Multiresidue Pesticide Research Articles

Simultaneous Analysis of 504 Pesticide Multiresidues in Crops Using UHPLC-QTOF at MS1 and MS2 Levels

Simultaneous Analysis of 504 Pesticide Multiresidues in Crops Using UHPLC-QTOF at MS1 and MS2 Levels

Monitoring and Risk Assessment of Multi-Pesticide Residues in Apples: A Focus on Consumer Safety

Pesticide residues in human diets pose significant health hazards, particularly for vulnerable populations such as infants and children. This study aimed to determine pesticide residues in apples and to assess the cumulatively chronic risk posed to adult and child consumers from simultaneous exposure to multiple residues. During the 2022–2023 harvest seasons, 100 apple samples from Turkey were analyzed for the presence of 225 different pesticide residues. Pesticide extraction was performed using the QuEChERS method, followed by detection through liquid chromatography coupled with tandem mass spectrometry. Fifteen distinct pesticides (ten insecticides and five fungicides) were detected in 64 out of the 100 apple samples analyzed. Eleven samples contained pesticide residues that exceeded the maximum residue limit (MRL) set by the Turkish Food Codex and the European Union. Thiophanate-methyl was the most frequently detected pesticide (34%) in apples, with concentrations ranging from 0.012 to 0.108 mg kg−1, all of which were well below the MRL of 0.5 mg kg−1. Other commonly detected residues included chlorantraniliprole (28%), acetamiprid (24%), sulfoxaflor (22%), bifenazate (18%), indoxacarb (13%), diflubenzuron (12%), and carbendazim (10%). Under a worst-case scenario, the hazard index (HI) values for adults and children were 0.85% and 2.60%, respectively, indicating that these values remain significantly below the risk threshold of 100%, suggesting no associated health risks from apple consumption. However, regular monitoring of pesticide residues in fresh fruits and vegetables remains critically important.

Determination of multi-pesticide residues in agricultural products with a modified QuEChERS process based on magnetic biochar from coconut clothing

In this study, the magnetic biochar material derived from coconut clothing was firstly successfully synthesized by in-situ polymerization method and applied as QuEChERS adsorbents for extracting multi-pesticides. The obtained magnetic coconut-clothing biochar (MCCBC) presented alveolate structure with abundant large irregular pores. The Fe3O4 particles was obviously attached on the surface of biochar. Under the optimized conditions, the modified QuEChERS process based on MCCBC coupled with HPLC-MS/MS for simultaneously extracting and determining 12 pesticides (organophosphorus insecticides and strobilurins) from different agricultural products (tomato, cucumber, cabbage, carrot, peach, pear, grape, apple) was established. After pretreated by MCCBC, most of pesticides had weak matrix effect. This proposed method showed good linearity (2–250 ng g−1) with R2 ≥ 0.9915, and the limits of detection and the limits of quantification were in the range of 0.01–2.67 ng g−1 and 0.03–8.91 ng g−1, respectively. The acceptable recovery was between 71.1 % and 114.0 % with relative standard deviations from 0.31 % to 13.94 %. These results fully demonstrated that the developed method was efficient for simultaneously extracting and determining organophosphorus insecticides and strobilurins in complex agricultural matrix, possessing obvious advantages of higher sensitivity, easier operation and good feasibility. More importantly, this study provided a useful strategy for magnetizing biochar, and the novel biochar from coconut clothing was also introduced as potential adsorbent for other trace organic pollutants.

A green extraction method based on aqueous two-phase system for trace-level enrichment of multi-residue pesticides in traditional Chinese medicine prior to HPLC-MS/MS quantitative analysis

A green extraction method based on aqueous two-phase system for trace-level enrichment of multi-residue pesticides in traditional Chinese medicine prior to HPLC-MS/MS quantitative analysis

A Robust Method for Simultaneous Determination and Risk Assessment of Multiresidual Pesticides in Fishery Products.

In this study, we developed and validated a multiresidue analytical method for the simultaneous detection of 24 pesticides in fishery products. Using the EN15662 extraction method and C18 as the adsorbent for purification, the validation results complied with Codex guidelines, achieving recovery rates between 70% and 120% and relative standard deviation values (%RSD) within 20%, indicating excellent performance. The limit of detection ranged from 0.25 to 0.8 ng/kg, and the limit of quantification was between 3 and 10 ng/g, providing sufficient sensitivity to comply with future regulatory standards. The calibration curves for all 24 pesticides exhibited great linearity (R2 > 0.98), also satisfying the Codex requirements. The matrix effect was less than 30% for some pesticides-within ±20%-indicating minimal interference from impurities. An analysis of 300 fishery samples from nine regions across South Korea detected lufenuron at 10 ng/g in eels; however, the risk assessment was below 0.19%, posing no significant hazard to public health. This newly developed analytical method proved effective for the multi-analysis of pesticide residues in fishery products, offering rapid and reliable monitoring of the import and export safety of fishery products.

Honey bees and mason bees as biological indicators of landscape pesticide loads: Different results but similar conclusions

Agricultural environments, including crop and non-crop areas, often provide important pollen and nectar resources for managed and wild bees. However, these resources may be contaminated with pesticides detrimental to bees and other non-target organisms, including humans. Differences in life-history traits among bee species influence food resource exploitation and pesticide exposure. This study assesses the potential of honey bees (Apis mellifera) and mason bees (Osmia), two bee species with highly contrasting functional traits, as biological indicators of pesticide exposure in 34 Italian agricultural farms. Pollen loads of both species were used to identify pollen species collected and to analyse multi-residue levels of pesticides. Pesticide risk indexes were calculated for honey bees, mason bees and humans. In mason bees, pesticide risk was not influenced by plant diversity. In agreement with their pollen preferences and short foraging ranges, mason bees collected a high proportion of pollen from flowers of the target crop. Conversely, pesticide risk decreased with increasing pollen diversity in honey bees. In agreement with their generalist foraging habits and long foraging ranges honey bees collected a greater diversity of pollen species and a lower proportion of target crop pollen. Although honey bees and mason bees showed similar toxic loads and pesticide composition, at a field scale pesticide risk of one species is not a good indicator of the risk to the other species. Our study confirms that bees in agricultural environments are pervasively exposed to multi-residue pesticide loads. Exposure is conditioned by specific bee traits but is also highly context-dependent.

Multiresidues of pesticides in the particulate matter (PM10) emitted by rural soils of the semiarid pampas, Argentina. A potential source of air pollution

The aim of this work was to evaluate the presence of 40 pesticides in the PM10 emitted by rural soils of the semiarid region of Argentina. Six agricultural soils for grain production under no till and with high use of pesticides (AG), 5 agricultural soils for forage and grain production under conventional tillage (AFG) and 5 unpaved rural roads (RR) were sampled. The PM10 was generated using the Easy Dust Generator and it was collected with an electrostatic precipitator. The presence of 20 herbicides, 14 insecticides and 6 fungicides was analyzed in the soil and in the PM10. More than 70% of the pesticides analyzed were detected in the soil and in the PM10. All agricultural soils and 87% of RR soils showed at least one residue of pesticides. Multiresidues of pesticides were found in the 100% of PM10 emitted by rural soils. The mean number of pesticides was higher in the PM10 (7) than in the soil (5). Some pesticides were not detected in the soils but they were detected in the PM10 (triticonazole, carbofuran, metsulfuron methyl) and vice versa. In general, the concentrations of herbicides were higher in the PM10 than in the soil, while the concentrations of insecticides and fungicides were lower in the PM10 than in the soil. These results suggest that the concentrations of pesticide in the PM10 (inhalable fraction) should be used instead the concentrations of pesticide in the soil to calculate the exposure factor to pesticides by dust inhalation. This study provides the initial evidence of the presence of multiple pesticide residues in PM10 emitted by rural soils under different land management. Also confirms that the PM10 is a potential source of air contamination with pesticides. Future studies should be driven to measure the concentrations of pesticides and their dynamics in the PM10.

Determination of multi-residue pesticides in dairy products using single-step emulsification/demulsification clean-up strategy combined with low-pressure gas chromatography-tandem mass spectrometry

In this study, a simple, sensitive, and rapid method was developed for the simultaneous determination of 99 kinds of pesticides in fatty milk samples. This novel emulsification-demulsification clean-up approach, coupled with an automatic demulsification-dehydration cartridge, allowed rapid single-step clean-up operation and high throughput. It also achieved effective and selective removal of lipids. The analysis was performed using low-pressure gas chromatography-tandem mass spectrometry (LPGC–MS/MS). Based on the optimal conditions, the targeted pesticides showed good linearity in the range of 5–250 μg/kg, with recoveries of 70–120% at spiking levels of 5, 10, and 20 μg/kg in cow milk, goat milk, and almond milk, respectively. The limit of quantification for most pesticides was 5 μg/kg, and the RSDs were lower than 20%. Analysis of real dairy products obtained from local markets revealed a potential risk in plant-derived almond milk, but no significant risks were found for cow and goat milk.

Higher early than late-season residue load of pesticides in honey bee bread in Slovakia

Bees are often exposed to pesticide residues during their foraging trips in agricultural landscapes. The analysis of in-hive stored pollen reflects the spectrum of visited plants and can be almost used to link the exposure to pesticides.In the current study, bee bread samples were collected in May and July from 17 sites located in southern Slovakia. Samples were analysed using a multi-residue pesticide analysis method for a broad spectrum of active substances and microscopic for pollen identification.Our results revealed a bee bread contamination with 19 different active substances, with fungicides being predominant. Sixteen of them are authorized in the EU, but chlorpyrifos, chlorpyrifos-methyl, and chloridazon are not. The highest concentrations for pendimethalin (1400 µg/kg), fluazifop-butyl (640 µg/kg), fenpropidin (520 µg/kg), fluopyram (130 µg/kg), and difenoconazole (95 µg/kg) were detected. The total residue load in bee bread sampled in the early season (May) was significantly higher than in the late season (July). The mean residue load of insecticides analysed in July comprised 46% of May’s load, which is alarming due to the importance of bee bread in the diet for winter-rearing bees. Moreover, results from both sampling periods showed that fungicides were positively associated with plant families Apiaceae and Papaveraceae and herbicides with Aceraceae, Salicaceae, and Brassica-type/Brassicaceae.Hence, bee bread can be considered a suitable matrix and a good bio-indicator reflecting honey bee exposure to pesticides over the season.

Simultaneous Determination of Multiresidues of Pesticides and Veterinary Drugs in Agricultural Soil Using QuEChERS and UHPLC–MS/MS

Simultaneous Determination of Multiresidues of Pesticides and Veterinary Drugs in Agricultural Soil Using QuEChERS and UHPLC–MS/MS

Silver-decorated three-dimensional ZnO nanoflowers enhancing the electromagnetic coupling for ultrasensitive SERS detection of multi-pesticide residues

—The development of sensitive analytical methods is of prime importance for the detection of pesticide residues on the surfaces of fruits and vegetables at extremely low concentrations. Here, we synthesized Ag-decorated three-dimensional ZnO nanoflowers (ZnO@Ag) composed of ultrathin nanosheets as surface-enhanced Raman spectroscopy (SERS) substrates. Combined with the finite-difference time-domain (FDTD) method, it is proven that the ultrathin nanosheets greatly improve the electromagnetic coupling between the two metal nanoparticles due to the high refractive index of ZnO and generate new “hot spots”. The nanosheets also endow the incident light with multiple reflections to motivate the local electromagnetic field. The substrate presents high sensitivity and the enhancement factor was as high as 2.98 × 107 utilizing R6G as probe molecules. The detection concentration of thiram and malachite green (MG) solutions can reach 10−10 M and 10−9 M, respectively. For the real-life sample assays, the substrate can simultaneously detect the two pesticides on apple skin with high sensitivity. The research also reveals the importance of semiconductors toward the local electromagnetic field enhancement in noble metal-semiconductor substrates, benefiting the realization of highly sensitive SERS substrates and the wide application of the SERS technology in real-world scenarios.

Evaluation of pesticide residues in rice marketed in Cape Verde by QuEChERS-LC/GC-MS analysis

In this work, a multiresidue pesticide analysis using both gas chromatography and ultra-high performance liquid chromatography coupled to mass spectrometry systems has been conducted to determine 151 pesticides in rice samples consumed by the population of Cape Verde. The extraction and clean-up procedures were carried out by the QuEChERS method. The validation of both methodologies achieved determination coefficients higher than 0.9902 in matrix-matched calibration, relative recovery values in the range 58–120% with relative standard deviation lower than 20%, and limits of quantification of the method in the range 0.008–0.017 mg/kg, which agreed with the legal limits established by both EU regulations and the Codex Alimentarius guidelines. Among the total of 98 rice samples analysed, 91 samples were contaminated by pesticides at concentrations up to 18.3 mg/kg, with pirimiphos-methyl, propiconazole, tebuconazole, and imidacloprid being the most frequently detected. Following EU regulations, 14 non-compliances were found in 13 samples, whereas only one non-compliance was identified according to the Codex. Besides, a risk assessment based on the dietary exposure was performed for the pesticides found in the analysed rice samples. The results showed the need to carry out stricter controls to ensure the security of food agricultural products to protect consumers’ health.

A facile in-situ ultrasonic-assisted synthesis of terephthalic acid-layered double hydroxide/bacterial cellulose: Application for eco-friendly analysis of multi-residue pesticides in vineyard soils

A novel nanostructure biosorbent comprised of bacterial cellulose (BC) and a Cu-Cr layered double hydroxide (LDH) intercalated with terephthalic acid (TPA) was prepared using the in-situ coprecipitation method. The synthesized TPA/CuCr-LDH@BC sorbent was used in quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction of multiclass pesticides (nine insecticides, five acaricides, one herbicide, and one fungicide) followed by gas chromatography-mass spectrometry. The extraction factors such as type and volume of eluent, sorbent dosage, adsorption and desorption times, sample pH, and salt were optimized. The sorbent was analyzed with field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and adsorption/desorption isotherms to check its chemical structure, crystallinity, and porosity. Matrix effect (15.3–19.6 %), linearity (20–2000 µg/L, r2 > 0.9982), limits of quantification (6–12 µg/L), and enrichment factor (42–65) were calculated. The efficiency and accuracy of the developed method were assessed with the analysis of five vineyard soil samples and the resulting recoveries were in the range of 60–130 % (RSD%=3.5–12.9). The green aspects of the procedure were evaluated by the Complex-GAPI, the AGREE, and the Analytical Eco-Scale tools. This study describes the first-time synthesis of TPA/CuCr-LDH@BC composite and its application as sorbent material for the microextraction of multi-residue pesticides in agricultural soils.

Simultaneous Analysis of 272 Pesticides in Agricultural Products by the QuEChERS Method and Gas Chromatography with Tandem Mass Spectrometry.

The aim of this study is to develop a rapid and accurate method for simultaneous analysis of multi-residue pesticides and conduct pesticide monitoring in agricultural products produced by the production and distribution stage in Korea. The representative agricultural products were selected as brown rice, soybean, potato, mandarin, and green pepper and developed using gas chromatography with tandem mass (GC-MS/MS) for the analysis of 272 pesticide residues. The experimental samples were extracted by the QuEChERS-EN method and then cleaned up by using d-SPE, including MgSO4 and primary secondary amine (PSA) sorbents. The established method was validated in accordance with Codex CAC-GL/40, and the limit of quantitation (LOQ) was determined to be 0.01 mg/kg. A total of 243 pesticides satisfied the guidelines in five samples at three levels with values of 60 to 120% (recovery) and ≤45% (coefficient of variation, CV). The remaining 29 pesticides did not satisfy the guidelines, and these pesticides are expected to be used as a screening method for the routine inspection of agricultural products. As a result of analyzing 223 agricultural products in South Korea by applying the simultaneous analysis method, none of the detected levels in the samples exceeded the standard values based on maximum residue limits (MRLs). The developed method in this study will be used to inspect residual pesticides in agricultural products, and it is anticipated to contribute to the distribution of safe agricultural products to consumers.

Africanized honey bee colonies in Costa Rica: first evidence of its management, brood nest structure and factors associated with varroa mite infestation.

Management, brood nest structure and factors associated with varroa mite infestation were studied in 60 apiaries of Africanized honey bees in the northwest region of the Central Valley of Costa Rica. Apiaries were monitored two times. The first monitoring was taken forward during the rainy season between May and November 2019. The second monitoring during the dry season between February and March 2020. Information about the beekeepers, apiaries and management was collected through a survey. Amount of open and capped brood, honey and pollen were measured in the field. The infestation rate of varroa (IRV) was quantified using standard laboratory methods. A determination of multi-residue pesticides in bee bread was made through GC-MS/MS and LC-MS/MS techniques. According to the results, most of the beekeepers produce honey (96.7%), participate in training activities (82.2%), and change the bee queens annually (70%). The first monitoring was characterized by a lower amount of capped brood and honey reserves compared to the second one. IRV was significantly higher in the first monitoring (6.0 ± 0.4) in comparison with the second one (3.0 ± 0.3) (U Mann-Whitney p < 0.001). The maximum value for the first monitoring exceeds 40%, while this value was close to 25% in the second monitoring. Mite infestation exposed significant differences in relation to the variables associated to the beekeeper's management, i.e., change of bee queen (p = 0.002) or when beekeepers monitor varroa mites (p = 0.004). Additionally, the IRV had inverse correlations (p < 0.01) with the number of comb sides with capped brood (Spearman's rho coefficient = -0.190), and honey reserves (Spearman's rho coefficient = -0.168). Furthermore, 23 of 60 bee bread samples presented one to five pesticide residues, being the most frequent antifungal agrochemicals.

Multiresidue Pesticide Analysis in Onion Using GC-MS/MS Using Modified QuEChERS Method with Zirconium Oxide Nanoparticle

Multiresidue Pesticide Analysis in Onion Using GC-MS/MS Using Modified QuEChERS Method with Zirconium Oxide Nanoparticle

Interrelationships of construction aspects of groundwater catchment wells for human consumption and pollution by multiresidues of pesticides

Human consumption of groundwater in catchment wells whose construction aspects are neglected in rural areas has been a growing reality, caused mainly by the deficient existence of public policies that enable the collective water supply system in these locations. However, it is also in rural areas that the most intensive use of pesticide compounds is made, which, depending on their physicochemical characteristics and the specificities of the environment where they are applied and the form of application, can pollute different environmental compartments, including groundwater. Therefore, the objective of this study was to carry out a comparative analysis between the constructive aspects of Underground Water Tubular Wells (UWTW) for human consumption purposes in a rural area of a municipality in the Missões Region of the state of Rio Grande do South (RS). and, the possible interrelationships with the presence of multiple pesticide residues. The constructive assessment considered Technical Standard N° 12.212:2017 (ABNT, 2017) and the determination of 26 pesticide compounds in 5 UWTW in the rural area of a municipality in RS. The results obtained inferred construction irregularities in all wells in the study, with emphasis on the absence of: sanitary protection slab, well identification plate, above-ground walls, sidewalks and, fencing. The presence of atrazine residues was also identified in concentrations above the LQm of UWTW-1 (0,107 µg L-1), UWTW-2 (0,019 µg L-1), UWTW-3 (0,019 µg L-1), UWTW-4 (0,066 µg L-1) and UWTW-5 (0,059 µg L-1). Finally, considering that the Serra Geral aquifer is of the fissural confined type, it is inferred that possible interrelationships between construction irregularities and the presence of the pesticide compound in the public water supply from catchment wells in rural areas may occur.

Pesticides in small volume plasma samples: Method development and application to smallmouth bass (Micropterus dolomieu) from the Chesapeake Bay watershed, USA

Nontarget organisms are exposed to pesticides following applications in agricultural and urban settings, potentially resulting in deleterious effects. Direct measurements of pesticides in biological tissues may aid in characterizing exposure, accumulation, and potential toxicity versus analyses in environmental media alone (e.g., water, soil, and air). Plasma represents a nonlethal sampling medium that can be used to assess recent exposures to contaminants. Herein, a method was developed to test the extraction of 210 pesticides and their transformation products in small volume plasma samples (100 μL). Plasma samples were protein precipitated with 0.5 % formic acid in acetonitrile added to the sample (ratio of 3.5:1). Pass-through solid phase extraction was used for sample matrix and lipid removal and samples were analyzed by liquid chromatography and gas chromatography with tandem mass spectrometry. Recoveries of 70.0–129.8 % were achieved for 182 pesticides and degradates across the low (25 ng mL−1), medium (100 ng mL−1), and high (250 ng mL−1) spike levels. Method detection levels ranged 0.4–13.0 ng mL−1. Following development, the method was applied to smallmouth bass (Micropterus dolomieu) plasma samples (n = 10) collected from adults in the Chesapeake Bay watershed. Individual plasma samples resulted in four to seven analytes detected with summed concentrations ranging 16.4–95.0 ng mL−1. Biological multiresidue pesticide methods help elucidate recent exposures of bioactive compounds to nontarget organisms.

New sorbent-based hydrophobic alginic acid derivatives for fat removal in multi-pesticide residues: analysis of a fatty food sample.

Hydrophobic alginic acid derivatives were synthesized with various aliphatic hydrocarbon chains for fat removal in an analysis of multi-pesticide residues in a fatty food sample. First, alginic acid was chemically modified using eco-friendly ultrasound-assisted esterification with different alcohols, namely, hydrophobic alginic acid-methanol (HAA-C1), hydrophobic alginic acid-butanol (HAA-C4), and hydrophobic alginic acid-octadecanol (HAA-C18). The degree of esterification (DE) was determined by titration, and the results ranged from 57.3% to 63.7%. The physicochemical properties of the synthesized hydrophobic alginic acids (HAAs) were studied using FT-IR, XRD, TGA, and FE-SEM. Subsequently, the performance of the HAAs was checked and evaluated for the removal of fat from a fatty food sample by calculating the fat removal percentage and the determination of 214 pesticide residues in the fatty food sample. For the fat removal percentage application, the HAAs were able to efficiently remove between 77% and 83% of the fat; HAA-C18 had the highest percentage. Regarding the pesticide residue application, HAAs were also able to remove the fat content from the fatty food sample without a significant effect on the pesticide substances. The recoveries of the detected pesticide compounds were between 80% and 120% for all HAAs. However, there were various missing pesticide compounds for HAAs. The number of missing pesticide compounds was 19, 6, and 33 for HAA-C1, HAA-C4, and HAA-C18, respectively. HAA-C4 had medium hydrophobicity and it lost fewer pesticides than the other HAAs. This was because the multi-pesticide mixture had various classes of chemical structure; hence, it had different polarity powers. We concluded that HAAs are developable and applicable to be safely used as a green material in diverse fatty food sample analysis applications.

(Multi-pesticides Residue Analysis in Cucumber under Greenhouse Conditions using QuEChERS methodology Coupled to GC-MS and HPLC)

(Multi-pesticides Residue Analysis in Cucumber under Greenhouse Conditions using QuEChERS methodology Coupled to GC-MS and HPLC)