Direct Immersion Solid-phase Microextraction Research Articles

Biopolymer-imidazolium based dicationic ionic liquid modified clay bionanocomposite coating for solid-phase microextraction of phthalate esters

In this study, biopolymer-ionic liquid modified clay bionanocomposite was used as a coating for solid phase microextraction fiber to improve the analysis of plasticizers. Montmorillonite (MMT) clay intercalated with carboxymethyl cellulose (CMC) and dicationic imidazolium-based ionic liquid (Im-DIL) was coated onto an etched and hydroxyl functionalized stainless steel wire. The prepared MMT/CMC/Im-DIL coated fiber was assessed for the determination of six phthalate esters (PAEs) using direct immersion solid-phase microextraction (DI-SPME) with gas chromatography/mass spectrometer (GC/MS). Compared to MMT, MMT/CMC, MMT/Im-DIL, MMT/CMC/Im-DIL coating displayed much better extraction performance (>nearly 486–20 times). Under optimized conditions, the proposed method performed wide linearity (0.01–400.0 µg L-1), low limit of detection (1.0 ng L-1), satisfactory extraction repeatability (RSD%, ⩽ 3.86) and preparation repeatability (RSD%, ⩽ 5.79). The proposed method was applied successfully for analyzing of PAEs in beer, mineral water and carbonated lemonade drink.

Membrane-protected covalent organic framework fiber for direct immersion solid-phase microextraction of 17beta-estradiol in milk

17beta-estradiol (E2) could accumulate in human body through milk and cause various diseases by interfering with the endocrine system. Herein, we coated stainless steel wire with covalent organic framework LZU1 (COF-LZU1) and Nafion protected by dialysis membrane for direct immersion solid phase microextraction (DI-SPME) and coupled with gas chromatography-flame ionization detection (GC-FID) for the detection of trace E2 in milk samples. With dialysis membrane protection, the stability of SPME fiber was improved and the extraction efficiency was only reduced by 7% after repeated use of 160 times. The extraction efficiency of E2 with the home-made fiber COF-LZU1 was 22.1, 8.4, 3.6 times higher than that of bare stainless steel wire, PDMS/DVB and PDMS, respectively. The method had been successfully applied to milk samples, and the relative recoveries were between 77.27% and 108.26%. It can provide an effective and general method for the pretreatment of complex matrix samples.

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.

High-efficiency solid-phase microextraction performance of polypyrrole enhanced titania nanoparticles for sensitive determination of polar chlorophenols and triclosan in environmental water samples.

In this work, a polypyrrole (PPy)/TiO2 nanocomposite coating was fabricated by the direct electropolymerization of pyrrole on annealed TiO2 nanoparticles and evaluated as a novel direct immersion solid phase microextraction (DI-SPME) fiber coating for extraction of trace amounts of pollutants in environmental water samples. The functionalized fiber is mechanically and chemically stable, and can be easily prepared in a highly reproducible manner. The effects of the pyrrole monomer concentration, polymerization voltage and polymerization time on the fiber were discussed. Surface morphological and compositional analyses revealed that the composite coating of nano polypyrrole and titanium dioxide nanoparticles (TiO2NPs) uniformly doped the Ti substrate. The as-fabricated fiber exhibited good extraction capability for phenolic compounds in combination with high performance liquid chromatography-UV detection (HPLC-UV). At the optimum SPME conditions, the calibration curves were linear (R2 ≥ 0.9965). LODs and LOQs of less than 0.026 μg L−1 and 0.09 μg L−1 , respectively, were achieved, and RSDs were in the range 3.5–7.2%. The results obtained in this work suggest that PPy/TiO2 is a promising coating material for future applications of SPME and related sample preparation techniques.

Development of a bimetal-organic framework-polypyrrole composite as a novel fiber coating for direct immersion solid phase microextraction in situ supercritical fluid extraction coupled with gas chromatography for simultaneous determination of furfurals in dates.

A new, simple, hyphenated technique couples supercritical fluid extraction and direct immersion SPME with GC-FID (SFE-DI-SPME-GC-FID) for the determination of 2-furaldehyde (2-F) and 5-hydroxymethylfurfural (5-HMF) in solid foods. A bimetal-organic framework-polypyrrole composite was grown in situ on stainless steel wire in solution and used as a novel solid phase microextraction (SPME) fiber coating. A central composite design based on a 2n-1 fractional factorial experimental design was employed to optimize the SFE conditions for 2-F and 5-HMF at a pressure of 325 atm, temperature of 35 °C, dynamic extraction time of 15 min, and modifier volume of 150 μL. Also, the factors related to the solid-phase microextraction method including ionic strength, desorption time and temperature together with extraction time and temperature were optimized prior to the gas chromatography analysis. Under the optimal conditions, the limits of detection were in the range of 1.28-5.92 μg kg-1. This method showed good linearity for 2-F and 5-HMF in the ranges of 40-50 000 and 4540-500 000 μg kg-1, respectively, with coefficients of determination more than 0.9995. Single fiber repeatability and fiber-to-fiber reproducibility were less than 6.76% and 9.12%, respectively. The new method was successfully utilized to determine the amounts of 2-F and 5-HMF in the real solid food matrix without the need for tedious pretreatments.

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.

Copper ferrite nanoparticles as novel coating appropriated to solid-phase microextraction of phthalate esters from aqueous matrices

The prepared CuFe2O4 nanoparticles (NPs) resulting from a facile citrate–nitrate combustion method were adhesived on stainless steel wire with epoxy glue as a novel fiber coating. A direct immersion solid-phase microextraction (DI-SPME) method based on the prepared coating was established through sensitively detecting four phthalate esters (PAEs) from aqueous media with gas chromatography-flame ionization detection (GC-FID). The effects of various parameters on the efficiency of SPME process such as extraction time, extraction temperature, pH, ionic strength, desorption time, and desorption temperature were studied. Under optimized conditions, the limit of detections (LODs) and quantifications (LOQs) for the phthalate esters varied in the range of 0.12–0.40 μg·L−1 and 0.40–1.33 μg·L−1, respectively. The inter-day and intra-day relative standard deviations for these varied phthalate esters at 10 μg·L−1 concentration level (n = 6) using a single fiber were 3.9–12.4% and 6.6–15.1%, respectively. The fiber to fiber repeatabilities (n = 3), expressed as relative standard deviation (RSD%), were between 9.9% and 16.5% at 10 μg·L−1 concentration levell, and the the linear ranges varied between 1 and 500 μg·L−1. The prepared fiber can be repeatedly used to exceed 80 times, revealing a long lifetime and good stability. The method was successfully applied to analysis of the mineral water samples with recoveries from 81.1 to 103.7%. This work also provided an interesting insight for stable SPME fiber prepared by spinel materials for efficient extraction of PAEs.

Assessment of Soybean Oil Oxidative Stability from Rapid Analysis of its Minor Component Profile

The minor components of vegetable oils are important for their oxidative stability. In order to know to what extent they can influence oil behaviour under oxidative conditions, two commercial soybean oils, one virgin and the other refined, both with very similar compositions in acyl groups but differing in their minor component profiles, were subjected to accelerated storage conditions. They were characterized by 1H nuclear magnetic resonance (NMR) and direct immersion solid-phase microextraction coupled to gas chromatography/mass spectrometry (DI-SPME-GC/MS), while oil oxidation was monitored by 1H-NMR. The lower levels of tocols and sterols in the virgin oil, together with its higher free fatty acid content when compared to the refined one, result in a lower oxidative stability. This is deduced from faster degradation of acyl groups and earlier generation of hydroperoxides, epoxides, and aldehydes in the virgin oil. These findings reveal that commercial virgin soybean oil quality is not necessarily higher than that of the refined type, and that a simple and rapid analysis of oil minor components by DI-SPME-GC/MS would enable one to establish quality levels within oils originating from the same plant species and similar unsaturation level regarding composition in potentially bioactive compounds and oxidative stability.

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.

Green solid-phase microextraction fiber coating based on the metal-organic framework CIM-80(Al): Analytical performance evaluation in direct immersion and headspace using gas chromatography and mass spectrometry for the analysis of water, urine and brewed coffee

A new solid-phase microextraction (SPME) fiber coating was prepared by the immobilization of the metal-organic framework (MOF) CIM-80(Al) on nitinol wires by a green in situ growth approach, using an aqueous synthetic approach, and without the need of any additional material to ensure the attachment of the MOF to the nitinol support. The coating was used for the development of headspace (HS) and direct immersion (DI) SPME methods in combination with gas chromatography and mass spectrometry (GC-MS) for the determination of polycyclic aromatic hydrocarbons (PAHs) as model compounds. Both methods were optimized and validated using the MOF-based fiber together with the commercial polydimethylsiloxane (PDMS) fiber. The MOF extraction phase exhibited superior analytical performance for most of the PAHs in HS-SPME mode (and particularly for less volatiles), while the PDMS fiber presented better results in the DI-SPME method. The analytical performance of the MOF sorbent coating in HS- and DI-SPME methods was also evaluated in urine and brewed coffee samples, without requiring any pretreatment step apart from dilution for DI-SPME experiments, thus showing suitability of the novel coatings for the analysis of complex samples. The proposed CIM-80(Al) fiber was efficient and biocompatible (for using a low cytotoxic sorbent and a biocompatible core support), and it also demonstrated stability and robustness, with inter-fiber (and inter-day) relative standard deviation values lower than 19%, and reusability for more than 80 extraction cycles using 280 °C as desorption temperature.

Molecularly imprinted polymers immobilized on graphene oxide film for monolithic fiber solid phase microextraction and ultrasensitive determination of triphenyl phosphate

Triphenyl phosphate (TPhP), a typical model of organophosphorus flame retardants (OPFRs), has been regarded as emerging environmental contaminants of health concern. In this study, TPhP molecularly imprinted polymers immobilized on graphene oxide (GO) film (TPhP-MIPs/GO) monolithic fiber for direct immersion solid phase microextraction (DI-SPME) was fabricated and evaluated. Compared with TPhP molecularly imprinted polymers (TPhP-MIPs) monolithic fiber, TPhP-MIPs/GO fiber had bigger extraction capacity, stronger hydrophilicity and faster mass transfer rate. Furthermore, TPhP-MIPs/GO fiber displayed excellent selectivity for TPhP among its structure analogues. It was thermally stable up to 320 °C so that it can withstand the high temperature of gas chromatography (GC) injection port for desorption and detection by flame photometric detector (FPD). Under optimal conditions, TPhP-MIPs/GO-SPME-GC/FPD method was developed by yielding satisfactory ultralow limit of quantification (0.4 ng L−1); linearity (≥0.99), good intra- and inter-day precision for a single fiber and fiber-to-fiber reproducibility. The method was applied for the determination of TPhP in environmental water and the relative recoveries were found to be in the range from 70 to 110%. TPhP was detected in three out of four environmental water samples at concentration levels from 0.04 to 0.12 ng mL−1, illustrating light pollution of TPhP in most environmental water.

Sample pre-treatment and analytical methodology for the simultaneous determination of pharmaceuticals and personal care products in sewage sludge

This work describes the design, optimization and validation of an analytical method for the simultaneous determination of 14 pharmaceuticals and personal care products (PPCPs) in sewage sludge. A thorough optimization of the sample pre-treatment was carried out. As a result, microwave-assisted extraction (MAE) was combined with an in-situ clean-up stage and a filtration step. A combination of MilliQ® water/MeOH 95:5 (v/v) adjusted to pH 9 turned out to be the optimal solvent mixture for extraction. The instrumental part of the method presents a significant novelty based on a fully automated sample preparation for the analysis of PPCPs. It consisted of a direct immersion solid phase microextraction followed by on-fiber derivatization, online coupled to gas chromatography - mass spectrometry (DI-SPME-On-fiber derivatization - GC-MS). An isotope dilution approach was used for quantifying, which conferred high reliability to the method. This methodology was validated for 10 compounds with good analytical performance, limit of detection below 20 ng g−1 and absolute recovery in the range of 30–70% for most of the compounds. It supposes an ecological analytical alternative for many routine analysis laboratories around the world. The developed method was applied to different real samples generated in both a pilot-scale thermal hydrolysis treatment plant and an anaerobic digester operated in mesophilic conditions. Salicylic acid and naproxen were found at concentrations above 1000 ng g−1.

Determination of phthalates in fish fillets by liquid chromatography tandem mass spectrometry (LC-MS/MS): A comparison of direct immersion solid phase microextraction (SPME) versus ultrasonic assisted solvent extraction (UASE)

Due to the increasing presence of plastic and plastic associated contaminants in the aquatic environments, the monitoring of this contamination in fish products and the understanding of possible human health implications is considered urgent. However, data are still relatively scarce, mostly due to the methodological challenges in the chemical analysis: these contaminants are ubiquitous and procedural contamination from the laboratory is frequent. In this work, we compared solid-phase microextraction (SPME) to ultrasonic assisted solvent extraction (UASE) as sample preparation methods for the liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) determination of phthalates in fish fillets. UASE was carried out with an acetone-hexane (1:1) solution and according to a reference procedure aimed to obtain the exhaustive extraction of the target analytes. SPME was carried out by applying C18 fibers in direct immersion mode and by using water/methanol 20:80 mixture to desorb the aliquot required for the analysis. Overall, SPME displayed an improved control of the background contamination and enabled lower LOQs. Precision, calculated as relative standard deviation (RSD) on replicates of a reference sample, was below 24% for both the method. Analysis of real samples purchased from Italian supermarkets showed that SPME might be an efficient tool for estimating the risk associated with fish consumption.

Application of in vivo solid phase microextraction (SPME) in capturing metabolome of apple (Malus \xd7domestica Borkh.) fruit

An in vivo direct-immersion SPME sampling coupled to comprehensive two-dimensional gas chromatography – time-of-flight mass spectrometry (GCxGC-ToFMS) was employed to capture real-time changes in the metabolome of ‘Honeycrisp’ apples during ripening on the tree. This novel sampling approach was successful in acquiring a broad metabolic fingerprint, capturing unique metabolites and detecting changes in metabolic profiles associated with fruit maturation. Several metabolites and chemical classes, including volatile esters, phenylpropanoid metabolites, 1-octen-3-ol, hexanal, and (2E,4E)-2,4-hexadienal were found to be up-regulated in response to fruit maturation. For the first time, Amaryllidaceae alkaloids, metabolites with important biological activities, including anti-cancer, anti-viral, anti-parasitic, and acetylcholinesterase (AChE) inhibitory activity, were detected in apples. Considering the elimination of oxidative degradation mechanisms that adversely impact the representativeness of metabolome obtained ex vivo, and further evidence that lipoxygenase (LOX) pathway contributes to volatile production in intact fruit, in vivo DI-SPME represents an attractive approach for global plant metabolite studies.

Optimization of a solid-phase microextraction technique for chloro‑ and nitro- substituted aromatic compounds using design of experiments

A rapid and sensitive direct immersion solid-phase microextraction (SPME) technique for the analysis of seven chloro (Cl-) and nitro (NO2-) substituted anilines, toluenes, and nitrobenzenes from small volume (1.5 mL) aqueous samples was optimized for gas chromatography using Design of Experiments (DoE). Screening of the SPME factors was performed by a fractional factorial DoE, and the optimization of influential factors was achieved with a central composite multi-response surface DoE. Extraction time, pre-SPME agitation speed, extraction temperature, and desorption temperature were identified as significant factors and their values were set using a desirability function that maximized the extraction of the seven target analytes. Extraction time and agitation speed showed significant interactions for most analytes (α = 0.05). The relative standard deviations (RSDs) for within-day and between-day analyses were below 8%, suggesting that the method was repeatable and reproducible. The obtained limits of detection were in the low μg/L range (1–10) using a Flame Ionization Detector, far below what is needed for industrial contaminated sites (usually >1 mg/L). The optimized SPME method increased the analyte concentration up to 2–3 orders of magnitude compared with direct GC injection. The optimized SPME method was applied to two groundwater samples from a contaminated site in which the concentrations of three of the target analytes were ranged from 0.06 to 9.42 mg/L with RSDs <11%. When the concentrations of the target analytes in the sample matrix were higher than 0.5 mg/L, a competition for the SPME extraction sites was observed where analytes with higher affinity for the fiber material replaced the analytes with lower affinity. As a result, dilution of highly contaminated samples is recommended. This study provided for the first time an analytical method for the quantification of frequently co-occurring contaminants from the chloro‑ and nitro- substituted aniline, toluene, and nitrobenzene families.

Sputtered silicon solid phase microextraction fibers with a polydimethylsiloxane stationary phase with negligible carry-over and phase bleed

We report the preparation of high performance, sputtered, polydimethylsiloxane (PDMS)-coated solid phase microextraction (SPME) fibers that show negligible carry-over and phase bleed. This process involves sputtering silicon onto silica fibers and functionalizing the resulting porous nanostructures with ultrathin films of vapor-deposited PDMS. Different thicknesses of silicon (0.25, 0.8, and 1.8 µm) and PDMS (8, 16, and 36 nm) were produced and their extraction efficiencies evaluated. The deposition of PDMS was confirmed by time-of-fight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), and contact angle goniometry on model, planar silicon substrates. These fibers were investigated using direct immersion SPME coupled with gas chromatography-mass spectrometry (GC–MS) analysis of a series of polycyclic aromatic hydrocarbons (PAHs), which are carcinogenic pollutants. The 1.8 µm thick silicon coating with 16 nm of PDMS (Si (1.8 µm)/PDMS (16 nm)) produced the best response among the combinations tested. Conditions for the extraction of PAHs with this fiber were optimized and its extraction performance was compared to that of a commercial 7 μm PDMS fiber. The linearity (1–110 µgL−1), repeatability (RSD%, n = 3) (17% ave.), and minimum detection limits (0.6–1.5 µgL−1) of the sputtered fibers were determined and found to be superior to the commercial 7 µm PDMS fiber in many respects. Carry-over and phase bleed from commercial PDMS-based SPME fibers are two of their major drawbacks, which decrease their lifetimes and usefulness. Minimal carry-over and phase bleed were observed for our sputtered PDMS-coated fibers. In particular, our fiber only shows 12% of the phase bleed of the comparable commercial fiber. In addition, it shows no carry-over for analytes with retention times greater than pyrene, and only 5% of the carry-over of the other analytes. Our fibers could be used for at least 300 injections without any significant loss of performance.

Preliminary Study on the Differences in Hydrocarbons Between Phosphine-Susceptible and -Resistant Strains of Rhyzopertha dominica (Fabricius) and Tribolium castaneum (Herbst) Using Direct Immersion Solid-Phase Microextraction Coupled with GC-MS.

Phosphine resistance is a worldwide issue threatening the grain industry. The cuticles of insects are covered with a layer of lipids, which protect insect bodies from the harmful effects of pesticides. The main components of the cuticular lipids are hydrocarbon compounds. In this research, phosphine-resistant and -susceptible strains of two main stored-grain insects, T. castaneum and R. dominica, were tested to determine the possible role of their cuticular hydrocarbons in phosphine resistance. Direct immersion solid-phase microextraction followed by gas chromatography-mass spectrometry (GC-MS) was applied to extract and analyze the cuticular hydrocarbons. The results showed significant differences between the resistant and susceptible strains regarding the cuticular hydrocarbons that were investigated. The resistant insects of both species contained higher amounts than the susceptible insects for the majority of the hydrocarbons, sixteen from cuticular extraction and nineteen from the homogenized body extraction for T. castaneum and eighteen from cuticular extraction and twenty-one from the homogenized body extraction for R. dominica. 3-methylnonacosane and 2-methylheptacosane had the highest significant difference between the susceptible and resistant strains of T. castaneum from the cuticle and the homogenized body, respectively. Unknown5 from the cuticle and 3-methylhentriacontane from the homogenized body recorded the highest significant differences in R. dominica. The higher hydrocarbon content is a key factor in eliminating phosphine from entering resistant insect bodies, acting as a barrier between insects and the surrounding phosphine environment.

Direct Immersion–Solid-Phase Microextraction Coupled to Gas Chromatography–Mass Spectrometry and Response Surface Methodology for Nontarget Screening of (Semi-) Volatile Migrants from Food Contact Materials

Toward a more rigorous inspection of food contact materials, the importance of sample preparation for nontarget screening should be addressed. Direct immersion-solid-phase microextraction coupled to gas chromatography mass spectrometry (DI-SPME-GC-MS) was optimized for nontarget screening of migrants in 3% acetic acid, 10% ethanol, and 95% ethanol food simulants by response surface methodology (RSM) in the present study. Optimum conditions were DVB/CAR/PDMS fiber, no pH adjustment for 10% and 95% ethanol simulant but pH adjustment to 7 for 3% acetic acid simulant, no salt addition, 5 min preincubation, 55 min extraction at 70 °C, and 8 min desorption at 250 °C. In addition, 9.5 times dilution of 95% ethanol samples prior to extraction was required. pH modification of 3% acetic acid samples was found to be critical for the extraction of amines. The proposed methodology was then evaluated by determining the limit of detection (LOD) as well as repeatability of 35 food contact materials-related substances. Except for those amines and diols which have a relatively high LOD, the LODs of the rest of the substances were 0.1-14.1 μg/kg with a precision of 1.9-23.0% in 10% ethanol and were 0.1-20.2 μg/kg with a precision of 2.5-19.6% in 3% acetic acid simulant. The LOD and precision in 95% ethanol simulant were 0.7-163.7 μg/kg and 1.4-26.8%, respectively. The proposed method can be applied for an overall screening of migrants from these three simulants at even trace levels, though attention should be paid to some specific analytes, e.g., diols and amines, which could have a high LOD and toxicity.

Determination of the mass transfer coefficients in direct immersion solid‐phase microextraction

Diffusion of the analytes across the diffusion boundary layers and subsequently through the fiber coatings determines the extraction kinetics of solid-phase microextraction in aqueous matrices. Besides, the matrix effects can distort the behaviors of the analytes transferring across the diffusion boundary layers. However, these processes were always studied via certain simplification, which often left the mass transfer through the fiber coatings unconsidered and the matrix effects partially investigated. Herein, a comprehensive study on the mass transfer processes in direct immersion solid-phase microextraction was presented. Under different agitation speeds, it was determined that the mass transfer coefficients across the diffusion boundary layers were three to six orders larger than those through the fiber coatings. However, the mass transfer across the diffusion boundary layers was generally the major rate-limiting step. In addition, the shuttle effect and the barrier effect, which were responsible for accelerating and retarding the extraction kinetics, respectively, were found to be the dominant matrix effect alternately under different agitation speeds. This study comprehensively illustrated the major rate-limiting step and the dominant matrix effects through recording the mass transfer coefficients.

Enhancing trace acrylamide analysis by bromine derivatization coupled with direct-immersion solid-phase microextraction in drinking water

ABSTRACT Acrylamide is a neurotoxic and genotoxic compound. It is abundant in drinking water because of the usage of polyacrylamide. Its high polarity and small molecular weight characteristics make it difficult to be extracted and analysed. In this study, a novel method was optimized for the determination of trace acrylamide in drinking water. The optimized method, uses bromine derivatization, can avoid false analysis of co-extractives and precursors effectively by transferring acrylamide to 2-bromopropenamide. The 2-bromopropenamide was extracted from water samples using DI-SPME and further analysed by GC-MS. This optimized method uses CAR/PDMS coating SPME fibre to extract at 55°C for 45 min after the addition of 12 g Na2SO4, and then desorbs the extractions in GC injector at 260°C for 3 min. The detection limit was 0.05 μg/L with linearity ranging from 0.5 to 500 μg/L. The repeatability and reproducibility relative standard deviation were 7.30% and 8.50%, respectively. The spiking recovery of tap water samples ranged from 100% to 106%. These results confirmed that this novel method was more precise and accurate than the previously reported SPME methods that used to analyse trace acrylamide in drinking water. The concentrations of acrylamide in the collected samples from clarification and filtration units were 0.80 and 0.71 g/L respectively.