Carbamate Pesticides Research Articles

A novel portable in situ analyzer for highly sensitive monitoring of organophosphorus and carbamate pesticides in food and environment

The presence of excessive residues of organophosphorus (OPs) and carbamate (CPs) pesticides in food and the environment poses a significant threat to human health and ecological sustainability. Herein, we reported a dual-readout, portable, and highly sensitive photoelectric analyzer (DPHP-analyzer) to achieve rapid and accurate monitoring of OPs and CPs. The dual signal strategy is mainly achieved by controlling the activity of acetylcholinesterase (AChE) in the presence of OPs to catalyze acetylthiocholine (ATCh) and generate thiocholine (TCh), which specifically induced the conversion of colorless Ellman's reagent (DTNB) into yellow 5-thio-2-nitrobenzoic acid (TNB). Simultaneously, the utilization of positively charged TNB as an absorber can induce a dynamic fluorescence quenching effect based on energy transfer mechanism. Fully cooperating with the above mechanism, a CD like, disposable array-based chip manufactured by 3D printing (CD-AN-chip) was designed and integrated to deliver reagents. By use of this dual-output strategy, the analyzer and chip can provide good sensitivity and selectivity for the monitoring of diazinon and carbendazim (case analysis) with a LOD 0.38 ng/mL for carbendazim. And the reproducibility, stability and practicability analysis of real sample have been thoroughly validated simultaneously. Importantly, with the features of fluorescence fingerprint map, the detector could be employed for the distinction of various analytes and further be used for monitoring the nutritional environment within residential and public settings.

High-sensitive detection of organophosphate and carbamate pesticide residues in milk based on bioluminescence method

Organophosphorus pesticides (OPs) and carbamate pesticides (CBs) are the most commonly used pesticides in agricultural cultivation. The pesticide residues in plant products can easily enter dairy cows through feed, resulting in the pesticide low-concentration residues in milk. Traditional acetylcholinesterase (AChE) inhibition-based colorimetric methods have low sensitivity and could not satisfy the detection of low-concentrations of OPs and CBs residues in dairy products. In this study, we combined firefly luciferase (FLuc)-mediated bioluminescence with the inhibition of AChE-catalyzed substrate activity by pesticides to develop a highly sensitive and rapid method for detecting OPs and CBs residues in milk. AChE breaks down D-luciferin acetate to produce D-luciferin, which is recognized by the FLuc and emits luminescence in the presence of ATP. However, the presence of OPs and CBs inhibits AChE, causing the reduction or disappearance of the luminescence signal. The luminescence signal can be detected using a hand-held luminescence photometer, eliminating the need for large instrumentation. The AChE-FLuc system accurately detected OPs and CBs in milk within 30 min, with detection limits of 7.89 ng/mL and 1.75 ng/mL, respectively. The sensitivity of this method is approximately ten times higher than that of traditional AChE inhibition methods, meeting the pesticide residue limits in milk set by China and the European Union.

First Voltammetric Determination of Karbutylate via Pencil Graphite, Glassy Carbon, and Boron-Doped Diamond Electrodes in Soil Sample

We investigated the electrochemical behavior of carbamate pesticide-type karbutylate (KB) with boron-doped diamond (BDD), glassy carbon (GC), and pencil graphite (PG) electrode, and analytical determination in real samples. Similar to organophosphate insecticides, carbamate pesticides are produced from carbamic acid and are extensively utilized in agriculture, gardens, and residences. Therefore, a rapid and simple detection of KB in real samples is important. Carbon-based electrodes are widely used in electroanalytical chemistry due to their rich surface chemistry, chemical inertness, broad potential window, low background current, and congruency for various demanding applications. Three different carbon-based electrodes were used. The effect of buffer solutions, scan rate, square wave (SWV), and differential pulse voltammetry parameters on the voltammetric response of KB was tested. The optimum working media for all three electrodes was determined as pH 2.00 phosphate buffer solution and voltammetric measurements were carried out in this media. Under optimum experimental conditions, linear calibration dependences for KB were obtained as 6.00 × 10−7–8.00 × 10−5 M, 4.00 × 10−7–8.00 × 10−5 M, and 8.00 × 10−8–8.00 × 10−5 M with a limit of detection of 2.18 × 10−7, 3.71 × 10−8 M, and 2.66 × 10−8 M by the BDD, GC, and PG electrodes, respectively, using SWV. As a result, sensitive determination of KB has been successfully performed using different carbon-based electrodes in real soil samples.

Hemoglobin targeting potential of aminocarb pesticide: Investigation into dynamics, conformational stability, and energetics in solvent environment

Aminocarb (AMC), a carbamate pesticide, due to its prevalent usage exhibits increased accumulation in the environment affecting both insects and humans. It enters the human body via food grains and be transported through bloodstream. AMC's chemical structure, containing specific molecular frameworks and functional groups, enables it to bind with proteins like albumin and hemoglobin. Given that molecules with similar architecture are known to bind with hemoglobin, we aimed to explore Aminocarb's binding capability and the potential mechanism or mode of its interaction with hemoglobin. Hb being a tetramer with a profound interface between amino acid chains offers multiple binding sites. It is therefore important to investigate the structural aspects of binding of AMC by employing various spectroscopic and in-silico methods. The surface of the α1 chain near the α1β2 interface emerges as the preferred binding site for AMC, primarily due to its conformational restrictions. In its bound state, AMC tends to maintain a relaxed conformation, closely resembling its globally optimized geometry, and resides in close proximity to the α1 chain via multiple hydrophobic contacts and water bridge as observed in molecular dynamics (MD) simulations. Fluorescence quenching experiments showed moderate binding strength (7.7 × 10⁴ L M⁻1 at 288 K, 7.8 × 10⁴ L M⁻1 at 298 K, 7.9 × 10⁴ L M⁻1 at 308 K) and spontaneous binding, driven by hydrophobic and van der Waals interactions, as indicated by enthalpy (0.80–0.91 kJ mol⁻1), entropy (0.0970–0.0974 kJ mol⁻1), and Gibbs free energy (−27.13 to - 29.08 kJ mol⁻1). Circular dichroism experiments reveal no major structural changes in Hb. Quantum chemical calculations and MD simulations reveal conformation-dependent energy differences, enhancing our understanding of AMC's binding mechanism to Hb.

High prevalence of genus aedes aegypti resistance to carbamate, organochloride, and pyrethroid (COP) pesticides in Adonkolo Campus Federal University Lokoja, Kogi State, Nigeria

Arthropod-borne viruses pose a significant health challenge. Increased prevalence necessitates immediate attention to vector control and resistance management. WHO-approved insecticides to control these mosquitoes include Carbamate, organophosphate and pyrethroid. Adonkolo Campus, Federal University Lokoja metropolis have a disturbing presence of these vectors and therefore the research was aimed to detect the presence of resistance in genus aedes aegypti to those insecticides, DDT (organochloride, dichlorodiphenyltrichloroethane 4%), Bendiocarp (carbamate, 0.1%) and a type ii pyrethroid (Alpha cyhalothrin). The LC99 value was used on larval samples to with the help of probit and compared with the diagnostic value from approved WHO values. Increasing resistance to all three insecticides was obtained with Bendiocarb recording the highest rate at an average of 16 (64%) in all three insecticides while that of DDT stands at an average of 18 (72%) The mortality of less than 90% was declared as resistant. The insecticide susceptibility test for genus aedes. aegypti against these insecticides in Adonkolo showing resistance with a mortality rate at an average of 84% with Bendiocarb recorded the highest of 94%. The results showed that genus aedes aegypti were resistant to all three insecticides used for the WHO Bioassay and the larval test with tempho. Conclusions: The study reveals that the genus aedes aegypti population in the Adonkolo Campus tends to resist exposure to insecticide chemicals approved for vector control by WHO.

Organophosphate, carbamate and synthetic pyrethroid pesticide residues in muscle tissues of fish from Loktak Lake, a Ramsar Site in Manipur, India

The muscle tissues of Channa punctatus and Anabas testudineus collected from the Loktak Lake (a Ramsar site) and its three major feeder rivers in Manipur, Northeastern India, were analyzed using high-performance liquid chromatography for the presence of residues of organophosphorus, carbamate, and synthetic pyrethroid pesticides. Pesticide residues of all the three types were detected in the fish tissues. Pesticide residues in Channa punctatus ranged from 0.002 – 0.043 µg g-1, and from 0.008 –0.027 µg g-1in Anabas testudineus from Loktak lake in pre-monsoon and post-monsoon seasons. Pesticide residues were detected only in Anabas testudineus (0.002 – 0.078 µg g-1) in Nambul river, while these were detected only in Channa puctatus (0.001 – 0.032 µg g-1) in Moirang river. In Nambol river, pesticide concentrations ranged from 0.002 – 0.026 µg g-1 in Channa punctatus, and from 0.004 – 0.005 µg g-1 in Anabas testudineus. Among the five pesticides detected, concentrations of dichlorvos residues detected in the present study (0.027 and 0.032 µg g-1 wet weight) exceeded the Codex Alimentarius maximum residue limit (MRL) of 0.01 mg kg-1 for animal tissues. The rest of the compounds were within the MRL. None of the pesticide residues was detected in the two fish species collected from the control or reference site. The present study indicates that pesticide contamination is emerging as a threat to the water quality and aquatic biodiversity of Loktak Lake, which calls for more detailed studies on the extent and magnitude of these threats.

Recognition of organophosphate and carbamate pesticides by cholinesterase sensor arrays on the basis of enzymes from different organisms

Herein, we developed a multisensor array utilizing multiple cholinesterase (ChE) and indoxyl acetate (IDA) sensors for the detection and differentiation of trichlorfon (Tri), profenofos (Pro), methomyl (Met), carbofuran (Car), phoxim (Pho), and pyridaphenthion (Pyr). The detection mechanism involves the inactivation of ChE by organophosphates (OPs) and carbamates (CMs), leading to a reduction in the production of indoxyl groups through IDA hydrolysis. We observed distinct and varied inhibition rates of the three enzymes in response to Tri, Pro, Met, Car, Pho, and Pyr. Linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA) plots illustrated the effectiveness of the system in accurately distinguishing both individual and mixed pesticides. Additionally, the platform showed the sensor array’s ability to identify pesticide mixtures and resist interference. Furthermore, the successful classification and determination of celery samples highlighted its practical applicability. This approach holds promise for developing a straightforward sensor array for detecting and discriminating pesticides in complex samples.

Comprehensive monitoring and prioritizing for contaminants of emerging concern in the Upper Yangtze River, China: An integrated approach

Contaminants of emerging concern (CECs) in aquatic environments can adversely impact ecosystems and human health even at low concentrations. This study assessed the risk of 162 CECs, including neonicotinoid pesticides, triazine pesticides, carbamate pesticides, psychoactive substances, organophosphate esters, antidepressants, per- and polyfluoroalkyl substances, and antibiotics in 10 drinking water sources and two tributaries (Jialing and Wujiang Rivers) of the Upper Yangtze River in Chongqing, China. Target screening detected 156 CECs at 0.01–2218.2 ng/L, while suspect screening via LC-QTOF-MS identified 64 CECs, with 13 pesticides, 29 pharmaceuticals and personal care products, and 2 industrial chemicals reported for the first time in the Yangtze River Basin. Risk quotient-based ecological risk assessment revealed that 48 CECs posed medium to high risks (RQ > 0.1) to aquatic life, with antibiotics (n = 20) as the main contributors. Non-carcinogenic risks were below negligible levels, but carcinogenic risks from neonicotinoids, triazines, antidepressants, and antibiotics were concerning. A multi-criteria prioritization approach integrating occurrence, physico-chemical properties, and toxicological data ranked 26 CECs as high priority. This study underscores the importance of comprehensive CEC screening in rivers and provides insights for future monitoring and management strategies.

Magnetic solid phase extraction of methiocarb pesticide from food samples prior to HPLC analysis with magnetic activated carbon cloth/zinc aluminate (magnetic ACC@ZnAl2O4) composite

Methiocarb is a carbamate pesticide and is widely used due to its short lifetime but is a health concern due to its toxicity. To address this challenge, a novel nano-sorbent (zinc aluminate hybrid doped onto a magnetic activated carbon cloth (magnetic ACC@ZnAl2O4)) was synthesized. The characterization of the composite was done using FTIR spectroscopy, SEM, XRD, and EDX. The synthesized composite was then employed for the efficient extraction of methiocarb from food samples. Under the optimum conditions of (pH: 7.0, vortex time: 0.5 min, adsorbent dose: 5 mg, initial volume of sample: 50 mL, volume of eluent: 1.0 mL), quantitative recovery values of methiocarb in food samples were obtained (80–114%). This method impresses with its exceptional sensitivity, achieving incredibly low detection (LOD: 20 µg L−1) and quantification (LOQ: 67 µg L−1) limits for methiocarb. Its efficiency is equally impressive, with high values of preconcentration factor (PF: 50) and enhancement factor (EF: 49.4), ensuring accurate and reliable analysis with a low value of relative standard deviation (RSD: 4.8%). The method’s impressive selectivity, evident in its minimal interference from other pesticides, paves the way for reliable methiocarb analysis in food samples.

Spatiotemporal variations and priority ranking of emerging contaminants in nanwan reservoir: A case study from the agricultural region in huaihe river basin in China

The presence of emerging contaminants (ECs) in drinking water sources is an increasing concern, yet limited data exists on their occurrence and risk in the upper Huaihe River Basin, an important agricultural region in Central China. This study investigated 70 ECs, including pesticide and antibiotics in surface water from drinking water source areas in Nanwan Reservoir along the upper reaches of the Huaihe River Basin to prioritize the ECs based on ecological risk and health risk assessment. A total of 66 ECs were detected in the surface water at least once at the selected 38 sampling sites, with concentrations ranging from 0.04 to 2508 ng/L. Ecological risk assessment using the risk quotient (RQ) method revealed high risks (RQ > 1) from 7 ECs in the dry season and 15 ECs in the wet season, with triazine pesticides as the main contributors. Non-carcinogenic risks were below negligible levels, but carcinogenic risks from neonicotinoid and carbamate pesticides and macrolide antibiotics were concerning for teenagers. Ciprofloxacin exhibited a high level of resistance risk during the wet season. A multi-indicator prioritization approach integrating occurrence, risk, and chemical property data ranked 6 pesticides and 3 antibiotics as priority pollutants. The results highlight EC contamination of drinking water sources in this agriculturally-intensive region and the need for targeted monitoring and management to protect water quality.

Metabolic engineering of Pseudomonas bharatica CSV86T to degrade Carbaryl (1-naphthyl-N-methylcarbamate) via the salicylate-catechol route.

Pseudomonas bharatica CSV86T displays the unique property of preferential utilization of aromatic compounds over simple carbon sources like glucose and glycerol and their co-metabolism with organic acids. Well-characterized growth conditions, aromatic compound metabolic pathways and their regulation, genome sequence, and advantageous eco-physiological traits (indole acetic acid production, alginate production, fusaric acid resistance, organic sulfur utilization, and siderophore production) make it an ideal host for metabolic engineering. Strain CSV86T was engineered for Carbaryl (1-naphthyl-N-methylcarbamate) degradation via salicylate-catechol route by expression of a Carbaryl hydrolase (CH) and a 1-naphthol 2-hydroxylase (1NH). Additionally, the engineered strain exhibited faster growth on Carbaryl upon expression of the McbT protein (encoded by the mcbT gene, a part of Carbaryl degradation upper operon of Pseudomonas sp. C5pp). Bioinformatic analyses predict McbT to be an outer membrane protein, and Carbaryl-dependent expression suggests its probable role in Carbaryl uptake. Enzyme activity and protein analyses suggested periplasmic localization of CH (carrying transmembrane domain plus signal peptide sequence at the N-terminus) and 1NH, enabling compartmentalization of the pathway. Enzyme activity, whole-cell oxygen uptake, spent media analyses, and qPCR results suggest that the engineered strain preferentially utilizes Carbaryl over glucose. The plasmid-encoded degradation property was stable for 75-90 generations even in the absence of selection pressure (kanamycin or Carbaryl). These results indicate the utility of P. bharatica CSV86T as a potential host for engineering various aromatic compound degradation pathways.IMPORTANCEThe current study describes engineering of Carbaryl metabolic pathway in Pseudomonas bharatica CSV86T. Carbaryl, a naphthalene-derived carbamate pesticide, is known to act as an endocrine disruptor, mutagen, cytotoxin, and carcinogen. Removal of xenobiotics from the environment using bioremediation faces challenges, such as slow degradation rates, instability of the degradation phenotype, and presence of simple carbon sources in the environment. The engineered CSV86-MEC2 overcomes these disadvantages as Carbaryl was degraded preferentially over glucose. Furthermore, the plasmid-borne degradation phenotype is stable, and presence of glucose and organic acids does not repress Carbaryl metabolism in the strain. The study suggests the role of outer membrane protein McbT in Carbaryl transport. This work highlights the suitability of P. bharatica CSV86T as an ideal host for engineering aromatic pollutant degradation pathways.

Advancing micro-electrometric techniques for the detection of organophosphate and carbamate residues using cricket cholinesterase.

The widespread use of organophosphate (OP) and carbamate (CM) pesticides requires efficient and cost-effective detection methods. This study introduces a micro-electrometric method using cricket cholinesterase (ChE) to detect OP and CM residues, providing a rapid and economical alternative to conventional chromatographic techniques. The parameters of the method, including the substrate concentration, incubation temperature, and incubation time, were optimized. By leveraging the sensitivity of cricket ChE to OP and CM inhibition, this approach translates enzyme inhibition into an electrical signal to quantify pesticide levels, achieving an impressive limit of detection (LOD) from 0.036 to 0.086 parts per million (ppm). This method demonstrated reproducibility and stability, making it suitable for field applications and on-site testing across various environmental matrices. This research represents a significant advancement in pesticide residue analysis with potential applications in the development of portable biosensor devices for real-time environmental monitoring and public health protection.

Sub-chronically exposing zebrafish to environmental levels of methomyl induces dysbiosis and dysfunction of the gut microbiota

The widespread use of carbamate pesticides has led to numerous environmental and health concerns, including water contamination and perturbation of endocrine homeostasis among organisms. However, there remains a paucity of research elucidating the specific effects of methomyl on gut microbial composition and physiological functions. This study aimed to investigate the intricate relationship between changes in zebrafish bacterial communities and intestinal function after 56 days of sub-chronic methomyl exposure at environmentally relevant concentrations (0, 0.05, 0.10, and 0.20 mg/L). Our findings reveal significant methomyl-induced morphological changes in zebrafish intestines, characterized by villi shortening and breakage. Notably, methomyl exposure down-regulated nutrient and energy metabolism, and drug metabolism at 0.05−0.10 mg/L, while up-regulating cortisol, inflammation-related genes, and apoptotic markers at 0.20 mg/L. These manifestations indicate physiological stress imposition and disruption of gut microbiota equilibrium, impacting metabolic processes and instigating low-grade inflammatory responses and apoptotic cascades. Importantly, changes in intestinal function significantly correlated with shifts in specific bacterial taxa abundance, including Shewanella, Rubrobacter, Acinetobacter, Bacillus, Luteolibacter, Nocardia, Defluviimonas, and Bacteroides genus. In summary, our study underscores the potential adverse effects of environmental methomyl exposure on aquatic organisms, emphasizing the necessity for further research to mitigate its repercussions on environmental health and ecosystem stability.

Sub-Chronic Methomyl Exposure Induces Oxidative Stress and Inflammatory Responses in Zebrafish with Higher Female Susceptibility.

The widespread use of carbamate pesticides has raised significant environmental and health concerns, particularly regarding water contamination and the disruption of defense systems in organisms. Despite these concerns, research on the differential impacts of pesticides on male and female organisms remains limited. This study focused on methomyl, investigating sex-specific differences in liver antioxidant defenses and inflammatory response indices in male and female zebrafish after 56 days of exposure to environmentally relevant concentrations (0, 0.05, 0.10, and 0.20 mg/L). Our findings indicate that methomyl exposure significantly increased ROS content in zebrafish livers, inducing oxidative stress and activating enzymatic antioxidant defenses such as SOD, CAT, and GSH-Px activities. Sub-chronic exposure altered the expression of apoptosis-related genes (Bax/Bcl2a and Caspases3a), resulting in liver cell apoptosis in a concentration-dependent manner, with the 0.20 mg/L concentration causing the most severe damage. Additionally, methomyl exposure at environmentally relevant concentrations triggered persistent inflammatory responses in liver tissues, evidenced by increased transcription levels of inflammatory factor genes and the activation of toll-like receptors, heightening susceptibility to exogenous allergens. It is noteworthy that oxidative damage indicators (AST, ROS, MDA) and inflammatory gene expressions (IL-1β, TNF-α) were significantly higher in female livers compared to male livers at 0.10-0.20 mg/L methomyl exposure. Consequently, our study underscores the potential adverse effects of environmental methomyl exposure on aquatic organisms and highlights the need for heightened consideration of the risks posed by environmental endocrine disruptors to female health and safety.

Pre-Conception And First Trimester Exposure To Pesticides And Associations With Stillbirth.

Associations of pesticide exposures during pre-conception with stillbirth have not been well explored. We linked Arizona pesticide use records with birth certificates from 2006-2020 and estimated associations of living within 500meters of any pyrethroid, organophosphate (OP), or carbamate pesticide applications during a 90 day pre-conception window or the first trimester, with stillbirth. We considered a binary measure of exposure (any exposure), as well as log-pounds and log-acres applied within 500m, in a negative control exposure framework with log-binomial regression. We included 1,237,750 births, 2,290 stillbirths, and 27 pesticides. During pre-conception, any exposure to pesticides were associated with stillbirth, including cyfluthrin (RR=1.97, 95% CI 1.17,3.32), zeta-cypermethrin (RR=1.81, 95%CI 1.20, 2.74), organophosphates as a class (RR=1.60, 95%CI 1.16, 2.19), malathion (RR=2.02, 95%CI 1.26, 3.24), carbaryl (RR=6.39, 95%CI 2.07, 19.74), and propamocarb hydrochloride (RR=7.72, 95%CI 1.10, 54.20) . During the first trimester, fenpropathrin (RR=4.36, 95%CI 1.09, 17.50), permethrin (RR=1.57, 95%CI 1.02, 2.42), organophosphates as a class (RR=1.50, 95%CI 1.11, 2.01), acephate (RR=2.31, 95%CI 1.22, 4.40), and formetanate hydrochloride (RR=7.22, 95%CI 1.03, 50.58) were associated with stillbirth. Interpretations were consistent when using continuous measures of pounds or acres of exposure. Pesticide exposures during pre-conception and first trimester may be associated with stillbirth.

A porous composite sorbent incorporating a metal organic framework and zinc oxide in cryogel to extract carbamate pesticides

A composite sorbent was designed and fabricated by incorporating the Materials of Institute Lavoisier (MIL-101) and zinc oxide (ZnO) into polyvinyl alcohol (PVA) cryogel. The composite sorbent was produced to extract carbamates (carbofuran, carbaryl, isoprocarb and diethofencarb) by in-syringe solid phase extraction (SPE). MIL-101 and ZnO enhanced the adsorption of the carbamates by creating π-π stacking and hydrogen bonding, while porous PVA cryogel acted as a solid support which helped to reduce backpressure in the system. The extraction of the target carbamates was optimized by varying the amount of MIL-101 and ZnO used in the sorbent fabrication, desorption conditions, sample pH, ionic strength, sample flow rate and sample volume. The extracted target carbamates were quantitatively determined using high performance liquid chromatography technique. The developed method exhibited linearity from 1.0 to 150.0 μgL−1 for all four target carbamate pesticides with a limit of detection 0.3 µg/L. The method identified carbamates in fruit juice and white wine, obtaining recoveries from 78.1 to 108.2 % and the relative standard deviation (RSD) lower than 6.3 %. The developed composite sorbent showed good accuracy, is simple to fabricate, works rapidly and can be used for 17 extraction-regeneration cycles.

Magnetic covalent organic framework for magnetic solid-phase extraction of carbamate pesticide residues

Herein, a new kind of magnetic covalent organic frameworks (MCOFs), named MCOF-DhaTab, using 1,3,5-tris (4-aminophenyl) benzene and 2,5-dihydroxy-1,4-phenylenedialdehyde as functional monomers of COFs and Fe3O4-NH2 nanoparticles as magnetic carrier was synthesized at room temperature through Schiff base reaction. With a large specific surface area (409.5 m2/g) and rich in benzene rings and hydroxyl groups, the prepared MCOF-DhaTab exhibited high extraction efficiency (73.8 %–88.9 %) for five carbamate pesticides (CPs). Based on it, a new method of magnetic solid phase extraction (MSPE) with MCOF-DhaTab as the sorbents coupling to high performance liquid chromatography (HPLC) − ultraviolet visible (UV) detection was developed for trace analysis of carbaryl (CAR), fenobucarb (FEN), isoprocarb (ISO), diuron (DIU), mercaptodimethur (MER). The developed method had the advantages of low limits of detection (0.1–200 μg/L for CAR, 0.2–100 μg/L for ISO, 0.2–200 μg/L for DIU, and 0.5–200 μg/L for FEN and MER), high sensitivity, simplicity and rapidity. It was successfully used for the analysis of trace CPs in tomato, cucumber and cigar samples, showing a great application potential in pesticide residues analysis in agricultural samples.

Long-term carbaryl exposure leads to behavioral abnormalities and reproductive toxicity in male marine medaka through apoptosis-mediated HPA and HPG axes dysregulation

Carbaryl is a widely used carbamate pesticide that has been detected in the marine environment, but its effects on marine fish are still unknown. This study was aimed to investigate the effects of long-term exposure of carbaryl on male marine medaka. For this purpose, we set up five exposure concentration groups of 0, 0.1, 1, 10, and 100 µg/L for 180 days. On the one hand, we observed increased aggression and decreased ability to avoid predators in males after exposure, which was affected by the levels of HPA-axis hormones, especially decreased cortisol level. On the other hand, after exposure, HPG axis hormone levels and gene transcription levels were disturbed. Males exhibited a decreased gonadosomatic index and a notable reduction in mature sperm proportion and the F1 generation displayed a significant increase in malformation rate. Additionally, the number of apoptotic cells and the transcription level of apoptosis-related genes in the brains of male marine medaka substantially increased after exposure. Apoptosis of brain cells may be responsible for the disturbance of HPA and HPG axes, consequently leading to behavioral and reproductive abnormalities. These findings provide novel insights into evaluating the toxic effects of carbaryl on male marine medaka and emphasizing the criticality of exploring the potential environmental risks posed by carbaryl in the marine environment, thus providing toxicity value basis for further strengthening marine environmental monitoring and the protection of biological resources.

Direct electrochemical detection of pirimicarb using graphene oxide and ionic liquid composite modified by gold nanoparticles

Carbamate pesticide residue assessments are important for water and environmental quality. An eco-friendly electrochemical sensor for direct determination of pirimicarb (PMC) based on graphene oxide (GO) and Ionic liquid (IL) composites decorated with gold nanoparticles has been developed. The resulting AuNPs@GO/IL@SPCE sensor was characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analysis. The electrode’s electrochemical characteristics were evaluated using cyclic voltammetry and electrochemical impedance spectroscopy. The impact of different modifier materials on the sensor performance and its stability was investigated systematically using a combination of experimental and theoretical studies. Under optimal conditions, the AuNPs@GO/IL@SPCE is used for sensitive detection of PMC in a concentration range from 50–1500 µM with a detection limit of 4.49 µM. Furthermore, the sensor exhibits excellent selectivity towards tested interfering species, reproducibility, and stability. Finally, the PMC detection in groundwater and surface water was achieved using the developed sensor with a 97.38 − 103.36 % recovery.

Determination and health risk assessment of carbamate pesticide residues in date palm fruits (Phoenix dactylifera) using QuEChERS method and UHPLC-MS/MS

This study aimed to investigate carbamate pesticide residues in different varieties of date palm fruits in the UAE, utilizing UHPLC-MS/MS. For sample preparation and clean-up, the efficiency and performance of different QuEChERS dispersive solid-phase extraction kits were compared. Precision and recovery were assessed at 10 μg kg−1 for the three kits, revealing that Kit 2 demonstrated the best performance. The selected QuEChERS method was validated to detect 14 carbamate residues in 55 date samples. The method exhibited strong linearity with R2 > 0.999 and low LOD (0.01–0.005 μg kg−1) and LOQ (0.003–0.04 μg kg−1). Excellent accuracy (recovery: 88–106%) and precision (RSD: 1–11%) were observed, with negligible matrix effect (− 4.98–13.26%). All samples contained at least one carbamate residue. While most detected residues were below their MRLs, carbosulfan was found in 21 samples, propoxur in 2 samples, and carbofuran in 1 sample above their MRLs. The hazard index (HI) was calculated for carbosulfan, phenmedipham, carbaryl, propoxur, carbofuran, and methomyl to assess potential health risks for date consumers. All HI values were below the safety limit of 1.0, indicating that the consumption of dates does not pose a non-carcinogenic health risk for adults and children.