Extraction of Common Small Microplastics and Nanoplastics Embedded in Environmental Solid Matrices by Tetramethylammonium Hydroxide Digestion and Dichloromethane Dissolution for Py-GC-MS Determination.

Determination of microplastics and nanoplastics (MNPs), especially small MPs and NPs (<150 µm), in solid environmental matrices is a challenging task due to the formation of stable aggregates between MNPs and natural colloids. Herein, a novel method for extracting small MPs and NPs embedded in soils/sediments/sludges has been developed by combining tetramethylammonium hydroxide (TMAH) digestion with dichloromethane (DCM) dissolution. The solid samples were digested with TMAH, and the collected precipitate was washed with anhydrous ethanol to eliminate the natural organic matter. Then, the MNPs in precipitate were extracted by dissolving in DCM under ultrasonic conditions. Under the optimized digestion and extraction conditions, the factors including sizes and concentrations of MNPs showed insignificant effects on the extraction process. The feasibility of this sample preparation method was verified by the satisfactory spiked recoveries (79.6-91.4%) of polystyrene, polyethylene, polypropylene, poly(methyl methacrylate), polyvinyl chloride, and polyethylene terephthalate MNPs in soil/sediment/sludge samples. The proposed sample preparation method was coupled with pyrolysis gas chromatography-mass spectrometry to determine trace small MPs and NPs with a relatively low detection limit of 2.3-29.2 µg/g. Notably, commonly used MNPs were successfully detected at levels of 4.6-51.4 µg/g in 6 soil/sediment/sludge samples. This proposed method is promising for evaluating small solid-embedded MNP pollution.

Hydroxyl-containing triazine-based conjugated microporous polymers for solid phase extraction of fluoroquinolone antibiotics in the environment and food samples.

Fluoroquinolones (FQs) are a category of broadly used antibiotics. Development of an effective and sensitive approach for determination of trace FQs in environmental and food samples is still challenging. Herein, the hydroxyl-containing triazine-based conjugated microporous polymers (CMPs-OH) was constructed and served as SPE absorbent for the efficient enrichment of FQs. Based on DFT simulations, the excellent enrichment capacity between CMPs-OH and FQs was contributed by hydrogen bonding and π-π interactions. In combination with high-performance liquid chromatography-tandem mass spectrometry, the proposed approach exhibited a wide linear range (0.2-400 ng L-1), low detection limits (0.05-0.15 ng L-1), and good intraday and interday precisions under optimal conditions. In addition, the established method was effectively utilized for the determination of FQs in fourteen samples with recoveries between 82.6 % and 109.2 %. This work provided a feasible sample pretreatment method for monitoring FQs in environmental and food matrices.

Cloud point extraction coupled with HPLC-UV for the determination of phthalate esters in environmental water samples.

A method based on cloud point extraction was developed to determine phthalate esters including di-ethyl-phthalate (DEP), di-(2-ethylhexyl)-phthalate (DEHP) and di-cyclohexyl-phthalate (DCP) in environmental water samples using high-performance liquid chromatography separation and ultraviolet detection (HPLC-UV). The non-ionic surfactant Triton X-114 was chosen as extraction solvent. The parameters affecting extraction efficiency, such as concentrations of Triton X-114 and Na2SO4, equilibration temperature, equilibration time and centrifugation time were evaluated and optimized. Under the optimum conditions, the method can achieve preconcentration factors of 35, 88, 111 and detection of limits of 2.0, 3.8, 1.0 ng/ml for DEP, DEHP and DCP in 10-ml water sample, respectively. The proposed method was successfully applied to the determination of trace amount of phathalate esters in effluent water of the wastewater treatment plant and the lixivium of plastic fragments.

Polydopamine-coated magnetic nanoparticles for enrichment and direct detection of small molecule pollutants coupled with MALDI-TOF-MS.

Polydopamine-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@PDA NPs) were synthesized and applied as matrix for the detection of pollutants by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The synthesis of Fe(3)O(4)@PDA NPs was accomplished in 30 min by in situ polymerization of dopamine without any toxic reagent. Using Fe(3)O(4)@PDA NPs as matrix of MALDI-TOF, eleven small molecule pollutants (molecular weight from 251.6 to 499.3), including Benzo(a)pyrene (BaP), three perfluorinated compounds (PFCs), and seven antibiotics, were successfully detected in either positive or negative reflection mode without background interference. Furthermore, the Fe(3)O(4)@PDA NPs can also enrich trace amounts of hydrophobic target, such as BaP, from solution to nanoparticles surface. Then the Fe(3)O(4)@PDA-BaP can be isolated through magnetic sedimentation step and directly spotted on the stainless steel plate for MALDI measurement. With Fe(3)O(4)@PDA NPs as adsorbent and matrix, we also realized the analysis of BaP in tap water and lake water samples. Thus, a magnetic solid-phase extraction (MSPE)-MALDI-TOF-MS method was established for the measurement of BaP.