Methiocarb metabolites are systemically distributed throughout corn plants grown from coated seeds

Funder: Università degli Studi di PadovaAbstract: Systemic insecticides such as neonicotinoids are widely used in seed coating practices for pest control in many crops, e.g., corn. Their success is due to their ability to protect the whole plant, from the roots to the upper leaves, but their use at high amounts is causing possible adverse effects on non-target animals exposed to contaminated pollen, nectar, leaves, and dust emitted during sowing. In 2018, the European Union banned some neonicotinoids and fipronil as seed coating insecticides in open fields. Consequently, the methylcarbamate methiocarb and less-toxic neonicotinoids, e.g., thiacloprid, have been authorized and largely used as alternative pesticides for corn seed coating. Here, an analytical protocol based on QuEChERS extraction/purification procedure and analysis by liquid chromatography-mass spectrometry has been optimized for the identification and the quantification of methiocarb, thiamethoxam, thiacloprid, and their metabolites in guttation drops, the xylem fluid excreted at leaf margins, and in leaves of corn plants grown from coated seeds. Although methiocarb is a non-systemic pesticide, we unexpectedly found high concentrations of its metabolites in both guttations and leaves, whereas methiocarb itself was below detection limits in most of the samples. The methiocarb main metabolite, methiocarb sulfoxide, was found at a mean concentration of 0.61 ± 1.12 µg mL−1 in guttation drops and 4.4 ± 2.1 µg g−1 in leaves. Conversely, parent compounds of neonicotinoids (thiamethoxam, thiacloprid) are systemically distributed in corn seedlings. This result raises safety concerns given that methiocarb sulfoxide is more toxic than the parent compound for some non-target species

Environmental fate and exposure; neonicotinoids and fipronil

Systemic insecticides are applied to plants using a wide variety of methods, ranging from foliar sprays to seed treatments and soil drenches. Neonicotinoids and fipronil are among the most widely used pesticides in the world. Their popularity is largely due to their high toxicity to invertebrates, the ease and flexibility with which they can be applied, their long persistence, and their systemic nature, which ensures that they spread to all parts of the target crop. However, these properties also increase the probability of environmental contamination and exposure of nontarget organisms. Environmental contamination occurs via a number of routes including dust generated during drilling of dressed seeds, contamination and accumulation in arable soils and soil water, runoff into waterways, and uptake of pesticides by nontarget plants via their roots or dust deposition on leaves. Persistence in soils, waterways, and nontarget plants is variable but can be prolonged; for example, the half-lives of neonicotinoids in soils can exceed 1,000 days, so they can accumulate when used repeatedly. Similarly, they can persist inwoody plants for periods exceeding 1 year. Breakdown results in toxic metabolites, though concentrations of these in the environment are rarely measured. Overall, there is strong evidence that soils, waterways, and plants in agricultural environments and neighboring areas are contaminated with variable levels of neonicotinoids or fipronil mixtures and their metabolites (soil, parts per billion (ppb)-parts per million (ppm) range; water, parts per trillion (ppt)-ppb range; and plants, ppb-ppm range). This provides multiple routes for chronic (and acute in some cases) exposure of nontarget animals. For example, pollinators are exposed through direct contact with dust during drilling; consumption of pollen, nectar, or guttation drops from seed-treated crops, water, and consumption of contaminated pollen and nectar from wild flowers and trees growing near-treated crops. Studies of food stores in honeybee colonies from across the globe demonstrate that colonies are routinely and chronically exposed to neonicotinoids, fipronil, and their metabolites (generally in the 1-100 ppb range), mixed with other pesticides some of which are known to act synergistically with neonicotinoids. Other nontarget organisms, particularly those inhabiting soils, aquatic habitats, or herbivorous insects feeding on noncrop plants in farmland, will also inevitably receive exposure, although data are generally lacking for these groups. We summarize the current state of knowledge regarding the environmental fate of these compounds by outlining what is known about the chemical properties of these compounds, and placing these properties in the context of modern agricultural practices

Assessment of the environmental exposure of honey bees to neonicotinoid insecticides coming from corn coated seeds.

Colony Collapse Disorder (CCD), the sudden loss of most honeybees of the hive represents a worldwide crisis. The consequent losses in crops productivity and plant pollination constitute a major emergency from both economical and ecological standpoints. Although on the causes of CCD several hypothesis have been advanced (parasitic mites, viruses, insecticides, etc.) up to the present no one has been clearly supported by experimental results. In several countries the phenomenon is mainly observed in the period of corn sowing (spring), that generally occurs using corn seeds coated with specific insecticides. As a consequence, seed-coating neonicotinoid insecticides that are extensively utilized in the corn crops have been blamed for CCD. In this connection, two possible ways of environmental exposure and intoxication of honeybees to neonicotinoid insecticides were studied: 1) the atmospheric emission of particulate matter containing the insecticide by the sowing-machine and 2) the translocation of the systemic neonicotinoids from the coated seed to guttation drops of young corn plants. Quantitative measurements conducted both in laboratory and in the field demonstrated that both mechanisms of environmental diffusion of neonicotinoids can produce high exposure levels for bees, with lethal effects compatible with CCD phenomenon: the death manifests within few minutes if bees consume guttation drops or within few hours if they are exposed to particulate matter produced by the sowing machine

Assessment of the environmental exposure of honey bees to neonicotinoid insecticides coming from corn coated seeds

Colony Collapse Disorder (CCD), the sudden loss of most honeybees of the hive represents a worldwide crisis. The consequent losses in crops productivity and plant pollination constitute a major emergency from both economical and ecol. standpoints. Although on the causes of CCD several hypothesis have been advanced (parasitic mites, viruses, insecticides, etc.) up to the present no one has been clearly supported by exptl. results. In several countries the phenomenon is mainly obsd. in the period of corn sowing (spring), that generally occurs using corn seeds coated with specific insecticides. As a consequence, seed-coating neonicotinoid insecticides that are extensively utilized in the corn crops have been blamed for CCD. In this connection, two possible ways of environmental exposure and intoxication of honeybees to neonicotinoid insecticides were studied: 1) the atm. emission of particulate matter contg. the insecticide by the sowing-machine and 2) the translocation of the systemic neonicotinoids from the coated seed to guttation drops of young corn plants. Quant. measurements conducted both in lab. and in the field demonstrated that both mechanisms of environmental diffusion of neonicotinoids can produce high exposure levels for bees, with lethal effects compatible with CCD phenomenon: the death manifests within few minutes if bees consume guttation drops or within few hours if they are exposed to particulate matter produced by the sowing machine

Rapid analysis of neonicotinoid insecticides in guttation drops of corn seedlings obtained from coated seeds

Regarding the hypothesis that neonicotinoid insecticides used for seed coating of agricultural crops mainly corn, sunflower and seed rape - are related to the extensive death of honey bees, the phenomenon of corn seedling guttation has been recently considered as a possible route of exposure of bees to these systemic insecticides. In the present study, guttation drops of corn plants obtained from commercial seeds coated with thiamethoxam, clothianidin, imidacloprid and fipronil have been analyzed by an optimized fast UHPLC-DAD procedure showing excellent detection limits and accuracy, both adequate for the purpose. The young plants grown both in pots - in greenhouse - and in open field from coated seeds, produced guttation solutions containing high levels of the neonicotinoid insecticides (up to 346 mg L(-1) for imidacloprid, 102 mg L(-1) for clothianidin and 146 mg L(-1) for thiamethoxam). These concentration levels may represent lethal doses for bees that use guttation drops as a source of water. The neonicotinoid concentrations in guttation drops progressively decrease during the first 10-15 days after the emergence of the plant from the soil. Otherwise fipronil, which is a non-systemic phenylpyrazole insecticide, was never detected into guttation drops. Current results confirm that the physiological fluids of the corn plant can effectively transfer neonicotinoid insecticides from the seed onto the surface of the leaves, where guttation drops may expose bees and other insects to elevated doses of neurotoxic insecticides

Methiocarb metabolites are systemically distributed throughout corn plants grown from coated seeds

Funder: Università degli Studi di PadovaAbstract: Systemic insecticides such as neonicotinoids are widely used in seed coating practices for pest control in many crops, e.g., corn. Their success is due to their ability to protect the whole plant, from the roots to the upper leaves, but their use at high amounts is causing possible adverse effects on non-target animals exposed to contaminated pollen, nectar, leaves, and dust emitted during sowing. In 2018, the European Union banned some neonicotinoids and fipronil as seed coating insecticides in open fields. Consequently, the methylcarbamate methiocarb and less-toxic neonicotinoids, e.g., thiacloprid, have been authorized and largely used as alternative pesticides for corn seed coating. Here, an analytical protocol based on QuEChERS extraction/purification procedure and analysis by liquid chromatography-mass spectrometry has been optimized for the identification and the quantification of methiocarb, thiamethoxam, thiacloprid, and their metabolites in guttation drops, the xylem fluid excreted at leaf margins, and in leaves of corn plants grown from coated seeds. Although methiocarb is a non-systemic pesticide, we unexpectedly found high concentrations of its metabolites in both guttations and leaves, whereas methiocarb itself was below detection limits in most of the samples. The methiocarb main metabolite, methiocarb sulfoxide, was found at a mean concentration of 0.61 ± 1.12 µg mL−1 in guttation drops and 4.4 ± 2.1 µg g−1 in leaves. Conversely, parent compounds of neonicotinoids (thiamethoxam, thiacloprid) are systemically distributed in corn seedlings. This result raises safety concerns given that methiocarb sulfoxide is more toxic than the parent compound for some non-target species

Methiocarb metabolites are systemically distributed throughout corn plants grown from coated seeds

Systemic insecticides such as neonicotinoids are widely used in seed coating practices for pest control in many crops, e.g., corn. Their success is due to their ability to protect the whole plant, from the roots to the upper leaves, but their use at high amounts is causing possible adverse effects on non-target animals exposed to contaminated pollen, nectar, leaves, and dust emitted during sowing. In 2018, the European Union banned some neonicotinoids and fipronil as seed coating insecticides in open fields. Consequently, the methylcarbamate methiocarb and less-toxic neonicotinoids, e.g., thiacloprid, have been authorized and largely used as alternative pesticides for corn seed coating. Here, an analytical protocol based on QuECh- ERS extraction/purification procedure and analysis by liquid chromatography-mass spectrometry has been optimized for the identification and the quantification of methiocarb, thiamethoxam, thiacloprid, and their metabolites in guttation drops, the xylem fluid excreted at leaf margins, and in leaves of corn plants grown from coated seeds. Although methiocarb is a non-systemic pesticide, we unexpectedly found high concentrations of its metabolites in both guttations and leaves, whereas methiocarb itself was below detection limits in most of the samples. The methiocarb main metabolite, methiocarb sulfoxide, was found at a mean concentration of 0.61 \ub1 1.12 \u3bcg mL 121 in guttation drops and 4.4 \ub1 2.1 \u3bcg g 121 in leaves. Conversely, parent compounds of neonicotinoids (thiamethoxam, thiacloprid) are systemically distributed in corn seedlings. This resul

Fatal powdering of bees in flight with particulates of neonicotinoids seed coating and humidity implication

Losses of honeybees have been reported in Italy concurrent with the sowing of corn coated with neonicotinoids using a pneumatic drilling machine. Being unconvinced that solid particles containing systemic insecticide, falling on the vegetation surrounding the sown area, could poison bees foraging on contaminated nectar and pollen, the effect of direct aerial powdering was tested on foragers in free flight near the drilling machine. Bees were conditioned to visit a dispenser of sugar solution whilst a drilling machine was sowing corn along the flight path. Samples of bees were captured on the dispenser, caged and held in the laboratory. Chemical analysis showed some hundred nanograms of insecticide per bee. Nevertheless, caged bees, previously contaminated in flight, died only if kept in conditions of high humidity. After the sowing, an increase in bee mortality in front of the hives was also observed. Spring bee losses, which corresponded with the sowing of corn-coated seed, seemed to be related to the casual encountering of drilling machine during foraging flight across the ploughed fields