Application of oxygen scavengers in gel electromembrane extraction: A green methodology for simultaneous determination of nitrate and nitrite in sausage samples.

The generation of oxygen from electrolysis in gel electromembrane extraction (G-EME) causes a negative error when applied to the analysis of easily oxidized species such as nitrite. Nitrite in G-EME is oxidized by oxygen to nitrate, leading to the negative error and the impossibility of simultaneous analysis. In this work, the application of oxygen scavengers to the acceptor phase of the G-EME system was attempted to minimize the oxidation effect. Several oxygen scavengers were selected and examined according to their compatibility with ion chromatography. The mixture of sulfite and bisulfite (14 mg L-1) showed the highest efficiency in preventing the oxidation of nitrite to nitrate. Under the optimized conditions, a good linear range was obtained (10-200 µg L-1; R2 > 0.998) with a detection limit of 8 µg L-1 for both nitrite and nitrate. This method was applied to the simultaneous determination of nitrite and nitrate in sausage samples.

Recent Developments and Applications of Microfluidic Paper-Based Analytical Devices for the Detection of Biological and Chemical Hazards in Foods: A Critical Review.

Nowadays, food safety has become a major concern for the sustainability of global public health. Through the production and distribution steps, food can be contaminated by either chemical hazards or pathogens, and the determination of these plays a critical role in the processes of ensuring food safety. Therefore, the development of analytical tools that can provide rapid screening of these hazards is highly necessary. Microfluidic paper-based analytical devices (µPADs) have advanced significantly in recent years as they are rapid and low-cost analytical screening tools for testing contaminated food products. This review focuses on recent developments of µPADs for various applications in the food safety field. A description of the fabrication of selected papers is briefly discussed, and evaluation of the µPADs' performance with regard to their precision and accuracy as well as their limits of detection is critically assessed. The advantages and disadvantages of these devices are highlighted.

Application of electrocolorimetric extraction for the determination of Ni(II) ions in chocolate samples: A green methodology for food analysis.

This study developed an electrocolorimetric extraction technique as a simple, rapid, and green method for the simultaneous preconcentration and determination of Ni(II) in chocolate samples. The system was designed using an agarose gel (3% w/v) solution containing 10% v/v 80 mM dimethylglyoxime (DMG) and 10% v/v 0.03 M ammonia as colorimetric reagents to determine Ni(II) ions. When voltage was applied to the system, Ni(II) ions were extracted from the donor solution into the gel and formed Ni-DMG complexes with a pink color. Under the optimal conditions, a good linear range was obtained from 30 to 750 µg L-1 (R2 > 0.998) with a detection limit of 1 µg L-1. Inter- and intra-assay results showing relative standard deviations were less than 2.6% and 1.9%, respectively. Our developed method was applied to determine Ni(II) in chocolate samples. The results were in agreement with those obtained using ICP-OES.

Online and offline preconcentration techniques on paper-based analytical devices for ultrasensitive chemical and biochemical analysis: A review.

Microfluidic paper-based analytical devices (µPADs) have attracted much attention over the past decade. They embody many advantages, such as abundance, portability, cost-effectiveness, and ease of fabrication, making them superior for clinical diagnostics, environmental monitoring, and food safety assurance. Despite these advantages, µPADs lack the high sensitivity to detect many analytes at trace levels than other commercial analytical instruments such as mass spectrometry. Therefore, a preconcentration step is required to enhance their sensitivity. This review focuses on the techniques used to separate and preconcentrate the analytes onto the µPADs, such as ion concentration polarization, isotachophoresis, and field amplification sample stacking. Other separations and preconcentration techniques, including liquid-solid and liquid-liquid extractions coupled with µPADs, are also reviewed and discussed. In addition, the fabrication methods, advantages, disadvantages, and the performance evaluation of the µPADs concerning their precision and accuracy were highlighted and critically assessed. Finally, the challenges and future perspectives have been discussed.

Electrocolorimetric gel-based sensing approach for simultaneous extraction, preconcentration, and detection of iodide and chromium (VI) ions.

A total integrated electrocolorimetric sensing approach consisting of gel-based electromembrane extraction and colorimetric detection in a one-step process was developed. This system was designed using colorimetric reagents preadded to the agarose gel for the determination of the following two model analytes: iodide and hexavalent chromium [Cr(VI)]. In this system, when a voltage was applied, the analytes were extracted and transferred from the sample solution (donor phase) to the gel (acceptor phase). The analytes then simultaneously reacted with the colorimetric reagents inside the gel, yielding blue and violet colors for iodide and Cr(VI), respectively. These colors were then analyzed using a portable spectrometer and could also be distinguished with the naked eye. Parameters affecting the extraction efficiency were studied and optimized for both analytes. The gel composition for iodide detection was 4% (w/v) agarose, 5% (v/v) H2O2, and 1% (w/v) starch in 2 mM HCl. The gel composition for Cr(VI) detection was 2% (w/v) agarose and 1% (w/v) DPC in 0.5 mM HNO3. Both analytes were extracted at an applied potential of 50 V, an extraction time of 15 min and a stirring rate of 600 rpm. Under the optimized conditions, the developed systems provided linear responses within 15 min for iodide concentrations ranging from 50 to 250 µg L-1 with a detection limit of 18 µg L-1 and for Cr(VI) concentrations ranging from 30 to 125 µg L-1 with a detection limit of 5 µg L-1. Finally, these systems were successfully applied to the determination of iodide in iodide food supplement samples and Cr(VI) in drinking water samples, showing a negligible matrix effect. This integration could also be extended to other analytes and detection systems to develop sensitive, on-site, and environmentally friendly sensing approaches.

Gel electromembrane microextraction followed by ion chromatography for direct determination of iodine in supplements and fortified food samples: Green chemistry for food analysis.

In this study, a sensitive, selective, and environmentally friendly analytical method for direct extraction and preconcentration of iodine was developed. Iodine, as an iodate ion or iodide ion, was simultaneously extracted and preconcentrated by gel electromembrane microextraction (G-EME) and analyzed for total iodine by ion chromatography. The total iodine was determined by combining the peak areas of both iodate and iodide ions. Under the optimized conditions, linear calibration for iodine using a mixture of iodate and iodide ions was obtained from 10 to 100 µg L-1 (r2 > 0.996). The detection limit was 7.0 µg L-1. Recoveries of spiked iodine (as iodate) in the samples were greater than 90%. The method was applied for the determination of iodine in dietary supplements and fortified food samples, i.e., iodine-enriched eggs. Our developed method could be directly applied for the determination of iodine in different matrix samples including eggs without a pretreatment step.

Combining graphite with hollow-fiber liquid-phase microextraction for improving the extraction efficiency of relatively polar organic compounds.

In this study, we have developed a simple and effective hybrid extraction method based on the incorporation of raw carbon nanosorbents and octanol in the pores of a hollow-fiber membrane for improving the extraction efficiency of relatively polar organic compounds. Trihalomethanes (THMs) were used as model analytes. Three types of carbon nanosorbents (graphite, graphene, and multi-walled carbon nanotubes) were studied. The carbon sorbent incorporating membrane was used in a two-phase mode liquid-phase microextraction, with 1-octanol as the acceptor solution. Using a graphite-reinforced hollow-fiber membrane and an extraction time of 10 min, enrichment factors of 40-71 were obtained for trichloromethane, bromodichloromethane, bromoform, and chlorodibromomethane. Linear working ranges of 0.2-100 µg L-1 and limits of detection ranging from 0.01 µg L-1 (for CHCl2Br and CHClBr2) to 0.1 µg L-1 (for CHCl3) were achieved. The minimum detectable concentrations were far below the maximum concentration levels (60-200 µg L-1) set by the WHO for drinking water. The carbon-sorbent-reinforced hollow-fiber liquid-phase microextraction afforded higher extraction efficiency and shorter extraction time compared with conventional hollow-fiber liquid-phase microextraction. Finally, the method was applied to the analysis of real water samples, such as drinking water, tap water, and swimming pool water samples.

Development of a Sample Treatment Method for a Flow Injection Determination of Iodine in Eggs: A Comparison Study.

A simple treatment method was proposed for the determination of iodine in eggs, followed by a flow-injection spectrophotometry based on the catalytic effect of iodine in the reduction reaction of Ce(IV) with As(III). The egg matrix was removed based on protein precipitation principles. Several protein precipitation methods were investigated. The treatment using trichloroacetic acid satisfactorily removed most of the egg matrix components. A colorless solution and a good signal were achieved. The method provided more reliable results compared to the conventional alkali dry ashing.

Chromium speciation using paper-based analytical devices by direct determination and with electromembrane microextraction.

In this study, we developed and compared three different methods for chromium speciation in water samples using microfluidic paper-based analytical devices (µPADs). In all methods, detection was based on the complexation reaction of Cr(VI) with diphenylcarbazide on the µPADs. Cr(III) ions were oxidized to Cr(VI) by Ce(IV) prior to colorimetric detection on the µPADs. In the first method, oxidization of Cr(III) to Cr(VI) in the solution containing both trivalent and hexavalent chromium was performed using a batch procedure to obtain total chromium. A dual electromembrane extraction (DEME) technique for simultaneous preconcentration and extraction of chromium species and a single electromembrane extraction (SEME) for preconcentration and extraction of Cr(VI)/total chromium [quantified as Cr(VI) content after oxidation of Cr(III) ions to Cr(VI)] were used in the second and third methods, respectively. The electromembrane extraction was based on the electrokinetic migration of cationic Cr(III) and anionic Cr(VI) toward the cathode and anode, respectively, into the two different hollow fibres. Octanol-1 and bis(2-ethylhexyl) phosphate (DEHP) in octanol-1 (0.7% v/v) were the most suitable supported liquid membranes for extraction of Cr(VI) and Cr(III), respectively. Among these methods, SEME showed the lowest limits of detection for both analytes. Under optimized conditions, linear calibrations were obtained for Cr(III) from 3 to 30 µg L-1 and for Cr(VI) from 3 to 70 µg L-1. The detection limits were 1.0 µg L-1 and 0.7 µg L-1 for Cr(III) and Cr(VI), respectively. Our developed method was applied to analyse water samples spiked with different concentrations of Cr(III) and Cr(VI) at the parts-per-billion (ppb) level. The statistical evaluation showed that the proposed method agreed well with the validation method, i.e., inductively coupled plasma atomic emission spectroscopy (ICP-AES).

Evaluation of dispersive liquid-liquid microextraction by coupling with green-based agarose gel-electromembrane extraction: An efficient method to the tandem extraction of basic drugs from biological fluids.

Nowadays, developing new methods for the effective extraction/separation of drugs (present at trace levels) from complicated matrices (as biological fluids) is certainly a great challenge for many operators. In this regard, green-based agarose gel electromembrane extraction (G-EME) was for the first time combined with dispersive liquid-liquid microextraction (DLLME) toward G-EME/DLLME methodology (i.e., tandem extraction approach). Two basic drugs such as trimipramine (TRI) and clomipramine (CLO) extracted from the urine samples, were used as model compounds. Regarding method workflow, analytes were extracted from the 5 mL sample, through a synthesized agarose gel membrane, to the 700 µL aqueous acceptor phase under the optimized conditions (pH of acceptor phase: 2.0; pH of gel membrane: 2.0; pH of donor phase: 4.0, voltage value: 30 V, and extraction time: 25 min). In the next step, acceptor solution was poured to a conic vial and mixed with 100 µL alkaline solution (NaOH, 1 M). Afterwards, DLLME procedure took place again at optimal conditions, i.e., extraction solvent was carbon tetrachloride (10 µL), and dispersive solvent was acetone (100 µL). Ultimately, gas chromatography (GC) was applied for the detection and quantification of drugs. Such G-EME/DLLME configuration has brought two main advantages. Firstly, interferences such as proteins and other large biological molecules were eliminated from biological fluids via G-EME. Further, high enrichment factors (EFs of 260-370 refer to extraction recoveries of 52-74%) were obtained using DLLME with acceptable detection limits (1.0-3.0 ng mL-1). Finally, the suggested approach was successfully utilized to determine drugs at trace levels in urine samples.

A colorimetric paper-based analytical device coupled with hollow fiber membrane liquid phase microextraction (HF-LPME) for highly sensitive detection of hexavalent chromium in water samples.

A simple and highly sensitive procedure based on the combination of hollow fiber membrane liquid phase microextraction and a microfluidic paper-based analytical device (µPAD) was developed for pre-concentration and determination of hexavalent chromium in water samples. The hexavalent chromium was pre-concentrated using the HF-LPME technique via ion exchange or a coupled transport process through a supported ionic liquid (Aliquat 336) prior to colorimetric detection with diphenylcarbazide on the µPAD. The violet colour could be seen by the naked eye. Images from the µPADs were scanned using a commercial desktop scanner at 600 dpi resolution. ImageJ software was used for quantitative analysis by measuring the intensity values at green colour channel since it gave the best sensitivity among the RGB colour. Under optimal conditions, the calibration curve was linear in the range 10-90 µg L-1, with a limit of detection of 3 µg L-1. The developed method was successfully applied to determine the level of hexavalent chromium spiked into natural water samples at the parts-per-billion (ppb) level, and the results were in good agreement with those obtained using inductively coupled plasma atomic emission spectroscopy (ICP-AES). The developed method was able to improve the detection limit of the conventional µPAD, and was expected to be used for the effective analysis of hexavalent chromium in natural water.

In-line carbon nanofiber reinforced hollow fiber-mediated liquid phase microextraction using a 3D printed extraction platform as a front end to liquid chromatography for automatic sample preparation and analysis: A proof of concept study.

A novel concept for automation of nanostructured hollow-fiber supported microextraction, combining the principles of liquid-phase microextraction (LPME) and sorbent microextraction synergically, using mesofluidic platforms is proposed herein for the first time, and demonstrated with the determination of acidic drugs (namely, ketoprofen, ibuprofen, diclofenac and naproxen) in urine as a proof-of-concept applicability. Dispersed carbon nanofibers (CNF) are immobilized in the pores of a single-stranded polypropylene hollow fiber (CNF@HF) membrane, which is thereafter accommodated in a stereolithographic 3D-printed extraction chamber without glued components for ease of assembly. The analytical method involves continuous-flow extraction of the acidic drugs from a flowing stream donor (pH 1.7) into an alkaline stagnant acceptor (20 mmol L-1 NaOH) containing 10% MeOH (v/v) across a dihexyl ether impregnated CNF@HF membrane. The flow setup features entire automation of the microextraction process including regeneration of the organic film and on-line injection of the analyte-laden acceptor phase after downstream neutralization into a liquid chromatograph (LC) for reversed-phase core-shell column-based separation. Using a 12-cm long CNF@HF and a sample volume of 6.4 mL, linear dynamic ranges of ketoprofen, naproxen, diclofenac and ibuprofen, taken as models of non-steroidal anti-inflammatory drugs, spanned from ca. 5-15 µg L-1 to 500 µg L-1 with enhancement factors of 43-97 (against a direct injection of 10 µL standards into LC), and limits of detection from 1.6 to 4.3 µg L-1. Relative recoveries in real urine samples ranged from 97% to 105%, thus demonstrating the reliability of the automatic CNF@HF-LPME method for in-line matrix clean-up and determination of drugs in urine at therapeutically relevant concentrations.

Dynamic single-interface hollow fiber liquid phase microextraction of Cr(VI) using ionic liquid containing supported liquid membrane.

The concept of dynamic single-interface hollow fiber membrane liquid-phase microextraction (HF-LPME), where the target analyte was extracted on-line and eluted inside the lumen of the HF membrane, was explored. An ionic liquid containing supported liquid membrane was used for the trace determination of Cr(VI) as a model compound. Since the extraction took place on-line inside the hollow fiber membrane, the mass transfer behavior was described and discussed in comparison with the conventional HF-LPME. The extraction efficiency was improved by a recirculation configuration of the sample solution at relatively high sampling flow rates as a result of the increased effective contact area. The positive pressure observed to be built up during extraction was overcome by a flow-balancing pressure design. The dynamic single-interface HF-LPME method with an enrichment factor of 41, a detection limit of 1.2µgL-1 and determination limit of 4.0µgL-1 was successfully applied to the reliable determination of Cr(VI) from environmental water samples. The quantification limit is below the maximum contaminant level in drinking water, set at 10µgL-1 of hexavalent chromium by the California Environmental Protection Agency.

Electro-enhanced hollow fiber membrane liquid phase microextraction of Cr(VI) oxoanions in drinking water samples.

Hollow fiber membrane liquid phase microextraction (HF-LPME) of metal oxoanions was studied using an ionic carrier enhanced by the application of an electric field (electro-enhanced HF-LPME). The Cr(VI) oxoanion was used as the model. The transportation of Cr(VI) oxoanions across the supported liquid membrane (SLM) was explored via the ion-exchange process and electrokinetic migration. The type of SLM, type of acceptor solution, extraction time, electric potential, and stirring rate were investigated and optimized using MilliQ water. Electro-enhanced HF-LPME provided a much higher enrichment factor compared to conventional HF-LPME (no electric potential) for the same extraction time. A mixture of an anion exchange carrier (methyltrialkyl-ammonium chloride, Aliquat 336) in the SLM facilitated the transportation of Cr(VI) oxoanions. The SLM that gave the best performance was 1-heptanol mixed with 5% Aliquat 336 with 1M NaOH as the acceptor. Linearity was obtained in the working range of 3-15 µg L(-1) Cr(VI) (R(2)>0.99) at 30 V with a 5 min extraction time. The limit of detection was below 5 µg L(-1). The relative standard deviation was less than 12%. The method was applied to drinking water samples. The recoveries of spiked Cr(VI) in drinking water samples were in the range of 96-101% based on the matrix-matched calibration curves. The method was limited to samples containing low levels of ions due to the occurrence of electrolysis. The type of SLM, particularly regarding its resistance, should be tuned to control this problematic phenomenon.

Hybrid flow analyzer for automatic hollow-fiber-assisted ionic liquid-based liquid-phase microextraction with in-line membrane regeneration.

The proof-of-concept of a new methodology for in-line hollow-fiber (HF)-assisted three-phase liquid-phase microextraction (LPME) allowing for handling of the feed and acceptor aqueous solutions and of minute volumes of the organic extracting phase in a programmable flow mode is reported in this paper. The flow analyzer fosters in-line anchoring of ionic-liquid-laden extracting solution (10 % (v/v) methyltrioctyl ammonium chloride in kerosene) in the pores of a single-strand microporous polypropylene HF, and regeneration of the liquid-phase membrane itself for each individual analysis cycle in a fully automated mode. Using hexavalent chromium as a model analyte and 1,5-diphenylcarbazide as a chromogenic probe in the acceptor solution, the flow-based HF-LPME hyphenated system was harnessed to the clean-up of troublesome samples (viz., domestic wastewater and soil leachates) with concomitant enrichment of target species. Distinct extraction modes and chemistries were assessed for enhanced Cr(VI) permeability. A single sample plug was subjected to a twofold backward-forward flow extraction so as to decrease the thickness of the boundary layer at the HF shell side for improved extraction efficiency. Under the optimized physicochemical variables, a limit of detection of 4.6 µg L(-1) Cr(VI), a dynamic linear range of up to 500 µg L(-1) and intermediate precision better than 10 % were obtained for a sample volume of 2.8 mL buffered at pH 4 and a volume of organic extractant of 120 µL, with an enrichment factor of ca. 11 for a sample residence time in the donor compartment of merely 4.5 min. Analyte recoveries in domestic wastewaters were ≥83 % using external calibration with relative standard deviations better than 14 %, thereby demonstrating the expedient clean-up of samples with elevated content of dissolved organic carbon. The automatic HF-LPME method was validated in terms of bias against the SRM 2701 (NIST soil) preceded by the EPA alkaline digestion method 3060A. No significant differences between Cr(VI) concentration as obtained with the automatic HF-LPME system (546 ± 57 mg kg(-1)) and the certified value (551.2 ± 17.2 mg kg(-1), expressed as mean ± combined uncertainty) were encountered at the 0.05 significance level.

Single strand hollow fiber membrane (SSHFM): an on-line sample preparation for the flow based colorimetric determination of free iron in fruit juices.

A single strand hollow fiber membrane (SSHFM) was developed for the on-line sample preparation for the flow based colorimetric determination of free iron levels in fruit juices. The SSHFM, as used, could separate Fe(2+) from some spectrophotometric interfering agents in the fruit juice, such as pigments, solid suspensions and polysaccharides. The screening process was likely to have been primarily based on dialysis, wherein only ions or molecules that are smaller than the pores of the membrane can diffuse through while relatively larger molecules or particles could not. Two flow modes, a continuous and stopped flow, were studied. Factors that influenced the sensitivity (%dialysis) of the method, such as the flow rate, sample volume, flow direction and stopped flow time, were optimized. The stopped flow mode was found to be relatively more sensitive than the continuous flow mode and displayed a linear range of 1-30 mg L(-1) Fe(2+), a limit of detection of 0.5 mg L(-1), and a % relative standard deviation of less than 2% (n=8) for the analysis of 10 mg L(-1) Fe(2+) spiked grape juice samples. A sample throughput of 24 samples h(-1), was attained without any further sample treatment.

In situ derivatization and hollow fiber membrane microextraction for gas chromatographic determination of haloacetic acids in water.

An alternative method for gas chromatographic determination of haloacetic acids (HAAs) in water using direct derivatization followed by hollow fiber membrane liquid-phase microextraction (HF-LPME) has been developed. The method has improved the sample preparation step according to the conventional US EPA Method 552.2 by combining the derivatization and the extraction into one step prior to determination by gas chromatography electron captured detector (GC-ECD). The HAAs were derivatized with acidic methanol into their methyl esters and simultaneously extracted with supported liquid hollow fiber membrane in headspace mode. The derivatization was attempted directly in water sample without sample evaporation. The HF-LPME was performed using 1-octanol as the extracting solvent at 55 degrees C for 60 min with 20% Na2SO4. The linear calibration curves were observed for the concentrations ranging from 1 to 300 microg L(-1) with the correlation coefficients (R2) being greater than 0.99. The method detection limits of most analytes were below 1 microg L(-1) except DCAA and MCAA that were 2 and 18 microg L(-1), respectively. The recoveries from spiked concentration ranged from 97 to 109% with %R.S.D. less than 12%. The method was applied for determination of HAAs in drinking water and tap water samples. The method offers an easy one step high sample throughput sample preparation for gas chromatographic determination of haloacetic acids as well as other contaminants in water.

A simple supported liquid hollow fiber membrane microextraction for sample preparation of trihalomethanes in water samples.

A simple and efficient liquid-phase microextraction (LPME) technique using a supported liquid hollow fiber membrane, in conjunction with gas chromatography-electron capture detector has been developed for extraction and determination of trihalomethanes (THMs) in water samples. THMs were extracted from water samples through an organic extracting solvent impregnated in the pores and filled inside the porous hollow fiber membrane. Our simple conditions were conducted at 35 degrees C with no stirring and no salt addition in order to minimize sample preparation steps. Parameters such as types of hollow fiber membranes, extracting solvents and extraction time were studied and optimized. The method exhibited enrichment factors ranged from 28- to 62-fold within 30 min extraction time. The linearity of the method ranged from 0.2 to 100 microg l(-1). The limits of detection were in the low microg l(-1) level, ranging between 0.01 and 0.2 microg l(-1). The recoveries of spiked THMs at 5 microg l(-1) in water were between 98 and 105% with relative standard deviations (RSDs) less than 4%. Furthermore, the method was applied for determination of THMs in drinking water and tap water samples was reported.