Selective determination of copper and iron in various food samples by the solid phase extraction

The solid phase extraction method developed using N-benzoyl-N-phenylhydroxylamine as a chelating reagent and Amberlite XAD-1180 as an adsorbent was used for the determination of Cu(II) and Fe(III) in various food samples by flame atomic absorption spectrometry. The samples were digested by using nitric acid and hydrogen peroxide. The Cu concentrations ranged from 1.01 to 5.81 μg g⁻¹ in cereals, from 0.40 to 9.67 μg g⁻¹ in vegetable and fruits and from 0.37 to 0.70 μg g⁻¹ in infusions while the Fe concentrations ranged from 7.48 to 34.3 μg g⁻¹ in cereals, from 5.74 to 260 μg g⁻¹ in vegetable and fruits, from 1.63 to 5.12 μg g⁻¹ in infusions and from 0.24 to 1.56 mg L⁻¹ in beverage samples. The Cu and Fe concentrations found were compared with the results obtained from the other food studies in the world.     

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.     

Rapid determination of formaldehyde and sulfur dioxide in food products and Chinese herbals

Simple, sensitive and rapid methods for the determination of formaldehyde and sulfur dioxide were developed. The formaldehyde determination is based on the reaction between formaldehyde and acetylacetone solution, producing yellow 3,5-diacetyl-l-1,4-dihydrolutidine. Sulfur dioxide was detected as the deoxidize of sulfurous acid by zinc in acidic medium, which produces sulfureted hydrogen that make lead acetate paper blackening due to lead sulfide formation. The detection limits were 0.8 μg mL⁻¹ and 6.0 μg mL⁻¹ for formaldehyde and sulfur dioxide, respectively. The linear range were 0.8–20.0 μg mL⁻¹ for formaldehyde and 6.0–100.0 μg mL⁻¹ for sulfur dioxide determination. The main advantages of the new analytical procedure are the low background level, high selectivity, and very little sample preparation for on-site analysis of formaldehyde and sulfur dioxide in food or Chinese herbal samples with reference color card for qualitative or semi-quantitative determination. The results from these methods correlated well with those obtained from the standard methods.     

Trace element levels in honeys from different regions of Turkey

A survey of 25 honey samples from different botanical origin, collected all over the Turkey was conducted to assess their trace element contents. The aim of this study was to determine the levels of cadmium (Cd), lead (Pb), iron (Fe), manganese (Mn), copper (Cu), nickel (Ni), chromium (Cr), zinc (Zn), aluminium (Al) and selenium (Se) in honey samples from different regions of Turkey. Trace element contents were determined by a flame and graphite furnace atomic absorption spectrometry technique after dry-ashing, microwave digestion and wet-digestion. The accuracy of the method was corrected by the standard reference material, NIST-SRM 1515 Apple leaves. The contents of trace elements in honey samples were in the range of 0.23–2.41 μg g⁻¹, 0.32–4.56 μg g⁻¹, 1.1–12.7 μg g⁻¹, 1.8–10.2 μg g⁻¹, 8.4–105.8 μg kg⁻¹, 2.6–29.9 μg kg⁻¹, 2.4–37.9 μg kg⁻¹, 0.9–17.9 μg kg⁻¹, 83–325 μg kg⁻¹ and 38–113 μg kg⁻¹ for Cu, Mn, Zn, Fe, Pb, Ni, Cr, Cd, Al and Se, respectively. Iron was the most abundant element while cadmium was the lowest element in the Turkish honeys surveyed. The results showed that trace element concentrations in the honeys from different regions were generally correlated with the degree of trace element contamination of the environment.     

Analysis of potential adulteration in herbal medicines and dietary supplements for the weight control by capillary electrophoresis

Four different phytopharmaceutical dosage forms for use in weight control programs were analyzed. Two different ground herbal blends and their correspondent infusions, a capsule and a tincture were investigated for the presence of compounds used as adulterants in these products. A capillary electrophoresis (CE) method was developed and validated. The optimized experimental conditions were: BGE, sodium tetraborate buffer 20 mM, pH 9.2, voltage applied 30 kV, capillary temperature 25 °C, injection sample at 0.5 Psi during 5 s. Ephedrine, norephedrine, caffeine and furosemide were baseline separated in less than 7 min; the migration times were found to be 2.65, 2.90, 3.75 and 6.58 min, respectively. The analysis showed in sample 3 concentrations of 0.45 ± 0.03 mg g⁻¹ (ephedrine), 0.33 ± 0.02 mg g⁻¹ (norephedrine), 1.09 ± 0.41 mg g⁻¹ (caffeine) and 0.80 ± 0.17 mg g⁻¹ (furosemide). Caffeine content in samples 1, 2 and 4 was 0.61 ± 0.06 mg g⁻¹, 15.66 ± 1.05 mg g⁻¹ and 2.27 ± 0.13 mg ml⁻¹, respectively. Linearity was obtained in the concentration range of 1–1000 μg ml⁻¹. Limits of detection (LOD) and quantification (LOQ) were determined as 0.42 μg ml⁻¹ and 1.40 μg ml⁻¹ (ephedrine), 0.47 μg ml⁻¹ and 1.40 μg ml⁻¹ (norephedrine), 0.12 μg ml⁻¹ and 0.48 μg ml⁻¹ (caffeine), 0.22 μg ml⁻¹ and 0.73 μg ml⁻¹ (furosemide).     

Analytical applications of 2,6-diacetylpyridine bis-4-phenyl-3-thiosemicarbazone and determination of Cu(II) in food samples

New synthesized reagent 2,6-diacetylpyridine bis-4-phenyl-3-thiosemicarbazone (2,6-DAPBPTSC) is proposed as a sensitive and selective analytical reagent for the spectrophotometric determination of copper(II) at pH 3.0 to form a yellowish orange colored 1:1 chelate complex. The maximum absorbance was measured at 370 nm. This method obeys Beer’s law in the concentration range 0.63–6.30 g ml⁻¹ and the correlation coefficient of Cu(II)–2,6-DAPBPTSC complex is 0.942, which indicates an adequate linearity between the two variables with good molar absorptivity and Sandell’s sensitivity, 0.847 × 10⁴ l mol⁻¹ cm⁻¹ and 0.0075 g cm⁻², respectively. The instability constant of complex calculated from Asmus′ method is 1.415 × 10⁻⁴ at room temperature. The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.777% and the detection limit value is 0.0056 g ml⁻¹. The interfering effect of various cations and anions has also been studied. The method was successfully applied for the determination of Cu(II) in food samples. The performance of present method was evaluated in terms of Student ‘t’ test and Variance ‘f’ test, which is indicates the significance of present method is an inter comparison of the experimental values, using atomic absorption spectrometer (AAS).     

Development of polyclonal antibody-based indirect competitive enzyme-linked immunosorbent assay for sodium saccharin residue in food samples

A sensitive and specific polyclonal antibody (PcAb)-based indirect competitive enzyme-linked immunosorbent assay (icELISA) for sodium saccharin is described. 6-Amino saccharin was coupled to carrier protein for artificial antigen by diazotisation. New Zealand white rabbits were immunised to obtain anti-sodium saccharin PcAb and then icELISA was developed. The assay showed high sensitivity and specificity to sodium saccharin, with the 50% inhibition value (IC₅₀) of 0.243 μg mL⁻¹, workable range (IC₃₀–IC₇₀) of 0.050–12.8 μg mL⁻¹ and limit of detection (LOD, IC₂₀) of 0.021 μg mL⁻¹. The average recoveries of sodium saccharin in spiked food samples were estimated ranging from 70.7% to 98.8%. A statistically significant correlation of results was obtained between this new ELISA and previously established HPLC approaches with the food-relevant sodium saccharin concentration range 0–320 μg mL⁻¹ (R² = 0.9887–0.9975). These results indicated that the established ELISA was a potential and useful analytical tool for rapid determination of sodium saccharin residue in food samples.     

Determination of total phenols in tea infusions,tomato and apple juice by terbium sensitized fluorescence method as an alternative approach to the Folin–Ciocalteu spectrophotometric method

A fast screening of total phenols in tea infusions, tomato and apple juice samples using terbium sensitized fluorescence is described. The proposed method is based on the fluorescence sensitization of terbium (Tb³⁺) by complexation with flavonols (quercein as a reference standard) (at pH 7.0), which fluoresces intensely with an emission maximum at 545 nm when excited at 310 nm. Quercetin and terbium cations (at pH 7.0) form a stable complex and the resulted emission at 545 nm can be used for the determination of the total phenols concentration expressed in terms of “quercetin equivalent”. Based on the obtained results, a sensitive, simple and rapid spectrofluorimetric method was developed for the determination of total phenols. In the optimum conditions, the calibration graph was linear from 0.01 to 2 μg mL⁻¹, with the limit of detection of 0.002 μg mL⁻¹. The relative standard deviation values were in the range of 0.75–2.3%. The total concentrations of quercetin equivalent in five tested samples were found in the range of 6.6–27.9 μg mL⁻¹ and the results compare favorably with those obtained by spectrophotometric method (r = 0.999).     

A simple and highly sensitive spectrophotometric determination of Cr(VI) in food samples by using 3,4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH)

A simple, rapid, sensitive and inexpensive method has been developed for the determination of trace amounts of chromium(VI) using 3,4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH). The metal ion gives a yellow coloured complex with 3,4-DHBINH in acetate buffer of pH 5.5 with 1:1 (metal:ligand) composition. The complex shows a maximum absorption at 400 nm. Beer’s law is obeyed in the range 0.5–7.7 ppm of Cr(VI). The molar absorptivity, Sandell’s sensitivity and detection limit were found to be 1.35 × 10⁴ L mol⁻¹ cm⁻¹, 0.0075 μg cm⁻² and 0.0045 μg mL⁻¹, respectively. The correlation co-efficient and regression co-efficient of the Cr(VI)–3,4-DHBINH complex were 0.99 and 0.12, respectively. Major cations and anions did not show any interference. The developed method has been successfully applied for the analysis of Cr(VI) in food samples (leafy vegetables), comparing the results simultaneously with those obtained using an Atomic Absorption Spectrophotometer, whereby the validity of the method has been tested.     

Flow injection chemiluminescent detection of gallic acid in olive fruits

One economic and environment friendly flow injection chemiluminescent method for the determination of gallic acid was developed. It was based on the inhibited chemiluminescent emission of alkaline luminol–KMnO₄ system by gallic acid. The logarithm of the difference of chemiluminesent intensity of the alkaline luminol–KMnO₄ system in the absence of gallic acid from that in the presence of gallic acid was linear with the logarithm of the concentration of gallic acid in the range from 1.0 × 10⁻⁹ to 5.0 × 10⁻⁵ g ml⁻¹ with a detection limit of 2.2 × 10⁻¹⁰ g ml⁻¹. The relative standard deviation of eleven determinations of 1.0 × 10⁻⁶ g ml⁻¹ gallic acid was 1.7%. The method was successfully applied to the determination of gallic acid in olive fruits.     

Chemiluminescence microflow injection analysis system on a chip for the determination of nitrite in food

A new microflow injection analysis (μFIA) system on a chip for the determination of nitrite is described. The chip is produced by using two transparent poly(methylmethacrylate) (PMMA) slices measured 50 × 40 × 5 mm, and the microchannels etched by CO₂ laser are 200 μm wide and 100 μm deep with the volume of reaction area about 1.8 μL. Nitrite is sensed by the chemiluminescence (CL) reaction of luminol with ferricyanide that is the product of the reaction of ferrocyanide with nitrite in acidic medium. The syringe pump with an accurate timer controls all reagents, including the sample. The linear range of the nitrite concentration is 8–100 μg L⁻¹ and the detection limit is 4 μg L⁻¹ (S/N = 3). The proposed method has good reproducibility with the relative standard deviation 4.1% for 50 μg L⁻¹ of nitrite (n = 9) and is very sensitive and simple. It has been successfully applied to the determination of nitrite in food.     

Determination of melamine by flow injection analysis based on chemiluminescence system

In this paper, based upon the phenomenon that melamine can obviously enhance the CL signal of the luminol–H₂O₂ system in basic medium, a simple, rapid and sensitive flow injection chemiluminescence (FI-CL) method for the determination of melamine has been developed. Under the optimum conditions, the linear range for the determination of melamine was 0.2–80 μg mL⁻¹ with a detection limit of 0.12 μg mL⁻¹ calculated as proposed by IUPAC and a relative standard deviation of 3.26% for 11 solutions of 10 μg mL⁻¹ melamine on the same day. The proposed method was satisfactorily applied to determine melamine in milk-based products and satisfactory results were obtained without interferences from the sample matrix. Moreover, one assay produce takes only 25 s and the minimum sampling rate is about 120 samples h⁻¹, which indicated that the FI-CL method was suitable for high throughput and real-time melamine analysis.     

Determination of biogenic amines in beers and brewing-process samples by capillary electrophoresis coupled to laser-induced fluorescence detection

We have developed a sensitive capillary electrophoretic method for the simultaneous determination of 10 biogenic amine which usually appears in beer samples, using laser induced-fluorescence. Sample amines were first derivatized and filtered and then separated with an uncoated capillary tubing in the presence of 50 mM sodium borate and 20% acetone at pH 9.3 at 30 kV. It was possible to analyze biogenic amines in brewing-process samples and in beer samples in less than 30 min, obtaining detection limits between 0.3 μg l⁻¹ for ethylamine and 11.9 μg l⁻¹ for 1,6-hexanodiamine.     

Synthesis and application of a new functionalized resin for use in an on-line,solid phase extraction system for the determination of trace elements in waters and reference cereal materials by flame atomic absorption spectrometry

The synthesis and characterization of the resin Amberlite XAD-4 functionalized with 2,6-pyridinedicarboxaldehyde and its application in an on-line system for the preconcentration of cadmium, cobalt, copper, lead and manganese prior to determination using flame atomic absorption spectrometry (FAAS) is proposed. Metal ions retained on the modified resin were eluted using 1.0 mol L⁻¹ HNO₃ solution and aspirated directly to the nebulizer–burner system of a FAAS instrument using a flow injection system. Detection limits (3σ) were determined to be 0.13 μg L⁻¹ for Cd, 0.29 μg L⁻¹ for Cu, 0.23 μg L⁻¹ for Mn, 0.58 μg L⁻¹ for Co and 2.19 μg L⁻¹ for Pb using a 10 mL of water sample loading volume. The limits of detection would be 100 times higher with units of μg kg⁻¹ for the solid samples in which their dilution ratios as (volume/weight) were 100. Enrichment factors ranged from 23.6 to 28.9 (for Co and Mn, respectively). The proposed method was successfully applied to determination of the analytes in natural water samples and certified reference materials.     

Rapid determination of three alkaloids from Lotus Plumule in human serum using an HPLC-DAD method with a short monolithic column

An HPLC-DAD with a short monolithic column method was used for rapid, sensitive and simultaneous determination of liensinine, isoliensinine and neferine in human serum. Chromatographic separation was achieved on an RP-HPLC chromolithic column (50 mm × 4.6 mm i.d.), with a mobile phase of methanol–water–triethylamine–acetic acid (70:30:0.2:0.05), at a flow rate of 1 ml min⁻¹. The calibration curves of three alkaloids exhibit good linear relationship in the concentration range of 0.5–80 μg ml⁻¹. The limits of detection (LODs) of three alkaloids were 20, 20 and 25 ng ml⁻¹, respectively, and the separation time was 4 min. A comparative study has been performed with a normal C₁₈ packed column (150 mm × 4.6 mm i.d., 5 μm). The separation time was 16 min and the LODs of three alkaloids were 56, 56 and 65 ng ml⁻¹, respectively.     

Chemical composition and antimicrobial activity of the essential oils from four Ruta species growing in Algeria

Antimicrobial properties of plants essential oils have been investigated in order to suggest them as potential tools to overcome the microbial drug resistance and the increasing incidence of food borne diseases problems. The aim of this research is to study the antibacterial and antifungal effects of four traditional plants essential oils, Ruta angustifolia, Ruta chalepensis, Ruta graveolens and Ruta tuberculata, against standard bacterial and fungal strains. The chemical compounds of the oils were examined by GC/MS. Results revealed a powerful antifungal activity against filamentous fungi. Aspergillus fumigatus and Cladosporium herbarum are the most sensitive strains to these oils with MIC values less than 3.5 μg ml⁻¹ for certain oils, reaching 7.8 μg ml⁻¹ for other. GC/MS essay exhibited ketones as the most abundant constituent of these oils except for R. tuberculata essential oil which has a completely different composition, monoterpenes alcohols being the most abundant. These compositions explain their potential antifungal activity.     

Utility of solid phase spectrophotometry for the modified determination of trace amounts of cadmium in food samples

A modified selective, highly sensitive and accurate procedure for the determination of trace amounts of cadmium which reacts with 1-(2-benzothiazolylazo)-2-hydroxy-3-naphthoic acid (BTAHNA) to give a deep violet complex with high molar absorptivity (7.05 × 10⁶ L mol⁻¹ cm⁻¹, 3.92 × 10⁷ L mol⁻¹ cm⁻¹, 1.78 × 10⁸ L mol⁻¹ cm⁻¹, and 4.10 × 10⁸ L mol⁻¹ cm⁻¹), fixed on a Dowex 1-X8 type anion-exchange resin for 10 mL, 100 mL, 500 mL, and 1000 mL, respectively. Calibration is linear over the range 0.2-3.5 μg L⁻¹ with RSD of ?1.14% (n = 10). The detection and quantification limits were calculated. Increasing the sample volume can enhance the sensitivity. The method has been successfully applied for the determination of Cd(II) in food samples, water samples and some salts samples without interfering effect of various cations and anions.     

Effect of modifiers for As,Cu and Pb determinations in sugar-cane spirits by GF AAS

Palladium plus magnesium nitrates with and without Ir, Ru and W were evaluated for the simultaneous determination of As, Cu and Pb in cachaça by graphite furnace atomic absorption spectrometry. For 20 μL of sample, 5 μL Pd(NO₃)₂ and 3 μL Mg(NO₃)₂ dispensed together onto the Ir-coated platform of the THGA, analytical curves in the 0–30.0 μg L⁻¹ As, 0–1.50 mg L⁻¹ Cu and 0–60.0 μg L⁻¹ Pb were built up and typical linear correlation coefficients were always better than 0.999. The limit of detection was 1.30 μg L⁻¹ As, 140 μg L⁻¹ Cu and 0.90 μg L⁻¹ Pb. As, Cu and Pb contents in 10 cachaça samples agreed with those obtained by ICP-MS. Recoveries of spiked samples varied from 96% to 106% (As), 97% to 112% (Cu) and 92% to 108% (Pb). The relative standard deviation (n = 12) was typically 2.7%, 3.3% and 1.9%.     

Response surface modelling of lead pre-concentration from food samples by miniaturised homogenous liquid–liquid solvent extraction: Box–Behnken design

In this study, a new method called miniaturised homogenous liquid–liquid extraction, followed by graphite furnace atomic absorption spectrometry, was developed for the extraction and determination of lead from food samples. The procedure was based on the fast extraction of lead from an acetic acid sample solution into 0.5 mL chloroform, as an extraction solvent. After adding water into the mixture, the extracting solvent phase immediately formed a distinct water-immiscible phase below the vial, which could easily be separated, evaporated and re-dissolved in 1.0 mL nitric acid 0.1 mol L⁻¹ for further analysis. The effects of various experimental parameters in extraction step were studied using two optimisation methods, one variable at a time and Box–Behnken design. The results showed that the amount of salt and extraction time did not have effect on the extraction efficiency. Therefore, a three-level Box–Behnken experimental design with three factors, which combined the response surface modelling, was used to optimise lead extraction. Three independent variables, including pH of solution (ranging from 6.5 to 10.5), concentration of dithizone as chelating agent (ranging from 0.05 to 0.5 μg L⁻¹) and extracting solvent volume (ranging from 300 to 900 μL) were respectively coded as pH, D and V at three different levels (−1, 0 and 1). In this study, the optimum condition was determined at pH 8.4, a volume of chloroform at 0.45 mL, and concentration of dithizone at 0.5 μg L⁻¹. Under the optimum condition, the limit of detection (LOD) was 0.05 μg L⁻¹. Furthermore, the relative standard deviation of the ten replicate was <5.0%. The developed procedure was applied to the extraction and determination of lead in the food samples.     

Determination of aflatoxins in eggs,milk, meat and meat products using HPLC fluorescent and UV detectors

Raw and pasteurised sheep’s, cow’s and goat’s milk, eggs, and beef samples from different local markets in Jordan were collected during a period of 5 months (January through May 2007) and examined for aflatoxins B1(AFB1), B2(AFB2), G1(AFG1), G2(AFG2), M1(AFM1) and M2(AFM2). The samples were analysed with high performance liquid chromatography (HPLC) using UV and Fluorescent detectors. The analysed samples of milk collected in January were found to contain 0.56 μg L⁻¹ AFM1 and 0.1 μg L⁻¹ AFM2 whilst, the concentration of AFM1 and AFM2 was < 0.05 μg L⁻¹ for milk samples collected between March and May. The AFB1, AFB2, AFG1 and AFG2 contents in the analysed food products ranged from 1.10 to 8.32 μg L⁻¹ and 0.15 to 6.36 μg L⁻¹ in imported and fresh meat samples collected during March, respectively. The mean recovery for the HPLC method was 92% to 109% and the quantification levels were 50 ng L⁻¹ for AFM1 and AFM2. The AFM1 was found in 10% of the tested samples with concentrations between 0.08 and 1.1 μg kg⁻¹ and AFM2 was only found in 1.82% of the tested samples with a level of 0.1 μg kg⁻¹. The AFM1 levels in the examined foods were higher than the maximum level of AFM1 in liquid milk set by the European Community and Codex Alimentarius of 50 ng L⁻¹.