Determination of organophosphorus and synthetic pyrethroid pesticide residues and their variability in large size fruit crops.

BACKGROUND: Variability of pesticide residues in food item plays a key role for the evaluation of consumer food safety. However, variability factors (VFs) derived from the large size fruit crops are still scarce. Therefore, the present work was aimed to quantify pesticide residues and to estimate VFs in large size fruit crops of mango and guava. RESULTS: A total of 140 mango and 130 guava samples from different marketplaces in Bangladesh were collected to estimate the variability of pesticide residues (acephate, diazinon, malathion, fenitrothion, chlorpyrifos, quinalphos, dimethoate and cypermethrin) by in-house validated methods based on modified QuEChERS extraction and gas chromatography coupled with electron capture detector (ECD) and flame thermionic detector (FTD). The method was validated at three fortification levels (0.01, 0.10 and 0.30 mg kg-1 ) and satisfactory recoveries (80-111%) with relative standard deviation (RSDr ) ≤ 13% were achieved. A wide variation of residues was found in the analyzed samples. In the case of mango, the ranges of residues were 0.011-0.314, 0.015-0.04, and 0.05-0.291 mg kg-1 , respectively, for cypermethrin, chlorpyrifos, and dimethoate, while in the case of guava, the ranges were 0.04-0.113, and 0.03-0.290 mg kg-1 , respectively, for cypermethrin and acephate. The average VF for mango was 4.06 and it was 5.70 for guava. CONCLUSION: VFs originating from the marketed samples of mango and guava are reported in this study for the first time. The estimated VFs were higher than the default value of 3, therefore, the default VFs should be reconsidered when more data are obtained regarding large size crops. © 2021 Society of Chemical Industry.

Ozone treatment pak choi for the removal of malathion and carbosulfan pesticide residues.

Since the beginning of the widespread use of pesticides, their removal from food has become a serious concern. In this study, the removal of residual pesticides (malathion and carbosulfan) from pak choi via treatment with ozonated water was investigated. Under the optimal treatment conditions, i.e., 2.0 mg/L ozonated water and a treatment duration of 15 min, malathion and carbosulfan were degraded by 53.0 and 33.0%, respectively, without any significant changes in color. Even though there was a slight decrease in vitamin C content (~7.9 mg/100 g) following the treatments, a significant decrease in the microbial colonies on the vegetables was observed. Additionally, the pesticide degradation mechanism showed good fitting with a "first + first"-order kinetic model (R2 > 0.9), and the slope (k) indicated that ozone had a more prominent degradation effect on malathion than on carbosulfan. Therefore, this study provides a theoretical basis for controlling agricultural pesticide residues in household applications.

Solvent-assisted dispersive liquid-solid phase extraction of organophosphorus pesticides using a polypyrrole thin film-coated porous composite magnetic sorbent prior to their determination with GC-MS/MS.

A porous composite magnetic sorbent was developed and used as a solid phase for the solvent-assisted preconcentration of organophosphorus pesticides. The hierarchical porous composite sorbent was composed of polypyrrole thin film coated on the surface of porous alginate beads with embedded magnetite nanoparticles. The pores in the alginate hydrogel beads were produced by carbon dioxide bubbles from the reaction of incorporated calcium carbonate with hydrochloric acid. The porous network was filled with dichloromethane to assist extraction. The fabricated porous composite sorbent was characterized and sorbent fabrication and extraction conditions were optimized to obtain the best extraction performance. The developed sorbent was coupled with GC-MS/MS to determine organophosphorus pesticides in fruit juices and vegetable. Under optimized condition, the developed method provided good linear range of 0.03-200 µg L-1 for dichlorvos, malathion, and fenthion, and 0.075-200 µg L-1 for mevinphos, dimethoate, and parathion methyl, respectively. Limits of detection were in the range 0.010 to 0.025 µg L-1. This method exhibited good relative recoveries in the range 84 to 99% and RSDs lower than 8%. The good stability of the sorbent enabled up to eight cycles of reuse.Graphical abstract.

Enantiomeric separation of malathion and malaoxon and the chiral residue analysis in food and environmental matrix.

Malathion is a widely used chiral phosphorus insecticide, which has a more toxic chiral metabolite malaoxon. In this work, the enantiomers of malathion and malaoxon were separated by high-performance liquid chromatography-mass/mass (HPLC-MS/MS) with chiral columns using acetonitrile/water or methanol/water as mobile phase, and the chromatographic conditions were optimized. Based on the chiral separation, the chiral residue analysis methods for the enantiomers in soil, fruit, and vegetables were set up. Two pairs of the enantiomers were better separated on CHIRALPAK IC chiral column, and baseline simultaneous separations of malathion and malaoxon enantiomers were achieved with acetonitrile/water (40/60, v/v) as mobile phase at a flow rate of 0.5 mL/min. The elution orders were -/+ for both malathion and malaoxon measured by an optical rotation detector. The chiral residue analysis in soil, fruit, and vegetables was validated by linearity, recovery, precision, limit of detection (LOD), and limit of quantification (LOQ). The LODs and LOQs for the enantiomers of malathion were 1 µg/kg and 3-5 µg/kg and 0.08 µg/kg and 0.20-0.25 µg/kg for malaoxon enantiomers. Good linear calibration curves for each enantiomer in the matrices were obtained within the concentration range of 0.02-12 mg/L. The mean recoveries of the enantiomers of malathion and malaoxon ranged from 82.26% to 109.04%, with RSDs of 0.71-8.63%.The results confirmed that this method was capable of simultaneously determining the residue of malathion and malaoxon in food and environmental matrix on an enantiomeric level.

Magnetic amino-functionalized hollow silica-titania microsphere as an efficient sorbent for extraction of pesticides in green and roasted coffee beans.

This study describes the synthesis and application of a magnetic amino-functionalized hollow silica-titania microsphere as a new sorbent for magnetic dispersive micro-solid phase extraction of selected pesticides in coffee bean samples. The sorbent was fully characterized by Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, transition electron microscopy, energy-dispersive X-ray spectroscopy, and vibrating sample magnetometry techniques. Significant extraction parameters affecting the proposed method, such as extraction time, sorbent amount, sample solution pH, salt amount, and desorption conditions (desorption solvent and time) were investigated and optimized. All the figures of merits were validated in coffee bean samples under the matrix-matched calibration method. Linear dynamic ranges were 5-250 µg/kg with the determination coefficients (R2 ) > 0.9980. The limits of detection for the pesticides of chlorpyrifos, malathion, hexaconazole, and atrazine were 1.42, 1.43, 1.35, and 1.33 µg/kg, respectively. Finally, the method was successfully applied for the determination of the pesticides in green and roasted coffee bean samples, and the obtained recoveries were in the range of 74-113% for spiked samples. The prepared sorbent could be used for the magnetic dispersive micro-solid phase extraction of pesticides in the plant-derived food matrix.

Peptide Nanotube Encapsulated Enzyme Biosensor for Vapor Phase Detection of Malathion, an Organophosphorus Compound.

This study explores the use of a butyrylcholinesterase (BChE)-based, reversible reaction biosensor using screen-printed electrodes (SPEs) having a smaller working surface area than the single-use electrodes previously studied. Previous research demonstrated the prospective application of a single-use biosensor fabricated with an acetylcholinesterase (AChE) enzyme encapsulated in peptide nanotubes (PNTs) and enhanced with horseradish peroxidase (HRP) to detect organophosphorus compounds (OPCs) in aqueous and gas phases. In the current study, potential improvements to the biosensor are investigated. BChE-based biosensors were fabricated using PNTs, HRP, and Nafion in combination to increase the reactive surface area, enhance sensitivity, and maintain enzyme stability. Cyclic voltammetry (CV) was used along with the new modified sensor to measure malathion concentration in the gas phase. The results show that a BChE-based biosensor could reliably measure gas phase malathion concentrations between 6-25 ppbv by CV with the extent of inhibition linearly proportional to the malathion concentration (R2 = 0.941). This research demonstrated that fabricated BChE-based biosensors could be stored without cold storage requirement for up to six weeks with minimal performance degradation. Moreover, the sensor electrodes were each reused several times, and were still useable at the conclusion of the research. This research demonstrates the potential of fabricating a reusable, inexpensive biosensor that is capable of OPC detection with high sensitivity and a low detection limit without a long-term cold storage requirement.

Ultra-sensitive detection of malathion using quantum dots-polymer based fluorescence aptasensor.

A novel detection platform with high malathion specificity has been developed, which operates based on the signal response in the fluorescence of CdTe@CdS quantum dots (QDs). The designed nanoprobe comprises of QDs, poly(N-(3-guanidinopropyl)methacrylamide) homopolymer (PGPMA) and malathion specific aptamer. The interaction of aptamer with malathion results in switching off of the fluorescence signal of the probe due to the availability of the cationic polymer, which causes quenching of the QDs. However, in the absence of malathion, the polymer interacts with the aptamer, via electrostatic interactions thereby rendering the fluorescence of QDs unaffected. The assay exhibited excellent sensitivity towards malathion with a detection limit of 4pM. A logarithmic correlation was observed in a wide range of malathion concentrations from 0.01nm to 1µM, facilitating the potential of proposed assay in the quantitative determination of the analyte of interest. The selectivity of the designed probe was confirmed in the presence of various pesticides, commonly employed in agricultural fields.

Preparation of N doped TiO2 via microwave-assisted method and its photocatalytic activity for degradation of Malathion.

We report herein, nitrogen doped TiO2 nanostructure synthesized by simple microwave assisted method, where ammonia was used as hydrolyzing agent. The synthesized nanomaterials were characterized by means of X-ray diffraction (XRD) which demonstrated that N-doped TiO2 is in anatase phase with average crystallite size of 10nm. Doping of N into the lattice of TiO2 was supported by X-ray photoelectron spectroscopy (XPS), Fourier transform-infrared spectroscopy (FT-IR), CHNS analysis, energy dispersive spectroscopy (EDS). The diffuse reflectance spectroscopy (DRS) showed shifting of absorption edge toward the visible region. Thermogravimetric-differential thermal analysis (TGA-DTA) points out N-doped TiO2 nanoparticles are thermally stable. In order to achieve maximum degradation efficiency, the effect of catalyst loading, pH and light sources (UV and sunlight) were studied. A maximum 97% degradation efficiency was achieved under optimized conditions. A 80% reduction in the chemical oxygen demand (COD) was observed after 150min that indicated mineralization of Malathion. The cytotoxicological studies indicate that photocatalytically degraded products were less toxic as compared to Malathion.

Removal of malathion from aqueous solution using De-Acidite FF-IP resin and determination by UPLC-MS/MS: equilibrium, kinetics and thermodynamics studies.

In the present study, De-Acidite FF-IP resin was used to remove a highly toxic and persistent organophosphorus pesticide (malathion) from the aqueous solution. Batch experiments were performed as a function of various experimental parameters such as effect of pH (2-10), contact time (10-120 min), resin dose (0.05-0.5 g), initial malathion concentration (0.5-2.5 µg mL(-1)) and temperature (25-65°C). The concentration of malathion was determined using a sensitive, selective and rapid ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. The uptake rate of malathion on De-Acidite FF-IP resin was rapid and equilibrium established within 40 min. Kinetics studies showed better applicability for pseudo-second-order model. The equilibrium data was fitted to Langmuir and Freundlich isotherm models and the isotherm constants were calculated for malathion. The values of thermodynamic parameters (ΔG(0), ΔH(0) and ΔS(0)) were computed from the Van't Hoff plot of lnKC vs. 1/T which showed that the adsorption of malathion was feasible, endothermic and spontaneous. The regeneration studies were carried out which demonstrated a decrease in the recovery of malathion from 95% to 68% after five consecutive cycles. Breakthrough and exhaustive capacities of malathion were found to be 1.25 mg g(-1) and 3.5 mg g(-1), respectively.

A rapid and inexpensive bioassay to evaluate the decontamination of organophosphates.

An inexpensive and rapid bioassay using adult red flour beetles was developed for use in assessing the decontamination of environments containing organophosphates and related chemicals. A decontamination protocol was developed which demonstrated that 2 to 3 applications of 5% bleach solution were required to obtain nearly complete decontamination of malathion. The bioassay was also used to screen common household cleaners as potential decontaminating agents, but only 5% bleach was effective at improving survival of insects on steel plates treated with 25% malathion. A toxic degradation product (malaoxon) was detected using gas chromatography/mass spectrophotometry; this toxin affected the decontamination efficacy and resulted in continued toxicity to the beetles until subsequent decontaminations. The bioassay provides evidence to support the use of red flour beetles as a sensitive, less expensive method for determining safety levels of environments contaminated with malathion and other toxins, and may have application in the study of chemical warfare agents.

A simple filter-based approach to surface enhanced Raman spectroscopy for trace chemical detection.

We demonstrate an extremely simple and practical surface enhanced Raman spectroscopy (SERS) technique for trace chemical detection. Filter membranes first trap silver nanoparticles to form a SERS-active substrate and then concentrate analytes from a mL-scale sample into a µL-scale detection volume. We demonstrate a significant improvement in detection limit as compared to colloidal SERS for the pesticide malathion and the food contaminant melamine. The measured SERS intensity exhibits low variation relative to traditional SERS techniques, and the data can be closely fit with a Langmuir isotherm. Thus, due to the simple procedure, the low-cost of the substrates, the quantitative results, and the performance improvement due to analyte concentration, our technique enables SERS to be practical for a broad range of analytical applications, including field-based detection of toxins in large-volume samples.

Study on the removal of pesticide in agricultural run off by granular activated carbon.

In this batch study, the adsorption of malathion by using granular activated carbon with different parameters due to the particle size, dosage of carbons, as well as the initial concentration of malathion was investigated. Batch tests were carried out to determine the potential and the effectiveness of granular activated carbon (GAC) in removal of pesticide in agricultural run off. The granular activated carbon; coconut shell and palm shells were used and analyzed as the adsorbent material. The Langmuir and Freundlich adsorption isotherms models were applied to describe the characteristics of adsorption behavior. Equilibrium data fitted well with the Langmuir model and Freundlich model with maximum adsorption capacity of 909.1mg/g. The results indicate that the GAC could be used to effectively adsorb pesticide (malathion) from agricultural runoff.

Adsorption of malathion on thermally treated egg shell material.

Thermally treated egg shell materials were prepared at different temperatures. The samples were investigated by means of FT-IR and thermogravimetric analysis (TGA). The adsorption behaviour of malathion on egg shell and its thermally treated samples was studied using batch method and gave uptake capacities up to 0.964 mmol/g. Adsorption kinetics as well as the adsorption isotherms were discussed. Regeneration of the loaded adsorbent beads towards the successive cycles was also clarified. The adsorption of malathion is maintained until the third cycle without a significant activity loss.

Analysis of pesticide residues by fast gas chromatography in combination with negative chemical ionization mass spectrometry.

A combination of fast GC with narrow-bore column and bench top quadrupole mass spectrometer (MS) detector in negative chemical ionization (NCI) mode (with methane as reagent gas) is set up and utilized for the ultratrace analysis of 25 selected pesticides. The observed pesticides, belonging to the endocrine disrupting chemicals (EDCs), were from different chemical classes. A comparative study with electron impact (EI) ionization was also carried out (both techniques in selected ion monitoring (SIM) mode). The programmed temperature vaporizer (PTV) injector in solvent vent mode and narrow-bore column (15mx0.15mm I.D.x0.15microm film of 5% diphenyl 95% dimethylsiloxane stationary phase) were used for effective and fast separation. Heptachlor (HPT) as internal standard (I.S.) was applied for the comparison of results obtained from absolute and normalized peak areas. Non-fatty food matrices were investigated. Fruit (apple - matrix-matched standards; orange, strawberry, plum - real samples) and vegetable (lettuce - real sample) extracts were prepared by a quick and effective QuEChERS sample preparation technique. Very good results were obtained for the characterization of fast GC-NCI-MS method analysing EDCs pesticides. Analyte response was linear from 0.01 to 150microgkg(-1) with the R(2) values in the range from 0.9936 to 1.0000 (calculated from absolute peak areas) and from 0.9956 to 1.0000 (calculated from peak areas normalized to HPT). Instrument limits of detection (LODs) and quantification (LOQs) were found at pgmL(-1) level and for the majority of analytes were up to three orders of magnitude lower for NCI compared to EI mode. In both ionization modes, repeatability of measurements expressed as relative standard deviation (RSDs) was less than 10% which is in very good agreement with the criterion of European Union.

Biodegradation of malathion by Acinetobacter johnsonii MA19 and optimization of cometabolism substrates.

To enhance the removal efficiency of malathion in the wastewater from organophosphate pesticide mill, a bacterium, Acinetobacter johnsonii MA19, that could degrade malathion with cometabolism was isolated from malathion-polluted soil samples using enrichment culture techniques. Four kinds of additional compounds, sodium succinate, sodium acetate, glucose, and fructose were tested to choose a favorite carbon source for the cometabolism of strain MA19. The results showed that sodium succinate and sodium acetate could promote malathion biodegradation and cell growth. The investigation results of the effects of sodium succinate concentrations on the malathion biodegradation indicated that the more sodium succinate supplied resulted in quick degradation of malathion and fast cells multiplied. Zero-order kinetic model was appropriate to describe the malathion biodegradation when the concentration of sodium succinate was more than 0.5144 g/L. The degradation rate constant (K) reached the maximum value of 3.5837 mg/(L x h) when the mass ratio of sodium succinate to malathion was 128.6 mg/mg. The aquatic toxicity of the malathion was evaluated using the test organism, Limnodrilus hoffmeisteri. The data obtained suggested that the toxicity of malathion could be ignored after 84 h biodegradation. Our result demonstrates the potential for using bacterium A. johnsonii MA19 for malathion biodegradation and environmental bioremediation when some suitable conventional carbon sources are supplied.

Single and joint acute toxicity of isocarbophos enantiomers to Daphnia magna.

Although enantioselectivity in the toxicity of chiral pesticides has received considerable attention over recent years, how coexisting enantiomers interact with each other during their toxic action remains unknown. In this study, we attempted to resolve the enantiomers of a chiral organophosphate insecticide, isocarbophos, and investigated the acute toxicity of individual enantiomers and various enantiomer mixtures. Baseline enantiomeric separation of isocarbophos was achieved on a Chiralcel OD column with the mobile phase of n-hexane/isopropanol (90/10, v/v) at a flow rate of 0.8 mL/min. The resolved enantiomers were differentiated by their responses on a circular dichroism detector. The median lethal concentrations (LC 50) of racemate, (+)-enantiomer, and (-)-enantiomer of isocarbophos toward Daphnia magna were 13.9, 7.08, and 353 microg/L, respectively, after 48 h of static exposure, displaying a 50-fold difference between the enantiomers. Toxic unit (TU) analysis was employed to evaluate the joint toxicity of isocarbophos enantiomer mixtures. The calculated TU mix for the acute toxicity (48 h test) of various binary mixtures ranged from 0.83 to 1.04, suggesting a mode of additive effect. Further evaluation of available literature data for chiral organophosphorus insecticides showed that the joint toxicity of enantiomers may be additive, synergistic, and antagonistic. Therefore, when significant enantioselectivity exists for a chiral pesticide, it is important to also evaluate the interaction of enantiomers in the joint toxicity effect when enantiomers are present in a mixture.

Extraction of chlorpyrifos and malathion from water by metal nanoparticles.

The nanoparticles of gold and silver in solution state and supported over activated alumina are effective systems for the quantitative removal of chlorpyrifos and malathion, two common pesticides found in surface waters of developing nations, from water. In the solution phase, these pesticides adsorb onto the nanoparticles' surfaces and upon interaction for a long time, the nanoparticles with adsorbed pesticides precipitate. In contrast, complete removal of these pesticides occurs when contaminated water is passed over nanoparticles supported on alumina. A prototype of an on-line filter was made using a column of activated alumina powder loaded with silver nanoparticles and the device was used for pesticide removal for extended periods. We believe that the method has great technological potential in drinking water purification, especially using silver nanoparticles.

Effect of alcohols and temperature on the direct chiral resolutions of fipronil, isocarbophos and carfentrazone-ethyl.

The enantiomeric separations of three pesticides fipronil (asymmetric nitrogen), isocarbophos (asymmetric phosphorus) and carfentrazone-ethyl (asymmetric carbon) were studied on cellulose-tri(3,5-dimethylphenylcarbamate) chiral stationary phase using high-performance liquid chromatography under normal phase. The mobile phase was n-hexane with alcohols including ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol as polar modifiers. The flow rate was 1.0 mL/min with UV detection at 280, 225 and 230 nm for fipronil, isocarbophos and carfentrazone-ethyl respectively. The influence of the modifiers and their volume content and temperature from 0 to 50 degrees C on the separations was investigated. The chiral stationary phase showed excellent stereoselectivity for the two enantiomers of fipronil and isocarbophos and certain chiral recognition for carfentrazone-ethyl. Iso-propanol was more suitable for the chiral separation of isocarbophos and carfentrazone-ethyl, and iso-butanol was better for fipronil. The resolutions increased with the decreasing modifier content and temperature for all the three chiral pesticides.

Solid-phase microextraction of organophosphorus pesticides from water.

Frequent occurrences of pollution in natural drainage by industrial chemicals, especially pesticides, have triggered interest in the development of fast and unambiguous analytical techniques to verify these pollutants in order to facilitate rapid remedial actions. In this work, we report the development of a solid-phase microextraction (SPME) method to analyse two common industrial pesticides in water, i.e. malathion and parathion. SPME analysis facilitates direct analysis of chemical species in aqueous systems and avoids lengthy sample preparation procedures. In this study, we compare five commercially available fibres: 7 microns polydimethylsiloxane, 30 microns polydimethylsiloxane. 85 microns polyacrylate, 65 microns Carbowax-divinylbenzene and 65 microns polydimethylsiloxane-divinylbenzene fibres. Profiles of uptake by the fibres against adsorption times were established. The results obtained indicated that the polarity of the fibres is not the main factor affecting the uptake. The structures of the fibres also affected the permeation of the analytes onto the fibres. The limits of detection were determined to be in the low ppb level with a flame ionization detector. These methods have great potential for use in rapid on-site analytical work which is highly demanded in environmental studies.

[The gas chromatographic determination of carbophos in cadaveric material]. / Gazokhromatogreaficheskoe opredelenie karbofosa v trupnom materiale.

The authors developed a method of malathion insecticide determination in the cadaveric material (blood and wall of the stomach) including extraction of 5 ml of blood (5 g of fragmented tissue of stomach wall) by hexan; preparative chromatographic purification of extract on silicagel layer L 5/40 mkm in hexan-diethyl ether system 10:2; Gas-liquid chromatographic investigation on column with 5% SE-30 and 5% XE-60 (Chromatograph "Colour-106" with thermionic detector). This method makes it possible to detect 72-76% of malathion added.