The management of the anthropogenic water cycle must ensure the preservation of the quality and quantity of water resources and their careful allocation to the different uses. Protection of water ...resources requires the control of pollution sources that may deteriorate them. This is a challenging task in multi-stressed catchments. This work presents an approach that combines pesticide occurrence patterns and stable isotope analyses of nitrogen (δ15N-NO3−, δ15N-NH4+), oxygen (δ18O-NO3−), and boron (δ11B) to discriminate the origin of pesticides and nitrogen-pollution to tackle this challenge. The approach has been applied to a Mediterranean sub-catchment subject to a variety of natural and anthropogenic pressures. Combining the results from both analytical approaches in selected locations of the basin, the urban/industrial activity was identified as the main pressure on the quality of the surface water resources, and to a large extent also on the groundwater resources, although agriculture may play also an important role, mainly in terms of nitrate and ammonium pollution. Total pesticide concentrations in surface waters were one order of magnitude higher than in groundwaters and believed to originate mainly from soil and/or sediments desorption processes and urban and industrial use, as they were mainly associated with treated wastewaters. These findings were supported by the stable isotope results that pointed to an organic origin of nitrate in surface waters and most groundwater samples. Ammonium pollution observed in some aquifer locations is probably generated by nitrate reduction. Overall, no significant attenuation processes could be inferred for nitrate pollution. The approach presented here exemplifies the investigative monitoring envisioned in the Water Framework Directive.
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•Assessment of pesticide and nitrogen pollution sources in a multistressed basin.•Combination of stable isotopes (δ15N−, δ18O, δ11B) and pesticide analysis.•Pesticide sources in surface water: soil/sediment desorption and urban use.•Nitrogen-species sources in surface and most groundwaters: organic origin.•Ammonium in aquifers associated with nitrate reduction.
Sustainable agriculture aims to meet the food needs of the growing world population while ensuring minimal impact on the environment and humans as well as productivity. Although pesticides represent ...the backbone of the agri-food sector in its endeavor to secure food production their application is perceived by many as an obstacle towards the achievement of sustainability; the main concerns are linked with their adverse effects on human health and the environment. Τhis review aims to present the status of chemical plant protection and provide insights into the use of pesticides within the context of sustainable agriculture. It mainly focuses on the strengthened legislation frameworks, which especially in the European Union and the United States of America ensure the placement in the market of pesticides with acceptable toxicological and environmental profiles without compromising crop production. Furthermore, the implementation of Integrated Pest Management principles plays a key role in the sustainable use of pesticides. The stringent regulatory requirements have resulted in the dramatic increase of the associated effort and costs in pesticide research and development (R&D) of improved products. Nevertheless, the investment of leading agrochemical companies in the R&D of new pesticides remains high. All the above set the ground for the sustainable use of pesticides in crop production while their successful application remains a challenge.
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•Sustainable use of pesticides is one way concerning anthroposphere and biosphere.•Pesticide authorization verifies an acceptable risk to humans and environment.•Management of pesticides can corroborate sustainability in agriculture.•The investment in pesticide R&D remains high.•Co-operation of all stakeholders is essential for the sustainable food production.
Massive use of pesticides in conventional agriculture leads to accumulation in soil of complex mixtures, triggering questions about their potential ecotoxicological risk. This study assessed cropland ...soils containing pesticide mixtures sampled from conventional and organic farming systems at La Cage and Mons, France. The conventional agricultural field soils contained more pesticide residues (11 and 17 versus 3 and 11, respectively) and at higher concentrations than soils from organic fields (mean 6.6 and 10.5 versus 0.2 and 0.6 μg kg−1, respectively), including systemic insecticides belonging to neonicotinoids, carbamate herbicides and broad-spectrum fungicides mostly from the azole family. A risk quotient (RQi) approach evaluated the toxicity of the pesticide mixtures in soil, assuming concentration addition. Based on measured concentrations, both conventional agricultural soils posed high risks to soil invertebrates, especially due to the presence of epoxiconazole and imidacloprid, whereas soils under organic farming showed negligible to medium risk. To confirm the outcome of the risk assessment, toxicity of the soils was determined in bioassays following standardized test guidelines with seven representative non-target invertebrates: earthworms (Eisenia andrei, Lumbricus rubellus, Aporrectodea caliginosa), enchytraeids (Enchytraeus crypticus), Collembola (Folsomia candida), oribatid mites (Oppia nitens), and snails (Cantareus aspersus). Collembola and enchytraeid survival and reproduction and land snail growth were significantly lower in soils from conventional compared to organic agriculture. The earthworms displayed different responses: L. rubellus showed higher mortality on soils from conventional agriculture and large body mass loss in all field soils, E. andrei showed considerable mass loss and strongly reduced reproduction, and A. caliginosa showed significantly reduced acetylcholinesterase activity in soils from conventional agriculture. The oribatid mites did not show consistent differences between organic and conventional farming soils. These results highlight that conventional agricultural practices pose a high risk for soil invertebrates and may threaten soil functionality, likely due to additive or synergistic “cocktail effects”.
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•soils from conventional farming contained more pesticides than organic farming soils.•conventional soils pose a high risk to soil invertebrates based on risk quotients.•soils under organic farming showed a negligible to medium risk.•conventional soils did show toxicity in bioassays with several soil invertebrates.•additive or synergistic “cocktail effects” of mixtures might explain the toxicity.
In this review, we examined the European legislative context on water protection concerning pesticide residues monitoring and the relevant National Action Plans and strategies that were undertaken in ...European countries to better identify and manage the problem in water bodies.
Furthermore, we illustrated the development of analytical methodologies and criticalities connected to determine pesticide residues in water matrices, including sampling, sample preparation approaches, instrumental analyses and specific applications emphasising those works published after 2015.
Details about sampling strategies, analytical feasibility, official methods, degradation products and behaviour in the environment for a subset of 160 pesticides are also provided.
•Need to monitor the use of pesticides continuously given the wide variety of molecules present in this category•An overview of official methods is provided for a subset of 160 pesticides•Sensitive technologies for micro-extraction include SBSE, SPME Arrows, Hi-SORBTM•New advances in preparation techniques focused on Ice Concentration Linked with Extractive Stirrer (ICECLES) have potentialities for more polar pesticides•Recent developments in pesticides analytical techniques focus on multiresidual LC-MS/MS based methods.
Pesticides present a significant risk for both humans and the environment. However, quantitative data for a broad range of airborne pesticides in agricultural areas are missing. During or after the ...application, pesticides can reach the atmosphere and partition between the particulate and gaseous phase. As part of the EU project SPRINT, weekly ambient air samples were collected from two agricultural areas in Portugal (vineyard) and the Netherlands (potatoes, onions, and sugarbeet) between April 2021 and June 2022 using high-volume air samplers. The samples were analysed for 329 pesticides, of which 99 were detected. The most frequently detected compounds included the fungicides folpet, fenpropidin and mandipropamid, the insecticide chlorpyrifos-methyl, the herbicide terbuthylazine, and the metabolite prothioconazole-desthio, which were found with detection frequencies between 40 and 57 %. Pesticide concentrations ranged between 0.003 ng/m3 and 10 ng/m3. Remarkably, 97 % of the samples contained at least one pesticide and in 95 % of the samples, pesticide mixtures were present. The calculated particle phase fractions correlated with the octanol-air partitioning coefficient for most of the investigated compounds. Furthermore, calculated daily inhalation rates for individual pesticides and pesticide mixtures were far below the Acceptable Daily Intake (ADI) with a margin of exposure (MOE) of >1000 for the highest calculated daily inhalation rate for a child. However, as this value only includes pesticide intake from food and drinking water and considering that 91 % of the detected pesticides are associated with potential adverse human health effects. These findings highlight the broad range of airborne pesticides in agricultural areas and the need for quantitative data to include the intake of mixtures of highly hazardous pesticides by inhalation in human risk assessment.
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•99 pesticides and metabolites detected (3 to 10,000 pg/m3) in ambient air.•Gas-/particle-bound fractions of frequently detected pesticides.•Multiple pesticides in most air samples.•11 pesticides reported for the first time in ambient air.•Intake by inhalation relevant for human health risk assessment.
Freshwater systems are facing a number of pressures due to the inputs of polar organic contaminants from a range of sources including agriculture, domestic and industry. The River Itchen and River ...Test are two sensitive chalk streams in Southern England that are experiencing a decline in invertebrate communities. We used Chemcatcher passive samplers to measure time-weighted average concentrations (14 days) of polar pollutants at nine sites on the River Itchen and eight sites on the River Test over a 12-month period. Sampler extracts were analysed using a targeted LC/MS method. In total, 121 plant protection products and pharmaceutical and personal care products were quantified (range of log Kow from - 1.5 to 7). Concentrations (sub ng L−1 to >500 ng L−1) in both rivers showed spatial and temporal variations. A greater number of compounds and higher concentrations were found in the River Test. The chemical profile was dominated by inputs from wastewater treatment plants and legacy plant protection products. On the River Itchen, high concentrations (∼100 ng L−1) of caffeine were observed directly downstream of a fish farm. Using the NORMAN database, the predicted no effect concentration (PNEC) freshwater values were exceeded by only five contaminants (2-hydroxy-terbuthylazine, alprazolam, azithromycin, diclofenac and imidacloprid). In addition, venlafaxine was detected above its EU Watch List concentration. These exceedances were mainly downstream of direct inputs from treatment plants. These compounds are known to have ecotoxicological effects on a range of aquatic biota including macroinvertebrates. Of concern is the ubiquitous presence of the ectoparasiticide imidacloprid, highlighting the need to control its use. The impact of the cocktail of pollutants found in this study on the long-term effects on chalk stream ecosystems remains unknown and needs further investigation.
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•Chemcatcher used to sequester polar pollutants in river catchments in southern England.•121 compounds quantified using a targeted mass spectrometric workflow.•Waste water treatment plant effluents were the main contributor of pharmaceuticals.•Five compounds were found at or above their predicted no effect concentrations.•Presence of imidacloprid could impact macroinvertebrate communities.
Pesticide applications in agricultural crops often comprise a mixture of plant protection products (PPP), and single fields face multiple applications per year leading to complex pesticide mixtures ...in the environment. Restricted to single PPP, the current European Union PPP regulation, however, disregards the ecological risks of pesticide mixtures. To quantify this additional risk, we evaluated the contribution of single pesticide active ingredients to the additive mixture risk for aquatic risk indicators (invertebrates and algae) in 464 different PPP used, 3446 applications sprayed and 830 water samples collected in Central Europe, Germany. We identified an average number of 1.3 different pesticides in a single PPP, 3.1 for complete applications often involving multiple PPP and 30 in stream water samples. Under realistic worst-case conditions, the estimated stream water pesticide risk based on additive effects was 3.2 times higher than predicted from single PPP. We found that in streams, however, the majority of regulatory threshold exceedances was caused by single pesticides alone (69% for algae, 81% for invertebrates). Both in PPP applications and in stream samples, pesticide exposure occurred in repeated pulses each driven by one to few alternating pesticides. The time intervals between pulses were shorter than the 8 weeks considered for ecological recovery in environmental risk assessment in 88% of spray series and 53% of streams. We conclude that pesticide risk assessment should consider an additional assessment factor to account for the additive, but also potential synergistic simultaneous pesticide mixture risk. Additionally, future research and risk assessment need to address the risk from the frequent sequential pesticide exposure observed in this study.
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•Comprehensive analysis of reported pesticide applications and stream water samples•Mixture risk compared in plant protection products, applications and stream water•Mixture risk and regulatory threshold exceedances driven by single pesticides•Simultaneous environmental pesticide mixture risk underestimated by a factor of 3.2•Frequency of pesticide exposure higher than considered in risk assessment
Neonicotinoid insecticides have been signaled as an important driver of widespread declines in bee diversity and abundance. Neonicotinoids were registered in the 1990s and by 2010 accounted for one ...third of the global insecticide market. Following a moratorium in 2013, their use on open-field crops was completely banned in the EU in 2018. Pesticide regulation should be based on solid and updated scientific evidence, whereby products showing unacceptable effects on the environment are not approved. Clearly, pesticide regulation failed to detect the ecological threats posed by neonicotinoids. We argue that at the time neonicotinoids were authorized, risk assessment (RA) protocols were inadequate to detect some of the risks associated with neonicotinoid properties, including high efficacy, long persistence, high systemicity, high mobility, and application versatility. We advocate for the adoption of a more holistic RA approach that should account for: a) temporal and spatial dimensions of pesticide exposure; b) co-exposure to multiple compounds; c) differences among bee species with different life histories in levels of exposure and sensitivity; and d) sublethal effects (mostly ignored in current RA procedures). We also argue that regulatory studies conducted to support pesticide registration should be publicly available, and that pesticide regulation should not be discontinued once a product has been authorized. We should use the knowledge acquired through the neonicotinoid experience as an opportunity to profoundly revise bee RA schemes. These efforts should be initiated promptly; the neonicotinoid story has also taught us that the regulatory system is reluctant to react.
•Neonicotinoids have been signaled as an important driver of bee declines.•Risk assessment (RA) schemes failed to detect some neonicotinoid-associated risks.•We should take advantage of the neonicotinoid experience to deeply revise RA schemes.
New transfer coefficient (TC) values were derived for vineyard workers handling treated grapevines during harvesting and crop maintenance activities. Re-entry exposure and dislodgeable foliar residue ...(DFR) studies were performed in Europe, covering hand harvesting, pruning/training, pruning/tying and pruning/shoot lifting. Foliar applications of fungicides (iprovalicarb, dimethomorph, dithianon, pyrimethanil and fenbuconazole) were made and 73 workers at 16 sites were monitored over one working day. Exposure was measured on inner and outer dosimeters, face/neck wipes and hand washes. In concurrent DFR studies, leaf punches were taken at each site during the time of worker re-entry. Potential exposure values correlated well with DFR values. TC values were derived for various re-entry activities for potential and actual exposure, with and without gloves. The harvesting task resulted in lower TC values than the other crop maintenance tasks. Additional TC values reflecting the use of protective gloves can be derived from the results. The TC values are much lower than current European Food Safety Authority (EFSA) default values. This project addresses a data gap identified by EFSA for specific EU TC values to permit more realistic and reliable re-entry worker exposure estimates for grapes.
•New transfer coefficient (TC) values derived for grape vineyard workers.•5 pairs of re-entry exposure & dislodgeable foliar residue (DFR) studies analyzed.•Potential exposure values correlated well with DFR values.•Total TC values are much lower than current EFSA default values.•Permit more realistic and reliable re-entry worker exposure estimates for grapes.
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