Impacts of Agrochemicals: Environmental Fate, Ecotoxicology, Risk Assessment, and Remediation

A special issue of Toxics (ISSN 2305-6304). This special issue belongs to the section "Agrochemicals and Food Toxicology".

Deadline for manuscript submissions: closed (31 January 2024) | Viewed by 11219

Special Issue Editors


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Guest Editor
Agro-Environmental Research Centre, Institute of Environmental Sciences, Hungarian University of Agriculture and Life Sciences, Budapest, Hungary
Interests: agricultural ecotoxicology; environmental safety; organic microcontaminants (pesticide residues and mycotoxins); environmental analysis; immunoassays

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Guest Editor
Agro-Environmental Research Centre, Institute of Environmental Sciences, Hungarian University of Agriculture and Life Sciences, Budapest, Hungary
Interests: ecotoxicology; environmental analysis; environmental toxicology; pesticide monitoring; experimental toxicology; statistics

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Guest Editor
Agro-Environmental Research Centre, Institute of Environmental Sciences, Hungarian University of Agriculture and Life Sciences, Budapest, Hungary
Interests: analytical chemistry; GC-MS; LC-MS; mycotoxin; pesticides; environmental chemistry; monitoring environmental fate

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Guest Editor
Agro-Environmental Research Centre, Institute of Environmental Sciences, Hungarian University of Agriculture and Life Sciences, Herman O. u. 15, H-1022 Budapest, Hungary
Interests: environmental and food safety; organic microcontaminants (pesticide residues and mycotoxins); environmental analysis; agricultural ecotoxicology; genetic safety
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Special Issue Information

Dear Colleagues,

The widespread application of plant protection products worldwide is releasing various agrochemicals into the environment. In many countries, various persistent and bio-accumulative active ingredients have been banned; however, due to their physico-chemical properties, they are detectable in our environment. Global warming is shifting climatic zones, thus changing the distribution of pests and diseases worldwide. As a result, in a certain climatic zone, new species can occur. A lot of new substances have been developed, but, today, we still do not have enough knowledge about their possible risks and adverse effects on the environment and humans.

Overall, intensive agrochemicals application results in several negative effects in the environment that cannot be ignored. Agrochemicals can enter the soil via spray drift during foliage treatment, wash-off from treated foliage, release from granulates, or from treated seeds in soil. They can enter water via drift during spraying, by runoff from treated areas, or leaching through the soil. In some cases, agrochemicals can be directly applied onto water surfaces, e.g., for the controlling mosquitoes. Water contamination mainly depends on the nature of chemicals (water solubility and hydrophobicity), soil properties, weather conditions, landscapes, and the distance from an application site to a water source. Rapid transport to groundwater may be caused by heavy rainfall shortly after application of the pesticide to wet soils.

Our Special Issue of Toxics aims to summarise the importance of ecotoxicological and environmental analysis studies providing appropriate data for a complete risk assessment of agrochemicals, including (but not limited to):

- Monitoring the occurrence of agrochemicals and their decomposition products in different environmental matrices (soil, surface water, and ground water) and assessing the potential effects of climate change trends on pesticide application;

- Novel or inventive methods of chemical analysis including chromatography, immunoassay, molecular biology, sensorics, and other means, including novel sample preparation methods;

- Methods of toxicological or ecotoxicological assessment, including cytotoxicity, genotoxicity, mutagenicity, and endocrine disruption, combined with chemical analysis;

- Ecotoxicological assessment of agrochemicals and their compounds (active ingredient, co-formulants, etc.) in soil and aquatic ecosystems through food chains;

- Assessment of remediation possibilities;

- Risk assessment issues of pesticides.

Dr. Eszter Takács
Dr. Szandra Klátyik
Dr. Mária Mörtl 
Prof. Dr. András Székács
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • monitoring
  • agrochemicals analysis
  • environmental matrices
  • instrumental analysis
  • immunoanalysis
  • sensorics
  • ecotoxicological assessment
  • cytotoxicity
  • genotoxicity
  • mutagenicity
  • endocrine disruption
  • remediation
  • risk assessment
  • mycotoxin

Published Papers (8 papers)

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Research

22 pages, 1472 KiB  
Article
Hormesis, the Individual and Combined Phytotoxicity of the Components of Glyphosate-Based Formulations on Algal Growth and Photosynthetic Activity
by Szandra Klátyik, Eszter Takács, Attila Barócsi, Sándor Lenk, László Kocsányi, Béla Darvas and András Székács
Toxics 2024, 12(4), 257; https://doi.org/10.3390/toxics12040257 - 30 Mar 2024
Viewed by 456
Abstract
The occurrence of the market-leading glyphosate active ingredient in surface waters is a globally observed phenomenon. Although co-formulants in pesticide formulations were considered inactive components from the aspects of the required main biological effect of the pesticide, several studies have proven the high [...] Read more.
The occurrence of the market-leading glyphosate active ingredient in surface waters is a globally observed phenomenon. Although co-formulants in pesticide formulations were considered inactive components from the aspects of the required main biological effect of the pesticide, several studies have proven the high individual toxicity of formulating agents, as well as the enhanced combined toxicity of the active ingredients and other components. Since the majority of active ingredients are present in the form of chemical mixtures in our environment, the possible combined toxicity between active ingredients and co-formulants is particularly important. To assess the individual and combined phytotoxicity of the components, glyphosate was tested in the form of pure active ingredient (glyphosate isopropylammonium salt) and herbicide formulations (Roundup Classic and Medallon Premium) formulated with a mixture of polyethoxylated tallow amines (POEA) or alkyl polyglucosides (APG), respectively. The order of acute toxicity was as follows for Roundup Classic: glyphosate < herbicide formulation < POEA. However, the following order was demonstrated for Medallon Premium: herbicide formulation < glyphosate < APG. Increased photosynthetic activity was detected after the exposure to the formulation (1.5–5.8 mg glyphosate/L and 0.5–2.2 mg POEA/L) and its components individually (glyphosate: 13–27.2 mg/L, POEA: 0.6–4.8 mg/L), which indicates hormetic effects. However, decreased photosynthetic activity was detected at higher concentrations of POEA (19.2 mg/L) and Roundup Classic (11.6–50.6 mg glyphosate/L). Differences were demonstrated in the sensitivity of the selected algae species and, in addition to the individual and combined toxicity of the components presented in the glyphosate-based herbicides. Both of the observed inhibitory and stimulating effects can adversely affect the aquatic ecosystems and water quality of surface waters. Full article
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17 pages, 632 KiB  
Article
Ecotoxicological Evaluation of Safener and Antimicrobial Additives in Isoxaflutole-Based Herbicide Formulations
by Eszter Takács, Diána Lázár, Augustine Siakwa, Szandra Klátyik, Mária Mörtl, László Kocsányi, Attila Barócsi, Sándor Lenk, Edina Lengyel and András Székács
Toxics 2024, 12(4), 238; https://doi.org/10.3390/toxics12040238 - 24 Mar 2024
Viewed by 650
Abstract
The environmental load by isoxaflutole and its formulated herbicide products has increasingly become apparent because, after the ban of atrazine, isoxaflutole has become its replacement active ingredient (a.i.). Obtaining information regarding the fate of this a.i. in environmental matrices and its ecotoxicological effects [...] Read more.
The environmental load by isoxaflutole and its formulated herbicide products has increasingly become apparent because, after the ban of atrazine, isoxaflutole has become its replacement active ingredient (a.i.). Obtaining information regarding the fate of this a.i. in environmental matrices and its ecotoxicological effects on aquatic organisms is essential for the risk assessment of the herbicide. In this study, the effects of Merlin Flexx- and Merlin WG75 formulated isoxaflutole-based herbicide products and two selected additives (cyprosulfamide safener and 1,2-benzisothiazol-3(2H)-one antimicrobial agent) were investigated on Raphidocelis subcapitata in growth inhibition assays. In ecotoxicological tests, two conventional (optical density and chlorophyll-a content) and two induced fluorescence-based (Fv*/Fp: efficiency of the photosystem PSII and Rfd* changes in the observed ratio of fluorescence decrease) endpoints were determined by UV-spectrophotometer and by our FluoroMeter Module, respectively. Furthermore, dissipation of isoxaflutole alone and in its formulated products was examined by an HPLC-UV method. In ecotoxicological assays, the fluorescence-based Rfd* was observed as the most sensitive endpoint. In this study, the effects of the safener cyprosulfamide and the antimicrobial agent 1,2-benzisothiazol-3(2H)-one on R. subcapitata is firstly reported. The results indicated that the isoxaflutole-equivalent toxicity of the mixture of the isoxaflutole–safener–antimicrobial agent triggered lower toxicity (EC50 = 2.81 ± 0.22 mg/L) compared to the individual effect of the a.i. (EC50 = 0.02 ± 0.00 mg/L). The Merlin Flexx formulation (EC50 = 27.04 ± 1.41 mg/L) was found to be approximately 50-fold less toxic than Merlin WG75, which can be explained by the different chemical characteristics and quantity of additives in them. The additives influenced the dissipation of the a.i. in Z8 medium, as the DT50 value decreased by approximately 1.2- and 3.5-fold under light and dark conditions, respectively. Full article
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17 pages, 4085 KiB  
Article
Preparation and Comprehensive Evaluation of the Efficacy and Safety of Chlorantraniliprole Nanosuspension
by Xiquan Ding, Liang Guo, Qian Du, Tingyu Wang, Zhanghua Zeng, Yan Wang, Haixin Cui, Fei Gao and Bo Cui
Toxics 2024, 12(1), 78; https://doi.org/10.3390/toxics12010078 - 16 Jan 2024
Cited by 1 | Viewed by 1005
Abstract
Chlorantraniliprole is a broad-spectrum insecticide that has been widely used to control pests in rice fields. Limited by its low solubility in both water and organic solvents, the development of highly efficient and environmentally friendly chlorantraniliprole formulations remains challenging. In this study, a [...] Read more.
Chlorantraniliprole is a broad-spectrum insecticide that has been widely used to control pests in rice fields. Limited by its low solubility in both water and organic solvents, the development of highly efficient and environmentally friendly chlorantraniliprole formulations remains challenging. In this study, a low-cost and scalable wet media milling technique was successfully employed to prepare a chlorantraniliprole nanosuspension. The average particle size of the extremely stable nanosuspension was 56 nm. Compared to a commercial suspension concentrate (SC), the nanosuspension exhibited superior dispersibility, as well as superior foliar wetting and retention performances, which further enhanced its bioavailability against Cnaphalocrocis medinalis. The nanosuspension dosage could be reduced by about 40% while maintaining a comparable efficacy to that of the SC. In addition, the chlorantraniliprole nanosuspension showed lower residual properties, a lower toxicity to non-target zebrafish, and a smaller effect on rice quality, which is conducive to improving food safety and the ecological safety of pesticide formulations. In this work, a novel pesticide-reduction strategy is proposed, and theoretical and data-based support is provided for the efficient and safe application of nanopesticides. Full article
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13 pages, 5299 KiB  
Article
Ultrastructural Changes in the Midgut of Brazilian Native Stingless Bee Melipona scutellaris Exposed to Fungicide Pyraclostrobin
by Caio E. C. Domingues, Lais V. B. Inoue, Aleš Gregorc, Leticia S. Ansaloni, Osmar Malaspina and Elaine C. Mathias da Silva
Toxics 2023, 11(12), 1028; https://doi.org/10.3390/toxics11121028 - 18 Dec 2023
Viewed by 1085
Abstract
Melipona scutellaris is a Brazilian stingless bee that is important for pollinating wild flora and agriculture crops. Fungicides have been widely used in agriculture, and floral residues can affect forager bees. The goal of our study was to evaluate the effects of sublethal [...] Read more.
Melipona scutellaris is a Brazilian stingless bee that is important for pollinating wild flora and agriculture crops. Fungicides have been widely used in agriculture, and floral residues can affect forager bees. The goal of our study was to evaluate the effects of sublethal concentrations of pyraclostrobin on the midgut ultrastructure of M. scutellaris forager workers. The bees were collected from three non-parental colonies and kept under laboratory conditions. The bees were orally exposed continuously for five days to pyraclostrobin in syrup at concentrations of 0.125 ng a.i./µL (FG1) and 0.005 ng a.i./µL (FG2). The control bees (CTL) were fed a no-fungicide sucrose solution, and the acetone solvent control bees (CAC) received a sucrose solution containing acetone. At the end of the exposure, the midguts were sampled, fixed in Karnovsky solution, and routinely processed for transmission electron microscopy. Ultrastructural analysis demonstrated that both the fungicide concentrations altered the midgut, such as cytoplasmic vacuolization (more intense in FG1), the presence of an atypical nuclear morphology, and slightly dilated mitochondrial cristae in the bees from the FG1 and FG2 groups (both more intense in FG1). Additionally, there was an alteration in the ultrastructure of the spherocrystals (FG1), which could be the result of cellular metabolism impairment and the excretion of toxic metabolites in the digestive cells as a response to fungicide exposure. The results indicate that ingested pyraclostrobin induced cytotoxic effects in the midgut of native stingless bees. These cellular ultrastructural responses of the midgut are a prelude to a reduced survival rate, as observed in previous studies. Full article
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18 pages, 7646 KiB  
Article
Toxic Effects of Methylene Blue on the Growth, Reproduction and Physiology of Daphnia magna
by Shuhui Li, Yixin Cui, Min Wen and Gaohua Ji
Toxics 2023, 11(7), 594; https://doi.org/10.3390/toxics11070594 - 07 Jul 2023
Cited by 5 | Viewed by 2428
Abstract
Methylene blue (MB) is a disinfectant used in aquaculture to prevent and treat fish diseases. However, the release of MB can pose a risk to the receiving water bodies. Zooplankton are the most sensitive organisms among aquatic life. Hence, this study examined the [...] Read more.
Methylene blue (MB) is a disinfectant used in aquaculture to prevent and treat fish diseases. However, the release of MB can pose a risk to the receiving water bodies. Zooplankton are the most sensitive organisms among aquatic life. Hence, this study examined the acute and chronic toxic effects of MB on zooplankton using Daphnia magna (D. magna) as a test organism to provide basic data for risk assessment. The results show that 48 h-EC50 and 24 h-LC50 were 61.5 ± 2.3 and 149.0 ± 2.2 μg/L, respectively. Chronic exposure to MB affected the heart rate, beat frequency of the thoracic limbs, and reproductive ability of D. magna at environmental concentrations higher than 4.7 μg/L. The cumulative molts, time to production of the first brood, and total number of living offspring were affected at different MB concentrations, while “abortions” were observed in high-exposure groups. The activity of superoxide dismutase was increased, while glutathione S-transferase activity was stimulated at low concentrations and inhibited at high concentrations. In addition, the malondialdehyde content increased with increasing concentrations of MB. Our findings demonstrate the impact of MB on the reproduction and growth of freshwater species, as well as their physiological responses. These results have implications for establishing guidelines on the use of MB in aquaculture and setting discharge standards. Full article
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13 pages, 2985 KiB  
Article
Toxicity of Difenoconazole and Atrazine and Their Photodegradation Products on Aquatic Biota: Environmental Implications in Countries Lacking Good Agricultural Practices
by Julia Mendieta Herrera, Carlos Iñiguez Armijos, Daniel Rosado Alcarria and Silvio Aguilar Ramírez
Toxics 2023, 11(3), 213; https://doi.org/10.3390/toxics11030213 - 24 Feb 2023
Cited by 1 | Viewed by 1400
Abstract
Agriculture is fundamental for human development, but it may also have a range of unwanted effects on ecosystems when pesticides inadvertently enter the environment. We determined the toxicity of difenoconazole and atrazine, as well as their photodegradation products, on the bioindicators Lemna minor [...] Read more.
Agriculture is fundamental for human development, but it may also have a range of unwanted effects on ecosystems when pesticides inadvertently enter the environment. We determined the toxicity of difenoconazole and atrazine, as well as their photodegradation products, on the bioindicators Lemna minor and Daphnia magna. For L. minor, we assessed the number of leaves, biomass, and chlorophyll content exposed to different concentrations of difenoconazole (0–8 mg/L) and atrazine (0–3.84 mg/L). For D. magna, we assessed the mortality to difenoconazole (0–1.6 mg/L) and atrazine (0–80 mg/L). We found that the higher the concentrations of the pesticides, the higher the toxicity for both bioindicators. In L. minor, the highest toxicity for atrazine was 0.96 mg/L, whereas for difenoconazole, it was 8 mg/L. For D. magna, the 48 h LC50 for difenoconazole was 0.97 mg/L, while for atrazine, it was 86.19 mg/L. For L. minor, the toxicity of difenoconazole and atrazine was not different compared to that of their photodegradation products. In contrast, for D. magna, difenoconazole, but not atrazine, was more toxic compared to its respective photodegradation products. Pesticides are a serious threat to aquatic biota, and their photodegradation products remain toxic in the environment. Additionally, the use of bioindicators can help monitor these pollutants in aquatic ecosystems in countries where the application of pesticides is imperative for agricultural production. Full article
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26 pages, 5979 KiB  
Article
Experiments on Pilot-Scale Constructed Floating Wetlands Efficiency in Removing Agrochemicals
by George Pavlidis, Ioanna Zotou, Helen Karasali, Anna Marousopoulou, Georgios Bariamis, Ioannis Nalbantis and Vassilios A. Tsihrintzis
Toxics 2022, 10(12), 790; https://doi.org/10.3390/toxics10120790 - 15 Dec 2022
Cited by 1 | Viewed by 1553
Abstract
The efficiency of constructed floating wetlands (CFWs) in their ability to remove agrochemicals (nutrients and pesticides) is here investigated in a series of pilot-scale systems. Four experimental CFWs were designed and constructed; three of them were planted with the aquatic plant species Lemna [...] Read more.
The efficiency of constructed floating wetlands (CFWs) in their ability to remove agrochemicals (nutrients and pesticides) is here investigated in a series of pilot-scale systems. Four experimental CFWs were designed and constructed; three of them were planted with the aquatic plant species Lemna minor, Azolla pinnata and Eichhornia crassipes. The fourth did not contain any plants and was used as the control. The aim of the study was to evaluate the efficiency of CFW containing aquatic macrophytes in the reduction of pesticides and nutrients, under field conditions. The CFWs operated continuously from May 2021 to September 2021, and their removal efficiencies of nitrogen and phosphorus ions, and five commonly used pesticides were examined. The CFW systems were fed daily with agricultural wastewater which was prepared by mixing a fertilizer and predetermined doses of pesticides. The hydraulic residence time was kept at 14 days. Samples were collected on a weekly basis from both the influent and the effluent of each experimental tank, and were subsequently analyzed in the laboratory. HPLC-DAD and Ion Chromatography were implemented for sample analysis following a very simple sample preparation. Reductions for nutrient ranged from no reduction to 100% removal, whereas for pesticides these varied from no reduction to 98.8% removal, indicating that these systems can be used as efficient and low-cost pollution control technologies for agrochemical wastewater treatment. Significant reduction for certain pesticides was also observed in the algae control tank, thus, proving the efficiency of algae in organic pollution reduction, and recognizing the limitations of aquatic plant use in decontamination. Full article
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9 pages, 1250 KiB  
Article
Selected Biochemical Markers Change after Oral Administration of Pesticide Mixtures in Honey Bees
by Pawel Migdal, Agnieszka Murawska, Ewelina Berbeć, Mateusz Plotnik, Anita Skorus and Krzysztof Latarowski
Toxics 2022, 10(10), 590; https://doi.org/10.3390/toxics10100590 - 05 Oct 2022
Cited by 3 | Viewed by 1543
Abstract
The honey bee is an important pollinator. In the environment, it can be exposed to many harmful factors, such as pesticides. Nowadays, attention is paid to evaluating the potentially harmful effects of these substances. This study aimed to evaluate the effect of worst-case [...] Read more.
The honey bee is an important pollinator. In the environment, it can be exposed to many harmful factors, such as pesticides. Nowadays, attention is paid to evaluating the potentially harmful effects of these substances. This study aimed to evaluate the effect of worst-case environmental concentrations of pesticide mixtures on honey bee survival and selected physiological markers (the activity of ALT, AST, ALP, and GGTP, and the concentration of albumin, creatinine, urea, and uric acid). Pesticides of three different groups (insecticide—acetamiprid, herbicide—glyphosate, and fungicide—tebuconazole) and their mixtures were resolved in 50% (w/v) sucrose solution and given to bees ad libitum. After 24 h, hemolymph was collected. All mixtures caused higher mortality than single pesticides. Pesticides in mixtures caused disturbances in biochemical markers, and in some cases the interaction between pesticides was synergistic. The mixtures had individual effects on physiology, and the results were sensitive to changes in proportions. Full article
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