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The aim of the present research was the development and validation of a selective and reliable method for the indirect and direct determination of acidic herbicide glucosides. Enzymatic deconjugation was investigated as a mild alternative to harsh alkaline hydrolysis. Various enzymatic options for deconjugation were exploited. One out of nine tested specific enzymes proved to be practical and repeatable for different matrices and concentration ranges, leading to the complete deconjugation of the glucosides. The method was validated according to the SANTE/11312/2021 guideline for cereals and oilseeds and for a rice-based infant formula. Additionally, for four acidic herbicide glucosides available on the market, a quantitative method for direct determination of the intact glucosides was optimized and validated. In both methods, the average recoveries were within 70-120%. The limits of quantification (LOQ) achieved were 10 µg kg-1 and 2.5 µg kg-1 for the intact glucosides and the free acids in cereal and oilseeds. For the rice-based infant formula, the LOQ was 1 µg kg-1 (3 µg kg-1 for dichlorprop). To confirm its applicability, the deconjugation approach was tested for fifteen samples (cereals, oilseeds, and citrus) with incurred residues. Comparisons were made between the method without deconjugation, and two methods with deconjugation, the here proposed enzymatic deconjugation and the more commonly used alkaline hydrolysis. The inclusion of enzymatic deconjugation during sample preparation led to an increase up to 2.7-fold compared to analysis without deconjugation. Enzymatic deconjugation resulted in comparable results to alkaline hydrolysis for 13 out of 15 samples.
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Herbicidas , Humanos , Lactante , Herbicidas/análisis , Cromatografía Liquida/métodos , Grano Comestible/química , Glucósidos/análisis , Espectrometría de Masas en Tándem/métodosRESUMEN
The presence of pesticide residues in waterbed sediments poses a significant concern for aquatic ecosystems' health. This study examined pesticide contamination in sediments of 38 water bodies, embedded in agricultural-dominated regions, across eight European countries. Three indicators were targeted: occurrence, type, and concentrations of multiple pesticide residues in sediments. 196 pesticide residues (including degradation products) were tested in the sediment samples. The analytical results showed that only one sample was 'pesticide-free', three samples contained a single pesticide residue, and the remaining 34 samples contained mixtures of residues. Overall, 99 different residues were found in the sediments, with a maximum of 48 in a single sample. Twenty-seven out of the 99 detected residues were not approved for agricultural use at the time of sampling. The numbers of detected residues and pesticide levels varied among countries. AMPA, glyphosate and DDTs were the most common residues in sediment samples with frequencies of 76, 61, and 52%, respectively. The sediments from the Czech Republic had the highest pesticide concentrations, with total pesticide concentrations ranging between 600 and 1200 µg kg-1. The lowest total pesticide concentrations were found in Slovenia, Switzerland, Croatia, and Denmark, ranging between 80 and 120 µg kg-1. Sediments presented a mix of non-persistent and persistent compounds. Twelve of the detected pesticides are very persistent/stable in sediments, raising concerns about the long-term impacts of pesticides. Our study on the distribution of pesticide residues in European sediments provides valuable insights into the extent of pesticide contamination and possible risks of pesticides to water bodies' health. It also underlines the need for monitoring, research, and policy efforts to mitigate the impacts of pesticides, and to evaluate potential risks of re-use of dredged sediments.
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A set of quality assurance/quality control (QA/QC) criteria for nontargeted measurement of pesticide exposure markers in a large-scale study of human urine has been proposed and applied across five laboratories within the HBM4EU project. Quality control material, including reference standards and fortified pooled urine samples (QC urine) were prepared in a centralized way and distributed across participants to monitor analytical performance and consistency of the liquid chromatography coupled to high-resolution mass spectrometry data generated with a harmonized workflow. Signal intensities, mass accuracy, and retention times of selected QA/QC markers covering a broad range of physicochemical properties were monitored across QC solvent standards, QC urine samples, study urine samples, and procedural blanks, setting acceptance thresholds for repeatability and accuracy. Overall, results showed high repeatability of the collected data. The RSDs of the signal intensities were typically below 20-30% in QC and study samples, with good stability of the chromatographic separation (retention time drift within 2-4 s intrabatch and 5 s interbatch) and excellent mass accuracy (average error < 2 ppm). The use of the proposed criteria allowed for the identification of handling errors, instrumental issues, and potential batch effects. This is the first elaboration of harmonized QA/QC criteria applied across multiple laboratories to assess the quality of data generated by nontargeted analysis of human samples.
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Plaguicidas , Biomarcadores , Cromatografía Liquida , Humanos , Espectrometría de Masas/métodos , Control de CalidadRESUMEN
The Human Biomonitoring for Europe initiative (HBM4EU) aims to study the exposure of citizens to chemicals and potentially associated health effects. One objective of this project has been to build a network of laboratories able to answer to the requirements of European human biomonitoring studies. Within the HBM4EU quality assurance and quality control scheme (QA/QC), a number of interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) were organized to ensure data consistency, comparability and reliability. Bisphenols are among the prioritized substance groups in HBM4EU, including bisphenol A (BPA), bisphenol S (BPS) and bisphenol F (BPF) in human urine. In four rounds of ICI/EQUAS, two target concentration levels were considered, related to around P25 and P95 of the typical exposure distribution observed in the European general population. Special attention was paid to the conjugated phase II metabolites known to be most dominant in samples of environmentally exposed individuals, through the analysis of both native samples and samples fortified with glucuronide forms. For the low level, the average percentage of satisfactory results across the four rounds was 83% for BPA, 71% for BPS and 62% for BPF. For the high level, the percentages of satisfactory results increased to 93% for BPA, 89% for BPS and 86% for BPF. 24 out of 32 participating laboratories (75%) were approved for the analyses of BPA in the HBM4EU project according to the defined criterion of Z-scores for both low and high concentration levels in at least two ICI/EQUAS rounds. For BPS and BPF, the number of qualified laboratories was 18 out of 27 (67%) and 13 out of 28 (46%), respectively. These results demonstrate a strong analytical capability for BPA and BPS in Europe, while improvements may be needed for BPF.
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Compuestos de Bencidrilo , Monitoreo Biológico , Compuestos de Bencidrilo/orina , Europa (Continente) , Humanos , Laboratorios , Fenoles , Reproducibilidad de los ResultadosRESUMEN
The European Human Biomonitoring Initiative (HBM4EU) is coordinating and advancing human biomonitoring (HBM). For this purpose, a network of laboratories delivering reliable analytical data on human exposure is fundamental. The analytical comparability and accuracy of laboratories analysing flame retardants (FRs) in serum and urine were investigated by a quality assurance/quality control (QA/QC) scheme comprising interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds performed from 2018 to 2020 for the determination of ten halogenated flame retardants (HFRs) represented by three congeners of polybrominated diphenyl ethers (BDE-47, BDE-153 and BDE-209), two isomers of hexabromocyclododecane (α-HBCD and γ-HBCD), two dechloranes (anti-DP and syn-DP), tetrabromobisphenol A (TBBPA), decabromodiphenylethane (DBDPE), and 2,4,6-tribromophenol (2,4,6-TBP) in serum, and four metabolites of organophosphorus flame retardants (OPFRs) in urine, at two concentration levels. The number of satisfactory results reported by laboratories increased during the four rounds. In the case of HFRs, the scope of the participating laboratories varied substantially (from two to ten) and in most cases did not cover the entire target spectrum of chemicals. The highest participation rate was reached for BDE-47 and BDE-153. The majority of participants achieved more than 70% satisfactory results for these two compounds over all rounds. For other HFRs, the percentage of successful laboratories varied from 44 to 100%. The evaluation of TBBPA, DBDPE, and 2,4,6-TBP was not possible because the number of participating laboratories was too small. Only seven laboratories participated in the ICI/EQUAS scheme for OPFR metabolites and five of them were successful for at least two biomarkers. Nevertheless, the evaluation of laboratory performance using Z-scores in the first three rounds required an alternative approach compared to HFRs because of the small number of participants and the high variability of experts' results. The obtained results within the ICI/EQUAS programme showed a significant core network of comparable European laboratories for HBM of BDE-47, BDE-153, BDE-209, α-HBCD, γ-HBCD, anti-DP, and syn-DP. On the other hand, the data revealed a critically low analytical capacity in Europe for HBM of TBBPA, DBDPE, and 2,4,6-TBP as well as for the OPFR biomarkers.
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Retardadores de Llama , Monitoreo Biológico , Monitoreo del Ambiente , Europa (Continente) , Retardadores de Llama/análisis , Éteres Difenilos Halogenados/análisis , HumanosRESUMEN
Hydrophilic interaction liquid chromatography is an alternative liquid chromatography mode for separation of polar compounds. In the recent years, this liquid chromatography mode has been recognized as an important solution for the analysis of compounds not amenable to reverse phase chromatography. In this work, we evaluated three different hydrophilic liquid chromatography stationary phases for the determination of 14 highly polar anionic molecules including pesticides such as glyphosate, glufosinate, ethephon and fosetyl, their main metabolites, and bromide, chlorate, and perchlorate. Several mobile phase compositions were evaluated combined with different gradients for the chromatographic run. The two columns that presented the best results were used to assess the performance for the determination of the 14 compounds in challenging highly complex feed materials. Very different matrix effects were observed for most of the compounds in each column, suggesting that different interactions can occur. Using isotopically labeled internal standards, acceptable quantitative performance and identification could be achieved down to 0.02 mg kg-1 (the lowest level tested) for most compounds. While one column was found to be favorable in terms of scope (suited for all 14 compounds), the other one was more suited for quantification and identification at lower levels, however, not for all analytes tested.
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Organophosphate pesticides (OPs) are known to inhibit acetylcholine esterase (AChE), a critical effect used to establish health-based guidance values. This study developed a combined in vitro-in silico approach to predict AChE inhibition by the OP profenofos in rats and humans. A physiologically based kinetic (PBK) model was developed for both species. Parameter values for profenofos conversion to 4-bromo-2-chlorophenol (BCP) were derived from in vitro incubations with liver microsomes, liver cytosol, and plasma from rats (catalytic efficiencies of 1.1, 2.8, and 0.19 ml/min/mg protein, respectively) and humans (catalytic efficiencies of 0.17, 0.79, and 0.063 ml/min/mg protein, respectively), whereas other chemical-related parameter values were derived using in silico calculations. The rat PBK model was evaluated against literature data on urinary excretion of conjugated BCP. Concentration-dependent inhibition of rat and human AChE was determined in vitro and these data were translated with the PBK models to predicted dose-dependent AChE inhibition in rats and humans in vivo. Comparing predicted dose-dependent AChE inhibition in rats to literature data on profenofos-induced AChE inhibition revealed an accurate prediction of in vivo effect levels. Comparison of rat predictions (BMDL10 of predicted dose-response data of 0.45 mg/kg bw) and human predictions (BMDL10 of predicted dose-response data of 0.01 mg/kg bw) suggests that humans are more sensitive than rats, being mainly due to differences in kinetics. Altogether, the results demonstrate that in vivo AChE inhibition upon acute exposure to profenofos was closely predicted in rats, indicating the potential of this novel approach method in chemical hazard assessment.
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Inhibidores de la Colinesterasa/toxicidad , Modelos Biológicos , Organotiofosfatos/toxicidad , Plaguicidas/toxicidad , Acetilcolinesterasa/efectos de los fármacos , Acetilcolinesterasa/metabolismo , Animales , Inhibidores de la Colinesterasa/administración & dosificación , Simulación por Computador , Relación Dosis-Respuesta a Droga , Femenino , Humanos , Masculino , Microsomas Hepáticos/efectos de los fármacos , Microsomas Hepáticos/enzimología , Organotiofosfatos/administración & dosificación , Ratas , Ratas Sprague-Dawley , Especificidad de la EspecieRESUMEN
We conducted this study in order to assess the pesticide residues in vegetables and examine the related human health risk. Therefore, residues of 23 pesticides (organophosphates, organochlorines, acaricides, fungicides, and insecticides of biological origin) were analysed in the three main vegetable crops grown in Southern Nepal: 27 eggplant, 27 chilli and 32 tomato samples representing (i) conventional (Nâ¯=â¯67) and ii) integrated pest management (IPM) fields (Nâ¯=â¯19). Pesticide residues were found in 93% of the eggplant samples and in all of the chilli and tomato samples. Multiple residues were observed in 56% of the eggplant samples, 96% of chilli samples and all of the tomato samples. The range (µg/kg) of total detected pesticide residues in eggplants, chillies and tomatoes was 1.71-231, 4.97-507, 13.1-3465, respectively. The most frequently detected pesticides in these vegetables were carbendazim and chloropyrifos. Pesticide residues in 4% of the eggplant, 44% of the tomato and 19% of the chilli samples exceeded the EU maximum residue limits (MRLs). The residues of triazophos, omethoate, chloropyrifos and carbendazim exceeded the EU MRLs. Compared to chilli and eggplant crops, more carbendazim was sprayed onto tomato crops (pâ¯<â¯0.05). We assessed adolescent and adult dietary exposure using hazard quotient (HQ) and hazard index (HI) equations for the identified pesticides. HQ>â¯1 was observed for chloropyrifos, triazophos and carbendazim in eggplants; profenofos, triazophos, dimethoate, omethoate, chloropyrifos and carbendazim in tomatoes; and dichlorvos and chloropyrifos in chillies. Of all of the HQs, the highest acute HQ (aHQ) was for triazophos (tomato) in adolescents (aHQ=657) and adults (aHQ=677), showing the highest risks of dietary exposure. The cumulative dietary exposure showed a higher HI for organophosphates (HI>83) and a lower HI for organochlorines, acaricides and biological insecticides (HI<1). The concentration of pesticide residues in the vegetable crops from the IPM field was considerably lower, suggesting a greater ability of IPM systems to reduce the dietary risks from exposure to pesticides.
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Contaminación de Alimentos , Residuos de Plaguicidas , Medición de Riesgo , Verduras , Adolescente , Adulto , Contaminación de Alimentos/análisis , Humanos , Nepal , Residuos de Plaguicidas/análisis , Verduras/químicaRESUMEN
In this work, we introduce an automated, efficient, and elegant model to combine all pieces of evidence (e.g., expected retention times, peak shapes, isotope distributions, fragment-to-parent ratio) obtained from liquid chromatography-tandem mass spectrometry (LC-MS/MS/MS) data for screening purposes. Combining all these pieces of evidence requires a careful assessment of the uncertainties in the analytical system as well as all possible outcomes. To-date, the majority of the existing algorithms are highly dependent on user input parameters. Additionally, the screening process is tackled as a deterministic problem. In this work we present a Bayesian framework to deal with the combination of all these pieces of evidence. Contrary to conventional algorithms, the information is treated in a probabilistic way, and a final probability assessment of the presence/absence of a compound feature is computed. Additionally, all the necessary parameters except the chromatographic band broadening for the method are learned from the data in training and learning phase of the algorithm, avoiding the introduction of a large number of user-defined parameters. The proposed method was validated with a large data set and has shown improved sensitivity and specificity in comparison to a threshold-based commercial software package.
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Flow injection combined with tandem mass spectrometry (MS/MS) was investigated for the rapid detection of highly polar pesticides that are not amenable to multi-residue methods because they do not partition into organic solvents and require dedicated chromatographic conditions. The pesticides included in this study were amitrole, chlormequat, cyromazine, daminozide, diquat, ethephon, fosetyl-Al, glufosinate, glyphosate and its metabolite aminomethylphosphonic acid, maleic hydrazide, mepiquat and paraquat. The composition of the flow-injection solvent was optimized to achieve maximum MS/MS sensitivity. Instrumental limits of detection varied between <0.05 and 1 pg. Fruit, vegetable, cereal, milk and kidney samples were extracted with water (1% formic acid in case of paraquat/diquat) and ten times diluted in either methanol/0.1% formic acid, methanol/0.1% ammonia or acetonitrile/0.1% ammonia, depending on the pesticide. The ion suppression observed depended strongly on both the matrix and the pesticide. This could be largely compensated for by matrix-matched calibration, but more accurate quantification was obtained by using isotopically labelled standards (commercially available for most of the pesticides studied). The method detection limits ranged from 0.02 mg/kg for chlormequat and mepiquat to 2 mg/kg for maleic hydrazide and were 0.05-0.2 mg/kg for most other pesticide/matrix combinations. This was sufficiently low to test compliance with EU maximum residue limits for many relevant pesticide/commodity combinations. The method substantially reduces the liquid chromatography-MS/MS capacity demand which for many laboratories is prohibitive for inclusion of these pesticides in their monitoring and surveillance programmes.
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Análisis de Inyección de Flujo/métodos , Residuos de Plaguicidas/análisis , Espectrometría de Masas en Tándem/métodosRESUMEN
Given that the determination of biocides in food and feed is currently not routinely done, more information on these compounds is useful for consumer's safety. This work describes a sensitive and reliable method for quantitative analysis of a wide range of biocides in dairy products and slurry feed. The method comprises acetate-buffered QuEChERS extraction without clean-up. Analyses were performed by LC-Q-Orbitrap™-MS and a full-scan acquisition event without fragmentation was followed by five fragmentation events (data-independent acquisition-DIA). The quantitative validation was performed according to SANTE/11312/2021 at 10, 50 and 200 ng g-1 spiking levels, and the results showed that the vast majority of the compounds met the criteria for trueness and precision. The LOQ was 10 ng g-1 for the majority of biocides depending on the matrix. The method was successfully applied to quantify biocides in dairy products and feed.
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Alimentación Animal , Productos Lácteos , Desinfectantes , Contaminación de Alimentos , Productos Lácteos/análisis , Desinfectantes/análisis , Contaminación de Alimentos/análisis , Alimentación Animal/análisis , Animales , Cromatografía Liquida/métodos , Residuos de Plaguicidas/análisis , Residuos de Plaguicidas/aislamiento & purificación , Cromatografía Líquida de Alta Presión , Espectrometría de Masas en Tándem , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
Organochlorine insecticide (OCI) exposures in terrestrial food chains from historical or current applications were studied in a vegetable production area in northwest Bangladesh. A total of 57 subsoil, 57 topsoil, and 57 vegetable samples, as well as 30 cow's milk samples, were collected from 57 farms. Multiple OCI residues were detected using GC-MS/MS with modified QuEChERS in 20 % of subsoils, 21 % of topsoils, 23 % of vegetables, and 7 % of cow's milk samples. Diversified OCI residues were detected in subsoils (17 residues with a concentration of 179.15 ± 148.61 µg kg-1) rather than in topsoils (3 DDT residues with a concentration of 25.76 ± 20.19 µg kg-1). Isomeric ratios indicate intensive historical applications of OCIs. According to Dutch and Chinese standards, the lower concentrations of individual OCI residues in the soil indicate negligible to slight soil pollution, assuming local farmers follow local pesticide use regulations. However, a maximum of 78.24 µg kg-1 ΣAldrines and 35.57 µg kg-1 ΣHCHs were detected (1-4 residues) in 60 % of brinjal, 28 % of cucumber, 29 % of sponge gourd, and 20 % of lady's finger samples, which could be a result of either historical or current OCI applications, or both. A strong positive correlation between aldrines in subsoils and cucurbit vegetables indicates greater bioaccumulation. Cow milk samples contained up to 6.96 µg kg-1 ΣDDTs, which resulted either from rationing contaminated vegetables or grazing on contaminated land. Individual OCI in both vegetables and cow's milk was below the respective maximum residue limits of US and FAO/WHO CODEX and poses little or no risk to human health. However, combined exposure to multiple pesticides could increase human health risks. A cumulative health risk assessment of multiple pesticide residues is suggested to assess the suitability of those soils for cultivation and grazing, as well as the safety of vegetables and cow's milk for human consumption.
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Hidrocarburos Clorados , Insecticidas , Residuos de Plaguicidas , Plaguicidas , Animales , Bovinos , Femenino , Humanos , Insecticidas/análisis , Verduras , Bangladesh , Cadena Alimentaria , Espectrometría de Masas en Tándem , Hidrocarburos Clorados/análisis , Residuos de Plaguicidas/análisis , Compuestos Orgánicos , Suelo , Contaminación de Alimentos/análisisRESUMEN
Background: Children in agricultural areas are exposed to organophosphate (OP) and pyrethroid (PYR) insecticides. This explorative study investigated child exposure to OPs and PYRs, comparing temporal and spatial exposure variability within and among urine, wristbands, and dust samples. Methods: During spraying season 2018, 38 South African children in two agricultural areas (Grabouw/Hex River Valley) and settings (farm/village) participated in a seven-day study. Child urine and household dust samples were collected on days 1 and 7. Children and their guardians were wearing silicone wristbands for seven days. Intraclass correlation coefficients (ICCs) evaluated temporal agreements between repeated urine and dust samples, Spearman rank correlations (Rs) evaluated the correlations among matrices, and linear mixed-effect models investigated spatial exposure predictors. A risk assessment was performed using reverse dosimetry. Results: Eighteen OPs/PYRs were targeted in urine, wristbands, and dust. Levels of chlorpyrifos in dust (ICC = 0.92) and diethylphosphate biomarker in urine (ICC = 0.42) showed strong and moderate temporal agreement between day 1 and day 7, respectively. Weak agreements were observed for all others. There was mostly a weak correlation among the three matrices (Rs = -0.12 to 0.35), except for chlorpyrifos in dust and its biomarker 3,5,6-trichloro-2-pyridinol in urine (Rs = 0.44). No differences in exposure levels between living locations were observed. However, 21% of the urine biomarker levels exceeded the health-risk threshold for OP exposure. Conclusions: Observed high short-term variability in exposure levels during spraying season highlights the need for repeated sampling. The weak correlation between the exposure matrices points to different environmental and behavioral exposure pathways. Exceeding risk thresholds for OP should be further investigated.
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Freshwater ecosystems face a particularly high risk of biodiversity loss compared to marine and terrestrial systems. The use of pesticides in agricultural fields is recognized as a relevant stressor for freshwater environments, exerting a negative impact worldwide on the overall status and health of the freshwater communities. In the present work, part of the Horizon 2020 funded SPRINT project, the occurrence of 193 pesticide residues was investigated in 64 small water bodies of distinct typology (creeks, streams, channels, ditches, rivers, lakes, ponds and reservoirs), located in regions with high agricultural activity in 10 European countries and in Argentina. Mixtures of pesticide residues were detected in all water bodies (20, median; 8-40 min-max). Total pesticide levels found ranged between 6.89 and 5860 ng/L, highlighting herbicides as the dominant type of pesticides. Glyphosate was the compound with the highest median concentration followed by 2,4-D and MCPA, and in a lower degree by dimethomorph, fluopicolide, prothioconazole and metolachlor(-S). Argentina was the site with the highest total pesticide concentration in water bodies followed by The Netherlands, Portugal and France. One or more pesticides exceeded the threshold values established in the European Water Framework Directive for surface water in 9 out of 11 case study sites (CSS), and the total pesticide concentration surpassed the reference value of 500 ng/L in 8 CSS. Although only 5 % (bifenthrin, dieldrin, fipronil sulfone, permethrin, and terbutryn) of the individual pesticides denoted high risk (RQ > 1), the ratios estimated for pesticide mixtures suggested potential environmental risk in the aquatic compartment studied.
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Residuos de Plaguicidas , Plaguicidas , Contaminantes Químicos del Agua , Agua , Ecosistema , Argentina , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente , Plaguicidas/análisis , Ríos/químicaRESUMEN
The chemical burden on the environment and human population is increasing. Consequently, regulatory risk assessment must keep pace to manage, reduce, and prevent adverse impacts on human and environmental health associated with hazardous chemicals. Surveillance of chemicals of known, emerging, or potential future concern, entering the environment-food-human continuum is needed to document the reality of risks posed by chemicals on ecosystem and human health from a one health perspective, feed into early warning systems and support public policies for exposure mitigation provisions and safe and sustainable by design strategies. The use of less-conventional sampling strategies and integration of full-scan, high-resolution mass spectrometry and effect-directed analysis in environmental and human monitoring programmes have the potential to enhance the screening and identification of a wider range of chemicals of known, emerging or potential future concern. Here, we outline the key needs and recommendations identified within the European Partnership for Assessment of Risks from Chemicals (PARC) project for leveraging these innovative methodologies to support the development of next-generation chemical risk assessment.
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Exposición a Riesgos Ambientales , Monitoreo del Ambiente , Humanos , Exposición a Riesgos Ambientales/análisis , Monitoreo del Ambiente/métodos , Monitoreo del Ambiente/normas , Contaminantes Ambientales/análisis , Sustancias Peligrosas/análisis , Espectrometría de Masas/métodos , Medición de Riesgo/métodosRESUMEN
Bacterial products based on Bacillus thuringiensis are registered in many countries as plant protection products (PPPs) and are widely used as insecticides and nematocides. However, certain B. thuringiensis strains produce harmful toxins and are therefore not allowed to be used as PPPs. The serotype B. thuringiensis thuringiensis produces the beta-exotoxin thuringiensin (ßeT) which is considered to be toxic for almost all forms of life including humans (WHO 1999). The use of a non-registered PPP based on B. thuringiensis thuringiensis called bitoxybacillin was established through the determination of ßeT. First, an analytical reference standard of ßeT was characterized by nuclear magnetic resonance, liquid chromatography-high-resolution mass spectrometry and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Then, a confirmatory quantitative method for the determination of ßeT in PPPs and selected greenhouse crops based on LC-MS/MS was developed and validated. A limit of quantitation of 0.028 mg/kg was established, and average recoveries ranged from 85.6 % to 104.8 % with repeatability (RSDr) of 1.5-7.7 % and within-lab reproducibility (RSD(WLR)) of 17 %. The method was used for analysis of >100 samples. ßeT was found in leaves of ornamentals, but no evidence was found for use in edible crops.
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Adenosina/análogos & derivados , Bacillus thuringiensis/química , Toxinas Bacterianas/análisis , Productos Agrícolas/química , Azúcares Ácidos/análisis , Espectrometría de Masas en Tándem/métodos , Adenosina/análisis , Cromatografía Liquida/métodos , Exotoxinas/análisis , Insecticidas/química , Límite de Detección , Espectroscopía de Resonancia Magnética , Verduras/químicaRESUMEN
Polycyclic aromatic hydrocarbons (PAHs) were included as priority substances for human biomonitoring (HBM) in the European Human Biomonitoring Initiative (HBM4EU), which intended to harmonise and advance HBM across Europe. For this project, a specific Quality Assurance and Quality Control (QA/QC) programme applying Inter-laboratory Comparison Investigations (ICIs) and External Quality Assurance Schemes (EQUASs) was developed to ensure the comparability and accuracy of participating analytical laboratories. This paper presents the results of four ICI/EQUAS rounds for the determination of 13 PAH metabolites in urine, i.e. 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 2-, 3- and 9-hydroxyfluorene, 1-, 2-, 3-, 4- and 9-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenzo(a)pyrene. However, 4 PAH metabolites could not be evaluated as the analytical capacity of participating laboratories was too low. Across all rounds and biomarkers, 86% of the participants achieved satisfactory results, although low limits of quantification were required to quantify the urinary metabolites at exposure levels of the general population. Using high-performance liquid or gas chromatography coupled with mass spectrometry (HPLC-MS; GC-MS) and isotope dilution for calibration as well as performing an enzymatic deconjugation step proved to be favourable for the accurate determination of PAHs in urine. Finally, the HBM4EU QA/QC programme identified an international network of laboratories providing comparable results in the analysis of urinary PAH biomarkers, although covering all parameters initially selected was still too challenging.
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Hidrocarburos Policíclicos Aromáticos , Humanos , Hidrocarburos Policíclicos Aromáticos/orina , Monitoreo Biológico , Cromatografía Líquida de Alta Presión/métodos , Europa (Continente) , Biomarcadores/orina , Monitoreo del Ambiente/métodosRESUMEN
Humans are exposed to a mixture of pesticides through diet as well as through the environment. We conducted a suspect-screening based study to describe the probability of (concomitant) exposure to a set of pesticide profiles in five European countries (Latvia, Hungary, Czech Republic, Spain and the Netherlands). We explored whether living in an agricultural area (compared to living in a peri-urban area), being a a child (compared to being an adult), and the season in which the urine sample was collected had an impact on the probability of detection of pesticides (-metabolites). In total 2088 urine samples were collected from 1050 participants (525 parent-child pairs) and analyzed through harmonized suspect screening by five different laboratories. Fourty pesticide biomarkers (either pesticide metabolites or the parent pesticides as such) relating to 29 pesticides were identified at high levels of confidence in samples across all study sites. Most frequently detected were biomarkers related to the parent pesticides acetamiprid and chlorpropham. Other biomarkers with high detection rates in at least four countries related to the parent pesticides boscalid, fludioxonil, pirimiphos-methyl, pyrimethanil, clothianidin, fluazifop and propamocarb. In 84% of the samples at least two different pesticides were detected. The median number of detected pesticides in the urine samples was 3, and the maximum was 13 pesticides detected in a single sample. The most frequently co-occurring substances were acetamiprid with chlorpropham (in 62 urine samples), and acetamiprid with tebuconazole (30 samples). Some variation in the probability of detection of pesticides (-metabolites) was observed with living in an agricultural area or season of urine sampling, though no consistent patterns were observed. We did observe differences in the probability of detection of a pesticide (metabolite) among children compared to adults, suggesting a different exposure and/or elimination patterns between adults and children. This survey demonstrates the feasibility of conducting a harmonized pan-European sample collection, combined with suspect screening to provide insight in the presence of exposure to pesticide mixtures in the European population, including agricultural areas. Future improvements could come from improved (harmonized) quantification of pesticide levels.
Asunto(s)
Plaguicidas , Adulto , Humanos , Plaguicidas/orina , Clorprofam , Agricultura , Europa (Continente) , Biomarcadores , Exposición a Riesgos Ambientales/análisisRESUMEN
Pesticides are widely used as plant protection products (PPPs) in farming systems to preserve crops against pests, weeds, and fungal diseases. Indoor dust can act as a chemical repository revealing occurrence of pesticides in the indoor environment at the time of sampling and the (recent) past. This in turn provides information on the exposure of humans to pesticides in their homes. In the present study, part of the Horizon 2020 funded SPRINT project, the presence of 198 pesticide residues was assessed in 128 indoor dust samples from both conventional and organic farmworker households across Europe, and in Argentina. Mixtures of pesticide residues were found in all dust samples (25-121, min-max; 75, median). Concentrations varied in a wide range (<0.01 ng/g-206 µg/g), with glyphosate and its degradation product AMPA, permethrin, cypermethrin and piperonyl butoxide found in highest levels. Regarding the type of pesticides, insecticides showed significantly higher levels than herbicides and fungicides. Indoor dust samples related to organic farms showed a significantly lower number of residues, total and individual concentrations than those related to conventional farms. Some pesticides found in indoor dust were no longer approved ones (29 %), with acute/chronic hazards to human health (32 %) and with environmental toxicity (21 %).
Asunto(s)
Contaminación del Aire Interior , Residuos de Plaguicidas , Plaguicidas , Humanos , Residuos de Plaguicidas/análisis , Monitoreo del Ambiente , Polvo/análisis , Agricultores , Argentina , Plaguicidas/análisis , Europa (Continente) , Contaminación del Aire Interior/análisisRESUMEN
Intensive and widespread use of pesticides raises serious environmental and human health concerns. The presence and levels of 209 pesticide residues (active substances and transformation products) in 625 environmental samples (201 soil, 193 crop, 20 outdoor air, 115 indoor dust, 58 surface water, and 38 sediment samples) have been studied. The samples were collected during the 2021 growing season, across 10 study sites, covering the main European crops, and conventional and organic farming systems. We profiled the pesticide residues found in the different matrices using existing hazard classifications towards non-target organisms and humans. Combining monitoring data and hazard information, we developed an indicator for the prioritization of pesticides, which can support policy decisions and sustainable pesticide use transitions. Eighty-six percent of the samples had at least one residue above the respective limit of detection. One hundred residues were found in soil, 112 in water, 99 in sediments, 78 in crops, 76 in outdoor air, and 197 in indoor dust. The number, levels, and profile of residues varied between farming systems. Our results show that non-approved compounds still represent a significant part of environmental cocktails and should be accounted for in monitoring programs and risk assessments. The hazard profiles analysis confirms the dominance of compounds of low-moderate hazard and underscores the high hazard of some approved compounds and recurring "no data available" situations. Overall, our results support the idea that risk should be assessed in a mixture context, taking environmentally relevant mixtures into consideration. We have uncovered uncertainties and data gaps that should be addressed, as well as the policy implications at the EU approval status level. Our newly introduced indicator can help identify research priority areas, and act as a reference for targeted scenarios set forth in the Farm to Fork pesticide reduction goals.