Organophosphorus Pesticides In Foods Research Articles

Photocatalytic degradation of four organophosphorus pesticides in aqueous solution using D-cys/Au NPs modified TiO2 by natural sunlight

The widespread use of organophosphorus pesticides (OPPs) in foods, poses a serious threat to human and environmental health, it is crucial to develop methods that can efficiently degrade residual OPPs. Herein, a chiral TiO2 photocatalyst was developed by modification TiO2 with D-cys/Au NPs (DAT) for the simultaneous degradation of four OPPs (chlorpyrifos, chlorpyrifos-methyl, malathion, and parathion) by natural light. The influence of D-Au NPs concentration on the degradation process was optimized, along with the initial pesticide concentration. Under optimal conditions, the photocatalytic degradation efficiencies of DAT for four OPPs were 96.7 %, 56.9 %, 42.6 %, and 49.2 %, respectively, after 12 h of natural light exposure. 12 degradation products of OPPs were identified, among which three products were identified for the first time. The degradation pathway revealed that the degradation of OPPs by DAT involves the oxidation of the P═S bond and the cleavage of the P-O bond and C-O bond. This study establishes a theoretical foundation for applying chiral TiO2 nanomaterials for the photocatalytic degradation of OPPs in foods.

Pesticides luminescent sensing by a Tb3+-doped Zn metal-organic framework with selectivity towards parathion

Organophosphorus pesticides (OPPs) such as parathion have extensive uses in agriculture and household applications. Chronic exposure to these pesticides can cause severe health and environmental issues. Therefore, a current ecological concern is associated with accumulating these noxious OPPs in food and water sources. In this work, a new Tb3+-doped Zn-LMOF (Zn-LMOF= (3D) {[Zn3(1,4 benzenedicarboxylate)3(EtOH)2]·(EtOH)0.6}∞) was synthesized by a solvent-free reaction between the Zn-LMOF and the salt TbCl3·6H2O using a high-speed ball milling. The Tb@Zn-LMOF was thoroughly characterized by multiple spectroscopic tools, including Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy, and studied in-depth as a luminescent sensor for a series of pesticides (parathion, malathion, methalaxil, carbofuran, iprodione, captan and glyphosate) in aqueous methanol. The Tb@Zn-LMOF is a long-lived green-emitting compound with luminescence originated by an efficient antenna effect from the excited energy levels of Zn-LMOF toward the 5D state of Tb3+ ions, as it is displayed by its strong emission bands at 488, 545, 585, and 620 nm and a lifetime of 1.01 ms upon excitation at 290 nm. Additions of pesticides to a neutral methanolic dispersion of Tb@Zn-LMOF modified its green emission intensity with a pronounced selectivity toward parathion within the micromolar concentration range. The detection limit for parathion was calculated to be 3.04 ± 0.2 μM for Tb@Zn-LMOF. Based on 31P NMR and mass spectrometry studies, it is attributed to the release of lanthanide ions from Tb@Zn-LMOF with the simultaneous formation of a Tb3+-parathion complex.

Rapid analysis of dichlorvos via releasing the phosphate core

Monitoring the residual dichlorvos (O,O-dimethyl-O-2,2-dichlorovinylphosphate, DDVP) in food has received extensive attention owing to its large consumption in agriculture. However, the previous sensing methods are not time-efficient enough due to the long incubation time for enzyme inhibition (tens of minutes to hours) or bottlenecked by the complicated procedures for senor fabrication. Herein, a novel sensing strategy is proposed based on the hydrolysis of DDVP into PO43−. By using alkaline phosphatase for hydrolysis, a certain portion of DDVP was transformed to PO43− within only 8 min. Then, the released PO43− was detected by a fluorescent terbium metal-organic framework (Tb-MOF). The coordination of the naked P–O groups to the metal nodes of the Tb-MOF disturbed the antenna effects of its ligands. Thus, DDVP was quantified by the decrease of the fluorescence of Tb ions. Based on this method, DDVP residues on plum surfaces were collected by swabs and successfully detected. The recovery of DDVP was determined in the range from 105 % to 115 %, demonstrating the quantification accuracy of this method. The detection limit reached 4.7 μM, which was lower than the restricted amount in fruit set by the National Standard of China. The present method provides an efficient and user-friendly way for the detection of DDVP and many other organophosphorus pesticides in food.

Molecularly imprinted electrochemiluminescence sensor based on flake-like Au@Cu:ZIF-8 nanocomposites for ultrasensitive detection of malathion

The combination of electrochemiluminescence (ECL) and molecularly imprinted polymer (MIP) techniques offers distinct for detecting organophosphorus pesticides (OPs). Herein, a novel flake-like nanocomposites Au@Cu:ZIF-8 was successfully synthesized, as to design a molecularly imprinted electrochemiluminescence (MIP-ECL) sensor for the detection of malathion (MAL). The doped Cu2+ as a co-reaction promoter facilitated the generation of the active intermediate SO4•− for the cathodic reaction system with K2S2O8 as the co-reactant, while AuNPs were used as an excellent catalyst, further enhancing the ECL strength of the overall reaction system. Subsequently, MIP film was formed by the electropolymerization of Benzo[1,2-b:4,5-b′]dithiophene-4,8-dione as a functional monomer and MAL as a template molecule on the electrode surface. Confirmation of this process was achieved through molecular docking technique, which indicated that template molecule and functional monomer were tightly bound through non covalent bonds. The ECL signal was controlled by the elution and incubation of MAL by the MIP, thus establishing a novel method for MAL detection. The sensor showed a good linear relationship in the range of 10 pg/mL to 0.1 μg/mL with a detection limit of 0.18 pg/mL (S/N = 3). Furthermore, the recoveries of MAL detection in apple, cabbage and tomato samples ranged from 91.94% to 104.50%, indicating that the sensor offers potential applications for trace analysis of OPs in food and agricultural products.

Platinum nanoflowers stabilized with aloe polysaccharides for detection of organophosphorus pesticides in food

Organophosphorus pesticides can inhibit the activity of acetylcholinesterase and cause neurological diseases. Therefore, it is crucial to establish an efficient and sensitive platform for organophosphorus pesticide detection. In this work, we extracted aloe polysaccharide (AP) from aloe vera with the number average molecular weight of 27760 Da and investigated its reducing property. We prepared aloe polysaccharide stabilized platinum nanoflowers (AP-Ptn NFs), their particle size ranges were 29.4–67.3 nm. Furthermore, AP-Ptn NFs exhibited excellent oxidase-like activity and the catalytic kinetics followed the typical Michaelis-Menten equation. They showed strong affinity for 3,3′,5,5′-tetramethylbenzidine substrates. More importantly, we developed a simple and effective strategy for the sensitive colorimetric detection of organophosphorus pesticides in food using biocompatible AP-Ptn NFs. The detection range was 0.5 μg/L − 140 mg/L, which was wider than many previously reported nanozyme detection systems. This colorimetric biosensor had good selectivity and good promise for bioassay analysis.

Enzyme-targeted near-infrared fluorescent probe for organophosphorus pesticide residue detection.

Pesticide residues significantly affect food safety and harmhuman health. In this work, a series of near-infrared fluorescent probes were designed and developed by acylating the hydroxyl group of the hemicyanine skeleton with aquenching moiety for monitoring the presence of organophosphorus pesticides in food and live cells. The carboxylic ester bond on the probe was hydrolyzed catalyticallyin the presence of carboxylesterase and thereby the fluorophore was releasedwith near-infrared emission. Notably, the proposed probe 1 exhibited excellent sensitivity against organophosphorus based on the carboxylesterase inhibition mechanism and the detection limit for isocarbophos achieved 0.1734μg/L in the fresh vegetable sample. More importantly, probe 1 allowed for situ visualization of organophosphorus in live cells and bacteria, meaning great potential for tracking the organophosphorus in biological systems. Consequently, this study presents a promising strategy for tracking pesticide residues in food and biological systems.

Preparation of Fe3O4@UiO-66(Zr)@Ag NPs core-shell-satellite structured SERS substrate for trace detection of organophosphorus pesticides residues.

Surface-enhanced Raman spectroscopy (SERS) technology has been revived and developed with the introduction of metal-organic frameworks (MOFs), while more valuable properties of MOFs for SERS substrates remain largely unexplored. This work constructed a new SERS substrate Fe3O4@UiO-66(Zr)@Ag nanoparticles (FUAs) with excellent SERS detection sensitivity, uniformity, reproducibility and stability, exhibiting a high Raman enhancement factor (5.62×106), low limit of detection (LOD, 2.11×10-11 M) and RSD (12.41%) for 4-NBT, and maintaining 81% SERS activity within 60days. The FUAs took full advantage of the strong affinity of UiO-66(Zr) for organophosphorus pesticides (OPs) to realize trace OPs detection. The LODs of phoxim, triazophos and methyl parathion in apple juice were 0.041, 0.021 and 0.0031mg/L, respectively, with good linearities ranging from 0.02 or 0.1-50mg/L, meeting the requirements of the food control standards, indicating that the potentials and prospects of the FUAs SERS substrate for trace detecting OPs in foods.

Design of zero-dimensional graphene quantum dots based nanostructures for the detection of organophosphorus pesticides in food and water: A review

Design of zero-dimensional graphene quantum dots based nanostructures for the detection of organophosphorus pesticides in food and water: A review. • A systematic study of zero-dimensional graphene quantum dots (GQDs) for organophosphorus pesticide (OPPs) sensing is summarised in brief. • Zero-dimensional GQDs pinpoint OPPs in food and water samples. • GQD-based nanostructures enable OPPs sensing via a variety of ways, including fluorescence resonance energy transfer (FRET), photo-induced electron transfer (PET), and the inner filter effect (IFE), etc. • The selectivity of an OPPs sensor has been reviewed in the presence of various interferences. • In the future, GQD nanostructures will open up new avenues for OPP sensing. From its inception, traditional analytical approaches have been the primary strategies for sensing organophosphorus pesticides (OPPs). Unfortunately, traditionally reported methods are suffering from plentiful limitations that include their cost factor, poor responsiveness, low specificity, tedious, etc. Recently, graphene quantum dots (GQDs) have been widely applied to researchers’ recognition of OPPs sensing in water and food samples, due to their outstanding and versatile attributes. Moreover, the combination of other nanomaterials like inorganic and organic materials, along with surface tuning of GQDs such as doping and functionalization, shows the potential to boost the performance of the sensing system. Despite this indubitable development, there is no detailed report on the design of zero-dimensional GQD-based nanostructures for the detection of OPPs in food and water. Therefore, we have addressed the GQDs-centered nanostructures for the recognition of OPPs in water and food. Importantly, it covers the consumption of OPPs and their impact on human health, while the synthesis and properties of nanosized GQDs have been reviewed. Besides, GQDs based on fluorescent, electrochemical, and colorimetric nanoprobe for monitoring OPPs have been illustrated. Moreover, sensing mechanisms, anti-interference potential, current challenges, and future research have been described. Fascinatingly, modification of GQDs enabled sensors exhibits supreme responsiveness and specificity for recognition of OPPs in provided samples. Accordingly, existing architectured GQDs mediated nanoprobes furnish the lower detection limit for OPPs up to a picogram. In near future, the nano-design of GQD-centered sensors will open up a new door for sensing OPPs in real-time samples.

Structural design of nanosize-metal–organic framework-based sensors for detection of organophosphorus pesticides in food and water samples: current challenges and future prospects

Structural design of nanosize-metal–organic framework-based sensors for detection of organophosphorus pesticides in food and water samples: current challenges and future prospects

PH and Redox Dual-Response Disulfide Bond-Functionalized Red-Emitting Gold Nanoclusters for Monitoring the Contamination of Organophosphorus Pesticides in Foods.

Most of the fluorescence sensors require choline oxidase or quenchers to detect organophosphorus pesticides (OPs) based on a single hydrolysate and suffer from high cost, complex procedures, weak stability, and low sensitivity. Here, we proposed a brand-new fluorescence strategy for highly sensitive detection of OPs based on both hydrolysate-response disulfide bond-functionalized gold nanoclusters (S-S-AuNCs) without additional substances. S-S-AuNCs were synthesized via a facile one-step redox reaction and emitted bright red light with ultrasmall size and high water dispersion. Interestingly, S-S-AuNCs displayed a unique response to thiol compounds and low pH values and were thus pioneered as a high-efficiency sensor for OPs based on acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylthiocholine into thiocholine and CH3COOH and OP inhibition of AChE activity. Further, S-S-AuNCs were employed to monitor the residue, distribution, and metabolization of methidathion in pakchoi with acceptable results. We believe that this work supplies a simpler and more highly sensitive approach for OP assay than the known ones and opens a new avenue to development of multistimulus-responsive and high-performance fluorescence substances.

Enzyme-based optical biosensors for organophosphate class of pesticide detection.

Organophosphorus pesticides, widely used as insecticides for crop protection, are classified as an extremely toxic class of chemical compounds by the World Health Organization (WHO). Organophosphorus pesticides show marked specificity for the enzyme acetylcholinesterase, and can cause irreversible harm to the nervous system. The excessive use of organophosphorus pesticides, specifically in developing countries, made WHO to impose a ban on certain organophosphorus pesticides being sold to the developing nations. WHO and the Food and Agriculture Organization of United Nations, in joint meetings on pesticide residues, have stressed the need to develop easy, rapid, and sensitive methods to detect the presence of organophosphorus pesticides in food and water. In this regard, a number of review articles have been published explaining a myriad of detection methods for organophosphorus pesticides. Among these, optical detection methods, using biological molecules as the recognition element, provide a number of advantages, such as, high sensitivity and selectivity, simple operation, fast response and cheap instrumentation, and can really prove to be an effective alternative to the time-consuming traditional methods in the current scenario. Therefore, in this review article, we have discussed the recent advances in the field of biosensors employing the optical detection of organophosphorus pesticides. Specifically, various biosensors developed, using enzymes acetylcholinesterase and organophosphate hydrolase, have been categorized on the basis of the material used for their fabrication. A systematic discussion of the working principles, analytical parameters, and advantages and disadvantages of the various biosensors, has been attempted, along with a future perspective, on the challenges and possible improvements in the field of optical detection of organophosphorus pesticides.

Up-Converting Nanoparticle-Based Immunochromatographic Strip for Multi-Residue Detection of Three Organophosphorus Pesticides in Food.

Organophosphorus (OP) pesticides are widely used to control pests because of their high activity. This study described a rapid and sensitive lateral flow immunochromatographic (LFIC) assay based on up-converting nanoparticles (UCNPs) for multi-residue detection of three OP pesticides. The developed assay integrated novel fluorescent material UCNPs labeled with a broad-specific monoclonal antibody. Based on the competitive platform by immobilized antigen in the test zone, the optimized UCNPs-LFIC assay enabled sensitive detection for parathion, parathion-methyl, and fenitrothion with IC50 of 3.44, 3.98, and 12.49 ng/mL (R2 ≥ 0.9776) within 40 min. The detectable ability ranged from 0.98 to 250 ng/mL. There was no cross-reactivity with fenthion, phoxim, isocarbophos, chlorpyrifos, or triazophos, even at a high concentration of 500 ng/mL. Matrix interference from various agricultural products was also studied in food sample detection. In the spiked test, recoveries of the three OP pesticides ranged from 67 to 120% and relative standard deviations were below 19.54%. These results indicated that the proposed strip assay can be an alternative screening tool for rapid detection of the three OP pesticides in food samples.

Determination of organophosphorus pesticide residues in vegetables by an enzyme inhibition method using α-naphthyl acetate esterase extracted from wheat flour

The widespread use of organophosphorus pesticides (OPs) poses a great threat to human health and has made the detection of OP residues in food an important task, especially in view of the fact that easy and rapid detection methods are needed. Because OPs have inhibitory effects on the activity of α-naphthyl acetate esterase (ANAE) in plants, in this work we evaluated the possibility of detecting OPs in vegetables with ANAE extracted from commercial flour. The limits of detection (LODs) obtained for methamidophos, dichlorvos, phoxim, dimethoate, and malathion in lettuce samples with crude ANAE were 0.17, 0.11, 0.11, 0.96, and 1.70 mg/kg, respectively. Based on the maximum residue limits (MRLs) for OPs in food stipulated by Chinese laws which are 0.05, 0.20, 0.05, 1.00, and 8.00 mg/kg for methamidophos, dichlorvos, phoxim, dimethoate, and malathion, respectively, the esterase inhibition method with crude ANAE had sufficient sensitivity to detect the residues of dichlorvos, dimethoate, and malathion in lettuce, but it could not be used to guarantee the safety of the same samples if methamidophos or phoxim residue was present. The sensitivity of the method was improved by the use of esterase purified by ammonium sulfate salting-out. The LODs obtained for methamidophos and phoxim with purified esterase were lower than the MRLs for these OPs in food. This is a very promising method for the detection of OP residues in vegetables using crude or purified esterase because of its cheapness, sensitivity, and convenience.

OP Pesticides in Children’s Bodies: The Effects of a Conventional versus Organic Diet

Conventional agriculture includes the use of pesticides to control insects in vegetable, fruit, wheat, and other crops, so it’s no surprise that foods derived from these crops can therefore contain pesticide residues. What’s in question, though, is what these exposures amount to in terms of body burden. Risk-defining data are lacking, and scant data exist on diet-derived pesticides levels in children’s bodies. Now researchers from Seattle and Atlanta characterize the relationship between eating a diet of conventionally grown food products and the amount of organophosphorus (OP) pesticide residues that make it into children’s bodies [EHP 114:260–263]. According to a 1993 National Research Council report titled Pesticides in the Diets of Infants and Children, diet delivers the bulk of children’s exposure to pesticides. This exposure poses a greater health risk to children as compared to adults, because not only do children consume more food on a per-weight basis than adults and consequently have higher exposure, they also may be more vulnerable to the effects of toxicants because they are still developing. The researchers employed a longitudinal design in which 23 children aged 3 to 11 years accustomed to eating a conventional diet switched to organic foods and back again during a 15-day study period. For the first three days, the children consumed their regular conventional diets. During the next five days, they substituted organic equivalents of their usual plant-derived food items (including fresh produce, juice, processed fruits and vegetables, and grain-based products). For the last seven days, they resumed their conventional diets. Each day, for the entire 15-day period, parents collected a urine sample in the morning when the children woke and again at bedtime. The urine samples were analyzed for metabolites of several OP pesticides. The most commonly detected metabolites were MDA (a metabolite of malathion) and TCPY (a metabolite of chlorpyrifos). During both conventional phases, 60% of samples contained MDA, and 78% of samples contained TCPY. When children switched to organic foods, the percentage of samples containing MDA dropped to 22% and the proportion with TCPY fell to 50%. Average concentrations of MDA and TCPY also were significantly lower during the organic phase compared to the conventional phases. During the two conventional phases, mean urinary MDA concentrations were 2.9 and 4.4 micrograms per liter (μg/L) compared with 0.3 μg/L in the organic phase. The mean TCPY level decreased from 7.2 to 1.7 μg/L between the first and second phases, and rose to 5.8 μg/L when the children resumed their conventional diets. Metabolite levels varied widely among the samples, however. Recent research suggests that fractions of MDA and TCPY form as the parent compounds degrade in foods and the environment. Therefore, some proportion of the children’s exposure may have been to the metabolites themselves in the foods. The current study provides insight into how residual OP pesticides in food correspond with the absorbed dose, and the researchers conclude that a diet of organic foods protects children from exposure. They caution against applying results to the general population, however. Given that people from different backgrounds and living in different areas may have different and more significant OP exposures, it would be a mistake to assume that switching to an organic diet would eliminate all exposure to these pesticides. The study does support the National Research Council’s conclusion that dietary intake is a major source of OP pesticide exposure, but some children may receive even more exposure from the use of pesticides in the home, and further research is needed.

Determination of organophosphorus pesticides in foods using an accelerated solvent extraction system.

Residual organophosphorus pesticides in foods were determined by accelerated solvent extraction (ASE), gel permeation chromatography and GC-FPD. Pesticides were extracted at 100 degrees C under 1500 psi pressure in less than 20 min. Wet samples were extracted after mixing with Extrelut drying agent. Four foods were spiked with 19 pesticides at 0.1 ppm or less. The average recoveries of these pesticides were 80-90% and the precision was < 10%. Both methamidophos and acephate gave 37-50% recoveries and 6-40% precision. These results suggested that ASE can be used to extract residues of organophosphorus pesticides in foods.

Simultaneous determination of 29 kinds of organophosphorus pesticides in foods by FPD-GC with capillary column.

Twenty nine kinds of organophosphorus pesticides were simultaneously measured by FPD-GC with two kinds of capillary columns (DB-210 and CBP-10). Reproducibility for peaks area of the pesticides in chromatograms were the range of 4.6-21.6%. Determination method of the 29 pesticides in foods was systematically established as follows. A) Pesticides in vegetables and fruits were extracted with acetone, re-extracted with 20% CH2Cl2-hexane and determined by GC. Recoveries of the pesticides in cucumber, potato, Japanese persimmon, cabbage, apple and mandarin orange were the range of 53.2-102.2%. B) Pesticides in garlic, onion, scallion were extracted, re-extracted by the same method with A, then purified by silica-gel column chromatography. Recoveries of the pesticides were the range of 31.2-89.9%. C) Pesticides in rice, wheat, soy bean and corn were extracted, re-extracted by the same method with A, then partitioned with hexane-acetonitrile and purified by silica-gel column chromatography. Recoveries of the pesticides were the range of 36.7-95.8%.

Multiresidue Method for Quantitative Determination of Organophosphorus Pesticides in Foods

A multiresidue method for the quantitative determination of organophosphorus pesticides in foods from the Food and Drug Administration's Total Diet Study is described. The organophosphorus pesticides are separated on the basis of polarity and determined in both fatty and nonfatty foods with a minimum of interferences. The foods analyzed included raw and cooked individual foods as well as combination dishes, water, and whiskey. Recoveries of 17 organophosphorus pesticides in 41 foods ranged from about 80 to 118%.

Residue analysis of organophosphorus pesticides in food with two‐dimensional gas chromatography using capillary columns and flame photometric detection

AbstractTwo‐dimensional gas chromatography with two capillary columns of different polarity (SP 2100 and OV 225) is used for pesticide residue analysis in food samples. By means of “live chromatography” applying pneumatic switching technique according to Deans, unequivocal identification of 57 organophosphorus pesticides in food samples is achieved at trace concentrations. The instrument is equipped with only one injection port and one flame photometric detector. On‐line data processing is very helpful, especially in calibration and checking the system's reliability with the multitude of test compounds. The complete pesticide residue analysis including clean‐up of about six food samples can be completed by one person in 8 hours.

Determination of residues of organophosphorus pesticides in foods. A review.

Download options Please wait... Article information DOI https://doi.org/10.1039/AN9679200475 Article type Review Article Download Citation Analyst, 1967,92, 475-492 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Determination of residues of organophosphorus pesticides in foods. A review D. C. Abbott and H. Egan, Analyst, 1967, 92, 475 DOI: 10.1039/AN9679200475 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author D. C. Abbott H. Egan