Pesticide residues in fresh Mazafati date fruit, soil, and water, and assessment of potential health risks to consumers.

A quantitative method based on quick, easy, cheap, effective, rugged, and safe technique (QuEChERS) sample extraction and ultra-performance liquid chromatography/tandem mass spectrometry (UHPLC-MS/MS) was evolved for the determination of 47 pesticide residues in fresh Mazafati date fruits from Bam City of Kerman Province, Iran. The recoveries for selected pesticides ranged from 88 to 110% with a relative standard deviation (RSD) of less than 20% at concentrations of 0.05 and 0.1 mg kg-1. The proposed method had a linear range from the limit of quantification (LOQ) to 1.00 mg kg-1, and the LOQ of the 47 pesticides was ≤ 0.005 mg kg-1. The coefficients of determination (R2) were more than 0.99. This technique was used on 12 fresh date fruits samples, three water samples, and three soil samples with three replications per sample. Forty-seven pesticide were detected collectively, but only diazinon was detected in the date fruit samples. The mean value of diazinon residues was 0.037 mg kg-1, and the concentration of diazinon in most samples was below the national maximum residue limit (MRL) for date fruit (0.05 mg kg-1). Among the pesticides measured, diazinon residues were also detected in the water samples, but not in the soil samples. The dietary intake assessment showed no health risk to humans from the consumption of fresh date fruit concerning the pesticides investigated.

Actinomycetota, a central constituent microbe during long-term exposure to diazinon, an organophosphorus insecticide.

Microbial biodegradation is a primary pesticide remediation pathway. Despite diazinon is one of the most frequently used organophosphate insecticides worldwide, its effect on soil microbial community remains obscure. We hypothesize that diazinon exposure reshapes microbial community, among them increased microbes may play a crucial role in diazinon degradation. To investigate this, we collected soil from an organic farming environment, introduced diazinon, cultivated it in a greenhouse, and then assessed its effects on soil microbiomes at three distinct time points: 20, 40, and 270 days after treatment (DAT). Results from HPLC showed that the level of diazinon was gradually degraded by 98.8% at 270 DAT when compared with day zero, whereas 16S rRNA gene analysis exhibited a significant reduction in the bacterial diversity, especially at the early two time points, indicating that diazinon may exert selection pressure to the bacteria community. Here, the relative abundance of phylum Actinomycetota increased at 20 and 40 DATs. In addition, the bacterial functional gene profile employing PICRUSt2 prediction also revealed that diazinon exposure induced the genomic function related to xenobiotics biodegradation and metabolism in soil, such as CYB5B, hpaC, acrR, and ppkA. To validate if bacterial function is caused by increased relative abundance in diazinon enriched soil, further bacteria isolation resulted in obtaining 25 diazinon degradation strains out of 103 isolates. Notably, more than 70% (18 out of 25) isolates are identified as phylum Actinomycetota, which empirically confirms and correlates microbiome and PICRUSt2 results. In conclusion, this study provides comprehensive information from microbiome analysis to obtaining several bacteria isolates responsible for diazinon degradation, revealing that the phylum Actinomycetota is as a key taxon that facilitates microbial biodegradation in diazinon spoiled soil. This finding may assist in developing a strategy for microbial detoxification of diazinon, such as using an Actinomycetota rich synthetic community (SynCom).

The concentration of pesticides in tomato: a global systematic review, meta-analysis, and health risk assessment.

To improve farming productivity, a large number of pesticides have been used worldwide in recent decades, leading to the pollution of soil, agri-products, and water, directly/indirectly affecting human health. In this regard, many studies were conducted in different countries on residual pesticides in the environment. In the current study, residual pesticides including chlorpyrifos, cypermethrin, diazinon, malathion, and metalaxyl in tomatoes were meta-analyzed and health risk of consumers was estimated. For this purpose, based on a systematic review, data from 47 studies were extracted and meta-analyzed, and the health impact of pooled concentrations was assessed via a health risk method. According to the results, metalaxyl had the most concentration followed by malathion, cypermethrin, diazinon, and chlorpyrifos, respectively. The non-carcinogenic risk (n-CR) was calculated from crop consumption also showed that exposure to malathion has the most risk. Among the investigated communities, Iranian consumers were in considerable health risk (THQ > 1). Considering that the potential for the use of pesticides will increase with the need for food in the future, hence, governments must manage the usage by governments via alternative methods such as cultural, biological, physical, and genetic modifications.

Pesticide residues in honey bee (Apis mellifera) pollen collected in two ornamental plant nurseries in Connecticut: Implications for bee health and risk assessment.

Honey bees (Apis mellifera L.) are one of the most important managed pollinators of agricultural crops. While potential effects of agricultural pesticides on honey bee health have been investigated in some settings, risks to honey bees associated with exposures occurring in the plant nursery setting have received little attention. We sought to identify and quantify pesticide levels present in honey bee-collected pollen harvested in two ornamental plant nurseries (i.e., Nursery A and Nursery B) in Connecticut. From June to September 2018, pollen was collected weekly from 8 colonies using bottom-mounted pollen traps. Fifty-five unique pesticides (including related metabolites) were detected: 24 insecticides, 20 fungicides, and 11 herbicides. Some of the pesticide contaminants detected in the pollen had not been applied by the nurseries, indicating that the honey bee colonies did not exclusively forage on pollen at their respective nursery. The average number of pesticides per sample was similar at both nurseries (i.e., 12.9 at Nursery A and 14.2 at Nursery B). To estimate the potential risk posed to honey bees from these samples, we utilized the USEPA's BeeREX tool to calculate risk quotients (RQs) for each pesticide within each sample. The median aggregate RQ for nurse bees was 0.003 at both nurseries, well below the acute risk level of concern (LOC) of ≥0.4. We also calculated RQs for larvae due to their increased sensitivity to certain pesticides. In total, 6 samples had larval RQs above the LOC (0.45-2.51), resulting from the organophosphate insecticide diazinon. Since 2015, the frequency and amount of diazinon detected in pollen increased at one of our study locations, potentially due to pressure to reduce the use of neonicotinoid insecticides. Overall, these data highlight the importance of considering all life stages when estimating potential risk to honey bee colonies from pesticide exposure.

A chemiluminescence biosensor based on the peroxidase-like property of molybdenum disulfide/zirconium metal-organic framework nanocomposite for diazinon monitoring.

BACKGROUND: Organophosphorus pesticides are widely used in agriculture owing to their high effectiveness as insecticides. Among these, diazinon is a common environmental contaminant that acts as an acetylcholinesterase (AChE) enzyme inhibitor. As the current methods are too expensive and time-consuming for routine analysis of diazinon, its trace monitoring by rapid and sensitive methods is critical to protect the environment and human health. RESULTS: A biosensor was introduced for the indirect detection of diazinon using a molybdenum disulfide/zirconium metal-organic framework (MoS2@MIP-202(Zr)) nanocomposite. The probe is based on the peroxidase mimic of the prepared nanocomposite on NaHCO3-H2O2 chemiluminescence system as well as the inhibitory effect of diazinon on the enzymatic activity of AChE. The chemiluminescence signal is gradually decreased with an increase in diazinon concentration, and there is a linear relationship between the analytical signal and diazinon concentration. Under the optimum conditions, the calibration plot is linear in the concentration range of 0.5-300.0 nmol L-1. The limit of detection and quantification limit of the method are 0.12 and 0.40 nmol L-1, respectively. The inter-day and intra-day relative standard deviations (% RSD n = 5, diazinon concentration; 100 nmol L-1) are 3.66 and 1.35%, respectively. The method was used for diazinon detection in real water samples, and the high relative recovery values for the spiked samples along with satisfactory results of a certified reference material analysis confirmed that the method is accurate and free from the matrix effect. SIGNIFICANCE AND NOVELTY: A nano-probe based on the peroxidase-like property of MoS2@MIP-202(Zr) nanocomposite was developed for the first time for indirect detection of residue levels of diazinon in water samples. The high stability of the nanocomposite makes it a good alternative for natural peroxidase enzymes such as horseradish peroxidase with low stability.

Separation and quantification of diazinon in water samples using liquid-phase microextraction-based effervescent tablet-assisted switchable solvent method coupled to gas chromatography-flame ionization detection.

This study used a liquid-phase microextraction-based effervescent tablet-assisted switchable solvent method coupled to gas chromatography-flame ionization detection as an eco-efficient, convenient-to-use, cost-effective, sensitive, rapid, and efficient method for extracting, preconcentrating, and quantifying trace amounts of diazinon in river water samples. As a switchable solvent, triethylamine (TEA) was used. In situ generation of CO2 using effervescent tablet containing Na2 CO3 and citric acid changed the hydrophobic TEA to the hydrophilic protonated triethylamine carbonate (P-TEA-C). CO2 removal from the specimen solution using NaOH caused P-TEA-C to be converted into TEA and led to phase separation, during which diazinon was extracted into the TEA phase. The salting-out process was helpful in enhancing extraction efficiency. In addition, a number of significant parameters that affect extraction recovery were examined. Under optimum conditions, the limit of detection and limit of quantitation were 0.06 and 0.2 ng/ml, respectively. The extraction recovery percentage and pre-concentration factor were obtained at 95 and 190%, respectively, and the precision (inter- and intra-day, relative standard deviation %, n = 5) was <5%.

Simultaneous Analysis of Mycotoxins, Potentially Toxic Elements, and Pesticides in Rice: A Health Risk Assessment Study.

Rice is a widely consumed food worldwide; however, it can be a source of pollutants, such as potentially toxic elements (PTEs), mycotoxins, and pesticides. Sixty rice samples imported from Pakistan (PAK), India (IND), and Thailand (THAI), as well as domestic Iranian (IRN) rice, were collected from Bushehr, Iran, and investigated for the contamination of PTEs, including arsenic (As), lead (Pb), cadmium (Cd), and nickel (Ni); pesticides, including chlorpyrifos, trichlorfon, diazinon, fenitrothion, and chlorothalonil; mycotoxins, such as aflatoxin B1 (AFB1), zearalenone (ZEN), ochratoxin A (OTA), and deoxynivalenol (DON); and molds. Estimated daily intake (EDI) and hazard quotient (HQ) of pollutants and hazard index (HI) and incremental lifetime cancer risk (ILCR) of rice types for the Iranian adult population were calculated. The content of PTEs in Iranian rice was not higher than Iran's national standard limits. In contrast, other types of rice (imported) had at least one PTE above the permissible level. OTA content was below the detection limit, and all other mycotoxins were within the allowable range in all rice types. Thai rice was the only group without pesticides. The HI order of rice types was as follows: HIPAK = 2.1 > HIIND = 1.86 > HIIRN = 1.01 > HITHAI = 0.98. As was the biggest contributor to the HI of Iranian and Thai rice, and diazinon in the HI of Pakistani and Indian rice. The calculation of ILCR confirmed that the concentrations of Ni and Pb in Pakistani and Ni and As in Indian, Thai, and Iranian rice were not acceptable in terms of lifetime carcinogenic health risks.

Microextraction of organophosphorus pesticides on a screw coated with PAN/calcined ZnMgAl-LDH electrospun nanofibers.

The present research is an attempt to expand the recently reported microextraction on screw method. For this purpose, polyacrylonitrile/calcined ZnMgAl-LDH nanofiber was fabricated by the electrospinning technique on the surface of a screw. It was applied to the extraction of organophosphorus pesticides (OPP) from agricultural samples. The separation and determination of OPPs were carried out by gas chromatography-mass spectrometry. The characterization of the fabricated nanofiber was performed utilizing Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction instruments. Effective parameters on the extraction efficiency of the analytes including sample pH, ionic strength, sample flow rate and number of cycles, type, volume, and flow rate of desorption solvent were optimized by one-variable-at-a-time method. Under optimized conditions, the limits of detection were 0.03 and 0.07 µg L-1 for diazinon and chlorpyrifos, respectively. This method showed wide linearity in the range 0.10-1000 µg L-1 for diazinon and 0.25-1000 µg L-1 for chlorpyrifos with R2 > 0.996. The intra- and inter-day precisions (RSD%, n = 3) were ≤ 6.4% and ≤ 7.7%, respectively. Also, RSD% values less than 11.1% were obtained for screw-to-screw reproducibility. The applicability of the method for the extraction and determination of the analytes in complex agricultural environments such as cabbage, potato, tomato, cucumber, and beetroot was investigated. The results led to acceptable relative recoveries in the range 81.0-108.2%.

Urinary metabolites of diazinon and chlorpyrifos in sprayer operators and farm workers of a potato farm.

In order to investigate the effect of diazinon and chlorpyrifos on agricultural workers exposed to pesticides, urinary metabolites 2-Isopropyl-6-methyl-4-pyrimidinol (IMPy) and 3,5,6-Trichloro-2-pyridinol (TPCy) in farm workers, sprayer operators, and non-exposed people as a control group were measured. The modified QuEChERS method was applied to extract samples and was measured using a gas chromatograph/nitrogen-phosphorus detector. The obtained results showed that the median concentrations of TCPy were 36.92-547.7 and 7.7-49.58 ng/mL for sprayer operators and farm workers, respectively. Moreover, the median concentrations of IMPy were 81.66-593.1 ng/mL for sprayer operators and 40.6-66.1 ng/mL for farm workers. The control group had no measurable metabolites. The IMPy level of 60% of sprayer operators was significantly higher (P ˂ 0.05) than the TCPy level. The analysis of variance highlighted the significant relationship (P ˂ 0.05) between the levels of each metabolite and the use of safety gloves, respiratory masks, safety goggles, working time per week, and type of insecticide exposure. Our findings revealed the need to measure the urinary metabolites of these insecticides in other exposed workers. Also, workers should be taught the impact of using personal protective equipment.

A modified quick-easy-cheap-effective-rugged-and-safe method involving carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction for pesticides from grapes.

A combination of modified quick easy cheap effective rugged and safe extraction approach with carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction was developed for the extraction of several pesticides (diazinon, chlorpyrifos, tebuconazole, deltamethrin, permethrin, haloxyfop-methyl, penconazole, and cyhalothrin) from grape before their analysis by gas chromatography-flame ionization detection. In the extraction approach, an aliquot of grape sample is chopped and after separating its juice, the pesticides that remained in the refuse are extracted by the quick, easy, cheap, effective, rugged, and safe extraction method. The obtained acetonitrile phase is mixed with juice and the analytes are extracted by the carbon nano-onions-based dispersive solid-phase extraction. The analytes are concentrated using the microextraction procedure to obtain high enrichment factors. The results showed low limits of detection (0.5-1.6 ng/g) and quantification (1.8-5.4 ng/g) with satisfactory linearity of the calibration curves (determination coefficient, r2 ≥ 0.994). The precision of the developed method expressed as relative standard deviations was good (≤7.2%). The method provided high enrichment factors (350-410) and extraction recoveries (70-82%). Finally, seven grape samples were analyzed successfully.

Impact of Micronutrient Supplementation on Pesticide Residual, Acetylcholinesterase Activity, and Oxidative Stress Among Farm Children Exposed to Pesticides.

The present interventional study aimed to assess the impact of micronutrient supplementation on pesticide-residues concentrations, vitamins, minerals, acetylcholinesterase activity and oxidative stress among 129 farm children (9-12 years, n = 66 and 13-15 years, n = 63) involved in farming activities in Ranga Reddy district, Telangana, India. Our data showed the presence of five organophosphorus pesticide residues (chlorpyrifos, diazinon, malathion, monocrotophos, and phosalone) among children before-supplementation (both age-groups); while post-supplementation, only two pesticide residues (chlorpyrifos and diazinon) were detected indicating improved metabolic rate. Vitamin E, copper, magnesium and zinc levels were also improved in both the age-groups and manganese levels were significantly increased only among children of 13-15 years age group. Further, post-supplementation also showed an improvement in acetylcholinesterase activity and a decrease in lipid peroxidation among both the age groups of children. However, further research for ascertaining the ameliorating effect of micronutrients in preventing adverse effects of organophosphorus pesticides must be conducted.

Risk assessment of organophosphorus pesticide residues in drinking water resources: Statistical and Monte-Carlo approach.

A large part of the world's agricultural production, despite its adverse effects on human health and water resources, depends on the use of pesticides. Despite strict regulations, the use of pesticides continues around the world. This study aimed to determine the residual concentrations of malathion and diazinon in samples of drinking water resources. To achieve this goal, 384 samples from 8 various sites from January to December 2020 were analyzed using gas chromatography (GC) with an electron capture detector (ECD) and liquid-liquid extraction technique. Besides, statistical analysis and a risk-modeling approach supported by an automatic Monte-Carlo procedure were applied. The results showed that there is a high carcinogenic risk regarding malathion and that the low age population is at the most non-carcinogenic risk regarding diazinon.

Mycodegradation of diazinon pesticide utilizing fungal strains isolated from polluted soil.

The current study aimed to isolate biodegradable soil fungi capable of metabolizing diazinon. The collected soil samples were investigated for diazinon pollution to detect the pesticide level in the polluted soil samples. Food poisoning techniques were utilized to preliminary investigate the biodegradation efficiency of the isolated fungal strains to diazinon pesticide using solid and liquid medium and also to detect their tolerance to different concentrations. GC-MS analysis of control and treated flasks were achieved to determine the diazinon residues for confirmation of the biodegradation efficiency. The total diazinon residues in the collected soil samples was found to be 0.106 mg/kg. Out of thirteen fungal strains isolated form diazinon polluted soils, six strains were potentially active in diazinon biodegradation. Food poisoning technique showed that A. niger, B. antennata, F. graminearum, P. digitatum, R. stolonifer and T. viride strains recorded fungal growth diameters of 65.2 ± 0.18, 57.5 ± 0.41, 47.2 ± 0.36, 56.5 ± 0.27, 85.0 ± 0.01, 85.0 ± 0.06 mm respectively in the treated group which were non significantly different compared to that of control (P > 0.05), indicating the high efficiency of these strains in diazinon degradation compared to the other isolated strains. GC-MS analysis revealed that B. antennata was the most efficient strain in diazinon degradation recording 32.24 ± 0.15 ppm concentration after 10 days incubation. Linear regression analysis confirmed that B. antennata was the most effective biodegradable strain recording the highest diazinon dissipation (83.88%) with the lowest T1/2 value of 5.96 days while T. viride, A. niger, R. stolonifer and F. graminearum exhibited a high biodegradable activities reducing diazinon to 80.26%, 78.22%, 77.36% and 75.43% respectively after 10 days incubation. In conclusion, these tolerant fungi could be considered as promising, eco-friendly and biodegradable fungi for the efficient and potential removal of hazardous diazinon from polluted soil.

Determination of organophosphorus compounds in water and food samples using a non-enzymatic electrochemical sensor based on silver nanoparticles and carbon nanotubes nanocomposite coupled with batch injection analysis.

This work presents, for the first time, a fast and highly sensitive electrochemical method for determination of three organophosphorus compounds (OPs), diazinon (DZN), malathion (MLT), and chlorpyrifos (CLPF), using a modified pyrolytic graphite electrode (PGE) coupled to batch injection analysis system with multiple pulse amperometric detection (BIA-MPA). The PGE was modified by a nanocomposite based on functionalized carbon nanotubes (CNTf) and silver nanoparticles (AgNPs). The OPs samples were directly analyzed on the modified working electrode surface by BIA-MPA system in Britton-Robinson (BR) buffer 0.15 mol L-1 at pH 6.0. The MPA detection of DZN, MLT and CLPF was performed using two potential pulses, which were sequentially applied on modified PGE at -1.3 V (100 ms) and +0.8 V (100 ms) for selective determination of these three OPs and working electrode cleaning, respectively. Under optimized conditions, the sensor presented a linear range of 0.1-20 µmol L-1 for DZN, 1.0-30 µmol L-1 for MLT and from 0.25 to 50 µmol L-1 for CLPF. The limits of detection (LOD) and quantification (LOQ) of 0.35 and 1.18 µmol L-1 for DZN, 0.89 and 2.98 µmol L-1 for MLT, and 0.53 and 1.78 µmol L-1 for CLPF were obtained. The proposed method exhibited high sensitivity of 0.068, 0.030 and 0.043 mA L µmol-1 for DZN, MLT and CLPF detection, respectively. Furthermore, the BIA-MPA system provided an analytical frequency of 71 determinations per hour for direct determination of these OPs in water and food samples. The modified PGE coupled to BIA-MPA system showed a high stability of electrochemical response for OPs detection with relative standard deviation (RSD) of 1.60% (n = 20). The addition-recovery studies of the proposed method were carried out in tap water, orange juice, and apple fruit real samples, which showed suitable recovery values between 77 and 124%. The analytical performance of the developed sensor provides an attractive alternative method for OPs determination with great potential for a fast and sensitive application in contaminated samples with these pesticides.

Engineering Novel Aptameric Fluorescent Biosensors for Analysis of the Neurotoxic Environmental Contaminant Insecticide Diazinon from Real Vegetable and Fruit Samples.

BACKGROUND: Diazinon is a widely used organophosphorus neurotoxic insecticide. It is a common environmental contaminant and a hazardous agri-waste. Its detection is critical to control entry into food systems and protect the environment. METHODS: In this study, three single-stranded DNA aptamers specific for diazinon were discovered using the systematic evolution of ligands by the exponential enrichment (SELEX) process. Since aptamer-based sensors are quick and straightforward to analyze, they could potentially replace the time-consuming and labor-intensive traditional methods used for diazinon detection. RESULTS: Here, we show the engineering of novel sensors for diazinon detection with a high affinity (Kd), specificity, and high sensitivity at the ppb level. Moreover, the aptamers were helpful in the simultaneous detection of two other structurally relevant insecticides, fenthion, and fenitrothion. Furthermore, the real vegetable and fruit samples confirmed the specific detection of diazinon using DIAZ-02. CONCLUSIONS: We developed novel biosensors and optimized the assay conditions for the detection of diazinon from food samples, such as vegetables and fruit. The biosensor could be adopted to analyze toxicants and contaminants in food, water, and nature as point-of-care technology.

Investigation and probabilistic health risk assessment of pesticide residues in cucumber, tomato, and okra fruits from Khuzestan, Iran.

In this study, 30 pesticide residues in 45 fresh-eating cucumber, tomato, and okra fruit samples collected from the Khuzestan province as the main agricultural products in Iran using the QuEChERS extraction method were analyzed. In addition, noncarcinogen and carcinogen health risk assessments were evaluated. Results indicated that 93% of cucumber samples had at least one pesticide, of course, less than the maximum residue limit (MRL). All tomato and okra fruit samples were contaminated by diazinon. All pesticides detected in tomato samples were below national MRL except for thiamethoxam in four samples. In okra fruit samples, all detected diazinon and malathion, but only tebuconazole fungicide exceeded MRL. In addition, the hazard index (HI) was 0.23 and 1.06 in cucumber samples, 0.33 and 1.51 in tomato samples, and 5.5E-03 and 0.025 in okra fruit samples in adults and children, respectively. The use of cucumber and tomato may have notable risks in the short term in children group age. Ranking based on total CR was 1.2E-05 in tomato, 7.7E-06 for cucumber, and in okra 9.1E-11 because of the difenoconazole residue. However, significant carcinogenic risk threatens cucumber and tomato consumers.

A modified quick, easy, cheap, effective, rugged, and safe method for determination of by-products originating from ozonation of chlorpyrifos and diazinon spiked in cherry tomato and perilla leaf.

In this study, sample pretreatment methods have been developed for the determination of chlorpyrifos, diazinon, and their by-products present in cherry tomato and perilla leaf using liquid chromatography-tandem mass spectrometry. To optimize a quick, easy, cheap, effective, rugged, and safe method, the recoveries at each step were evaluated. The steps improved the recoveries of chlorpyrifos, chlorpyrifos oxon, diazinon, diazoxon, and 2-isopropyl-6-methyl-4-pyrimidinol up to 80% or more by removing interferents, but diethyl phosphate was almost lost during the partition procedure, and the 3,5,6-trichloro-2-pyridinol recovery was below 65%. Therefore, the compounds were evaluated using different solvent compositions based on a quick polar pesticides method; note that 100% methanol showed acceptable extraction results. The optimized method provided method detection limits ranging from 0.03 to 1.22 ng/g and good linearities (R2  > 0.996). The recovery values were between 82.1 and 113.3%. The intra- and interday reproducibility was evaluated to be within 8.6 and 9.9%, respectively. The method was applied to determine the degradation efficiency of chlorpyrifos and diazinon and their by-products formed during plasma treatment.

An ultra-sensitive electrochemiluminescence probe based on ternary nanocomposite and boron nitride quantum dots for detection of diazinon.

A new enzyme-free electrochemiluminescence (ECL) pesticide sensor was fabricated based on ternary nanocomposite of ruthenium nanoparticles/silver nanoparticles/graphene oxide on the surface of glassy carbon electrode for ultratrace determination of diazinon. Due to some drawbacks of enzyme-based sensors such as enzyme instability at elevated temperature, humidity, changes of pH, and high price of the enzyme, the use of enzyme was omitted in the construction of the developed sensor. The silver nanoparticles with good electrocatalytic proficiency as a signal improving agent and tris(2,2bipyridine) ruthenium(II) as a popular luminophore were uniformly deposited on the surface of the prepared graphene oxide/GC electrode at nanoscale. Boron nitride quantum dots as an efficient co-reactant created the superior efficiency in amplifying the ECL intensity of the ruthenium-based ECL system. The prepared electrode was utilized for the detection of diazinon via the robust ECL method. For the present sensor, a wide linear dynamic range and low detection limit were achieved (3.0 × 10-15 to 6.5 × 10-9 M and 9.5 × 10-16 M, respectively). The obtained results confirmed the fabrication of the robust ECL probe, which is characterized by the cooperative effect of silver nanoparticles and the attached luminophore species. The main advantage of the presented sensor was that the samples could be diluted so that the effect of the interference species was negligible. Due to excellent properties toward accurate determination of diazinon, the ECL sensor as a new practical platform was applied for quantitative detection of diazinon in some real samples.

A selective method for quantification of diazinon in human plasma by GC-MS.

Diazinon is a synthetic molecule known as an organophosphorus insecticide. It is used for gardens and for agriculture. This molecule represents a toxicological concern for humans. For this reason, the detection and the quantification of the diazinon in human samples are important in order to monitor an exposure and to diagnose intoxications. The aim of this work is to develop a selective method for the quantification of diazinon in human plasma by means of a gas chromatography (GC) with a mass spectroscopy (MS) detector. The method presented in this article includes a liquid-liquid extraction (LLE) using dichloromethane/propanol-2/heptane. The correlation coefficient for the calibration curve is 0.992. The limit of detection (LOD) and the limit of quantification (LOQ) are respectively 5 µg/L and 2 µg/L. The average recovery of the three different concentrations (15, 250 and 375 µg/L) varies from 22.8% to 31%. A test of stability at ambient temperature for 24 hours and at 4 °C for 48 hours was conducted. The relative error factor was found to be inferior to 15%. The results obtained show that the method developed gives satisfying validation parameters in human plasma. Therefore, the compound could be detected at very low concentration with a good linearity. This method can be used with other matrices, such as blood or urine, for a partial validation.

Selective solid-phase extraction of organophosphorus pesticides and their oxon-derivatives from water samples using molecularly imprinted polymer followed by high-performance liquid chromatography with UV detection.

A molecularly imprinted polymer was synthesized and characterized to be used as solid-phase extraction sorbent for simultaneous chlorpyrifos and diazinon and their oxon derivatives. Several imprinted polymers were prepared and evaluated in a retention study of these analytes compared with a non-printed polymer. Several parameters affecting the extraction of imprinted polymer such as washing solvent, composition and volume of the eluting solvent and sample volume, were also investigated. Under the optimum conditions, the developed method provided satisfactory limits of detection ranging between 0.07 µg L-1 to 0.12 µg L-1 and the material showed an excellent reusability (> 50 reuses). The method was applied to the extraction and preconcentration of these analytes in water samples. The average recoveries ranged from 79 ± 6 to 104 ± 3 %.