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Microbial remediation is a viable and eco-friendly approach for decontaminating pollution. However, its effectiveness can be limited by the microorganisms' survival and growth in changing environments. Hydrochar materials have been utilized in this study to increase the growth and atrazine degradation capabilities of Paenarthrobacter sp. KN0901, a strain capable of atrazine biodegradation. Acid-modified hydrochars exhibited a higher carbonation rate, specific surface area, and number of defect sites compared to raw hydrochar. Following three days of incubation at 15 °C, the atrazine degradation rate increased from 90.7 % to 98.2 % when utilizing H 3 PO 4 -modified hydrochar (PHC). Additionally, the addition of PHC resulted in an increase in both bacterial concentration and cell viability of strain KN0901, by 1.6 and 1.4 times, respectively. Under various conditions, including temperatures of 4 ºC and 35 ºC, as well as pH levels of 5 and 9, and dd·H 2 O media, PHC exhibited a significant enhancement in atrazine degradation and cell viability of strain KN0901. Furthermore, PHC demonstrated the ability to sustain high proliferation and viability of strain KN0901 over five cycles, indicating its remarkable stability and biocompatibility. This study offers a new perspective on the development and application of bioremediation approaches in restoring atrazine-polluted environments, even under challenging conditions., 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 B.V. All rights reserved.)

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.)

Biodegradation, while cost-effective, is hindered by the requirement for specialized microorganisms and co-contaminants. Innovative biological technologies like the microbially driven Fenton reaction, hold promise for enhancing degradation efficiency. However, the intricate biochemical processes and essential steps for effective degradation in such systems have remained unclear. In this study, we harnessed the potential of the microbially driven Fenton reaction by employing Shewanella oneidensis MR-1 (MR-1). Our approach showcased remarkable efficacy in degrading a range of contaminants, including sulfadimethoxine (SDM), 4,4'-dibromodiphenyl ether (BDE-15) and atrazine (ATZ). Using SDM as a model contaminant of emergent contaminants (ECs), we unveiled that biodegradation relied on the generation of hydroxyl radicals (•OH) and involvement of oxidoreductases. Transcriptomic analysis shed light on the pivotal components of extracellular electron transfer (EET) during both anaerobic and aerobic periods. The presence of reactive oxidizing species induced cellular damage and impeded DNA repair, thereby affecting the Mtr pathway of EET. Moreover, the formation of vivianite hindered SDM degradation, underscoring the necessity of maintaining iron ions in the solution to ensure sustainable and efficient degradation. Overall, this study offers valuable insights into microbial technique for ECs degradation, providing a comprehensive understanding of degradation mechanisms during aerobic/anaerobic cycling., 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 B.V. All rights reserved.)

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.)

Microbial herbicide degradation is an efficient bioremediation method. In this study, a strain of Streptomyces nigra, LM01, which efficiently degrades atrazine and nicosulfuron, was isolated from a corn field using a direct isolation method. The degradation effects of the identified strain on two herbicides were investigated and optimized using an artificial neural network. The maximum degradation rates of S. nigra LM01 were 58.09 % and 42.97 % for atrazine and nicosulfuron, respectively. The degradation rate of atrazine in the soil reached 67.94 % when the concentration was 10 8 CFU/g after 5 d and was less effective than that of nicosulfuron. Whole genome sequencing of strain LM01 helped elucidate the possible degradation pathways of atrazine and nicosulfuron. The protein sequences of strain LM01 were aligned with the sequences of the degraded proteins of the two herbicides by using the National Center for Biotechnology Information platform. The sequence (GE005358, GE001556, GE004212, GE005218, GE004846, GE002487) with the highest query cover was retained and docked with the small-molecule ligands of the herbicides. The results revealed a binding energy of - 6.23 kcal/mol between GE005358 and the atrazine ligand and - 6.66 kcal/mol between GE002487 and the nicosulfuron ligand., 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 B.V. All rights reserved.)

Herein, a straightforward protocol was developed for the one-pot synthesis of N-doped lignosulfonate-derived carbons (NLDCs) with a tunable porous structure using natural amino acids-templated self-assembly strategy. Specifically, histidine was employed as a template reagent, leading to the preparation of 10-NLDC-21 with remarkable characteristics, including the large specific surface area (S BET  = 1844.5 m 2 /g), pore volume (V mes  = 1.22 cm 3 /g) and efficient adsorption for atrazine (ATZ) removal. The adsorption behavior of ATZ by NLDCs followed the Langmuir and pseudo-second-order models, suggesting a monolayer chemisorption nature of ATZ adsorption with the maximum adsorption capacity reached up to 265.77 mg/g. Furthermore, NLDCs exhibited excellent environmental adaptability and recycling performance. The robust affinity could be attributed to multi-interactions including pore filling, electrostatic attraction, hydrogen bonding and π-π stacking between the adsorbents and ATZ molecules. This approach offers a practical method for exploring innovative bio-carbon materials for sewage treatment., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pesticides and fertilisers are frequently used and may co-exist on farmlands. The overfertilisation of soil may have a profound influence on pesticide residues, but the mechanism remains unclear. The effects of chemical fertilisers on the environmental behaviour of atrazine and their underlying mechanisms were investigated. The present outcomes indicated that the degradation of atrazine was inhibited and the half-life was prolonged 6.0 and 7.6 times by urea and compound fertilisers (NPK) at 1.0 mg/g (nitrogen content), respectively. This result, which was confirmed in both sterilised and transfected soils, was attributed to the inhibitory effect of nitrogen fertilisers on soil microorganisms. The abundance of soil bacteria was inhibited by nitrogen fertilisers, and five families of potential atrazine degraders (Micrococcaceae, Rhizobiaceae, Bryobacteraceae, Chitinophagaceae, and Sphingomonadaceae) were strongly and positively (R > 0.8, sig < 0.05) related to the decreased functional genes (atzA and trzN), which inhibited hydroxylation metabolism and ultimately increased the half-life of atrazine. In addition, nitrogen fertilisers decreased the sorption and vertical migration behaviour of atrazine in sandy loam might increase the in-situ residual and ecological risk. Our findings verified the weakened atrazine degradation with nitrogen fertilisers, providing new insights into the potential risks and mechanisms of atrazine in the context of overfertilisation., 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 B.V. All rights reserved.)

The first systematic and comprehensive investigation of herbicide residues was conducted by identifying their spatial distribution, influencing factors and ecological risk in cropland soils from the Mollisols region covering 109 million hm 2 in Northeast China. Fifty-six herbicides were detected with total herbicide concentrations ranging from 1.01 to 1558.13 μg/kg (mean: 227.45). Atrazine, its degradates deethyl atrazine (DEA) and deisopropyl atrazine (DIA), trifluralin and butachlor were the most frequently detected herbicides, while DEA, clomazone, nicosulfuron, fomesafen, and mefenacet exhibited the highest concentrations. Despite being less frequently reported in Chinese soils, fomesafen, nicosulfuron, clomazone, and mefenacet were found widely present. Although most of the compounds posed a minimal or low ecological risk, atrazine, nicosulfuron and DEA exhibited medium to high potential risks. The key factors identified to regulate the fate of herbicides were soil chemical properties, amount of herbicides application, and the crop type. The soybean soils showed highest herbicide residues, while the soil mineral contents likely adsorbed more herbicides. This study provides a valuable large-scale dataset of herbicide residues across the entire Mollisols region of China along with fine-scale characterization of the ecological risks. Mitigation and management measures are needed to reduce the herbicide inputs and residues in the region., 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 B.V. All rights reserved.)

The abuse and residue of herbicides in the black soil area had seriously affected the soil structure, function and crop growth, posing severe threats to agricultural soil environment and public health. Given the limitation of routine microbial remediation, innovative and eco-friendly functional bacterial biofilm which could adapt under adverse conditions was developed on the biochar to investigate its enhanced bioremediation and metabolic characteristics of typical herbicide atrazine. Results revealed that the atrazine degrading strain Acinetobacter lwoffii had competitive advantage in soil indigenous microorganisms and formed dense biofilms on the biochar which was beneficial to cell viability maintenance and aggregations. Metatranscriptomics and RT-qPCR analysis demonstrated that the biochar-mediated biofilm improved the frequency of intercellular communications through quorum sensing and two-component signal regulation systems, and enhanced the atrazine biodegradation efficiency through horizontal gene transfer in co-metabolism mode, providing important scientific basis for the biological remediation of farmland soil non-point source pollution., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The coexistence of herbicide atrazine (ATZ) and the nanomaterial graphene oxide (GO) in natural water bodies will be an inevitable scenario due to their widespread application and consequent release into aquatic ecosystems. But the dissipation of ATZ with GO and the response of the microbial community to their combination are still not clear. Here, we investigated the dissipation dynamics and transformation of ATZ with and without GO in river water after 21-d incubation. In the presence of GO, ATZ residue significantly decreased by 11%-43%; the transformation of ATZ markedly increased by 11%-17% when ATZ concentrations were not above 1.0 mg∙L -1 . The direct adsorption of ATZ on GO, mainly via π-π interactions, proton transfer and hydrogen bonding, contributed 54%-68% of the total increased ATZ dissipation by GO. ATZ and ATZ+GO exerted effects of similar magnitude on microbial OTU numbers with an increase of bacterial diversity. The coexisting GO increased the relative abundance of ATZ-degradation bacteria and Chitinophagales, thus improving ATZ transformation. This work indicated that the coexistence of GO at environmentally relevant concentrations can effectively reduce ATZ residues and promote the transformation of ATZ to degradation products in river water; nevertheless, the potential risk of GO acting as an ATZ carrier should be given more prominence., 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 B.V.)

A challenge to successfully implementing an injection-based remedial treatment in aquifers is to ensure that the oxidative reaction is efficient and lasts long enough to contact the contaminated plume. Our objective was to determine the efficacy of zinc ferrite nanocomposites (ZnFe 2 O 4 ) and sulfur-containing reductants (SCR) (i.e., dithionite; DTN and bisulfite; BS) to co-activate persulfate (S 2 O 8 2- ; PS) and treat herbicide-contaminated water. We also evaluated the ecotoxicity of the treated water. While both SCRs delivered excellent PS activation in a 1:0.4 ratio (PS:SCR), the reaction was relatively short-lived. By including ZnFe 2 O 4 in the PS/BS or PS/DTN activations, herbicide degradation rates dramatically increased by factors of 2.5 to 11.3. This was due to the SO 4 - and OH reactive radical species that formed. Radical scavenging experiments and ZnFe 2 O 4 XPS spectra results revealed that SO 4 - was the dominant reactive species that originated from S(IV)/PS activation in solution and from the Fe(II)/PS activation that occurred on the ZnFe 2 O 4 surface. Based on liquid chromatography mass spectrometry (LC-MS), atrazine and alachlor degradation pathways are proposed that involve both dehydration and hydroxylation. In 1-D column experiments, five different treatment scenarios were run using 14 C-labeled and unlabeled atrazine, and 3 H 2 O to quantify changes in breakthrough curves. Our results confirmed that ZnFe 2 O 4 successfully prolonged the PS oxidative treatment despite the SCR being completely dissociated. Toxicity testing showed treated 14 C-atrazine was more biodegradable than the parent compound in soil microcosms. Post-treatment water (25 %, v/v) also had less impact on both Zea Mays L. and Vigna radiata L. seedling growth, but more impact on root anatomies, while ≤4 % of the treated water started to exert cytotoxicity (<80 % viability) on ELT3 cell lines. Overall, the findings confirm that ZnFe 2 O 4 /SCR/PS reaction is efficient and relatively longer lasting in treating herbicide-contaminated groundwater., 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 B.V. All rights reserved.)

In this study, natural molybdenite (MoS 2 ) was applied to activate peroxymonosulfate (PMS) for the removal of atrazine (ATZ) and its degradation mechanism was investigated. Molybdenite exhibits superior catalytic performance. The best condition for atrazine degradation efficiency (>99%) was obtained with molybdenite concentration of 0.4 g/L, PMS concentration of 0.1 mM, and ATZ concentration of 12 μM within 10 min under experimental conditions. Electron paramagnetic resonance (EPR) test and chemical probe test further proved that HO • and SO 4 •- played important roles in the molybdenite/PMS system, and SO 4 •- was dominant. Meanwhile, Electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) tests showed that sulfur vacancies and edge sulfur played important roles in the system. Edge sulfur was conducive to Mo 4+ exposure, while sulfur vacancy facilitated electron transfer and reduced Mo 6+ back to Mo 4+ . Combined with DFT calculation, the role of sulfur in the degradation process was verified. Besides, five ATZ degradation pathways were proposed. Finally, the degradation ability of the molybdenite/PMS system for different pollutants and in actual water bodies was also explored. This work provided ideas for exploring the degradation of organic contaminants by natural minerals., (Copyright © 2022. Published by Elsevier B.V.)

The present study developed an analytical technique to investigate the possible covalent adduct formation of albumin with the herbicide atrazine, and to characterize the protein modifications in vitro using liquid chromatography separation coupled with high resolution time-of-flight mass spectrometry (LC-TOF-MS). Tandem mass spectrum analysis (MS/MS) with collision induced dissociation (CID) revealed the specific sites of rat, human and bovine serum albumin adduct with atrazine. The formation of b-ion, y-ion series in MS/MS showed a covalent adduct with an addition mass of 179.1 Da located on Cys-34 of serum albumin from rats, human and bovine. This clearly indicated that the chemical group C 8 H 13 N 5 forms an adduct with Cys-34 despite the sequences differences between of rat, human and bovine serum albumin. To confirm the method reliability, concentration-dependent and time-dependent formation of adducts between serum albumins and atrazine were also investigated. Our results confirmed that atrazine can directly react with Cys-34 of serum albumin and form covalent adducts without prior metabolism., (Crown Copyright © 2020. Published by Elsevier B.V. All rights reserved.)

Two injectable reactive and sorption-active particle types were evaluated for their applicability in permeable reaction zones for in-situ removal of herbicides ("nanoremediation"). As model substances, atrazine and bromacil were used, two herbicides frequently occurring in groundwater. In order to provide recommendations for best use, particle performance was assessed regarding herbicide degradation and detoxification. For chemical reduction, Carbo-Iron® was studied, a composite material consisting of zerovalent iron and colloidal activated carbon. Carbo-Iron reduced bromacil with increased activity compared to nanoscale zerovalent iron (nZVI). The sole reaction product, 3-sec-butyl-6-methyluracil, showed 500-fold increase in half-maximal-effect concentration (EC 50 ) towards the chlorophyte Scendesmus vacuolatus compared to the parent compound. The detoxification based on dehalogenation confirmed the dependency of the specific mode-of-action on the carbon-halide bond. For atrazine, neither nZVI nor Carbo-Iron showed significant degradation under the conditions applied. As novel subsurface treatment option, Trap-Ox® zeolite FeBEA35 was studied for generation of in-situ permeable oxidation barriers. Both adsorbed atrazine and bromacil underwent fast unselective oxidation. The transformation products of the Fenton-like reaction were identified, and oxidation pathways derived. For atrazine, a 300-fold increase in EC 50 for S. vacuolatus was found over the duration of the reaction, and a loss of phytotoxicity to non-detectable levels for bromacil., 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 B.V. All rights reserved.)

Iron ligands as 1,2-dihydroxybenzenes (1,2-DHBs) have been used to increase the oxidizing ability of Fenton systems. However, these kinds of ligands become toxic quinones in the process creating an environmental problem since these compounds cannot be easily separated from a solution. To avoid this problem, in the present work, water-insoluble tannins, obtained from Pinus radiata bark, were used as a source of 1,2-DHBs to promote the oxidizing ability of the Fenton process. The developed system was tested using atrazine, as a substrate, which is a toxic and recalcitrant compound, present in different sources of water. The best reaction conditions established by the experimental design were as follows: pH of 3.6; 2.4 mmol L -1 of H 2 O 2 ; 150 μmol L -1 of Fe(III); and 800 mg L -1 of tannins. A significant increase in the efficiency of the degradation of atrazine by the heterogeneous Fenton process was observed under these conditions. The repetitive use of the insoluble tannins for Fenton-like processes showed a similar oxidizing ability and did not produce the lixiviation of phenols or other aromatic compounds. Together, the results showed that insoluble tannins could be used safely at least five times to promote the reactivity of Fenton systems., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Atrazine (ATZ) is an herbicide that has been considered an environmental pollutant worldwide. ATZ contaminates groundwaters and can persist in soils for up to a year causing several environmental and health problems. This study aimed to investigate ATZ degradation catalyzed by manganese porphyrins as biomimetic cytochrome P450 models. We used PhIO, PhI(OAc) 2 , H 2 O 2 , t-BuOOH, m-CPBA, or Oxone ® as oxidant under mild conditions and evaluated a range of manganese porphyrins as catalyst. Concerning oxidant, iodosylbenzene provided the best result-ATZ degradation catalyzed by one of the studied manganese porphyrins in acetonitrile was as high as 47%. We studied the same catalyst/oxidant systems in natural water from a Brazilian river as solvent and obtained up to 100% ATZ degradation when iodobenzene diacetate was the oxidant, regardless of the manganese porphyrin. Besides the already known ATZ degradation products, we also identified unexpected degradation compounds (ring-opening products). Toxicity tests showed that the latter products were capable of proliferate blood cells because they did not show toxicity under the evaluated conditions., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) is a triazine herbicide intensively used in agricultural production and is often detected in different environmental matrices at concentrations above the permitted limit. This study investigated the influence of two earthworm species (epigeic Eisenia foetida and endogeic Amynthas robustus) on atrazine speciation and the degradation pathway. Our results revealed that both earthworms significantly accelerated atrazine degradation in a 28-day vermiremediation, and the residual atrazine declined from 4.23 ± 0.21 mg/kg in bulk soils to 0.51 ± 0.29 mg/kg (E. foetida) and 0.43 ± 0.19 mg/kg (A. robustus). By consuming organic matter (from 40.37 ± 1.14 to 36.31 ± 1.55 and 34.59 ± 1.13 g/kg for E. foetida and A. robustus) and neutralizing the soil pH (from 5.37 ± 0.27 to 6.36 ± 0.11 and 6.61 ± 0.30 for E. foetida and A. robustus), both earthworms reduced humus-fixed atrazine and increased the available atrazine. The percentage of available atrazine increased from 8.80 ± 0.21% in bulk soil to 10.30 ± 0.29% and 16.42 ± 0.18% in the vermiremediation treatments. Both earthworms promoted the hydroxyatrazine pathway by consuming soil organic matter and encouraged the deethylatrazine/deisopropylatrazine pathway by neutralizing the soil pH. Our findings unravel a new mechanism of vermiremediation by improving the soil physical-chemical properties and altering the atrazine degradation pathway, providing new insights into the influential factors on atrazine bioremediation in red soil., (Copyright © 2018. Published by Elsevier B.V.)

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.)

Given the need for innovations in advanced oxidation processes to deal with challenges such as OH scavenging, this paper addresses the removal of pharmaceuticals with a large variety in ozone reactivity (k O3  = 0.15-3 × 10 5 M -1 s -1 ) by use of the novel ozone-activated peroxymonosulfate (O 3 /PMS) process. A clear improvement in removal efficiency (up to 5 times higher) is noticed as a result of the generation of SO 4 - radicals, mainly for slow-ozone reacting compounds (k O3 ≤ 250 M -1 s -1 ) and in the presence of a OH scavenger. Depending on the target compound, SO 4 - are assessed to contribute for 50-90% to the overall removal of the micropollutants, both in single-compound and mixture experiments. Ozone-based PMS activation occurs at neutral to alkaline pH and, in the presence of a OH scavenger, removal efficiencies during O 3 /PMS are up to 3 times higher than with the O 3 /H 2 O 2 process. In optimizing the O 3 /PMS process, a trade-off has to made between the desired removal and the PMS:O 3 ratio. A molar ratio of 1:10 already results in a clear benefit compared to the ozonation process. Further increase of the PMS content up to a 1:1 ratio improved the removal by an additional factor of 1.3-1.5., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Passivation of anode is a main challenge in the electrochemical synthesis of ferrate(VI) (Fe VI O 4 2- , Fe(VI)). A series of electrochemical approaches were employed including polarization curve, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS) to analyze the physicochemical processes involved in electrochemical synthesis of Fe(VI) using sponge iron and cast iron anodes. The results demonstrate that the sponge iron anode achieved higher yield of Fe(VI) compared to grey cast iron anode. The optimum condition to generate Fe(VI) using sponge iron was 35-50°C and 30mA/cm 2 . Significantly, the sponge iron anode could generate Fe(VI) for a long duration (>10h) under these conditions; possibly suitable for large scale synthesis of Fe(VI). The prepared Fe(VI) solution was used to treat antibiotic (sulfamethoxazole (SMX)) and pesticide (atrazine (ATZ)) in water. At a molar ratio of Fe(VI) to SMX as 20:1 in the pH range from 5.0 to 9.0, almost complete oxidative transformation of SMX could be obtained. Comparatively, oxidative transformation of ATZ was incomplete (∼70%) even when [Fe(VI)]:[ATZ]=87 at pH 5.0-9.0. Fluorescence spectra and cytotoxicity studies suggest that the oxidative transformation products of both SMX and ATZ possess lower toxicity than the parent antibiotic and pesticide, respectively., (Copyright © 2017. Published by Elsevier B.V.)

Drinking water treatment residuals (WTRs) are safe byproducts of water treatment plants containing iron. This work studies the degradation of atrazine (ATZ) by WTR-catalyzed peroxymonosulfate (PMS) in aqueous solutions. Factors that affect the catalytic performance (the PMS concentration, catalyst dose, initial solution pH, reaction temperature and water matrix species) were investigated. The results show that the catalytic degradation efficiency of ATZ increases with the increase in PMS concentration and temperature, whereas a higher content of WTRs results in lower removal efficiency because of the quenching effect and negative effect of high pH. For an initial solution pH of 3 and 5, 94.1% and 87.4% of ATZ degradation can be achieved within 6h, whereas the value is only 26% for pH of 7. The production of sulfate radicals (SO 4 - ) and hydroxyl radicals (OH) was confirmed by classic radical quenching and electron spin resonance (ESR) tests. Based on the GC-MS and LC-MS results, the main degradation pathways of ATZ may contain dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation processes. In addition to the ATZ removal ability, the WTRs/PMS system can simultaneously remove phosphorus. This article provides a new idea for wastewater treatment and usage of WTRs as a resource., (Copyright © 2017 Elsevier B.V. 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.)

Photocatalytically active TiO 2 -patterned polyimide (PI) films (PI-TiO 2 ) were fabricated using thermal transfer patterning (TTP). When subjected to hot pressing, the TiO 2 nanoparticles electrosprayed on steel mesh templates were successfully transferred and formed checker plate patterns on PI film. FE-SEM studies confirmed that pressing at 350°C and 100MPa was optimum for obtaining patterns with uniform TiO 2 coverage. When the quantity of TiO 2 on the template increased, the amount of it immobilized on PI film also increased from 0.3245 to 1.2378mg per 25cm 2 . XPS studies confirmed the presence TiO 2 on the patterns, and indicated the formation of carboxylic acid and amide groups on the PI surface during TTP. When tested under UVA irradiation, PI-TiO 2 with 1.2378mg/25cm 2 TiO 2 loading exhibited the highest photocatalytic performance for methylene blue (10μM) degradation, with a rate constant of 0.0225min -1 and stable photocatalytic efficacy for 25 cycles of reuse. The PI-TiO 2 was also successfully used to degrade amoxicillin, atrazine, and 4-chlorophenol. During photocatalysis, the toxicity of 4-chlorophenol against Vibrio fischeri and the antibiotic activity of amoxicillin against Escherichia coli were decreased. Overall, TTP was found to be a potentially scalable method for fabricating robust immobilized TiO 2 photocatalyst., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Capillary isotachophoresis (ITP) is an electrophoretic technique offering high sensitivity due to permanent stacking of the migrating analytes. Its combination with electrospray-ionization mass-spectrometric (ESI-MS) detection is limited by the narrow spectrum of ESI-compatible components but can be compensated by experienced system architecture. This work describes a methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides, based on implementation of the concepts of moving-boundary isotachophoresis and of H + as essential terminating component into cationic ITP with ESI-MS detection. Theoretical description of such kind of system is given and equations for zone-related boundary mobilities are derived, resulting in a much more general definition of the effective mobility of the terminating H + zone than used so far. Explicit equations allowing direct calculation for selected simple systems are derived. The presented theory allows prediction of stacking properties of particular systems and easy selection of suitable electrolyte setups. A simple ESI-compatible system composed of acetic acid and ammonium with H + and ammonium as a mixed terminator was selected for the analysis of 2-hydroxyatrazine and 2-hydroxyterbutylazine, degradation products of s-triazine herbicides. The proposed method was tested with direct injection without any sample pretreatment and provided excellent linearity and high sensitivity with limits of detection below 100ng/L (0.5nM). Example analyses of unspiked and spiked drinking and river water are shown., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The oxidation of s-triazines (using atrazine (ATZ) as a model compound) by a solar-enhanced Fenton-like process involving persulfate and ferrous ion was studied. A flow-through tubular photoreactor was employed for the experiments. The solar-enhanced oxidative system involving ferrous ion and persulfate (Solar/S 2 O 8 2- /Fe 2+ ) showed the highest ATZ degradation efficiency when compared with other treatments (unactivated S 2 O 8 2- , Solar - sunlight only, S 2 O 8 2- /Fe 2+ , Solar/S 2 O 8 2- ). Complete degradation of ATZ and 20% reduction in total organic carbon (TOC) content were observed after 30min of the treatment. The in situ generated • ОН and SO 4 -• radicals were shown to be involved in ATZ oxidation using the radical scavengers methanol and tert-butyl alcohol. Furthermore, iron compounds were shown to act not only as catalysts but also as photo-sensitizers, as the introduction of ferrous ion into the reaction mixture led to an increased absorbance of the solution and expansion of the absorption spectrum into the longer wavelength spectral region., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The facile preparation of poly(l-DOPA)-tyrosinase (PDM-Tyr) composite and its application both in substrate (phenol) and inhibitor (atrazine) sensing is reported here for the first time. Effective immobilization of enzyme is realized via in-situ entrapping Tyr in poly(l-DOPA) (PDM), which is formed by Tyr catalytic polymerization of l-DOPA. The Tyr modified electrode is simply prepared by dipping the PDM-Tyr composite on an Au electrode and then covered by Nafion. The thus-prepared Tyr-immobilized electrode exhibits excellent performance superior to most Tyr-based electrochemical biosensors, the sensitivity to phenol is as high as 5122 μA mM(-1) in the linear range of 10nM~1.25 μM, the apparent Michaelis-Menten constant (KM(app)) determined as low as 3.13μM indicates strong substrate binding and high catalytic activity of the immobilized Tyr. The biosensor also works well in atrazine biosensing, with a linear detection range of 50ppb~30ppm and a low detection limit of 10ppb obtained. In addition, the biosensor shows excellent stability, precision, high sensitivity and fabrication simplicity., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this work, it is studied the removal of atrazine from spiked soils by soil washing using surfactant fluids, followed by the treatment of the resulting washing waste by electrolysis with boron doped diamond (BDD) anode. Results confirm that combination of both technologies is efficient for the removal and total mineralization of atrazine. Ratio surfactant/soil is a key parameter for the removal of atrazine from soil and influences significantly in the characteristic of the wastewater produced, affecting not only to the total organic load but also to the mean size of micelles. The higher the ratio surfactant soil, the lower is the size of the particles. Electrolyses of this type of waste attain the complete mineralization. TOC and COD are removed from the start of the treatment but the key of the treatment is the reduction in size of the micelles, which lead to a higher negative charge in the surface and to the faster depletion of the surfactant as compared with the pesticide., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The degradation of atrazine was investigated in aqueous solution by gamma-ray irradiation. 8.11 μM initial atrazine concentration could be completely removed in N₂ saturated solution by applying 3500 Gy radiation dose at a dose rate of 296 Gy h(-1). Significant removal of atrazine (i.e., 39.4%) was observed at an absorbed dose of 1184 Gy in air saturated solution and the removal efficiency was promoted to 50.5 and 65.4% in the presence of N₂O and N₂ gases, respectively. The relative contributions of hydrated electron, hydroxyl radical and hydrogen radical toward atrazine degradation were determined as ratio of observed dose constant (kobs) and found to be 5: 3: 1 for keaq(-): k·OH: kH·, respectively. The degradation efficiency of atrazine was 69.5, 55.6 and 37.3% at pH 12.1, 1.7 and 5.7, respectively. A degradation mechanism was proposed based on the identified degradation by-products by gas chromatography-mass spectrometry. Taking the relative contributions of oxidative and reductive species to atrazine degradation into account, reductive pathway proved to be a better approach for the radiolytic treatment of atrazine contaminated water., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The widespread occurrence of atrazine in waters poses potential risk to ecosystem and human health. In this study, we investigated the underlying mechanisms and transformation pathways of atrazine degradation by cobalt catalyzed peroxymonosulfate (Co(II)/PMS). Co(II)/PMS was found to be more efficient for ATZ elimination in aqueous solution than Fe(II)/PMS process. ATZ oxidation by Co(II)/PMS followed pseudo-first-order kinetics, and the reaction rate constant (k(obs)) increased appreciably with increasing Co(II) concentration. Increasing initial PMS concentration favored the decomposition of ATZ, however, no linear relationship between k(obs) and PMS concentration was observed. Higher efficiency of ATZ oxidation was observed around neutral pH, implying the possibility of applying Co(II)/PMS process under environmental realistic conditions. Natural organic matter (NOM), chloride (Cl(-)) and bicarbonate (HCO3(-)) showed detrimental effects on ATZ degradation, particularly at higher concentrations. Eleven products were identified by applying solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC/MS) techniques. Major transformation pathways of ATZ included dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation. Detailed mechanisms responsible for these transformation pathways were discussed. Our results reveal that Co(II)/PMS process might be an efficient technique for remediation of groundwater contaminated by ATZ and structurally related s-triazine herbicides., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Formation of nonextractable residue was widely observed as a sink of atrazine (ATZ) in soil. However, the mechanisms by which ATZ binds to soil organic matter remain unclear. In this study, we demonstrated that neucleophilic substitution could serve an important pathway causing ATZ sequestration. The carbon bonded to the chlorine in ATZ molecule is partially positively charged due to the strong electronegativity of chlorine and is susceptible to the attack of nucleophiles such as aniline. Since aromatic amines are relatively rare in natural soils, amino acids/peptides were hypothesized to act as the main nucleophiles in real environment. However, substantially ATZ transformation was only observed in the presence of those species containing thiol functionality. Thus, we speculated that it was the thiol group in amino acids/peptides acting as the nucleophile. Nitrogen in amino acids was in fact not an active nucleophile toward ATZ. In addition to the sulfur-containing amino acids, other thiol compounds, and sulfide were also proved to be reactive to ATZ. Thus, the sequestration potential of ATZ probably correlates to the availability of thiol compounds in soil., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A soft chemical process was successfully used to immobilize Pseudomonas sp. strain ADP (ADP), a well-known atrazine (herbicide) degrading bacterium, within a Mg2Al-layered double hydroxide host matrix. This approach is based on a simple, quick and ecofriendly direct coprecipitation of metal salts in the presence of a colloidal suspension of bacteria in water. It must be stressed that by this process the mass ratio between inorganic and biological components was easily tuned ranging from 2 to 40. This ratio strongly influenced the biological activity of the bacteria towards atrazine degradation. The better results were obtained for ratios of 10 or lower, leading to an enhanced atrazine degradation rate and percentage compared to free cells. Moreover the biohybrid material maintained this biodegradative activity after four cycles of reutilization and 3 weeks storage at 4°C. The ADP@MgAl-LDH bionanohybrid materials were completely characterized by X-ray diffraction (XRD), FTIR spectroscopy, thermogravimetric analysis and scanning and transmission electronic microscopy (SEM and TEM) evidencing the successful immobilization of ADP within the inorganic matrix. This synthetic approach could be readily extended to other microbial whole-cell immobilization of interest for new developments in biotechnological systems., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Degradation of atrazine by heterogeneously catalyzed ozonation was carried out with TiO2 in the form of rutile as the catalyst. Some experimental factors such as catalyst dose, ozone dose and initial concentration of atrazine were investigated for their influence on catalyzed ozonation process. Although atrazine was effectively removed from aqueous solution by catalyzed ozonation process, the mineralization degree only reached 56% at the experimental conditions. Five transformation products were identified by GC/MS analysis. The degradation of atrazine involved de-alkylation, de-chlorination and de-amination. Diaminotriazine and 5-azauracil were the de-chlorinated and de-aminated products, respectively. The evolution of concentration of transformation products during catalyzed ozonation process was compared with uncatalyzed ozonation to show the degradation pathway. Toxicity tests based on the inhibition of the luminescence emitted by Vibrio fisheri indicated the detoxification of atrazine by catalyzed ozonation., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The effectiveness of sonolysis (US), photolysis (UV), and sonophotolysis (USUV) for the degradation of atrazine (ATZ) was investigated. An untypical kinetics analysis was found useful to describe the combined process, which is compatible to pseudo first-order kinetics. The heterogeneous environments of two different ultrasounds (20 and 400 kHz) were evaluated. The heterogeneous distribution of ATZ in the ultrasonic solution was found critical in determining the reaction rates at different frequencies. The presence of NaCl would promote/inhibit the rates by the growth and decline of "salting out" effect and surface tension. The benefits of combining these two processes were for the first time investigated from the aspect of promoting the intermediates degradation which were resistant in individual processes. UV caused a rapid transformation of ATZ to 2-hydroxyatrazine (OIET), which was insensitive to UV irradiation; however, US and USUV were able to degrade OIET and other intermediates through •OH attack. On the other hand, UV irradiation also could promote radical generation via H2O2 decomposition, thereby resulting in less accumulation of more hydrophilic intermediates, which are difficult to degradation in the US process. Reaction pathways for ATZ degradation by all three processes are proposed. USUV achieved the greatest degree of ATZ mineralization with more than 60% TOC removed, contributed solely by the oxidation of side chains. Ammeline was found to be the only end-product in both US and USUV processes., (Copyright © 2014 Elsevier B.V. All rights reserved.)

While karst aquifers are considered as rapid flow and transport systems, their high potential for long-term storage is often ignored. However, to achieve a sustainable raw water quality for drinking water production, the understanding of this potential is highly essential. In this study, the transport dynamics of the two herbicides metazachlor and atrazine as well as a degradation product of the latter (desethylatrazine) were investigated at a karst spring over 1 year. Even 20 years after its ban in Germany, atrazine and its degradation product were almost always detectable in the spring water in the low ng L(-1) range (up to 5.2ng L(-1)). Metazachlor could only be detected after precipitation events, and the observed concentrations (up to 82.9ng L(-1)) are significantly higher than atrazine or desethylatrazine. Comparing the dynamics of the herbicides with the inorganic ions Ca(2+), Mg(2+) and electrical conductivity, a positive correlation of atrazine with these parameters could be observed. From this observation, atrazine is concluded to be located within the aquifer matrix. To achieve a sustainable raw water management at karst springs, the rapidness of these systems needs to be highlighted as well as their long-term storage potential. Persistent substances or transformation products are prone to deteriorate the raw water quality for decades., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this study, we investigated adsorption characteristics of nine selected micropollutants (six pharmaceuticals, two pesticides, and one endocrine disruptor) in water using an activated carbon. The effects of carbon dosage, contact time, pH, DOM (dissolved organic matter), and temperature on the adsorption removal of micropollutants were examined. Increasing carbon dosage and contact time enhanced the removal of micropollutants. Sorption coefficients of hydrophilic compounds (caffeine, acetaminophen, sulfamethoxazole, and sulfamethazine) fit a linear isotherm and hydrophobic compounds (naproxen, diclofenac, 2, 4-D, triclocarban, and atrazine) fit a Freundlich isotherm. The removal of hydrophobic pollutants and caffeine were independent of pH changes, but acetaminophen, sulfamethazine, and sulfamethoxazole were adsorbed by mainly electrostatic interaction with activated carbon and so were affected by pH. The decrease in adsorption removal in surface water samples was observed and this decrease was more significant for hydrophobic than hydrophilic compounds. The decline in the adsorption capacity in surface water samples is caused by the competitive inhibition of DOM with micropollutants onto activated carbon. Low temperature (5°C) also decreased the adsorption removal of micropollutants, and affected hydrophobic compounds more than hydrophilic compounds. The results obtained in this study can be applied to optimize the adsorption capacities of micropollutants using activated carbon in water treatment process., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Nanoparticles of poly(epsilon-caprolactone) containing the herbicide atrazine were prepared, characterized, and evaluated in terms of their herbicidal activity and genotoxicity. The stability of the nanoparticles was evaluated over a period of three months, considering the variables: size, polydispersion index, pH, and encapsulation efficiency. Tests on plants were performed with target (Brassica sp.) and non-target (Zea mays) organisms, and the nanoparticle formulations were shown to be effective for the control of the target species. Experiments using soil columns revealed that the use of nanoparticles reduced the mobility of atrazine in the soil. Application of the Allium cepa chromosome aberration assay demonstrated that the nanoparticle systems were able to reduce the genotoxicity of the herbicide. The formulations developed offer a useful means of controlling agricultural weeds, while at the same time reducing the risk of harm to the environment and human health., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this study, the roles of TaON and Ta3N5 in the degradation of atrazine by the visible-Fenton-like system were examined in detail. The TaON and Ta3N5 samples prepared by the nitridation of Ta2O5 and characterized by XRD, DRS, BET and PL analyses. The results showed that the TaON sample had weaker absorption in the visible region but higher specific surface area than the Ta3N5 sample. The degradation rate of atrazine in visible-TaON-Fenton-like system was 2.64 times than that in visible-Ta3N5-Fenton-like system. Both Fe(2+) and H2O2 could be reduced by eCB (electrons in the conduction band) in TaON or Ta3N5, while atrazine could not be oxidized by hVB (holes in the valance band). OH is the active species for the degradation of atrazine in visible-TaON/Ta3N5-Fenton-like systems. Majority of OH originated from Fenton reaction. After Fe(3+) was reduced by eCB to Fe(2+), Fe(2+) reacted quickly with H2O2 to generate OH. In addition, by capturing eCB, a little of H2O2 was reduced to yield OH, which contributed a small fraction of atrazine degradation. Based on the experimental results, the roles of TaON and Ta3N5 in the visible-Fenton-like system were proposed. And the higher photocatalytic activity of TaON than Ta3N5 was suggested to be due to the higher separation efficiency of electrons and holes, which may be related to the larger specific surface area., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Two different nonthermal plasma reactors at atmospheric pressure were assessed for the removal of organic micropollutants (atrazine, chlorfenvinfos, 2,4-dibromophenol, and lindane) from aqueous solutions (1-5 mg L(-1)) at laboratory scale. Both devices were dielectric barrier discharge (DBD) reactors; one was a conventional batch reactor (R1) and the other a coaxial thin-falling-water-film reactor (R2). A first-order degradation kinetics was proposed for both experiments. The kinetic constants (k) were slightly faster in R1 (0.534 min(-1) for atrazine; 0.567 min(-1) for chlorfenvinfos; 0.802 min(-1) for 2,4-dibromophenol; 0.389 min(-1) for lindane) than in R2 (0.104 min(-1) for atrazine; 0.523 min(-1) for chlorfenvinfos; 0.273 min(-1) for 2,4-dibromophenol; 0.294 min(-1) for lindane). However, energy efficiencies were about one order of magnitude higher in R2 (89 mg kW(-1) h(-1) for atrazine; 447 mg kW(-1) h(-1) for c hlorfenvinfos; 47 mg kW(-1) h(-1) for 2,4-dibromophenol; 50 mg kW(-1) h(-1) for lindane) than in R1. Degradation by -products of all four compounds were identified in R1. As expected, when the plasma treatment (R1) was applied to industrial wastewater spiked with atrazine or lindane, micropollutant removal was also achieved, although at a lower rate than with aqueous solutions (k = 0.117 min(-1) for atrazine; k = 0.061 min(-1) for lindane)., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Multi-walled carbon nanotubes (MWCNTs), nano-graphene platelets (NGPs), and superfine powdered activated carbon (S-PAC) were comparatively evaluated for their applicability as adsorptive coatings on microfiltration membranes. The objective was to determine which materials were capable of contaminant removal while causing minimal flux reduction. Methylene blue and atrazine were the model contaminants. When applied as membrane coatings, MWCNTs had minimal retention capabilities for the model contaminants, and S-PAC had the fastest removal. The membrane coating approach was also compared with a stirred vessel configuration, in which the adsorbent was added to a stirred flask preceding the membrane cell. Direct application of the adsorbent to the membrane constituted a greater initial reduction in permeate concentrations of the model contaminants than with the stirred flask setup. All adsorbents except S-PAC showed flux reductions less than 5% after application as thin-layer membrane coatings, and flux recovery after membrane backwashing was greater than 90% for all materials and masses tested., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In order to investigate sustainable alternatives to current water treatment methods, the effect of NF-titania film thickness and subsequent photocatalysis in combination with oxidants was examined under simulated solar light. Such a combination presents a theoretical possibility for a synergistic interaction between the photocatalyst and the oxidant (activation of the oxidant by the catalyst under conditions under which it may not conventionally be activated). To investigate, peroxymonosulfate (PMS) and persulfate (PS) were used as oxidants, and two pesticides, amitrole and atrazine, were used as target contaminants. In the absence of a film, activation of PMS under simulated solar conditions is demonstrated by removal of atrazine, whereas PS provided minimal removal, suggesting inefficient activation. Combining photocatalytic films with PMS and PS manifested synergies for both oxidants. The effect was most pronounced for PS since PMS already underwent significant activation without the photocatalyst. Amitrole degradation results indicated a lack of removal of amitrole by activated PS alone, suggesting that this sulfate radical-based treatment technology may be ineffective for the removal of amitrole. The NF-TiO₂ films demonstrated reusability under solar light both with and without oxidants. Finally, the degradation intermediates were analyzed, and a new intermediate appeared upon incorporating oxidants into the system., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The effects of repeated atrazine application (40 mg a.i.kg(-1)) on its degradation, microbial communities and enzyme activities were studied in a peat based biomixture composed by straw, soil and peat in the volumetric proportions of 2:1:1 that can be used in on-farm biopurification system. Atrazine removal efficiency was high (96%, 78% and 96%) after each atrazine application and did not show a lag phase. Microbial enzyme activities were reduced significantly with atrazine application but rapidly recovered. Microbial diversity obtained by BiologEcoplate was similar after the first and second atrazine application. However, an inhibitory effect was observed after the third application. After each atrazine application, culturable fungi were reduced, but rapidly recovered without significant changes in culturable bacteria and actinomycetes compared to the control. Denaturing gradient gel electrophoresis (DGGE) patterns demonstrated that microbial community structure remained relatively stable in time when compared to the controls. In conclusion, our results demonstrated that after successive ATZ applications, the peat based biomixture had a good degradation capacity. Moreover, microbiological assays demonstrated the robustness of the peat based biomixture from a microbiological point of view to support pesticide degradation., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this work, humic substances (HS) immobilized, as a thin layer or as aggregates, on silica gel were tested as material for solid phase extraction. Some triazines (simazine, atrazine, therbutylazine, atrazine-desethyl-desisopropyl-2-hydroxy, ametryn and terbutryn), have been selected as test analytes due to their environmental importance and to span a large range of solubility and octanol/water partition coefficient (logP). The sorbent was obtained immobilizing a thin layer of HS via physisorption on a pre-coated silica gel with a cationic polymer (polybrene). While the sorbent could be used as it is, it was demonstrated that additional HS could be immobilized, via weak interactions, to form stable humic aggregates. However, while a higher quantity of HS could be immobilized, no significant differences were observed in the sorption parameters. This sorbent have been tested for solid phase extraction to concentrate triazines from aqueous matrixes. The sorbent demonstrated performances equivalent to commercial alternatives as a concentration factor between 50 and 200, depending on the type of triazines, was obtained. Moreover the low cost and the high flow rate of sample through the column allowed using high quantity of sorbent. The analytical procedure was tested with different matrixes including tap water, river water and estuarine water., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The interconversion of Fe(III)/Fe(II) in Fenton (Fe(2+)/H2O2) and Fenton-like (Fe(3+)/H2O2) reactions has been studied to better understand their intrinsic mechanisms. The reactions were conducted at an initial pH of 3.0, with H2O2 in excess and iron in catalytic concentrations, and with nitrobenzene and atrazine as model organic compounds. The results of this study have shown that some intermediate species in the degradation of aromatic compounds can influence the interconversion of Fe(III)/Fe(II) in the Fenton and Fenton-like reactions, and hence influence the rate and course of the reactions. Thus, from the point of view of Fe(III)/Fe(II) interconversion, a Fenton-like reaction inevitably involves a classical Fenton reaction, and a Fenton reaction may also involve a Fenton-like reaction step. These two reactions may be somewhat interchangeable and proceed simultaneously. In the case of the degradation of aromatic compounds, the Fenton-like reactions display autocatalytic character, but no such effect is observed for non-aromatic compounds., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Biochars were produced from pig manure to elucidate the influence of biochars with high ash contents on the fate of pesticides. Adsorption and catalytic hydrolysis of carbaryl and atrazine on original biochars and deashed biochars were investigated. The two pesticides were substantially adsorbed by the biochars, with organic carbon normalized sorption coefficient (K(oc)) values of 10(2.65)-10(3.66) L/kg for carbaryl and 10(1.90)-10(3.57) L/kg for atrazine at C(e) of 0.5 mg/L. Hydrophobic effect alone could not explain the sorption, and several other processes including pore-filling and π-π electron donor-acceptor interactions were involved in pesticide adsorption. Adsorption increased greatly on the deashed biochar, indicating that some organic sorption sites in the original biochars were blocked or difficult to access due to their interactions with inorganic moiety. The pesticides were found to hydrolyze faster in the presence of biochars, and in the presence of biochar pyrolyzed at 700 °C, carbaryl and atrazine were decomposed by 71.8% and 27.9% in 12 h, respectively. The elevated solution pH was the main reason for the enhanced hydrolysis; however both the mineral surface and dissolved metal ions released from the biochars were confirmed to catalyze the hydrolysis., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Application of low cost amendment for pesticide retention in soil is an important area of research in environmental sciences. The present study reports the potential of coal fly ash (Inderprastha and Badarpur), a waste from thermal power stations, for retaining soil applied metolachlor and atrazine within the application zone. Both the fly ashes were highly effective in reducing the leaching losses of metolachlor and atrazine and at 2% and 5% fly ash amendment levels the herbicides were retained in the top 15 cm profile of the column. However, fly ashes varied in their capacity in reducing the downward mobility of herbicides, as the Inderprastha fly ash was more effective than the Badarpur fly ash. Although fly ash contained heavy metals like Cr, Cu or Pb, but they were not detected in the leachate. Also, concentration of other metals like Zn, Mn and Fe in leachate decreased after fly ash amendment. Results of this study have implications in reducing the leaching losses of these herbicides in agricultural soils., (Copyright © 2012 Elsevier Inc. All rights reserved.)

We studied the sorption-desorption behaviour of two herbicides (diuron and artrazine) in a soil rich in Fe and Al oxides (Ferrosol), either amended freshly with two different types of biochars or that contained biochars aged under field conditions. Standard batch sorption-desorption experiments were conducted on soil samples freshly amended with two biochars, (namely, poultry litter - PL and paper mill - PM sludge) as well on those collected from field 32 months after biochar application. Soils that were freshly amended with biochars @ 10 t ha(-1) showed a two (PM) to five (PL) fold increase in sorption of herbicides as compared with that in the unamended soil. For example, the fresh amendments with PL biochar at 10 t ha(-1) led to a highly significant (P<0.001) increase in the Freundlich sorption coefficient (K(f)) of atrazine; i.e. 20.71 (n=0.40) as compared with 4.02 (n=0.70) for the control soil. Sorption was reversible in the unamended soil but sorption-desorption hysteresis was prominent in the soil amended with fresh biochars. In contrast, the soil containing aged biochars (at 10 t ha(-1)) exhibited sorption-desorption properties that were statistically similar to that of the control soil, especially for atrazine. Ageing of biochars in the soil over a 32 months period reduced the sorption capacity by 47% (PM) to 68% (PL) for diuron. These findings may have implications for herbicide efficacy in biochar amended soils., (Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.)

In order to overcome the limitation of the application of nanoparticles, tantalum (oxy)nitrides nanotube arrays on a Ta foil were synthesized and introduced in vis (visible light)-Fenton-like system to enhance the degradation of atrazine. At first, the anodization of tantalum foil in a mild electrolyte solution containing ethylene glycol and water (v:v=2:1) plus 0.5wt.% NH(4)F produced tantala nanotubes with an average diameter of 30nm and a length of approximately 1μm. Then the nitridation of tantala nanotube arrays resulted in the replacement of N atoms to O atoms to form tantalum (oxy)nitrides (TaON and Ta(3)N(5)), as testified by XRD and XPS analyses. The synthesized tantalum (oxy)nitrides nanotubes absorb well in the visible region up to 600nm. Under visible light, tantalum (oxy)nitrides nanotube arrays were catalytically active for Fe(3+) reduction. With tantalum (oxy)nitrides nanotube arrays, the degradation of atrazine and the formation of the intermediates in vis/Fe(3+)/H(2)O(2) system were significantly accelerated. This was explained by the higher concentration of Fe(2+) and thus the faster decomposition of H(2)O(2) with tantalum (oxy)nitrides nanotubes. In addition, tantalum (oxy)nitrides nanotubes exhibited stable performance during atrazine degradation for three runs. The good performance and stability of the tantalum (oxy)nitrides nanotubes film with the convenient separation, suggest that this film is a promising catalyst for vis-Fenton-like degradation., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] is the most widely used herbicide in the United States. In recent years, there has been controversy about atrazine's potential endocrine/reproductive and neurological adverse effects in wildlife and humans. The controversy triggered several environmental and epidemiologic studies, and it generated needs for sensitive and selective analytical methods for the quantification of atrazine, atrazine metabolites, and degradation or hydrolysis products. We developed a two-dimensional high performance liquid chromatography (2D-HPLC) method with isotope dilution tandem mass spectrometry detection to measure atrazine in urine, along with 11 atrazine metabolites and hydrolysis products, including 6-chloro (Cl), 6-mercapto (Mer) and 6-hydroxy (OH) derivatives, and their desethyl, desisopropyl and diamino atrazine analogs (DEA, DIA and DAA, respectively). The 2D-HPLC system incorporated strong cation exchange and reversed phase separation modes. This versatile approach can be used for the quantitative determination of all 12 compounds in experimental animals for toxicological studies. The method requires only 10 μL of urine, and the limits of detection (LODs) range from 10 to 50 μg/L. The method can also be applied to assess atrazine exposure in occupational settings by measurement of 6-Cl and 6-Mer analogs, which requires only 100 μL of urine with LODs of 1-5 μg/L. Finally, in combination with automated off-line solid phase extraction before 2D-HPLC, the method can also be applied in non-occupational environmental exposure studies for the determination of -6-Cl and 6-Mer metabolites, using 500 μL of urine and LODs of 0.1-0.5 μg/L., (Published by Elsevier B.V.)

We present experimental breakthrough curve (BTC) data and a modeling investigation of conservative and sorbing tracer transport in natural soils. By analyzing the data using the continuous time random walk (CTRW) model, we probe the traditional approach of using conservative tracer model parameters as a basis for quantifying the transport of sorbing solutes in the same domain when non-Fickian transport is present. Many known contaminants in groundwater are sorbed to the host solid porous medium, to varying extents, while being transported; this enhances the long tailing of BTCs which often already occurs because of the inherent non-Fickian nature of the transport. The CTRW framework has been shown to account very well for non-Fickian conservative (nonsorbing) transport. Here, we examine two BTC data sets in laboratory columns packed with natural soils; the first (previously analyzed by Mao and Ren (2004)) comprises transport of (conservative) bromide and (sorbing) atrazine tracers, while the second presents new data with bromide and tribromoneopentyl alcohol (TBNPA), a key flame retardant, as a sorbing solute. TBNPA has received little attention in the past, and is shown to be sorbed onto Bet Dagan soil in a nonlinear manner. We find that the transport behavior of bromide is non-Fickian in all cases, which is caused by the heterogeneity of the soil. Comparative model analysis of the non-Fickian BTCs of the conservative, and sorbing tracers and examination of the fitting parameters, exemplify the coupling between transport and adsorption/desorption processes. The difference in transport parameters used to match the conservative and sorbing data sets shows that conservative tracer parameters (average velocity and dispersion coefficient) are not valid for the transport of reactive tracers., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Human exposure to atrazine and other triazine herbicides results in urinary excretion of traces of parent compounds and of their metabolites formed by N-dealkylation or conjugation with mercapturic acid. In contrast to N-dealkylated metabolites, which are not compound-specific, the measurement of atrazine mercapturate and unchanged atrazine provides an unambiguous confirmation of exposure to this herbicide. The aim of this study was to investigate the levels of these two compounds in a group of agricultural workers who may be considered representative for typical behaviour and procedures during the atrazine application in Croatia. The spot urine samples were collected at the beginning (samples A) and at the end (samples B) of a working day and 12h after exposure has ended (samples C). Atrazine and atrazine mercapturate were extracted from acidified urine samples (pH 2) with ethyl acetate and the extracts were analysed using high performance liquid chromatography-tandem mass spectrometry with a turbo ion spray (electrospray) ionization interface. The detection limits based on treatment of 2ml urine samples were 0.2ngml(-1) for both analytes. Atrazine was not detected in any of 27 analysed urine samples but traces of atrazine mercapturate were measured in about a third of pre-exposure and in all post-exposure urine samples in mass concentrations ranging from 0.3 to 10.4ngml(-1) (0.3 to 8.0μgg(-1) of creatinine). The metabolite concentrations in B and C group of post-exposure samples were not significantly different. The urinary atrazine mercapturate post-exposure concentrations were comparable to those reported for U.S. farmers engaged in a single field application of atrazine., (Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.)