Biological Monitoring of Glyphosate Exposure among Knapsack Sprayers in Khon Kaen, Thailand.

Sprayers' exposure to glyphosate was analyzed through detection of its biomarker in spot urine biological monitoring, and the health risk was assessed using the biomatrix model. Urine samples were collected from 15 sprayers after spraying, and the glyphosate concentration was determined by using the DLLME-HPLC method with a UV detector. The calibration curve for glyphosate was linear in the range of 0.4-100 µg/L, while the limits of detection and quantification were 0.1 µg/L and 0.4 µg/L, respectively. The human health risk was estimated using the hazard quotient (HQ) and the biomatrix of risk assessment. The internal dose ranged from 0.0001 to 0.0021 mg/kg b.w./day. The non-cancer HQ showed no potential health risk concerns (HQ < 1). The biomatrix of health risk assessment, based on urinary glyphosate concentration, exhibited a strong correlation with the health risk matrix model. This correlation was determined by considering the likelihood of exposure, calculated from the quantity of glyphosate used and the usage of personal protective equipment (r = 0.854, p < 0.001). Although low risk was observed in sprayers, proper PPE use and the application of more knowledge are required. The simplified health risk assessment can be used for easy self-assessment of risk in preventive action regarding health risk awareness among sprayers.

A sensitive paper-based vapor-test kit for instant formalin detection in food products.

A colorimetric sensing method based on a paper-based vapor-test kit was successfully developed for the selective and sensitive real-time monitoring of formalin in food samples. The device was specifically designed to efficiently extract and detect formalin simultaneously. A microcentrifuge tube was used as the sample solution container, with the inner cap serving as the reaction and detection zone. Formalin was converted into gaseous formaldehyde through controlled heating, which was then extracted and collected on a filter paper coated with Nash's reagent. The color change on paper was used for formalin quantification using a smartphone for detection and image analysis. Under optimal conditions, our method provided a linear range of 0.5-75 mg L-1 with a detection limit of 0.11 mg L-1. This method effectively determined formalin in fresh food and vegetable samples, with recoveries ranging from 92 to 111%, demonstrating comparable accuracy to the standard method for practical food quality control and safety.

Electrochemical detection of methyl parathion using calix[6]arene/bismuth ferrite/multiwall carbon nanotube-modified fluorine-doped tin oxide electrode.

A highly sensitive electrochemical sensor using a calix[6]arene/bismuth ferrite/multiwall carbon nanotube-modified fluorine-doped tin oxide electrode (CA6/BFO/MWCNTs/FTO) was fabricated for the detection of methyl parathion. The MWCNTs, BFO, and CA6 were consecutively cast onto the FTO electrode surface to enhance the surface area, electron transfer, and selectivity of sensors. The electrochemical behavior of CA6/BFO/MWCNTs/FTO was studied via cyclic voltammetry and electrochemical impedance spectroscopy. MP was detected via cyclic voltammetry in a phosphate buffer solution at pH 7.0. The working principle of the sensor involves a linear decrease in the anodic peak current of BFO with increasing MP concentration. The linear working ranges are 0.005-0.05 nM and 0.07-1.5 nM. The CA6/BFO/MWCNTs/FTO sensor provides a low detection limit (S/N = 3) of 5 pM and a high electrochemical sensitivity of 1.23 A µM-1 cm-2. The fabricated sensor was successfully applied to assess the presence and amount of MP in vegetables and fruits (recoveries of 82.0-106.8%), with results comparable to high-performance liquid chromatography.

Modified Peanut Shell as an Eco-Friendly Biosorbent for Effective Extraction of Triazole Fungicide Residues in Surface Water and Honey Samples before Their Determination by High-Performance Liquid Chromatography.

An eco-friendly sample preparation method that is based on the use of a modified peanut shell as an efficient biosorbent for the extraction of triazole residues before their analysis by high-performance liquid chromatography was reported. The four triazole fungicides were separated on a Purospher STAR RP-18 endcapped (4.6 × 150 mm, 5 µm) column with a mobile phase of 50% (v/v) acetonitrile at a flow rate of 1.0 mL min-1 and detection wavelength set at 220 nm. Peanut shells modified by didodecyldimethylammonium bromide were selected as an effective biosorbent material in the microextraction method. Scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to characterize the biosorbent. The effect of dominant parameters on the proposed microextraction method including the amount of sorbent, kind and concentration of surfactant, sodium hydroxide concentration, kind and amount of salt, sample volume, adsorption time, kind and volume desorption solvent, and desorption time was studied. Under the optimum condition, a good analytical performance for the proposed microextraction method was obtained with a wide linear range within the range of 9-1000 µg L-1, and low limits of detection (0.03 µg L-1 for all analytes) were obtained. Enrichment factors were achieved within the range of 30-51. The intra and interday precision values were evaluated in terms of percentage relative standard deviations (%RSD) and were less than 0.09 and 5.34% for the retention time and peak area, respectively. The proposed microextraction methods were used for extraction and analysis of triazole fungicides in water and honey samples. The recoveries in a satisfactory range of 70.0-118.8% were obtained.

Simultaneous Preconcentration of Triazole Fungicide Residues Using In-Situ Coacervative Extraction Based on a Double-Solvent Supramolecular System Prior to High Performance Liquid Chromatographic Analysis.

An in situ coacervative extraction (IS-CAE) based on a double-solvent supramolecular system coupled to liquid-liquid microextraction is investigated for extraction and enrichment of triazole fungicides. The formation of a double-solvent supramolecular system was generated by in situ formation and used as an extraction solvent for the coacervative extraction method. No disperser solvent was required. This new double-solvent supramolecular system has a higher extraction ability than any of its components alone. The different factors that could affect the extraction capability were studied and optimized, including the type of double extractant and its volume, salt addition, vortex time, and centrifugation time. Under optimum extraction conditions, this method provides high enrichment factors (EFs) of 73-318 with low limits of detection (LODs) of 0.3-1 µg L-1 and limits of quantitation (LOQs) of 1-3 µg L-1. In addition, the proposed method was prosperously applied for the determination of triazole fungicides in water, fruit juice, and soy milk samples.

An In Situ Formation of Ionic Liquid for Enrichment of Triazole Fungicides in Food Applications Followed by HPLC Determination.

An in situ formation of ionic liquid was used for preconcentration of four triazole fungicides in food samples. The microextraction method was used for the first time in the literature for preconcentration of triazole fungicides. In the developed method, tributylhexadecylphosphonium bromide ([P44412]Br) and potassium hexafluorophosphate (KPF6) were used for the formation of hydrophobic ionic liquid. After centrifugation, the fine microdroplets were produced in one step, providing the extraction step in a quick and environmentally friendly manner. The functional group of the hydrophobic ionic liquid was investigated using FT-IR. Various extraction parameters were studied and optimized. In the extraction method, 0.01 g of [P44412]Br and 0.01 g of KPF6, centrifugation at 4500 rpm for 10 min were used. The optimized technique provided a good linear range (90-1000 µg L-1) and high extraction recovery, with a low limit of detection (30-50 µg L-1). Methods for the proposed in situ formation of ionic liquid were successfully applied to honey, fruit juice, and egg matrices. The recoveries were obtained in a satisfactory range of 62-112%. The results confirmed the suitability of the proposed microextraction method for selective extraction and quantification of triazole fungicides.

Facile liquid colorimetric sensor using high-density deep eutectic solvent for trace detection and speciation of iron in milk.

An efficient colorimetric sensor was developed using a high-density deep eutectic solvent (HD-DES) for the trace detection and speciation of iron in various milk samples. A liquid colorimetric probe was fabricated by dissolving ferrozine (FZ) in HD-DES prepared from TBABr and PBA. The prederivatization of Fe2+ via complexation with FZ on the HD-DES/FZ probe provided the [Fe(FZ)3]4- complex, which led to a color change from pale yellow to purple before it was simultaneously extracted by HD-DES. The Fe3+ content was calculated by subtracting the amount of Fe2+ from the total Fe content following the reduction of Fe3+ to Fe2+ by L-ascorbic acid in an acid buffer. Under the optimized conditions, the proposed colorimetric sensor exhibited appreciable linearity in the concentration range of 0.003-0.04 mg L-1, a low limit of detection (0.95 µg L-1), high enrichment factor (50), and outstanding repeatability. The liquid colorimetric probe was successfully applied for the determination and speciation of iron in milk samples, and the results were compared with those obtained using the standard atomic absorption spectrometry method. Moreover, quantitative analysis was performed on a smartphone using the Image J application to estimate the color intensity change, which eliminated the requirement of sophisticated scientific instruments.

Co-precipitation based on layered double hydroxides and anionic surfactants for preconcentration of six benzoylurea insecticides in soft drinks before simultaneous analysis by high-performance liquid chromatography.

Layered-double hydroxides (LDHs) modified with anionic surfactants via a co-precipitation method were developed for preconcentrating and simultaneous analysis of six benzoylurea insecticides (BUs) by high-performance liquid chromatography (HPLC). The anionic surfactants with different chain lengths, including sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), sodium 1-nonane sulfonate (SNS), and sodium 1-hexane sulfonate monohydrate (SHS) were investigated to improve the extraction efficiency of LDHs. The SDBS-LDHs provided the highest efficiency for the enrichment of the BUs studied. Under the chosen conditions, enrichment factors in the range of 38-69 and detection limits in the range of 0.1-0.3 µg L-1 were achieved. Good reproducibilities (RSD < 13.8%) and recoveries (71.4-118.7%) were also obtained. The proposed preconcentration method, used as an in situ procedure offers rapid and simple simultaneous preparation of LDHs and extraction of BUs. The method was successfully applied for residue analysis of BUs in fruit- and flower-derived soft drink samples.

Surface Plasmon Resonance Sensor for Novel Detection of Histidine Based on the Hg2+ Induced Aggregation of AuNPs Followed by Preconcentration with Chitosan Gel as Solid Phase Biosorbent.

This research work aims to propose an extraction method using chitosan as the sorbent and gold nanoparticles (AuNPs) as the colorimetric sensor for the development of a simple, cost-effective, rapid, sensitive, and selective detection method for histidine. The colorimetric assay is based on the aggregation of AuNPs in the presence of Hg2+ ions and histidine. The state of AuNPs generally changes from dispersion to aggregation. The change in state is accompanied by a corresponding change in color (from red wine to blue). Therefore, the solid phase extraction (SPE) method using chitosan as the sorbent was used to extract the AuNPs to improve the sensitivity of detection. It was found that the extraction by means of a sensor system using chitosan could increase the detection signal for histidine by 10 times. The calibration curve, which is the plot of absorbance ratio (A650/A528) against the concentration of histidine, shows a linear relation in the concentration range of 100 - 800 nM. The limit of detection (LOD) and limit of quantitation (LOQ) of the method were found to be 99.88 and 107.45 nM, respectively. Good recoveries were also obtained (range: 99.75 - 104.43%) with relative standard deviations (RSDs) below 5.89% in real water samples. Moreover, this method can be used for the selective detection of histidine even in the presence of other amino acids. The proposed method has been successfully used in the determination of histidine in mineral water samples.

A novel liquid colorimetric probe for highly selective and sensitive detection of lead (II).

A novel liquid colorimetric sensor based on deep eutectic solvent (DES) was developed for the preconcentration and detection of Pb2+ in fruit juice, milk and cereal samples. The colorimetric probe was simply fabricated by adding dithizone (DZ) into DES, prepared from choline chloride and phenol. Pb2+ was formed complex with DZ in the probe, providing hydrophobic complex of [Pb-DZ] which was simultaneously extracted into DES and the color was changed from light orange to carmine red. The enriched [Pb-DZ] in DES was detected using spectrophotometer at 520 nm and naked-eyes. In addition, a smartphone in combination with an Image J program was used as an alternative detection device. Under optimal conditions, the enrichment factor was 92 with LOD of 2.1 µg L-1 and the linear range was 0.007-0.075 mg L-1. The proposed liquid colorimetric sensor was successfully applied for Pb2+ detection in various food samples and the results were in good agreement with those obtained by FAAS. The advantages of this method are simple, rapid, environmental friendly and low cost.

An electrochemical sensor for voltammetric detection of ciprofloxacin using a glassy carbon electrode modified with activated carbon, gold nanoparticles and supramolecular solvent.

A highly sensitive and novel electrochemical sensor for ciprofloxacin (CIP) has been developed using gold nanoparticles deposited with waste coffee ground activated carbon on glassy carbon electrode (AuNPs/AC/GCE) and combined with supramolecular solvent (SUPRAS). The fabricated AuNPs/AC/GCE displayed good electrocatalytic activity for AuNPs. The addition of SUPRAS, prepared from cationic surfactants namely didodecyldimethylammonium bromide (DDAB) and dodecyltrimethylammonium bromide (DTAB), increased the electrochemical response of AuNPs. The detection of CIP was based on the decrease of the cathodic current of AuNPs. The electrochemical behavior of the modified electrode was investigated using cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy. Under optimum conditions, the calibration plot of CIP exhibited a linear response in the range 0.5-25 nM with a detection limit of 0.20 nM. The fabricated electrochemical sensor was successfully applied to determine CIP in milk samples with achieved recoveries of 78.6-110.2% and relative standard deviations of <8.4%. The developed method was also applied to the analysis of pharmaceutical formulation and the results were compared with high-performance liquid chromatography.Graphical abstract.

In-Situ Formation of Modified Nickel-Zinc-Layered Double Hydroxide Followed by HPLC Determination of Neonicotinoid Insecticide Residues.

A single-step preconcentration procedure using the in-situ formation of modified nickel-zinc-layered double hydroxides (LDHs) prior to high-performance liquid chromatography (HPLC) is investigated for the determination of neonicotinoid insecticide residues in honey samples. The LDHs could be prepared by the sequential addition of sodium hydroxide, sodium dodecyl sulfate, nickel nitrate 6-hydrate and zinc nitrate 6-hydrate, which were added to the sample solution. The co-precipitate phase and phase separation were obtained by centrifugation, and then the precipitate phase was dissolved in formic acid (concentrate) prior to HPLC analysis. Various analytical parameters affecting extraction efficiency were studied, and the characterization of the LDHs phase was performed using Fourier-transformed infrared spectroscopy and scanning electron microscopy. Under optimum conditions, the limit of detection of the studied neonicotinoids, in real samples, were 30 µg L-1, for all analytes, lower than the maximum residue limits established by the European Union (EU). The developed method provided high enrichment, by a factor of 35. The proposed method was utilized to determine the target insecticides in honey samples, and acceptable recoveries were obtained.

Dissolvable Mg/Al layered double hydroxides and surfactant as an extractant for trace analysis of benzoylurea insecticides by high performance liquid chromatography.

A rapid and simple preconcentration method using dissolvable Mg/Al layered-double hydroxides (LDHs) and high performance liquid chromatography-photodiode array detection (HPLC-PDA) was developed for the analysis of benzoylurea insecticides (BUs) in water and honey samples. The proposed dissolvable LDHs for the extraction can be prepared in one step by the sequential addition of sodium hydroxide, magnesium chloride, aluminium chloride, and sodium dodecyl sulfate into the sample solution containing the target BUs. The co-precipitate phase was simply obtained after centrifugation, and the phase was then dissolved with formic acid before analysis by HPLC. The developed method provided an enrichment factor of 12.5-23.7. LODs were obtained in the range of 0.1-0.3 µg L-1 for deionized water, 0.2-2.0 µg L-1 for environmental waters, and 0.5-2.0 µg L-1 for the analyzed honey samples. Good recoveries ranging from 78.4 to 117.8% and 72.7 to 117.9% for water and honey samples, respectively, were obtained.

A rapid and simple method for the removal of dyes and organophosphorus pesticides from water and soil samples using deep eutectic solvent embedded sponge.

A new treatment method using a deep eutectic solvent embedded melamine sponge (DES-MS) was studied for the removal of organic pollutants from water and soil samples. Five organophosphorus pesticides (OPPs) consisting of azinphos-methyl (AZP), parathion-methyl (PRT), fenitrothion (FNT), diazinon (DIZ) and chlorpyrifos (CPF), and two dyes including acid blue 29 (AB29) and malachite green (MG) were used as the model pollutants. DESs were easily prepared from tetrabutylammonium bromide (TBABr) and various fatty acids. The synthesised DESs were loaded into the sponge before being utilized for the removal of the studied pollutants. After the removal, the residual OPPs or dyes in the supernatant was quantified by high performance liquid chromatography or derivative spectrophotometry, respectively. The proposed method was simple, rapid, environmentally friendly and effective with the removal efficiency higher than 70% for various samples. Moreover, the removal of various dyes was successfully achieved with the efficiency greater than 65% under the optimum condition.

An Eco-Friendly Hydrophobic Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Neonicotinoid Insecticide Residues in Water, Soil and Egg Yolk Samples.

A green, simple and sensitive hydrophobic DES-based dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography (HPLC) was developed for the analysis of neonicotinoid insecticide residues in various samples. A hydrophobic deep eutectic solvent (DES) was synthesized using decanoic acid as a hydrogen bond donor and tetrabutylammonium bromide (TBABr) as a hydrogen bond-acceptor. DESs were synthesized and characterized by Fourier transform-infrared (FTIR) spectroscopy. Two disperser solvents were substituted with surfactants and acetonitrile, which could afford more effective emulsification and make the extraction relatively greener. The hydrophobic DES extraction phase occurred 10 min after centrifugation, being easy to be collected for analysis. Several parameters were investigated and optimized. Under the optimum condition, the calibration curve of this method was linear in the range of 0.003-1.0-µg·mL-1, with a correlation coefficient (R2) higher than 0.99 and a good repeatability, with the relative standard deviations (RSDs) were less than 5.00%. The limits of detection were in the range of 0.001-0.003 µg·mL-1; the limits of quantitation were in the range of 0.003-0.009 µg·mL·mL-1. Finally, the presented method was implemented to determine the neonicotinoid insecticide residues in water, soil, egg yolk samples and acceptable recoveries were obtained.

Supramolecular Electrochemical Sensor for Dopamine Detection Based on Self-Assembled Mixed Surfactants on Gold Nanoparticles Deposited Graphene Oxide.

A new supramolecular electrochemical sensor for highly sensitive detection of dopamine (DA) was fabricated based on supramolecular assemblies of mixed two surfactants, tetra-butylammonium bromide (TBABr) and sodium dodecyl sulphate (SDS), on the electrodeposition of gold nanoparticles on graphene oxide modified on glassy carbon electrode (AuNPs/GO/GCE). Self-assembled mixed surfactants (TBABr/SDS) were added into the solution to increase the sensitivity for the detection of DA. All electrodes were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The supramolecular electrochemical sensor (TBABr/SDS⋅⋅⋅AuNPs/GO/GCE) showed excellent electrocatalytic activity toward the oxidation of DA. Under the optimum conditions, the concentration of DA was obtained in the range from 0.02 µM to 1.00 µM, with a detection limit of 0.01 µM (3s/b). The results displayed that TBABr/SDS⋅⋅⋅AuNPs/GO/GCE exhibited excellent performance, good sensitivity, and reproducibility. In addition, the proposed supramolecular electrochemical sensor was successfully applied to determine DA in human serum samples with satisfactory recoveries (97.26% to 104.21%).

A Simple in Syringe Low Density Solvent-Dispersive Liquid Liquid Microextraction for Enrichment of Some Metal Ions Prior to Their Determination by High Performance Liquid Chromatography in Food Samples.

A simple and highly sensitive method is developed for the simultaneous determination of Ni2+, Cr2O72-, Co2+, and Hg2+ by using in syringe low density solvent-dispersive liquid liquid microextraction (ISLD-DLLME), followed by high performance liquid chromatography with a UV detector. The four metal ions were derivatized with pyrrolidine dithiocarbamate (PDC) based on complexation before their enrichment by ISLD-DLLME in which 1-octanol and methanol were used as the extraction solvent and the dispersive solvent, respectively. The extraction was performed in a commercially available syringe under vortex agitation. Phase separation was achieved without centrifugation, and the extraction phase was easily collected by moving the syringe plunger. Parameters affecting the extraction efficiency were studied and optimized. Under the optimum conditions, the four metal-PDC complexes were detected within 18 min, and ISLD-DLLME could increase the detection sensitivity in the range of 64-230 times compared to the direct HPLC analysis. The obtained limits of detection (LODs) were found to be in the range of 0.011-2.0 µg L-1. The applicability of the method is demonstrated for freshwater fish, shrimp, and shellfish samples. In addition, the results are in good agreement with those obtained by inductively-coupled plasma-optical emission spectrometry (ICP-OES).

Supramolecular Solvent-Based Liquid Phase Microextraction Combined with Ion-Pairing Reversed-Phase HPLC for the Determination of Quats in Vegetable Samples.

In this study, we used anion supramolecular solvent (SUPRAS) prepared from a mixture of an anionic surfactant, sodium dodecyl sulfate (SDS), and a cationic surfactant, tetrabutylammonium bromide (TBABr), as the extraction solvent in liquid phase microextraction (LPME) of paraquat (PQ) and diquat (DQ). The enriched PQ and DQ in the SUPRAS phase were simultaneously analyzed by ion-pairing reversed-phase high performance liquid chromatography. PQ and DQ were successfully extracted by LPME via electrostatic interaction between the positive charge of the quats and the negative charge of SUPRAS. PQ, DQ, and ethyl viologen (the internal standard) were separated within 15 min on a C18 column, with the mobile phase containing 1-dodecanesulfonic acid and triethylamine, via UV detection. The optimized conditions for the extraction of 10 mL aqueous solution are 50 µL of SUPRAS prepared from a mixture of SDS and TBABr at a mole ratio of 1:0.5, vortexed for 10 s at 1800 rpm, and centrifugation for 1 min at 3500 rpm. The obtained enrichment factors were 22 and 26 with limits of detection of 1.5 and 2.8 µg L-1 for DQ and PQ, respectively. The precision was good with relative standard deviations less than 3.86%. The proposed method was successfully applied for the determination of PQ and DQ in vegetable samples and recoveries were found in the range of 75.0% to 106.7%.

ß-Cyclodextrin Assisted Liquid-Liquid Microextraction Based on Solidification of the Floating Organic Droplets Method for Determination of Neonicotinoid Residues.

An efficient and environment-friendly microextraction method, namely, ß-cyclodextrin assisted liquid-liquid microextraction, based on solidification of the floating organic droplets method coupled with HPLC is investigated for the sensitive determination of trace neonicotinoid pesticide residues. In this method, ß-cyclodextrin is used as a disperser solvent, while 1-octanol is selected as an extraction solvent. ß-cyclodextrins was found to decrease interfacial tension and increase the contact area between the organic and water phases with the help of centrifugation. A cloudy solution was rapidly formed and then centrifuged to complete phase separation. Various key parameters influencing extraction efficiency were systematically investigated and optimized; they include salt addition, concentration of ß-cyclodextrin, and volume of extraction solvent (1-octanol). Under optimum conditions, good linearity was obtained with coefficient for determination (R2) greater than 0.99. A low limit of detection, high enrichment factor, and good recovery (83 - 132) were achieved. This proves that the proposed method can be applied to determine trace neonicotinoid pesticide residues in natural surface water samples.

Vesicular supramolecular solvent-based microextraction followed by high performance liquid chromatographic analysis of tetracyclines.

A simple liquid phase microextraction (LPME) using a vesicular supramolecular solvent (SUPRAS) as the green extraction solvent has been developed for the enrichment of tetracycline antibiotics (TCs) prior to their analysis by reversed phase high performance liquid chromatography. SUPRAS was prepared from a mixture of cationic surfactants: didodecyldimethylammonium bromide (DDAB) and dodecyltrimethylammonium bromide (DTAB) under salt (NaCl) addition for coacervation. The LPME is based on electrostatic interaction between TCs and SUPRAS under salt induced phase separation. Under the optimum conditions, high enrichment factors (EFs) of 48-198, low limits of detection (LODs) in the range of 0.7-3.4 µg L-1 and good precisions with relative standard deviations (RSDs) less than 7.85% were obtained. The applicability of the proposed method was demonstrated for the determination of TCs in milk, egg and honey samples. In addition, morphology, particle sizes and zeta potential of SUPRAS were also investigated.