The uptake of organic contaminants by root vegetables involves diffusion, transport by xylem and phloem saps, degradation, and volatilization. To understand the role of uptake and elimination routes ...in the bioconcentration modeling of organic contaminants, a two-compartment uptake model (root and leaf compartments) was proposed. The results showed that for the root compartment, logarithm values of bioconcentration factors (log BCF, the concentration ratio between plant tissues and soil) of chemicals fell within a narrow range when the logarithm of octanol-water partition coefficient (log KOW) was less than 3.0, whereas log BCF values decreased rapidly with increasing log KOW values when log KOW was greater than 3.0. This is because the diffusion route had a significant impact on the root uptake of chemicals, wherein the first-order rate constant dropped rapidly for high-lipophilicity chemicals, resulting in very low log BCF values. For the leaf compartment, chemicals with moderate lipophilicity (log KOW of 3.0–4.0) had the highest simulated log BCF values. This is because moderate log KOW values generated the highest transpiration stream concentration factors (TSCFs, the concentration ratio between xylem or phloem saps and water), resulting in high uptake efficiency of chemicals by leaves. Furthermore, we improved the uptake model by considering the surface-deposition route for pesticides (foliar spray), and the simulation results indicated that this uptake route cannot be neglected for lipophilic compounds. Although the simulations agreed with an experimental study and some reported data, future studies should focus on factors, such as plant physiology (plant varieties, periderm effects and compositions of xylem and phloem saps) and environmental conditions (soil properties and weather conditions), to improve the plant uptake model.
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•Diffusion dominates the overall uptake of organic contaminants by roots.•Xylem and phloem uptake routes are crucial for chemical uptake by leaves.•Moderate lipophilicity chemicals have high BCFs in both roots and leaves.
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.
The biodiversity crisis is one of the greatest challenges facing humanity, but our understanding of the drivers remains limited. Thus, after decades of studies and regulation efforts, it remains ...unknown whether to what degree and at what concentrations modern agricultural pesticides cause regional-scale species losses. We analyzed the effects of pesticides on the regional taxa richness of stream invertebrates in Europe (Germany and France) and Australia (southern Victoria). Pesticides caused statistically significant effects on both the species and family richness in both regions, with losses in taxa up to 42% of the recorded taxonomic pools. Furthermore, the effects in Europe were detected at concentrations that current legislation considers environmentally protective. Thus, the current ecological risk assessment of pesticides falls short of protecting biodiversity, and new approaches linking ecology and ecotoxicology are needed.
In addition to fertilisers, plant protection products are essential in today's agricultural production. The increase in the human population leads to the need to optimise agricultural production, ...with an increasing demand for plant protection products. Historically, there have been serious fires at plant protection product storage facilities with devastating consequences for the environment. For this reason, it is worth investigating what risks arise for people and the environment during a fire at storage sites for these substances. In this article, tests were carried out for three plant protection products containing azoxystrobin as the active substance, in order to investigate the effects of the additives on combustion processes. Tests of combustion parameters were performed using a cone calorimeter. A tube furnace with asphyxiating and irritant gas analysers and gas chromatography with a mass spectrometer were used to analyse the resulting gas products. The Plant Protection Products tested achieved high values for combustion parameters. Analysis of the substances produced during their combustion showed that large amounts of asphyxiating and irritating gases (CO, N2O, NO, SO2, NH3, HCl, CH2O, HCN) were generated.
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•The flammability of PPPs was investigated.•Purser furnace was used to achieve stable combustion conditions.•IR analyser was used to analyse asphyxiating and irritant gases in fire effluents.•SPME-GC–MS method was used to analyse volatile and semi-volatile combustion products.
Characterizing human exposure to pesticides is challenging because their metabolites have a broad diversity of chemical structures. We aimed to study the interest of associating suspect screening and ...targeted analysis to identify multiple pesticide exposure of pregnant women. Approximately 300 urinary samples collected during early pregnancy (France) were analyzed by UHPLC/HRMS using both a suspect screening approach and targeted multiresidue analysis. Sixty-eight pesticides were selected according to available data on agricultural practices and analytical feasibility and 435 known or putative metabolites were added based on the literature. Compounds detected using the two approaches were compared and the place of residence was studied as a determinant of exposure for illustrative purposes. Suspect screening resulted in the characterization of 28 pesticide metabolites, corresponding to three fungicides (azoxystrobin, fenpropimorph, and procymidone), three herbicides (an arylphenoxypropionic acid derivative, chlorpropham, and phenmedipham), and one insecticide (carbofuran). The targeted approach led to the identification of pyrethroids, organophosphorus, fluazifop-P-butyl, and chlorpyrifos in >60% of samples and prochloraz, bromoxynil, diazinon, and procymidone in 10 to 50%. Both urban and rural areas were identified as being determinants of exposure, depending on the active substance. This combined strategy better characterizes pesticide mixtures. Suspect screening allows the detection of metabolites of pesticides that are rarely studied and not measured in biomonitoring studies, mainly because it allows the detection of conjugated phase II metabolites (azoxystrobin and fenpropimorph). The targeted approach complements it with the detection of highly polar and low molecular-weight metabolites, the confirmation of the parent compound, and the quantification of compounds for which analytical standards are commercially available or may be synthesized (organophosphorous, pyrethroids, and fluazifop-P-butyl). In addition, we detected several metabolites that have never been described in humans (fenpropimorph and azoxystrobin), which deserve to be candidates in the selection of markers of exposure.
Illustration of two complementary approaches to characterize human exposure to pesticides. Suspect screening for the detection of pesticide metabolites that are not routinely measured in biomonitoring studies. Targeted quantitative analysis for the detection of highly polar and low molecular-weight metabolites, the confirmation of parent compounds, and the quantification of compounds. Display omitted
•Suspect screening and target analyses were combined for mixture identification.•Both approaches were used on the same urine samples from pregnant women.•Exposure to various pesticide families occurred both in rural and urban areas.•Suspect screening identified highly detected metabolites that are rarely studied.•Target analysis is a complementary approach for the quantification of specific compounds.
The use of agrochemical and pharmaceutical active ingredients is essential in our modern society. Given the increased concern and awareness of the potential risks of some chemicals, there is a ...growing need to align with ‘green chemistry’ and ‘safe and sustainable by design’ principles and thus to evaluate the hazards of agrochemical and pharmaceutical active ingredients in early stages of R&D. We give an overview of the current challenges and opportunities to assess the principle of biodegradability in the environment. Development of new medium/high-throughput methodologies, combining predictive tools and wet-lab experimentation are essential to design biodegradable chemicals early in the active ingredient discovery and selection process.
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•LC-HRMS was used for the detection of metabolites of the two co-formulants.•Three and five metabolites were found from the two co-formulants in vegetables.•Three metabolites were ...more toxic than their original molecule.•Most metabolites are persistent, detected at 21 days with high concentrations.
Plant protection products contain co-formulants that could end up in vegetables, and they can generate transformation products that can be more toxic than their original molecule, which are a potential risk to food safety. Therefore, this study evaluated the dissipation of two co-formulants, dodecylbenzenesulfonic acid and 1-ethyl-2-pyrrolidone, in courgette and tangerine samples to determine possible harmful metabolites under laboratory conditions. The analyses of these substances were performed by liquid chromatography coupled to quadrupole-Orbitrap high-resolution mass spectrometry (LC-Q-Orbitrap-HRMS). For the degradation of both compounds, a single-phase kinetic model was fitted, with R2 values greater than 0.99. In courgette and tangerine, half-lives (DT50) for dodecylbenzene sulfonic acid were 1.83 and 1.42 days, while DT50 was 6.26 and 5.04 days for 1-ethyl-2-pyrrolidone, respectively. Three metabolites of dodecylbenzenesulfonic acid and five metabolites of 1-ethyl-2-pyrrolidone were found in courgette, while the same metabolites were detected in tangerine samples, except benzoic acid and 4-aminobutanoic acid. These metabolites were identified for the first time from these compounds except for benzoic acid, observing that 5-hydroxy-N-ethylpyrrolidone was the most concentrated metabolite in tangerine 14 days after application, reaching a maximum concentration of 149 µg/kg. Furthermore, some of the detected metabolites possessed a value of LD50 lower than their original molecules. In consequence, such metabolites, derived from these co-formulants, should be controlled to prevent negative health effects, and ensure food safety.
The document Plant Protection Products 2022 gives an overview of plant protection products permitted for use in the Republic of Croatia in 2022. All plant protection products that are put in ...distribution in the Republic of Croatia must be registered with the competent authority of the Ministry of Agriculture. Information on registered plant protection products can be found on the website of the Ministry of Agriculture (the FIS Web Portal). Plant protection products are, according to their application, divided into three major groups: herbicides, fungicides and zoocides. Each group offers an overview of products according to active substances. Each plant protection product, along with a list of pests and crops for which a permit for application was obtained, includes the following information: trade name, formulation, amount of active ingredients, manufacturer and distributor, and suppression concentration or dosage. Also listed are due pre-harvest intervals of crops for which the application is allowed. The number of applications is given for each crop individually, eg. potato (3), which indicates three applications to the potatoes in the one growing season. Due to the numerous amendments to relevant decisions and registration procedures, plant protection products may only be used according to the instructions for use indicated on the packaging. Any application of plant protection products in any manner other than specified in the instructions for use and on the label shall be considered performed exclusively at one’s own risk.
Losses of honey bees have been repeatedly reported from many places worldwide. The widespread use of synthetic pesticides have led to concerns regarding their environmental fate and their effects on ...pollinators. While the impact of insecticides on bees has received substantial attention, relatively little is known about the consequences of the use of non-insecticidal pesticides for bee health, and no comprehensive review is available. Here, we used a standardized method to review scientific papers with classifiable outcomes on bee health of non-insecticidal applications (i.e., fungicides, herbicides, and other non-specific pesticides) and their interactive effect on bee health. We comprehensively summarize for the first-time overall outcomes and outcomes per bee species, as well as the individual and combinatory outcomes for specific chemicals, types, and classes. The available information indicates minimal impact for nearly all fungicides and fungicide combinations, confirming that, with some exceptions, fungicides are not as harmful as insecticides. However, when interactions were found, fungicide-fungicide combinations were just as harmful as fungicide-insecticide interactions. Herbicide and other groups were more harmful than fungicides and showed similar interactive effects. Because exposure to multiple chemicals is likely to be common in most agricultural landscapes, we recommend that the detrimental interactive effects through co-application be made available on pesticide labels.
•Fungicides are relatively harmless by themselves.•Fungicides may have interactive effects with insecticides that are highly toxic.•Herbicides are more toxic than fungicides and can show similar interactive potential.•Bee species may have different reactions and tolerances to the same pesticide.
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