The analysis of pesticide residues in aquatic products is challenging due to low residue levels and the complex matrix interference. In this study, we developed a simple, fast method for the trace ...analysis of 90 pesticides and metabolites in aquatic products. The analytes covered a wide polarity range with log Kow (log octanol-water partition coefficient) ranging from -1.2 to 6.37. Grass carp (
) and prawn (
) samples were chosen to validate the quantification method. The samples were extracted by 0.2% formic-acetonitrile, cleaned by solid-phase extraction (PRiME HLB), and analyzed by high performance liquid chromatography-tandem mass spectrometry. The results showed good linearities for the analytes and were observed in the range of 0.05-50 μg/L. The recoveries of the method were within 50.4-118.6%, with the relative standard deviations being lower than 20%. The limits of quantifications (LOQs) of the method were in the range of 0.05-5.0 μg/kg, which were superior to values compared with other research. The developed method was applied to detect pesticide residues in prawn samples from eastern coastal areas of China. Three herbicide residues of diuron, prometryn, and atrazine were detected in prawn samples. The method was sensitive and efficient, which is of significance in expanding the screening scope and improving the quantitative analysis efficiency in aquatic products.
Milk and dairy products present considerable socioeconomic importance but are also a regular pesticide residue contamination source, which is considered a worldwide public health concern and a major ...international trade issue. Thus, a literature review was conducted to assess pesticide residue levels in milk and dairy products, as well as the residue degradation capacity during its processing. Organochlorine, organophosphate, synthetic pyrethroid and/or triazine were found in fluid milk, powder products, yogurts, cheese, butter, and sour cream. Thermal processing reduced most residue levels, although some treatments increased total hexachlorocyclohexane and its isomers (α-, γ-, δ-, and β-). Emerging non-thermal treatments presented promising results, but some by-products had higher toxicity than their precursors. Biodegradation by lactic acid bacteria were effective during yogurt and cheese fermentation. However, β-hexachlorocyclohexane level seems to increase in yogurts containing Lactobacillus acidophilus and Bifidobacterium animalis subsp. lactis, while increase or maintenance of pesticide residue concentration was observed during coagulation and cheese maturation. Deep research is needed to understand the isomerization and degradation mechanisms after thermal, non-thermal, and fermentation processing. Emerging heat technology can be an excellent topic to be investigated for pesticide residues degradation in the future. These mitigation approaches can be a feasible future alternative to milk and dairy production.
The intensive development of agriculture means that more and more toxic organic and inorganic compounds are entering the environment. Because of their widespread use, stability, selective toxicity ...and bioaccumulation, pesticides are among the most toxic substances contaminating the environment. They are particularly dangerous in fruit and vegetables, by which people are exposed to them. It is therefore crucial to monitor pesticide residues in fruit and vegetables using all available analytical methods.
We set out the problems in the determination of organonitrogen and organophosphorus pesticides in samples of fruit and vegetables, including the complexity and the diversity of matrices in biological materials, and the very low level of pesticides present, as a result of which target analytes have to be isolated and then enriched prior to final determination.
We discuss the various stages in the determination of pesticide residues in fruit and vegetables. We present results from the literature in the context of Maximum Residue Levels (MRLs) of target pesticides in fruit and vegetable samples. We discuss the merits of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) technique and two-dimensional gas chromatography.
Penicillin G is a widely used antimicrobial in food-producing animals, and one of the most predominant drug residues in animal-derived food products. Due to reduced sensitivity of bacteria to ...penicillin, extralabel use of penicillin G is common, which may lead to violative residues in edible tissues and cause adverse reactions in consumers. This study aimed to develop a physiologically based pharmacokinetic (PBPK) model to predict drug residues in edible tissues and estimate extended withdrawal intervals for penicillin G in swine and cattle. A flow-limited PBPK model was developed with data from Food Animal Residue Avoidance Databank using Berkeley Madonna. The model predicted observed drug concentrations in edible tissues, including liver, muscle, and kidney for penicillin G both in swine and cattle well, including data not used in model calibration. For extralabel use (5× and 10× label dose) of penicillin G, Monte Carlo sampling technique was applied to predict times needed for tissue concentrations to fall below established tolerances for the 99th percentile of the population. This model provides a useful tool to predict tissue residues of penicillin G in swine and cattle to aid food safety assessment, and also provide a framework for extrapolation to other food animal species.
Display omitted
•A population PBPK model for procaine penicillin G in swine and cattle was developed.•The dissolution process of procaine penicillin G was incorporated into the model.•The model predicted drug concentrations in edible tissues well for swine and cattle.•The model can estimate withdrawal intervals after extralabel use of penicillin G.
Interactions between proteins are vital in almost all biological processes. The characterization of protein-protein interactions helps us understand the mechanistic basis of biological processes, ...thereby enabling the manipulation of proteins for biotechnological and clinical purposes. The interface residues of a protein-protein complex are assumed to have the following two properties: (a) they always interact with a residue of a partner protein, which forms the basis for distance-based interface residue identification methods, and (b) they are solvent-exposed in the isolated form of the protein and become buried in the complex form, which forms the basis for Accessible Surface Area (ASA)-based methods. The study interrogates this popular assumption by recognizing interface residues in protein-protein complexes through these two methods. The results show that a few residues are identified uniquely by each method, and the extent of conservation, propensities, and their contribution to the stability of protein-protein interaction varies substantially between these residues. The case study analyses showed that interface residues, unique to distance, participate in crucial interactions that hold the proteins together, whereas the interface residues unique to the ASA method have a potential role in the recognition, dynamics, and specificity of the complex and can also be a hotspot. Overall, the study recommends applying both distance and ASA methods so that some interface residues missed by either method but crucial to the stability, recognition, dynamics, and function of protein-protein complexes are identified in a complementary manner.
Seven pesticides, profenofos, metalaxyl, λ-cyhalothrin, 4,4′-DDT, 4,4′-DDE, and α- and β-endosulfan, were determined in vegetables (tomato, onion) from 20 locations and surface waters from 12 ...locations in the Central Rift Valley (CRV) of Ethiopia. Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) and solid phase extraction (SPE) methods were used for the vegetables and water, respectively. In 2.5% of the tomato samples, profenofos was detected above European maximum residue limits (MRLs), in 12.5% of the samples metalaxyl, and in 2.5% α- and β-endosulfan. In 5% of the onion samples, profenofos was detected above European MRLs, in 7.5% of the onion samples metalaxyl, and in 5% λ-cyhalothrin. In surface water, profenofos was detected at the highest concentration of 2300 μg/L in the Bulbula River, 890 μg/L near the agricultural land north of Lake Ziway (ANLZ-1), 1700 μg/L in the floriculture effluent (FE-1), and 900 μg/L in tap water at the Batu Drinking Water (BDW) supply. These results show that the levels of pesticides are in several cases substantially elevated, and emphasize the need of regular pesticide monitoring programs for surface waters and vegetables in the Ethiopian CRV.
Bees are essential pollinators of many plants in natural ecosystems and agricultural crops alike. In recent years the decline and disappearance of bee species in the wild and the collapse of honey ...bee colonies have concerned ecologists and apiculturalists, who search for causes and solutions to this problem. Whilst biological factors such as viral diseases, mite and parasite infections are undoubtedly involved, it is also evident that pesticides applied to agricultural crops have a negative impact on bees. Most risk assessments have focused on direct acute exposure of bees to agrochemicals from spray drift. However, the large number of pesticide residues found in pollen and honey demand a thorough evaluation of all residual compounds so as to identify those of highest risk to bees. Using data from recent residue surveys and toxicity of pesticides to honey and bumble bees, a comprehensive evaluation of risks under current exposure conditions is presented here. Standard risk assessments are complemented with new approaches that take into account time-cumulative effects over time, especially with dietary exposures. Whilst overall risks appear to be low, our analysis indicates that residues of pyrethroid and neonicotinoid insecticides pose the highest risk by contact exposure of bees with contaminated pollen. However, the synergism of ergosterol inhibiting fungicides with those two classes of insecticides results in much higher risks in spite of the low prevalence of their combined residues. Risks by ingestion of contaminated pollen and honey are of some concern for systemic insecticides, particularly imidacloprid and thiamethoxam, chlorpyrifos and the mixtures of cyhalothrin and ergosterol inhibiting fungicides. More attention should be paid to specific residue mixtures that may result in synergistic toxicity to bees.
Pharmaceutical and personal care products (PPCPs) are continuously introduced into the soil-plant system, through practices such as agronomic use of reclaimed water and biosolids containing these ...trace contaminants. Plants may accumulate PPCPs from soil, serving as a conduit for human exposure. Metabolism likely controls the final accumulation of PPCPs in plants, but is in general poorly understood for emerging contaminants. In this study, we used diclofenac as a model compound, and employed 14C tracing, and time-of-flight (TOF) and triple quadruple (QqQ) mass spectrometers to unravel its metabolism pathways in Arabidopsis thaliana cells. We further validated the primary metabolites in Arabidopsis seedlings. Diclofenac was quickly taken up into A. thaliana cells. Phase I metabolism involved hydroxylation and successive oxidation and cyclization reactions. However, Phase I metabolites did not accumulate appreciably; they were instead rapidly conjugated with sulfate, glucose, and glutamic acid through Phase II metabolism. In particular, diclofenac parent was directly conjugated with glutamic acid, with acyl-glutamatyl-diclofenac accounting for >70% of the extractable metabolites after 120-h incubation. In addition, at the end of incubation, >40% of the spiked diclofenac was in the non-extractable form, suggesting extensive sequestration into cell matter. The rapid formation of non-extractable residue and dominance of diclofenac-glutamate conjugate uncover previously unknown metabolism pathways for diclofenac. In particular, the rapid conjugation of parent highlights the need to consider conjugates of emerging contaminants in higher plants, and their biological activity and human health implications.
Display omitted
•A tiered approach involving 14C trace technique and liquid chromatography-high resolution mass spectrometry (LC-HRMS) was used to obtain a comprehensive fate of diclofenac in Arabidopsis (i.e. phase I, phase II, and phase III).•Target, suspect, and non-target analysis was multi-applied to identify the metabolites.•Eleven phase I and phase II metabolites were identified in Arabidopsis cells and validated in seedlings.•>40% non-extractable residue was observed in cells after 120-h incubation with diclofenac.•Acyl-glutamatyl-diclofenac was newly found phyto-transformation product of diclofenac.
Diclofenac was quickly metabolized by A. thaliana cells, resulting in a number of Phase I metabolites and Phase II conjugates, as well as Phase III non-extractable residue.
The study uses gas chromatography with tandem mass spectrometry (GC-MS/MS) to develop a reliable analytical approach for detecting multiclass pesticides, polycyclic aromatic hydrocarbons (PAHs) and ...polychlorinated biphenyls (PCBs) in poultry meat and chicken eggs. The meat (2 g) and egg (4 g) samples were extracted with acidified acetonitrile (10 mL) as part of the optimized sample preparation technique. The cleanup consisted of freezing an aliquot of the extract (5 mL) at −20 °C, followed by dispersive solid phase extraction using 50 mg PSA + 100 mg C
18
+150 mg MgSO
4
. The matrix co-extractives were effectively removed and the method performance met the European Commission's analytical quality control criteria (SANTE/12682/2019). The method was validated at two spiking levels (10 and 20 ng/g of 225 pesticides, 9 PAHs and 8 PCBs), and good recoveries (70-120%) and precision-RSDs (≤20%) were achieved for 90% of the targeted pesticide residues. For 80% of the compounds, the LOQs were ≤10 ng/g. The results of the intra-laboratory (involving six analysts) and inter-laboratory validation studies (involving eight ISO 17025 accredited laboratories) established satisfactory ruggedness and reproducibility. It created potential applications in commercial residue testing laboratories for regulatory compliance check purposes.
In this study, a new rapid cleanup method was developed for the analysis of 111 pesticide multi-residues in lettuce and Chinese chives by GC-MS/MS and LC-MS/MS. QuEChERS (quick, easy, cheap, ...effective, rugged and safe)-based sample extraction was used to obtain the extracts, and the cleanup procedure was carried out using a Sin-QuEChERS nano cartridge. Comparison of the cleanup effects, limits of quantification and limits of detection, recoveries, precision and matrix effects (MEs) between the Sin-QuEChERS nano method and the classical dispersive solid phase extraction (d-SPE) method were performed. When spiked at 10 and 100 μg/kg, the number of pesticides with recoveries between 90% to 110% and relative standard deviations < 15% were greater when using the Sin-QuEChERS nano method. The MEs of Sin-QuEChERS nano and d-SPE methods ranged between 0.72 to 3.41 and 0.63 to 3.56, respectively. The results verified that the Sin-QuEChERS nano method was significantly more effective at removing pigments and more convenient than the d-SPE method. The developed method with the Sin-QuEChERS nano cleanup procedure was applied successfully to determine pesticide residues in market samples.
PDF
