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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.

The use of nano- and microparticles as a release system for agrochemicals has been increasing in agricultural sector. However, the production of eco-friendly and smart carriers that can be easily handled in the environment is still a challenge for this technology. In this context, we have developed a biodegradable release system for the herbicide atrazine with magnetic properties. Herein, we investigated the (a) physicochemical properties of the atrazine-loaded magnetic poly(ε-caprolactone) microparticles (MPs:ATZ), (b) in vitro release kinetic profile of the herbicide, and (c) phytotoxicity toward photosynthesis in the aquatic fern Azolla caroliniana . The encapsulation efficiency of the herbicide in the MPs:ATZ was ca. 69%, yielding spherical microparticles with a diameter of ca. 100 μm, a sustained-release profile, and easily manipulated with an external magnetic field. Also, phytotoxicity issues showed that the MPs:ATZ maintained their herbicidal activity via inhibition of PSII, showing lower toxicity compared with the nonencapsulated ATZ at 0.01 and 0.02 μmol·L -1 . Therefore, this technology may conveniently promote a novel magnetic controlled release of the herbicide ATZ (with the potential to be collected from a watercourse) and act as a nutrient boost to the nontarget plant, with good herbicidal activity and reduced risk to the environment.

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.)

Removal of commonly used pesticide, atrazine was examined by employing chitin based nanohydrogel. Chitin-cl-poly (acrylamide-co-itaconic acid) nanohydrogel was synthesized by microwave method. Dissolution of chitin was done by freezing thawing method in NaOH/urea solution. The morphology and functional characteristics were confirmed by FTIR, XRD, SEM, TGA, TEM, and EDX techniques. Maximum swelling capacity, isotherm study, kinetics, adsorption and desorption of atrazine pesticide were evaluated in this study. Maximum adsorption capacity of designed nanohydrogel was found to be 204.08 mg/g. Langmuir and pseudo- second order models were determined to be applicable for explaining the undertaken adsorption process. Neutral pH was found to be favorable for maximum adsorption. In addition, results have specified the pH responsive nature of nanohydrogel for controlled release of atrazine., (Copyright © 2020 Elsevier Ltd. 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.)

This study describes the synthesis and application of a magnetic amino-functionalized hollow silica-titania microsphere as a new sorbent for magnetic dispersive micro-solid phase extraction of selected pesticides in coffee bean samples. The sorbent was fully characterized by Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, transition electron microscopy, energy-dispersive X-ray spectroscopy, and vibrating sample magnetometry techniques. Significant extraction parameters affecting the proposed method, such as extraction time, sorbent amount, sample solution pH, salt amount, and desorption conditions (desorption solvent and time) were investigated and optimized. All the figures of merits were validated in coffee bean samples under the matrix-matched calibration method. Linear dynamic ranges were 5-250 µg/kg with the determination coefficients (R 2 ) > 0.9980. The limits of detection for the pesticides of chlorpyrifos, malathion, hexaconazole, and atrazine were 1.42, 1.43, 1.35, and 1.33 µg/kg, respectively. Finally, the method was successfully applied for the determination of the pesticides in green and roasted coffee bean samples, and the obtained recoveries were in the range of 74-113% for spiked samples. The prepared sorbent could be used for the magnetic dispersive micro-solid phase extraction of pesticides in the plant-derived food matrix., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.)

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.)

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5 L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150 rpm and catalyst concentration 0.66 g L -1 .

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.

Atrazine, one of the most widespread herbicides in the world, is considered as an environmental estrogen and has potential carcinogenicity. In this study, atrazine was degraded on boron-fluorine co-doped TiO 2 nanotube arrays (B, F-TiO 2 NTAs), which had similar morphology with the pristine TiO 2 NTAs. The structure and morphology of TiO 2 nanotube samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-visible diffuse reflectance spectroscopy (DRS). It showed that the decoration of fluorine and boron made both the absorption in the visible region enhanced and the band edge absorption shifted. The efficiency of atrazine degradation by B, F-TiO 2 NTAs through photoelectrocatalysis was investigated by current, solution pH, and electrolyte concentration, respectively. The atrazine removal rate reached 76% through photoelectrocatalytic reaction by B, F-TiO 2 NTAs, which was 46% higher than that under the photocatalysis process. Moreover, the maximum degradation rate was achieved at pH of 6 in 0.01 M of Na 2 SO 4 electrolyte solution under a current of 0.02 A and visible light for 2 h in the presence of B, F-TiO 2 NTAs. These results showed that B, F-TiO 2 NTAs exhibit remarkable photoelectrocatalytic activity in degradation of atrazine.

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.)

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.)

Usage of atrazine, a widely used herbicide, is now banned in many countries. Although forbidden to use, significant concentration of this herbicide is still present in the environment. The study focused not only on the toxicity of atrazine itself but also on products of homogeneous photocatalytic degradation. Such degradation was very fast in given conditions (sufficient amount of Fe(III) in the reaction system)-more than 95% of the initial amount of atrazine was eliminated after 30 min of irradiation. The toxicity of atrazine and its photodegradation products were examined on the aquatic plant Lemna minor and microcrustacean Daphnia magna in both acute and chronic tests. While the growth inhibition assay of atrazine for Lemna minor revealed EC 50 value of 128.4 μg dm -3 , the herbicide did not affect Daphnia in the acute toxicity assay. A degradation product, desethyl-atrazine, has been demonstrated to have a pronounced negative effect on the plant growth. Both atrazine and desethyl-atrazine affect negatively the number of juveniles and number of clutches of Daphnia magna in the chronic toxicity assay. Photocatalytic degradation lowers the negative effect of atrazine in Daphnia magna while photodegradation products still negatively affect Lemna growth.

Background: Pesticides are potentially toxic to humans and can produce both acute and chronic health effects, depending on the quantity and the ways in which a person is exposed. Exposure to pesticides can cause serious health problems. Infants and young children are particularly sensitive to these contaminants because their brains and organ systems are not fully developed. For this reason, it is important to determine the quantities of pesticides in baby food., Results: The aim of this study was to develop a kinetic-spectrophotometric method for atrazine determination and to apply it to determine pesticide in baby-food samples, using solid-phase extraction (SPE) followed by the kinetic-spectrophotometric method and the high-performance liquid chromatography (HPLC) method. This method is based on the inhibition effect of atrazine (the oxidation of sulfanilic acid (SA) by hydrogen peroxide in the alkaline medium in the presence of the Co 2+ ion). Under the experimental conditions used, atrazine showed a linear dynamic range of 0.5 to 5.0 μg mL -1 , and from 5.0 to 70.00 μg mL -1 with relative standard deviations (RSD) from 1.91% to 9.41%. The limit of detection and the limit of quantification were 0.074 and 0.225 μg mL -1 , respectively. The kinetic method was successfully applied to determine the atrazine concentration in spiked samples after SPE of samples. High-performance liquid chromatography was used to verify the results., Conclusion: The proposed method is highly sensitive, simple, easy, requires cheap reagents, and leads to good recovery levels. It is linear, precise, and accurate. It can be used successfully for the routine analysis of atrazine in infant formulae and cereal-based food samples. © 2019 Society of Chemical Industry., (© 2019 Society of Chemical Industry.)

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.

A fluorometric assay is described for the determination of the herbicide atrazine. The assay is based on the use of tyrosinase and fluorescent nitrogen-doped graphene quantum dots (N-GQDs). The N-GQDs were synthesized via one-pot hydrothermal reaction starting from citric acid and ammonia. Their fluorescence excitation and emission maxima are at 355 and 435 nm, and the quantum yield is 18%. Tyrosinase catalyzes the oxidation of dopamine to form dopaquinone which reduces the fluorescence of the N-GQDs through a dynamic quenching process. On addition of atrazine, the catalytic activity of tyrosinase is inhibited. This leads to less formation of dopaquinone and less reduction of fluorescence. The assay has a linear response in the 2.5-100 ng·mL -1 atrazine concentration range, and the detection limit is 1.2 ng·mL -1 . The assay was applied to the determination of atrazine in spiked environmental water samples. Graphical abstract Schematic presentation of the fluorometric assay of atrazine detection based on tyrosinase-induced fluorescence (FL) quenching effect on the nitrogen-doped graphene quantum dots (N-GQDs) and inhibitory effect of atrazine on tyrosinase.

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.

Atrazine is one of the most used herbicides and has been associated with persistent surface and groundwater contamination, and novel formulations derived from nanotechnology can be a potential solution. We used poly(ε-caprolactone) nanoencapsulation of atrazine (NC+ATZ) to develop a highly effective herbicidal formulation. Detailed structural study of interaction between the formulation and Brassica juncea plants was carried out with evaluation of the foliar uptake of nanoatrazine and structural alterations induced in the leaves. Following postemergent treatment, NC+ATZ adhered to the leaf and penetrated mesophyll tissue mainly through the hydathode regions. NC+ATZ was transported directly through the vascular tissue of the leaves and into the cells where it degraded the chloroplasts resulting in herbicidal activity. Nanocarrier systems, such as the one used in this study, have great potential for agricultural applications in terms of maintenance of herbicidal activity at low concentrations and a substantial increase in the herbicidal efficacy.

In this work, CuWO 4 is prepared and its effect of improving photocatalytic degradation of atrazine by TiO 2 as well as the synergetic mechanism is studied. Results show that the addition of CuWO 4 (50 mg/L) into the reaction system can significantly enhance the efficiency of atrazine degradation, resulting in an increased degradation efficiency of 92.1% after 270 min, which is 1.94 times higher than that of the single TiO 2 . As the sintering temperate of CuWO 4 was increased, the degradation efficiency of atrazine increased initially and then deceased after reaching a maximum at 500 °C. The origin of the synergistic effect of TiO 2 -CuWO 4 is attributed to the introduction of solid CuWO 4 . The photochemical test results indicate that the photogenerated electrons transfer from irradiated TiO 2 to CuWO 4 , which is beneficial to the O 2 reduction and H 2 O 2 formation in aqueous solution thus promoting the photocatalytic activity of TiO 2 . These observations unveil the importance of improving photocatalytic activity of TiO 2 with Cu-bearing semiconductors.

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.)

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.)

Degradation of atrazine by catalytic ozonation in the presence of iron scraps (ZVI/O 3 ) was carried out. The key operational parameters (i.e., initial pH, ZVI dosage, and ozone dosage) were optimized by the batch experiments, respectively. This ZVI/O 3 system exhibited much higher degradation efficiency of atrazine than the single ozonation, ZVI, and traditional ZVI/O 2 systems. The result shows that the pseudo-first-order constant (0.0927 min -1 ) and TOC removal rate (86.6%) obtained by the ZVI/O 3 process were much higher than those of the three control experiments. In addition, X-ray diffraction (XRD) analysis indicates that slight of γ-FeOOH and Fe 2 O 3 were formed on the surface of iron scrap after ZVI/O 3 treatment. These corrosion products exhibit high catalytic ability for ozone decomposition, which could generate more hydroxyl radical (HO • ) to degrade atrazine. Six transformation intermediates were identified by liquid chromatography-mass spectrometry (LC-MS) analysis in ZVI/O 3 system, and the degradation pathway of atrazine was proposed. Toxicity tests based on the inhibition of the luminescence emitted by Photobacterium phosphoreum and Vibrio fischeri indicate the detoxification of atrazine by ZVI/O 3 system. Finally, reused experiments indicate the approving recyclability of iron scraps. Consequently, the ZVI/O 3 system could be as an effective and promising technology for pesticide wastewater treatment.

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.)

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.)

In this work, the suitability of the UV/H 2 O 2 process for commercial herbicides mixture degradation was studied. Glyphosate, the herbicide most widely used in the world, was mixed with other herbicides that have residual activity as 2,4-D and atrazine. Modeling of the process response related to specific operating conditions like initial pH and initial H 2 O 2 to total organic carbon molar ratio was assessed by the response surface methodology (RSM). Results have shown that second-order polynomial regression model could well describe and predict the system behavior within the tested experimental region. It also correctly explained the variability in the experimental data. Experimental values were in good agreement with the modeled ones confirming the significance of the model and highlighting the success of RSM for UV/H 2 O 2 process modeling. Phytotoxicity evolution throughout the photolytic degradation process was checked through germination tests indicating that the phytotoxicity of the herbicides mixture was significantly reduced after the treatment. The end point for the treatment at the operating conditions for maximum TOC conversion was also identified.

The use of herbicides plays a vital role in controlling weeds and conserving crops; however, its usage generates both environmental and economic problems. For example, herbicides pose a financial issue as farmers must apply large quantities to protect crops due to absorption rates of less than 0.1%. Therefore, there is a great need for the development of new methods to mitigate these issues. Here, we report for the first time the synthesis of poly(lactic- co-glycolic-acid) (PLGA) nanoherbicides loaded with atrazine as an active ingredient. We used potato plants as a biological model to assess the herbicidal activity of the engineered PLGA nanoherbicides. Our method produced nanoherbicides with an average size of 110 ± 10 nm prior to lyophilization. Fifty percent of the loaded atrazine in the PLGA matrix is released in 72 h. Furthermore, we performed Monte Carlo simulations to determine the chemical interaction among atrazine, PLGA, and the solvent system. One of the most significant outcomes of these simulations was to find the formation of a hydrogen bond of 1.9 Å between PLGA and atrazine, which makes this interaction very stable. Our in vitro findings showed that as atrazine concentration is increased in PLGA nanoparticles, potato plants undergo a significant decrease in stem length, root length, fresh weight, dry weight, and the number of leaves, with root length being the most affected. These experimental results suggest the herbicidal effectiveness of atrazine-loaded PLGA nanoherbicides in inhibiting the growth of the potato plant. Hence, we present the proof-of-concept for using PLGA nanoherbicides as an alternative method for inhibiting weed growth. Future studies will involve a deep understanding of the mechanism of plant-nanoherbicide interaction as well as the role of PLGA as a growth potentiator.

The rapid industrialization and modern agriculture, increasing emission of heavy metals, and abusing application of pesticide have changed biochemical features of the soil system and water system. Additionally, heavy metals and pesticide compounds may occur together in environments, giving rise to more serious damage to the environment because of their combined toxicity and carcinogenic properties. Therefore, there is a growing need for the development of low-cost adsorbents for their removal. Porous carbon materials have been considered as highly effective materials for pollutant ion control. In this thesis, a novel porous "carbon sponge" is produced using sucrose (S-PCS) with gas-producing molten salt KHCO 3 as the activator at different pyrolysis temperatures under a limited-oxygen condition. Results from these characterizations have indicated that the as-prepared carbon sponges share high surface area (up to 457.6434 m 2  g -1 ) and abundant oxygen-containing functional groups existed on the surface. The essential factors of contact time, initial concentrations, and cyclic availability on adsorption of lead ions and atrazine onto the as-prepared porous samples are also discussed. The typical kinetic and thermodynamic models are carried out to interpret the adsorption behaviors of lead ions and atrazine. The interactive effects and mechanism of lead ions and atrazine adsorption onto S-PCS samples are examined by simultaneous adsorption and preloading adsorption procedures. Combined with the economic and environmental merits of the raw materials, the porous carbon sponges of sucrose by KHCO 3 activated are promising materials for potential practical applications. Graphical abstract The schematic diagram on the preparation of porous carbon sponse from sucrose.

In this study we reported that the presence of functionalized multi-walled carbon nanotubes (FCNT-H) would greatly enhance the degradation of atrazine (ATZ), a model contaminant, in the Fe(III)-mediated Fenton-like system. Efficient ATZ degradation (>90%) was achieved within 30 min in the presence of 20 mg.L -1 FCNT-H, 2.0 mg.L -1 Fe(III), and 170 mg.L -1 H 2 O 2 , whereas negligible ATZ degradation occurred in FCNT-H free system. The structure and surface chemistry of FCNT-H and other CNTs were well characterized. The formed active species were determined based on ESR analysis, and the mass balance of Fe species during the reaction was monitored. In particular, a new method based on ferrozine complexation was proposed to track the formed Fe(II). The results indicated that ATZ was mainly degraded by the generated hydroxyl radical (HO·), and Fe(III)/Fe(II) cycling was still the rate-limiting step. Besides a small fraction of Fe(III) reduced by FCNT-H, a new pathway was revealed for fast reduction of most Fe(III), i.e., reaction of FCNT-H-Fe(III) complexes with H 2 O 2 . Comparison of different CNTs-mediated Fe(III)/H 2 O 2 systems indicated that such enhanced effect of CNTs mainly resulted from the surface carboxyl group instead of hydroxyl and carbonyl group. Combined with X-ray photoelectron spectroscopy (XPS) analysis, the electron density migration from Fe(III) to FCNT-H possibly resulted in the fast reduction of FCNT-H-Fe(III) complexes by H 2 O 2 . This study enables better understanding the enhanced Fe(III)-mediated Fenton-like reaction in the presence of MWCNTs and thus, will shed new light on how to develop more efficient similar Fenton systems via Fe(III) complexation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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.)

Urban agriculture is crucial to local populations, but the risk of it contaminating water has rarely been documented. The aim of this study was to assess pesticide contamination of surface waters from the Méfou watershed (Yaoundé, Cameroon) by 32 selected herbicides, fungicides, and insecticides (mainly polar) according to their local application, using both grab sampling and polar organic compounds integrative samplers (POCIS). Three sampling campaigns were conducted in the March/April and October/November 2015 and June/July 2016 rainy seasons in urban and peri-urban areas. The majority of the targeted compounds were detected. The quantification frequencies of eight pesticides were more than 20% with both POCIS and grab sampling, and that of diuron and atrazine reached 100%. Spatial differences in contamination were evidenced with higher contamination in urban than peri-urban rivers. In particular, diuron was identified as an urban contaminant of concern because its concentrations frequently exceeded the European water quality guideline of 0.200 μg/L in freshwater and may thus represent an ecological risk due to a risk quotient > 1 for algae observed in 94% of grab samples. This study raises concerns about the impacts of urban agriculture on the quality of water resources and to a larger extent on the health of the inhabitants of cities in developing countries. Graphical abstract ᅟ.

In this study, the impact of hydration status on dermal uptake of pesticides in two species of amphibians is examined. Absorption of pesticides in anurans occurs primarily through a highly vascularized dermal seat patch; however, pesticides can also enter through the superficial dermis following exposure. Despite the growing body of literature on dermal exposure in amphibians, little is known on how hydration status influences uptake. Thus, the objective of this study was to investigate the influence of hydration status on absorption of pesticides (atrazine, triadimefon, metolachlor, chlorothalonil, and imidacloprid) in southern leopard frogs (Lithobates sphenocephala) and Fowler's toads (Anaxyrus fowleri). Amphibian treatments included dehydration periods of 0, 2, 4, 6, 8, or 10 h prior to exposure to pesticide-contaminated soils for 8 h. Following exposure, soil and whole-body homogenates were extracted and analyzed by LC-MS/MS. Dehydration time was then regressed against post-exposure concentrations to infer the impact of dehydration on dermal pesticide uptake. Increased dehydration time resulted in significantly lowered pesticide concentrations in both species (F 6, 293  = 67.66, p = 0.007) for the five pesticides studied. This phenomenon could be due to an energy and/or dilution effect.

We investigated the effects of sodium and calcium chlorides on the conformation and composition of a purified Aldrich humic acid (PAHA), as well as on the adsorption of atrazine. The PAHA was treated with 1, 10, and 100 mM NaCl, CaCl 2 , or a mixture of NaCl and CaCl 2 (molar ratio 5:1) at pH 7.5 and 8.5. The conformation of treated PAHA was characterized by atomic force microscopy (AFM) and transmission electron microscopy (TEM) and spectral changes of functional groups of PAHA by Fourier transform infrared spectroscopy (FTIR). AFM and TEM images showed an increase in the aggregation of the PAHA as salinity increased. FTIR spectra revealed that changes in the aggregation of the PAHA were principally due to the formation of bridged interactions between calcium and carboxylate groups in the PAHA. The adsorption of atrazine on > 0.45 μm PAHA decreased as salt concentrations and pH increased. This reduction of atrazine adsorption was explained by the decrease in available adsorption sites due to agglomeration of PAHA.

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) is a worldwide-used herbicide and often detected in agricultural soils and groundwater at concentrations above the permitted limit, because of its high mobility, persistence, and massive application. This study applied pot experiments to investigate the atrazine contents and speciation during the phytoremediation process by Pennisetum alopecuroides (L.) Spreng. in laterite soils. From the change of the total atrazine and bioavailable atrazine measured by diffusive gradients in thin film (DGT), P. alopecuroides significantly improved atrazine degradation efficiency from 15.22 to 51.46%, attributing to the increasing bioavailable atrazine in rhizosphere. Only a small amount of atrazine was taken up by P. alopecuroides root and the acropetal translocation from roots to shoots was limited. The atrazine speciation was significantly different between rhizosphere and non-rhizosphere, attributing to the declining pH and organic matters in rhizosphere. The relationship between pH and soil-bound/humus-fixed atrazine illustrated the pH-dependant release of the atrazine from soils and the competition between humus adsorption and uptake by P. alopecuroides. The present study reveals the important roles of soil pH and organic matters in atrazine speciation and availability in laterite soils, and provides new insights in the rhizospheric effects on effective phytoremediation of atrazine.

Recent national regulatory assessments of potential pesticide exposure of threatened and endangered species in aquatic habitats have led to increased need for watershed-scale predictions of pesticide concentrations in flowing water bodies. This study was conducted to assess the ability of the uncalibrated Soil and Water Assessment Tool (SWAT) to predict annual maximum pesticide concentrations in the flowing water bodies of highly vulnerable small- to medium-sized watersheds. The SWAT was applied to 27 watersheds, largely within the midwest corn belt of the United States, ranging from 20 to 386 km 2 , and evaluated using consistent input data sets and an uncalibrated parameterization approach. The watersheds were selected from the Atrazine Ecological Exposure Monitoring Program and the Heidelberg Tributary Loading Program, both of which contain high temporal resolution atrazine sampling data from watersheds with exceptionally high vulnerability to atrazine exposure. The model performance was assessed based upon predictions of annual maximum atrazine concentrations in 1-d and 60-d durations, predictions critical in pesticide-threatened and endangered species risk assessments when evaluating potential acute and chronic exposure to aquatic organisms. The simulation results showed that for nearly half of the watersheds simulated, the uncalibrated SWAT model was able to predict annual maximum pesticide concentrations within a narrow range of uncertainty resulting from atrazine application timing patterns. An uncalibrated model's predictive performance is essential for the assessment of pesticide exposure in flowing water bodies, the majority of which have insufficient monitoring data for direct calibration, even in data-rich countries. In situations in which SWAT over- or underpredicted the annual maximum concentrations, the magnitude of the over- or underprediction was commonly less than a factor of 2, indicating that the model and uncalibrated parameterization approach provide a capable method for predicting the aquatic exposure required to support pesticide regulatory decision making. Integr Environ Assess Manag 2018;14:358-368. © 2017 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC)., (© 2017 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC).)

Remarkable atrazine degradation in the S(IV) autoxidation process catalyzed by Fe 2+ -Mn 2+ (Fe 2+ /Mn 2+ /sulfite) was demonstrated in this study. Competitive kinetic experiments, alcohol inhibiting methods and electron spin resonance (ESR) experiments proved that sulfur radicals were not the major oxidation species. Mn(III) was demonstrated to be the primary active species in the Fe 2+ /Mn 2+ /sulfite process based on the comparison of oxidation selectivity. Moreover, the inhibiting effect of the Mn(III) hydrolysis and the S(IV) autoxidation in the presence of organic contaminants indicated the existence of three Mn(III) consumption routes in the Fe 2+ /Mn 2+ /sulfite process. The absence of hydroxyl radical and sulfate radical was interpreted by the competitive dynamics method. The oxidation capacity of the Fe 2+ /Mn 2+ /sulfite was independent of the initial pH (4.0-6.0) because the fast decay of S(IV) decreased initial pH below 4.0 rapidly. The rate of ATZ degradation was independent of the dissolved oxygen (DO) because that the major DO consumption process was not the rate determining step during the production of SO 5 •- . Phosphate and bicarbonate were confirmed to have greater inhibitory effects than other environmental factors because of their strong pH buffering capacity and complexing capacity for Fe 3+ . The proposed acetylation degradation pathway of ATZ showed the application of the Fe 2+ /Mn 2+ /sulfite process in the research of contaminants degradation pathways. This work investigated the characteristics of the Fe 2+ /Mn 2+ /sulfite process in the presence of organic contaminants, which might promote the development of Mn(III) oxidation technology., (Copyright © 2018. Published by Elsevier Ltd.)

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.)

The metal-organic framework [(La 0.9 Sm 0.1 ) 2 (DPA) 3 (H 2 O) 3 ] ∞ was synthetized and characterized by X-ray diffractometry, differential thermogravimetric analysis, and infrared spectroscopy. The material was tested for the development and validation of a matrix solid-phase dispersion procedure for extraction of atrazine, bifenthrin, bromuconazole, clofentezine, fenbuconazole, flumetralin, procymidone, and pirimicarb, from peppers, with analysis using gas chromatography with mass spectrometry in the selected ion monitoring mode. The method developed was linear over the range tested (50.0-1000.0 μg/kg for procymidone and 200.0-1000.0 μg/kg for all other pesticides), with correlation coefficients ranging from 0.9930 to 0.9992. Experiments were carried out at 250.0, 500.0, and 1000.0 μg/kg fortification levels, and resulted in recoveries in the range of 52.7-135.0%, with coefficient of variation values between 5.2 and 5.4%, respectively, for [(La 0.9 Sm 0.1 ) 2 (DPA) 3 (H 2 O) 3 ] ∞ sorbent. Detection and quantification limits ranged from 16.0 to 67.0 μg/kg and from 50.0 to 200.0 μg/kg, respectively, for the different pesticides studied. The results were compared with literature data. The developed and validated method was applied to real samples. The analysis detected the presence of residues of pesticides procymidone, fenbuconazole, flumetralin, clofentezine, atrazine, and bifenthrin., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)