Direct Immersion Solid-phase Microextraction Method Research Articles

Insight into the interaction of tetrabromobisphenol A with sediment-derived dissolved organic carbon in a multiphase system by direct immersion solid phase microextraction

Tetrabromobisphenol A (TBBPA), a ubiquitously used commercial brominated flame retardant (BFR), has been widely detected in aquatic environments, and has aroused much attention due to its potential adverse effects on aquatic organisms. However, current research on the environmental fate and transport of TBBPA in the sediment–dissolved organic carbon (DOC)–water polyphase system is lacking. In this study, the sorption behavior of TBBPA in a water–DOC–sediment system was investigated using the direct-immersion solid-phase microextraction (DI-SPME) method, and the free dissolved concentration (Cw-SPME) and DOC adsorption concentration (CDOC) of TBBPA in water were measured by applying this DI-SPME approach. In addition, the effects of pH, ionic strength, and soluble organic concentration on the adsorption of TBBPA in the multiphase system were evaluated. The adsorption kinetics experimental results show that the adsorption behavior of TBBPA on sediments conforms to a linear model, suggesting that it could be mainly absorbed by sediments. The solid–water partition coefficient (Kd) of TBBPA was artificially reduced 1.54 times using the traditional liquid–liquid extraction method because the sorption behavior of the DOC was ignored, which could be accurately corrected using the DI-SPME method. The logKd and logKOC of TBBPA in the multiphase system were 4.12 ± 0.25 and 6.48 ± 0.25, respectively. Finally, the interference experiment revealed that the sorption behavior of TBBPA was affected by the pH, ionic strength (calcium ion), and humic acid concentration, apart from the lead ion concentration itself.

Spatiotemporal Distribution of Hydrophobic Organic Contaminants in Spiked-Sediment Toxicity Tests: Measuring Total and Freely Dissolved Concentrations in Porewater and Overlying Water.

The sediment–water interface of spiked‐sediment toxicity tests is a complex exposure system, where multiple uptake pathways exist for benthic organisms. The freely dissolved concentration (C free) in sediment porewater has been proposed as a relevant exposure metric to hydrophobic organic contaminants (HOCs) in this system. However, C free has rarely been measured in spiked‐sediment toxicity tests. We first developed a direct immersion solid‐phase microextraction method for measuring C free in overlying water and porewater in a sediment test using polydimethylsiloxane‐coated glass fibers, resulting in sensitive and repeatable in situ measurements of HOCs. Then, we measured C free and total dissolved concentrations (C diss) in the sediment test systems with the freshwater amphipod Hyalella azteca and thoroughly evaluated the temporal and spatial profiles of four HOCs (phenanthrene, pyrene, benzo[a]pyrene, and chlorpyrifos). Furthermore, we examined the relationship between the measured concentrations and the lethality of H. azteca. We found that the test system was far from an equilibrium state for all four chemicals tested, where C diss in overlying water changed over the test duration and a vertical C free gradient existed at the sediment–water interface. In porewater C diss was larger than C free by a factor of 170 to 220 for benzo[a]pyrene because of the strong binding to dissolved organic carbon. Comparison of the median lethal concentrations of chlorpyrifos in the sediment test and those in water‐only tests indicates that C free in porewater was the most representative indicator for toxicity of this chemical. The method and findings presented in the present study warrant further research on the chemical transport mechanisms and the actual exposure in sediment tests using different chemicals, sediments, and test species. Environ Toxicol Chem 2021;40:3148–3158. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Carboxylation modified meso-porous carbon aerogel templated by ionic liquid for solid-phase microextraction of trace tetracyclines residues using HPLC with UV detection

A carbon aerogel composite templated and catalyzed by ionic liquid was fabricated to obtaina meso-porous and cross-linked structure while avoiding the freeze and supercritical drying. It was then carboxylated to obtain favorable surface groups. The easily prepared material displayed excellent extraction effect of six tetracyclines (TCs) compared to the non-carboxylated carbon aerogel. A direct immersion solid-phase microextraction method to determine six TCs in aqueous samples was developed coupling with high-performance liquid chromatography (HPLC) with UV-Vis detector set at 355nm. The experimental parameters affecting the analytical performance of this method, including sample pH, ionic strength, extraction and desorption time, extraction volume, and temperature, were optimized. Adsorption kinetics and thermodynamics models were used to clarify the extraction mechanism. Under the optimized conditions, this method has awide linear range of 2-1000μgL-1, low limits of detection of 0.36-0.71μgL-1, repeatability of 1.85-10.96%, and reproducibility of 4.92-13.47% for six TCs. The method was successfully applied to detect TC residues in egg and poultry farm wastewater samples.

Carbon aerogel as a solid-phase microextraction fiber coating for the extraction and detection of trace tetracycline residues in food by coupling with high-performance liquid chromatography.

A direct immersion solid-phase microextraction method for determining tetracyclines (TCs) was developed by coupling with high-performance liquid chromatography. A carbon aerogel (CA) was synthesized as a fiber coating with high extractive properties and a low density of 0.1855 g cm-3via ambient pressure drying and carbonization. The as-synthesized CA exhibited a high specific surface area and a cross-linked structure; it was characterized via scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and Brunauer-Emmett-Teller analysis, etc. The extraction performance for six TCs was investigated, and the main experimental parameters were optimized by the Box-Behnken design. Adsorption kinetics, Langmuir and Freundlich models were used to clarify the extraction mechanism. This method showed wide linear ranges of 1-500 μg L-1, low limits of detection of 0.52-1.05 μg L-1, good repeatability of 1.37-12.47%, and satisfactory inter-fiber reproducibility of 8.51-15.81% relative standard deviation for the detection of six TCs. Moreover, this study provided an interesting insight into the detection of TCs residues in food samples.

Overcoming matrix effects in the analysis of pyrethroids in honey by a fully automated direct immersion solid-phase microextraction method using a matrix-compatible fiber

Pyrethroids insecticides may constitute a major hazard to honeybees, leading to colony collapse disorder. However, the determination of pyrethroids in honey has remained a challenging undertaking for analysts to date due to the high complexity of this matrix as well as the MRLs. This paper presents a fully automated method to overcome matrix influences using matrix-compatible overcoated SPME fiber for quantitative analysis of pyrethroids in diluted honey by GC–MS. The developed method was optimized using a multivariate approach providing LOQ values much lower than the stablished MRL (0.10–10 ng/g), while granting satisfactory linearity (R2 > 0.998) in a wide linear range of 0.1–2000 ng/g, repeatability with RSDs < 10%, reproducibility RSDs < 20%, and accuracy ranging from 75 to 118% and from 82 to 120 % for inter-day and intra-day assays, respectively by using five replicates. The method herein proposed overcomes challenges presented by complex matrices while minimizing sample handling and the overall complexity of the procedure.

Magnesium/aluminum-layered double hydroxide modified with hydrogen peroxide as a novel fiber coating for solid-phase microextraction of phthalate esters in aqueous samples

A novel coating material for solid-phase microextraction (SPME) was synthesized by treating magnesium/aluminum-layered double hydroxide (Mg/Al-LDH) with hydrogen peroxide in the presence of potassium iodide and was confirmed to be chemically and thermally stable. A direct immersion solid-phase microextraction method to determine phthalate esters (PAEs) in aqueous samples was developed using the constructed fiber coating to couple with gas chromatography. Several factors on SPME procedure were investigated in detail. Under the optimized conditions, the linear ranges of the developed method were between 1 and 500 μg L−1. The limits of detection and the limits of quantification for various phthalates were in the range of 0.42–1.29 μg L−1 and 1.40–4.13 μg L−1, respectively. The run-to-run RSD (n = 5) and the fiber-to-fiber RSD (n = 3) were 8.30–20.0% and 8.50–20.4%, respectively. This method was successfully applied to the analysis of PAEs from Yangtze River water samples and bottled mineral samples.

Improved method for quantification of persistent organic pollutants and its remediation using modified clays materials

This study reports a direct immersion solid-phase microextraction method (DI-SPME) for the analysis of persistent organic pollutants (POPs), especially pesticide endosulfan, and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) present at trace levels in water samples. The identification and quantification was performed by gas chromatography coupled to mass spectrometry (GC/MS). The optimized and validated methodology showed LOQs for endosulfan α and endosulfan β of 916.0 and 126.0 ng L−1 respectively, and for 2,3,7,8-TCDD of 10.0 ng L−1. Subsequently bentonite and vermiculite materials modified with cetyltrimethylammonium (CTA+) (B3CTA, B7CTA and B15CTA; V3CTA, V7CTA and V15CTA) were prepared, characterized and studied for the remediation of POPs in water.

Application of headspace and direct immersion solid-phase microextraction in the analysis of organothiophosphates related to the Chemical Weapons Convention from water and complex matrices

The successful application of headspace (HS) and direct immersion (DI) solid phase microextraction (SPME) for the unambiguous identification and characterization of a series of toxic thiophosphate esters, such as Amiton (I), from aqueous phases and complex matrices (e.g. grass and foliage) has been demonstrated. A Thermo Scientific gas chromatograph (GC) – tandem mass spectrometer (MS/MS) system with a TriPlus RSH® autosampler and a SPME tool was used to investigate the effect of different parameters that influence the extraction efficiency: e.g. pH of the sample matrix and extraction temperature.The developed methods were employed for the detection of several Amiton derivatives (Schedule II of the CWC) that are structurally closely related to each other; some of which are new and have not been reported in literature previously. In addition, a novel DI SPME method from complex matrices for the analysis of organophosphates related to the CWC was developed. The studies clearly show that DI SPME for complex matrices is superior to HS extraction and can potentially be applied to other related compounds controlled under the CWC.

Direct immersion solid-phase microextraction with gas chromatography and mass spectrometry for the determination of specific biomarkers of human sweat in melted snow.

To provide a reliable tool for investigating diffusion processes of the specific components of the human odor 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol through the snowpack, we developed and optimized an analytical method based on direct immersion solid-phase microextraction followed by gas chromatography with mass spectrometry. Direct immersion solid-phase microextraction was performed using polyacrylate fibers placed in aqueous solutions containing 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol. After optimization, absorption times of 120 min provided a good balance to shorten the analysis time and to obtain suitable amounts of extractable analytes. The extraction efficiency was improved by increasing the ionic strength of the solution. Although the absolute extraction efficiency ranged between 10 and 12% for 3-hydroxy-3-methylhexanoic acid and 2-3% for 3-methyl-3-sulfanylhexan-1-ol, this method was suitable for analyzing 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol concentrations of at least 0.04 and 0.20 ng/mL, respectively. The precision of the direct immersion solid-phase microextraction method ranged between 8 and 16%. The variability within a batch of six fibers was 10-18%. The accuracy of the method provided values of 88-95 and 86-101% for 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol, respectively. The limit of detection (and quantification) was 0.01 ng/mL (0.04 ng/mL) for 3-hydroxy-3-methylhexanoic acid and 0.06 ng/mL (0.20 ng/mL) for 3-methyl-3-sulfanylhexan-1-ol. The signal versus concentration was linear for both compounds (r(2) = 0.973-0.979). The stability of these two compounds showed that 3-hydroxy-3-methylhexanoic acid was more stable in water than 3-methyl-3-sulfanylhexan-1-ol. We applied the method to environmental samples in correspondence with an olfactory target buried previously.

Automated direct-immersion solid-phase microextraction using crosslinked polymeric ionic liquid sorbent coatings for the determination of water pollutants by gas chromatography.

Four different crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were evaluated in an automated direct-immersion solid-phase microextraction method (automated DI-SPME) in combination with gas chromatography (GC). The crosslinked PIL coatings were based on vinyl-alkylimidazolium- (ViCnIm-) or vinylbenzyl-alkylimidazolium- (ViBzCnIm-) IL monomers, and di-(vinylimidazolium)dodecane ((ViIm)2C12-) or di-(vinylbenzylimidazolium)dodecane ((ViBzIm)2C12-) dicationic IL crosslinkers. In addition, a PIL-based hybrid coating containing multi-walled carbon nanotubes (MWCNTs) was also studied. The studied PIL coatings were covalently attached to derivatized nitinol wires and mounted onto the Supelco assembly to ensure automation when acting as SPME coatings. Their behavior was evaluated in the determination of a group of water pollutants, after proper optimization. A comparison was carried out with three common commercial SPME fibers. It was observed that those PILs containing a benzyl group in their structures, either in the IL monomer and crosslinker (PIL-1-1) or only in the crosslinker (PIL-0-1), were the most efficient sorbents for the selected analytes. The validation of the overall automated DI-SPME-GC-flame ionization detector (FID) method gave limits of detection down to 135 μg · L(-1) for p-cresol when using the PIL-1-1 and down to 270 μg · L(-1) when using the PIL-0-1; despite their coating thickness: ~2 and ~5 μm, respectively. Average relative recoveries with waters were of 85 ± 14 % and 87 ± 15 % for PIL-1-1 and PIL-0-1, respectively. Precision values as relative standard deviation were always lower than 4.9 and 7.6 % (spiked level between 10 and 750 μg · L(-1), as intra-day precision). Graphical Abstract Automated DI-SPME-GC-FID using crosslinked-PILs sorbent coatings for the determination of waterpollutants.