Analytical application of food dye Sunset Yellow for the rapid kinetic determination of traces of copper(II) by spectrophotometry

A sensitive and rapid kinetic method for trace determination of Cu(II) was developed and validated, based on its catalytic effect on the oxidation of disodium-6-hydroxy-5-[(4-sulphophenyl)azo]-2-naphtalenesulphonic acid (wide used, food colour “Sunset Yellow FCF”, E110, in text selected as SY) by hydrogen peroxide in borate buffer at pH 10.5. The reaction was monitored spectrophotometrically by measuring the decrease in the absorbance of SY at 478.4 nm. The optimum operating conditions regarding concentration of reagents, pH and temperature were established. The calibration curve was linear up to 318 ng mL⁻¹ of Cu(II) and the limit of detection (3σ/S) is 5.0 ng mL⁻¹, and limit of quantification (10σ/S) is 16.67 ng mL⁻¹. The proposed kinetic procedure was successfully applied to monitoring of the concentration of Cu(II) in fruit, wine and milk samples from different areas. The results obtained by the proposed kinetic procedure were compared by those obtained by ICP-OES method, and shown good agreement. The proposed kinetic method could be used for monitoring of quality of drinks or fruit depending on Cu(II) concentration, because of its important role as nutritional element.     

Determination of copper with 5,5-dimethylcyclohexane-1,2,3-trione 1,2-dioxime 3-thiosemicarbazone in olive oils by adsorptive stripping square wave voltammetry

In the present paper a method for the determination of Cu in olive oil samples by adsorptive stripping square wave voltammetry (Ad-SSWV) is presented. It has been proven that Cu reacts with 5,5-dimethylcyclohexane-1,2,3-trione 1,2-dioxime 3-thiosemicarbazone, DCDT, in strongly acid media giving rise to a complex. In Ad-SSWV the complex Cu–DCDT experiments an adsorptive reductive process which promotes the appearance of a peak at −0.570 V. The extraction process of Cu from olive oil is carried out with hot concentrated HCl. Calibration graph has been constructed from 0 to 35 ng mL⁻¹ and the detection limit was 0.49 ng mL⁻¹. The method has been applied to commercial olive oils samples and the amounts of Cu found are very similar to those obtained when samples are analysed by AAS.     

Application of acetylacetone chelation solid-phase extraction to GFAAS measurements of trace amounts of beryllium in livers and muscles of poultry and livestock

Trace amounts (0.004–0.55 ng) of beryllium (Be) in a dried bovine liver sample (20 mg) can be accurately determined by graphite-furnace atomic absorption spectrophotometry (GFAAS) after treating with microwave digestion (HNO₃/H₂O₂) at 85 °C for 10 min and using acetylacetone as a chelating agent in the presence of an acetate buffer (pH 6.0). The method detection limit (MDL, 3σ) for Be was found to be 0.18 ng g⁻¹ and the limit of quantification (LOQ, 10σ) was found to be 0.60 ng g⁻¹; the calibration graph was linear up to 27 ng g⁻¹. The Be contents measured in four liver and four muscle samples (BCR CRM-185R bovine liver, BCR CRM-384 pork muscle, and six samples collected in Kaohsiung, Taiwan, ROC) were between 2.3 and 4.7 ng g⁻¹. Good spiked recoveries (96.0–103.0%) were obtained for these eight samples with a relative standard deviation (RSD, n = 3) ?3.0%. The method could be applied to measurements of Be in livers and muscles of poultry and livestock.     

Highly selective optical nitrite sensor for food analysis based on Lauth’s violet-triacetyl cellulose membrane film

A new sensor has been developed for the determination of nitrite based on the immobilisation of Lauth’s violet on triacetyl cellulose membrane using absorption spectrophotometry. The optical sensor signal is based on the reaction of Lauth’s violet with bromate as an oxidant in the presence of nitrite to produce a colourless product. Nitrite has a strong catalytic effect on the oxidation of Lauth’s violet with bromate in acidic media. The difference in the absorbance of the optode at 617 nm between uncatalysed and catalysed reactions (ΔA) was directly proportional to the concentration of nitrite in sample solution. A linear calibration curve (r² = 0.985) was observed in the nitrite concentration range of 10.12-1012 ng mL⁻¹ and a detection limit of 8.3 ng mL⁻¹ was found.     

Pharmacokinetics and residues of tetracycline in crucian carp muscle using capillary electrophoresis on-line coupled with electrochemiluminescence detection

A novel and sensitive determination for tetracycline (TC) in crucian carp muscle was developed by using capillary electrophoresis coupled with electrochemiluminescence (ECL) detection. The conditions affected separation and detection were examined in detail. The linearity range of TC concentration was from 0.005 to 10 μg mL⁻¹ with a correlation coefficient of 0.9992. The detection limit of TC (S/N = 3) was 1.8 ng mL⁻¹. The relative standard deviations of the ECL intensity and the migration time for eleven consecutive injections of 1.0 μg mL⁻¹ TC were 1.6% and 0.8%, respectively. The recovery of TC was 97.8% (n = 5). After administration of 75 mg kg⁻¹ TC, the maximum concentration and peak time of TC in crucian carp muscle were 7.33 mg kg⁻¹ and 8 h, respectively. After administration of TC, TC concentration demonstrated trivial variation in the period from 48 to 96 h.     

A novel quantum dot-based fluoroimmunoassay method for detection of Enrofloxacin residue in chicken muscle tissue

A rapid indirect competitive fluorescence-linked immunosorbent assay (cFLISA) based on quantum dots (QDs) as the fluorescent marker has been developed for the detection of Enrofloxacin (ENR) in chicken muscle tissue. The end-point fluorescent detection system was carried out using QDs conjugated with goat anti-mouse secondary antibody. The cFLISA method allowed for ENR determination in a liner working range of 1–100 ng mL⁻¹ with the 50% inhibition value (IC₅₀) of 8.3 ng mL⁻¹ and the limit of detection (LOD) of 2.5 ng mL⁻¹. The recoveries for chicken muscle samples spiked with ENR at levels of 50–200 μg kg⁻¹ ranged from 81% to 94% with coefficients of variation (CV) of 10–13%. In real chicken tissue sample analysis, the results of cFLISA were similar to those obtained from an indirect competitive enzyme-linked immunosorbent assay (cELISA) to a high performance liquid chromatography method (HPLC), which indicated that cFLISA is suitable as screening method for the monitoring of veterinary drug residues.     

Square wave voltammetry for analytical determination of paraquat at carbon paste electrode modified with fluoroapatite

This paper describes the construction of a carbon paste electrode (CPE) impregnated with fluoroapatite (FAP). The new electrode (FAP–CPE) was revealed an interesting determination of paraquat. The latter was accumulated on the surface of the modified electrode by adsorbing onto fluoroapatite and reduced in 0.1 mol L⁻¹ K₂SO₄ electrolyte at −0.70 and −1.0 V for peaks 1 and 2, respectively. Experimental conditions were optimized by varying the accumulation time, FAP loading and measuring solution pH. Under the optimized working conditions, calibration graphs were linear in the concentration ranging from 5 × 10⁻⁸ to 7 × 10⁻⁵ mol L⁻¹ with detection limits (DL, 3σ) of 3.5 × 10⁻⁹ and 7.4 × 10⁻⁹ mol L⁻¹, respectively, for peaks 1 and 2.     

Determination of formaldehyde in beer based on cloud point extraction using 2,4-dinitrophenylhydrazine as derivative reagent

A cloud point extraction method was developed for extraction of formaldehyde in beer prior to high performance liquid chromatography analysis. The formaldehyde was taken into complex with 2,4-dinitrophenylhydrazine in aqueous nonionic surfactant Triton X-114 medium and concentrated in the surfactant-rich phase by bringing the solution to the temperature of 60 °C. Under optimal conditions, the limit of detection of formaldehyde is 0.7 ng mL⁻¹. The intra- and inter-day precisions expressed as relative standard deviations are 4.2% and 5.5%, respectively. The proposed method was successfully applied for determination of formaldehyde in various beer samples. The contents of formaldehyde in these samples are in the range of 172-385 ng mL⁻¹. The results were in agreement with those obtained by the state standard method (steam-distillation and spectrophotometry analysis) used in China. The developed method was demonstrated to be rapid and sensitive for extraction and determination of formaldehyde in beer.     

Immunoassay based on monoclonal antibody for aflatoxin detection in poultry feed

An indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) based on an anti-aflatoxin B₁ monoclonal antibody was standardised and validated for aflatoxin screening in poultry feed samples and its performance was compared to high-performance liquid chromatography (HPLC). The ic-ELISA showed good linearity (r² = 0.994) and detection limits of 1.25 ng g⁻¹ for broiler feed and 1.41 ng g⁻¹ for laying hen feed. Mean aflatoxin recovery rates by ic-ELISA were 102% (laying hen feed) and 98% (broiler feed). Aflatoxins were detected in 88.2% of the 34 broiler feed samples by ic-ELISA and HPLC at means of 10.48 ng g⁻¹ and 8.41 ng g⁻¹, respectively, while 92% of laying hen feed samples (n = 36) showed aflatoxin contamination at means of 20.83 and 19.75 ng g⁻¹. The standardised ic-ELISA showed reliability and a high correlation with HPLC of 0.97 (broiler feed) and 0.98 (laying hen feed) indicating its potential for aflatoxin screening in poultry feed samples.     

Chemiluminescent imaging detection of staphylococcal enterotoxin C1 in milk and water samples

A sensitive, simple and rapid technique for high throughput simultaneous detection of staphylococcal enterotoxin C₁ (SEC₁) has been developed. The proposed method has the advantage of showing the specificity of enzyme-linked immunosorbent assays (ELISA), sensitivity of luminol-based enhanced chemiluminescence (ECL) assay, and high throughput of chemiluminescence (CL) imaging assay. It was based on a standard sandwich immunoassay format; 96-well ELISA plates were used as solid phase material. A commercial high-sensitivity cooled CCD camera has been applied to image the weak CL. Under the optimum conditions, the increased CL intensity was proportional with the concentration of SEC₁ in the range of 8.0–125.0 ng ml⁻¹ and the detection limit was 0.5 ng ml⁻¹ (3σ). The relative standard deviation (RSD) for eight parallel measurements of 25.0 ng ml⁻¹ SEC₁ was 0.06. The proposed method has been successfully applied to the determination of SEC₁ in milk and water samples. The results obtained compared well with those by ELISA.     

Dispersive liquid–liquid microextraction combined with sweeping micellar electrokinetic chromatography for the determination of some neonicotinoid insecticides in cucumber samples

A rapid, simple and sensitive method has been developed for the analysis of some neonicotinoid insecticides in cucumber samples by using dispersive liquid–liquid microextraction (DLLME) coupled with sweeping in micellar electrokinetic chromatography (MEKC). Under optimised conditions, the enrichment factors were achieved in the range from 4000 to 10,000. The linearity of the method was in the range from 2.7 to 200 ng g⁻¹ for thiacloprid, acetamiprid and imidacloprid, and in the range from 4.0 to 200 ng g⁻¹ for imidaclothiz in cucumber samples, with the determination coefficients (r²) ranging from 0.9924 to 0.9968. The limits of detection (LODs, S/N = 3) ranged from 0.8 to 1.2 ng g⁻¹. The relative standard deviations (RSDs) at the concentration levels of 10.0 and 50.0 ng g⁻¹ each of the neonicotinoid insecticides in cucumber samples varied from 3.8% to 6.3%. The developed method has been successfully applied to the analysis of the neonicotinoid insecticides in cucumbers with a satisfactory result.     

Selenium concentration in St. John’s wort (Hypericum perforatum L.) herb after foliar spraying of young plants under different UV-B radiation levels

St. John’s wort (Hypericum perforatum L.) was grown under different levels of UV-B radiation, with selenium (10 mg l⁻¹ Se applied by foliar spraying in the form of sodium selenate) or without foliar Se application. The different levels of UV-B radiation comprised an enhanced level simulating 17% ozone depletion, ambient level, and a reduced level of UV-B radiation. The concentration of Se in unsprayed plants was from 20 ng g⁻¹ to 120 ng g⁻¹. The concentration of Se in the organs of plants foliarly sprayed with Se ranged from 1000 ng g⁻¹ to 12,000 ng g⁻¹, the highest concentration being detected in plants grown under reduced levels of UV-B radiation. Foliar application of Se fertiliser is feasible and effective in St. John’s wort and results in Se-enriched nutritional supplements.     

Oral bioaccessibility and human risk assessment of organochlorine pesticides (OCPs) via fish consumption,using an invitro gastrointestinal model

The oral bioaccessibility of dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexanes (HCHs) in twenty fish species were evaluated using an in vitro gastrointestinal model. Relatively high concentrations of ∑HCH (0.33–9.88 ng g⁻¹, mean 1.57 ng g⁻¹) and ∑DDT (0.74–131 ng g⁻¹, mean 12.2 ng g⁻¹) were observed in all market fish. The average bioaccessibilities for ∑HCHs were 3.35% and 8.73% in gastric and intestinal conditions, respectively, and for ∑DDTs were 5.48% and 17.6%, respectively. Significant (p < 0.05) correlations were observed between OCP congener digestible concentrations in fish muscle and their corresponding concentrations in human tissues of Hong Kong residents. The health risk assessments based on solvent and digestible concentrations were found to be contradictory due to the fact that only a limited proportion of OCP was bioaccessible. It was concluded that human health risk assessment based on solvent concentrations should be modified by taking bioaccessibility of the contaminant into account.     

Analytical determination of hydroxytyrosol in olive extract samples by micellar liquid chromatography

Hydroxytyrosol is a well-known natural phenolic component obtained from olive extract samples with antioxidant effects. A micellar liquid chromatography method to detect and quantify hydroxytyrosol in olive extract samples is described. Matrix resolution was performed using a Kromasil C18 column and a micellar mobile phase of sodium dodecyl sulphate (SDS) 0.05 M and 4% methanol buffered at pH 7. Detection was set by absorbance at 280 nm. Samples were diluted with 0.05 M SDS at pH 3 and directly injected, thus avoiding long tedious extractions. Hydroxytyrosol was eluted in 3.5 min without overlapping other matrix compounds. Validation was performed following the US FDA guideline. The main analytical parameters studied were: linearity (0.03–250 μg mL⁻¹; r² = 0.999), limit of detection and quantification (3 and 30 ng mL⁻¹, respectively), intra- and inter-day precision (RSD, % <1.4 and <8.2, respectively), and robustness (RSD, % < 6.6). Recoveries were in the 88.5–98.9% range.     

Effects of ageing and low internal temperature of grilling on the formation of heterocyclic amines in beef Longissimus dorsi muscle

The mutagenic heterocyclic amines (HAs) originate in processed proteinaceous food. The effects of ageing (non-aged - i.e. 24 h post mortem vs. 14 and 28 days post mortem kept at 1 °C) and final internal temperature on cooking (T_i, 65 and 80 °C) on the content of HAs in grilled steaks (two-plated grill, temperature of 220 °C) were studied. HA precursors (creatine, creatinine, and free amino acids) and ageing indicators, such as instrumentally measured colour values, pH_ultimate values and length of myofibrilar fragments on raw and cutting values on grilled beef Longissimus dorsi muscles were determined. The muscles originated from eight commercially slaughtered Simmental bulls, 19-20 months old. The content of HAs was determined by a solid-phase extraction procedure. Meat ageing is accompanied by large changes in the chemical composition and structure of muscle tissues. In general, all the ageing indicators and precursors of HAs were influenced by ageing time at the 5% level or less. Creatine content declined significantly (non-aged: 6.00 mg g⁻¹, 14 days: 5.82 mg g⁻¹, and 28 days: 5.55 mg g⁻¹) and creatinine increased with days of ageing (non-aged: 0.19 mg g⁻¹, 14 days: 0.24 mg g⁻¹, and 28 days: 0.26 mg g⁻¹). Higher contents of total free amino acids were determined after 14 and 28 days of storage (28.18 μmol g⁻¹ and 37.59 μmol g⁻¹) than in non-aged beef (19.00 μmol g⁻¹). In this study, two HAs were determined: MeIQx (2-amino-3,8-dimethyl-imidazo[4,5-f]quinoxaline) and PhIP (2—amino-1-methyl-6-phenylimidazo-[4,5-b]pyridine). The content of HAs increases with ageing. At lower T_i, more MeIQx was formed; at higher T_i, more PhIP was formed. MeIQx was present in all samples while PhIP was found only in samples grilled to higher T_i. Samples treated to T_i = 80 °C generally contained less HAs (non-aged meat: 0.20 ng g⁻¹, 14 days: 0.26 ng g⁻¹, and 28 days: 0.28 ng g⁻¹) than samples treated to T_i = 65 °C (non-aged meat: 0.19 ng g⁻¹, 14 days: 0.36 ng g⁻¹, and 28 days: 0.39 ng g⁻¹) on account of MeIQx thermolability.     

Heterocyclic amines and azaarenes in pan-fried meat and its gravy fried without additives and in the presence of onion and garlic

The effect of onion and garlic on the formation of heterocyclic amines (HAs, aminoazaarenes) and azaarenes (aza-PAHs) was evaluated by comparing the concentrations of several compounds in meat and gravy samples, obtained from three pork dishes prepared in the presence and absence of these spices. The concentrations of individual HAs (8-MeIQx, MeIQ, 4,8-DiMeIQx, PhIP) were from 0.5 ng g⁻¹ to 10.5 ng g⁻¹ of meat and of azaarenes (benzo[a]acridine, benzo[c]acridine, dibenzo[a,c]acridine, dibenzo[a,j]acridine and dibenzo[a,h]acridine) – from 0.06 ng g⁻¹ to 0.99 ng g⁻¹. The addition of onion (30 g/100 g of meat) in the dishes investigated, caused a decrease in heterocyclic amines concentration (considering total contents in meat and gravy) in the range of 31–49% and of azaarenes by 21–48%. Garlic (15 g/100 g of meat) lowered the concentration of HAs by 26–36% and azaarenes by 33–40%; the changes in concentrations caused by these spices were different for particular compounds. Components of onion and garlic intensify the extraction of heterocyclic amines and azaarenes from meat in gravy.     

Spectrophotometric determination of melamine in milk by rank annihilation factor analysis based on pH gradual change-UV spectral data

A new spectrophotometric method has been developed in this paper to determine melamine in milk by applying rank annihilation factor analysis (RAFA) based on pH gradual change-UV spectral data (pH-spectra). In the proposed method, the spectra of the sample solutions at different pH data points were recorded and the pH-spectra bilinear data matrix was generated. Based on these data, the RAFA was then applied to calculate the concentration of melamine in milk. The experiments have been conducted and the results were satisfactory. Under the optimised conditions, linearity of the proposed method was in the range of 0.04–4.0 μg mL⁻¹ for calibration samples, and 0.04–3.5 μg mL⁻¹ for the mixed solutions of melamine with the background milk components. The detection limit (DL) was 12 ng mL⁻¹. The relative predictive error (RPEs) and root mean square error of prediction (RMSEP) of applying RAFA were 0.91% and 0.0151, respectively.     

Determination of lead and cadmium in food samples by the coprecipitation method

In this study, the coprecipitation method developed using a combination of 2-mercaptobenzothiazole (MBT) as a chelating reagent and copper as coprecipitate carrier was used for the determination of trace lead and cadmium in various food samples by graphite furnace atomic absorption spectrometry (GFAAS). The method was applied for the determination of Pb(II) and Cd(II) in salami, sausage, chicken, anchovy, spinach, cabbage, onion, dill, parsley, lettuce, tea and rice samples. The matrix modifiers were added as 50 μg NH₄H₂PO₄ + 3 μg Mg(NO₃)₂ for both Pb(II) and Cd(II). The signals were measured as peak area. The concentrations of Pb(II) and Cd(II) in the food samples were found to be in the range of 6.63 ng g⁻¹ (anchovy) −3.30 μg g⁻¹ (spinach) and 2.67 ng g⁻¹ (salami) −0.51 μg g⁻¹ (lettuce), respectively.     

Hollow fibre-based liquid phase microextraction combined with high-performance liquid chromatography for the analysis of flavonoids in Echinophora platyloba DC. and Mentha piperita

A simple, inexpensive and efficient three phase hollow fibre liquid phase microextraction (HF-LPME) technique combined with HPLC was used for the simultaneous determination of flavonoids in Echinophora platyloba DC. and Mentha piperita. Different factors affecting the HF-LPME procedure were investigated and optimised. The optimised extraction conditions were as follows: 1-octanol as an organic solvent, pH_donor = 2, pH_acceptor = 9.75, stirring rate of 1000 rpm, extraction time of 80 min, without addition of salt. Under these conditions, the enrichment factors ranged between 146 and 311. The values of intra and inter-day relative standard deviations (RSD) were in the range of 3.18–6.00% and 7.25–11.00%, respectively. The limits of detection (LODs) ranged between 0.5 and 7.0 ng mL⁻¹. Among the investigated flavonoids quercetin was found in E. platyloba DC. and luteolin was found in M. piperita. Concentration of quercetin and luteolin was 0.015 and 0.025 mg g⁻¹ respectively.     

Pyridine-functionalized mesoporous silica as an adsorbent material for the determination of nickel and lead in vegetables grown in close proximity by electrothermal atomic adsorption spectroscopy

A new, sensitive, and low cost solid-phase extraction method using pyridine-functionalized MCM-48 mesoporous silica for the extraction, pre-concentration, and electrothermal atomic absorption spectrometric determination of nickel and lead in food samples at ng mL⁻¹ levels is described herein. The levels of nickel and lead in different types of vegetables grow in Shiraz–Iran and Rafsanjan–Iran were determined by electrothermal atomic absorption spectrometry. The use of two standard reference materials and also comparing the results to a standard reference procedure ensured the accuracy of this method. Factors, such as flow rate of extraction, and the type, pH, concentration, and volume of eluent, were appraised. The effect of various ions on recovery was also investigated. Detection limits of 0.11 and 0.14 ng mL⁻¹ were obtained for lead and nickel, respectively.