Biomass waste-derived magnetic material coated with dual-dummy-template molecularly imprinted polymer for simultaneous extraction of organophosphorus and carbamate pesticides.

An eco-friendly biomass waste-derived magnetic material coated with a dual-dummy-template molecularly imprinted polymer was fabricated using aqueous ethanol as a green porogen, lower amounts of toxic compounds as template molecules, and tyrosine and tryptophan as biocompatible binary monomers. The binding characteristics and selectivity of the material toward pesticides were assessed. High adsorption capacities ranging from 150.11 to 509.09 mg g-1 and imprinting factors reaching 2.2 were achieved within just 30 s. The material was applied for extraction of organophosphorus and carbamate pesticides prior to HPLC analysis. Under the optimum conditions, low limits of detection and quantitation were achieved, with ranges of 0.05-1.49 µg/L and 0.18-5.00 µg/L, respectively. The established approach enables efficient analysis of vegetable and fruit samples, yielding satisfactory recoveries ranging between 80 and 110 %. The method showed promise as an analytical method for the sensitive enrichment of pesticide residues in vegetable and fruit samples.

Molecularly imprinted polymer-coated paper for the selective extraction of organophosphorus pesticides from fruits, vegetables, and cereal grains.

Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule, terephthalic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and aqueous ethanol as a green porogenic solvent. The material was subsequently composited onto cellulose paper, which served as the natural substrate, by dip coating with the aid of chitosan and citric acid natural adhesive. The properties, such as static and dynamic adsorption, selectivity, and reusability, were assessed. At rapid adsorption equilibrium (10 min), the MIP@paper had a high adsorption capacity in the range of 2.5-3.7 mg g-1 and good recognition with imprinting factors up to 2.1. In addition, the proposed MIP@paper was utilized efficiently as a sorbent for dispersive solid phase extraction (d-SPE) of eight organophosphorus pesticides (OPPs) prior to high-performance liquid chromatography (HPLC) analysis. The d-SPE-HPLC method displayed low detection limits of 1.2-4.5 µg kg-1 and significant enrichment factors (up to 320-fold). The proposed method was effectively applied for the determination of OPP residues in agricultural products, including fruits, vegetables, and cereal grains, with satisfactory spiked recoveries (80.1-119.1 %). Thus, the MIP@paper material provided a selective and environmentally favorable method for extracting and determining organophosphorus pesticides.

Eco-friendly fabrication of a magnetic dual-template molecularly imprinted polymer for the selective enrichment of organophosphorus pesticides for fruits and vegetables.

A magnetic dual-template molecularly imprinted polymer (DMIP) was successfully prepared in an aqueous medium and used as a sorbent for the selective extraction of organophosphorus pesticides prior to analysis by high-performance liquid chromatography (HPLC). The binding properties and selectivity of DMIP toward organophosphorus were evaluated and compared with those of a non-imprinted polymer. The established magnetic dispersive solid-phase extraction (MDSPE) method using DMIP exhibited fast enrichment of the target analytes within 60 s for adsorption and 30 s for desorption. Good linearities in the range of 0.5-2000 µg L-1 with coefficients of determination (R2) greater than 0.9930 were observed. The method provides low limits of detection of 0.062-0.195 µg L-1 and limits of quantification of 0.210-0.640 µg L-1 with relative standard deviations of less than 9.5% for intra- and inter-day analyses. The enrichment factors ranged from 464 to 621. Satisfactory recoveries ranged from 81.3 to 110.0% with relative standard deviations below 11%.

Simple magnetization of Fe3 O4 /MIL-53(Al)-NH2 for a rapid vortex-assisted dispersive magnetic solid-phase extraction of phenol residues in water samples.

The present work describes a simple route to magnetize MIL-53(Al)-NH2 sorbent for rapid extraction of phenol residues from environmental samples. To extend the applications and performances of the metal-organic frameworks in the field of adsorption materials, we combined the properties of metal-organic frameworks and magnetite to decrease the extraction time and simplify the extraction process as well. In this study, a simple and quick vortex-assisted dispersive magnetic solid phase extraction method for the extraction of ten United States Environmental Protection Agency's priority phenols from water samples prior to analysis by high-performance liquid chromatography with photodiode array detection was proposed. The developed method exhibits a rapid enrichment of the target analytes within 10 s for extraction and 10 s for desorption. Low detection limits of 1.8-41.7 µg/L and quantitation limits of 6.0-139.0 µg/L with the relative standard deviations for intra- and interday analyses less than 12% were achieved. Satisfactory recoveries in the range of 80-111% with the relative standard deviations less than 11% demonstrated that Fe3 O4 /MIL-53(Al)-NH2 is promising sorbent in the field of magnetic solid-phase extraction for environmental samples.

Prevalence of per- and polyfluoroalkyl substances (PFASs) in drinking and source water from two Asian countries.

The present study focuses on the determination of the occurrence and levels of per- and polyfluoroalkyl substances (PFASs) in the drinking and source water from the Philippines and Thailand. A total of 46 samples (18 commercial bottled waters, 5 drinking water from vending machine (re-fill stations) and 23 source water) were analyzed using liquid chromatography with tandem high-resolution mass spectrometry. Using the targeted method, 12 different PFASs were detected in the drinking water samples with total quantifiable PFASs (∑PFASs) levels ranging from 7.16 to 59.49 ng/L; 15 PFASs were detected in source water with ∑PFASs ranging from 15.55 to 65.65 ng/L. A 100% detection frequency was observed for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorosulfonic acid (PFOS) in all water samples. Six other PFASs, not included in the targeted analysis, were detected using the suspect screening approach. For the first time, the presence of 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA) in drinking water is reported, and 3 novel PFASs (C5H5OF8, C6H4O2F6, and C9H2O2F16) were detected using suspect screening in source water. Combined results from target and suspect screening analysis showed that PFASs detected were predominantly (52%) short-chain (with fluorinated alkyl chain of ≤6) which could be explained by their high mobility in the environment. The detected PFASs levels in drinking water will not likely pose immediate health risk to consumers according to US EPA health advisory for PFOS and PFOA of 70 ng/L, but inclusion of bottled and drinking water from re-fill stations in monitoring programs is warranted.

Evaluation of metal-organic framework NH2-MIL-101(Fe) as an efficient sorbent for dispersive micro-solid phase extraction of phenolic pollutants in environmental water samples.

This work proposes an application of amine-functionalized metal-organic framework (NH2-MIL-101(Fe)) as sorbent for dispersive micro-solid phase extraction (D-µSPE) of ten priority phenolic pollutants. The sorbent was simply synthesized under facile condition. The entire D-µSPE process was optimized by studying the effect of experimental parameters affecting the extraction recovery of the target analytes. The final extract was analyzed using high performance liquid chromatography with photodiode array detector. Under the optimum condition, the proposed procedure can be applied for wide linear calibration ranges between 1.25-5000 µg L-1 with the correlation coefficients of greater than 0.9900. The limits of detection (LODs) and limits of quantitation (LOQs) were in the ranges of 0.4-9.5 µg L-1 and 1.25-30 µg L-1, respectively. The precision evaluated in terms of the relative standard deviations (RSDs) of the intra- and inter-day determinations of the phenol compounds at their LOQ concentrations were below 13.9% and 12.2%, respectively. High enrichment factors up to 120 were reached. The developed method has been successfully applied to determine phenol residues in environmental water samples. The satisfactory recoveries obtained by spiking phenol standards at two different concentrations (near LOQs and 5 times as high as LOQs) ranged from 68.4-114.4%. The results demonstrate that the NH2-MIL-101(Fe) material is promising sorbent in the D-µSPE of phenolic pollutants.