Unlocking the interaction of organophosphorus pesticide residues with ecosystem: Toxicity and bioremediation.

Organophosphorus adulteration in the environment creates terrestrial and aquatic pollution. It causes acute and subacute toxicity in plants, humans, insects, and animals. Due to the excessive use of organophosphorus pesticides, there is a need to develop environmentally friendly, economical, and bio-based strategies. The microbiomes, that exist in the soil, can reduce the devastating effects of organophosphates. The use of cell-free enzymes and yeast is also an advanced method for the degradation of organophosphates. Plant-friendly bacterial strains, that exist in the soil, can help to degrade these contaminants by oxidation-reduction reactions, enzymatic breakdown, and adsorption. The bacterial strains mostly from the genus Bacillus, Pseudomonas, Acinetobacter, Agrobacterium, and Rhizobium have the ability to hydrolyze the bonds of organophosphate compounds like profenofos, quinalphos, malathion, methyl-parathion, and chlorpyrifos. The native bacterial strains also promote the growth abilities of plants and help in detoxification of organophosphate residues. This bioremediation technique is easy to use, relatively cost-effective, very efficient, and ensures the safety of the environment. This review covers the literature gap by describing the major effects of organophosphates on the ecosystem and their bioremediation by using native bacterial strains.

Ambient long-term exposure to organophosphorus pesticides and the human gut microbiome: an observational study.

BACKGROUND: Organophosphorus pesticides (OP) have been associated with various human health conditions. Animal experiments and in-vitro models suggested that OP may also affect the gut microbiota. We examined associations between ambient chronic exposure to OP and gut microbial changes in humans. METHODS: We recruited 190 participants from a community-based epidemiologic study of Parkinson's disease living in a region known for heavy agricultural pesticide use in California. Of these, 61% of participants had Parkinson's disease and their mean age was 72 years. Microbiome and predicted metagenome data were generated by 16S rRNA gene sequencing of fecal samples. Ambient long-term OP exposures were assessed using pesticide application records combined with residential addresses in a geographic information system. We examined gut microbiome differences due to OP exposures, specifically differences in microbial diversity based on the Shannon index and Bray-Curtis dissimilarities, and differential taxa abundance and predicted Metacyc pathway expression relying on regression models and adjusting for potential confounders. RESULTS: OP exposure was not associated with alpha or beta diversity of the gut microbiome. However, the predicted metagenome was sparser and less evenly expressed among those highly exposed to OP (p = 0.04). Additionally, we found that the abundance of two bacterial families, 22 genera, and the predicted expression of 34 Metacyc pathways were associated with long-term OP exposure. These pathways included perturbed processes related to cellular respiration, increased biosynthesis and degradation of compounds related to bacterial wall structure, increased biosynthesis of RNA/DNA precursors, and decreased synthesis of Vitamin B1 and B6. CONCLUSION: In support of previous animal studies and in-vitro findings, our results suggest that ambient chronic OP pesticide exposure alters gut microbiome composition and its predicted metabolism in humans.

Smartphone-assisted hydrogel platform based on BSA-CeO2 nanoclusters for dual-mode determination of acetylcholinesterase and organophosphorus pesticides.

A dual-mode sensor was developed for detecting acetylcholinesterase (AChE) and organophosphorus pesticides (OPs) via bifunctional BSA-CeO2 nanoclusters (NCs) with oxidase-mimetic activity and fluorescence property. The dual-mode sensor has the characteristics of self-calibration and self-verification, meeting the needs of different detection conditions and provide more accurate results. The colorimetric sensor and fluorescence sensor have been successfully used for detecting AChE with limit of detection (LOD) of 0.081 mU/mL and 0.056 mU/mL, respectively, while the LOD for OPs were 0.9 ng/mL and 0.78 ng/mL, respectively. The recovery of AChE was 93.9-107.2% and of OPs was 95.8-105.0% in actual samples. A novel strategy was developed to monitor pesticide residues and detect AChE level, which will motivate future work to explore the potential applications of multifunctional nanozymes.

Deep Eutectic Solvents-Based Ultrasonic-Assisted Dispersive Liquid-Liquid Microextraction for the Determination of Organophosphorus Pesticides in Honeysuckle Dew Samples.

A deep eutectic solvent (DES) with the ability to change from hydrophilic to hydrophobic was designed and synthesized and applied to the determination of organophosphorus (OPP) pesticides in honeysuckle dew samples. Choline chloride, phenol, and tetrahydrofuran (THF) were used as the hydrogen bond acceptor, hydrogen bond donor, and demulsifier, respectively. Eight OPP pesticides were extracted by DES coupled with ultrasonic-assisted extraction (UA) and then chromatographed by GC-MS. DES used as an extract solvent has the advantages of high extraction efficiency, low cost, and environmental protection. Furthermore, DES is compatible with GC-MS. The single factor experiment design and Box-Behnken design (BBD) were applied to the optimization of experimental factors, including the type and composition of extraction solvent, type of demulsifier solvent, the volume of DES and THF, pH of sample solution, and ultrasonic time. Under the optimum experimental conditions, the high degree of linearity from 0.1 to 20.0 ng mL-1 (R2 ≥ 0.9989), the limits of detection from 0.014 to 0.051 ng mL-1 (S/N = 3), and the recoveries of analytes from 81.4 to 104.4% with relative standard deviation below 8.6%. In addition, the adsorption mechanism of OPPs on DES was explored by adsorption kinetic studies. These results have demonstrated that the present method has offered an effective, accurate, and sensitive methodology for OPP pesticides in honeysuckle dew samples, and this method provides a reference for the detection of pesticide residues in traditional Chinese medicine.

Advances on removal of organophosphorus pesticides with electrochemical technology.

Widespread use of organophosphorus pesticides (OPs), especially superfluous and unreasonable use, had brought huge harm to the environment and food chain. It is because only a small part of the pesticides sprayed reached the target, and the rest slid across the soil, causing pollution of groundwater and surface water resources. These pesticides accumulate in the environment, causing environmental pollution. Therefore, in recent years, the control and degradation of OPs have become a public spotlight and research hotspot. Due to its unique advantages such as versatility, environmental compatibility, controllability, and cost-effectiveness compatibility, electrochemical technology has become one of the most promising methods for degradation of OPs. The fundamental knowledge about electrochemical degradation on OPs was introduced in this review. Then, a comprehensive overview of four main types of practical electrochemical technologies to degrade pesticides were presented and evaluated. The knowledge contained herein should conduce to better understand the degradation of pesticides by electrochemical technology, and better exploit the degradation of pesticides in the environment and food. Overall, the objective of this review is to provide comprehensive guidance for rational design and application of electrochemical technology in the degradation of OPs for the safety of the environment and food chain in the future.

Novosphingobium album sp. nov., Novosphingobium organovorum sp. nov. and Novosphingobium mangrovi sp. nov. with the organophosphorus pesticides degrading ability isolated from mangrove sediments.

Members of the genus Novosphingobium were frequently isolated from polluted environments and possess great bioremediation potential. Here, three species, designated B2637T, B2580T and B1949T, were isolated from mangrove sediments and might represent novel species in the genus Novosphingobium based on a polyphasic taxonomy study. Phylogenomic analysis revealed that strains B2580T, B1949T and B2637T clustered with Novosphingobium naphthalenivorans NBRC 102051T, 'N. profundi' F72 and N. decolorationis 502str22T, respectively. The average nucleotide identity (ANI) and digital DNA-DNA hybridization (dDDH) values between isolates and their closely related species were less than 94 and 54 %, respectively, all below the threshold of species discrimination. The sizes of the genomes of isolates B2580T, B2637T and B1949T ranged from 4.4 to 4.6 Mb, containing 63.3-66.4 % G+C content. Analysis of their genomic sequences identified genes related to pesticide degradation, heavy-metal resistance, nitrogen fixation, antibiotic resistance and sulphur metabolism, revealing the biotechnology potential of these isolates. Except for B2637T, B1949T and B2580T were able to grow in the presence of quinalphos. Results from these polyphasic taxonomic analyses support the affiliation of these strains to three novel species within the genus Novosphingobium, for which we propose the name Novosphingobium album sp. nov. B2580T (=KCTC 72967T=MCCC 1K04555T), Novosphingobium organovorum sp. nov. B1949T (=KCTC 92158T=MCCC 1K03763T) and Novosphingobium mangrovi sp. nov. B2637T (KCTC 72969T=MCCC 1K04460T).

The porous hollow cobalt-based oxides encapsulated with bimetallic PdAu Nanoparticles of electrochemical biosensor for highly sensitive pesticides detection.

Efficient and portable electrochemical biosensors are received to evaluation of pesticides in the environment, which can make great significance for food safety. In this study, the Co-based oxides with a kind of hierarchical porous hollow and nanocages were constructed, in which the materials (Co3O4-NC) were encapsulated with PdAu nanoparticles (NPs). Due to the unique porous structure, the changeable valence state of cobalt and the synergistic effect of bimetallic PdAuNPs, PdAu@Co3O4-NC possessed excellent electron pathways, and showed more exposed active sites. Accordingly, the porous Co-based oxides have been applied to construct an acetylcholinesterase (AChE) electrochemical biosensor, which showed good performance for organophosphorus pesticides (OPs) detection. The optimum biosensing platform based on nanocomposites was applied to exhibit highly sensitive determination of omethoate and chlorpyrifos, with the relative low detection limit of 6.125 × 10-15M and 5.10 × 10-13M, respectively. And a wide detection range of 6.125 × 10-15∼ 6.125 × 10-6M and 5.10 × 10-13∼ 5.10 × 10-6M for these two pesticides were achieved. Therefore, the PdAu@Co3O4-NC may represent a powerful tool for ultrasensitive sensing of OPs, and have great potential application.

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

Pesticide residues significantly affect food safety and harm human 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 a quenching moiety for monitoring the presence of organophosphorus pesticides in food and live cells. The carboxylic ester bond on the probe was hydrolyzed catalytically in the presence of carboxylesterase and thereby the fluorophore was released with 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 0.1734 µg/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.

Engineering an Ag/Au bimetallic nanoparticle-based acetylcholinesterase SERS biosensor for in situ sensitive detection of organophosphorus pesticide residues in food.

Developing simple, efficient, and inexpensive method for trace amount organophosphorus pesticides' (OPs) detection with high sensitivity and specificity is of significant importance for guaranteeing food safety. Herein, an Ag/Au bimetallic nanoparticle-based acetylcholinesterase (AChE) surface-enhanced Raman scattering (SERS) biosensor was constructed for in situ simple and sensitive detection of pesticide residues in food. The principle of this biosensor exploited 4-mercaptophenylboronic acid (4-MPBA)-modified Ag/Au bimetallic nanoprobes as SERS signal probe to improve sensitivity and stability. The combination of AChE and choline oxidase (CHO) can hydrolyze acetylcholine (ATCh) to generate H2O2. The product of H2O2 selectively oxidizes the boronate ester of 4-MPBA, decreasing the Raman intensity of the B-O symmetric stretching. In the presence of OPs, it could inhibit the production of H2O2 by destroying the AChE activity, so the reduction of the SERS signal was also alleviated. Based on the principle, an Ag/Au bimetallic nanoparticle-based AChE SERS sensor was established without any complicated pretreatments. Benefiting from the synergistic effects of Ag/Au bimetallic hybrids, a linear detection range from 5×10-9 to 5×10-4 M was achieved with a limit of detection down to 1.7×10-9 M using parathion-methyl (PM) as the representative model of OPs. Moreover, the SERS biosensor uses readily available reagents and is simple to implement. Importantly, the proposed SERS biosensor was used to quantitatively analyze OP residues in apple peels. The levels of OPs detected in real samples by this method were consistent with those obtained using gas chromatography-mass spectrometry (GC-MS), suggesting the proposed assay has great potential applications for OPs in situ detection in food safety fields.

Accumulation of organophosphorus pollutants in adipose tissue of obese women - metabolic alterations.

Organophosphorus pesticides (OPPs) and organophosphate esters (OPEs) are organophosphorus compounds created as substitutes for persistent environmental pollutants, namely organochlorines pesticides and brominated flame retardants, respectively. However, there is evidence that organophosphorus compounds are also widespread across the environment and have adverse effects on biota. In humans, OPPs and OPEs were reported to be carcinogenic, neurotoxic, hepatotoxic, nephrotoxic, amongst others. As lipophilic compounds, these accumulate in fat tissues as adipose tissue. Yet biomonitoring studies and analytical methodologies to assess these compounds in the human body are scarce, particularly in adipose tissue. In this study, the presence of six OPPs and seven OPEs was determined in samples of subcutaneous adipose tissue (scAT) and visceral adipose tissue (vAT) from 188 adult obese women. OPPs and OPEs were quantified by gas chromatography (GC) flame photometric detection and confirmed in GC tandem mass spectrometry. The detection frequencies ranged between 0.5-1.6% and 48-53%, respectively for OPPs and OPEs. Organophosphorus pollutants were present in both adipose tissues and median concentrations were 0.008 ± 0.020 µg/g scAT and 0.009 ± 0.020 µg/g vAT. A total of 32 Spearman's correlations were found between organophosphorus pollutants concentrations in adipose tissue and several biochemical parameters (18 positive and 14 negative). Our results show that anthropometric and hormonal parameters, cholesterol, glycaemia, macrominerals, urea and sedimentation velocity might be influenced by the presence of these compounds. The presence of organophosphorus pollutants in the environmental and their possible effect on female metabolic processes is concerning. Particularly because presently OPEs usage is not controlled or limited by any regulation. More studies are needed to fully understand these pollutants behaviour and hazard effects on human health, biota, and the environment so control regulations can be drawn to prevent and lessen their effects.

A dual-emission ratiometric fluorescence strategy with enzyme-based inhibition for organophosphorus pesticides determination.

A fast, eco-friendly and accurate ratiometric fluorescent strategy is presented for the determination of organophosphorus pesticides (OPs) using intrinsic dual-emission silica nanoparticles modified with Rhodamine 6G (SiNPs-Rho6G). SiNPs-Rho6G had intrinsic dual-emission at 410 and 550 nm. The substrate acetylcholine was catalyzed by acetylcholinesterase (AChE) to produce thiocholine (TCh). TCh triggered the specific reaction of Ellman's reagent 5, 5-dithiobis (2-nitrobenzoic acid) to obtain 5-thio-2-nitrobenzoic acid, which caused the decrease in fluorescence intensity of SiNPs-Rho6G at 410 nm by the inner filter effect, while the fluorescence intensity of SiNPs-Rho6G at 550 nm was not significantly changed. OPs caused the recovery of the fluorescence at 410 nm by inhibiting the activity of AChE. Thus, the quantitative detection of OPs could be achieved through utilizing the catalytic characteristic of AChE. The linear curve from 0.010 to 0.250 µg mL-1 with a detection limit of 7 ng mL-1 was obtained for the determination of chlorpyrifos (Cpf). The ratiometric probe was used to detect the spiked Cpf in environmental and food samples with good recoveries. Therefore, combined with the dual emission characteristics of SiNPs-Rho6G and the specificity of the enzyme, the ratio fluorescence sensing platform has potential application prospects in OPs determinations.

Introducing Mn into ZIF-8 nanozyme for enhancing its catalytic activities and adding specific recognizer for detection of organophosphorus pesticides.

In order to design and establish a highly efficient and selective nanozyme-based sensing platform for the UV-vis detection of organophosphorus pesticides (OPs), Mn was introduced into ZIF-8 nanozyme for enhancing its catalytic activities and adding specific recognizer. The Mn-doped ZIF-8 (Mn-ZIF-8) nanocomposites were synthesized with a very facile one-pot method by heating the mixture of ZnO, 2-methylimidazole (Hmin) and Mn(CH3COO)2·4H2O in a solvent-free system at 180 °C for 8 h. The Mn-ZIF-8 nanocomposite showed a higher peroxidase activity and an additional thiocholine (TCh)-degradable property compared to the pristine ZIF-8. OPs could inhibit acetylcholinesterase (AChE) to catalyze the hydrolysis of acetylthiocholine (ATCh) to produce TCh, thus blocking the degradation of Mn-ZIF-8 and protecting the catalysis of the oxidation of colorless 3,3',5,5'-tetramethylbenzydine (TMB) to blue oxidized TMB (ox-TMB). Accordingly, a detection method for OPs with high sensitivity and selectivity was designed and established on the basis of the Mn-ZIF-8 nanozyme with a linear range of 0.1-20 nM and a limit of detection (LOD) as low as 54 pM.

Organophosphate-Pesticide-Mediated Immune Response Modulation in Invertebrates and Vertebrates.

Organophosphate pesticides (OPs) have greatly facilitated food production worldwide, and their use is not limited to agriculture and the control of pests and disease vectors. However, these substances can directly affect the immune response of non-target organisms. In this sense, exposure to OPs can have negative effects on innate and adaptive immunity, promoting deregulation in humoral and cellular processes such as phagocytosis, cytokine expression, antibody production, cell proliferation, and differentiation, which are crucial mechanisms for host defense against external agents. This review focuses on the scientific evidence of exposure to OPs and their toxic effects on the immune system of non-target organisms (invertebrates and vertebrates) from a descriptive perspective of the immuno-toxic mechanisms associated with susceptibility to the development of bacterial, viral, and fungal infectious diseases. During the exhaustive review, we found that there is an important gap in the study of non-target organisms, examples of which are echinoderms and chondrichthyans. It is therefore important to increase the number of studies on other species directly or indirectly affected by Ops, to assess the degree of impact at the individual level and how this affects higher levels, such as populations and ecosystems.

Contamination, ecological, and health risk assessment of heavy metals and organophosphorus pesticides in single, double, and ratoon cropping of rice: a case study in Mazandaran, North of Iran.

This study investigated the contamination and health risk assessment of heavy metals and organophosphorus pesticides in single, double, and ratoon cropping of rice in Mazandaran province, north of Iran. A total of 17 sampling locations in rice farms were selected and soil and rice samples were collected from farms in 5 counties of Mazandaran. Soil and rice samples were then transferred to the lab for further analysis. The concentration of pesticides and heavy metals was then analyzed using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma mass spectrometry (ICP-MS), respectively. Mercury was analyzed using a Leco mercury analyzer. Target hazard quotient (THQ), total target hazard quotient (TTHQ), carcinogenic risk (CR), and total carcinogenic risk (TCR) in children and adults were used. Potential ecological risk also was used to test the possible hazards of heavy metals to the environment. Heavy metals concentration in rice and soil samples in different farming steps revealed different levels. THQ showed no considerable risk in consuming contaminated rice to adults and children considered, while TTHQ revealed potential non-carcinogenic risks. Ni had the most carcinogenic risks to target human groups, and TCR showed carcinogenicity for carcinogenic heavy metals in all stations. Findings showed no ecological risks of metals to the environment. In conclusion, rice farmers in Mazandaran use the lands multiple times during the year to increase the performance, function, quality, and quantity of rice, but the possible toxic effects of heavy metals and pesticides on consumers and the environment should not be overlooked.

Development of a noncompetitive magnetic-phage anti-immunocomplex assay for detecting of organophosphorus pesticides with a thiophosphate group.

Organophosphorus pesticides (OPs) are widely used in agriculture and the monitoring of their residues is very important to protect human health. Immunoassays are important tools for the analysis of small molecules. Generally, noncompetitive mode of immunoassay is considered to be more sensitive than competitive mode. In this study, peptides that can identify immunocomplex of OPs were screened from a phage display library. Subsequently, a second-generation peptide library was constructed and peptides with better performance were isolated. Then, a rapid and sensitive noncompetitive magnetic-phage anti-immunocomplex assay (MPHAIA) for OPs was developed based on the best phage-peptide and single chain antibody immunomagnetic beads. The MPHAIA showed broad specificity for OPs with a thiophosphate group. The half-saturated concentration (SC50) values and limits of detection (LODs) of MPHAIA to 12 OPs were ranged from 15.04 to 105.48 ng/mL and 4.07-14.19 ng/mL, respectively. The accuracy and reliability of MPHAIA were verified by gas chromatography-tandem mass spectrometry (GC-MS/MS) parallel analysis of six kinds of OPs in spiked cucumber samples. The recovery rates were in range of 81.2-116.3% with coefficient of variation from 4.1% to 14.1%, which were consistent with the results of GC-MS/MS.

A dual-signal sensing strategy based on ratiometric fluorescence and colorimetry for determination of Cu2+ and glyphosate.

Herein, a dual-signal sensing strategy based on ratiometric fluorescence and colorimetry for Cu2+ and glyphosate determination was constructed. Fluorescence silicon nanoparticles (SiNPs) were prepared by hydrothermal reaction, which has maximum fluorescence intensity under the excitation of 355 nm. o-Phenylenediamine (OPD) was oxidized through Cu2+ to generate 2,3-diaminophenazine (oxOPD). The obtained oxOPD showed a strong absorption peak at 417 nm and quenched the fluorescence of SiNPs at 446 nm due to fluorescence resonance energy transfer (FRET). Meanwhile, oxOPD produced a new fluorescence emission at 556 nm forming a ratiometric state. With increasing Cu2+, the original solution changed from colorless to yellow. When glyphosate was present, the interaction between Cu2+ and the functional groups of glyphosate could reduce the oxidation of oxOPD, resulting in the enhancement of fluorescence at 446 nm and the decrease of fluorescence at 556 nm. Furthermore, the addition of glyphosate changed yellow solution to colorless. Under the optimal conditions of OPD (1 mM), 20 mM Tris-HCl buffer (pH 7.5), and incubation time (4 h), the ratiometric fluorescence sensor had good selectivity and showed a wide linear range of 0.025-20 µM with the LOD of 0.008 µM for Cu2+ and 0.15-1.5 µg/mL with the LOD of 0.003 µg/mL for glyphosate, respectively. Besides, it is worth mentioning that this developed sensing system showed good performance in real samples, providing a simple and reliable dual-signal detection strategy.

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.

Spatiotemporal distribution and risk assessment of organophosphorus pesticides in surface water and groundwater on the North China Plain, China.

90 groundwater samples and 14 surface water samples were collected in wet season (summer) and dry season (winter) in the North China Plain (NCP), and analyzed for 11 organophosphorus pesticides (OPPs). The results showed that the main types of OPPs in surface water and groundwater were dimethoate, dichlorvos, methyl-parathion, malathion in both summer and winter. The OPP concentrations in groundwater and surface water were higher in summer than in winter. In the vertical direction, the distribution characteristics of different four types of groundwater sampling points are different. In the horizontal direction: farmland adjacent to a river (FAR) > central farmland (CF) > nonfarm area adjacent to a river (NFAR) > central nonfarm area (CNF). The OPPs concentrations in surface water adjacent to farmland were higher than that in surface water adjacent to nonfarm area. The main factors influencing the distribution of OPPs in the groundwater and surface water were the interaction process between them, the groundwater flow field and the OPPs used in agricultural activities. The ecological risk of OPPs to surface water was greater in summer than in winter. Water Flea was at medium risk, and malathion had the greatest influence on Water Flea in both summer and winter. The non-carcinogenic and carcinogenic risks of the four main OPPs in surface water were higher than in groundwater, and were higher in summer than in winter, but they would not lead to adverse health effects on local residents.

Recent advances in assessment methods and mechanism of microbe-mediated chlorpyrifos remediation.

Chlorpyrifos (CP) is one of the Organophosphorus pesticides (OPs) primarily used in agriculture to safeguard crops from pests and diseases. The pervasive use of chlorpyrifos is hazardous to humans and the environment as it inhibits the receptor for acetylcholinesterase activity, leading to abnormalities linked to the central nervous system. Hence, there is an ardent need to develop an effective and sustainable approach to the on-site degradation of chlorpyrifos. The role of microbes in the remediation of pesticides is considered the most effective and eco-friendly approach, as they have strong degradative potential due to their gene and enzymes naturally adapted to these sites. Several reports have previously been published on exploring the role of microbes in the degradation of CP. However, detection of CP as an environmental contaminant is an essential prerequisite for developing an efficient microbial-mediated biodegradation method with less harmful intermediates. Most of the articles published to date discuss the fate and impact of CP in the environment along with its degradation mechanism but still fail to discuss the analytical portion. This review is focused on the latest developments in the field of bioremediation of CP along with its physicochemical properties, toxicity, fate, and conventional (UV-Visible spectrophotometer, FTIR, NMR, GC-MS, etc) and advanced detection methods (Biosensors and immunochromatography-based methods) from different environmental samples. Apart from it, this review explores the role of metagenomics, system biology, in-silico tools, and genetic engineering in facilitating the bioremediation of CP. One of the objectives of this review is to educate policymakers with scientific data that will enable the development of appropriate strategies to reduce pesticide exposure and the harmful health impacts on both Human and other environmental components. Moreover, this review provides up-to-date developments related to the sustainable remediation of CP.

Evaluation of green silicone surfactant-based vortex assisted dispersive liquid-liquid microextraction for sample preparation of organophosphorus pesticide residues in honey and fruit sample.

A vortex-assisted surfactant enhanced emulsification liquid-liquid microextraction based on non-ionic silicone surfactant was successfully developed for the determination of organophosphorus pesticides in food samples coupled to gas chromatography-mass spectrometry. A new type of non-ionic silicone surfactant composed of polysiloxane chains was employed as a green emulsifier to facilitate the emulsification of extraction solvent into the sample matrix, thereby intensifying the mass transfer of target analytes into the organic phase. The variables that affect the extraction were systematically optimized: 80 µl of hexane and 0.5% (v/v) of silicone surfactant were used as extraction solvent and surfactant respectively, the solution was mixed well under vortex agitation for 1 min with the addition of 4% (w/v) sodium sulfate. Under optimum conditions, the linearity of the method was obtained in the range of 0.1-200 µg/kg with a good coefficient of determination varying from 0.9986 to 0.9996. The limit of detection and the limit of quantitation were between 0.008-0.1 and 0.02-0.3 µg/kg, respectively. Application of the proposed method to real samples gave satisfactory recovery values (80%-118%) for the target analytes. The suggested approach has also proven to be convenient, expeditious, and environmentally benign.