the Fe 3 O 4 -ECH-CS nanoparticles were quasi-spherical with an average diameter of 30 nm to which chitosan was successfully attached through epichlorohydrin. The saturation magnetization value of the nanoparticles was 21.88 emu/g, and ferrous and ferric irons were simultaneously observed in the magnetic nanoparticles. Data of atrazine removal by yeasts showed that both inactivated and live yeasts could decrease the concentration of atrazine effectively. The inactivated yeasts achieved 20% removal rate, which indicated that adsorption by the yeasts also played a role in the removal. Removal efficiency of atrazine was maximized at 88% under 25 °C, pH of 7 and an initial atrazine concentration of 2 mg/L. When the magnetic bionanocomposite was recycled and reused twice, only 12% and 20% drop in removal efficiency was observed at the first time and the second time severally. So, atrazine could be used by the yeasts as the sole carbon source for growth and multiplication, and both adsorption and biodegradation by the bionanocomposite contributed to atrazine removal., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Vermicomposting is an effective and environmentally friendly approach for eliminating soil organic contamination. Atrazine is one of the most commonly applied triazinic herbicides and frequently detected in agricultural soils. This study investigated the roles and mechanisms of two earthworm species (epigeic Eisenia foetida and endogeic Amynthas robustus) in microbial degradation of atrazine. Both earthworms accelerated atrazine degradation performance from 39.0% in sterile soils to 94.9%-95.7%, via neutralizing soil pH, consuming soil humus, altering bacterial community structure, enriching indigenous atrazine degraders and excreting the intestinal atrazine-degrading bacteria. Rhodoplanes and Kaistobacter were identified as soil indigenous degraders for atrazine mineralization and stimulated by both earthworm species. A. robustus excreted the intestinal Cupriavidus and Pseudomonas, whereas Flavobacterium was released by E. foetida. This study provides a comprehensive understanding of the distinct effects of two earthworm species on soil microbial community and atrazine degradation, offering technical supports to apply vermicomposting in effective soil bioremediation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Recently, polyaniline (PANI) has received widespread attention for the free volume, optical transmittance and electrical conductivity. In this study, a chemical vapor deposition method was developed to synthesize the conductive PANI-clay composite catalyzed by Fe(III)-saturated attapulgite (Fe(III)-ATTP). The reaction is initiated by the electron transfer from aniline (ANI) to Fe(III), subsequently generating ANI radical cation. The radical could further polymerize and form PANI in the constrained micropore structure of ATTP. The Raman, Fourier transform infrared and X-ray photoelectron spectra confirmed the formation of PANI on Fe(III)-ATTP surface by comparison with the PANI standard. The newly synthesized Fe(III)-ATTP-PANI composite exhibited superior reactivity as indicated by the efficient dissipation of atrazine in the presence of hydrogen peroxide (H 2 O 2 ), and the degradation rate increased up to almost 150 times compared to Fe(III)-ATTP. The higher reactivity of Fe(III)-ATTP-PANI/H 2 O 2 system was attributed to the accelerated electron transfer, the formation of ferrous ions, and the enhanced adsorption of atrazine onto attapulgite. Furthermore, our experimental results demonstrated that Fe(III)-ATTP-PANI showed good stability and it could be reused for several reaction cycles with high reactivity. This new material could act as an environmental-friendly catalyst in Fenton-like reaction system and show promising potential to effectively eliminate many persistent organic contaminants., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A novel advanced oxidation process using boron-doped diamond (BDD) anode to activate persulfate (PS) with low concentration of electrolyte was systematically investigated in this study. Compared to direct electrochemical oxidation of atrazine (ATZ) using BDD anode, the addition and activation of PS significantly declined the demand for electrolytes. It was confirmed by scavenger experiments that both radical and non-radical oxidation occurred in this system. Degradation of ATZ was enhanced with the increase of current density and dosage of PS, and decrease of initial pH. However, the increase of current density can also lead to the decrease of current efficiency, then increase of energy consumption. Besides, the inhibitory effect of anions on the degradation of ATZ followed the order of HCO 3 - >H 2 PO 4 - >NO 3 - , while the presence of Cl - accelerated the degradation of ATZ. Furthermore, the degradation products mainly resulting from de-alkylation, de-chlorination, and hydroxylation were detected. Due to the distinctive preference to ethyl group in BDD/PS system, the formation of deethyl-atrazine was quicker than that of deisopropyl-atrazine. The study aims to provide a comprehensive understanding on the potential application of BDD/PS system in water treatment., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The widely used herbicide atrazine is a potent endocrine disruptor known to cause increased aromatase expression and transient increase in testicular weight followed by remarkable testis atrophy. However, whether the effects of atrazine on the testes are primary or secondary to dysfunctions in other components of male reproductive tract remains unknown. Given the high sensitivity of the efferent ductules to estrogen imbalance and the similarity to alterations previously described for other disruptors of these ductules function, and the testicular alterations observed after atrazine exposure, we hypothesized that the efferent ductules could be a target for atrazine. Herein we characterized the efferent ductules and the ventral prostate of adult Wistar rats treated with 200 mg/kg/day of atrazine for 7, 15, and 40 days. Additionally, we evaluated if the effects of atrazine in these organs could be reduced after discontinuation of the treatment. Atrazine exposure resulted in mild effects on the ventral prostate, but remarkable alterations on the efferent ductules, including luminal dilation, reduced epithelial height, and disruption of the epithelial homeostasis, which coincides with increased aromatase expression. Together with our previous data, these results suggest that at least part of the testicular effects of atrazine may be secondary to the alterations in the efferent ductules., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Atrazine is widely used in agriculture. In this study, dissolved organic matter (DOM) from soils under four types of land use (forest (F), meadow (M), cropland (C) and wetland (W)) was used to investigate the binding characteristics of atrazine. Fluorescence excitation-emission matrix-parallel factor (EEM-PARAFAC) analysis, two-dimensional correlation spectroscopy (2D-COS) and Stern-Volmer model were combined to explore the complexation between DOM and atrazine. The EEM-PARAFAC indicated that DOM from different sources had different structures, and humic-like components had more obvious quenching effects than protein-like components. The Stern-Volmer model combined with correlation analysis showed that log K values of PARAFAC components had a significant correlation with the humification of DOM, especially for C3 component, and they were all in the same order as follows: meadow soil (5.68)>wetland soil (5.44)>cropland soil (5.35)>forest soil (5.04). The 2D-COS further confirmed that humic-like components firstly combined with atrazine followed by protein-like components. These findings suggest that DOM components can significantly influence the bioavailability, mobility and migration of atrazine in different land uses., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Generally, biochar plays an important role in controlling migration and accumulation of pollutants in soil. In this dissertation, biochars derived from wheat straws at various pyrolysis temperatures are used to investigate how biochar amendment affects adsorption and microbial degradation of atrazine (typical diffuse herbicide) in soils. In order to explore the influence of soil components, soil samples with different organic matter content are collected from typical agricultural sites, which are characterized as black soils in the northeast region of China. The basic sorption characteristics of biochars from wheat straws prepared at diverse pyrolysis temperature are analyzed, along with the comparisons of the sorption difference in the raw soil and soil amended with biochars at four levels of ratio (0.1%, 0.5%, 1.0% and 2.0%). By incubation experiments, atrazine degradation in non-sterile and sterile soils and effects of atrazine degradation rate after biochar amendment are also studied. Atrazine degradation is significantly enhanced in biochar amended soils, which may be because that biochar supplement can promote the growth and metabolism of microorganisms in the soil. Our findings reveal that wheatstraw- derived biochars may be effective remediation reagents for activating degradation of the soil functional microorganism and enhancing sorption of organic matter content, which can be applied to environmental-friendly accelerate the remediation of atrazine contaminated black soils., (Copyright © 2017. Published by Elsevier Ltd.)