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This study was aimed at monitoring the occurrence and potential sources of emerging contaminants in water sources within the Modder River catchment. Selected water quality indicators were analysed by Hanna multi-parameter meters. Emerging contaminants such as acetaminophen, carbamazepine, ibuprofen, atrazine, simazine, metolachlor, terbuthylazine, 17-alpha-ethinyl-estradiol, estradiol, progesterone, and testosterone were analysed by high performance liquid chromatography mass spectrometry. The sources of emerging contaminants were determined by statistical methods such as Pearson correlation and hierarchical cluster analysis. Results showed that all the sampled water sources have some level of questionable drinking water quality and necessitate some amount of treatment to reduce the contamination before consumption, especially DO, EC, and pH. The 17-alpha-ethinyl-estradiol mean values in rivers (7.79 and 31.55 µg/L), dams (1.83 and 6.90 µg/L), and treated drinking water (0.2 and 0.73 µg/L) were the highest in summer and autumn seasons, respectively. Wastewater effluents, domestic sewage, urban surface runoff, agricultural runoff, and illegal dumping were identified as the possible sources of emerging contaminants pollution. Waste management education, proper application of herbicides, and advance wastewater treatment methods were some of the suggested mitigation strategies. The outcomes may be relevant for environmental protection and water sustainability in the catchment. [ABSTRACT FROM AUTHOR]

Xenobiotics never appear as single, isolated substances in the environment but instead as multi-component mixtures. However, our understanding of the ecotoxicology of mixtures is far from sufficient. In this study, three active pharmaceutical ingredients (carbamazepine, diclofenac, and ibuprofen) and three pesticides (S-metolachlor, terbuthylazine, and tebuconazole) from the most frequently detected emerging micropollutants were examined for their acute cytotoxicity, both individually and in combination, by bioluminescence inhibition in Aliivibrio fischeri (NRRL B-11177). Synergy, additive effects, and antagonism on cytotoxicity were determined using the combination index (CI) method. Additionally, PERMANOVA was performed to reveal the roles of these chemicals in binary, ternary, quaternary, quinary, and senary mixtures influencing the joint effects. Statistical analysis revealed a synergistic effect of diclofenac and carbamazepine, both individually and in combination within the mixtures. Diclofenac also exhibited synergy with S-metolachlor and when mixed with ibuprofen and S-metolachlor. S-metolachlor, whether alone or paired with ibuprofen or diclofenac, increased the toxicity at lower effective concentrations in the mixtures. Non-toxic terbuthylazine showed great toxicity-enhancing ability, especially at low concentrations. Several combinations displayed synergistic effects at environmentally relevant concentrations. The application of PERMANOVA was proven to be unique and successful in determining the roles of compounds in synergistic, additive, and antagonistic effects in mixtures at different effective concentrations. [ABSTRACT FROM AUTHOR]

This study was aimed at monitoring the occurrence and potential sources of emerging contaminants in water sources within the Modder River catchment. Selected water quality indicators were analysed by Hanna multi-parameter meters. Emerging contaminants such as acetaminophen, carbamazepine, ibuprofen, atrazine, simazine, metolachlor, terbuthylazine, 17-alpha-ethinyl-estradiol, estradiol, progesterone, and testosterone were analysed by high performance liquid chromatography mass spectrometry. The sources of emerging contaminants were determined by statistical methods such as Pearson correlation and hierarchical cluster analysis. Results showed that all the sampled water sources have some level of questionable drinking water quality and necessitate some amount of treatment to reduce the contamination before consumption, especially DO, EC, and pH. The 17-alpha-ethinyl-estradiol mean values in rivers (7.79 and 31.55 µg/L), dams (1.83 and 6.90 µg/L), and treated drinking water (0.2 and 0.73 µg/L) were the highest in summer and autumn seasons, respectively. Wastewater effluents, domestic sewage, urban surface runoff, agricultural runoff, and illegal dumping were identified as the possible sources of emerging contaminants pollution. Waste management education, proper application of herbicides, and advance wastewater treatment methods were some of the suggested mitigation strategies. The outcomes may be relevant for environmental protection and water sustainability in the catchment.

Pesticide compounds can influence denitrification processes in groundwater in many ways. This study observed behavior of three selected pesticides under denitrifying conditions. Alachlor, terbuthylazine, and tebuconazole, in a concentration of 0.1 mL L−1, were examined using two laboratory denitrifications assays: a "short" 7-day and a "long" 28-day test. During these tests, removal of pesticides via adsorption and biotic decomposition, as well as the efficiency of nitrate removal in the presence of the pesticides, were measured. No considerable inhibition of the denitrification process was observed for any of the pesticides. On the contrary, significant stimulation was observed after 21 days for alachlor (49%) and after seven days for terbuthylazine (40%) and tebuconazole (36%). Adsorption was in progress only during the first seven days in the case of all tested pesticides and increased only negligibly afterwards. Immediate adsorption of terbuthylazine was probably influenced by the mercuric chloride inhibitor. A biotic loss of 4% was measured only in the case of alachlor. [ABSTRACT FROM AUTHOR]

Pesticide compounds can influence denitrification processes in groundwater in many ways. This study observed behavior of three selected pesticides under denitrifying conditions. Alachlor, terbuthylazine, and tebuconazole, in a concentration of 0.1 mL L−1, were examined using two laboratory denitrifications assays: a “short” 7-day and a “long” 28-day test. During these tests, removal of pesticides via adsorption and biotic decomposition, as well as the efficiency of nitrate removal in the presence of the pesticides, were measured. No considerable inhibition of the denitrification process was observed for any of the pesticides. On the contrary, significant stimulation was observed after 21 days for alachlor (49%) and after seven days for terbuthylazine (40%) and tebuconazole (36%). Adsorption was in progress only during the first seven days in the case of all tested pesticides and increased only negligibly afterwards. Immediate adsorption of terbuthylazine was probably influenced by the mercuric chloride inhibitor. A biotic loss of 4% was measured only in the case of alachlor.

Xenobiotics never appear as single, isolated substances in the environment but instead as multi-component mixtures. However, our understanding of the ecotoxicology of mixtures is far from sufficient. In this study, three active pharmaceutical ingredients (carbamazepine, diclofenac, and ibuprofen) and three pesticides (S-metolachlor, terbuthylazine, and tebuconazole) from the most frequently detected emerging micropollutants were examined for their acute cytotoxicity, both individually and in combination, by bioluminescence inhibition in Aliivibrio fischeri (NRRL B-11177). Synergy, additive effects, and antagonism on cytotoxicity were determined using the combination index (CI) method. Additionally, PERMANOVA was performed to reveal the roles of these chemicals in binary, ternary, quaternary, quinary, and senary mixtures influencing the joint effects. Statistical analysis revealed a synergistic effect of diclofenac and carbamazepine, both individually and in combination within the mixtures. Diclofenac also exhibited synergy with S-metolachlor and when mixed with ibuprofen and S-metolachlor. S-metolachlor, whether alone or paired with ibuprofen or diclofenac, increased the toxicity at lower effective concentrations in the mixtures. Non-toxic terbuthylazine showed great toxicity-enhancing ability, especially at low concentrations. Several combinations displayed synergistic effects at environmentally relevant concentrations. The application of PERMANOVA was proven to be unique and successful in determining the roles of compounds in synergistic, additive, and antagonistic effects in mixtures at different effective concentrations.

Copyright of Progress in Plant Protection is the property of Institute of Plant Protection and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Although pesticides are often discharged into surface waters in pulses as opposed to a sustained release, the effect of episodic pollution events on freshwater crayfish is largely unknown. We monitored change in heart rate and distance moved to assess the response of signal crayfish Pacifastacus leniusculus to short-term exposure to environmentally relevant concentrations of metazachlor (MTZ), terbuthylazine (TER), and thiacloprid (TCL). Crayfish exposed to 20 µg/L of MTZ exhibited a significant increase in mean heart rate and distance moved. Increased heart rate was detected at 118 ± 74 s post-exposure to MTZ. There were no significant differences in mean heart rate and distance moved in crayfish exposed to 6 µg/L of TCL and 4 µg/L of TER. A significant correlation between heart rate and distance moved was found in all exposed groups. These results suggest that pulse exposure to MTZ impact crayfish physiology and behavior during short-term period. With pulse exposure to TCL and TER, crayfish not exhibiting a locomotor response may continue to be exposed to lower, but potentially harmful, levels of pollutants. Evidence of the impacts of pesticide pulse at environmentally relevant concentrations on crayfish is scarce. Further study is required to determine the ecological effects of such events on freshwater crayfish. [ABSTRACT FROM AUTHOR]

In this study, two herbicides (Isoxaflutole 225 g/l + Thiencarbazone-Methyl 90 g/l + Cyrosulfamide 150 g/l and Dimethenamid-P 280 g/l + Terbuthylazine 250 g/l), which are commonly used pre-emergence period against weeds that cause problems in corn planting areas were investigated. The experiments were carried out under field conditions in order to investigate the effect of registered dose of the herbicides to the weeds and corn yield components at the Konya province in 2018 -- 2019 years. Herbicides Isoxaflutole 90 g/l + Thiencarbazone methyl 150 g/l + Cyprosulfamide and 280 g/l Dimethenamide-p + 250 g/l Terbuthylazine were tested in the pre-emergence period of the corn plant at doses of 35 ml/da and 300 ml/da, respectively. As a result of the experiments, Isoxaflutole 90 g/l + Thiencarbazone methyl 150 g/l + Cyprosulfamide were determined as the most effective herbicide to control weeds and increase corn yield components when it was applied during pre-emergence period. The effectiveness of herbicides was determined according to the biomass of weeds and their number in m2. In addition, in both years, A. retroflexus was determined as the most intense species with 16.83 plants/m2 and 32.97 plants/m2 ratios respectively, in the experimental areas. Considering the corn stem diameter, cob length, corn stem length, corn stem dry and fresh weight, dry and fresh cob weight, thousand-grain weight and yield per decare in both years, it was determined that the active substances used increased in yield 2 to 3 times compared to the weed control plots. [ABSTRACT FROM AUTHOR]

Many countries are now facing the problem of increase in resistant biotypes of weeds. The spread of herbicide-resistant weeds across agrophytocenoses poses a threat of decrease in the effectiveness of use of herbicides in agricultural fields. In order to develop anti-resistant compositions of herbicides for protection of maize (Zea mays L.) crops, we studied effects of interaction and efficiency of weed control in greenhouse and field experiments. We studied the possibility of combined use of 4-hydroxyphenyl pyruvate dioxygenase-inhibiting herbicide tolpyralate and inhibitor of transport of electrons in photosystem 2 of chloroplasts – terbuthylazine – and acetolactate synthase-inhibiting rimsulfuron. In greenhouse experiments on model objects, we found that interaction in the mixtures of tolpyralate with rimsulfuron was antagonistic, but the antagonism may be overcome by increasing the rate of applied rimsulfuron. At joint use of tolpyralate and terbuthylazine, a synergistic increase in phytotoxic effect was observed, caused by increase in the effectiveness of the blocking electron-transport chain and increase in intensity of formation of reactive oxygen species. According to the results of the field experiments, we drew the conclusion that the efficacy of using the mixture of tolpyralate and rimsulfuron depends on the species composition of weeds. In the presence of rimsulfuron-resistant weeds, interaction with tolpyralate becomes antagonistic even in the conditions of increased rate of application of rimsulfuron, and thus the effectiveness of the protection significantly decreases. At the same time, after applying tank mixture of tolpyralate with terbuthylazine, the synergistic character of the interaction was maintained toward a broad range of species of grass and dicotyledonous weeds, providing high efficiency of maize crop protection. The herbicide compositions that were analyzed and are presented in the article allow one to decrease the possibility of emergence of resistant biotypes of weeds, and also to effectively control the already existing resistant biotypes.

Terbuthylazine (TBA) is a common triazine herbicide used in agricultural production, which causes toxic damage in multiple tissues. Hesperidin (HSP) is a flavonoid derivative that has anti-inflammatory, antioxidant and cytoprotective effects, but its role in reducing toxic damage caused by pesticides is still unclear. In this study, we aimed to investigate the toxic effect of TBA exposure on chicken hepatocytes and the therapeutic effect of HSP on the TBA-induced hepatotoxicity. Our results demonstrated that HSP could alleviate TBA exposure-induced endoplasmic reticulum (ER) stress. Interestingly, TBA significantly disrupted the integrity of mitochondria-associated endoplasmic reticulum membrane (MAM), while HSP treatment showed the opposite tendency. In addition, TBA could significantly trigger ferroptosis in liver, and HSP treatment reversed ferroptosis under TBA exposure. These results suggested that HSP could inhibit ER stress and alleviate ferroptosis under TBA exposure via maintaining MAM integrity, which provided a novel strategy to take precautions against TBA toxicity. [Display omitted] • TBA induce ferroptosis via maintenance of MAM integrity. • HSP is a novel strategy to take precautions against TBA toxicity. • ER stress and MAM integrity play crucial roles in TBA-induced liver injury. [ABSTRACT FROM AUTHOR]

Terbuthylazine (TBA) is a widely employed pesticide that has been found to be a significant source of food and environmental pollution. Excessive exposure to TBA raises considerable apprehension regarding its potential impact on biological health, but its underlying toxic mechanisms have not been reported. Our findings indicated that TBA exposure could cause intestinal damage, as evidenced by decrease in the quantity of cupped cells and decrease in the expression of intestinal barrier-related proteins (Claudin-1, Occludin, ZO-1, and JAM-1). Additionally, exposure to TBA resulted in a significant decrease in the expression levels of oxidative stress-related genes and proteins. Furthermore, the expression of 8-hydroxy-2′-deoxyguanosine was significantly upregulated. Additionally, excessive exposure to TBA led to a substantial release of mitochondrial DNA, which further activated the cGAS-STING pathway and caused TBK1 and IRF3 phosphorylation. Meanwhile, mitophagy was activated under TBA exposure, as evidenced by decrease in the protein and gene levels of p62 and increase in the levels of PINK1, PARKIN and LC3 II. Therefore, our results suggested that TBA exposure induced oxidative stress in the jejunum and caused mtDNA leakage, for activating the cGAS-STING pathway, which in turn promoted mitophagy. These findings revealed the toxicity mechanisms of TBA, which provided new insights into food safety caused by pesticide contamination. [Display omitted] • TBA exposure damaged the intestinal barrier function of jejunum. • TBA exposure induced jejunal oxidative stress and mitophagy. • TBA-induced mitochondrial DNA release activated the cGAS-STING pathway. • cGAS-STING pathway participated in TBA-induced mitophagy. [ABSTRACT FROM AUTHOR]

Aquatic ecosystems are exposed to pesticides through various pathways such as spray-drift, agricultural runoff, and chemical spills. Understanding the impact of pesticides on freshwater ecosystems requires not only understanding how pesticides affect aquatic organisms but also knowledge of their interactions with other stressors, such as those related to global climate change. Heatwaves are extended periods of temperature increase relative to the climatological mean. They are increasing in frequency and magnitude and pose an emerging threat to shallow freshwater ecosystems. In this study, we evaluated the single and combined effects of the herbicide terbuthylazine and a simulated heatwave on freshwater zooplankton communities using indoor microcosms. Terbuthylazine was applied at an environmentally relevant concentration (15 µg/L). The heatwave consisted of an increase of 6°C above the control temperature for a period of 7 days. When applied individually, the heatwave increased the total abundance of zooplankton by 3 times. The terbuthylazine exposure led to an indirect effect on the zooplankton community structure, reducing the relative abundance of some taxa. The combination of the heatwave and terbuthylazine had no significant impact on the zooplankton community, indicating additive effects dominated by the herbicide. The interaction between the two stressors increased chlorophyll-a concentrations and apparently changed the structure of the phytoplankton community, which may have benefitted cyanobacteria over green algae. Overall, this study shows that understanding the effects of chemical and non-chemical stressors on aquatic communities remains a challenging task. Further studies should be conducted to improve our mechanistic understanding of multiple stressor interactions at different levels of biological organisation.

Different advanced oxidation processes (AOPs) (ultraviolet radiation, hydrogen peroxide photolysis and photo-Fenton) were applied to test the degradation of terbuthylazine in three types of water: (a) ultrapure water, (b) surface water from the Gaditana area (Los Hurones reservoir, Cádiz, Spain) and (c) groundwater from the Tempul spring in Jerez de la Frontera (Cádiz, Spain). The experiments were carried out on a laboratory scale, using two different types of reactors, batch and semi-continuous. In batch reactors, the most efficient process for the experiments carried out with both ultrapure water and underground groundwater was ultraviolet radiation, whereas for surface water from the Gaditana area, the process that obtained the best results was the photolysis of hydrogen peroxide with 2.5 mg L−1 of H2O2. In semi-continuous reactors, the most efficient process was the photolysis of hydrogen peroxide with 2.5 mg L−1 of H2O2 for all the matrices studied. In both types of reactors, terbuthylazine degradation percentages higher than 90% were achieved; the main difference was in the reaction time, which varied from minutes in the batch reactor to seconds in the semi-continuous reactor. In all the applied AOPs, N-terbutyl-6-hydroxy-N′ethyl-1,3,5-triazine-2,4-diamine (TBA-212) was generated as a reaction intermediate. [ABSTRACT FROM AUTHOR]

A mathematical model is presented to simulate the photocatalytic degradation of terbuthylazine in a continuous stirred tank reactor. The flow field is described by the continuity equation and the momentum equation. An advection-diffusion-reaction equation is used to simulate the transport of terbuthylazine. The chemical reactions take place on the inner wall surface coated with the catalyst, which is described by a third-kind boundary condition. A transient differential equation is used to describe the variation of inlet concentration with time. All governing equations are solved using the commercial computational fluid software ANSYS Fluent. The simulation results agree with the experimental data at different temperatures and different flow rates. The radial distribution of terbuthylazine in the reactor is discussed in detail. The velocity depicts a parabolic curve with a maximum velocity of 0.0005 m s-1, 0.001 m s-1, 0.00022 m s-1 and 0.0032 m s-1 for 50 mL min-1, 100 mL min-1, 200 mL min-1, and 300 mL min-1, respectively. At the flow rate of 300 mL min-1, concentration of terbuthylazine decreases from 3.6 mg dm-3 to 0.8 mg dm-3 whereas concentration of cyanuric acid increases from 0.05 mg dm-3 to 0.28 mg dm-3. It shows that the radial effect of velocity and concentration should be taken into account. The mathematical model used in this study is suitable for simulating the photocatalytic degradation process of terbuthylazine in continuous stirred tank reactors. [ABSTRACT FROM AUTHOR]

Background: The present study aimed to gain a comprehensive knowledge of the presence and environmental risks of pesticide and repellent residues in Lake Balaton and its sub-catchment area (Hungary). A unique analysis of 439 active substances and 17 metabolites was carried out on surface waters and one effluent wastewater as the only direct discharge into Lake Balaton from June 2017 until August 2020. Altogether 203 water- and 85 sediment samples were collected and analysed during the 3-year monitoring period. To determine the environmental risks of the detected pesticides to aquatic ecosystems, environmental risk assessment (ERA) was carried out using two approaches (worst- and general-case scenarios). Results: Fifty-two pesticides and one insect repellent were detected, of which 26 belonged to herbicides (24 active substances and two metabolites), 15 to fungicides (15 active substances), and 11 to insecticides (eight active substances and three metabolites), of which only nine of the total analysed compounds are listed to be monitored in surface waters with threshold limit values (TLVs). The most frequently detected compounds were terbuthylazine, diethyltoluamide (DEET), desethyl-atrazine, and metolachlor. Glyphosate, aminomethylphosphonic acid (AMPA), and DEET were found with the highest concentrations of 3.0, 2.0, and 1.57 µg/L, respectively. The pesticide exposures were higher during the summer periods indicating a stable seasonal pattern. According to the performed ERA, the calculated Risk Quotients (RQs) indicated 18 compounds with a high level of risk including nine that had been banned for at least a decade. Discussion: This study expands knowledge on the spatiotemporal occurrence of pesticides in inland surface waters and highlights the need to consider widening the number of analysed pesticides beyond the European Water Framework Directive (EWFD). According to our results, additional authority and legislation procedures should come into force for pesticides not indexed in the priority European Union Watch List. [ABSTRACT FROM AUTHOR]

Many countries are now facing the problem of increase in resistant biotypes of weeds. The spread of herbicide-resistant weeds across agrophytocenoses poses a threat of decrease in the effectiveness of use of herbicides in agricultural fields. In order to develop anti-resistant compositions of herbicides for protection of maize (Zea mays L.) crops, we studied effects of interaction and efficiency of weed control in greenhouse and field experiments. We studied the possibility of combined use of 4-hydroxyphenyl pyruvate dioxygenase-inhibiting herbicide tolpyralate and inhibitor of transport of electrons in photosystem 2 of chloroplasts – terbuthylazine – and acetolactate synthase-inhibiting rimsulfuron. In greenhouse experiments on model objects, we found that interaction in the mixtures of tolpyralate with rimsulfuron was antagonistic, but the antagonism may be overcome by increasing the rate of applied rimsulfuron. Atjoint use of tolpyralate and terbuthylazine, a synergistic increase in phytotoxic effect was observed, caused by increase in the effectiveness of the blocking electron-transport chain and increase in intensity of formation of reactive oxygen species. According to the results of the field experiments, we drew the conclusion that the efficacy of using the mixture of tolpyralate and rimsulfuron depends on the species composition of weeds. In the presence of rimsulfuron-resistant weeds, interaction with tolpyralate becomes antagonistic even in the conditions of increased rate of application of rimsulfuron, and thus the effectiveness of the protection significantly decreases. At the same time, after applying tank mixture of tolpyralate with terbuthylazine, the synergistic character of the interaction was maintained toward a broad range of species of grass and dicotyledonous weeds, providing high efficiency of maize crop protection. The herbicide compositions that were analyzed and are presented in the article allow one to decrease the possibility of emergence of resistant biotypes of weeds, and also to effectively control the already existing resistant biotypes. [ABSTRACT FROM AUTHOR]

The presence of weeds in cultivated fields can significantly reduce the yield of crops. In recent years, however, more and more attention has been paid to limiting the amount of chemical plant protection products used in agriculture. Numerous studies are carried out using substances of natural origin, like essential oils, as herbicides, fungicides and insecticides. In the conducted experiment, the use of clove (Eugenia caryophyllus (Spreng.) Bullock & S.G. Harrison) and pine (Pinus sylvestris L.) essential oils applied pre- and post-emergence as herbicides was investigated. Commercial source materials were selected. Emulsified essential oils were applied at 5, 10, 15, and 20 L ha-1. The test plants were winter oilseed rape (Brassica napus L. subsp. oleifera (Delile) Sinskaya) and maize (Zea mays L.) The comparative herbicides were mesotrione and terbuthylazine (applied in doses registered in maize cultivation). Pre-emergence treatment was performed 1 d after sowing, and post-emergence essential oils and herbicide were applied when oilseed rape was in the 2-3 leaf stage and the maize was in the 3-4 leaf stage. Clove essential oil applied post-emergence contributed to the damage to both plant species (3 d after treatment: 7.5%-46.3% damage of volunteer oilseed rape; 2.5%-25.0% damage of maize, depending on dose). It also influenced the maximum photochemical efficiency of photosystem II. However, its effect was transient, unlike the synthetic herbicide. Applied pre-emergence, it did not affect the development of maize and rape (0% plant damage). Pine essential oil did not damage the test plants in soil and foliar application (0% plant damage). [ABSTRACT FROM AUTHOR]

Copyright of Julius-Kühn-Archiv is the property of Julius Kuehn Institut and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Background: Among other negative effects, herbicides induce oxidative stress, leading to lipid peroxidation and protein oxidation. Therefore, there is a growing need to identify natural compounds with sufficient antioxidant capacity and mitigate the negative effects of herbicides without side effects. Objective: Our study aimed to examine the protective effect of the phenolic extract of wild garlic (WG) leaves on terbuthylazine-treated erythrocytes. Material and methods: In human erythrocytes treated with the herbicide terbuthylazine (4.5 mg/L) alone and a combination of terbuthylazine and WG extract, we measured malondialdehyde (MDA) and haemoglobin (Hb) concentrations and the antioxidant activities of CuZn superoxide dismutase (SOD1; EC 1.15.1.1) and catalase (CAT; EC 1.11.1.6) in vitro. Results: In comparison with terbuthylazine, WG extract reduced the concentrations of MDA and Hb from 59.69 to 43.45 nmol/gHb (27%, p < 0.001) and 165.08 to 128.64 g/L (22%, p < 0.05), respectively. Catalase activity was induced for samples treated with both WG extract and terbuthylazine compared with terbuthylazine alone (p < 0.05). Conclusions: The results demonstrated that WG may reduce the toxicity of terbuthylazine, and the erythrocyte membrane may be the primary site of phenolic action. Therefore, the lipid peroxidation intensity could be a biomarker of oxidative damage caused by terbuthylazine and the protective effect of WG. [ABSTRACT FROM AUTHOR]

Sex reversal is a mismatch between genetic sex (sex chromosomes) and phenotypic sex (reproductive organs and secondary sexual traits). It can be induced in various ectothermic vertebrates by environmental perturbations, such as extreme temperatures or chemical pollution, experienced during embryonic or larval development. Theoretical studies and recent empirical evidence suggest that sex reversal may be widespread in nature and may impact individual fitness and population dynamics. So far, however, little is known about the performance of sex-reversed individuals in fitness-related traits compared to conspecifics whose phenotypic sex is concordant with their genetic sex. Using a novel molecular marker set for diagnosing genetic sex in agile frogs (Rana dalmatina), we investigated fitness-related traits in larvae and juveniles that underwent spontaneous female-to-male sex reversal in the laboratory. We found only a few differences in early life growth, development, and larval behavior between sex-reversed and sex-concordant individuals, and altogether these differences did not clearly support either higher or lower fitness prospects for sex-reversed individuals. Putting these results together with earlier findings suggesting that sex reversal triggered by heat stress may be associated with low fitness in agile frogs, we propose the hypothesis that the fitness consequences of sex reversal may depend on its etiology.

A molecularly imprinted solid-phase extraction (MISPE) procedure was developed for the GC-MS analysis of four high priority pesticides (atrazine, terbuthylazine, acetochlor and alachlor) in a cannabis bud sample matrix. The study demonstrated that the synthesised polymer had a high affinity and good selectivity for either chloroacetamide or triazine classes of pesticide used as a template molecule during the molecularly imprinted polymerisation reaction. The MISPE procedure was optimised in terms of loading, washing and elution fractions utilising a range of aqueous methanol solutions for optimal recovery and minimal matrix interferences. The optimal wash fraction was 20% (v/v) methanol in an aqueous solution, whilst 70% (v/v) was used for the elution fraction. The selectivity, accuracy and recovery of the MISPEs were verified using a synthesised non-imprinted polymer and a commercial C18 cartridge as reference sorbents in comparative experiments. Approximately 3 g of the cannabis bud sample was spiked at a 0.05 mg/kg maximum residue limit (MRL) concentration. The recovery of the four selected pesticides extracted from the spiked samples ranged between 76.4-85.0% when utilising the optimised MISPE methods, compared to 91.6-96.9% for the C18 SPE. However, the use of the MISPE resulted in enhanced selectivity, as evidenced by GC-MS analysis, due to the extraction of less matrix interferences. Therefore, it can be concluded that the MISPE is a viable pre-treatment method for selective pesticide analysis in cannabis flowers using GC-MS when selectivity is valued for the extraction of target pesticides from a complex sample matrix. [ABSTRACT FROM AUTHOR]

Different advanced oxidation processes (AOPs) (ultraviolet radiation, hydrogen peroxide photolysis and photo-Fenton) were applied to test the degradation of terbuthylazine in three types of water: (a) ultrapure water, (b) surface water from the Gaditana area (Los Hurones reservoir, Cádiz, Spain) and (c) groundwater from the Tempul spring in Jerez de la Frontera (Cádiz, Spain). The experiments were carried out on a laboratory scale, using two different types of reactors, batch and semi-continuous. In batch reactors, the most efficient process for the experiments carried out with both ultrapure water and underground groundwater was ultraviolet radiation, whereas for surface water from the Gaditana area, the process that obtained the best results was the photolysis of hydrogen peroxide with 2.5 mg L−1 of H2O2. In semi-continuous reactors, the most efficient process was the photolysis of hydrogen peroxide with 2.5 mg L−1 of H2O2 for all the matrices studied. In both types of reactors, terbuthylazine degradation percentages higher than 90% were achieved; the main difference was in the reaction time, which varied from minutes in the batch reactor to seconds in the semi-continuous reactor. In all the applied AOPs, N-terbutyl-6-hydroxy-N′ethyl-1,3,5-triazine-2,4-diamine (TBA-212) was generated as a reaction intermediate.

We investigated the sensitivity of two freshwater crayfish species (Astacus astacus and Procambarus virginalis) during embryonic development to chronic exposure to the herbicide terbuthylazine under laboratory conditions. The assessed parameters included time of embryonic development, survival rate, hatching weight and histopathology of hepatopancreas. LC50 (median lethal concentration) and ED50 (median effective concentration) were estimated. We were able to determine effects of terbuthylazine for every investigated parameter. For noble crayfish, the LC50 value after 45 days was 0.11 mg/L, and the histology of the hepatopancreas showed effects starting from 0.025 mg/L. Other parameters revealed effects starting at concentrations of 1.6 mg/L for weight and 6.4 mg /L for embryonic development time and hatching rate. Marbled crayfish only showed effects concerning the hatching rate and survival rate at concentrations without a clear dose-effects curve. As a conclusion, our data shows the risk of terbuthylazine in existing concentrations in freshwater ecosystems to non-target organisms and also the need of toxicological studies on directly affected species in addition to the use of model organisms. [ABSTRACT FROM AUTHOR]

Abstract According to Article 12 of Regulation (EC) No 396/2005, EFSA has reviewed the maximum residue levels (MRLs) currently established at European level for the pesticide active substance terbuthylazine. To assess the occurrence of terbuthylazine residues in plants, processed commodities, rotational crops and livestock, EFSA considered the conclusions derived in the framework of Commission Regulation (EC) No 33/2008 as well as the European authorisations reported by Member States (including the supporting residues data). Based on the assessment of the available data, MRL proposals were derived and a consumer risk assessment was carried out. Although no apparent risk to consumers was identified, some information required by the regulatory framework was missing. Hence, the consumer risk assessment is considered indicative only and some MRL proposals derived by EFSA still require further consideration by risk managers.

New strategies, such as biochar soil amendment, are continuously developed to restore the agricultural environment from the adverse effects of agrochemicals. The sorption efficiency of a biochar depends on the specific raw materials and pyrolysis variables applied, such as temperature and heating time, that shape its physico-chemical properties. In this study, the sorption capacity of two biochars obtained from coppiced hardwoods at two different pyrolysis temperatures (650°C and 1100°C, denominated BCLT and BCHT, respectively) was assessed for Lumax®, a pre-emergence selective herbicide used for maize cultivation. Lumax® is composed of S-metolachlor (MTC), terbuthylazine (TBZ), and mesotrione (MST), therefore the sorption behaviour of active ingredients, alone or mixed as in the commercial formulation, was studied on two biochar samples to identify the best product to mitigate Lumax® pollution. Our results show that, although biochar performance depends on the physico-chemicals properties of both the biochar and the pollutants, BCHT was the most suitable in retaining the Lumax® active ingredients, likely due to its high aromaticity. [ABSTRACT FROM AUTHOR]

According to Article 12 of Regulation (EC) No 396/2005, EFSA has reviewed the maximum residue levels (MRLs) currently established at European level for the pesticide active substance terbuthylazine. To assess the occurrence of terbuthylazine residues in plants, processed commodities, rotational crops and livestock, EFSA considered the conclusions derived in the framework of Commission Regulation (EC) No 33/2008 as well as the European authorisations reported by Member States (including the supporting residues data). Based on the assessment of the available data, MRL proposals were derived and a consumer risk assessment was carried out. Although no apparent risk to consumers was identified, some information required by the regulatory framework was missing. Hence, the consumer risk assessment is considered indicative only and some MRL proposals derived by EFSA still require further consideration by risk managers. [ABSTRACT FROM AUTHOR]

The occurrence of polar pesticides in sediments has not been extensively investigated because of their relatively poor hydrophobicity and apparently less persistence in the environment. However, their continuous release into the aquatic systems calls for the evaluation of their potential accumulation in sediments and the role of this matrix as a potential source of these compounds. Considering this, a method based on pressurized liquid extraction (PLE), extract clean-up by solid phase extraction (SPE), and analyte determination by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated to analyze 50 relevant (frequently used and/or regulated or found in water) medium to highly polar pesticides in sediments. The method showed good performance regarding accuracy (relative recoveries between 76 and 124%), precision (relative standard deviation values < 20%), sensitivity (LODs in the low nanogram per gram for most compounds), linearity (coefficients of determination > 0.99), and matrix effects (negligible for all analytes). The use of an isotope dilution approach for quantification ensures result reliability. As a part of the validation process, the method was applied to the analysis of the target pesticides in sediments from the Llobregat River (NE Spain) showing the presence of five of them, namely, terbutryn, dichlorvos, terbuthylazine, diazinon, and irgarol. All 5 pesticides, due to both the concentrations found and their physical-chemical characteristics, demonstrate high potential for bioaccumulation and risk to aquatic organisms. Additional multi-disciplinary studies that investigate pesticide occurrence in different aquatic compartments and evaluate the potential risks for aquatic ecosystems are required to assess the environmental impact and significance of the presence of pesticides in sediments. [ABSTRACT FROM AUTHOR]

Terbuthylazine (TBA), a triazine herbicide, is extensively employed in agriculture for its wide range of effectiveness. However, prolonged utilization of TBA can pose a potential hazard to animals and human health. Here, a total of 180 broiler chickens (Gallus gallus) were stochastically assigned to three groups (control group, 0.4 mg/kg TBA group, and 4 mg/kg TBA group) for investigating the impact of TBA on cardiotoxicity. The results revealed that TBA exposure resulted in pathological alterations in the myocardium. Moreover, TBA exposure activated cGAS-STING pathway and markedly elevated the mRNA and protein expression levels of innate immune response (cGAS, STING, TBK1, and IRF3) in myocardium. Additionally, NF-κB signal was also activated under TBA exposure, which was characterized by the increasing mRNA expression levels of NF-κB, IKKα and the protein expression levels of p-NF-κB/NF-κB, IKKα, p-IκBα/IκBα in the TBA treatment groups. Meanwhile, the expression of pro-inflammatory cytokines (TNF-α and IL-1β) were also significantly increased. In summary, our findings suggested that cGAS-STING/NF-κB pathway functionated in the innate immune response and inflammation in myocardium brought on by TBA exposure, which provided new insights into the TBA toxicology. [Display omitted] • TBA induced pathological damage in chicken myocardium. • The innate immune response and inflammation were activated by TBA. • cGAS-STING and NF-κB pathway mediated innate immune response under TBA exposure. [ABSTRACT FROM AUTHOR]

Terbuthylazine (TBA) is one of the most commonly used and effective herbicides. However, due to its affinity for soil organic matter and water solubility, TBA can lead to biological health concerns. This study exposed broilers to TBA (0 mg/kg bw, 0.4 mg/kg bw, 4 mg/kg bw) for 28 days. The results showed significant pathological damage in broiler myocardial tissue, such as widening of the interstitial space, rupture of muscle fibers, and deposition of myocardial collagen fibers. In addition, Under the 0.4 mg/kg bw TBA exposure, myocardial oxidative stress was observed in broilers, which was accompanied by the activation of Nrf2/HO-1 pathway and the increased protein and mRNA levels of NQO1, NOX2 and SOD2 antioxidant enzymes. However, Nrf2/HO-1 protein and mRNA levels were reversed at 4 mg/kg bw TBA exposure. Meanwhile, the Nrf2/HO-1 mediated antioxidant defense was impaired. In contrast with the low dose, the protein and gene expression levels of NQO1, NOX2, and SOD2 were reduced in 4 mg/kg bw TBA group. The expression of GPX4 and SLC7A11 was significantly downregulated at both protein and mRNA levels. Beyond that, ACSL4 expression was significantly up-regulated, and the protein result was consistent with the mRNA expression, demonstrating the occurrence of ferroptosis. In general, TBA exposure activated the Nrf2/HO-1 pathway, resulting in ferroptosis. This study links ferroptosis to the Nrf2/HO-1 pathway, providing new insights into the potential role of TBA in myocardial toxicity. [Display omitted] • TBA exposure damages the myocardium of broiler chickens. • TBA induces oxidative stress and ferroptosis in broiler myocardium. • Low-dose exposure to TBA activated the Nrf2/HO-1 pathway. • An imbalance in redox occurs when exposed to a high dose of TBA. [ABSTRACT FROM AUTHOR]

Poa annua is a cosmopolitan, cool-season grass species regarded as one of the most significant weeds of turfgrass. It is mainly controlled by herbicides; however, repeated use of herbicides in golf turf has resulted in the evolution of multiple-herbicide resistant P. annua. Four field experiments were performed in autumn and spring in golf turf to identify effective herbicide options to control multiple herbicide-resistant P. annua. In herbicide resistance screening, the trial site population (SA1) was found to be susceptible to amicarbazone and terbuthylazine, but resistant to simazine and metribuzin at the field rate of each herbicide. Consistent with the results of the pot study, the PSII-inhibiting herbicides amicarbazone and terbuthylazine provided the best control (80–100%) of P. annua in both autumn and spring trials with minimal damage to the turf. In contrast, the other two PSII-inhibiting herbicides, metribuzin and simazine, were relatively ineffective in controlling P. annua in the field. Indaziflam also performed well in both autumn trials and reduced P. annua occurrence by >75%. Pyroxasulfone and s-metolachlor only provided moderate weed control in both the autumn and spring trials, reducing P. annua occurrence by 50%. Among the nine different herbicides, amicarbazone and terbuthylazine were found to be most effective for spring and autumn application in turf. As resistance to some PSII-inhibiting herbicides has already evolved in this field population, the use of amicarbazone and terbuthylazine needs to be integrated with other herbicide modes of action and non-chemical tactics to delay the onset of resistance to them.

Field experiments to evaluate the split application of mesotrione + s-metolachlor, mesotrione + terbuthylazine, dicamba + prosulfuron, terbuthylazine + mesotrione + s-metolachlor, and sulcotrione in the cultivation of sorghum var. Rona 1 were carried out in 2012 and 2013. The field tests were conducted at the field experimental station in Winna Góra, Poznań, Poland. Treatments with the herbicides were performed directly after sowing (PE) and at leaf stage 1–2 (AE1) or at leaf stage 3–4 (AE2) of sorghum. The treatments were carried out in a laid randomized block design with 4 replications. The results showed that the tested herbicides applied at split doses were effective in weed control. After the herbicide application weed density and weed biomass were significantly reduced compared to the infested control. The best results were achieved after the application of mesotrione tank mixture with s-metolachlor and terbuthylazine. Application of split doses of herbicides was also correlated with the density, biomass, and height of sorghum.

Abstract The conclusions of EFSA following the peer review of the initial risk assessment carried out by the competent authority of the rapporteur Member State, the United Kingdom, for the pesticide active substance terbuthylazine are reported. The context of the peer review was that requested by the European Commission following the submission and evaluation of confirmatory data on groundwater metabolites. The conclusions were reached on the basis of the evaluation of the representative uses of terbuthylazine as a herbicide on maize and sorghum and taking into account the scientific opinion of the EFSA Panel on Plant Protection Products and their Residues (PPR) on the setting of health‐based reference values for metabolites of the active substance terbuthylazine. The reliable endpoints concluded as being appropriate for use in regulatory risk assessment, derived from the available studies and literature in the dossier peer reviewed, are presented. Concerns are identified.

Abstract The EFSA Panel on Plant Protection Products and their Residues was requested to establish health‐based reference values for groundwater metabolites (LM2, LM3, LM4, LM5 and LM6) of the active substance terbuthylazine based on the available evidence, unless the evidence was considered insufficient to do so. The request was accepted under the explicit circumstance that the reassessment would be made according to a different methodology than the routine methodology currently applied for the assessment of metabolites in groundwater. While for metabolites LM2, LM4 and LM5, it was concluded that the reference values for terbuthylazine are applicable, substance‐specific reference values could not be derived for metabolites LM3 and LM6. The applied threshold of toxicological concern (TTC) approach has shown that metabolites LM3 and LM6 are of potential concern for consumer health, since at least one representative groundwater leaching scenario results in exposure above the relevant threshold. Moreover, other sources of exposure to LM3 and LM6 could not be excluded with certainty. It is therefore recommended to address the specific toxicities of metabolites LM3 and LM6.

The conclusions of EFSA following the peer review of the initial risk assessment carried out by the competent authority of the rapporteur Member State, the United Kingdom, for the pesticide active substance terbuthylazine are reported. The context of the peer review was that requested by the European Commission following the submission and evaluation of confirmatory data on groundwater metabolites. The conclusions were reached on the basis of the evaluation of the representative uses of terbuthylazine as a herbicide on maize and sorghum and taking into account the scientific opinion of the EFSA Panel on Plant Protection Products and their Residues (PPR) on the setting of health-based reference values for metabolites of the active substance terbuthylazine. The reliable endpoints concluded as being appropriate for use in regulatory risk assessment, derived from the available studies and literature in the dossier peer reviewed, are presented. Concerns are identified. [ABSTRACT FROM AUTHOR]

Abstract Recently, a bioremediation tool consisting of freshly grown cells of the Arthrobacter aurescens strain TC1 proved successful in the cleanup of terbuthylazine (TBA) contaminated soil, with potential to prevent TBA dispersal via the soil-water pathway. The present work aimed at examining the feasibility of preparing and formulating bioaugmentation bacterial cells in advance which retain adequate viability and herbicide-degrading activity during storage and transport to contaminated sites. Three different types of formulation of A. aurescens TC1 cells were performed, namely cell paste, lyophilized, and adsorbed onto the mineral carrier vermiculite. Vermiculite-based cell material and cell paste offered survival rates significantly higher (≥78% of cells recovered viable, when compared to the initial numbers) than lyophilized cells (≥65%) after storage at 4 °C for up to a maximum period of 30 days. Inocula prepared from the three types of formulated and stored cells supported adequate levels of herbicide-biodegradation activity, ultimately allowing an almost complete removal of TBA from either liquid buffer or soil. In soil microcosms, the efficacy of bioremediation of TBA-contaminated soil in terms of decontamination (%) based on the ecotoxicity assessment of soil eluates towards a freshwater microalga was found to differ within formulations in the order: lyophilized cells (~100% efficacy at the end of one or two weeks of bioremediation treatment with an initial inoculum of ~2.5 × 107 viable cells/g of soil; similar to fresh cells) > vermiculite-adsorbed cells (81% with ~2.4 × 108 cells/g) > cell paste (68% with ~2.4 × 108 cells/g). The limitations and advantages of each type of bacterial formulation, together with the prediction of their applicability in the field are discussed. Graphical abstract Unlabelled Image [ABSTRACT FROM AUTHOR]

Abstract S-metolachlor (SMOC) and terbuthylazine (TBA) are herbicides that commonly appear as active ingredients (a.i.) in the composition of plant protection products. In a previous work, experimental bioassays were performed using those chemicals to find suitable molecular biomarkers to assess its toxicity to the non-target species Scrobicularia plana. The results obtained showed that the pollutants produce mortality and biochemical changes at the species, namely in protein contents and enzymatic activity levels. Thus, for a better understanding of the total biochemical impacts of those pollutants in S. plana, the composition of fatty acids (FA) and carbohydrates (CH) of the survival organisms are investigated here. In addition, since this species is edible its biochemical profile is directly related to its nutritious quality, which is analysed in this study. Furthermore, the analyses were performed in two types of tissue - the muscle and visceral mass of each survival organism. The greatest changes in FA composition are observable in small size class, being the most sensitive size class both at the toxicological and biochemical level. FA contents are higher in small organisms, both at the field and under laboratory conditions, being the disparity between size classes higher in visceral masses than in muscles. Indeed, muscles adequately represent the FA profile since those molecules appear in higher content in this tissue compared to visceral masses, becoming the better indicator tissue of biochemical changes. Besides, using muscles, less amount of biomass is needed, so it turns out to be the most cost-effective tissue to be used as endpoint in future studies. FA profiles observed at SMOC and TBA exposure are different, organisms from TBA exposure presenting a lower nutritious quality, in terms of FA abundance and diversity, than the organisms exposed to SMOC. Still, SMOC produces reductions of HUFA, essential fatty acids that cannot be synthesized by the species. Moreover, HUFA (mostly EPA and DHA) occupied the greatest part of the FA composition of organisms exposed to the control treatments and to TBA; however, the decreases of HUFA caused by the SMOC exposure change the profiles and make SFA the most dominant group. These findings represent a risk of low occurrence of essential fatty acids in entire aquatic environments exposed to the chemicals studied. Regarding CH, glucose is the only monosaccharide found in S. plana which was expected since glycogen is the main polysaccharide in animal tissues. In general, the glucose content increases with a concentration of pollutants, whereas the glycogen concentration decreases, suggesting that the glucose is being released as a response to chemical stress. Thus, this work presents tools to assess biochemical impacts of S-metolachlor and terbuthylazine in aquatic systems and to goes deeper in the knowledge of these pollutants' toxicity to non-target species to predict its propagation through aquatic trophic webs. Highlights • S-metolachlor decreases highly unsaturated fatty acids in S. plana. • Terbuthylazine diminishes the fatty acid content and diversity of S. plana. • Terbuthylazine prejudices the most the nutritious quality of S. plana. • Muscles of S. plana exhibit superior fatty acid content that visceral masses. • S. plana releases glucose under chemical stress. [ABSTRACT FROM AUTHOR]

Abstract Various methods for shifting the optical response of TiO 2 into the visible (Vis) range have been reported. Herein, we reported the application of a TiO 2 /H 2 O 2 /Vis process and the effects of TiO 2 crystalline structure on the degradation of terbuthylazine. The results indicated that TiO 2 crystalline structure and H 2 O 2 addition had significant effects on terbuthylazine degradation: its degradation rate could be increased from 7% to 70% with H 2 O 2 addition after 180 min of reaction, the synergistic degradation of terbuthylazine by TiO 2 -Fe3 + was substantially accelerated, with the degradation rate reaching up to 100% after 20 min of reaction, and rutile TiO 2 showed better photocatalytic activity and a more obvious synergistic effect than anatase TiO 2. The addition of free-radical scavengers (tert -butyl alcohol or methanol) inhibited the degradation efficiency of rutile TiO 2 , but had a relatively minor effect on anatase TiO 2. Fluorescence spectrophotometry analysis indicated that hydroxyl free radicals could be continuously produced when using rutile TiO 2 as the photocatalyst. Degradation of terbuthylazine catalyzed by rutile TiO 2 occurred mainly in solution, but occurred on the particle surface of the photocatalyst when catalyzed by anatase TiO 2. This study provides new insight into the role of TiO 2 crystalline structure on the degradation of terbuthylazine and its photocatalytic degradation mechanism. Graphical abstract Unlabelled Image [ABSTRACT FROM AUTHOR]

Terbuthylazine has been introduced to replace atrazine in most of the EU countries; nowadays, this herbicide is one of the most frequently detected in environmental waters. The persistence and the endocrine disruptor activity of this chemical of emerging concern have been established. Conventional treatments applied in drinking water plants do not lead to the complete removal of pesticides and among them, adsorption provides the greatest efficiency. Hydrochar obtained through the hydrothermal carbonization of sewage sludge has been activated and its adsorption capacity has been tested. Moreover, an innovative electrochemical reactor with a Solid Polymer Electrolyte (SPE) has been applied for removing terbuthylazine from an aqueous medium. The activated hydrochar demonstrated an adsorption capacity of 422 mg g-1, reached in 6 hours. Considering the reduction of the volume of sludge to be disposed of obtained if hydrothermal carbonization is carried out, and the thermovalorization of the exhausted hydrochar if used for pollutant removal, further analysis is encouraged to evaluate its effectiveness as adsorbent media in filtration vessels. Up to 88% of the herbicide has been completely removed by the electrolytic treatment in the first hour of treatment, while only 1% has been converted in minor metabolites. Both the sorbent and the advanced oxidation technique investigated here could be applied for the removal of other pesticides and drugs metabolites in water treatment facilities, while the fast removal attained by the SPE technology also offers a prospective for the insitu remediation of pesticides-polluted groundwater. [ABSTRACT FROM AUTHOR]

Highlights • A hydrophilic deep eutectic solvent (DES) was easily synthesized. • The DES was used in reversed liquid-liquid microextraction. • Vortex was used to assist the extraction from edible oil samples. • DoE was used for the method optimization. Abstract In this study, four triazine herbicides—namely, simazine, ametryn, prometryn and terbuthylazine—were separated and determined using high-performance liquid chromatography coupled with ultraviolet detector (HPLC-UVD). The deep eutectic solvent (DES) formed by tetrabutylammonium chloride ([N 4444 ]Cl, TBA) and ethylene glycol (EG) was selected as the extraction solvent of vortex-assisted reversed-phase liquid-liquid microextraction (VA-RPLLME). The application of the hydrophilic DES expands the range of choice for LLME. The experimental parameters affecting the extraction recoveries, including the amount of the DES, the sample volume and the vortex time, were investigated and optimized by the design of experiments (DoE) methodology. A quadratic model, namely central composite face-centered (CCF) design featuring 20 runs was used instead of the conventional trial and error approach. Under optimum conditions, the limits of determination (LODs) of the method were 0.60–1.50 μg L−1. The enrichment factors for the analytes ranged from 27 to 31. The extraction recoveries were in the range of 84.1–104.9%, and the intra-day, inter-day and intermediate relative standard deviations (RSDs) were less than 8.4%. Finally, the method was applied for the determination of triazine herbicides in vegetable oil samples. The obtained recoveries were in the range of 60.1–107.2% and RSDs were lower than 8.1%. In general, VA-RPLLME can be complementary to the present available methods for the determination of triazine herbicides in vegetable oil samples. [ABSTRACT FROM AUTHOR]

Abstract Knowledge of long-term pesticide behavior in biochar (BC) amended soil is still contradictory. In this work, we compared the sorption of three highly persistent and ionizable pesticides [two anionic (imazamox and picloram) and one weak base (terbuthylazine)] on both fresh and field-aged BC as well as on a soil amended with these biochars. The aging process was performed by burying the biochar at 10 cm in a silt loam soil [Upper Midwest USA (Wisconsin)] for six months. Field aged BC removed the three pesticides from solution to a higher extent (>85%) than the fresh BC (<16%). This removal was attributed to water-soluble components on the biochar. Laboratory incubation experiments demonstrated that dissipation in soil and biochar mixtures were both a function of pesticide and biochar type. The amounts of soil extractable (i.e, bioavailable) pesticide were inversely related to the extent of sorption. Similar dissipation and sorption of imazamox was observed in unamended and BC-amended soils. Terbuthylazine dissipated similarly in all treatments, but sorption increased with incubation time in the aged BC-amended soil. Conversely, picloram dissipated to a higher extent in aged BC-amended soil when compared to unamended or fresh BC-amended soil. This work demonstrates temporal variability of biochar sorption capacities due to soil exposure, which alters the efficacy and bioavailability of soil applied pesticides. Highlights • Aged biochar removed greater amounts of herbicides from solution than fresh biochar. • Herbicide sorption by aged biochar was attributed to a dissolvable surface coating. • Degradation of picloram in soil was accelerated by the presence of aged biochar. • Slow sorption occurred for terbuthylazine and imazamox in aged biochar amended soil. [ABSTRACT FROM AUTHOR]

Highlights • S-metolachlor and terbuthylazine produce mortality in Scrobicularia plana. • Each active ingredient is more toxic to S. plana than the commercial formulation. • GRed is a suitable specific biomarker to determine the presence of terbuthylazine. • GST is an appropriate biomarker to determine the presence of S-metolachlor. Abstract The overexploitation of the farmlands in the Mediterranean region contributes to an overuse of herbicides that have the potential to pollute surrounding aquatic systems, like the Mondego estuary, located near the city of Figueira da Foz (Portugal). Primextra® Gold TZ is the most-used herbicide in this area and it is constituted by two main active ingredients, S-metolachlor (SMOC) and terbuthylazine (TBA) that have exhibited toxicity to aquatic animal species in previous studies. The benthic bivalve species Scrobicularia plana was selected to carry out bioassays because of its capacity to filter pollutants and its important position in the structure and functioning of estuarine communities. Organisms of two size classes (big and small) were exposed individually to a range of concentrations of the mentioned compounds to assess their responses in terms of mortality. S. plana showed a clear higher sensitivity to SMOC (big – LC 50 = 40.702 mg/L; small – LC 50 = 41.517 mg/L) than to TBA (big – LC 50 = 118.590 mg/L; small – LC 50 = 108.418 mg/L), and big size class organisms, generally, showed to be more tolerant than the ones of small size class. In order to evaluate contaminated aquatic systems, it is necessary to develop laboratory strategies to rapidly assess the potential impacts of pollutants in the environment and in human health. Thus, a battery of biomarkers was selected, including the activity of antioxidant enzymes (glutathione peroxidase (tGPx), glutathione reductase (GRed) and glutathione-S-transferase (GST)) and the lipid peroxidation occurrence (by quantification of TBARS levels). This work reports that GRed and GST activate under the chemicals' exposure at concentrations that surpass the levels for environment protection. Moreover, GRed shows specificity to detect TBA presence and GST results more accurate to assess SMOC contamination. [ABSTRACT FROM AUTHOR]

Abstract Water pollution is becoming alarming since thousands contaminants are dispersed in the aquatic environments, and agricultural practices, for the massive use of pesticides, are contributing to exacerbating this problem. In this context, a research aimed at investigating the ability of duckweed (Lemna minor), a free-floating aquatic species widespread throughout the world, to remediate water polluted with five different concentrations of a herbicide - terbuthylazine (TBA) - was carried out. In addition, duckweed was treated with a plant biostimulant and a safener with the aim of increasing the plant's capacity to tolerate and remove the TBA from the water. The results evidenced that the herbicide affected the duckweed already at the lower concentrations, reducing its capacity to proliferate and the area of its fronds. On the contrary, when the TBA treatments were performed in combination with the biostimulant or the safener the average area of the fronds was affected of lesser extents, compared to the plants treated with the herbicide only. Antioxidant enzymes, namely ascorbate peroxidases (APX) and catalases (CAT), were investigated and it was found that the biostimulated and safened duckweed showed increased activities of these enzymes, compared to the plants treated with TBA only. At last, some phytofiltration experiments were planned. The biostimulated and safened duckweed removed more TBA from polluted water than the plants treated with the herbicide alone. In conclusion, this research showed that duckweed is suitable for cleaning water polluted with TBA and this potential can be successfully improved by treating the species with a biostimulant or a safener. Graphical abstract Unlabelled Image Highlights • Terbuthylazine (TBA) toxicity to duckweed was assessed. • TBA severely affected duckweed especially at the higher concentrations. • The effects of a biostimulant and a safener on duckweed were investigated. • Biostimulant and safener reduced TBA toxicity to the species. • Biostimulated and safened plants adsorbed higher amounts of TBA from polluted water. [ABSTRACT FROM AUTHOR]

Terbuthylazine (TBA) is an emerging environmental contaminant that poses moderate to high risk to non-target organisms. In this study, a newly TBA-degrading strain, Agrobacterium rhizogenes AT13, was isolated. This bacterium degraded 98.7% of TBA (100 mg/L) within 39 h. Based on the six detected metabolites, three novel pathways of strain AT13, including dealkylation, deamination–hydroxylation, and ring-opening reactions, were proposed. The risk assessment demonstrated that most degradation products might be substantially less harmful than TBA. Whole-genome sequencing and RT-qPCR analysis revealed that ttzA , which encodes S-adenosylhomocysteine deaminase (TtzA), is closely related to TBA degradation in AT13. Recombinant TtzA showed 75.3% degradation of 50 mg/L of TBA within 13 h and presented a K m value of 0.299 mmol/L and a V max value of 0.041 mmol/L/min. The molecular docking results indicated that the binding energy of TtzA to TBA was −32.9 kcal/mol and TtzA residue ASP161 formed two hydrogen bonds with TBA at distances of 2.23 and 1.80 Å. Moreover, AT13 efficiently degraded TBA in water and soil. Overall, this study provides a foundation for the characterization and mechanism of TBA biodegradation and may enhance our understanding of the TBA biodegradation by microbes. [Display omitted] • A newly terbuthylazine-degrading strain AT13 was charactered. • Six degradation products were identified and three novel pathways were proposed. • The key gene ttzA was verified to be responsible for TBA biodegradation. • Strain AT13 efficiently degraded TBA in water and soil. [ABSTRACT FROM AUTHOR]