Article

Currently and recently used pesticides in Central European arable soils

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Abstract

Although large amounts of pesticides are used annually and a majority enters the soil to form short- or long-term residues, extensive soil surveys for currently used pesticides (CUPs) are scarce. To determine the status of CUPs' occurrence in arable land in Central Europe, 51 CUPs and 9 transformation products (TPs) were analysed in 75 arable soils in the Czech Republic (CR) several months after the last pesticide application. Moreover, two banned triazines (simazine and atrazine) and their TPs were analysed because of their frequent detection in CR waters. Multi-residue pesticide analysis on LC-MS/MS after soil QuEChERS extraction was used. The soils contained multiple pesticide residues frequently (e.g. 51% soils with ≥5 pesticides). The levels were also noticeable (e.g. 36% soils with ≥3 pesticides exceeding the threshold of 0.01mg/kg). After triazine herbicides (89% soils), conazole fungicides showed the second most frequent occurrence (73% soils) and also high levels (53% soils with total conazoles above 0.01mg/kg). Frequent occurrence was found also for chloroacetanilide TPs (25% of soils), fenpropidin (20%) and diflufenican (17%). With the exception of triazines' negative correlation to soil pH, no clear relationships were found between pesticide occurrence and soil properties. Association of simazine TPs with terbuthylazine and its target crops proved the frequent residues of this banned compound originate from terbuthylazine impurities. In contrast, frequent atrazine-2-hydroxy residue is probably a legacy of high atrazine usage in the past. The occurrence and levels of compounds were closely associated with their solubility, hydrophobicity and half-life. The results showed links to CR water-monitoring findings. This study represents the first extensive survey of multiple pesticide residues in Central European arable soils, including an insight into their relationships to site and pesticide properties.

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... The research conducted focused on currently used herbicides. While modern herbicides, and pesticides in general, are designed to be highly effective at the smallest possible doses, with low persistence and toxicity towards non-target organisms, many currently utilized pesticides remain persistent and harmful [7,33]. Also, some currently used herbicides are on the list of priority water pollutants [34]. ...
... Despite agricultural soil being a primary sink and key reservoir for pesticides, extensive surveys that examine numerous sites and a wide range of current-use pesticides in agricultural soils are very rare [7]. The accumulation of pesticides in agricultural lands is a consequence of intensive plant protection [15]. ...
... In accordance with our research, monitoring across the European Union has revealed the presence of pesticide residues in all agricultural soil samples [7,10,15,20], with 83% containing more than three active pesticide substances. In France, an analysis of 47 soil samples across different land uses revealed the presence of 111 pesticides. ...
Article
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Pesticides in soils raise concerns about the biodiversity, food safety, and contamination of watercourses, contributing to unsustainable land management practices. Monitoring the residue levels in agricultural soils is essential, as this offers valuable insights into the current extent of soil contamination and potential environmental risks attributed to their application. This study aimed to address the occurrence of the currently used herbicides in soil under intensive crop production, comparing the results of monitoring at two depths (0–30 and 30–60 cm) in 2013 and 2023. The research concerned the main agricultural area in Vojvodina Province (Serbia) and evaluated the presence of 41 herbicides in 128 localities. Pesticides were found in all samples, finding even more than six different herbicides per sample. The significant concentrations of s-metolachlor, etofumesate, clomazone, diflufenican, pendimethalin, and terbuthylazine found can be attributed to application practices, as they are typically applied pre-emergence, either through direct soil treatment with or without incorporation. Moreover, the correlation between different depths, herbicide residues, and soil properties was not significant. The decrease in the herbicide residues found in 2023 compared to the residues found in 2013 can be attributed to the implementation of good agricultural practices, which promote sustainable agricultural strategies through controlled pesticide application.
... Conventional agriculture has been applying pesticides to control pests such as weeds, insects, and fungi and maintain high levels of productivity (Hvězdová et al. 2018, Li 2022. According to the Food and Agricultural Organization of the United Nations (FAO), the global agricultural use of pesticides in 2020 was 2.7 Mt of active ingredients (ai), and the average application per crop area was 1.8 kg/ha (FAO 2022). ...
... Despite the benefits of pesticides in terms of food production and crop yields (Silva et al. 2019), their intensive and long-term application can negatively impact the environment (Sabzevari andHofman 2022, Wang et al. 2020). Currently used pesticides (CUPs) are considered more environmental friendly, effective and safe than for instance the banned organochlorine pesticides (Hvězdová et al. 2018). However, some CUPs can still persist in soil (Geissen et al. 2021, Riedo et al. 2021, appear in remote areas (Hvězdová et al. 2018), contaminate plant tissues (Kalyabina et al. 2021), affect food safety (Carvalho 2017, Seneff 2021, Zikankuba et al. 2019), occur in drinking or surface waters (de Souza et al. 2020, Syafrudin et al. 2021, and generally represent a risk for human health (Lewis et al. 2016, Seneff 2021, Sidhu et al. 2019, and the environment (Carvalho 2017, Lewis et al. 2016, Md Meftaul et al. 2020, Tudi et al. 2021, Zikankuba et al. 2019. ...
... Currently used pesticides (CUPs) are considered more environmental friendly, effective and safe than for instance the banned organochlorine pesticides (Hvězdová et al. 2018). However, some CUPs can still persist in soil (Geissen et al. 2021, Riedo et al. 2021, appear in remote areas (Hvězdová et al. 2018), contaminate plant tissues (Kalyabina et al. 2021), affect food safety (Carvalho 2017, Seneff 2021, Zikankuba et al. 2019), occur in drinking or surface waters (de Souza et al. 2020, Syafrudin et al. 2021, and generally represent a risk for human health (Lewis et al. 2016, Seneff 2021, Sidhu et al. 2019, and the environment (Carvalho 2017, Lewis et al. 2016, Md Meftaul et al. 2020, Tudi et al. 2021, Zikankuba et al. 2019. ...
Article
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We present an analytical method to detect and quantify residues of currently used pesticides (CUPs), which include 31 active ingredients (ai) and seven transformation products (TPs) in tropical and agricultural soils of Cuba. Ten isotopically labeled analogous compounds served as internal standards (IL-IS). The novelty of this research is the inclusion of different tropical soils type scarcely studied for CUPs and TPs, based on the QuEChERS (quick, easy, cheap, effective, rugged and safe) method, followed by chromatography tandem mass spectrometry. All figures of merit proved to be satisfactory according to SANTE guidelines 2020 and 2021. Matrix effects (ME) calculated by the external standard method were significant (|ME| > 20% for almost all compounds; grand mean ± standard deviation (STD) 104 ± 108%) in all soils. The internal standard method compensated ME to non-significant levels (8 ± 50%), even for analytes with a non-structure identical IL-IS (STD, 13 ± 57%). Repeatability (relative standard deviation, RSDr) and reproducibility (RSDR) for skeletic regosol (SR) were 7.5 ± 2.8% and 11.7 ± 4.7%, respectively. Absolute (quantified for 11 analytes with structure identical IL-IS) and relative recovery from SR was 92 ± 13% (mean ± STD) and 90 ± 12%, respectively. Limits of quantification for SR ranged from 0.1 to 10 ng/g, except metalaxyl and oxyfluorfen (25 ng/g each). Linearity of matrix-matched (MM) calibration curves (5 to 100 ng/g) had an R² of ≥ 0.99 for all soils and almost all analytes. The method was successfully applied to 30 real soil samples.
... Studies conducted in agricultural regions worldwide have consistently revealed that agricultural soils are the most pesticide-contaminated (Froger et al., 2023;Geissen et al., 2021;Hvězdová et al., 2018;Riedo et al., 2021). Frequently, multiple residues were detected in agricultural soil samples, resulting in cumulative total measured pesticide concentrations ranging from 300 to 2870 (Froger et al., 2023;Kosubová et al., 2020;Silva et al., 2019). ...
... To analyze pesticide residues in the soil of sugar beet fields, soil samples were taken from the topsoil from 0 to 20 cm. This layer is most concerned with the accumulation of pesticides (Hvězdová et al., 2018). The soil samples were taken from fields in September before the start of the agricultural season. ...
... The presence of pesticides in soil depends on the application history, soil properties, pesticide properties, and climatic conditions (Hvězdová et al., 2018). In this study, the relationships between the maximum residual concentration of pesticides (Max), their frequency in soils (Freq), and their properties (K oc , DT 50 , S w , Vp, Gus index, and Log P) were explored using PCA (Fig. 4). ...
Article
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With the long-term application of pesticides on sugar beet farms in the irrigated perimeter of Tadla in Morocco for over 50 years, pesticide monitoring is necessary to assess soil health. The objective of our study was to monitor multiple pesticide residues in topsoil samples collected from post-harvest sugar beet fields and verify their migration to deep soil layers. Topsoil and deep soil samples were collected from arbitrarily selected sugar beet fields in the IPT. In this study, a target-screening method was applied. All target pesticides were detected in soil samples, with tefluthrin being the most frequently detected pesticide. The residue with the highest concentration in soil samples was DDE. All the soil samples contained a mixture of pesticide residues, with a maximum of 13 residues per sample. The total pesticide content decreased toward more profound layers of soil, except in one field where it reached a concentration of 348 µg/kg at the deeper soil layer. For pesticides detected at the three soil depths, only tefluthrin concentration increased in the deep soil layer. The results provide comprehensive and precise information on the pesticide residue status in sugar beet soils warning against the multiple risks that this contamination can cause. This study indicates the need of regular monitoring of pesticides over a large area of the perimeter to enable decision-makers to pronounce the impacts of the extension and intensification of sugar beet cultivation at the irrigated perimeter of Tadla.
... The period between land treatment with pesticides and soil sampling represents a key issue, the time directly influencing the pesticides' chemical degradation. Various studies indicated the sampling period, a quarter of them reporting that the sampling was achieved during harvesting (spring-summer) [41,54,55], and another 20% reporting sampling in autumn-winter [56,57]. ...
... The pesticides having the highest concentrations were diflufenican (up to 150 µg/kg), chlorotoluron (up to 90 µg/kg), pendimethalin (up to 300 µg/kg), and tebuconazole (up to 150 µg/kg) [82]. An older investigation was performed for 75 agricultural soils from the Czech Republic, for the detection of 68 pesticides [56]. A total of 99% of the soils contained residues from at least one pesticide, with 81% of samples containing at least one pesticide above the national generic soil limit of non-chlorinated pesticides (0.01 mg/kg) [54]. ...
Article
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The application of pesticides remains a necessary measure for pest management in agriculture, particularly in the cultivation of fruits and vegetables. After harvest, the presence of pesticide residues in greengrocery (fruits and vegetables) is significantly influenced by various factors, including storage conditions, handling practices, and subsequent processing methods. The mitigation of these residues to levels compliant with regulated maximum thresholds ensures the safety of raw and processed fruits and vegetables for consumption. A contemporary survey of pesticide residues in greengrocery has gathered considerable attention from consumers, driven by concerns over the potential health risk of pesticide exposure. Consequently, consumers want to be extensively informed about household processing techniques to minimize associated risks. Meanwhile, a critical question arises: does household processing effectively eliminate pesticide residues? A comprehensive review of the literature reveals that conventional methods, such as washing and soaking, offer only limited reduction in residue levels, while emerging treatments, suitable both at household and industrial scale, demonstrate increased efficiency in residues mitigation. This study aims to emphasise the ubiquitous use of pesticides in crop cultivation while providing recommendations for the implementation of efficient treatment protocols to address residue concerns. Following upon available evidence and database mining, the worldwide purpose must be to outline agriculturally and economically viable strategies that prioritize both the health and safety of consumers, as well as the green cultivation and processing of fruits and vegetables.
... Therefore, they do not take the real-life effects of environmental mixtures ("cocktail effect") into account. 11 Several monitoring studies found that mixtures in soil contain not only residues from currently used PPPs 12,13 but also residues from PPPs that have been banned, some for over a decade. 14−16 Additive or synergistic effects of such environmental mixtures on soil life have scarcely been studied. ...
... 18 Geissen et al. 15 detected two different DDT metabolites each in 20−50% of their analyzed samples; additionally, Silva et al. 14 were able to not only detect but also quantify DDE p,p' in 23% of their analyzed samples. As most of the recent European studies focus on residues of currently used PPPs, 12,13,16,31 further subsumption of the pollution with DDT and its metabolites as well as HCB is difficult. ...
Article
Full-text available
During the growing season of 2021, 201 soil samples from conventionally and organically managed fields from 10 European countries and 8 cropping systems were taken, and 192 residues of synthetic pesticides were analyzed. Pesticide residues were found in 97% of the samples, and 88% of the samples contained mixtures of at least 2 substances. A maximum of 21 substances were found in conventionally managed fields, and a maximum of 12 were found in organically managed fields. The number and concentration of pesticide residues varied significantly between conventional and organic fields in 70 and 50% of the case study sites, respectively. Application records were available for a selected number of fields (n = 82), and these records were compared to the detected substances. Residues from 52% of the applied pesticides were detected in the soils. Only 21% of the pesticide residues detected in the soil samples were applied during the 2021 growing season. From the application data, predicted environmental concentrations of residues in soil were calculated and compared to the measured concentrations. These estimates turned out not to be accurate. The results of this study show that most European agricultural soils contain mixtures of pesticide residues and that current calculation methods may not reliably estimate their presence.
... refuges and connectivity recolonization) expected from untreated areas within the agricultural landscape mosaic (see for instance Dalkvist et al. (2013) about the role of landscape features in the impacts of pesticides on vole population dynamics). Moreover, recurring treatments over seasons and years and use over large surfaces may lead to pseudopersistence within the environment (Hvězdová et al., 2018) and thus likely limit the possibility for recovery. Indirect effects may thus occur in addition to direct toxic effects. ...
... Various pesticide mixtures have been measured in recent years in agricultural soils [2][3][4][5]8,11,29,30 and nonagricultural soils 5,31 as well as in the vegetation of nontarget areas 7,9,10,32 using multicomponent analytical methods. During a study in Switzerland, agricultural soil samples with 14 years of pesticide history were investigated 33 . ...
Article
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Current use pesticides (CUPs) are recognised as the largest deliberate input of bioactive substances into terrestrial ecosystems and one of the main factors responsible for the current decline in insects in agricultural areas. To quantify seasonal insect exposure in the landscape at a regional scale (Rhineland-Palatine in Germany), we analysed the presence of multiple (93) active ingredients in CUPs across three different agricultural cultivation types (with each three fields: arable, vegetable, viticulture) and neighbouring meadows. We collected monthly soil and vegetation samples over a year. A total of 71 CUP residues in different mixtures was detected, with up to 28 CUPs in soil and 25 in vegetation in single samples. The concentrations and numbers of CUPs in vegetation fluctuated over the sampling period, peaking in the summer months in the vegetation but remaining almost constant in topsoil. We calculated in-field additive risks for earthworms, collembola, and soil-living wild bees using the measured soil concentrations of CUPs. Our results call for the need to assess CUP mixture risks at low concentrations, as multiple residues are chronically present in agricultural areas. Since this risk is not addressed in regulation, we emphasise the urgent need to implement global pesticide reduction targets.
... However, real-world applications often involve combinations of multiple pesticides with diverse targets. Studies indicate that over 51% of agricultural topsoils in the European Union contained more than five pesticides ( 12 ), and over 58% of managed grassland soils contained two or more pesticide residues ( 13 ). Therefore, pesticide diversity (i.e., the number of pesticides used) poses an environmental stress that requires urgent investigation ( 6 , 14 , 15 ). ...
Article
Pesticide application is essential for stabilizing agricultural production. However, the effects of increasing pesticide diversity on soil microbial functions remain unclear, particularly under varying nitrogen (N) fertilizer management practices. In this study, we investigated the stochasticity of soil microbes and multitrophic networks through amplicon sequencing, assessed soil community functions related to carbon (C), N, phosphorus (P), and sulfur (S) cycling, and characterized the dominant bacterial life history strategies via metagenomics along a gradient of increasing pesticide diversity under two N addition levels. Our findings show that higher pesticide diversity enriches the abundance of bacterial specialists and opportunists capable of degrading or resisting pesticides, reducing the proportion of bacterial generalists in the absence of N addition. These shifts can complicate multitrophic microbial networks. Under increased pesticide diversity, selective pressure may drive bacteria to streamline their average genome size to conserve energy while enhancing C, N, P, and S metabolic capacities, thus accelerating soil nutrient loss. In comparison, N addition was found to reduce bacterial niche differentiation at higher pesticide diversity, mitigating the impacts of network complexity and functional traits associated with pesticide diversity, ultimately alleviating soil nutrient loss. Our results reveal the contrasting impacts of pesticide diversity on microbial functions under different N input scenarios and emphasize that strategic N fertilizer management can mitigate the ecological effects of pesticide use in agricultural systems.
... Chemical pesticides are the most common and effective means of controlling soil-borne pathogens. Most pesticides enter the soil directly following application, and indeed certain pesticides are applied directly via root irrigation (Hvězdová et al. 2018). Pesticide use, however, is oftentimes accompanied by changes in the soil microbiome, such as the relative abundance and functions of the numerous bacterial species that comprise the microbiome (Huang et al. 2021;Zhang et al. 2021). ...
Article
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The effect of fungicides on the plant-rhizosphere microbiome is a subject of ongoing debate, but whether any alteration in the rhizosphere microbiome could affect plant health is an issue that has not been thoroughly investigated. To address this deficiency, we analyzed the rhizosphere microbiome of wilt disease—resistant and disease-susceptible cucumber cultivars to determine whether (and which) plant-associated microorganisms have a role in disease resistance. We further assessed whether the fungicides thiophanate-methyl and carbendazim affect the rhizosphere microbiome, which may contribute to the plant’s immune response. Based on results acquired with both radicle-inoculation and soil-inoculation methods, cultivars Longyuanxiuchun (LYXC) and Shuyan2 (SY2) were identified as being disease resistant, whereas Zhongnong6 (ZN6) and Zhongnong38 (ZN38) were susceptible. The microbiome structure differed substantially between the resistant and susceptible plants, with LYXC and SY2 each having a significantly greater Shannon index than Zhongnong38. These results revealed that the disease-resistant cucumber cultivars recruited more beneficial bacteria, i.e., Bacillus, in their rhizosphere soil; as such, Bacillus was identified as a keystone genus in the microbial co-occurrence network. Thus, the presence of Bacillus may help cucumbers defend against fungal pathogens within the rhizosphere. Bacillus subtilis strain LD15, which was isolated from LYXC rhizosphere soil, could suppress pathogen growth, in vitro, and reduce disease severity in pot assays. Moreover, evidence also confirmed the accumulation of LD1 in the rhizosphere soil of resistant cucumber cultivars. For LYXC, application of thiophanate-methyl or carbendazim altered the microbiome structure, decreased bacterial diversity, and reduced the abundance of Bacillus species. Finally, pot assays verified that fungicide application decreased the proportion of LD15 in rhizosphere soil. From a microbial perspective, thiophanate-methyl and carbendazim may weaken the rhizobacteria-mediated defense response of cucumbers against cucumber Fusarium wilt disease. Our findings reveal a role for the rhizosphere microbiome in protecting plants from pathogens and constitute a reference for assessing the ecotoxicological risk of pesticides to non-target soil microorganisms. Supplementary Information The online version contains supplementary material available at 10.1007/s42994-024-00181-5.
... Furthermore, several pesticides with adverse effects are known to persist in soils for a long time after use, such as some banned organochlorines [2]. Recent studies have pointed to the large amount of pesticides present in agricultural soils, including the very commonly used herbicide glyphosate [3][4][5]. Due to its permanently ionic nature, glyphosate ( Figure 1) cannot be analyzed in multiresidue methods, and is often quantified separately [3]. To our knowledge, no method has ever been published which could determine permanently ionic pesticides and their degradation products (glyphosate, aminomethylphosphonic acid, glufosinate) along with other pesticide residues: This work presents a first attempt. ...
Article
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A new method is presented for the simultaneous determination of 13 multiclass pesticides along with glyphosate. The multiclass pesticides were extracted by creating a soil slurry with 2% ethanol in water (v/v), and then, applying direct-immersion solid-phase microextraction (DI-SPME) with a new type of semi-disposable SPME fiber configuration called LC-Tips. The fibers were then retroextracted to ethanol, and aqueous ammonia was added to the slurry to extract glyphosate. Derivatization of the glyphosate extract was accomplished with a mixture of trifluoroacetic anhydride and trifluoroethanol, after which the reaction mixture was dried and resuspended with the SPME ethanol extract. To this, a mixture of analyte protectants was added, and it was analyzed by GC-MS/MS in multiple-reaction-monitoring mode. All analytes showed a coefficient of determination greater than 0.95 in the 0.1–100 µg/kg calibrated range, and the limits of detection were between 0.1 and 1 µg/kg, except for glyphosate, which was 0.01 µg/kg. The method shows relatively high replicate relative standard deviation (as much as 37% for five extractions at 20 µg/kg), but the isotopically labeled internal standard was effective at mitigating this effect for some analytes.
... Lastly, our review underlines the lack of data on the spatiotemporal variability of non-target organism exposure to PPP (Devine and Furlong 2007). Few recent studies have found high concentrations of PPP mixtures in PPP-treated crop soils (Chiaia-Hernandez et al. 2017;Hvezdova et al. 2018). Conversely, very little information is available on soil contamination in other landscape features, such as semi-natural habitats and organically managed plots. ...
Article
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Plant protection products (PPP) are extensively used to protect plants against harmful organisms, but they also have unintended effects on non-target organisms, especially terrestrial invertebrates. The impact of PPP on ecosystem functions provided by these non-target invertebrates remains, however, unclear. The objectives of this article were to review PPP impacts on the ecosystem functions provided by pollinators, predators and parasitoids, and soil organisms, and to identify the factors that aggravate or mitigate PPP effects. The literature highlights that PPP alter several ecosystem functions: provision and maintenance of biodiversity, pollination, biotic interactions and habitat completeness in terrestrial ecosystems, and organic matter and soil structure dynamics. However, there are still a few studies dealing with ecosystem functions, with sometimes contradictory results, and consequences on agricultural provisioning services remain unclear. The model organisms used to assess PPP ecotoxicological effects are still limited, and should be expanded to better cover the wide functional diversity of terrestrial invertebrates. Data are lacking on PPP sublethal, transgenerational, and “cocktail” effects, and on their multitrophic consequences. In empirical assessments, studies on PPP unintended effects should consider agricultural-pedoclimatic contexts because they influence the responses of non-target organisms and associated ecosystem functions to PPP. Modeling might be a promising way to account for the complex interactions among PPP mixtures, biodiversity, and ecosystem functioning. Graphical Abstract
... Various experimental studies have previously been conducted on the degradation of MTZ using AOPs. The major degradation products of MTZ are stated to be derivatives of oxanilic acid and ethane sulfonic acid from the oxidation process in the chlorothalonil-treated soil (Chen et al. 2017;Hvězdová et al. 2018;Lewis et al. 2016;Velisek et al. 2020). Under the chlorine dioxide treatment in water, MTZ decomposes to 2-hydroxyacetamide and 1H-pyrazole-1-carboxylic acid (Kodranov et al. 2020). ...
Article
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The atmospheric and aqueous ozonolysis of metazachlor (MTZ) is investigated using high-level quantum chemical and kinetic calculations (M06-2X/6–311 + + G(3df,3pd)//M06-2X/6–31 + G(d,p) level of theory). The ozone (O3)-initiated degradation pathways of MTZ under three different mechanisms, namely cycloaddition, oxygen-addition, and single electron transfer (SET), are explored in the temperature range of 283–333 K and 1 atm pressure. As a result, the cycloaddition reaction at the C16C18 double bond of the benzene ring of MTZ is found to be the most dominant channel in the atmosphere with the standard Gibbs free energy of reaction (ΔrG⁰g) of − 129.13 kJ mol⁻¹ and the highest branching ratio of 95.18%. In the aqueous phase, the main reaction channel turns into the SET mechanism, which owns the lowest Gibbs free energy of activation (ΔG#aq) of 73.8 kJ mol⁻¹ and contributes 87.8% to the ktotal. Over the temperature range of 283–333 K, the total rate constant (ktotal) significantly increases from 8.42 to 5.82 × 10¹ M⁻¹ s⁻¹ in the atmosphere and from 4.10 × 10² to 2.40 × 10⁴ M⁻¹ s⁻¹ in the aqueous environment. Remarkably, the ecotoxicity assessment shows that MTZ may be harmful to fish and chronically harmful to daphnia. In contrast, its main ozonolysis products exhibit no acute or chronic toxicity or mutagenic effects. Graphical Abstract
... Additionally, pesticide residues in soils, especially as a result of repeated applications, might affect subsequent crops (Grahovac, 2016). Besides this, only a small portion of pesticides reach the intended targets; the remainder are environmental contaminants that could have a variety of harmful (Hvězdová et al., 2018). For example, while only a portion of pesticides applied to the leaves and stem parts of crops reaches the soil, this rate is higher for pesticides applied to the soil (nematicides, disinfectants, and mostly herbicides) (Navarro et al., 2007). ...
Thesis
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This study investigated the influence of two common tillage practices, No Tillage (NT) and Conventional Tillage (CT), on the distribution of pesticide residues in soil profiles. Specifically, glyphosate residues were examined in both the upper (0-5 cm) and lower (5-20 cm) soil layers. Soil samples were collected from a pre-existing field experiment at two distinct time points. While the first sampling was collected immediately after Glyphosate application (end of May), the second soil samples were taken six weeks after the first samples (in the first week of June). The water extraction method was initially employed for glyphosate residue analysis, with a Liquid Chromatography-Spectrometry (LC-MS) system utilized for glyphosate detection. Unfortunately, no glyphosate residues were detected in any of the samples, where at this stage a methanol extraction was undertaken to search for a wider range of pesticides. Here, Pendimethalin and Diflufenican residues were identified in soil samples following LC-MS, and their concentrations in samples quantified based on standard curves. The results indicate that Pendimethalin concentrations were significantly higher by soil depth (0-5 cm) during the first sampling date (F(1,10) = 25.39, P= 0.001), while no significant of tillage (F(1,11) = 0.05, p = 0.827) or depth (F(1,11) = 0.39, p = 0.546) were observed during the second field visit. For Diflufenican, neither tillage (F(1,10) = 0.46, p = 0.513) nor depth (F(1,10) = 4.42, p = 0.062) had significant effects on concentrations during the first sampling date, though depth approached significance. No significant effects of tillage (F(1,12) = 0.03, p = 0.873), depth (F(1,12) = 0.34, p = 0.571), or their interaction were found during the second sampling date. This research underscores the importance of considering depth-related factors when assessing pesticide residue distributions in soil profiles.
... The use of pesticides has been shown to have detrimental effects on earthworms and overall soil biodiversity [21,22]. As AS residues are frequently found in soils across Europe [68][69][70][71], the potential threat to soil organisms is obvious. ...
Article
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Pesticides affect biota inside and outside agricultural fields due to their intrinsic mode of action. This study investigated whether pesticide active substances (AS) approved for conventional agriculture in Europe differ in their ecotoxicity from AS approved for organic agriculture. The evaluation was based on official ecotoxicological data for surrogate honeybee, bird, and earthworm species, which also serve as a reference for official environmental risk assessments in the pesticide authorization process. In October 2022, 268 chemical-synthetic AS approved for conventional and 179 nature-based AS approved for organic agriculture were listed in the EU Pesticide Database. Ecotoxicological data were only available for 254 AS approved for use in conventional agriculture and 110 AS approved for use in organic agriculture. The results showed a higher ecotoxicity of conventional AS: 79% (201 AS), 64% (163 AS) and 91% (230 AS) were moderately to acutely toxic to honeybees, birds, and earthworms, respectively, compared to 44% (48 AS), 14% (15 AS) and 36% (39 AS) of AS approved for organic agriculture. We have only considered the potential ecotoxicities of individual substances in this assessment; actual exposure in the field, where multiple AS formulations with other chemicals (including impurities) are applied, will be different. Nevertheless, these results emphasize that an increase in organic agriculture in Europe would reduce the ecotoxicological burden on biodiversity and associated ecosystem services.
... However, a group of specific organic soil compoundshumus -stands out. A lack or excess of the components of fertility reduces the productivity of agricultural crops [7][8][9][10]. ...
Article
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The use of soil for the production of crop products leads to changes in the natural properties of soils and their natural state. When various situations arise, soil properties can change in different forms and with unequal degrees of severity; a process that worsens quantitative and qualitative properties is defined as soil degradation. The significant role of soil in people’s lives should serve as an incentive for its rational use and to prevent the occurrence of degradation transformations leading to a decrease in its environmental and production functions. The purpose of the research is to assess soil contamination of agricultural lands in the Samara region with insecto-acaricides and herbicides. Objectives: - to establish the average and maximum content of residual quantities of pesticides in soils; - determine the area of contamination with residual quantities of pesticides. The research was carried out in 7 districts (Bezenchuksky, Syzransky, Stavropolsky, Volzhsky, Privolzhsky, Bolshechernigovsky, Elkhovsky) of the Samara region in 2020-2022. To assess soil contamination with residual amounts of pesticides, soil samples were taken in spring and autumn to the depth of the arable layer. In selected soil samples, the residual amount of insectoacaricides (DDT, HCH, HCB, metaphos) and herbicides (prometrin, atrazine, simazine, 2.4-D, trifluralin, THAN, dalapon) was determined. The analysis of contamination of agricultural land in the study region showed that the content of controlled pesticides in soils depended on both the period of soil sampling and the year of research.
... In general, there might be some time periods when amphibians are active in agricultural fields and no pesticides are applied. However, even then amphibians might be exposed, as European agricultural topsoil can be contaminated with pesticides even several months after the last application (Hvězdová et al., 2018). When aquatic bodies are contaminated with pesticides, amphibians might be exposed during their whole aquatic phase. ...
Technical Report
This report is a product of the COST Action CA18221 PERIAMAR, PEsticide RIsk AssessMent for Amphibians and Reptiles As part of the pesticide risk assessment, a characterization of the exposure of amphibians and reptiles to pesticides is necessary. In the first-tier assessment, it is common practice to estimate pesticide exposure using worst-case scenarios and simplified models, while in higher tiers the exposure assessment is refined based on a wider range of environmental parameters that affect pesticide fate and degradation and more sophisticated modelling approaches. Despite the use of pesticide models, refined exposure assessments require a good understanding of the ecological scenario in which the species inhabits, including potential exposure pathways, life cycle characteristics and biological traits that make each species vulnerable to pesticide pollution (Rico et al. 2016). Therefore, the aim of this paper is to review those aspects of amphibian and reptilian biology, ecology and ecophysiology that should be taken into account for the high-tier exposure assessment of pesticides. By reviewing aspects of the ecology and physiology of amphibians and reptiles, we aim to improve our understanding of the presence and activities of animals in the areas that may be exposed to pesticides and, consequently, contribute to identify key exposure routes and scenarios. This review also provides recommendations for further research to complete a useful scheme for the pesticide exposure assessment of herpetofauna. The full report is available at: https://periamar.com/assets/Uploads/482e81020a/Deliverable_04+06.pdf
... Additionally, pesticide residues in soils, especially as a result of repeated applications, might affect subsequent crops (Grahovac, 2016). Besides this, only a small portion of pesticides reach the intended targets; the remainder are environmental contaminants that could have a variety of harmful (Hvězdová et al., 2018). For example, while only a portion of pesticides applied to the leaves and stem parts of crops reaches the soil, this rate is higher for pesticides applied to the soil (nematicides, disinfectants, and mostly herbicides) (Navarro et al., 2007). ...
Thesis
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This study investigated the influence of two common tillage practices, No Tillage (NT) and Conventional Tillage (CT), on the distribution of pesticide residues in soil profiles. Specifically, glyphosate residues were examined in both the upper (0-5 cm) and lower (5-20 cm) soil layers. Soil samples were collected from a pre-existing field experiment at two distinct time points. While the first sampling was collected immediately after Glyphosate application (end of May), the second soil samples were taken six weeks after the first samples (in the first week of June). The water extraction method was initially employed for glyphosate residue analysis, with a Liquid Chromatography-Spectrometry (LC-MS) system utilized for glyphosate detection. Unfortunately, no glyphosate residues were detected in any of the samples, where at this stage a methanol extraction was undertaken to search for a wider range of pesticides. Here, Pendimethalin and Diflufenican residues were identified in soil samples following LC-MS, and their concentrations in samples quantified based on standard curves. The results indicate that Pendimethalin concentrations were significantly higher by soil depth (0-5 cm) during the first sampling date (F(1,10) = 25.39, P= 0.001), while no significant of tillage (F(1,11) = 0.05, p = 0.827) or depth (F(1,11) = 0.39, p = 0.546) were observed during the second field visit. For Diflufenican, neither tillage (F(1,10) = 0.46, p = 0.513) nor depth (F(1,10) = 4.42, p = 0.062) had significant effects on concentrations during the first sampling date, though depth approached significance. No significant effects of tillage (F(1,12) = 0.03, p = 0.873), depth (F(1,12) = 0.34, p = 0.571), or their interaction were found during the second sampling date. This research underscores the importance of considering depth-related factors when assessing pesticide residue distributions in soil profiles.
... In order to address the EU's soil protection policies, including the EU biodiversity strategy for 2030 [4] and the EU soil strategy for 2030 [5], a new Soil Monitoring Law [6] has been proposed to ensure a high level of soil environment protection. However, large-scale studies on soil contamination by pesticide residues are scarce and limited mainly to one or only a few compounds [7][8][9][10][11][12]. Therefore, the real scale of pesticide residue contamination in agricultural soils and their aging processes are still unrecognized, which makes rational and sustainable soil management difficult. ...
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Humin (HUM) is the most stable fraction of the soil organic matter, whose properties determine the soil health and sustainable development of agroecosystems. The aim of the paper was to determine changes in the properties of the HUM after interaction with selected pesticides, which can be visualized using photoluminescence methods. The HUM was isolated from the mollic horizon of Phaeozems arable soils derived from different parent materials in Poland. The isolated and purified HUM were saturated in a batch experiment with selected herbicides and insecticides, then analyzed for chemical composition and spectroscopic properties: Electron Paramagnetic Resonance, fluorescence, and delayed luminescence. The research showed that the interaction of the HUM with selected pesticides caused significant changes in the elemental composition of the HUM; however, no changes in their aromaticity/aliphaticity were found. The impact of pesticides was also marked by a reduction in the concentration of radicals, fluorescence and delayed luminescence intensity and properties. Changes in spectroscopic characteristics and their relationship with soil organic matter (SOM) structure properties require further research so that their results can be used in the management of agroecosystems in accordance with the principles of sustainable development.
... The study strongly recommends that the Royal Government of Cambodia be provided with a concrete public health policy on pesticide management and suitable training on pesticide applications. generate pesticide pollution of surface and ground waters (Pérez-Lucas et al., 2019;Hvězdová et al., 2018). Assessment of pesticide residues in soils, most of these studies reported from the US (Marburger et al., 2002), China (Liu et al., 2016), India (Mishra et al., 2012), Brazil (Laabs et al., 2002), South Korea (Park et al., 2020), Japan (Asaoka et al., 2019), or EU countries (Silva et al., 2019). ...
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Pesticides have been one of the most extensively used throughout the world. In low-and middle-income countries, pesticides are extensively used in agriculture. Agriculture is Cambodia's most important economic sector. Around 80% of the population lives in rural areas and is mainly involved in subsistence farming. Cambodian farmers use synthetic pesticides to protect their agricultural products from pest infestation. The increase in agricultural products and the rapid population growth have led to the rise of farming pesticides, which causes concerns about the negative impact on environmental issues and food security in Cambodia. The routes of exposure, toxicity, and pesticide residues in daily food intake are all ambiguous in Cambodia. The scientific reports available in Cambodia could be more extensive and consistent. Therefore, this report provides an overview of the current status of pesticide practices in Cambodia and relates knowledge of pesticide use among local farmers. The contents described the risk assessment of pesticide contamination based on the Cambodian local market. In the same way, the pesticides that farmers use were considered extremely hazardous, highly hazardous, or moderately hazardous by the World Health Organization. This study also discussed the integrated pesticide use management approach and the future perspectives for pesticide practices in Cambodia. The review's findings raised serious concerns regarding environmental safety and human health. Although some pesticides have been banned, most local farmers still use them for agriculture. The study strongly recommends that the Royal Government of Cambodia be provided with a concrete public health policy on pesticide management and suitable training on pesticide applications .
... The study strongly recommends that the Royal Government of Cambodia be provided with a concrete public health policy on pesticide management and suitable training on pesticide applications. generate pesticide pollution of surface and ground waters (Pérez-Lucas et al., 2019;Hvězdová et al., 2018). Assessment of pesticide residues in soils, most of these studies reported from the US (Marburger et al., 2002), China (Liu et al., 2016), India (Mishra et al., 2012), Brazil (Laabs et al., 2002), South Korea (Park et al., 2020), Japan (Asaoka et al., 2019), or EU countries (Silva et al., 2019). ...
Article
Full-text available
Pesticides have been one of the most extensively used throughout the world. In low- and middle-income countries, pesticides are extensively used in agriculture. Agriculture is Cambodia’s most important economic sector. Around 80% of the population lives in rural areas and is mainly involved in subsistence farming. Cambodian farmers use synthetic pesticides to protect their agricultural products from pest infestation. The increase in agricultural products and the rapid population growth have led to the rise of farming pesticides, which causes concerns about the negative impact on environmental issues and food security in Cambodia. The routes of exposure, toxicity, and pesticide residues in daily food intake are all ambiguous in Cambodia. The scientific reports available in Cambodia could be more extensive and consistent. Therefore, this report provides an overview of the current status of pesticide practices in Cambodia and relates knowledge of pesticide use among local farmers. The contents described the risk assessment of pesticide contamination based on the Cambodian local market. In the same way, the pesticides that farmers use were considered extremely hazardous, highly hazardous, or moderately hazardous by the World Health Organization. This study also discussed the integrated pesticide use management approach and the future perspectives for pesticide practices in Cambodia. The review’s findings raised serious concerns regarding environmental safety and human health. Although some pesticides have been banned, most local farmers still use them for agriculture. The study strongly recommends that the Royal Government of Cambodia be provided with a concrete public health policy on pesticide management and suitable training on pesticide applications.
... The occurrence of pesticide residues is repeatedly confirmed in agricultural soils (Karasali, et al., 2016;Hvězdová, et al., 2018;Silva, et al., 2019;Geissen, et al., 2021;Bakanov, et al., 2023;Riedo, et al., 2023), but no limits have yet been set. ...
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The Hranice hypogenic karst region includes urban, spa and agricultural areas and industry complexes that affect water quality in the region. Emerging organic contaminants (EOCs), especially pesticides and pharmaceuticals, are released into the complex aquatic system. These substances and their metabolites can affect aquatic and human life, as well as the regional development of the wider area traditionally associated with the spa. In this study, we conducted preliminary screening for pesticides and pharmaceuticals at 33 sampling sites and across different location types, including surface water, drainage water, a shallow well, groundwater and thermal karst water. Sampling occurred between February 2022 and June 2023. The results generally confirm that current land use is causing pollution in the karst system. The monitored substances were present in all water types, and in most cases the concentrations of pesticides were lower than those of their metabolites. Chloridazon desphenyl (DESPH) is the most widespread pesticide in surface, ground and hypogenic waters. Its concentrations in surface waters were 5.7 ng·L⁻¹–2,230 ng·L⁻¹, in groundwaters were 11.3 ng·L⁻¹–1,490 ng·L⁻¹ and in karst hypogenic waters 5.4 ng·L⁻¹–378 ng·L⁻¹. Diclofenac was the most widespread substance from the pharmaceutical group. Its concentrations ranged from 5.6 ng·L⁻¹–549 ng·L⁻¹ in surface waters, 8.4 ng·L⁻¹–112 ng·L⁻¹ in groundwaters and 5.1 ng·L⁻¹–47.4 ng·L⁻¹ in karst hypogenic waters. Directly in the karst hypogenic waters, the following EOCs were repeatedly detected: atrazine and its metabolites, simazin, metazachlor ethane sulfonic acid (ESA), metolachlor ESA, alachlor ESA, chloridazon DESPH, diclofenac, ibuprofen, azithromycin, bisphenol A and diethyltoluamide (DEET). The initial research hypothesis is that hydrothermal karst waters are of sub-recent age and deep circulation and, unlike surface and groundwaters, are not contaminated by recent pollutants. A certain component of these waters is therefore a shallow and shorter circulation.
... Overall, our findings in terms of concentration ranges, number of observed residues, and major fate and behavior processes responsible for such exposure are largely in agreement with the published scientific literature. [20][21][22][23] ...
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Synthetic pesticides are widely applied in modern agriculture, where they are used against diseases, pests, and weeds to secure crop yield and quality. However, their intensive application has led to widespread contamination of the environment, including soils. Due to their inherent toxicity, they might pose a risk to soil health by causing harm to non-target organisms and disrupting ecosystem services in both agricultural and other exposed soils. Following the Swiss National Action Plan on the reduction of pesticide risks, Agroscope has conducted several soil monitoring studies that are briefly presented here. All of them resort to different multi-residue trace analytical approaches to simultaneously quantify up to about 150 modern pesticides by either accelerated solvent, or Quick, Easy, Cheap, Efficient, Rugged, Safe (QuEChERS) extraction, followed by separation and detection with liquid chromatography-triple quadrupole mass spectrometry. While partly still in progress, our investigations led to the following major findings this far: Multiple pesticides are commonly present in soils, with individual concentrations in agricultural soils often reaching up to a few tens of µg/kg. Pesticide occurrence and concentrations in agricultural soils primarily depend on land use, land use history and cultivated crops. Pesticides can prevail much longer than predicted by their half-lives, and were found in soils even decades after conversion from conventional to organic farming. Corresponding residual fractions can be in the order of a few percent of the originally applied amounts. We further found negative associations of pesticide residues with the abundance of beneficial soil life, underpinning their potential risk to the fertility of agricultural soils. Traces of pesticides are also detected in soils to which they were never applied, indicating contamination, e.g., via spray drift or atmospheric deposition. These results confirm the general notion of both scientists and legislators that prospective risk assessments (RA; as executed during registration and use authorization) should be confirmed and adjusted by retrospective RA (e.g., by environmental monitoring studies of currently used compounds) to jointly lead to an overall reduced environmental risk of pesticides.
... TEB stands out as one of the most commonly detected pesticides in agricultural soil samples, often found at the highest concentrations [6]. Over 70% of investigated Central European soils have at least one conazole fungicide present in them, with the second most frequent being TEB (36% soil), and it often exceeds the threshold of 0.01 mg/kg [7]. Silva et al. ([6]) reported a median TEB concentration of 0.02 mg/kg, with maximum values ranging from 0.16 to 0.31 mg/kg in European agricultural soils. ...
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Tebuconazole (TEB), a widely used triazole fungicide, is effective against soil-borne and foliar fungal pathogens. Toxicants can exhibit varying effects depending on the life stage of organisms, although standard toxicity tests typically focus on adult individuals. This study aimed to assess TEB’s potential adverse effects on the earthworm Dendrobaena veneta throughout its life cycle. Effects were evaluated by exposing cocoons to varying TEB concentrations, monitoring hatching, newly hatched juvenile mass, and growth to adulthood. A reproduction test assessed impacts on adults, offering insights into how these results compared with cocoon exposure findings. Results revealed that TEB delayed hatching at concentrations of 25, 50, and 100 mg/kg by 6, 8, and 15.5 days, respectively. Newly hatched juveniles exhibited a 15.96% (50 mg/kg) and 27.37% (100 mg/kg) reduction in body mass compared to controls, with no subsequent compensation during growth. Results from the reproduction tests showed no adverse effects on adult survival, but the effects are observed on juveniles, indicating a higher sensitivity of this developmental stage. While several adverse effects were observed, it is important to note that these occurred at concentrations exceeding recommended application rates. TEB appears safe for earthworms when used correctly, but the presence of multiple contaminants and stressors warrants consideration.
... Metolachlor and boscalid were, respectively, the herbicide and the fungicide the most sold in France in 2021 [22]. Some pesticides detected and quantified in the soils of Centre-Val de Loire region in France were also found in previous studies of French soils [8][9][10] and soils of other countries [23][24][25][26][27][28][29][30][31][32][33]. ...
Article
Agricultural soils are not controlled in France for the massive use of pesticides. The quadrupole mass spectrometer is used for targeted analysis of a few dozen pesticides, while the high-resolution time-of-flight quadrupole mass spectrometer (QTOF-MS) allows both targeted and non-targeted analysis of hundreds of pesticides. In this study, a targeted method was developed in soils using pressurised-liquid extraction (PLE) and liquid chromatography (LC) coupled with a QTOF-MS. This method development was necessary to carry out next suspect and non-target screening in soils and has been validated for triazines, phenylureas and emerging pesticides in soils. The internal calibration of pesticides was validated for low levels (0.5 to 12.5 µg L−1) and high levels (12.5 to 400 µg L−1) using labelled internal standards. The determination coefficient (R2) of calibration curve of each pesticide was greater than 0.99. Excepted DCPU and IPPU, the mean recoveries of pesticides in five reference soils spiked at 40 µg kg−1 and 10 µg kg−1 were greater than 93.5% and 106.2%, and the variation coefficients lower than 14.7% and 22.5%, respectively. So, multiplier factors were applied to the quantification results of DCPU and IPPU, respectively, 2.5 and 1.7 for correction. This validated method has been applied to a selection of 40 French soils of Centre-Val de Loire region. The limit of quantification (LOQ) of pesticides varied between 0.005 and 0.175 µg kg−1 in soils. Seven pesticides were the most detected in soils. Seventeen pesticides were detected between 10 and 50% of cases and very low detection frequencies (<10%) were found for 10 pesticides in soils. The mean concentrations were 0.730 µg kg−1 dw for triazines, 1.367 µg kg−1 dw for phenylureas and 7.638 µg kg−1 dw for emerging pesticides. DCPMU and epoxiconazole were detected in all the 40 soils.
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Pesticides are inevitable agrochemicals employed as plant protection agents and their application follows good agricultural practice (GAP). Although pesticides are primarily used for plant protection purposes, the residual pesticides may pose a threat to the next crops and/or off-target biota. Another important aspect of applied pesticides is the transformation into toxic metabolites. As a result, misuse or overuse of pesticides can lead to raised residual uncertainty, hidden risk of transformed metabolites, and potential risk to off-target biota. As per pesticide safety guidelines, regulations for the maximum limit of residual pesticides, addressing toxic metabolites derived from parent pesticides, and managing the potential risk of pesticides for off-targets are considered vital components. Despite the countable number of studies that have already been published on pesticide fate, residual risk, and metabolism in soils and plants, several vital research gaps remain untouched. In this study, the vital research gap of pesticide fate and transport is explored through vital keyword searches, followed by sorting of relevant articles using scholarly search engines. According to the study outcomes, residual uncertainty, secondary pollution, diversified fate and transport, and toxic metabolites, including their persistence, were detected as key research pitfalls. Thus, this paper critically addresses the current trends and research gaps and suggests specific recommendations for pesticide fate and potential risk studies.
Article
Agricultural pesticides occurring in surface freshwaters can be transported back to land via various transport routes, such as emerging insects or flooding. However, we lack information about whether flooding events can contribute to this transport in smaller agricultural catchments and the potential cascading effect of these pesticides on the recipient food web. We used UHPLC-MS/MS to measure 98 pesticides and metabolites in five riparian plant species and root-zone soils collected in five streams in Southwest Germany. All sampling locations included two paired sites differing in their flooding frequency. Six fungicides and three herbicides were frequently detected in regularly flooded sites. The regularly flooded sites contained more pesticides and higher concentrations compared with the rarely flooded sites. This pattern was present in both plants and root-zone soil, suggesting flooding as a vector for the aquatic–terrestrial transport in small streams. Prosulfocarb, pendimethalin, cyflufenamid, and flufenacet occurred at higher concentrations in plants than in soil, while the opposite result was found for spiroxamine, metrafenone, and boscalid. Our study provides evidence from the field that flooding events, which may increase due to climate change, can transport pesticides to riparian soils and plants with potential cascading effects on terrestrial food webs.
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Atrazine, a herbicide used for controlling broadleaf weeds, has been one of the predominant pollutants constituting 80–90% of detection frequency in the samples collected from rivers, estuaries, oceans, sediments, agricultural lands, and crops. The fate of atrazine is highly unpredictable depending on the physio-chemical, physiological and geographical conditions. Range of metabolites such as deethylatrazine (DEA), deisopropyl atrazine (DIA), and didealkylatrzine (DDA) are formed as a result of biotic as well as abiotic degradation process in the environment following cyanuric acid, ammelide, CO2 and NH3 are formed as final products. Atrazine degraded products has shown more hazardous nature than the parent compound, atrazine. Atrazine is banned in Italy, India, Germany and European union but widely used in China, Australian, Canadian and US agriculture. To date, reviews evaluating the assimilation of synerigistic treatment technologies and comparative degration mechanism have not been highlighted. This work focuses on (1) the spatiotemporal distribution of atrazine and its metabolites globally and the factors governing it (2) provides an in-depth discussion about the various studies showing the toxicity of atrazine in microbes, cattle, human, terrestrial and aquatic organisms; (3) discusses the contaminants of emerging concern which are continuously replacing atrazine like terbuthylazine and their intermediate compounds posing more risk to wildlife and humans; (4) summarises the different treatment technologies which have been predominantly applied for the removal of atrazine in water and soil systems and also discusses the synergistic or mutualistic aspects of treatment methods in degrading atrazine.
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Pesticide residues in soils and farmlands have long been an important concern in agricultural safety. In developing countries, ignorance and illiteracy among untutored farmers have greatly contributed to this issue, as several pesticides (herbicides, insecticides, etc.) can leave residues in the soil. The study was carried out in selected arable farms in Ogbomoso South Local Government Area of Oyo state to evaluate and determine the possibility of pesticide residues in the soils of farmers who are fond of using pesticides in crop production. Questionnaires were administered to farmers in the study area and soil samples were collected from some of the farms owned by farmers interviewed and found to have relevant pesticide usage history. Additionally, soil samples were collected from farms with no records of pesticide usage which served as control. Subsequently, these soil samples were then taken to the laboratory for analysis of pesticide residue. The average pH was 5.56 mg/kg for farmlands with pesticide usage and 5.63 mg/kg for those with no pesticide usage, respectively. The average level of metabolites of d-BHC, Chlorothalonil, Alachlor, Aldrin, Dacthal, Heptachlor epoxide, g-Chlordane, and Trans-nonachlor for arable lands where there was pesticide usage and where none were used were 32.41 mg/kg and 39.27 mg/kg, 0.62 mg/kg and 1.05 mg/kg, 1.39 mg/kg and 2.14 mg/kg, N.D and 1.5 mg/kg, 3.91 mg/kg and 10.65 mg/kg, 5.43 mg/kg and 7.62 mg/kg, 6.68 mg/kg and 7.47 mg/kg, and 4.78 mg/kg and 6.4 mg/kg, respectively. The results showed that pesticide usage left residues in the soil and the standard of measuring the amount (whether low or high) is still unavailable in the literature and most importantly for many herbicides in use within the study area. Since there is a leftover chemical residue in the soil, there is therefore the need for a quality assurance body to evaluate what is placed on the table of consumers from the markets and this is currently lacking in the food supply chain in Nigeria and if not in Africa. In conclusion, there is a need for public awareness and education among farmers to know the dangers inherent in the use of pesticides so that precautionary measures will be taken in the application of pesticides.
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Intricate agricultural ecosystems markedly influence the dynamics of organic micropollutants, posing substantial threats to aquatic organisms and human health. This study examined the occurrence and distribution of organic micropollutants across soils, ditch sediment, and water within highly intensified farming setups. Using a nontargeted screening method, we identified 405 micropollutants across 10 sampling sites, which mainly included pesticides, pharmaceuticals, industrial chemicals, and personal care products. This inventory comprised emerging contaminants, banned pesticides, and controlled pharmaceuticals that had eluded detection via conventional monitoring. Targeted analysis showed concentrations of 3.99–1021 ng/g in soils, 4.67–2488 ng/g in sediment, and 12.5–9373 ng/L in water, respectively, for Σ40pesticides, Σ8pharmaceuticals, and Σ3industrial chemicals, indicating notable spatial variability. Soil organic carbon content and wastewater discharge were likely responsible for their spatial distribution. Principal component analysis and correlation analysis revealed a potential transfer of micropollutants across the three media. Particularly, a heightened correlation was decerned between soil and sediment micropollutant levels, highlighting the role of sorption processes. Risk quotients surpassed the threshold of 1 for 13–23 micropollutants across the three media, indicating high environmental risks. This study highlights the importance of employing non-targeted and targeted screening in assessing and managing environmental risks associated with micropollutants.
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Introduction Pollution has emerged as a significant threat to humanity, necessitating a thorough evaluation of its impacts. As a result, various methods for human biomonitoring have been proposed as vital tools for assessing, managing, and mitigating exposure risks. Among these methods, urine stands out as the most commonly analyzed biological sample and the primary matrix for biomonitoring studies. Objectives This review concentrates on exploring the literature concerning residual pesticide determination in urine, utilizing liquid and gas chromatography coupled with mass spectrometry, and its practical applications. Method The examination focused on methods developed since 2010. Additionally, applications reported between 2015 and 2022 were thoroughly reviewed, utilizing Web of Science as a primary resource. Synthesis Recent advancements in chromatography-mass spectrometry technology have significantly enhanced the development of multi-residue methods. These determinations are now capable of simultaneously detecting numerous pesticide residues from various chemical and use classes. Furthermore, these methods encompass analytes from a variety of environmental contaminants, offering a comprehensive approach to biomonitoring. These methodologies have been employed across diverse perspectives, including toxicological studies, assessing pesticide exposure in the general population, occupational exposure among farmers, pest control workers, horticulturists, and florists, as well as investigating consequences during pregnancy and childhood, neurodevelopmental impacts, and reproductive disorders. Future directions Such strategies were essential in examining the health risks associated with exposure to complex mixtures, including pesticides and other relevant compounds, thereby painting a broader and more accurate picture of human exposure. Moreover, the implementation of integrated strategies, involving international research initiatives and biomonitoring programs, is crucial to optimize resource utilization, enhancing efficiency in health risk assessment.
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Agricultural practices are a major cause of the current loss of biodiversity. Among postwar agricultural intensification practices, the use of plant protection products (PPPs) might be one of the prominent drivers of the loss of wildlife diversity in agroecosystems. A collective scientific assessment was performed upon the request of the French Ministries responsible for the Environment, for Agriculture and for Research to review the impacts of PPPs on biodiversity and ecosystem services based on the scientific literature. While the effects of legacy banned PPPs on ecosystems and the underlying mechanisms are well documented, the impacts of current use pesticides (CUPs) on biodiversity have rarely been reviewed. Here, we provide an overview of the available knowledge related to the impacts of PPPs, including biopesticides, on terrestrial vertebrates (i.e. herptiles, birds including raptors, bats and small and large mammals). We focused essentially on CUPs and on endpoints at the subindividual, individual, population and community levels, which ultimately linked with effects on biodiversity. We address both direct toxic effects and indirect effects related to ecological processes and review the existing knowledge about wildlife exposure to PPPs. The effects of PPPs on ecological functions and ecosystem services are discussed, as are the aggravating or mitigating factors. Finally, a synthesis of knowns and unknowns is provided, and we identify priorities to fill gaps in knowledge and perspectives for research and wildlife conservation. Graphical Abstract
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The Scientific Advisory Board of the National Action Plan on the Sustainable Use of Plant Protection Products (NAP) advises the Federal Ministry of Food and Agriculture (BMEL). It has commented on the effects of plant protection on biodiversity in agricultural ecosystems. The decline in biodiversity in the agricultural landscape is striking. Butterfly and bird populations have declined by 50 % since 1990 and 1980 respectively, and the biomass of flying insects has fallen by 75 % since 1989. Species and individual numbers of arable wild herbs, amphibians, fish, sensitive invertebrates in water bodies, wild bees, hoverflies, ground beetles, ladybirds and many other groups of organisms are declining. Of the 14 open land biotope types directly dependent on utilisation, 80 % are endangered in Germany. Other habitats (moors, forest and riparian fringes, herbaceous meadows, etc.) are impaired by agricultural use in the surrounding area. The direct and indirect effects of plant protection products are documented by a large number of scientific studies in Germany and other European countries. The use of plant protection products (insecticides, fungicides, herbicides) represents a significant influencing factor in the complex overall system of factors with mostly significantly negative, but in exceptional cases also positive effects on biodiversity in agroecosystems. Plant protection products get into and onto plants, animals and soils, into the atmosphere and into water bodies and groundwater; they develop their harmful side effects in both short and very long periods of time. They can cause direct toxic effects on non-target organisms and indirectly reduce the food and habitats of a large number of organisms. In addition, there are cumulative and sequential effects, as plant protection products are often applied together 4 and a combined effect of environmental stressors and plant protection products becomes particularly relevant when applied in the field. The NAP Scientific Advisory Council therefore proposes the following measures for sustainable plant protection: 1. the further development of biodiversity should be assessed in a standardised way by introducing a representative, comprehensive long-term biodiversity monitoring system that focuses on the effects of plant protection products. 2. the authorisation procedure for plant protection products should be reviewed for possible gaps in the assessment of effects on biodiversity on the basis of the latest knowledge, and these findings should be incorporated into the amendment of European authorisation law. 3. positive and negative incentives should be created for agricultural practice in order to reduce the use of plant protection products in practice. To this end, a levy on plant protection products should also be examined and, in the medium term, a scientifically based system of internalising environmental costs (true cost accounting) should be proposed. 4. integrated plant protection methods should be further strengthened through research and advice, and breeding should focus on pest-tolerant or pest-resistant varieties. 5. the framework conditions for organic farming should be further improved in order to achieve the Federal Government's goal of increasing its share of land to 20 % as quickly as possible. 6. within the framework of the Common Agricultural Policy (CAP) and the agri-environmental measures (EAFRD), diverse landscape elements, habitats and preferred ecological areas and buffer zones integrated into the production area should be promoted to a much greater extent than before.
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Arthropods represent an entry point for pesticide transfers in terrestrial food webs, and pesticide accumulation in upper chain organisms, such as predators can have cascading consequences on ecosystems. However, the mechanisms driving pesticide transfer and bioaccumulation in food webs remain poorly understood. Here we review the literature on pesticide transfers mediated by terrestrial arthropods in food webs. The transfer of pesticides and their potential for bioaccumulation and biomagnification are related to the chemical properties and toxicokinetic of the substances, the resistance and detoxification abilities of the contaminated organisms, as well as by their effects on organisms’ life history traits. We further identify four critical areas in which knowledge gain would improve future predictions of pesticides impacts on terrestrial food webs. First, efforts should be made regarding the effects of co-formulants and pesticides mixtures that are currently understudied. Second, progress in the sensitivity of analytical methods would allow the detection of low concentrations of pesticides in small individual arthropods. Quantifying pesticides in arthropods preys, their predators, and arthropods or vertebrates at higher trophic level would bring crucial insights into the bioaccumulation and biomagnification potential of pesticides in real-world terrestrial food webs. Finally, quantifying the influence of the trophic structure and complexity of communities on the transfer of pesticides could address several important sources of variability in bioaccumulation and biomagnification across species and food webs. This narrative review will inspire future studies aiming to quantify pesticide transfers in terrestrial food webs to better capture their ecological consequences in natural and cultivated landscapes.
Chapter
Medicinal plants have been used in traditional medicine, health food supplements, rituals, and for health care purposes for thousands of years. According to the Food and Agriculture Organization of the United Nations (FAO), the worldwide production of medicinal and aromatic plants is estimated to be 330 million tons for a total area of 77 million ha. Nowadays, the sector of medicinal plants is subject to inconstancy, and issues about the yield, quality, and efficacy of plant extracts have been reported. The present review describes the current status of medicinal plants worldwide, including a detailed description of the sector in France. The suitability of vertical farming for the production of medicinal plants is discussed, and its advantages and drawbacks are presented. Indoor cultivation in a controlled environment requires appropriate adjustment of abiotic factors to optimize biomass and secondary metabolite contents. Light quantity and quality, nutrient solution, temperature, and CO2 concentration are presented in relation with their impact on plants and on the production of the targeted phytocompound. A case-study on the technic feasibility and economic viability of producing a plant-based drug in a vertical container is presented, including plant cultivation and drug extraction steps. Based on the costs related directly to the production activity, it provides a rapid estimate of the direct production cost of each step. The largest contributor to cultivation costs is labor, averaging 48%, followed by energy (20%) and investment cost (20%). The largest contributor to extraction and purification costs is the operating and maintenance cost of equipment (47%), followed by energy cost (31%) and labor cost (16%). The largest contributor to the whole plant-based drug production process, from plant cultivation to drug production, is the research and development cost (98–67%), followed by cultivation and extraction costs (1–24%) and drug manufacturing costs (1–8%), depending on the number of containers, i.e., on the productivity of the cultivation and extraction steps.
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Natural systems are under increasing pressure by a range of anthropogenic global change factors. Pesticides represent a nearly ubiquitously occurring global change factor and have the potential to affect soil functions. Currently the use of synthetic pesticides is at an all-time high with over 400 active ingredients being utilized in the EU alone, with dozens of these pesticides occurring concurrently in soil. However, we presently do not understand the impacts of the potential interaction of multiple pesticides when applied simultaneously. Using soil collected from a local grassland, we utilize soil microcosms to examine the role of both rate of change and number of a selection of ten currently used pesticides on soil processes, including litter decomposition, water stable aggregates, aggregate size, soil pH, and EC. Additionally, we used null models to enrich our analyses to examine potential patterns caused by interactions between pesticide treatments. We find that both gradual and abrupt pesticide application have negative consequences for soil processes. Notably, pesticide number plays a significant role in affecting soil health. Null models also reveal potential synergistic behavior between pesticides which can further their consequences on soil processes. Our research highlights the complex impacts of pesticides, and the need for environmental policy to address the threats posed by pesticides.
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The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State, France, and co-rapporteur Member State, Belgium, for the pesticide active substance iprodione are reported. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012. The conclusions were reached on the basis of the evaluation of the representative uses of iprodione as a fungicide on carrots and lettuce. The reliable endpoints, appropriate for use in regulatory risk assessment are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.
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Extensive soil sampling and screening assessment of ecosystem risks combined with a multidimensional statistical analysis were used to estimate and spatially characterize the ecosystem risks stemming from the contamination of floodplain soils in the Czech Republic. We proved structural differences in regional pollution patterns where different regional/local pollution sources led to various nature and extent of the environmental load of floodplain soils. The established spatial patterns helped reveal the areas where soils do not meet soil quality standards and where the ecosystem risks were elevated. Furthermore, the results allowed to establish priority contaminants of flood affected areas in various catchments in the Czech Republic. Combining both the magnitudes of estimated ecosystem risks and structural characteristics of pollution profiles, the highest estimated risks showed the localities with high contents of organochlorine pesticides, several samples connected to geochemical anomalies of metallogenic zones (deposits), and localities with a long history of industrial load. Since extreme weather events have recently become more frequent, our results highlight the importance of a continual monitoring of pollutant turnover in floodplain soils with a high flood frequency.
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In recent years, countries both developed and developing ones have experienced a rapid economic globalization expanding economic activities. Although this economic globalization process is fruitful for the economy; however, what role it plays in the promotion of the human development index is still unknown. To this end, the study tries to explore the linkage among economic globalization, real income, and human development index in Asian countries from 1990 to 2015. The advanced econometric techniques that allow dependencies across countries are employed. The panel cointegration approach, Westerlund (2007) panel cointegration test, confirms the cointegration relationship among study variables, and the study estimates long-run cointegration parameters. Results reveal that economic globalization has not a significant impact on human development. However, real income promotes human development in Asian countries.
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The purpose of this work was to evaluate the acetochlor degradation rate in soils and investigate acetochlor contamination of maize grains and soil. Two kinds of soil: medium silty loam (soil A) and heavy loamy sand (soil B) were collected for the laboratory experiment. The degradation data were plotted. Good linearity was found between logarithmic concentration of acetochlor residues and time, indicating first-order rates of degradation. The t1/2values varied from 10.5 days for soil A to 15.1 days for soil B. The degradation rate depends on the soil properties. In the soil A (higher content of clay and organic carbon) the t1/2value was shorter than in the soil B. Monitoring tests were carried out during the 2010–2012 time period on maize fields located in the south-western Poland. Soil and maize grain samples were collected at harvest time. The determination of acetochlor residues was conducted using gas chromatography with electron capture detection. Based on the analysis of a total of 124 environmental samples, acetochlor residues were detected in 17.4% of soil and 8.1% of maize grain samples. None of the examined samples showed a herbicide concentration exceeding the maximum residue level. © 2014, Institute of Agricultural and Food Information. All rights reserved.
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In this work, a total of 38 pesticides was monitored in the Danube River Basin in Serbia during ten sampling campaigns in 2009, 2010, and 2011. The quantification of analytes was performed using procedures based on solid-phase extraction (SPE) followed by LC–MS/MS or GC–MS. In general, low pesticide levels were found, except for the samples collected during May–June of 2010 and June of 2011. During this period, pesticide application is high and rainfall was described as extremely above normal or above normal, leading to very pronounced runoff and very high detected pesticide levels. At the sampling site Smederevo (the Danube River), high concentrations of terbuthylazine (200 ng L−1) and metolachlor (150 ng L−1) were found. In the Danube tributary Morava, high concentrations of carbendazim (269 ng L−1), atrazine (188 ng L−1), terbuthylazine (180 ng L−1), and acetochlor (110 ng L−1) were detected, while in the tributary Tisa only terbuthylazine was present at high levels (130 ng L−1). In other sampling campaigns, pesticides were present at low concentrations. The most frequently found pesticide was carbendazim, probably due to slow degradation rate in environment.
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A series of monitoring studies were carried out to evaluate the residue level of pesticides in different native soils from 1999 to 2006. The nation-wide collection of soil samples from paddy, greenhouse, upland and orchard, were analyzed by GLC (ECD or NPD) and GC/MS. The results obtained are summarized as follows; out of 14 pesticides detected from paddy soils in 1999, the highest residue level was 0.25 mg , and the frequency was 21.7% as butachlor, 20.0% as isoprothiolane, and 16.7% as iprobenfos. In 2003, 7 pesticides were detected and their frequencies were 0~36.0%; the frequency was 36.0% as isoprothiolane and 33.3% as oxadiazon. In the year 2000, 57 pesticides in the greenhouse soil samples were detected with the highest frequency of 65.3%. Of the pesticides detected, endosulfan and procymidone showed the frequency of 65.3 and 50.0%, respectively. In 2004, 19 pesticides were detected from greenhouse soils, and their frequencies and residue levels were decreased. Endosulfan and procymidone showed high detection frequencies and concentrations of 21.3 and 9.3% and 0.76 and 0.31 mg , respectively. In 2001, a total of 25 pesticides were detected through monitoring in 170 upland soils and the highest residue level was 2.24 mg . The detection frequencies showed the range of 0~53.5%. Especially, endosulfan showed the highest frequency of 53.5%. Residue levels and frequencies of pesticide in the year 2005 were almost the same compared with that of the year 2001. As a result of monitoring in 150 orchard soils in 2002, 26 pesticides were detected and the highest residue level was 1.43 mg . Of them, the frequency of endosulfan showed the highest as 45.3%. In 2006, 20 pesticides were detected in orchard soils. The frequency of total endosulfan was the highest as 5.3% but was lower than that of the year 2002.
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Abstract Conventional risk assessments for crop protection chemicals compare the potential for causing toxicity (hazard identification) to anticipated exposure. New regulatory approaches have been proposed that would exclude exposure assessment and just focus on hazard identification based on endocrine disruption. This review comprises a critical analysis of hazard, focusing on the relative sensitivity of endocrine and non-endocrine endpoints, using a class of crop protection chemicals, the azole fungicides. These were selected because they are widely used on important crops (e.g. grains) and thereby can contact target and non-target plants and enter the food chain of humans and wildlife. Inhibition of lanosterol 14α-demethylase (CYP51) mediates the antifungal effect. Inhibition of other CYPs, such as aromatase (CYP19), can lead to numerous toxicological effects, which are also evident from high dose human exposures to therapeutic azoles. Because of its widespread use and substantial database, epoxiconazole was selected as a representative azole fungicide. Our critical analysis concluded that anticipated human exposure to epoxiconazole would yield a margin of safety of at least three orders of magnitude for reproductive effects observed in laboratory rodent studies that are postulated to be endocrine-driven (i.e. fetal resorptions). The most sensitive ecological species is the aquatic plant Lemna (duckweed), for which the margin of safety is less protective than for human health. For humans and wildlife, endocrine disruption is not the most sensitive endpoint. It is concluded that conventional risk assessment, considering anticipated exposure levels, will be protective of both human and ecological health. Although the toxic mechanisms of other azole compounds may be similar, large differences in potency will require a case-by-case risk assessment.
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Available from: http://www.intechopen.com/articles/show/title/endocrine-disrupting-pesticides
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Hydroxyatrazine (HA) is the major metabolite of atrazine in most surface soils. Knowledge of HA sorption to soils, and its pattern of stream water contamination suggest that it is persistent in the environment. Soils with different atrazine use histories were collected from four sites, and sediments were collected from an agricultural watershed. Samples were exhaustively extracted with a mixed—mode extractant, and HA was quantitated using high performance liquid chromatography with UV detection. Atrazine, deethylatrazine (DEA), and deisopropylatrazine (DIA) were also measured in all samples. Concentrations of HA were considerably greater than concentrations of atrazine, DEA, and DIA in all soils and sediments studied. Soil concentrations of HA ranged from 14 to 640 μg/kg with a median concentration of 84 μg/kg. Sediment concentrations of HA ranged from 11 to 96 μg/kg, with a median concentration of 14 μg/kg. Correlations of HA and atrazine concentrations to soil properties indicated that HA levels in soils were controlled by sorption of atrazine. Because atrazine hydrolysis is known to be enhanced by sorption and pH extremes, soils with high organic matter (OM) and clay content and low pH will result in greater atrazine sorption and subsequent hydrolysis. Significant correlation of HA concentrations to OM, pH, and cation exchange capacity of sediments indicated that mixed—mode sorption (i.e., binding by cation exchange and hydrophobic interactions) was the mechanism controlling HA levels in sediment. The presence of HA in soils and stream sediments at the levels observed support existing hypotheses regarding its transport in surface runoff. These results also indicated that persistence of HA in terrestrial and aquatic ecosystems is an additional risk factor associated with atrazine usage.
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As one of the worlds’ most heavily applied herbicides, atrazine is still a matter of controversy. Since it is regularly found in ground and drinking water, as well as in sea water and the ice of remote areas, it has become the subject of continuous concern due to its potential endocrine and carcinogenic activity. Current findings prove long-held suspicions that this compound persists for decades in soil. Due to the high amount applied annually all over the world, the soil burden of this compound is considered to be tremendous, representing a potential long-term threat to the environment. The persistence of chemicals such as atrazine has long been underestimated: Do we need to reconsider the environmental risk? Electronic supplementary material The online version of this article (doi:10.1007/s11356-010-0431-y) contains supplementary material, which is available to authorized users.
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It is known that the sources of soil contamination can be endogenous or exogenous and that exogenous contamination may be direct or indirect. In this work, an environmental pesticide fate study was conducted in soil profiles collected from 23 rice field sites in an important Mediterranean wetland (Albufera Natural Park, Valencia, Spain) from April 1996 to November 1997. Temporal and spatial distribution of 44 pesticide residues in an alluvial Mediterranean soil (gleyic-calcaric Fluvisol, Fluvaquent) were monitored. During this period, the levels of pesticide residues in different soil horizons (Ap1 0-12 cm, Ap2 12-30 cm, ApCg 30-50 cm, C1gr 50-76 cm, and C2r 76-100 cm) were investigated. In addition, information was collected on agricultural pesticide application practices and soil characteristics. Distribution throughout the soil profile showed that pesticide concentrations were always higher in the topsoil (Ap1 horizon), in the autumn season, and in the border with citrus-vegetable orchard soils (calcaric Fluvisol, Xerofluvent). Chlorpyrifos (organophosphorus), endosulfan (organochlorine), and pyridaphenthion (organophosphorus) insecticides were, respectively, the most detected of all the pesticides investigated. These results were associated with processes, such as nonleaching, transport by movement into surface waters, retention, volatilization, and chemical and biological degradation in the topsoil, as well as with direct and indirect exogenous contamination sources.
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A simple, fast, and inexpensive method for the determination of pesticide residues in fruits and vegetables is introduced. The procedure involves initial single-phase extraction of 10 g sample with 10 mL acetonitrile, followed by liquid-liquid partitioning formed by addition of 4 g anhydrous MgSO4 plus 1 g NaCl. Removal of residual water and cleanup are performed simultaneously by using a rapid procedure called dispersive solid-phase extraction (dispersive-SPE), in which 150 mg anhydrous MgSO4 and 25 mg primary secondary amine (PSA) sorbent are simply mixed with 1 mL acetonitrile extract. The dispersive-SPE with PSA effectively removes many polar matrix components, such as organic acids, certain polar pigments, and sugars, to some extent from the food extracts. Gas chromatography/mass spectrometry (GC/MS) is then used for quantitative and confirmatory analysis of GC-amenable pesticides. Recoveries between 85 and 101% (mostly > 95%) and repeatabilities typically < 5% have been achieved for a wide range of fortified pesticides, including very polar and basic compounds such as methamidophos, acephate, omethoate, imazalil, and thiabendazole. Using this method, a single chemist can prepare a batch of 6 previously chopped samples in < 30 min with approximately 1 dollar (U.S.) of materials per sample.
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Pesticides are intensively used in agriculture, and much effort is expended to manage and reduce possible deleterious effects on the environment. The soil compartment has a major influence on the fate and behaviour of pesticides applied to crops preemergence or early postemergence or chemicals subject to washoff from crop surfaces. Once in the soil, pesticide molecules partition between the aqueous and solid phases, which affects many other aspects of their behaviour: sorption can be rate limiting to volatilization, bioavailability (and thus efficacy and biodegradation rate), and subsurface transport. Understanding the fate of a pesticide in soil is fundamental to the accurate assessment of its environmental behaviour and vital in ensuring the safe use of new and existing products. It is also necessary to develop and validate computer simulation models for use as predictive tools in future environmental fate assessments.
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Simazine [2-chloro-4,6-bis(ethylamino)- s -triazine] was applied annually at 4.5 kg/ha to uncultivated sandy loam of peach ( Prunus persica Batsch) for 7 yr (orchard A) and 9 yr (orchard B). Simazine and the metabolite, hydroxysimazine [2-hydroxy-4,6-bis (ethylamino)- s -triazine] as determined by gas chromatography (GC) persisted for 40 and 28 months in soil of orchard A and B, respectively. However, no progressive accumulation of either compound in large quantities occurred from repeated annual applications of simazine to the orchard soils. No metabolites other than hydroxysimazine were detected. Hydroxysimazine was degraded more slowly than simazine and the residue levels of hydroxysimazine were at least 40 times those of simazine 40 months and 28 months after the final application in orchard A and B, respectively. Both simazine and hydroxysimazine residues were detected in the upper 30 cm of the soil profile.
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For polar and more degradable pesticides, not many data on long-term persistence in soil under field conditions and real application practices exist. To assess the persistence of pesticides in soil, a multiple-compound screening method (log Kow 1.7-5.5) was developed based on pressurized liquid extraction, QuEChERS and LC-HRMS. The method was applied to study 80 polar pesticides and >90 transformation products (TPs) in archived topsoil samples from the Swiss Soil Monitoring Network (NABO) from 1995 to 2008 with known pesticide application patterns. The results reveal large variations between crop type and field sites. For the majority of the sites 10 to 15 pesticides were identified with a detection rate of 45% at concentrations between 1 and 330 µg/kgdw in soil. Furthermore, TPs were detected in 47% of the cases where the "parent-compound" was applied. Overall, residues of about 80% of all applied pesticides could be detected with half of these found as TPs with a persistence of more than a decade.
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Ongoing systematic monitoring of pesticide residues in environmental matrices in Hungary since 1999 revealed extensive point contamination of both surface water and soil throughout the country. Major soil contaminant pesticides appeared to be DDT (and its metabolite DDE), lindane and atrazine at highest levels of 10 to 400 ng g-1. Most common water polluting pesticide active ingredients include atrazine and acetochlor at concentrations of 0.1 to 10 ng ml-1, as well as diazinone and trifluralin at lower levels. Chlorophenoxy acid type herbicide residues, dichlorprop, MCPA and 2,4,5-T, detected by a novel derivatization technique, were occasionally found at concentrations of 0.004-0.03 ng ml-1. Irrigation water is often contaminated with diazinone, atrazine or trifluralin, causing unintended pesticide exposure of irrigated soil and the environment, in general. Particularly at risk are watershed areas of pesticide production or formulation facilities and depositories, as well as corn growing regions. Atrazine and acetochlor contamination of the river Danube reaches raw drinking water, possibly causing continuous exposure as a prerequisite for chronic diseases. Some of the detected pesticide contamination appear to be persistent, questioning sustainability of certain existing agricultural technologies.
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Despite a changing world in terms of data sharing, availability, and transparency, there are still major resource issues associated with collating datasets that will satisfy the requirements of comprehensive pesticide risk assessments, especially those undertaken at a regional or national scale. In 1996, a long-term project was initiated to begin collating and formatting pesticide data to eventually create a free-to-all repository of data that would provide a comprehensive transparent, harmonized, and managed extensive dataset for all types of pesticide risk assessments. Over the last 20 years, this database has been keeping pace with improving risk assessments, their associated data requirements, and the needs and expectations of database end users. In 2007, the Pesticide Properties DataBase (PPDB) was launched as a free-to-access website. Currently, the PPDB holds data for almost 2300 pesticide active substances and over 700 metabolites. For each substance around 300 parameters are stored, covering human health, environmental quality, and biodiversity risk assessments. With the approach of the twentieth anniversary of the database, this article seeks to elucidate the current data model, data sources, its validation, and quality control processes and describes a number of existing risk assessment applications that depend upon it.
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In the Netherlands, environmental risk limits (ERLs) are used as policy tools for the protection of ecosystems. Species Sensitivity Distributions (SSDs) play an important role in deriving ERLs, which are subsequently used by the Dutch government to set environmental quality standards (EQSs) for various policy purposes. This chapter aims to make transparent how the ERLs are derived and for which purposes they are used. The information may thus be useful for interested parties in other countries for developing their own ERLs, by adoption of one or more of the methodologies, or by providing insight into the procedure. The chapter provides an overview of the methodologies that are used for deriving the ERLs. SSDs are preferred over other methods, such as using safety factors. In addition, it will show which type of information is needed as input for SSDs and for deriving ERLs. Reference is made as to where to find the numerical values for both ERLs and EQSs.
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A new method for simultaneous determination of 36 pesticides, including 15 organophosphorus, six carbamate and some other pesticides in soil was developed by liquid chromatography with tandem quadruple linear ion trap mass spectrometry. The extraction and clean-up steps were optimized based on the quick, easy, cheap, effective, rugged, and safe method. The data were acquired in multiple reaction monitoring mode combined with enhanced product ion to increase confidence of the analytical results. Validation experiments were performed in soil samples. The average recoveries of pesticides at four spiking levels (1, 5, 50 and 100 μg kg(-1) ) ranged from 63 to 126% with relative standard deviation below 20%. The limits of detection of pesticides were 0.04-0.8 μg kg(-1) , and the limits of quantification were 0.1-2.6 μg kg(-1) . The correlation coefficients (r(2) ) were higher than 0.990 in the linearity range of 0.5-200 μg L(-1) for most of the pesticides. The method allowed for the analysis of the target pesticides in the lower μg kg(-1) concentration range. The optimized method was then applied to the test of real soil samples obtained from several areas in China, confirming the feasibility of the method. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.
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Sorption is one of the major processes that determine the fate, effects, efficacy and ecological risks of pesticides in terrestrial and aquatic environments. In this chapter we provide an overview of sorption and its dependence on soil properties. Soil solid phase consists of mineral and organic matter; both in strong association with each other make a contribution towards sorption of pesticides, depending on their relative abundance in soil/sediments, chemistry and the chemical nature of the pesticide molecule. We discuss the roles of organic matter and clay contents as well their chemistries in determining sorption of pesticides, and assess the partition theory in terms of its adequacy in describing the observed sorption behavior of pesticides in soil. The complex interactions and heterogeneities associated with the soil solid phase contribute to the large degree of variation in Koc , a parameter that is often used to extrapolate the pesticide sorption estimate, among soils. A more comprehensive approach incorporating soil organic matter as well as soil minerals (both contents as well as their chemistries) is therefore desirable to fully incorporate the role of soil surfaces in sorption of organic compounds. Therefore, we introduce some emerging approaches based on chemometrics and infrared spectroscopy that appear promising for comprehensive representations of the combined role of organic matter, mineralogy and other soil properties in estimating pesticide sorption in soil.
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This research has evaluated the agricultural impact of the use of pesticides in small agricultural areas in the Águeda river basin, which straddles the Spanish-Portuguese border. Sixteen pesticides frequently used in the area, including herbicides, fungicides and insecticides and some of their degradation products, were monitored in 52 groundwater samples and 42 soil samples taken around them, using a developed multi-residual analytical method based on SPE-LC-MS. Sampling was carried out in two different seasons (winter and summer). The results indicated the presence of pesticides at several levels, both in groundwaters and soils. Thirteen of the pesticides studied were detected in one or more of the groundwater samples analysed, but only three pesticides were detected in the soil samples. Terbuthylazine, cyprodinil, tebuconazole and chlorpyrifos were the pesticides most frequently detected in groundwaters, whereas terbuthylazine, metalaxyl and tebuconazole were the sole compounds detected in soils. The distribution of the concentrations in groundwaters indicated that up to 80% and 70% of the samples collected in the summer on the Spanish and Portuguese sides, respectively, exceed the quality standards of 0.1 µg L−1 for one or more individual compounds and, in turn, up to 64% and 40% exceed the quality standards of 0.5 µg L−1 for all compounds. The presence of pesticide residues in the groundwaters and soils analysed may well be explained by the use of these compounds in agricultural practices.
Article
In the development of a complex soil contamination monitoring system including the detection of agriculture-related micropollutants, heavy metal contamination and ecotoxicity, a survey has been carried out in Békés county and at certain water catchment areas in Hungary, using different techniques for the characterisation of soil and surface water status. Besides the representativity optimisation of the sampling technique, instrumental analysis, biological tests (soil biology and aquatic toxicity) were also applied, and results obtained were presented in a spatial informatics system. The target analyte group, indicators and methodology is in compliance with recommendations of the European Environment Agency monitoring working group. Contaminant concentrations of soil profiles have been characterised down to the ground water table. Pesticide residues were monitored by using gas chromatography coupled with mass spectrometry and enzyme-linked immunosorbent assay. Target analytes included triazine, phenoxyacetic acid, acetanilide, dinitroaniline and phosphonomethylglycine type herbicides, chlorinated hydrocarbons (CHCs), organophosphate and carbamate insecticides, an insect hormonal agonist and a triazole fungicide. Besides banned persistent CHC insecticides (DDT, HCH, etc.), atrazine and acetochlor herbicides are common contaminants in Hungary, reaching 200 ng/g and 300 ng/mL concentration in the soil and surface water samples studied, and trifluralin, glyphosate and metolachlor were also detected in some cases. Heavy metal and other microelement contamination was detected by inductively coupled plasma atomic emission spectroscopy, and within-plot heterogeneities were studied throughout soil profiles. Nickel has been found as a relatively common contaminant in arable lands in the area, however, relation of the contamination pattern to fertiliser usage in the region could not be confirmed. Total microbiological activity was analysed by using fluoresce in diacetate (FDA) hydrolysis. The results of this measurement did not show correlation with heavy metal content or with land use types. Toxic effects of water and soil samples were determined on Daphnia magna Straus (Cladocera, Crustacea) according to the ISO 6341:1996 standard. The vast majority of the samples exerted no observable toxicity on this bioindicator organism. Overall toxicity often occurred not asthe sum of the reported toxicity of the individual contaminants found: cases of antagonistic and synergistic effects in toxicity were both observed.
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Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) is an extraction and clean-up technique originally developed for recovering pesticide residues from fruits and vegetables. Since its introduction, and until December 2013, about 700 papers have been published using the QuEChERS technique, according to a literature overview carried out using SciFinder, Elsevier SciVerse, and Google search engines. Most of these papers were dedicated to pesticide multiresidue analysis in food matrices, and this topic has been thoroughly reviewed over recent years. The QuEChERS approach is now rapidly developing beyond its original field of application to analytes other than pesticides, and matrices other than food, such as biological fluids and non-edible plants, including Chinese medicinal plants. Recently, the QuEChERS concept has spread to environmental applications by analyzing not only pesticides but also other compounds of environmental concern in soil, sediments, and water. To the best of our knowledge, QuEChERS environmental applications have not been reviewed so far; therefore, in this contribution, after a general discussion on the evolution and changes of the original QuEChERS method, a critical survey of the literature regarding environmental applications of conventional and modified QuEChERS methodology is provided. The overall recoveries obtained with QuEChERS and other extraction approaches (e.g., accelerated solvent extraction, ultrasonic solvent extraction, liquid/solid extraction, and soxhlet extraction) were compared, providing evidence for QuEChERS higher recoveries for various classes of compounds, such as biopesticides, chloroalkanes, phenols, and perfluoroalkyl substances. The role of physicochemical properties of soil (i.e., clay and organic carbon content, as well as cation exchange capacity) and target analytes (i.e., log KOW, water solubility, and vapor pressure) were also evaluated in order to interpret recovery and matrix effect data.