Direct Immersion Solid-phase Microextraction Research Articles

Rapid and simultaneous analysis of tetrabromobisphenol A and hexabromocyclododecane in water by direct immersion solid phase microextraction: Uniform design to explore factors

Direct immersion solid phase microextraction (DI-SPME) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) is of significant research interest because of its low solvent consumption, simple design, and efficient, sensitive, fast performance. In this work, a combination of these two methods (DI-SPME-LC-MS) for the determination of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) in water was developed. Important factors, which included temperature, stirring rate, salt concentration, pH value and adsorption time, were evaluated in for the optimization of solid phase microextraction (SPME) method. The method was developed using spiked natural waters in a concentration range of 0.1–10 ng mL−1, and showed notable linearity with regression coefficients ranging between 0.992 and 0.999. The limits of detection varied from 0.01 to 0.04 ng mL−1 (at S/N = 3) and relative standard deviation (RSD < 11%) were obtained showing that the precision of the method was reliable. Recoveries were in relatively high levels for both analytes and ranged from 88% to 108%. Moreover, in comparison with the performance time of traditional sample pretreatment methods such as solid-phase extraction (SPE), accelerated solvent extraction (ASE), and liquid-liquid extraction (LLE), DI-SPME-LC-MS takes only approximately 35 min to perform. The optimized method was successfully applied for monitoring concentrations of TBBPA and HBCD in water.

Task-specific solid-phase microextraction based on ionic liquid/polyhedral oligomeric silsesquioxane hybrid coating for sensitive analysis of polycyclic aromatic hydrocarbons by gas chromatography–mass spectrometry

A direct immersion solid-phase microextraction (DI-SPME) approach for gas chromatography-mass spectrometry (GC–MS) based on hybrid fiber coating of ionic liquid and polyhedral oligomeric silsesquioxane (POSS) is presented. To fabricate the task-specific coating for the enrichment of polycyclic aromatic hydrocarbons (PAHs), 1-butyl-3-vinylimidazolium bis[(trifluoromethyl)sulfonyl]imide (IL) and POSS were rapidly photoinitiated copolymerized within 5 min on a stainless steel fiber. The high efficient extraction of target analytes can be attributed to a combined result of multiple interactions including the strong CF⋯HC pseudohydrogen bonding, π-π stacking, hydrophobic force, and molecular sieve effect. A wide linear range (0.04–400 ng L−1) with low detection limits in the range of 0.004 and 0.5 ng L−1 were obtained for PAHs by GC–MS. The applicability of this coupling method was successfully demonstrated by the analysis of trace PAHs in real river water and soil samples, with satisfied recoveries (84.2–108.6%) and relative standard deviations (<8.1%). Compared to the other commercial fiber-based SPME methods, the IL/POSS hybrid coating-based SPME is much cheaper, thermally stable and capable of eliminating possible deleterious effects as well.

Applications of three-dimensional graphenes for preconcentration, extraction, and sorption of chemical species: a review.

This review (with 115 refs) summarizes applications of 3-dimensional graphene (3DGs) and its derivatives in the fields of preconcentration, extraction, and sorption. Following an introduction into the field (including a definition of the materials treated here), the properties and synthetic strategies for 3DGs are described. The next section covers applications of 3DG-based adsorbents in solid phase extraction of organic species including drugs, phthalate esters, chlorophenols, aflatoxins, insecticides, and pesticides. Another section treats applications of 3DGs in solid phase microextraction of species such as polycyclic aromatic hydrocarbons, alcohols, and pesticides. We also describe how the efficiency of assays may be improved by using these materials as a sorbent. A final section covers conclusions and perspectives. Graphical abstract Graphical abstract contains poor quality and small text inside the artwork. Please do not re-use the file that we have rejected or attempt to increase its resolution and re-save. It is originally poor, therefore, increasing the resolution will not solve the quality problem. We suggest that you provide us the original format. We prefer replacement figures containing vector/editable objects rather than embedded images. Preferred file formats are eps, ai, tiff and pdf.Tiff file of graphical abstract was attached. Schematic presentation of synthesis of three-dimensional graphene (3DG) from two-dimensional graphene (2DG) with self-assembly, template-assisted and direct deposition methods. Application of 3DG-based nanoadsorbents in direct immersion-solid phase microextraction (DI-SPME), headspace-SPME (HS-SPME), magnetic-solid phase extraction (Magnetic-SPE), dispersive-SPE, and magnetic sheet-SPE.

Optimization of a DI-SPME-GC–MS/MS method for multi-residue analysis of pesticides in waters

This paper discusses the optimization and validation of a complete and simple method for the simultaneous determination of 48 pesticides in water by combining direct immersion solid-phase micro-extraction (DI-SPME) and gas chromatography-ion trap tandem mass spectrometry (GC-ITMS/MS). For the extraction, the different SPME parameters were tested and optimized. As a result, the polyacrylate fiber (PA 85 μm) was selected in direct immersion mode; the extraction temperature was set to 60 °C with an extraction time of 45 min and a stirring speed of 500 rpm; the thermal desorption time of the fiber in the injector port was fixed to 10 min at 275 °C. Concerning the analysis, MS/MS parameters were optimized and figures of merit were compared. Later, the method was validated and showed good linearity in the concentration ranging from 0.05 to 100 μg L−1. The reproducibility of measurements expressed as the relative standard deviation (% RSD) was found to be satisfactory. Furthermore, the detection limits for all the compounds were between 0.001 and 0.458 μg L−1, except for methomyl and hexachlorobenzene (1.09 and 0.99 μg L−1 respectively). Finally, the proposed DI-SPME-GC–MS/MS method was tested successfully for water samples collected along the watershed of Abou Ali River (North Lebanon).

Development of a highly sensitive gas chromatography-mass spectrometry method preceded by solid-phase microextraction for the analysis of propofol in low-volume cerebral microdialysate samples.

To date, the commonly used intravenous anesthetic propofol has been widely studied, and fundamental pharmacodynamic and pharmacokinetic characteristics of the drug are known. However, propofol has not yet been quantified in vivo in the target organ, the human brain. Here, cerebral microdialysis offers the unique opportunity to sample propofol in the living human organism. Therefore, a highly sensitive analytical method for propofol quantitation in small sample volumes of 30 μL, based on direct immersion solid‐phase microextraction was developed. Preconcentration was followed by gas chromatographic separation and mass spectrometric detection of the compound. This optimized method provided a linear range between the lower limit of detection (50 ng/L) and 200 μg/L. Matrix‐matched calibration was used to compensate recovery issues. A precision of 2.7% relative standard deviation between five consecutive measurements and an interday precision of 6.4% relative standard deviation could be achieved. Furthermore, the permeability of propofol through a cerebral microdialysate system was tested. In summary, the developed method to analyze cerebral microdialysate samples, allows the in vivo quantitation of propofol in the living human brain. Additionally the calculation of extracellular fluid levels is enabled since the recovery of the cerebral microdialysis regarding propofol was determined.

The use of solid phase microextraction for metabolomic analysis of non-small cell lung carcinoma cell line (A549) after administration of combretastatin A4

Use of solid phase microextraction (SPME) for cell culture metabolomic analysis allows for the attainment of more sophisticated data from in vitro cell cultures. Moreover, considering that SPME allows the implementation of multiple extractions from the same sample due to its non/low-depletive nature, time course studies using the same set of samples are thus facilitated via this method. Such an approach results in a reduction in the number of samples needed for analysis thus eliminates inter-batch variability related to biological variation occurring during cell culturing. The current work aims to demonstrate the capability of SPME for measurements of combretastatin A4 (CA4) effectiveness on non-small cell cancer cell line. A cultivation protocol was established in the 96-well plate, and a fiber format of SPME was selected for metabolite extraction. The extracellular metabolic pattern of cells was changed after administration of the tested drug. This suggests pharmacological activity of the administered compound towards the studied cell line model. Results support that the use of direct immersion SPME for analysis of cell cultures does not affect cells growth or contaminate sample. Consequently, SPME allows the attainment of accurate information regarding drug uptake, metabolism, and metabolomic changes in the studied cells induced by exposure to the drug simultaneously in a single experiment.

Porous graphene-coated stainless-steel fiber for direct immersion solid-phase microextraction of polycyclic aromatic hydrocarbons

Porous graphene was prepared by combustion method and fabricated as a new coating on stainless-steel fiber for direct immersion solid-phase microextraction of PAHs in environmental water.

Development and validation of a fully automated solid phase microextraction high throughput method for quantitative analysis of multiresidue veterinary drugs in chicken tissue

This paper presents the development and validation of a fully automated, high-throughput multiclass, multiresidue method for quantitative analysis of 77 veterinary drugs in chicken muscle via direct immersion solid phase microextraction (DI-SPME) and ultra-high pressure liquid chromatography-electrospray ionization - tandem mass spectrometry (UHPLC-ESI-MS/MS). The selected drugs represent more than 12 different classes of drugs characterized by varying physical and chemical properties. A Hydrophilic–lipophilic balance (HLB)/polyacrylonitrile (PAN) extraction phase, prepared using HLB particles synthesized in-house, yielded the best extraction/desorption performance among four different SPME extraction phases evaluated in the current work. The developed SPME method was optimized in terms of SPME coating and geometry, desorption solvent, extraction and rinsing conditions, and extraction and desorption times. Multivariate analysis was performed to determine the optimal desorption solvent for the proposed application. The developed method was validated according to the Food and Drug Administration (FDA) guidelines, taking into account Canadian maximum residue limits (MRLs) and US maximum tolerance levels for veterinary drugs in meat. Method accuracy ranged from 80 to 120% for at least 73 compounds, with relative standard deviation of 1–15%. Inter-day precision ranged from 4 to 15% for 70 compounds. Determination coefficients values were higher than 0.991 for all compounds under study with no significant lack of fit (p > 0.05) at the 5% level. In terms of limits of quantitation, the method was able to meet both Canadian and US regulatory levels for all compounds under study.

Application of Direct Immersion Solid-Phase Microextraction (DI-SPME) for Understanding Biological Changes of Mediterranean Fruit Fly (Ceratitis capitata) During Mating Procedures.

Samples from three different mating stages (before, during and after mating) of the Mediterranean fruit fly Ceratitis capitata were used in this experiment. Samples obtained from whole insects were subjected to extraction with the two mixtures of solvents (acetonitrile/water (A) and methanol/acetonitrile/water (B)) and a comparative study of the extractions using the different solvents was performed. Direct immersion-solid phase microextraction (DI-SPME) was employed, followed by gas chromatographic-mass spectrometry analyses (GC/MS) for the collection, separation and identification of compounds. The method was validated by testing its sensitivity, linearity and reproducibility. The main compounds identified in the three different mating stages were ethyl glycolate, α-farnesene, decanoic acid octyl ester, 2,6,10,15-tetramethylheptadecane, 11-tricosene, 9,12-(Z,Z)-octadecadienoic acid, methyl stearate, 9-(Z)-tricosene, 9,11-didehydro-lumisterol acetate; 1,54-dibromotetrapentacontane, 9-(Z)-hexadecenoic acid hexadecyl ester, 9-(E)-octadecenoic acid and 9-(Z)-hexadecenoic acid octadecyl ester. The novel findings indicated that compound compositions were not significantly different before and during mating. However, new chemical compounds were generated after mating, such as 1-iodododecane, 9-(Z)-tricosene and 11,13-dimethyl-12-tetradecen-1-acetate which were extracted with both (A) and (B) and dodecanoic acid, (Z)-oleic acid, octadecanoic acid and hentriacontane which were extracted with (A) and ethyl glycolate, 9-hexadecenoic acid hexadecyl ester, palmitoleic acid and 9-(E)-octadecenoic acid, which were extracted with solvent (B). This study has demonstrated that DI-SPME is useful in quantitative insect metabolomics by determining changes in the metabolic compounds in response to mating periods. DI-SPME chemical extraction technology might offer analysis of metabolites that could potentially enhance our understanding on the evolution of the medfly.

Silver-based polymeric ionic liquid sorbent coatings for solid-phase microextraction: Materials for the selective extraction of unsaturated compounds

A new generation of silver-based polymeric ionic liquid (PIL) sorbent coatings has been developed and applied in solid-phase microextraction (SPME). The new materials are based on ionic liquid monomers formed by cations containing the silver(I) ion coordinated with two 1-vinylimidazole ligands. Up to seven different silver-based PIL sorbent coatings were developed by polymerizing the silver-IL monomer in the presence of either silver bis[(trifluoromethyl)sulfonyl]imide, and/or a dicationic ionic liquid crosslinker. The obtained sorbent coatings were found to possess adequate thermal stability despite the presence of the silver(I) ions. Thermal desorption of the analytes at 175 °C was effectively used without any significant decrease in extraction efficiency. The developed sorbent coatings were used in two different applications: the determination of alkenes/alkynes via headspace SPME and the determination of unsaturated fatty acids using direct-immersion SPME. In the former approach, the silver-based PILs were particularly selective for the determination of unsaturated compounds with terminal double bonds such as 1,5-hexadiene, 2-methyl-1,5-hexadiene, and 1,8-nonadiene. A study of the extraction mechanism of the analytes to the sorbent coating revealed a competitive partitioning of the analytes. In the second approach, the most selective silver-based PILs were applied for the determination of oleic acid, linoleic acid, and linolenic acid. After proper optimization of the method, the coatings were found to be more or as sensitive as the commercial polydimethylsiloxane fiber. Limits of detection between 2.6 and 8.2 μg L−1 in ultrapure water and from 12 to 14 μg L−1 in tap water were obtained for the best silver-based PIL, with relative standard deviations lower than 13% in all cases at a spiked level of 160 μg L−1. Finally, the fiber was effectively applied for the analysis of rinse water from a dairy farm, with adequate detection of the analytes at concentrations between 52 and 179 μg L−1.

Determinations of Triclosan and Parabens in Household Dusts by Solid-Phase Microextraction with Microwave Assisted Extraction

Indoor dust has been known as a sink for many semi-volatile organic compounds, such as triclosan and parabens. Since indoor environment can protect dust from sunlight, rain and biological degradation, pollutants then could be persistent and accumulated in the residential environment. Up to now, the analysis of triclosan and parabens in dust is solvent and time consuming. Therefore, a method for the measurement of triclosan and parabens in dusts simultaneously by using microwave assisted direct-immersion solid-phase microextraction (MAE-DI-SPME) has been developed to determine the distributions in Taiwan. In this study, commercial vacuum cleaner was used to collect household dusts while particles with diameter smaller than 150&amp;#956;m were filtered out by stainless mesh. Afterwards, 0.02g dust sample was spiked with 2.5 &amp;#956;g/g of surrogate in a 4mL vial and stood for overnight. RO water of 2.5mL was added into the sample the next day, followed by the filtration and MAE-DI-SPME extraction procedures. Gas chromatograph-tandem mass spectrometer (GC/MS/MS) was employed for the analysis. Several parameters affecting the SPME extraction efficiency were optimized. The results showed that the desorption efficiency was 100% when the desorption time was 20 min under 250 degree C. The best suitable fiber coating was 65&amp;#956;m PDMS/DVB and the optimum condition of MAE-DI-SPME for extraction of triclosan and parabens in dust was 20 minutes at 80 degree C. For indoor dust samples in Taiwan, the median, mean and rage of triclosan and paraens concentrations were determined, respectively. Relatively to headspace extraction, the established method of MAE-DI-SPME for the measurements of triclosan and parabens in indoor dust provides good linearity and precisions. Besides, compared with traditional extraction methods, the MAE-DI-SPME provides a time saving, easy for operation and solvent-free procedure.

Magnetic Field-Assisted Direct Immersion SPME of Endogenous Aldehydes in Human Urine

Direct immersion solid-phase microextraction (DI-SPME) is an effective microsampling strategy for polar and ionic species in aqueous media. Nevertheless, the fiber coating is in direct contact with sample solution and affected by its conditions. To compensate this limitation and to improve the extraction efficiency, a magnetic fiber coating was prepared and employed for DI-SPME sampling under the enhancing effect of a magnetic field. Magnetic iron oxide core–shell silica nanoparticles were synthesized and embedded in polypyrrole using an in situ electropolymerization method along with simultaneous coating on the surface of a platinized stainless-steel fiber. It was then applied for magnetic-assisted DI-SPME (MA-DI-SPME) sampling of endogenous aldehydes in human urine. Sample solution pH, the magnetic field intensity, ionic strength and extraction time were evaluated as the important affecting variables. Limits of detection were obtained 0.01–0.1 ng mL−1; the calibration graphs were linear over the range of 0.1–10000 ng mL−1. The inter-fiber (fiber-to-fiber) reproducibility was found to be 10.7–12.5%. Matrix effect from urine samples was not observed at concentration levels of 0.2, 2, and 8 µg mL−1. The results showed that magnetic field increased the efficiency of DI-SPME method about two to four times. The developed strategy was successfully applied for the extraction and quantification of hexanal and heptanal (as the most important aldehyde biomarkers) in urine samples.

Effect of Transport Parameters and Device Geometry on Extraction Kinetics and Efficiency in Direct Immersion Solid-phase Microextraction.

An alternative strategy to increase mass transfer entails geometry optimization of the extraction systems including design of solid-phase microextraction (SPME) probes. In this work, a computational model was employed to elucidate practical aspects such as efficiency and kinetics of extraction by employing several new geometries. Extraction of a model analyte at static conditions with the configurations, such as thin-film, fiber, coated tip, and nanoparticles, was numerically simulated to obtain an in-depth understanding of the advantages and limitations of each geometry in microextraction and exhaustive modes. The attained results associated with the equilibration time dependency on shape were in good agreement with previously reported experimental observations. They demonstrate that the mass-transfer is highly dependent on the size and shape of the coatings and increases with a decrease in size of the devices particularly rapidly below 10 μm caused by radial diffusion effect. Nevertheless, extractions performed using octadecyl-functionalized magnetic nanoparticles demonstrated that higher enrichment factors are achievable with the use of a fewer number of particles in comparison to factors achieved via exhaustive extraction, where a larger number of particles must be employed, confirming theoretical predictions. The conclusions reached are valid for any extraction method. The results obtained herein are very useful toward the design and optimization of future extraction technologies and approaches.

Evaluation of polypyrrole/silver/polyethylene glycol nanocomposite sorbent for electroenhanced direct-immersion solid-phase microextraction of carvacrol and thymol from medicinal plants

The unique features of nanostructured polypyrrole, conductivity enhancement effect of silver nanoparticles and high polar adsorptivity of polyethylene glycol were merged into polypyrrole/silver/polyethylene glycol (PPy/Ag/PEG) nanocomposite. It was synthesized and simultaneously coated on the surface of a stainless-steel fiber using an amended electropolymerization procedure. Before coating, the fiber substrate was made porous and sticky by allocating platinum dots on the surface of the stainless-steel fiber using the electrophoretic method. The prepared fiber was applied for the extraction of carvacrol and thymol (the most important antioxidants in medicinal plants) through an electroenhanced direct-immersion solid-phase microextraction (EE-DI-SPME) sampling strategy, followed by GC-FID quantification. To achieve the best efficiency, the effectual experimental variables including pH of sample solution, applied voltage, extraction temperature and time, stirring rate, and ionic strength were investigated. Under the optimal experimental conditions, the calibration curves were linear over the range of 0.5–30 µg mL−1 for thymol and 0.01–30 µg mL−1 for carvacrol. The detection limits (3Sb) and relative standard deviation (RSD%, n = 6) were obtained to be 0.15, 0.003 µg mL−1 and 10.2, 8.7% for thymol and carvacrol, respectively. The results demonstrated the priority of the proposed fiber compared with polypyrrole and polyacrylate fibers, in terms of extraction efficiency, durability and stability. The developed method was successfully employed for the analysis of thymol and carvacrol in medicinal plants.

Iron oxide/silica/polypyrrole nanocomposite sorbent for the comparison study of direct-immersion and headspace solid-phase microextraction of aldehyde biomarkers in human urine

The short chain alkyl aldehydes, especially hexanal and heptanal, in urine are considered as potential biomarkers of several diseases and their determination in biological fluids has gained a great attention in recent years. Magnetic iron oxide core-shell silica (Fe3O4/SiO2) nanoparticles was synthesized and embedded in polypyrrole (PPy) during the in-situ electropolymerization on the surface of a stainless-steel wire. The Fe3O4/SiO2/PPy coated steel wire was used as a novel and effective solid-phase microextraction (SPME) fibre. It was employed for the extraction and preconcentration of hexanal and heptanal through direct-immersion (DI-) and headspace (HS-) SPME sampling strategies, followed by GC-FID quantification. The prepared nanocomposite fiber was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). All influential variables on the extraction efficiency of the DI- and HS-SPME sampling modes were studied and optimized. The calibration curves showed acceptable linearity (R2 > 0.99) over the range of 0.01–10 μg mL−1 for the DI-SPME-GC-FID and 0.01–15 μgmL-1 for HS-SPME-GC-GID methods. The limit of detections (LODs) corresponding to the analytes amounts for which signal-to-noise ratios were equal to 3, estimated to be 0.1 and 0.5 ng mL-1, for hexanal and heptanal using HS-SPME-GC-FID, respectively. The LODs for DI-SPME-GC-FID method were 0.1 and 1.0 for hexanal and heptanal. For six replicated analyses of 0.5 μg mL-1 of the analytes, the relative standard deviations (RSDs) were calculated 6.5–6.6% and 5.1–5.3%, for DI-SPME and HS-SPME, respectively. The two developed methods were successfully applied for analysis of hexanal and heptanal in urine samples without derivatization step. The HS-SPME-GC-FID sampling/determination strategy showed better analytical figures of merit and longer lifetime for the prepared nanocomposite fiber.

Silver nanoparticles supported onto a stainless steel wire for direct-immersion solid-phase microextraction of polycyclic aromatic hydrocarbons prior to their determination by GC-FID.

The authors describe a new coating for use in solid-phase microextraction (SPME). Silver nanoparticles (AgNPs) were prepared by using gallic acid or glucose as the reducing agents, and then supported onto a stainless steel wire that was previously coated with a silver mirror. Coating with AgNPs was performed by a layer-by-layer approach of up to eight cycles of consecutive deposition of AgNPs and the thiol linker 1,8-octanedithiol. This procedure allows proper control of the coating thickness. Thicknesses are 3.2μm and 3.5μm with AgNPs obtained with gallic acid and glucose, respectively. This is in agreement with theoretical estimations (3.8μm). The fibers were used in the direct-immersion SPME-GC-FID determination of 16 polycyclic aromatic hydrocarbons (PAHs) from different waters. The performance of the method was compared to the one using polydimethylsiloxane fibers (100μm), which is the most suitable commercial SPME fiber for PAHs. Despite the low thickness of the AgNP coatings (compared to PDMS), the analytical features of the method using the most adequate coating (AgNPs prepared with gallic acid) include: (a) limits of detection down to 0.6ng·mL-1; (b) intra-day, inter-day, and inter-fiber precisions (expressed as RSDs) lower than 22, 26 and 25%, respectively; and (c) an operational lifetime of ~150 extractions/desorption cycles. The analysis of various spiked environmental waters using these fibers resulted in adequate analytical performance. Graphical abstract Silver nanoparticle based coatings for solid-phase microextraction fibers were prepared by a layer-by-layer approach. They were used for determination of 16 PAHs in waters by gas chromatography. Limits of detection are < 14μg·L-1 and intra-day, inter-day, and inter-fiber precisions are <26%.

Solid-phase microextraction of heavy metals in natural water with a polypyrrole/carbon nanotube/1, 10–phenanthroline composite sorbent material

A simple and sensitive method for simultaneous microextraction and determination of heavy metals using a new direct immersion solid-phase microextraction (DI–SPME) sorbent material combined with inductively coupled plasma mass spectrometry (ICP–MS) was investigated. In this method, sorbent coating composites were prepared by simultaneous electropolymerization of pyrrole on pencil lead in the presence of carbon nanotubes (CNTs) and different metal chelating ligands. Among the coatings evaluated, a polypyrrole coating with entrapped CNTs and the chelator 1, 10 phenanthroline allowed the determination of silver, cadmium, cobalt, iron, nickel, lead, and zinc. Parameters influencing microextraction efficiency including pH, extraction time, and desorption time were optimized. The linear dynamic ranges were 1–1000 μg L−1 for Ag, 1–750 μg L−1 for Cd, Pb, and Zn, and 1–500 μg L−1 for Co, Fe, and Ni with limits of detection of 0.012–0.163 μg L−1 and limits of quantification of 0.039–0.542 μg L−1. The relative standard deviations (RSDs, n = 5) ranged from 1.85% to 5.01%. The effect of inorganic interferences on the determination of the heavy metals also was examined and finally, the method was successfully applied for the determination of heavy metals in real water samples.

Direct immersion solid-phase microextraction analysis of multi-class contaminants in edible seaweeds by gas chromatography-mass spectrometry

The present work aimed at the development of a simple and accurate direct immersion-solidphase microextraction-gas-chromatography-mass spectrometry (DI-SPME-GC-MS) method for simultaneous determination of PAHs, PCBs, and pesticide residues in edible seaweeds. As the target contaminants possess a wide range of physical-chemical properties, multivariate experimental design was used for method optimization. In particular, two different methods were optimized and validated: one that allows for simultaneous determination of all targets, and an ad hoc method for determination of hydrophobic analytes, a class that often poses a challenge for extraction from food matrices. Optimum conditions suitable for simultaneous quantitation of all targeted compounds, namely buffer at pH = 7.0, 20% acetone (v/v), 10% NaCl (w/w), 0.02% NaN3, 60 min DI extraction at 55 °C, and 20 min desorption at 270 °C, afforded limits of quantitation (LOQs) in the range of 1–30 μg kg−1, a wide linear range of 5–2000 μg kg−1, the attainment of satisfactory determination coefficients (R2˃0.99) with no significant lack of fit (p > 0.05) at the 5% level, and satisfactory accuracy and precision values. By modifying the extraction conditions to favor extraction of the most hydrophobic analytes (e.g. higher amount of organic modifier and pH, and lower salt content) lower LOQs were obtained for these compounds ranging from 0.2 to 13.3 μg kg−1. The established methods were then used for screening of commercial, edible dry seaweeds, with PCBs (≤16.0 ng g−1) and PAHs (≤15.5 ng g−1) detected in some samples. This method overcomes most challenges commonly encountered in dry sample analysis applications, and represents the first report of a DI-SPME method employing the matrix-compatible fiber for simultaneous multiclass and multiresidue analysis of seaweeds.

Comparison of the Conventional and Electroenhanced Direct-Immersion Solid-Phase Microextraction for Sampling of Nicotine in Biological Fluids of the Human Body.

A stainless steel fiber was made porous and adhesive by platinization and then coated by nanostructured polypyrrole (PPy), using an appropriate electrophoretic deposition (EPD) method. The morphological surface structure and functional groups of the PPy-coated fiber were studied using SEM (Scanning electron microscope) instrument. The prepared fiber was used for comparison of direct immersion (DI) and electroenhanced direct immersion solid-phase microextraction (EE-DI-SPME) of nicotine in human plasma and urine samples followed by gas chromatography flame ionization detector (GC-FID) determination. The effects of the influential experimental parameters on the efficiency of the DI-SPME and EE-DI-SPME methods, including the pH and ionic strength of the sample solution, applied Direct current (DC) voltage, extraction temperature and time and stirring rate, were optimized. Under the optimal conditions, the calibration curves for the DI-SPME-GC-FID and EE-DI-SPME-GC-FID methods were linear over the ranges of 0.1–10.0 μg mL−1 and 0.001–10.0 μg mL−1, respectively. The relative standard deviations (RSDs, n = 6) were found to be 6.1% and 4.6% for the DI and EE strategies, respectively. The LODs (limit of detection) of the DI-SPME-GC-FID and EE-DI-SPME-GC-FID methods were found to be 10 and 0.3 ng mL−1, respectively. The relative recovery values (for the analysis of 1 µg mL−1 nicotine) were found to be 91–110% for EE-DI-SPME and 75–105% for DI-SPME. The enrichment factors for DI-SPME and EE-DI-SPME sampling were obtained as 38,734 and 50,597, respectively. The results indicated that EE-SPME was more efficient for quantitation of nicotine in biological fluids. The developed procedure was successfully carried out for the extraction and measurement of nicotine in real plasma and urine samples.

Multiresidue analytical method for pharmaceuticals and personal care products in sewage and sewage sludge by online direct immersion SPME on-fiber derivatization – GCMS

The work here presented aimed at developing an analytical method for the simultaneous determination of 22 pharmaceuticals and personal care products, including 3 transformation products, in sewage and sludge. A meticulous method optimization, involving an experimental design, was carried out. The developed method was fully automated and consisted of the online extraction of 17 mL of water sample by Direct Immersion Solid Phase MicroExtraction followed by On-fiber Derivatization coupled to Gas Chromatography – Mass Spectrometry (DI-SPME – On-fiber Derivatization – GC – MS). This methodology was validated for 12 of the initial compounds as a reliable (relative recoveries above 90% for sewage and 70% for sludge; repeatability as %RSD below 10% in all cases), sensitive (LODs below 20 ng L−1 in sewage and 10 ng g−1 in sludge), versatile (sewage and sewage-sludge samples up to 15,000 ng L−1 and 900 ng g−1, respectively) and green analytical alternative for many medium-tech routine laboratories around the world to keep up with both current and forecast environmental regulations requirements. The remaining 10 analytes initially considered showed insufficient suitability to be included in the final method. The methodology was successfully applied to real samples generated in a pilot scale sewage treatment reactor.