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Ozone-based advanced oxidation processes (AOPs) have emerged a promising avenue for water treatment, offering effective removal of micropollutants. Recent research underscores the potential of ozone microbubbles to enhance ozone mass transfer during water treatment, particularly when combined with pre-treatment steps. This study aimed to evaluate the efficacy of three different combined processes (chlorine/KMnO 4 /PAC pre-treatment followed by ozonation) in removing atrazine, a common micropollutant from natural source water. Results revealed that all combined processes achieved higher atrazine removal rates compared to individual pre-treatment or ozonation methods. Notably, the highest atrazine removal rates were observed under alkaline pH conditions, with treatment outcomes influenced by oxidant dose and pH levels. Among the combined processes, chlorine pre-treatment followed by ozonation emerged as the most effective approach, achieving a removal rate of 59.7% that exceeded the sum of individual treatments. However, this treatment efficacy was affected by water quality parameters, particularly the presence of organic matter and elevated ammonia nitrogen concentration (> 0.5 mg/L). This study highlights the potential for utilizing ozone micro/nanobubbles to enhance ozone mass transfer and offers valuable insights for optimizing the combined application of pre-treatment and ozonation strategies for efficient atrazine removal from natural water sources., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Atrazine (ATZ) is widely used in agriculture as a triazine herbicide, and its long-term use can cause serious environmental pollution. This paper independently designed a multi-electrode reactor, explored the output power and energy utilization efficiency of the dielectric barrier discharge reactor, and used the dielectric barrier discharge reactor to treat ATZ solution. The results showed that the degradation efficiency of ATZ was 96.39% at 30 min at an initial ATZ concentration of 14 mg/L, an input voltage of 34 kV, an input current of 1.38 mA, an aeration rate of 100 L/h, and a treatment water volume of 150 mL. The degradation of ATZ was significantly increased by the addition of persulfate (PS), Fe 2+ , and H 2 O 2 . After adding radical quenchers (EtOH, p-BQ, and FFA), the degradation efficiency of ATZ decreased, indicating that free radicals (•OH, •O 2 - , and 1 O 2 ) played a key role in the degradation process of ATZ., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Atrazine, a widely used herbicide in agriculture, is detrimental to both the ecological environment and human health owing to its extensive use, poor degradability, and biotoxicity. The technology commonly used to remove atrazine from water is activated carbon adsorption, but it has the problems of difficult recovery, secondary contamination, and a low removal rate. To efficiently remove atrazine from agricultural wastewater, in this study, a new environmental material, embedding immobilization (EI)-Co- and Zr-modified activated carbon powder (Co/Zr@AC), was prepared by immobilizing the bimetallic Co/Zr@AC via EI technique and employed to remove atrazine. When preparing EI-Co/Zr@AC, the single-factor experiment was conducted and determined the optimal preparation conditions: sodium alginate 2.5% (wt), calcium chloride 4.0% (wt), Co/Zr@AC 1.0% (wt), and bentonite 2.0% (wt). The prepared EI-Co/Zr@AC has a three-dimensional mesh structure and many pores and also possesses good mass transfer performance and mechanical properties. The removal efficiency by EI-Co/Zr@AC for the removal of 5.0 mg/L atrazine from 50 mL was 94.1% at pH 7.0 and 25°C, with an EI-Co/Zr@AC dosage of 0.8 g. The mechanistic study showed that the pseudo-second-order kinetic model could describe the removal process better than the pseudo-first-order kinetic model, and the Freundlich isotherm model fit better than other isotherm models. Additionally, the synthesized EI-Co/Zr@AC spheres demonstrated good reusability, with the atrazine removal rate remaining 70.4% after five cycles, and the mechanical properties of the spheres were stable., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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.

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.

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.

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 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.

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.

In this study, biochars (BC, ZnBC, and PBC) produced from wheat straw at relatively lower pyrolysis are successfully fabricated using different pretreatment techniques (without and with ZnCl 2 or H 3 PO 4 ). The specific surface area (SSA), elemental analysis, and Fourier transform infrared spectra (FTIR) are used to analyze physicochemical properties of unmodified and modified biochars. ZnBC and PBC show higher specific surface area and more micropore structure than pure BC. Kinetic models (pseudo-first order, pseudo-second order, and intra-particle diffusion) as well as isotherm models (Langmuir and Freundlich) are applied to analyze adsorption behavior. Adsorption on biochars can be better fitted by the pseudo-second-order and intra-particle diffusion models, indicating that micropores and mesopores play important roles on adsorption process and chemisorption is dominant. The adsorption process is also affected by physical and chemical adsorption. In conclusion, biochar is a low-cost, effective, and environment-friendly adsorbent implicating in the environment for pesticide removal. Graphical abstract.

Accelerated degradation is the increased breakdown of a pesticide upon its repeated application, which has consequences for the environmental fate of pesticides. The herbicide atrazine was repeatedly applied to soils previously untreated with s-triazines for >5 years. A single application of atrazine, at an agriculturally relevant concentration, was sufficient to induce its rapid dissipation. Soils, with a range of physico-chemical properties and agricultural histories, showed similar degradation kinetics, with the half-life of atrazine decreasing from an average of 25 days after the first application to <2 days after the second. A mathematical model was developed to fit the atrazine-degrading kinetics, which incorporated the exponential growth of atrazine-degrading organisms. Despite the similar rates of degradation, the repertoire of atrazine-degrading genes varied between soils. Only a small portion of the bacterial community had the capacity for atrazine degradation. Overall, the microbial community was not significantly affected by atrazine treatment. One soil, characterised by low pH, did not exhibit accelerated degradation, and atrazine-degrading genes were not detected. Neutralisation of this soil restored accelerated degradation and the atrazine-degrading genes became detectable. This illustrates the potential for accelerated degradation to manifest when conditions become favourable. Additionally, the occurrence of accelerated degradation under agriculturally relevant concentrations supports the consideration of the phenomena in environmental risk assessments.

Atrazine is an herbicide widely used in crops and has drawn attention due to potential pollution present in soil, sediment, water, and food. Since conventional methods are not potentially efficient to persistent degradation of organic compounds, new technology has been developed to remove them, especially practices utilizing advanced oxidation processes (AOPs). This work aims to evaluate the use of different energies (ultraviolet (UV), microwaves (MW), and radiations (MW-UV)) to the herbicide atrazine through the process of photo-oxidation. These systems found degradation rates of around 12 % (UV), 28 % (MW), and 83 % (MW-UV), respectively, with time intervals of 120 s. After the photolytic processes, the samples were analyzed at a wavelength scanning the range of 190 to 300 nm, where the spectral analysis of the signal was used to evaluate the degradation of atrazine and the appearance of some other peaks (degradation products). The spectrum evaluation resulting from photolytic processes gave rise to a new signal which was confirmed by chromatography. This spectrum indicated the possible pathway of atrazine degradation by the process of photolytic MW-UV, generating atrazine-2-hydroxy, atrazine-desethyl-2-hidroxy, and atrazine-desisopropyl-2-hydroxy. The process indicated that in all situations, chloride was present in the analytic structure and was substituted by a hydroxyl group, which lowered the toxicity of the compound through the photolytic process MW-UV. Chromatographic analysis ascertained these preliminary assessments using spectrophotometry. It was also significantly observed that the process can be optimized by adjusting the pH of the solution, which was evident by an improvement of 10 % in the rate of degradation when subjected to a pH solution equal to 8.37.

Degradation of herbicide atrazine in aqueous solution was investigated using a plate type dielectric barrier discharge (DBD) plasma reactor. DBD plasma was generated at the gas-liquid interface of the formed water film. At discharge time of 14 min, atrazine was degradated effectively with a degradation rate of 99 % at the discharge power of 200 W. The experimental data fitted well with first-order kinetics and the energy efficiency for 90 % degradation of atrazine (G value) was calculated, obtaining a rate constant of 0.35 min(-1) and a G value of 1.27 × 10(-10) mol J(-1) (98.76 mg kW(-1) h(-1)) at a discharge power of 200 W, respectively. The addition of Fe(2+) increased the rate constant and G value dramatically, and a significant decrease of the rate constant and G value was observed with the addition of radical scavengers (tert-butyl alcohol, isopropyl alcohol, or Na2CO3). The generated aqueous O3 and H2O2 were determined, which promoted the degradation of herbicide atrazine. Dechlorination was observed and the experimentally detected Cl(-) was 1.52 mg L(-1) at a discharge time of 14 min. The degradation intermediates of atrazine were detected by means of liquid chromatography-mass spectrometry; dechlorination, hydroxylation, dealkylation, and alkyl oxidation processes were involved in the degradation pathways of atrazine.

An atrazine-degrading enrichment culture was used to study degradation of atrazine metabolites viz. hydroxyatrazine, deethylatrazine, and deisopropylatrazine in mineral salts medium. Results suggested that the enrichment culture was able to degrade only hydroxyatrazine, and it was used as the sole source of carbon and nitrogen. Hydroxyatrazine degradation slowed down when sucrose and/or ammonium hydrogen phosphate were supplemented as the additional sources of carbon and nitrogen, respectively. The enrichment culture could degrade high concentrations of atrazine (up to 110 μg/mL) in mineral salts medium, and neutral pH was optimum for atrazine degradation. Further, except in an acidic soil, enrichment culture was able to degrade atrazine in three soil types having different physico-chemical properties. Raising the pH of acidic soil to neutral or alkaline enabled the enrichment culture to degrade atrazine suggesting that acidic pH inhibited atrazine-degrading ability. The study suggested that the enrichment culture can be successfully utilized to achieve complete degradation of atrazine and its persistent metabolite hydroxyatrazine in the contaminated soil and water.

Pyrolyzing municipal wastewater treatment sludge into biochar can be a promising sludge disposal approach, especially as the produced sludge-derived biochar (SDBC) is found to be an excellent sorbent for heavy metals and atrazine. The aim of this study was to investigate how and why the coexisting humic acids influence the sorption capacity, kinetic, and binding of these contaminants on SDBC surface. Results showed humic acids enhanced Pb(II)/Cr(VI) sorption binding, and increased the corresponding Pb(II) Langmuir sorption capacity at pH 5.0 from 197 to 233 μmol g(-1), and from 688 to 738 μmol g(-1) for Cr(VI) at pH 2.0. It can be mainly attributed to the sorbed humic acids, whose active functional groups can offer the additional sites to form stronger inner-sphere complexes with Pb(2+), and supply more reducing agent to facilitate the transformation of Cr(VI) to Cr(III). However, humic acids reduced the atrazine adsorption Freundlich constant from 1.085 to 0.616 μmol g(-1). The pore blockage, confirmed by the decreased BET-specific surface area, as well as the more hydrophilic surface with more sorbed water molecules may be the main reasons for that suppression. Therefore, the coexisting humic acids may affect heavy metal stabilization or pesticide immobilization during SDBC application to contaminated water or soils, and its role thus should be considered especially when organic residues are also added significantly to increase the humic acid content there.

Soil organic matter (SOM) content is the major soil component affecting pesticide sorption. However, recent studies have highlighted the fact that it is not the total carbon content of the organic matter, but its chemical structure which have a profound effect on the pesticide's sorption. In the present study, sorption of atrazine and metsulfuron-methyl herbicides was studied in four SOM fractions viz. commercial humic acid, commercial lignin, as well as humic acid and humin extracted from a compost. Sorption data was fitted to the Freundlich adsorption equation. In general, the Freundlich slope (1/n) values for both the herbicides were <1. Except for atrazine sorption on commercial humic acid, metsulfuron-methyl was more sorbed. Desorption results suggested that atrazine was more desorbed than metsulfuron-methyl. Lignin, which showed least sorption of both the herbicides, showed minimum desorption. Sorption of atrazine was best positively correlated with the alkyl carbon (adjusted R (2) = 0.748) and carbonyl carbon (adjusted R (2) = 0.498) but, their effect was statistically nonsignificant (P = 0.05). Metsulfuron-methyl sorption showed best positive correlation with carbonyl carbon (adjusted R (2) = 0.960; P = 0.05) content. Sorption of both the herbicides showed negative correlation with O/N-alkyl carbon. Correlation of herbicide's sorption with alkyl and carbonyl carbon content of SOM fractions suggested their contribution towards herbicide sorption. But, sorption of metsulfuron-methyl, relatively more polar than atrazine, was mainly governed by the polar groups in SOM. IR spectra showed that H-bonds and charge-transfer bonds between SOM fraction and herbicides probably operated as mechanisms of adsorption.

Sorption-desorption behavior of six pesticides and some degradation products was assessed on seven agricultural volcanic and nonvolcanic soils belonging to Andisol, Ultisol, Mollisol, and Alfisol orders. The global interpretation of sorption data was performed by principal component analysis. Results showed exceptionally high sorption of glyphosate and aminomethylphosphonic acid (AMPA) (the breakdown product) on volcanic soils (K f > 1500 μg(1 - 1 / n) mL(1 / n) g(-1)) related mainly to contents of amorphous aluminum oxides (Andisols) and crystalline minerals (Ultisols). The lower sorption on nonvolcanic soils was associated to low organic matter contents and lack of significant minerals. Metsulfuron-methyl and 3,5,6-trichloro-2-pyridinol (metabolite of chlorpyrifos) were weakly to substantially sorbed on Andisols and Ultisols, but the first one was not sorbed at pH > 6.4, including nonvolcanic soils. The metabolite of diazinon, 2-isopropyl-4-methyl-6-hydroxypyrimidine, was weakly sorbed on all soils (K f = 0.4 to 3.6 μg(1 - 1 / n) mL(1 / n) g(-1)). Acidic compounds would be lixiviated in Mollisols and Alfisols, but they could leach also in Andisols and Ultisols if they reach greater depths. Atrazine and deethylatrazine sorption was related to organic carbon content; therefore, they were weakly retained on nonvolcanic soils (K f = 0.7 to 2.2 μg(1 - 1 / n) mL(1 / n) g(-1)). Chlorpyrifos was highly sorbed on all soils reaching K OC values of >8000. Finally, the significant retention of chlorothalonil and diazinon on Mollisols and Alfisols in spite of their low OC contents showed the contribution of clay minerals in the sorption process.

In the current study, a mechanical dispersion method was employed to separate clay (<2 μm), silt (2-20 μm), and sand (20-50 μm) fraction in six bulk soils. Batch equilibrium method was used to conduct atrazine sorption and desorption experiments on soil organo-mineral fractions with bulk soils and their contrasting size fractions separately. The potential contribution of total organic carbon (TOC) for atrazine retention in different fractions was further investigated. It was found that clay fraction had the highest adsorption but the least desorption capacities for atrazine, while sand fraction had the lowest adsorption but the highest desorption capacities for atrazine. The adsorption percentage of atrazine, as compared with adsorption by the corresponding bulk soils, ranged from 53.6 to 80.5%, 35.7 to 56.4%, and 0.2 to 4.5% on the clay, silt, and sand fractions, respectively. TOC was one of the key factors affecting atrazine retention in soils, with the exact contribution dependent on varying degree of coating with mineral component in different soil size fractions. The current study may be useful to predict the bioavailability of atrazine in different soil size fractions.

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87 × 10(18)-3.6 × 10(18) photons L(-1) s(-1) and [ATZ]0 = 5 and 20 mg L(-1) were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.

Displacement of lindane presorbed on the pristine and OH-functionalized multiwalled carbon nanotubes (MWCNTs) by phenanthrene, naphthalene, and atrazine, and competition of these compounds with lindane on the aforementioned sorbents were investigated. Displacement of lindane presorbed on MWCNTs by atrazine, naphthalene, and phenanthrene, and competitive sorption effect of these chemicals with lindane on MWCNTs followed the same order: atrazine > naphthalene > phenanthrene. The lowest competition and displacement of lindane by phenanthrene were mainly because of the strong interactions between these two chemicals, whereas interaction of lindane with atrazine and naphthalene was quite low. The more pronounced displacement of lindane by atrazine than naphthalene and higher competitive sorption of lindane with atrazine than with naphthalene can be ascribed to the larger molecular volume of atrazine; thus, the steric hindrance effect is higher relative to naphthalene. This study is valuable for evaluating influence of the coexisting organic compounds on sorption of primary solute towards MWCNTs in the environment.

The present study reports the effect of surfactants (rhamnolipids and triton X-100) on biodegradation of atrazine herbicide by strain A6, belonging to the genus Acinetobacter. The strain A6 was able to degrade nearly 80 % of the 250-ppm atrazine after 6 days of growth. The bacterium degraded atrazine by de-alkylation process. Bacterial cell surface hydrophobicity as well as atrazine solubility increased in the presence of surfactant. However, addition of surfactant to the mineral salt media reduced the rate and extent of atrazine degradation by decreasing the bioavailability of herbicide. On the contrary, addition of surfactant to atrazine-contaminated soil increased the rate and extent of biodegradation by increasing the bioavailability of herbicide. As compared to triton X-100, rhamnolipids were more efficient in enhancing microbial degradation of atrazine as a significant amount of atrazine was removed from the soil by rhamnolipids. Surfactants added for the purpose of hastening microbial degradation may have an unintended inhibitory effect on herbicide degradation depending upon contiguous condition, thus highlighting the fact that surfactant must be judiciously used in bioremediation of herbicides.

The effect of coexisting pesticide on adsorption/desorption and mobility of another one was investigated with carbendazim (CBD), imidacloprid (IDP), and atrazine (ATR). The data indicated that adsorption of CBD, ATR, and IDP on the tested soil was fitted well by Freundlich equation and increased with an order of IDP < ATR ≪ CBD. Adsorption of a pesticide was decreased by the coexistence of another one through their competitive adsorption. The presence of coexisting solute of the more adsorbability played a more important role than that of the lesser adsorbability. The adsorption of IDP and ATR was easier to be affected by 28.9-52.0 % and 31.1-60.7 % with the addition of CBD, while that of CBD was much less influenced by 3.4-18.1 % and 6.9-31.8 % with the presence of ATR and IDP, respectively. An adsorbability-related enhancement in desorption of the three pesticides by the co-adsorbed solute was also observed. As a result of competitive adsorption/desorption, the mobility of the pesticides estimated from soil thin-layer chromatography was altered. The results clearly illustrated that adsorbability and concentration-related alteration in adsorption/desorption and mobility will be caused by the coexistence of pesticides.

Photochemical degradation of atrazine under different conditions was studied and compared, namely degradation via photocatalysis on TiO2, UV C photolysis, and homogeneous photocatalysis in the presence of added ferric ions. The reaction rate constants in heterogeneous photocatalytic reactions on TiO2 and of photolytic degradation by means of UV C light are similar, 0.018 min(-1) and 0.020 min(-1), respectively. The reaction rate constants in homogeneous photocatalytic reactions with Fe(III) added depend strongly on the Fe(III) concentration, 0.0017 min(-1) for 1.6 × 10(-6) mol l(-1) Fe(III) to 0.105 min(-1) for 3.3 × 10(-4) mol l(-1) Fe(III). In all types of reactions, dechlorination was observed; in homogeneous photocatalytic reactions and in UV C (250-300 nm) photolysis, dechlorination proceeds with a 1 : 1 stoichiometry to atrazine degradation, in photocatalytic reactions on TiO2, dechlorination measured as chloride ion release reaches only 1/5 of the substrate degradation. In photocatalytic reactions on TiO2, mineralisation of 40% carbon was observed.

The effect of two fly ashes as soil amendment on the adsorption-desorption of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl)] and atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was studied in alluvial and laterite soils. The adsorption data for both the herbicides fitted well the Freundlich equation, and Freundlich adsorption coefficient (K (f)) increased with an increase of fly ash amount. Both the fly ashes differed in their extent to increase herbicide sorption, and the effect was different in different soils. Atrazine was sorbed more in the soils/soils + fly ash mixtures than the metolachlor. The K (f) values showed significant correlation with the amount of fly ash amendment (correlation coefficient, R > 0.982). The desorption isotherms also fitted the Freundlich equation, and desorption showed hysteresis which increased with an increase in the content of fly ash amendment. The free energy change (ΔG) indicated that the sorption process is exothermic, spontaneous, and physical in nature. The study has shown that fly ash as soil amendment significantly increased the sorption of metolachlor and atrazine, but the effect is soil- and fly ash-specific.

Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine-2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine-herbicide; (2) bromophos-O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate-insecticide; (3) chloridazon-5-amino-4-chloro-2-phenylopyridazin-3(2H)-one-herbicide; (4) linuron-3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea-herbicide; (5) metoxychlor-1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane-insecticide and acaricide; and (6) trichlorfon-dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate-insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method.

Introduction: Magnetic Fe3O4 nanoparticles were prepared by coprecipitation and then were coated with SiO2 on the surface., Materials and Methods: Fe3O4@SiO2 composite microspheres were modified by KH570. Using molecular imprinting technology, atrazine magnetic molecularly imprinted polymer was prepared by using atrazine as template molecule, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linkers. The morphology, composition and magnetic properties of magnetic nanoparticles were characterized. The recognition selectivity of polymer was studied for template molecule and simulation by UV spectrophotometry. The adsorption properties and selectivity ability were analyzed by Scatchard analysis., Results: Scatchard linear regression analysis indicated that there are two binding sites of the target molecules. The magnetic molecularly imprinted polymer has been applied to the analysis of atrazine in real samples., Conclusion: The results show that: the recovery rates and the relative standard deviation were 94.0∼98.7% and 2.1∼4.0% in corn, the recovery rates and the relative standard deviation were 88.7∼93.5% and 2.8∼7.2% in water.

A method for the determination of residues of mesotrione, atrazine and its degradation products: deethylatrazine, hydroxyatrazine, deisopropylatrazine, desethyldesisopropylatrazine in a variety of water and soil matrices has been developed. Mesotrione is a new selective herbicide for use in corn, which has been substituted for atrazine, which has been banned in European Union countries since 2007. Although atrazine has not been used for three vegetative periods, it is still detected in the environment. The analysis was conducted by means of ultra-high-pressure liquid chromatography with ultraviolet detection and liquid chromatography with diode array detection. The procedures for analyte separation from water and soil matrices were also established. The optimal conditions for solid-phase extraction (SPE) were determined. The recoveries were compared with that obtained by means of SPE. Method fortification recoveries from water samples averaged 78-97% and for soil 80-97% depending on the analyte and type of sample. The limits of detection were 0.04-0.61 μg/L for water samples and for soil samples 0.02-0.88 μg/g. The soil samples were collected in spring 2009 from three different fields with water samples being made from effluents from these fields. Samples collection was conducted in the day of mesotrione (Callisto 100SC) application and then done weekly, until the mesotrione concentration was below the limit of quantification. The results enabled the monitoring of mesotrione degradation in soil and its permeability into surface waters; simultaneously, the same studies were conducted for atrazine.

A method for the determination of herbicides residues, triazine (atrazine, metribuzin, ametryn, and terbutryn), in soil samples with high-performance liquid chromatography (HPLC)-UV detection is described. The proposed method is based on microwave-assisted extraction (MAE) of soil samples for 4 min at 80% of 850-W magnetron outputs in the presence of mixture of solvents (methanol/acetonitrile/ethylacetate). Related important factors influencing the MAE efficiency, such as the solvent type and volume, irradiation energy, and time, were optimized in detail. Calibration curve ranges established using HPLC for metribuzin, atrazine, ametryn, and terbutryn are 1.0-19.0, 0.9-18.0, 0.6-11.0, and 0.7-11.0 µg mL( -1), respectively. The limits of detection of metribuzin, atrazine, ametryn, and terbutryn are 0.30, 0.24, 0.16, and 0.20 µg mL( -1) while limits of quantification are 1.0, 0.80, 0.50, and 0.60 µg mL( -1), respectively. A Plackett-Burman factorial design was used as a screening method in order to select the variables that influence MAE extraction. The recoveries of the method at three different spiked levels were assessed by analyzing real soil samples and were found to be in the range of 83.33 ± 0.12-96.33 ± 0.23 with good precision (<8%).

Background, Aim and Scope: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate., Methods: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations., Results and Discussion: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides., Conclusions: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage., Recommendations and Perspectives: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.

Background, Aim and Scope: Modelling of the fate of environmental chemicals can be done by relatively simple multi-media box models or using complex atmospheric transport models. It was the aim of this work to compare the results obtained for both types of models using a small set of non-ionic and non-polar or moderately polar organic chemicals, known to be distributed over long distances., Materials and Methods: Predictions of multimedia exposure models of different types, namely three multimedia mass-balance box models (MBMs), two in the steady state and one in the non-steady state mode, and one non-steady state multicompartment chemistry-atmospheric transport model (MCTM), are compared for the first time. The models used are SimpleBox, Chemrange, the MPI-MBM and the MPI-MCTM. The target parameters addressed are compartmental distributions (i.e. mass fractions in the compartments), overall environmental residence time (i.e. overall persistence and eventually including other final sinks, such as loss to the deep sea) and a measure for the long-range transport potential. These are derived for atrazine, benz-[a]-pyrene, DDT, alpha and gamma-hexachlorocyclohexane, methyl parathion and various modes of substance entry into the model world., Results and Discussion: Compartmental distributions in steady state were compared. Steady state needed 2-10 years to be established in the MCTM. The highest fraction of the substances in air is predicted by the MCTM. Accordingly, the other models predict longer substance persistence in most cases. The results suggest that temperature affects the compartmental distribution more in the box models, while it is only one among many climate factors acting in the transport model. The representation of final sinks in the models, e.g. burial in the sediment, is key for model-based compartmental distribution and persistence predictions. There is a tendency of MBMs to overestimate substance sinks in air and to underestimate atmospheric transport velocity as a consequence of the neglection of the temporal and spatial variabilities of these parameters. Therefore, the long-range transport potential in air derived from MCTM simulations exceeds the one from Chemrange in most cases and least for substances which undergo slow degradation in air., Conclusions and Perspectives: MBMs should be improved such as to ascertain that the significance of the atmosphere for the multicompartmental cycling is not systematically underestimated. Both types of models should be improved such as to cover degradation in air in the particle-bound state and transport via ocean currents. A detailed understanding of the deviations observed in this work and elsewhere should be gained and multimedia fate box models could then be 'tuned in' to match better the results of comprehensive multicompartmental transport models.