Determination of Trace Amounts of Cd(II), Cu(II), and Ni(II) in Food Samples Using a Novel Functionalized Magnetic Nanosorbent

This work describes a novel sorbent based on functionalization of magnetic nanoparticles by 2-aminobenzothiazole and its application in the extraction and preconcentration of trace amount of Cd(II), Cu(II), and Ni(II) ions. This nanosorbent was characterized by Fourier transfer infrared spectroscopy, thermal analysis, X-ray powder diffraction, elemental analysis, and scanning electron microscopy. The effects of various factors such as pH value, sorption time, sorbent dosage, type, volume, and concentration of the eluent as well as the elution time were investigated. Following the sorption and the elution of target analytes, the Cd(II), Cu(II), and Ni(II) ions were determined by flame atomic absorption spectrometry. Under the optimal conditions, the limits of detection (LODs) were 0.03, 0.009, and 0.1 μg L^?1 for Cd(II), Cu(II), and Ni(II), respectively. Linearity was within the range of 0.1–75 ng mL^?1 for Cd(II), 0.03–50 ng mL^?1 for Cu(II), and 0.5–100 ng mL^?1 for Ni(II) in the initial solution with r ² values greater than 0.9978. The relative standard deviations of the method were less than 8.4 %. The preconcentration factor of the method was 277. The sorption capacity of this new sorbent was 65, 78, and 49 mg g^?1 for Cd(II), Cu(II), and Ni(II), respectively. The proposed method was validated using two certified reference materials (LGC 6010 hard drinking water and NIST SRM 1515 apple leaves) in order to exhibit its applicability. Ultimately, this method was applied to the rapid extraction of the trace quantities of Cd(II), Cu(II), and Ni(II) ions in different food samples, and satisfactory results were obtained.     

A Nanocomposite Based on Dipyridylamine Functionalized Magnetic Multiwalled Carbon Nanotubes for Separation and Preconcentration of Toxic Elements in Black Tea Leaves and Drinking Water

A novel functionalized magnetic multiwalled carbon nanotube composite was prepared and utilized as a nanosorbent for separation and preconcentration of Cr(III), Cd(II), Cu(II), Pb(II), and Ni(II) ions. The synthesized nanosorbent was characterized with various techniques. The parameters influencing the preconcentration efficiency were optimized through experimental design methodology by using Box-Behnken design method. Uptake time, pH of sample, and magnetic nanosorbent amount were evaluated in the sorption step as the main affecting factors, while four variables including type, volume, concentration of the eluent, and elution time were considered in the elution step. After sorption and elution steps, the target analytes were determined by flame atomic absorption spectrometry. Limit of detection was 0.5, 0.08, 0.7, 0.4, and 0.1 ng mL^?1 for Cr(III), Cu(II), Pb(II), Ni(II), and Cd(II) ions, respectively. All relative standard deviations of the method were <9.5%. The capacity of the sorbent ranged between 184 and 215 mg g^?1. Finally, the developed method was successfully applied to the rapid extraction of trace amounts of these ions from black tea leaf samples and drinking water.     

Graphene Reinforced Hollow Fiber Liquid-Phase Microextraction Combined with HPLC for the Determination of Bisphenol A and 4-Tert-Butylphenol in Bottled Juice

A new analytical method by graphene-reinforced hollow fiber liquid-phase microextraction combined with high-performance liquid chromatography fluorescence detection was developed for the determination of bisphenol A and 4-tert-butylphenol in bottled juices. Several important experimental parameters were studied to get optimal extraction conditions for the analytes. Under the optimized conditions, the method showed a good performance having a linear response in the range from 0.05 to 10.0 ng mL^?1 with the correlation coefficients (r) of 0.9965–0.9994 and limits of detection of 0.01 ng mL^?1. The relative standard deviations were in the range from 6.4 to 7.2 % at the spiked concentration of 1.0 ng mL^?1. The method combines the high-adsorption capacity of graphene and the excellent clean-up performance of hollow fiber liquid-phase microextraction and has been successfully applied to the analysis of the analytes in bottled juice samples.     

Vortex-Assisted Liquid–Liquid Microextraction Combined with HPLC for the Simultaneous Determination of Five Phthalate Esters in Liquor Samples

A vortex-assisted liquid–liquid microextraction (VALLME) method using hexanoic acid as extractant followed by high-performance liquid chromatography–diode array detection was developed for the extraction and determination of five phthalate esters (PAEs) including bis-methylglycol ester (DMEP), benzyl butyl phthalate (BBP), dicyclohexyl phthalate (DCHP), di-n-butyl phthalate (DBP), and di-n-octyl phthalate (DNOP) from liquor samples. In this method, hexanoic acid was employed as extraction solvent, because its density is lower than water. And vortex mixing was utilized as a mild emulsification procedure to reduce emulsification time and improve the effect of extraction. Under the studied conditions, five phthalate esters were successfully separated within 20 min and the limits of detection were 2.3 ng mL^?1 for DMEP, 1.1 ng mL^?1 for BBP, 1.9 ng mL^?1 for DCHP, 1.2 ng mL^?1 for DBP, and 1.5 ng mL^?1 for DNOP, respectively. Recoveries of the PAEs spiked into liquor samples were ranged from 89 to 93 %. The precisions of the proposed method were varied from 1.6 to 2.6 % (RSD). The VALLME method has been proved to have the potential to be applied to the preconcentration of the target analytes. Moreover, the method is simple, high sensitivity, consumes much less solvent than traditional methods and environmental friendly.     

Synthesis,characterisation and analytical application of Fe3O4@SiO2@polyaminoquinoline magnetic nanocomposite for the extraction and pre-concentration of Cd(II) and Pb(II) in food samples

This work describes a novel Fe₃O₄@SiO₂@polyaminoquinoline magnetic nanocomposite and its application in the pre-concentration of Cd(II) and Pb(II) ions. The parameters affecting the pre-concentration procedure were optimised by a Box–Behnken design through response surface methodology. Three variables (extraction time, magnetic sorbent amount and pH) were selected as the main factors affecting the sorption step, while four variables (type, volume and concentration of the eluent, and elution time) were selected as main factors in the optimisation study of the elution step. Following the sorption and elution of analytes, the ions were quantified by flame atomic absorption spectrometry (FASS). The limits of detection were 0.1 and 0.7 ng ml^?1 for Cd(II) and Pb(II) ions, respectively. All the relative standard deviations were less than 7.6%. The sorption capacities of this new sorbent were 57 mg g^?1 for Cd(II) and 73 mg g^?1 for Pb(II). Ultimately, this nanocomposite was successfully applied to the rapid extraction of trace quantities of these heavy metal ions from seafood and agricultural samples and satisfactory results were obtained.     

A novel 4-(2-pyridylazo) resorcinol functionalised magnetic nanosorbent for selective extraction of Cu(II) and Pb(II) ions from food and water samples

This paper describes a novel sorbent based on 4-(2-pyridylazo) resorcinol functionalised magnetic nanoparticles and its application for the extraction and pre-concentration of trace amounts of Cu(II) and Pb(II) ions. The nanosorbent was characterised by Fourier transform infrared spectroscopy, X-ray powder diffraction, thermal analysis, elemental analysis and scanning electron microscopy. The effects of various parameters such as pH, sorption time, sorbent dosage, elution time, volume and concentration of eluent were investigated. Following the sorption and elution of analytes, Cu(II) and Pb(II) ions were quantified by flame atomic absorption spectrometry. The limits of detection were 0.07 and 0.7 μg l^?1 for Cu(II) and Pb(II), respectively. The relative standard deviations of the method were less than 7%. The sorption capacity of this new sorbent were 92 and 78 mg g^?1 for Cu(II) and Pb(II), respectively. Finally this nanosorbent was applied to the rapid extraction of trace quantities of Cu(II) and Pb(II) ions in different real samples and satisfactory results were obtained.     

Method for the determination of cadmium,lead, nickel,cobalt and copper in seafood after dispersive liquid–liquid micro-extraction

A method using dispersive liquid–liquid micro-extraction (DLLME) and detection by inductively coupled plasma optical emission spectroscopy (ICP-OES) was developed for the determination of trace elements in seafood samples. The procedure allowed the simultaneous determination of Cd(II), Pb(II), Ni(II) Cu(II) and Co(II) after pre-concentration using sodium diethyldithiocarbamate (DDTC) as a chelating agent. Under optimised conditions, the method had a limit of detection (LOD) of 0.03, 0.11, 0.12, 0.18 and 0.12 µg l^?1 for Cd(II), Pb(II), Ni(II) Cu(II) and Co(II), respectively. The following enrichment factors were obtained: 16 (Cd), 34 (Pb), 20 (Ni) 34 (Cu) and 12 (Co). The procedure was applied for the determination of these elements in seafood (shrimp, mussel, bass and mullet) samples. The method is simple, efficient and easy to perform for the simultaneous determination of elements in seafood samples by ICP-OES.     

Urinary aflatoxin exposure monitoring in rural and semi-urban populations in Ogun state,Nigeria

Aflatoxins are a major class of fungal toxins that have food safety importance due to their economic and health impacts. This pilot aflatoxin exposure biomonitoring study on 84 individuals was conducted in a rural (Ilumafon) and a semi-urban community (Ilishan Remo) of Ogun state, Nigeria, to compare aflatoxin exposures among the two population cohorts. First morning urine samples were obtained from the participants, and the urinary aflatoxin M₁ (AFM₁) levels were measured by a quantitative Helica Biosystems Inc. ELISA kit assay. About 99% (83 out of 84) of the urine samples had detectable AFM₁ levels in the range of 0.06 to 0.51 ng mL^?1 (median: 0.27 ng mL^?1). The mean urinary AFM₁ levels were significantly (p = 0.001) higher in the semi-urban population (0.31 ± 0.09 ng mL^?1) compared to the rural population (0.24 ± 0.07 ng mL^?1). There were, however, no significant differences in mean urinary AFM₁ levels of males and females, and among children, adolescents and adults. This study indicates high aflatoxin exposure to the extent of public health concerns in the studied populations. Thus, more efforts are required for aflatoxin exposure monitoring and control in high-risk regions.     

Determination of Cobalt in Food and Water Samples by Ultrasound-assisted Surfactant-enhanced Emulsification Microextraction and Graphite Furnace Atomic Absorption Spectrometry

A novel method based on ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) has been developed for the preconcentration of cobalt prior to its determination by graphite furnace atomic absorption spectrometry. In the UASEME technique, chloroform was used as the extraction solvent, sodium dodecyl sulfate was adopted as emulsifier, and ultrasound was applied to assist emulsification. There is no need of using organic dispersive solvent which is typically required in conventional dispersive liquid–liquid microextraction method. Several parameters that affect the extraction efficiency, such as the kind and volume of the extraction solvent, the type and concentration of the surfactant, pH of sample solution, concentration of the chelating agent, and extraction time and temperature were investigated and optimized. Under the optimal conditions, the linearity of calibration curve was in the range of 0.1–5 ng mL^?1 with a correlation coefficient (R ²) of 0.9992. An enrichment factor of 58 was achieved with a sample volume of 5.0 mL. The detection limit of this method for Co was 15.6 ng L^?1, and the relative standard deviation (RSD) was 4.3 % at 1.0 ng mL^?1 concentration level of Co. The accuracy of the developed method was evaluated by analysis of the certified reference materials GBW07605 tea leaf and GBW10015 spinach. The method was successfully applied to determine trace cobalt in food and water samples with satisfactory results.     

Determination of heavy metal ions in vegetable samples using a magnetic metal–organic framework nanocomposite sorbent

This paper describes the synthesis and application of a novel magnetic metal–organic framework (MOF) [(Fe₃O₄-benzoyl isothiocyanate)/Cu₃(benzene-1,3,5-tricarboxylate)₂] to pre-concentrate trace amounts of Cd(II), Pb(II), Zn(II) and Cr(III) ions and their determination by flame atomic absorption spectrometry. A Box–Behnken design was used to find the parameters affecting the pre-concentration procedure through response surface methodology. Three factors including uptake time, amount of the magnetic sorbent and pH of the sample were selected as affecting factors in the sorption step, and four factors including type, volume and concentration of the eluent as well as the elution time were selected in the elution step for the optimisation study. The opted values were 30 mg, 10.1 min, 5.9, EDTA, 4.0 ml, 0.57 mol l^–1 EDTA solution and 13.0 min for the amount of the magnetic sorbent, uptake time, pH of the sample, type, volume, concentration of the eluent, and elution time, respectively. The limits of detection (LODs) were 0.12, 0.7, 0.16, and 0.4 ng ml^?1 for Cd(II), Pb(II), Zn(II) and Cr(III) ions, respectively. The relative standard deviations (RSDs) of the method were less than 7.2% for five separate batch experiments for the determination of 30 μg l^?1 of Cd(II), Pb(II), Zn(II) and Cr(III) ions. The sorption capacity of the [(Fe₃O₄-benzoyl isothiocyanate)/MOF] was 175 mg g^?1 for Cd(II), 168 mg g^?1 for Pb(II), 210 mg g^?1 for Zn(II) and 196 mg g^?1 for Cr(III). It was found that the magnetic MOF nanocomposite demonstrated a higher capacity compared with Fe₃O₄-benzoyl isothiocyanate. Finally, the magnetic MOF nanocomposite was successfully applied to the rapid extraction of trace amounts of the heavy metal ions from vegetable samples.     

Cadmium Ions Determination in Sea Food Samples Using Dipyridyl-Functionalized Graphene Nano-sheet

In this work, graphene nano-sheets was modified by dipyridyl amine group and used as a novel sorbent for selective separation and preconcentration of cadmium ions. The sorbent was characterized by infrared spectroscopy, transmission electron microscopy, thermal analysis, and elemental analysis. The application of this sorbent was investigated in determination of cadmium ions in sea food samples by flame atomic absorption spectrometry. The effective parameters on adsorption and desorption of cadmium were optimized. The limit of detection, the relative standard deviation and the recovery of the established method were found to be 0.19 ng mL^?1, 1.6 %, and 99.1 %, respectively. The method was validated using various standard reference materials and was applied for cadmium determination in sea food sample.     

Rapid Analysis of Styrene in Drinking Water and Tea Samples Using Dispersive Liquid-Liquid Microextraction Combined with Liquid Chromatography-Ultraviolet Detection

In this project, a simple, low-cost and rapid procedure based on dispersive liquid–liquid microextraction (DLLME) technique coupled with high performance liquid chromatography-ultraviolet detector (HPLC-UV) has been used for the extraction and determination of styrene in aqueous solutions. Several factors, such as type of extraction and dispersive solvents and their volumes, salt addition, and pH were optimized. Under optimal conditions, the recoveries of styrene for tea and water samples spiked with 10 and 15 ng mL^?1 were in the range of 91.4–97.8 %, whereas the temperature was set at 0, 4, 20, 70 and 91 °C for 15, 30, 60, 1440, and 14,400 min. The linear range was obtained in the interval of 1.86–50 ng mL^?1. The limits of detection (S/N = 3) and quantitation (S/N = 10) were 0.6 and 1.86 ng mL^?1, respectively. The relative standard deviations (RSDs) for three replicated analysis of styrene in aqueous samples ranged from 0.01 to 0.3 %.     

Sensitive Determination of Bromate in Water Samples by Capillary Electrophoresis Coupled with Electromembrane Extraction

Electromembrane extraction (EME) as a novel sample preparation technique was firstly applied for the purification and enrichment of bromate (BrO₃ ^?) in drinking water prior to capillary zone electrophoresis with capacitively coupled contactless conductivity detection (CZE-C⁴D). BrO₃ ^?, as the primary disinfection by-product of ozonation, could be well separated with the major inorganic anions coexisting in water samples using a 300 mmol L^?1 acetic acid solution as the running buffer. Under the optimum conditions, the calibration curve showed good linearity (r ²?=?0.996), and the limit of detection was down to 0.12 ng mL^?1 with the enrichment factor at 267. The relative standard deviation (RSD) values for peak area and migration time at a spiked concentration of 10 ng mL^?1 of bromate were below 8.8 and 2.5 %, respectively. This proposed EME-CZE-C⁴D method has been successfully applied to analyze bottled drinking water and tap water samples with recoveries in the range of 85~98 %, providing an alternative to the determination of bromate in drinking water.     

One-Step Synthesis of Zirconia and Magnetite Nanocomposite Immobilized Chitosan for Micro-Solid-Phase Extraction of Organophosphorous Pesticides from Juice and Water Samples Prior to Gas Chromatography/Mass Spectroscopy

In this research, a magnetic sorbent was prepared by immobilizing zirconia and magnetite (Fe₃O₄) nanoparticles in chitosan, which is characterized and used as an effective nanosorbent in magnetic dispersive micro-solid-phase extraction (MDMSPE) of organophosphorous pesticides (OPPs) from juice and water samples prior to gas chromatography-mass detection (GC-MS). The properties and morphology of synthesized sorbent were characterized by scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), and differential scanning calorimetric (DSC) analysis. The main experimental parameters including pH level, extraction time, sorbent mass, salt concentration, and desorption conditions were investigated and optimized to maximize extraction efficiency. Under optimized conditions, the calibration curves were obtained in the concentration range of 0.1–500 ng mL^?1 with correlation coefficients between 0.9993 and 0.9999. The limits of detection (signal-to-noise ratio (S/N) = 3) and limits of quantification (S/N = 10) of the method ranged from 0.031 to 0.034 ng mL^?1 and 0.105–0.112 ng mL^?1, respectively. The intra-day and inter-day RSDs were 2.2–5.7 and 2.5–7.5%, respectively. The method was successfully applied to the analysis of OPPs in fruit juices (apple, peach, and cherry) and water (mineral, tap, and river) real samples, with recoveries in the range of 86.0–106.0% for the spiked juice and water samples. The results showed that with combination of high selectivity of zirconia and magnetic property of magnetite as well as immobilizing ability of chitosan, the fabricated sorbent exhibited exceptional extraction ability toward the OPPs.     

Application of Polypropylene Amine Dendrimers (POPAM)-Grafted MWCNTs Hybrid Materials as a New Sorbent for Solid-Phase Extraction and Trace Determination of Gold(III) and Palladium(II) in Food and Environmental Samples

A new method which utilizes a polypropylene amine dendrimers (POPAM)-grafted multi-walled carbon nanotubes (MWCNTs) hybrid materials as an effective sorbent in solid-phase extraction has been developed for separation and preconcentration of Au(III) and Pd(II) trace levels in food, water and soil samples. The optimum experimental conditions such as pH, flow rates, type, concentration, and volume of the eluent for elution of gold and palladium ions, breakthrough volume, and effect of potentially interfering ions on separation and determination of these noble metals were investigated. The extraction recoveries for the mentioned noble metals were greater than 98 % and the limits of detection were 0.08 and 0.12 ng mL^?1 for gold and palladium, respectively. The relative standard deviations of the method were less than 4 % for eight separate column experiments for determination of 5.0 μg of gold and palladium ions. The adsorption capacity of the modified MWCNT was 92 mg g^?1 for gold and 74 mg g^?1 for palladium on POPAM-grafted MWCNTs. Validation of the suggested method was performed by analyzing certified reference materials. Finally, the proposed method was applied for determination of gold(III) and palladium(II) in real samples, including fish, shrimp, water, and soil.     

Simplified multi-element analysis of ground and instant coffees by ICP-OES and FAAS

A simplified alternative to the wet digestion sample preparation procedure for roasted ground and instant coffees has been developed and validated for the determination of different elements by inductively coupled plasma optical emission spectrometry (ICP-OES) (Al, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn) and flame atomic absorption spectrometry (FAAS) (Ca, Fe, K, Mg, Na). The proposed procedure, i.e. the ultrasound-assisted solubilisation in aqua regia, is quite fast and simple, requires minimal use of reagents, and demonstrated good analytical performance, i.e. accuracy from ?4.7% to 1.9%, precision within 0.5–8.6% and recovery in the range 93.5–103%. Detection limits of elements were from 0.086 ng ml^?1 (Sr) to 40 ng ml^?1 (Fe). A preliminary classification of 18 samples of ground and instant coffees was successfully made based on concentrations of selected elements and using principal component analysis and hierarchic cluster analysis.     

Highly Sensitive Detection of Okadaic Acid in Seafood Products via the Unlabeled Piezoelectric Sensor

The affinity reaction between the antibodies to okadaic acid immobilized on the sensor’s surface and the toxin in the solution has been investigated. The affinity constant, as well as the association rate constant and the dissociation rate constant, has been calculated. The unlabeled affinity sensor for the detection of okadaic acid has been developed. The calibration plot is linear in the range of concentrations of 5–500 ng mL^?1; the limit of detection is 1.4 ng mL^?1. The developed sensor can be successfully used for the detection of toxins in real samples.     

A Miniaturized Preconcentration Method Based on Dispersive Liquid–Liquid Microextraction for the Spectrophotometric Determination of Aziridine in Food Simulants

In this work a simple, rapid and sensitive method using dispersive liquid–liquid microextraction (DLLME) combined with UV–Vis spectrophotometry has been developed for the preconcentration and determination of trace amounts of aziridine in food simulants. The method is based on derivatization of aziridine with Folin's reagent (1,2-naphthoquione-4-sulphonic acid) and extraction of color product using DLLME technique. Some important parameters, such as reaction conditions, and type and volume of extraction solvent and disperser solvent were studied and optimized. Under optimum conditions, a linear calibration curve in the range of 2.0–350 ng mL^?1 of aziridine was obtained. Detection limit based on 3S_b was 1.0 ng mL^?1, and the relative standard deviation for 50 ng mL^?1 of aziridine was 2.49c (n?=?7). The proposed method was applied for the determination of aziridine in food simulants.     

Determination of Amaranth in Beverage by Indirect Competitive Enzyme-linked Immunosorbent Assay (ELISA) Based on Anti-amaranth Monoclonal Antibody

Amaranth (E 123) is a member of azo dyes, and it is allowed to use in various foods. The acceptable maximum addition of amaranth is strictly fixed because of its potential risk to physical health. The objective of this study was to prepare a specific anti-amaranth monoclonal antibody and develop an indirect competitive ELISA for amaranth quantification analysis. The immunogen and the coating antigen were designed by introducing a carboxyl group into amaranth for the conjugation with carrier proteins. Based on the immunogen, the monoclonal antibody exhibits satisfactory performances and the proposed ELISA shows an IC₅₀ of 20.33 ng mL^?1. The limit of detection is as low as 3.35 ng mL^?1, and the linear standard curve of the method ranges from 3.0 to 243.0 ng mL^?1. Additionally, the antibody reflects minimal cross-reactivity (<1 %) with six related food dyes (erythrosine, ponceau 4R, allura red, tartrazine, sunset yellow FCF, and brilliant blue). The recoveries of amaranth spiked beverage samples are in the range of 85.8–100.7 % with low coefficient of variation values (<11.5 %). The data shows that the developed ELISA provides a simple, sensitive, specific, and accurate alternative for amaranth determination and monitoring. Furthermore, it is the first time that icELISA of amaranth is developed based on monoclonal antibodies.     

Multi-element determination in some foods and beverages using silica gel modified with 1-phenylthiosemicarbazide

ABSTRACT

1-Phenylthiosemicarbazide bonded modified silica gel (PTC-SG) was synthesised and characterised by FTIR, SEM and elemental analysis for a novel separation/preconcentration of multiple elements based on solid phase extraction. The analytical parameters including pH of solutions, amounts of PTC-SG, flow rates of sample, eluent type and sample volume were optimised. The adsorption capacities of PTC-SG were found to be 7.9, 6.4, 6.3, 8.3, 7.2, 8.9 and 6.6 mg/g for Cu(II), Cd(II), Pb(II), Co(II), Cr(III), Ni(II) and Mn(II), respectively. The limit of detection (LOD) was calculated as 3x the standard deviation(s) of the reagent blank (k = 3, N = 21) and the LOD values were obtained to be 0.98 µg L^?1 (Cu), 0.65 µg L^?1 (Cd), 0.57 µg L^?1 (Pb), 1.12 µg L^?1 (Co), 1.82 µL^?1 (Cr), 1.67 µg L^?1 (Ni) and 0.55 µg L^?1 (Mn). Certified reference materials were used to test the validation of the present method. The new solid phase extraction method was successfully applied to determination of the amount of multiple elements in food and beverage samples.