Development of In-Needle SPME Devices for Microextraction Applied to the Quantification of Pesticides in Agricultural Water.

The chemical industry explosion in the 20th century has led to increased environmental pollution, affecting fauna, flora, and waterways. These substances alter water's taste, color, and smell, making it unfit for consumption or toxic. Agricultural water networks face threats from pollution before and after treatment. Some chemical contaminants, like pesticides, are embedded in natural biogeochemical cycles. In this study, we developed a simple and low-cost procedure for the fabrication of needles coated with polydimethylsiloxane (PDMS) as an efficient sorbent for the microextraction of organic pollutant traces from water. The prepared needles were used as an alternative for commercial solid-phase micro-extraction (SPME) devices in analytical chemistry. The PDMS polymeric phase was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The PDMS-coated needles were used for extraction of thirteen pesticides by direct-immersion solid-phase microextraction (DI-SPME) from contaminated waters, followed by determination with gas chromatography-mass spectrometry (GC-MS). The developed analytical method showed limits of detection (LODs) between 0.3 and 2.5 ng mL-1 and RSDs in the range of 0.8-12.2%. The homemade needles were applied for the extraction of pesticides in surface and ground aqueous samples collected from an agricultural area. Several target pesticides were identified and quantified in the investigated water samples.

Molecularly imprinted polymer-coated silica microbeads for high-performance liquid chromatography.

Molecularly imprinted polymer (MIP)-based chromatographic separation materials, owing to their advantages of unique selectivity, low cost, suitable reproducibility, and acceptable stability, have attracted a great deal of research in different fields. In this investigation, a new type of MIP-coated silica (MIP/SiO2) separation material was developed using sulfamethoxazole as a template; the specific recognition ability of MIP and appropriate physicochemical properties (abundant Si-OH, suitable pore structure, good stability, etc.) of SiO2 microbeads were combined. The MIP/SiO2 separation materials were characterized carefully. Then, various compounds (such as sulfonamides, ginsenosides, nucleosides, and several pesticides) were used to comprehensively evaluate the chromatographic performances of the MIP/SiO2 column. Furthermore, the chromatographic performances of the MIP/SiO2 column were compared with those of other separation materials (such as non-imprinted polymer-coated silica, C18/SiO2, and bare silica) packed columns. The resolution value of all measured compounds was more than 1.51. The column efficiencies of 13 510 plates per meter (N m-1) for sulfamethoxazole, 11 600 N m-1 for ginsenoside Rd, and 10 510 N m-1 for 2'-deoxyadenosine were obtained. The acceptable results verified that the MIP/SiO2 column can be applied to separate highly polar drugs such as sulfonamides, ginsenosides, nucleosides, and pesticides.

A new sustainable filtration membrane extraction method based on nanoconfined liquid phase extraction: Determination of organochlorinated pesticides and pyrethroids in tea samples.

BACKGROUND: Pesticides are used in agricultural production for prevent and control crop diseases and pests, but it is easy to cause excessive pesticides residues in agricultural products, polluting the environment and endangering human health. Due to their unmatched and sustainable capabilities, nanoextraction procedures are becoming every day more important in Analytical Chemistry. In particular, nanoconfined liquid phase extraction has shown extraction capabilities toward polar, medium polar, and/or nonpolar substances, which can be easily modulated depending on the nanoconfined solvent used. Furthermore, this "green" technique showed excellent characteristics in terms of recoveries, extraction time (≤1 min), reliability, and versatility. (97) RESULTS: In this work, the advantages of this technique have been coupled with those of filtration membrane extraction, making use of carbon nanofibers (CnFs) growth on carbon microspheres (CµS). This substrate has been deposited on a filter, which combined with gas chromatographic mass spectrometry (GC-MS) analysis successfully employed for the nanoextraction of 30 pesticides (18 organochlorine and 12 pyrethroids) in tea samples. Under the optimized extraction conditions, the linear range with standard solutions was from 1 to 1000 ng mL-1 (R2 ≥ 0.99), the limit of detections in tea samples were in the range 0.56-17.98 µg kg-1. The accuracy of the developed method was evaluated by measuring the extraction recovery of the spiked tea samples, and recoveries between 74.41 % and 115.46 %. (119) SIGNIFICANCE: Considering the versatility of nanoconfined liquid phase extraction and the functionality of the filtration membrane extraction procedure, this new extraction method can be considered a powerful candidate for automatized high-throughput analyses of real samples. (34).

Enhancing LC×LC separations through multi-task Bayesian optimization.

Method development in comprehensive two-dimensional liquid chromatography (LC×LC) is a challenging process. The interdependencies between the two dimensions and the possibility of incorporating complex gradient profiles, such as multi-segmented gradients or shifting gradients, make trial-and-error method development time-consuming and highly dependent on user experience. Retention modeling and Bayesian optimization (BO) have been proposed as solutions to mitigate these issues. However, both approaches have their strengths and weaknesses. On the one hand, retention modeling, which approximates true retention behavior, depends on effective peak tracking and accurate retention time and width predictions, which are increasingly challenging for complex samples and advanced gradient assemblies. On the other hand, Bayesian optimization may require many experiments when dealing with many adjustable parameters, as in LC×LC. Therefore, in this work, we investigate the use of multi-task Bayesian optimization (MTBO), a method that can combine information from both retention modeling and experimental measurements. The algorithm was first tested and compared with BO using a synthetic retention modeling test case, where it was shown that MTBO finds better optima with fewer method-development iterations than conventional BO. Next, the algorithm was tested on the optimization of a method for a pesticide sample and we found that the algorithm was able to improve upon the initial scanning experiments. Multi-task Bayesian optimization is a promising technique in situations where modeling retention is challenging, and the high number of adjustable parameters and/or limited optimization budget makes traditional Bayesian optimization impractical.

COF-SiO2@Fe3O4 Composite for Magnetic Solid-Phase Extraction of Pyrethroid Pesticides in Vegetables.

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

Ultrasonic-induced grafted lanthanum sulfide decorated multi-walled carbon nanotube onto bacterial cellulose applied for adsorption of pesticides in environmental waters.

A new biosorbent was fabricated by modification of bacterial cellulose biopolymer grafted with lanthanum sulfide decorated carboxylated multiwall carbon nanotube (La2S3@MWCNT@BC). The sorbent was employed in a green alternative dispersive-solid phase extraction of a variety of 14 pesticides in environmental water samples. The analyses were performed using GC-µECD. The properties and structure of La2S3@MWCNT@BC nanocomposite were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and adsorption-desorption isotherms. The composition of the sorbent was also investigated to evaluate the adsorptive properties of its constituents. The impact of various parameters influencing extraction efficacies such as sorbent dose, adsorption time, sample pH, ionic strength, and desorption conditions was investigated. The method was validated by specificity, matrix effect % (-0.4 to -7.4), enrichment factor (4-10), limits of quantification (0.007-0.31 µg L-1), matrix-matched calibration linearity (0.01-200 µg L-1), determination coefficients (r2=0.9921-0.9998), and precision. The optimized method was applied for the analysis of multiclass pesticides in seven environmental and drinking waters and the recoveries were obtained in the 81-108 % range with RSDs of 2.5-4.7 %. This paper is the first report on the synthesis and use of La2S3@MWCNT@BC nanocomposite to extract pesticides from different water samples. The greenness of the procedure was evaluated by the AGREE protocols.

The effectiveness and feasibility of ball-milled powdered activated carbon (BPAC) for removal of organic pesticides in conventional drinking water treatment process.

In the conventional drinking water treatment process (CDWTP), powdered activated carbon (PAC) is commonly used for removing organic pesticides, or other organic contaminants. However, the hydraulic retention time (HRT) in CDWTP is insufficient for fulfilling PAC adsorption equilibrium to realize its full capacity. This study examined the adsorption kinetics, adsorption thermal dynamics, and removal efficiency for six organic pesticides using the ball-milled PAC (BPAC) with varying particle sizes in CDWTP. Based on the experiments with the pesticides of atrazine, diazinon, dimethoate, fenitrothion, isoproturon and thiometon, the results indicated that as the particle size reduced from around 38 µm for the commercial PAC to 1 µm for the BPAC, the adsorption rates for hydrophobic pesticides increased up to twentyfold. Diffusional adsorption from the bulk solution to the external PAC surface is the most likely predominant mechanism. This could allow a sufficient pesticides' adsorption within the limited HRT and to achieve a great depth removal of these toxic compounds. However, the addition of BPAC with a diameter of 1 µm was observed to significantly increase residual particles in treated water after the conventional treatment process. With a further systematic evaluation of both adsorption rate and particle penetration, a particle size of around 6 µm BPAC was considered a practical compromise between the adsorption rate and particle penetration for real application. Results from five surface waters of different water quality indicated that, compared to commercial PAC, application of 6 µm BPAC could achieve up to a 75% reduction in adsorbent dosage while maintaining around the same pesticide removal efficiencies. Additionally, thermodynamic analyses suggest that adsorption of these pesticides could be enthalpically or entropically driven depending on the degree of pesticide hydrophobicity.

NiFe-LDH/nylon 6 composite electrospun on polypropylene membrane: A new extractive device development for porous membrane protected micro-solid-phase extraction of organophosphate pesticides from fresh fruit juice samples coupled with liquid chromatography tandem mass analysis.

A unique strategy for developing porous membrane protected micro-solid phase extraction has been provided. An electrospun composite was fabricated on the sheet of membrane. To this end, NiFe-layered double hydroxide/Nylon 6 composite nanofibers were coated on a polypropylene membrane sheet followed by folding into a pocket shape, which were then utilized as a novel extractive device to extract of organophosphorus pesticides from fresh fruit juice samples prior to liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The fabricated hybrid composites were successfully characterized. The effective parameters on extraction performance were investigated. LODs were 0.020-0.065 ng mL-1. Excellent linearity (R2≥0.996) was observed between 0.05 and 100.0 ng mL-1. RSDs% were in the range of 3.1-5.8% (intra-day, n = 3) and 2.6-5.5% (inter-day, n = 3×3). Satisfactory related recovery values within the acceptable range of 90.7-111.2% with RSDs% below 6.7% were achieved for the analysis of real samples.

Removal of multiple pesticides from water by different types of membranes.

Pesticides are used in agriculture to protect crops from pathogens, insects, fungi and weeds, but the release of pesticides into surface/groundwater by agriculture runoff and rain has raised serious concerns not only for the environment but also for human health. This study aimed to investigate the impact of surface properties on the performance of seven distinct membrane types utilized in nanofiltration (NF), reverse osmosis (RO) and forward osmosis (FO) processes in eliminating multiple pesticides from spiked water. Out of the membranes tested, two are self-fabricated RO membranes while the rest are commercially available membranes. Our results revealed that the self-fabricated RO membranes performed better than other commercial membranes (e.g., SW30XLE, NF270, Duracid and FO) in rejecting the targeted pesticides by achieving at least 99% rejections regardless of the size of pesticides and their log Kow value. Despite the marginally lower water flux exhibited by the self-fabricated membrane compared to the commercial BW30 membrane, its exceptional ability to reject both mono- and divalent salts renders it more apt for treating water sources containing not only pesticides but also various dissolved ions. The enhanced performance of the self-fabricated RO membrane is mainly attributed to the presence of a hydrophilic interlayer (between the polyamide layer and substrate) and the incorporation of hydrophilic nanosheets in tuning its surface characteristics. The findings of the work provide insight into the importance of membrane surface modification for the application of not only the desalination process but also for the removal of contaminants of emerging concern.

A novel honeycomb-like 3D-printed device for rotating-disk sorptive extraction of organochlorine and organophosphorus pesticides from environmental water samples.

In this study, 3D-printing based on fused-deposition modeling (FDM) was employed as simple and cost-effective strategy to fabricate a novel format of rotating-disk sorptive devices. As proof-of-concept, twenty organochlorine and organophosphorus pesticides were determined in water samples through rotating-disk sorptive extraction (RDSE) using honeycomb-like 3D-printed disks followed by gas chromatography coupled to mass spectrometry (GC-MS). The devices that exhibited the best performance were comprised of polyamide + 15 % carbon fiber (PA + 15 % C) with the morphology being evaluated through X-ray microtomography. The optimized extraction conditions consisted of 120 min of extraction using 20 mL of sample at stirring speed of 1100 rpm. Additionally, liquid desorption using 800 µL of acetonitrile for 25 min at stirring speed of 1100 rpm provided the best response. Importantly, the methodology also exhibited high throughput since an extraction/desorption platform that permitted up to fifteen simultaneous extractions was employed. The method was validated, providing coefficients of determination higher than 0.9706 for all analytes; limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.15 to 3.03 µg L-1 and from 0.5 to 10.0 µg L-1, respectively. Intraday precision ranged from 4.01 to 18.73 %, and interday precision varied from 4.83 to 20.00 %. Accuracy was examined through relative recoveries and ranged from 73.29 to 121.51 %. This method was successfully applied to analyze nine groundwater samples from monitoring wells of gas stations in São Paulo. Moreover, the greenness was assessed through AGREEprep metrics, and an overall score of 0.69 was obtained indicating that the method proposed can be considered sustainable.

Synthesis of metal-organic framework @molecularly imprinted polymer adsorbents for solid phase extraction of organophosphorus pesticides from agricultural products.

The novel core-shell structural zeolitic imidazolate framework-8 @molecularly imprinted polymers were successfully synthesized by surface imprinting technique and used as adsorbents for solid-phase extraction of organophosphorus pesticides. The obtained hybrid composites were characterized by scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared, and their adsorbing and recognition performance were evaluated by binding experiments. The results showed that zeolitic imidazolate framework-8 @molecularly imprinted polymers presented a typically core-shell structure with molecularly imprinted shell (about 50 nm) homogeneously polymerized on the surface of zeolitic imidazolate framework-8 core, and exhibited specific recognition towards organophosphorus pesticides with fast adsorption capacity. The adsorption and desorption conditions including sample loading solvent, sample pH, washing and elution solvent were optimized. Under optimum conditions, the solid-phase extraction based on zeolitic imidazolate framework-8 @molecularly imprinted polymers combined with high liquid chromatography-tandem mass spectrometry method for determining organophosphorus pesticides was established and exhibited good linearity (R2 ≥ 0.9927) in the range of 1-200 µg/L. With spiked at three different concentration levels in agricultural products (cauliflower, radish, pear, muskmelon), the recoveries ranged from 82.5% to 123.0% with relative standard deviations lower than 8.24%. The developed method was sensitive, convenient and efficient. More importantly, this study could provide a promising strategy for designing new adsorbents with extremely fast mass transfer rate for other potential trace contaminants.

Determination of Pesticides in Soybean Seeds Incorrectly Discarded Near a Spring of the Paranaíba River, GO-Brazil.

The objective of this research was to evaluate the contamination of pesticides of carbamate and benzimidazole classes in soil, water and soybean seeds, incorrectly discarded near a spring in the state of Goiás-Brazil. The Solid-Liquid and Liquid-Liquid Extraction with Low Temperature Partition (SLE/LTP or LLE/LTP) methods were used for pesticide extraction and the analyses were performed by HPLC-UV. A high resolution mass spectrometer was used to confirm the identity of the compounds present in the seeds. The results showed that the soybeans were treated with the pesticide carbendazim and the dosage was three times higher than established by Brazilian legislation. In the soil and water analyzed there was no presence of the pesticides researched, nor of the carbendazim detected in the seeds. Since this was an environmental crime due to incorrect disposal, it is not known how long ago it occurred. Thus, depending on how long the seeds had been exposed there, the pesticide could have leached out, and caused contamination in the spring and soil. Thus, we conclude that the incorrect disposal of seeds treated with pesticides can be a risk to the permanence of life on the site.

Method validation for determination of nine pesticides in okra and their mitigation using different solutions.

In this paper we optimized QuEChERS method for extraction of nine pesticides viz. acephate, acetamiprid, chlorpyrifos, cypermethrin, imidacloprid, thiamethoxam, profenofos (insecticides), carbendazim and tebuconazole (fungicides) and performed their quantitative estimation in okra crop by HPLC-UV and GC-ECD. Decontamination treatments namely washing with running tap water, soaking in lukewarm water (50-60°C), soaking in solutions of 1% NaCl, 5% NaHCO3, 2% CH3COOH, 0.01% KMnO4 and three commercial formulations were also done for ten minutes every time, to calculate the extent of pesticide removal from okra. Results revealed that the proposed extraction method was efficient, inexpensive, accurate, rapid and precise and can suitably be used for the simultaneous quantitative determination of the above pesticides. The standard curve was linear over the concentration range of 0.05-5µg g-1 with R2 close to one (0.999). Soaking of okra in 2% acetic acid and then washing proved as the best decontamination treatments for all the pesticides. It showed the highest relative decontaminating capacity in comparison to the other solutions tested. Since the pesticide residues are usually present in higher amount in vegetables being consumed, it is of utmost importance to keep an eye over the use of pesticides to protect the crops.

Isolation, characterization and identification of pesticide degrading bacteria from contaminated soil for bioremediation.

In this study, malathion and chlorpyrifos degrading bacteria were isolated from agricultural soil samples taken from the Himachal region in India. A total of 52 organisms were isolated which were further screened for their efficiency for chlorpyrifos and malathion degradation. Screening was done by checking the growth on Nutrient Agar, Mineral Salt Medium and MacConkey agar plates containing chlorpyrifos and malathion; 37 isolates showed growth in these. Biomass assay and minimum inhibitory concentration (MIC) determination were carried out for the selection of most efficient bacterial isolates. Out of the seven isolates which showed good biomass assay and MIC, only three isolates (PDM-2, PDM-15 and PDM-20) were selected for further studies. These were characterized by various biochemical tests, Gram staining, indole test, methyl red test, Voges-Proskauer test, citrate utilization test and carbohydrate fermentation test. Out of three isolates, PDM-15 showed good resistance against the antibiotics such as erythromycin, chloramphenicol, ampicillin and penicillin and identified as Kocuria assamensis. Degradation of 71.3% of chlorpyrifos and 85% of malathion was observed by the gas chromatography. Therefore, the Kocuria assamensis can be used in the bioremediation of pesticide-contaminated soil.

Residual characteristics of etofenprox in the processing stages of rice cakes and cookies.

The changes in residual amounts of an insecticide (etofenprox) in processed rice cakes and cookies were investigated in this study. Test samples were sprayed with etofenprox during rice cultivation, and brown rice samples were dipped in a pesticide solution to investigate the effects of washing and processing. A multiresidue method for multiclass pesticides was employed for etofenprox analysis using a high-performance liquid chromatography-ultraviolet detector setup. Etofenprox was not detected in polished rice that was processed into rice cakes and cookies. The etofenprox residue levels were 2.13 mg/kg in each processing stage of brown rice products that were dipped in 400 mg/kg etofenprox solutions. The residual amounts of etofenprox in washed/polished rice and rice flour obtained by grinding were 1.25 and 0.77 mg/kg, respectively. The residual levels were 0.38 mg/kg in rice cakes prepared by cooking rice flour in a steamer for 20 min (a decrease of 82.1% compared to that in polished rice), 0.47 mg/kg in rice cookies baked in an oven for 20 min (a decrease of 78.0%), and 0.21 mg/kg in fried rice cookies (a decrease of 90.2%). Overall, the residual levels of etofenprox decreased in a range of 40-100% during the processing of rice cakes and cookies.

Chitosan-Graphene Oxide Composite Membranes for Solid-Phase Extraction of Pesticides.

Solid-phase extraction (SPE) coupled to LC/MS/MS analysis is a valid approach for the determination of organic micropollutants (OMPs) in liquid samples. To remove the greatest number of OMPs from environmental matrices, the development of innovative sorbent materials is crucial. Recently, much attention has been paid to inorganic nanosystems such as graphite-derived materials. Graphene oxide has been employed in water-purification processes, including the removal of several micropollutants such as dyes, flame retardants, or pharmaceutical products. Polysaccharides have also been widely used as convenient media for the dispersion of sorbent materials, thanks to their unique properties such as biodegradability, biocompatibility, nontoxicity, and low cost. In this work, chitosan-graphene oxide (CS_GO) composite membranes containing different amounts of GO were prepared and used as sorbents for the SPE of pesticides. To improve their dimensional stability in aqueous medium, the CS_GO membranes were surface crosslinked with glutaraldehyde. The composite systems were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, swelling degree, contact angle, and mechanical measurements. As the GO content increased, a decrease in surface homogeneity, an improvement of mechanical properties, and a reduction of thermal stability of the CS-based membranes were observed. The increased dimensional stability in water, together with the presence of high GO amounts, made the prepared composite membranes more efficacious than the ones based just on CS in isolating and preconcentrating different hydrophilic/hydrophobic pollutants.

Current Applications of Magnetic Nanomaterials for Extraction of Mycotoxins, Pesticides, and Pharmaceuticals in Food Commodities.

Environmental pollutants, such as mycotoxins, pesticides, and pharmaceuticals, are a group of contaminates that occur naturally, while others are produced from anthropogenic sources. With increased research on the adverse ecological and human health effects of these pollutants, there is an increasing need to regularly monitor their levels in food and the environment in order to ensure food safety and public health. The application of magnetic nanomaterials in the analyses of these pollutants could be promising and offers numerous advantages relative to conventional techniques. Due to their ability for the selective adsorption, and ease of separation as a result of magnetic susceptibility, surface modification, stability, cost-effectiveness, availability, and biodegradability, these unique magnetic nanomaterials exhibit great achievement in the improvement of the extraction of different analytes in food. On the other hand, conventional methods involve longer extraction procedures and utilize large quantities of environmentally unfriendly organic solvents. This review centers its attention on current applications of magnetic nanomaterials and their modifications in the extraction of pollutants in food commodities.

Application of a fast and sensitive method for the determination of contaminants of emerging concern in wastewater using a quick, easy, cheap, effective, rugged and safe-based extraction and liquid chromatography coupled to mass spectrometry.

The inefficiency of wastewater treatment plants (WWTPs) to remove contaminants of emerging concern (CECs) leads to their continuous release to the environment. Consequently, CECs are present at low concentrations in the treated wastewater (TWW), producing unpredicted and unwanted effects on living organisms as they are discharged into water receiving bodies. This work presents a fast and reliable method for the determination of CECs in TWW based on the innovative application of a QuEChERS (quick, easy, cheap, effective, rugged and safe) method for water extraction and determination by sensitive liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry (LC-QqLIT-MS/MS). The scope of the proposed QuEChERS-based method allows the monitoring of 107 CECs, including pharmaceuticals (58), antibiotics (16) and pesticides (33). The proposed method was successfully validated in urban TWW at two concentration levels (50 and 500 ng L-1) and it is a feasible alternative to conventional and time-consuming solid-phase extraction (SPE) methodologies. 89% of the CECs presented mean recovery values in the 70-120% range with relative standard deviations (RSDs) always < 20% (intra and inter-day precision), and limits of quantification (LOQs) in the range 5-500 ng L-1 (89% of the compounds showed a LOQ ≤ 50 ng L-1). The applicability of the method was demonstrated by the analysis of urban TWW samples (7 sampling events). In total, 35 CECs (23 pharmaceuticals, 2 antibiotics and 10 pesticides) were detected in the monitored samples with concentrations ranging from 5 to 677 ng L-1.

Dispersive Solid-Phase Extraction of Multiresidue Pesticides in Food and Water Samples.

Pesticides has become an essential part of our life and have entered and bioaccumulated in water, air, soil ecosystem, and food. However, the majority of the pesticides are not biodegradable and eco-friendly, and the accumulation of them in food and the ecosystem could constitute a serious risk to human and environmental health. It is critical to understand pesticides' identities and level of residues present in environment and food. Robust analytical techniques that offer easy, fast, and reliable extraction of multiresidue pesticides in water, soil and food with matrix interference-free quantification are necessary for proper risk assessment. Although various methods have been reported for pesticides extraction in food and environment samples, dispersive solid-phase extraction (d-SPE) has become the most popular sample preparation method for pesticides analysis today. Multiresidue pesticides extraction in food and environmental sample using a novel d-SPE method, dispersive pipette extraction (DPX), is described step-by-step in this chapter.

Magnetic molecularly imprinted polymer nanoparticles for the extraction and clean-up of thiamethoxam and thiacloprid in light and dark honey.

In this work, new selective and sensitive dual-template molecularly imprinted polymer nanoparticles (MIPs) were synthesized and characterized. Sorbent MIPs were investigated for simultaneous extraction and clean-up of thiamethoxam and thiacloprid from light and dark honey samples. In this study, ultra-high-performance liquid chromatography-tandem mass spectrometry triple-quadrupole (UHPLC-MS/MS) (QQQ) was used to detect and quantify the pesticides. The kinetic model with adsorption kinetics of sorbent was investigated. The optimal adsorption conditions were 80 mg of polymer MIPs, a 30-min extraction time, and a pH of 7. The detection limit (LOD) and the quantification limit (LOQ) varied from 0.045 to 0.070 µg kg-1 and from 0.07 to 0.10 µg kg-1, respectively. The intra-day and inter-day precision (RSD, %) ranged from 1.3 to 2.0% and from 8.2 to 12.0%, respectively. The recovery of thiamethoxam and thiacloprid ranged from 96.8 to 106.5% and 95.3 to 104.4%, respectively, in light and dark honey samples.