Pesticides EEE201 Handout PDF

EEE201 Biogeochemische Kreisläufe und globale Umweltveränderungen Pesticides 1) Description and environmental fate Stefanie Lutz , Gilda Dell’Ambrogio, Marcel van der Heijden University of Zurich and Agroscope 22.1...

EEE201 Biogeochemische Kreisläufe und globale Umweltveränderungen Pesticides 1) Description and environmental fate Stefanie Lutz , Gilda Dell’Ambrogio, Marcel van der Heijden University of Zurich and Agroscope 22.11.2024 Why pesticides? Growing world population Pests pose a thread to food security Pests cause huge economic losses Source: https://www.fao.org/coag/en/ Source: https://www.fao.org/plant-production-protection/about/en 2  Whatare What arepesticides? pesticides Latin: pestis (plague) and caedere (kill) Pesticides: Any substance or mixture of substances made up of chemical or biological ingredients and intended to repel, destroy or control pests, or to regulate plant growth. “Pesticide means any substance or mixture of substances intended for preventing, destroying or controlling any pest, including vectors of human or animal disease, unwanted species of plants or animals causing harm during or otherwise interfering with the production, processing, storage, transport or marketing of food, agricultural commodities, wood and wood products or animal feedstuffs, or substances which may be administered to animals for the control of insects, arachnids or other pests in or on their bodies. The term includes substances intended for use as a plant growth regulator, defoliant, desiccant or agent for thinning fruit or preventing the premature fall of fruit, and substances applied to crops either before or after harvest to protect the commodity from deterioration during storage and transport.” Source: International Code of Conduct on the Distribution and Use of Pesticides". Food and Agriculture Organization of the United Nations. 2002 3  Whatare What arepesticides? pesticides Latin: pestis (plague) and caedere (kill) Pesticides: Any substance or mixture of substances made up of chemical or biological ingredients and intended to repel, destroy or control pests, or to regulate plant growth Mostly synthetic pesticides (organic and inorganic), some natural pesticides (e.g. plant extracts) organic inorganic natural (e.g. glyphosate) (e.g. copper) (e.g. neem oil) 4 What are pesticides? Latin: pestis (plague) and caedere (kill) Pesticides: Any substance or mixture of substances made up of chemical or biological ingredients and intended to repel, destroy or control pests, or to regulate plant growth Mostly synthetic pesticides (organic and inorganic), some natural pesticides (e.g. plant extracts) Contain active ingredients and inert ingredients Pest control Surfactants (improve plant tissue penetration) Solvents (improve applicability) Adjuvants (improve adhesion and adsorption by plants) Preservatives (improve shelf life) Anti-foaming agents (prevent foaming during mixing or spraying) 5 What are pesticides? Latin: pestis (plague) and caedere (kill) Pesticides: Any substance or mixture of substances made up of chemical or biological ingredients and intended to repel, destroy or control pests, or to regulate plant growth Mostly synthetic pesticides (organic and inorganic), some natural pesticides (e.g. plant extracts) Contain active ingredients and inert ingredients Classification: - Plant protection prodcuts (protect plants) - Biocides (protect humans and animals) 6 What are pesticides? Latin: pestis (plague) and caedere (kill) Pesticides: Any substance or mixture of substances made up of chemical or biological ingredients and intended to repel, destroy or control pests, or to regulate plant growth Mostly synthetic pesticides (organic and inorganic), some natural pesticides (e.g. plant extracts) Contain active ingredients and inert ingredients Classification: - Mode of application - Target species - Selectivity - Chemical composition 7 Classification – Mode of application Most active ingredients in formulations are mixed with additives to modify their properties and behaviour to make them more suitable for use, e.g. to dissolve insoluble compounds so that they can be sprayed. Mode of application depends on target pest: Dry form (mixed with solid material, e.g. clay): − Dust − Granules − Seed coating https://www.seedpoly.com/ Liquid form (suspended, dissolved in water) − Aqueous concentrate − Wettable powder − Emulsifiable concentrate Others: − Fumigation (gaseous form) https://cleanindiajournal.com/ 8 Classification – Target species Herbicides Insecticides Fungicides Acaricides/miticides Nematicides Molluscicides Rodenticides Avicides https://www.biorender.com/ 9  Pesticide selectivity Classification – Selectivity Herbicides Herbicides Broad-spectrum: all annual and perennial plants kills a wide range of organisms Selective: creeping thistle and annual kills only organisms in the target group dicotyledonous weeds 10 Classification – Chemical composition Organochlorines Organophosphates Carbamates Pyrethroids Neonicotinoid Triazines Triazoles 11 Classification – Organochlorine insecticides Mode of Action Five or more chlorine atoms - Sodium channel modulators, disruptors of nervous system → Convulsion and paralysis Environmental behavior - High chemical stability - Little soluble in water and highly lipohilic 1,1,1-trichloro-2,2-bis (p-chlorophenyl)ethane (DDT) → Highly persistent and high tendency for bioaccumulation Toxicity - Highly toxic for birds and mammals aldrin dieldrin γ-BHC (lindane) (carcinogenity and genetic damage) 12 Classification – Organochlorine insecticides History: - First synthesised during WWI - DDT great success because of its broad-spectrum activity, https://www.panna.org/ persistence, insolubility, low cost and ease of use - Widely used for spraying crops, but also, for example, to protect Allied troops from insect-borne diseases such as malaria in the South Pacific islands - Followed by several others used intensively in agriculture https://news.mongabay.com/ ("Green Revolution"), crop yields increased dramatically - Publication of "Silent Spring“ in 1958: first evidence and awareness of their toxicity, persistence and bioaccumulation potential - Most banned in 2001 under the Stockholm Convention (some exceptional uses still allowed) https://www.pops.int/ - Still found in the environment 13 Classification – Organophosphate insecticides Mode of action Phosphate groups with - Acetylcholinesterase inhibitors R1 and R2 usually methyl or ethyl groups - Failure of nervous impulses and rapid twitching of voluntary muscles → Paralysis and death Environmental behaviour - Wide range of different properties, but generally less persistent than organochlorines (especially the newest ones) 14 Classification – Organophosphate insecticides Toxicity Phosphate groups with - Wide range of different toxicities, not just specific to R1 and R2 usually insects methyl or ethyl groups - Can affect the nervous system of other non-target organisms (neuroteratogenic and genotoxic) → Can be highly toxic to non-target invertebrates, arthropods, aquatic organisms, and humans (Muhammad et al. 2017, Perry et al. 2020, Sun et al. 2016) Widely used after prohibition of organochlorine Development of insect resistance with time 15 Classification – Carbamate insecticides, molluscicides and nematicides Mode of action - Cholinesterase inhibitors - Failure of nervous impulses and rapid twitching of voluntary muscles → Paralysis and death Environmental behaviour - Moderate to high solubility in water, relatively rapid degradation and low lipohilicity → Low potential for persistence in soil and for bioaccumulation Toxicity - Expected to be less toxic as species specific and reversible Used primarily to control insects that have developed resistance to organophosphates Development of insect resistance over time 16 Classification – Pyrethroid insecticides Mode of action - Affecting the sodium and chloride channels - Neurotoxin and endocrine disruptors → Paralysis and death Synthetic analogues of naturally occurring pyrethrins (plant extract from Chrysanthemum cinerariaefolium) Environmental behaviour - More stable than pyrethrum and lipohile - Rapid biodegradation → Relatively persistent in soils and sediments Toxicity - Expected to have low toxicity to non-target species - Toxic to aquatic species (Antwi and Reddy, 2015) and mammals (Gajendiran and Abraham, 2018) at high exposure doses 17 Classification – Neonicotinoid insecticides Mode of action - nAChRs (nicotinic acetylcholine receptor) antagonists - Disruption of the nervous system → Paralysis and death Synthetic analogues of the naturally occurring nicotine but more stable, selective and effective Great success because expected to be low toxicity to non- target species and moderately persistent in the environment Simon-Delso et al. 2014 18 Classification – Neonicotinoid insecticides Environmental behavior - Moderate to high solubility and relatively high chemical stability → High tendency to leach but also to accumulate in soils Evidence of widespread distribution and accumulation in water, soil and sediments, and toxic effects on pollinators, birds and important soil invertebrates (EASAC 2015) Banned in 2018 (some exceptions still allowed, e.g. emergency use) Simon-Delso et al. 2014 19 Classification – Triazine herbicides Classification Mode of Action Aromatic heterocyclic - Photosynthesis inhibitors herbicides with three → Interfere with vital physiological processes that contribute to nitrogens and three carbons plant growth Very effective in controlling weeds resistant to other herbicides Environmental behaviour - Solubility and other properties vary between groups, but generally relatively stable → Very persistent, especially in soil Atrazine Simazine Toxicity - Expected to have low toxicity to humans - Evidence of toxicity of some compounds to humans, non- target plants, and animals (Breckenridge et al., 2010; Dikshith, 2016; Ghirardelli et al., 2021; Velisek et al., 2013) Terbuthylazine 20 Classification – Triazole fungicides Mode of action - Inhibitors of ergosterol biosynthesis Azole functional group → Convulsion and paralysis Most widely used as a broad-spectrum fungicide Environmental behaviour - Very stable and persistent in soil Difenoconazole → High potential to accumulate in soil Toxicity - May cause carcinogenicity, reproductive toxicity, hepatotoxicity and potential endocrine disruption (Lv et al. 2017, Hester et al., Tebuconazole 2012; Juberg et al., 2006; Peffer et al., 2007) → Very toxic to mammals 21 History Pre-industrial ages: mostly metals and plant extracts Some examples 1000 b.C. Sulfur (fumigation agent) I century Arsenic (insecticide) https://wildfoodism.com/ XVI century Rotenone (insecticide) XVII century Nicotine (insecticide) Pyrethrum (insecticide) XIX century Copper (fungicide) https://www.gardeningknowhow.com/ → Mostly abandoned because of their toxicity and ineffectiveness 22 History Industrial revolution: development of organic synthesis in chemistry Ex. insecticides 1930 In parallel with the extensive use of synthetic Organochlorine insecticides, most target insects have gradually 1940 Organophosphorous developed resistance to the pesticides used. 1950 Carbamates By the 1980s, very few target insect populations were 1960 Pyrethroids completely susceptible to currently used insecticides. 1970 Phenylpyrazoles → Constant need to find new replacements 1980 Neonicotinoids 1990 23 Global pesticide use Global increase in pesticide use Herbicides most used category Americas are today the biggest users FAO. 2024. FAOSTAT: Pesticides Use. [Accessed July 2024]. 24 http://www.fao.org/faostat/en/#data/RP Licence: CC-BY-4.0. Global pesticide use Large disparities between countries FAO. 2024. FAOSTAT: Pesticides Use. [Accessed July 2024]. http://www.fao.org/faostat/en/#data/RP Licence: CC-BY-4.0. 25 Pesticide use in Switzerland Large disparities between countries FAO. 2024. FAOSTAT: Pesticides Use. [Accessed July 2024]. http://www.fao.org/faostat/en/#data/RP Licence: CC-BY-4.0. 26 Pesticide use in Switzerland per area total use Herbicides Fungicides Insecticides Molluscicides Growth regulators Others Switzerland: ca. 1900 tonnes/year https://2016.agrarbericht.ch/ 27  Main sources and pathways into the environment Main use Source Path into environment Plant Crop Agriculture, Effluents, protection protection, Urban areas diffuse products gardening entries Biocides Wood Urban areas, Effluents, preservatives, households, diffuse animal and industry entries, human disposal sites protection, desinfestation, paints Ochoa and Maestroni 2018 28 Environmental fate Transfer and distribution of a compound between different compartments depends on the physico-chemical properties of the compound and of the environment Usually in equilibrium between different phases (partitioning) Key physico-chemical properties: - Mobility air - Persistence - Bioaccumulation water biota soil sediment 29  Environmentl Fate Environmental fate - Mobility For a substance «𝑖»: Adsorption 𝐶𝑖,𝑜𝑐 𝐾𝑜𝑐 = Many non-ionic pesticides are hydrophobic and have a 𝐶𝑖,𝑤 𝑘𝑔 greater affinity to bind to organic carbon and clays 𝑐𝑖,𝑜𝑐 = concentration sorbed to organic carbon (𝑘𝑔) 𝑘𝑔 𝑐𝑖,𝑤 = concentration in acqueous phase ( ) (greater surface area). 𝑙 Log Koc Classification 𝑙 5 Immobile - Lower mobility https://www.fao.org Higher persistence of pesticides in soils with high organic matter/clay content Lousada et al., 2023 30 Environmental fate - Mobility Solubility 𝑚𝑔 Water solubility (S)[ ] 𝑙 - Maximum amount that can be dissolved in water - Potential for leaching/run-off into water bodies For most non-ionic pesticides Koc and solubility are negatively correlated Arias-Estévez et al. 2008 Water solubility Classification ~1/3 of pesticides are acidic or basic and do not (mg/L) follow the same regression. Their behaviour 100 Highly soluble 31 https://www.fao.org  Environmental Fate Environmental fate - Mobility Volatilisation For a substance «𝑖»: Vapour pressure (Pa) [𝑎𝑡𝑚] 𝑝𝑖 𝐾𝐻 = - Pressure of a gas in equilibrium with the liquid/solid 𝐶𝑖,𝑤 - Potential for volatilisation 𝑝𝑖 = partial pressure in gaseous phase (𝑎𝑡𝑚) - High vapour pressur = high tendency to volatilise 𝑚𝑜𝑙 𝑐𝑖,𝑤 = concentration in aqueous phase ( 𝑚3 ) 𝑎𝑡𝑚×𝑚3 𝐾𝑎𝑤 = 𝐾𝐻 × 𝑅𝑇 −1 Henry’s constant (KH) [ ] 𝑎𝑡𝑚×𝑚3 𝑚𝑜𝑙 𝑅 = ideal gas constant (8.2 × 10−5 𝑚𝑜𝑙×𝐾 ) - Potential for volatilisation from water to gas phase 𝑇 = temperature (𝐾) - Can be estimated from vapour pressure and KH Classification 𝑎𝑡𝑚×𝑚3 solubility (Pa/S) ( 𝑚𝑜𝑙 ) Less volatile than < 3 × 10−7 water Air-water partition coefficient (Kaw) [𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑙𝑒𝑠𝑠] 3 × 10−7 to 10−5 Semi-volatile - Based on KH and temperature 10−5 to 10−3 Significantly volatile > 10−3 32Volatile Environmental fate - Degradation Degradation VS persistence 100% Chemical concentration − E.g. hydrolysis (dissociation in water) − Frequent especially for soluble compounds 50% − pH dependent Physical − E.g. photolysis (UV exposure) DT50 time − Rupture of chemical bonds − Photon absorption, excitement and subsequent release of electrons Biological − Breakdown by microorganisms − Depends on native microbial communities, and environmental conditions (habitat for microbes) Half life time (t½) (DT50): − Time needed to degrade half of the compound 33 Environmental fate - Degradation Degradation is highly dependent on environmental conditions − e.g., different degradation rates in different soils for the same compound (neonicotinoids) Some metabolites may have different properties to their parent compound and Goulson 2013 Solubility in therefore behave differently in the Compound water (mg l⁻¹) environment. Atrazine − E.g. Atrazine vs DEA 35 Desethylatrazine (DEA) 2700 PPDB 2024 34  Environmental Fate Environmental fate - Bioaccumulation Hydrophobicity For a substance «𝑖»: 𝐶𝑖,𝑜 Octanol-water partition coefficient (Kow) 𝐾𝑜𝑤 = [𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑙𝑒𝑠𝑠] 𝐶𝑖,𝑤 − Ratio in octanol (non-polar – fat-like liquid) 𝐶𝑖,𝑐𝑜𝑛𝑠. − Potential to accumulate in biological tissues 𝐵𝐶𝐹 = 𝐶𝑖,𝑤 Bioaccumulation/biomagnification factors (BCF/BMF) [𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑙𝑒𝑠𝑠] 𝐶𝑖,𝑝𝑟𝑒𝑑. 𝐵𝑀𝐹 = − Ratio in organism to water (BCF) 𝐶𝑖,𝑝𝑟𝑒𝑦 − Ratio in fish to diet (BMF) 𝑐𝑖,𝑜 = concentration in octanol ( 𝑚𝑔 𝑙 ) 𝑚𝑔 𝑐𝑖,𝑤 = concentration in water ( 𝑙 ) 𝑚𝑔 𝑐𝑖,𝑐𝑜𝑛𝑠. = concentration in the consumer ( 𝑘𝑔 ) Log Kow ≥ 3; BCF ≥ 100; BMF > 1 often indicate a 𝑐𝑖,𝑝𝑟𝑒𝑑. = concentration in the predator ( 𝑘𝑔 ) 𝑚𝑔 𝑚𝑔 high potential for bioaccumulation (e.g., EC TGD 𝑐𝑖,𝑝𝑟𝑒𝑦 = concentration in the prey ( 𝑘𝑔 ) 𝑚𝑔 𝑐𝑖,𝑤 = concentration in water ( ) 2003, ECHA 2017) 𝑙 35 Evironmental distribution – Assessment of pesticide presence Measured Environmental Concentrations (MEC) Collection of environmental samples (water, soil, sediments...) Extraction (e.g. using a solvent) Targeted (e.g. quantitative) vs. non-targeted (e.g. qualitative, screening) approaches Analysis using e.g. gas chromatography, liquid chromatography, mass spectrometry Zhang et a., 2020 36 Evironmental distribution – Assessment of pesticide presence Measured Environmental Concentrations (MEC) PSM150+ method: - 146 pesticides and transformation products - High sensitivity (up to 0.05 µg/kg) 37 Evironmental distribution – Assessment of pesticide presence Predicted Environmental Concentrations (MEC Input identification (e.g. agricultural application) Identification of variables (e.g. substance properties, crop type, climate, landscape) Modelling according to different predefined scenarios e.g. initial concentration immediately after application (peak), background concentration after n applications (plateau) Models provided by the European Food and Safety Authority (EFSA) for pesticide risk assessment 38 Evironmental distribution - Water In Europe, several monitoring programmes have been established to measure the levels of pesticides in water. This is mainly due to the Water Framework Directive (WFD), which sets environmental quality standards Water Framework Directive - based on (eco-)toxicological data for several priority European Commission substances. National programmes to monitor contaminants in water (e.g. NAWA in CH). 39 Evironmental distribution - Water The most common pesticides found in European waters are herbicides, followed by fungicides and insecticides (Moschet et al., 2014; Papadakis et al., 2015; Schreiner et al., 2016; Casado et al., 2019). Some are no longer authorised (e.g. 2,4-D, atrazine, some organochlorines...) Most commonly detected pesticides in 10 European (and 1 Argentinian) regions with high agricultural activity from water bodies of distinct typologies. Navarro et al. 2024 40 Evironmental distribution - Soil Unlike water, there is still no legal basis for soil monitoring in Europe. Although some work is underway: A proposal for a European soil monitoring Soil health - European Commission law was recently adopted. In Switzerland, the Federal Action Plan on Plant Protection Products aims to develop a monitoring programme for pesticides in agricultural soils. So far, the information available comes mainly from independent studies. 41 Evironmental distribution – Soil monitoring studies in Europe 42 Evironmental distribution – Soil monitoring conclusions Most environmental samples analysed contain residues of more than one pesticide Most frequently detected in soil: − Herbicides (Glyphosate, AMPA, Terbutylazine, Diflufenican, Chlorotoluron, Isoproturon, Linuron, Diuron, Tebutam, Atrazine, Alachlor) − Fungicides (Boscalid, Epoxiconazole, Tebuconazole, Pendimethalin, Carbendazim) − Insecticides (Bifenthrin, Chlorpyrifos) − Transformation products … Several pesticides detected are either banned at the time of the study (e.g. atrazine, alachlor) or not applied in the sampled area (e.g. chlorpyrifos) → Many pesticides can persist for long periods of time (up to decades) after they have ceased to be used and/or can contaminate adjacent areas, e.g. by spray drift from adjacent treated fields. 43 Evironmental distribution - Soil monitoring studies in Switzerland 44 Evironmental distribution - Soil monitoring studies in Switzerland The number of pesticide residues was two times higher in conventional compared to organic fields. Decrease of the number of pesticide residues in soils with the duration of organic management. Even after 20 years of organic agriculture, up to 16 different pesticide residues were present. 45 Current reserach in Swiss vineyards 62 vineyards 3 regions Management conventional organic https://2016.agrarbericht.ch/ Current reserach in Swiss vineyards Synthetic pesticides: Copper: Up to 60 per vineyard Overall all Conventional > organic (13x) Conventional = Organic Barmettler et al. Submitted. 47 Current research on Swiss farms www.pestired.ch PestiRed: Reduction of pesticides through innovation Collaborative project between Agroscope, farmers and cantonal offices for agriculture Double plots per farm Conventional Reduction of pesticides by 75% Innovative Maximal yield loss of 10 % Monitoring of agronomic, economic and ecologic aspects Impact on soil fertility PestiRed: Innover pour réduire les phytos / Innovation zur Reduktion von Pflanzenschutzmitteln - YouTube 48 Literature Antwi, F.B., Reddy, G.V.P., 2015. Toxicological effects of pyrethroids on non-target aquatic insects. Environ. Toxicol. 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