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Food Chemistry May 2022A method for the determination of 80 pesticides (including five metabolites) in passion fruit using ethyl acetate extraction and dispersive solid-phase extraction...
A method for the determination of 80 pesticides (including five metabolites) in passion fruit using ethyl acetate extraction and dispersive solid-phase extraction followed by LC-MS/MS and GC-MS/MS was validated at LOQ of 0.005 or 0.010 mg kg (70 to 120% recovery; RSD ≤ 20%). Fifty-five passion fruit samples were obtained from producers, and 30 samples of frozen pulp and 12 samples of flour purchased. About 27% of the pesticides were detected; at least one in 60% of the peel samples, mainly imidacloprid and carbendazim (max. of 0.274 mg kg). Median processing factor was 0.5 for washed peel and 6.5 for dried peel (flour). About 63% of frozen pulp samples were positive, and 4 flour samples contained residues, mainly methamidophos. About 70% of the detected pesticides are not authorized in passion fruit in Brazil. Chronic and acute exposure from the consumption of passion fruit products did not indicate a health concern.
Topics: Chromatography, Liquid; Fruit; Gas Chromatography-Mass Spectrometry; Passiflora; Pesticide Residues; Risk Assessment; Tandem Mass Spectrometry
PubMed: 34836670
DOI: 10.1016/j.foodchem.2021.131643 -
Environmental Science and Pollution... Apr 2023Pesticides use increased worldwide with a record in Brazil. Although several works addressed the effects of pesticides on living organisms, only a few considered their...
Pesticides use increased worldwide with a record in Brazil. Although several works addressed the effects of pesticides on living organisms, only a few considered their mixture, and even fewer tried to unravel their role in tumoral progression. Due to the relevance of cancer, in the present study, the effects of the mixture of pesticides widely used in Brazil (Glyphosate, 2,4-dichlorophenoxyacetic acid, Mancozeb, Atrazine, Acephate, and Paraquat) and their main metabolites (Aminomethylphosphonic Acid, 2,4-diclorophenol, Ethylenethiourea, Desethylatrazine, Methamidophos, and Paraquat) were investigated on the malignancy phenotype of murine melanoma B16-F1 cells after acute (24 h) and chronic (15 days) exposures. The tested concentrations were based on the Acceptable Daily Intake (ADI) value established by Brazilian legislation. The set of results showed that these chemicals modulate important parameters of tumor progression, affecting the expression of genes related to tumor aggressiveness (Mmp14 and Cd44) and multidrug resistance (Abcb1, Abcc1, and Abcc4), as well as tissue inhibitors of metalloproteinases (Timp1, Timp2, and Timp3). These findings revealed an absence of cytotoxicity but showed modulation of migration, invasion, and colonization capacity of B16-F1 cells. Together, the results point to some negative ways that exposure to pesticides can affect the progression of melanoma and raise a concern related to the increasing trend in pesticide use in Brazil, as the country is one of the major world food suppliers.
Topics: Animals; Mice; Pesticides; Paraquat; Melanoma; Phenotype; Complex Mixtures
PubMed: 36738412
DOI: 10.1007/s11356-023-25603-7 -
Environmental Pollution (Barking, Essex... Oct 2021Studies have shown that the mixture toxicity of compounds with similar modes of action (MOAs) is usually predicted by the concentration addition (CA) model. However, due...
Studies have shown that the mixture toxicity of compounds with similar modes of action (MOAs) is usually predicted by the concentration addition (CA) model. However, due to the lack of toxicological information on compounds, more evidence is needed to determine whether the above conclusion is generally applicable. In general, the same type of compounds with similar chemical structures have similar MOAs, so whether the toxicities of the mixture of these compounds are additive needs to be further studied. In this paper, three types of pesticides with similar chemical structures (three organophosphoruses, two carbamates and two neonicotinoids) that may have similar MOAs were selected and five binary mixture systems were constructed. For each system, five mixture rays with different concentration ratios were designed by the direct equipartition ray design (EquRay) method. The mortality of Caenorhabditis elegans was regarded as the endpoint for the toxicity exposure to single pesticides and binary mixtures. The combined toxicities were evaluated simultaneously using the CA model, isobologram and combination index. The structural similarity of the same type of pesticides was quantitatively analyzed according to the MACCS molecular fingerprint and the slope of dose-response curve at pEC. The results show that the toxicities of neonicotinoid mixtures and carbamate mixtures are almost antagonistic. The entire mixture system of dichlorvos and dimethoate produced synergism, and four of the five mixture rays of dimethoate and methamidophos induced antagonism, while among the mixture rays of dichlorvos and methamidophos, different concentrations showed different interaction types. The results of structural similarity analysis show that the size of structural similarity showed a certain quantitative relationship with the toxicity interaction of mixtures, that is, the structural similarity of the same type of pesticides may show an additive action in a certain range.
Topics: Animals; Caenorhabditis elegans; Dichlorvos; Dimethoate; Neonicotinoids; Pesticides
PubMed: 33975210
DOI: 10.1016/j.envpol.2021.117207 -
The Science of the Total Environment Nov 2020During water years (WY) 2013-2017, the U.S. Geological Survey, National Water-Quality Assessment (NAWQA) Project, sampled the National Water Quality Network - Rivers and...
During water years (WY) 2013-2017, the U.S. Geological Survey, National Water-Quality Assessment (NAWQA) Project, sampled the National Water Quality Network - Rivers and Streams (NWQN) year-round and reported on 221 pesticides at 72 sites across the United States in agricultural, developed, and mixed land use watersheds. The Pesticide Toxicity Index (PTI) was used to estimate the potential chronic and acute toxicity to three taxonomic groups - fish, cladocerans, and benthic invertebrates. For invertebrates (either cladocerans, benthic invertebrates, or both), the maximum PTI score exceeded the predicted acute toxicity screening level at 18 of the 72 sites (25%) at some point during WY 2013-2017. The predicted toxicity of a single pesticide compound was found to overwhelm the toxicity of other pesticides in the mixtures after concentrations were toxicity weighted. For this study, about 71%, 72%, and 92% of the Fish-, Cladoceran-, and Benthic Invertebrate-PTI scores, respectively, had one pesticide compound primarily contributing to sample potential toxicity (>50%). There were 17 (13 insecticides, 2 herbicides, 1 fungicide, and 1 synergist) of the 221 pesticide compounds analyzed that were the primary drivers of potential toxicity in each water sample in which the PTI and TUmax (toxic unit score for the pesticide that makes the single largest contribution to the PTI) scores were above predicted chronic (>0.1) or acute (>1) toxicity levels for one of the three taxa. For cladocerans and benthic invertebrates, the drivers of predicted chronic (>0.1) and acute (>1) PTIs were mostly insecticides. For cladocerans, the pesticide compounds driving the PTI scores were bifenthrin, carbaryl, chlorpyrifos, diazinon, dichlorvos, dicrotophos, diflubenzuron, flubendiamide, and tebupirimfos. For benthic invertebrates, atrazine (an herbicide), as well as the insecticides - bifenthrin, carbaryl, carbofuran, chlorpyrifos, diazinon, dichlorvos, fipronil, imidacloprid, and methamidophos - were the drivers of predicted toxicity. For fish, there were three pesticide types that contributed the most to predicted chronic (>0.1) PTIs - acetochlor, an herbicide; carbendazim, a fungicide degradate; and piperonylbutoxide, a synergist.
Topics: Animals; Environmental Monitoring; Pesticides; Rivers; United States; Water; Water Pollutants, Chemical
PubMed: 32943215
DOI: 10.1016/j.scitotenv.2020.141285 -
Frontiers in Bioengineering and... 2022O-Acetylhomoserine (OAH) is an important platform chemical for the synthesis of L-methamidophos and l-methionine. It has been produced efficiently in . However, a wider...
O-Acetylhomoserine (OAH) is an important platform chemical for the synthesis of L-methamidophos and l-methionine. It has been produced efficiently in . However, a wider range of key factors had not been identified, limiting further increases in OAH production. This study successfully identified some limiting factors and regulated them to improve OAH titer. Firstly, an efficient clustered regularly interspaced short palindromic repeats/dead CRISPR associated protein 9 (CRISPR-dCas9) system was constructed and used to identify the key genes in central metabolism and branch pathways associated with OAH biosynthesis. Then, the gene involved in TCA cycle was identified as the most critical gene. A sequential promoter P, which showed different transcriptional intensity in different strain growth periods, was used to control the expression of gene, resulting in OAH production of 7.0 g/L at 48 h. Finally, the OAH titer of the engineered strain reached 25.9 g/L at 72 h in a 5-L bioreactor. These results show that the identification and regulation of key genes are critical for OAH biosynthesis, which would provide a better research basis for the industrial production of OAH in .
PubMed: 36185436
DOI: 10.3389/fbioe.2022.978686 -
Journal of Hazardous Materials Mar 2022The microbial degradation of acephate in pure cultures has been thoroughly explored, but synergistic metabolism at the community level has rarely been investigated....
The microbial degradation of acephate in pure cultures has been thoroughly explored, but synergistic metabolism at the community level has rarely been investigated. Here, we report a novel microbial consortium, ZQ01, capable of effectively degrading acephate and its toxic product methamidophos, which can use acephate as a source of carbon, phosphorus and nitrogen. The degradation conditions with consortium ZQ01 were optimized using response surface methodology at a temperature of 34.1 °C, a pH of 8.9, and an inoculum size of 2.4 × 10 CFU·mL, with 89.5% of 200 mg L acephate degradation observed within 32 h. According to the main products methamidophos, acetamide and acetic acid, a novel degradation pathway for acephate was proposed to include hydrolysis and oxidation as the main pathways of acephate degradation. Moreover, the bioaugmentation of acephate-contaminated soils with consortium ZQ01 significantly enhanced the removal rate of acephate. The results of the present work demonstrate the potential of microbial consortium ZQ01 to degrade acephate in water and soil environments, with a different and complementary acephate degradation pathway.
Topics: Biodegradation, Environmental; Microbial Consortia; Organothiophosphorus Compounds; Phosphoramides; Soil; Soil Microbiology
PubMed: 34844804
DOI: 10.1016/j.jhazmat.2021.127841 -
Journal of Hazardous Materials Jun 2020The objective of this study was to design a versatile and reusable pesticide detection surface-enhanced Raman scattering (SERS) substrate in combination with SERS...
The objective of this study was to design a versatile and reusable pesticide detection surface-enhanced Raman scattering (SERS) substrate in combination with SERS enhancement and self-cleaning properties. In this paper, we present an inexpensive way to synthesize three-dimensional tilted ZnO micron rods with an Ag hierarchical structure (ZMRs/Ag arrays). Although expensive materials and complex methods were not used, the detection limit of thiram residue was 10 M, with a quantitative relationship (R = 0.9929) between the thiram concentration and the intensity of the SERS peaks. Additionally, the substrates exhibited fast and efficient photocatalytic activity for the degradation of adsorbed thiram, and the degradation rate in 30 min was close 100 % under visible-light irradiation. The enhancement and photocatalytic mechanism of this substrate were meticulously analyzed in detail. Furthermore, the residues of several mixed pesticides (e.g., thiram and methamidophos compounds) in various juices (such as grape, pear, orange, apple, and cherry juices) were quickly detected using ZMRs/Ag substrates. The main advantages of this substrate are recyclability, stability, selectivity, handiness, and cost-eff ;ectiveness. The substrate can prevent single-use problems associated with conventional SERS substrates and can be applied in pesticide residue and food security.
Topics: Food Contamination; Fruit and Vegetable Juices; Limit of Detection; Pesticides; Recycling; Silver; Spectrum Analysis, Raman; Thiram; Zinc Oxide
PubMed: 32062540
DOI: 10.1016/j.jhazmat.2020.122222 -
F1000Research 2020: Developmental delay among children under 5 years of age is a serious global public health problem and much research has been carried out to find potential causes....
: Developmental delay among children under 5 years of age is a serious global public health problem and much research has been carried out to find potential causes. Pesticides - especially organophosphates - are suspected to be one of the main causes of the problem. This study aimed to investigate the association between pesticide use by the mother during pregnancy and preschool children development using a case-control study. : Data on prenatal and postnatal pesticide exposure of 442 children with suspected developmental delay, and 413 controls with normal development were included for analysis. The children were matched for gender, age, and residency. Data on pesticide exposure were collected via interview with the mother, and data on pregnancy outcomes abstracted from hospital records. : Chlorpyrifos exposure significantly increased the risk of developmental delay with an odds ratio (OR) of 3.71 (95% CI 1.03-13.36) for ever use of the pesticide, and an OR of 5.92 (95% CI 1.01-34.68) for postnatal exposure (p <0.05). Some other pesticides also had a positive association with developmental delay but none were statistically significant (p <0.05). Those pesticides were insecticide, fungicide, herbicide, and molluscicide. Individual pesticides with a positive association were glyphosate, paraquat, butachlor, methyl parathion (pholidon), savin, methomyl, endosulfan, carbosulfan, methamidophos, monochrotofos, mancozeb, and bordeaumixture. : This case-control study found that chlorpyrifos and some other pesticides exposure during pregnancy were positively associated with developmental delay in children aged under 5 years. Further research should be conducted to better understand this potential effects of pesticides on child neurodevelopment, and the public - especially those who plan to have families - should be informed.
Topics: Case-Control Studies; Child, Preschool; Chlorpyrifos; Female; Humans; Pesticides; Pregnancy; Pregnancy Outcome; Thailand
PubMed: 34557296
DOI: 10.12688/f1000research.27874.5 -
Biosensors & Bioelectronics Aug 2023The development of a common and anti-interference acetylcholinesterase (AChE) inhibition assay for plant-originated food samples has been of great challenge because of...
The development of a common and anti-interference acetylcholinesterase (AChE) inhibition assay for plant-originated food samples has been of great challenge because of the prevalent and strong signal interferences from natural pigments. Plant pigments normally exhibit non-negligible absorbance in the UV-visible region. As a result, the signals of a typical near-infrared (NIR) fluorescent probe could be disturbed through primary inner filter effect if it is excited by UV-visible light during plant sample analysis. In this work, an NIR-excitable AChE-activated fluorescent probe was biomimetically designed and synthesized. And the NIR-excitation strategy was utilized for the anti-interference detection of organophosphate and carbamate pesticides in colored samples with this probe. Sensitive and rapid response to AChE and pesticides was achieved due to the high affinity of the biomimetic recognition unit in the probe. The limits of detection for four representative pesticides including dichlorvos, carbofuran, chlorpyrifos and methamidophos reached 0.0186 μg/L, 2.20 μg/L, 12.3 μg/L and 13.6 μg/L, respectively. Most importantly, fluorescent response to pesticide contents could be accurately measured in the coexistence of different plant pigments by this probe, and the measured results showed completely irrelevance to the plant pigments and their colors. Taking advantage of such probe, the new developed AChE inhibition assay showed good sensitivity and anti-interference ability in the detection of organophosphate and carbamate pesticides in real samples.
Topics: Pesticides; Acetylcholinesterase; Fluorescent Dyes; Biosensing Techniques; Carbofuran; Chlorpyrifos
PubMed: 37099980
DOI: 10.1016/j.bios.2023.115341 -
Analytical and Bioanalytical Chemistry May 2021Mycotoxins and pesticides regularly co-occur in agricultural products worldwide. Thus, humans can be exposed to both toxic contaminants and pesticides simultaneously,...
Development, validation, and application of a multi-method for the determination of mycotoxins, plant growth regulators, tropane alkaloids, and pesticides in cereals by two-dimensional liquid chromatography tandem mass spectrometry.
Mycotoxins and pesticides regularly co-occur in agricultural products worldwide. Thus, humans can be exposed to both toxic contaminants and pesticides simultaneously, and multi-methods assessing the occurrence of various food contaminants and residues in a single method are necessary. A two-dimensional high performance liquid chromatography tandem mass spectrometry method for the analysis of 40 (modified) mycotoxins, two plant growth regulators, two tropane alkaloids, and 334 pesticides in cereals was developed. After an acetonitrile/water/formic acid (79:20:1, v/v/v) multi-analyte extraction procedure, extracts were injected into the two-dimensional setup, and an online clean-up was performed. The method was validated according to Commission Decision (EC) no. 657/2002 and document N° SANTE/12682/2019. Good linearity (R > 0.96), recovery data between 70-120%, repeatability and reproducibility values < 20%, and expanded measurement uncertainties < 50% were obtained for a wide range of analytes, including very polar substances like deoxynivalenol-3-glucoside and methamidophos. However, results for fumonisins, zearalenone-14,16-disulfate, acid-labile pesticides, and carbamates were unsatisfying. Limits of quantification meeting maximum (residue) limits were achieved for most analytes. Matrix effects varied highly (-85 to +1574%) and were mainly observed for analytes eluting in the first dimension and early-eluting analytes in the second dimension. The application of the method demonstrated the co-occurrence of different types of cereals with 28 toxins and pesticides. Overall, 86% of the samples showed positive findings with at least one mycotoxin, plant growth regulator, or pesticide.
Topics: Alkaloids; Chromatography, Liquid; Edible Grain; Food Contamination; Mycotoxins; Pesticides; Plant Growth Regulators; Reproducibility of Results; Tandem Mass Spectrometry; Tropanes
PubMed: 33713146
DOI: 10.1007/s00216-021-03239-1