Determination of Histamine in Some Foods by Isotachophoretic Method with Simple Sample Preparation

A one-dimensional capillary isotachophoretic method in cationic system of the separation has been applied for histamine determination in food samples. The proposed electrolyte system consisted of 0.01 M potassium hydroxide with l-valine to pH = 9.9 as the leading electrolyte and 0.02 M 2-amino-2-hydroxymethyl-propane-1,3-diol adjusted to pH = 8.3 with 0.1 M hydrochloric acid as terminating electrolyte. Proposed method was characterized by linearity range 5–50 mg L⁻¹ and R ² = 0.9982, accuracy (recoveries ranged from 95% to 102%), detection (2.10 mg L⁻¹), and quantification (7.01 mg L⁻¹) limits. The sample preparation for proposed electrophoretic method included only simple extraction with trichloroacetic acid with filtration and derivatisation stage are avoided. The histamine concentration was determined in meat (turkey, chicken, beef and pork) and meat products (ripened sausage and dry-cured ham), fish (smoked salmon and mackerel), and different kind of mildew and mold ripened cheeses samples. The histamine content ranged from not detected level for fresh meat to 29.63 mg 100 g⁻¹ for cheese samples. The reversed phase HPLC was applied as reference method and the F-Snedecor test and the t test were employed to compare the precision and accuracy of the both methods. Positive correlations were found between the two analytical methods for histamine determination in food products. The obtained results indicate that the proposed electrophoretic method is simple, precise, accurate, and convenient.     

A Highly Sensitive Adsorptive Stripping Voltammetric Method for Simultaneous Determination of Lead and Vanadium in Foodstuffs

This work describes a procedure for the simultaneous determination of vanadium and lead in some food and water samples using adsorptive stripping voltammetric method. The method is based on the adsorptive accumulation of cupferron complexes of these elements onto hanging mercury drop electrode, followed by reduction of adsorbed species by voltammetric scan using differential pulse modulation. Optimal analytical conditions were found to be cupferron concentration of 8.00 × 10⁻⁵ M, pH of 4.8 (phosphate buffer), an accumulation potential at −100 mV, and a scan rate of 80 mV s⁻¹. With an accumulation time of 50 s, the peak currents proportional to the concentration of lead and vanadium over the 0.05–80.00 and 0.10–105.00 ng mL⁻¹ ranges with detection limit of 0.02 and 0.01 ng mL⁻¹, respectively. The procedure was applied to simultaneous determination of vanadium and lead in some food and water samples with satisfactory results.     

Electrochemical Determination of Phenothrin in Agricultural Formulations, Vegetables, and Storage Bags of Wheat and Rice by Differential Pulse Adsorptive Stripping Voltammetry (DP-AdSV)

An electroanalytical method has been developed for the determination of the pesticide phenothrin by differential pulse adsorptive stripping voltammetry on a hanging mercury drop electrode in universal buffer as supporting electrolyte. The best adsorption conditions were found to be pH 6.0, an accumulation potential of −0.6 V, and an accumulation time of 75 s. Effects of stirring rate, scan rate, pulse amplitude, and purge time were examined for the optimization of instrumental conditions. Calibration curve is linear in the range 2 × 10⁻⁹ to 2 × 10⁻⁷ mol l⁻¹ with a detection limit of 1.9 × 10⁻¹⁰ mol l⁻¹. The correlation coefficient and relative standard deviation were 0.995% and 1.1%. The method is applied to the determination of the phenothrin in agricultural formulations, vegetables, and storage bags of wheat and rice under Food Corporation of India’s storage system.     

Optimization and Modeling of Process Parameters for Lipase Production by Bacillus brevis

Statistical evaluation of fermentation conditions and nutritional factors by Plackett–Burman two-level factorial design followed by optimization of significant parameters using response surface methodology for lipase production by Bacillus brevis was performed in submerged batch fermentation. Temperature, glucose, and olive oil were found to be the significant factors affecting lipase production. Maximum lipase activity of 5.1 U ml⁻¹ and cell mass of 1.82 g l⁻¹ at 32 h were obtained at the optimized conditions of temperature, 33.7 °C; initial pH, 8; and speed of agitation, 100 rpm, with the medium components: olive oil, 13.73 ml l⁻¹; glucose, 13.98 g l⁻¹; peptone, 2 g l⁻¹; Tween 80, 5 ml l⁻¹; NaCl, 5 g l⁻¹; CH₃COONa, 5 g l⁻¹; KCl, 2 g l⁻¹; CaCl₂·2H₂O, 1 g l⁻¹; MnSO₄·H₂O, 0.5 g l⁻¹; FeSO₄·7H₂O, 0.1 g l⁻¹; and MgSO₄·7H₂O, 0.01 g l⁻¹. The lipase productivity and specific lipase activity were found to be 0.106 U (ml h)⁻¹ and 2.55 U mg⁻¹, respectively. Unstructured kinetic models and artificial neural network models were used to describe the lipase fermentation. The kinetic analysis of the lipase fermentation by B. brevis shows that lipase is a growth-associated product.     

A Rapid Spectrophotometric Method for Trace Determination of Zinc

A simple, sensitive, and highly selective method is proposed for the determination of zinc(II) using a bis-azo dye, 2,6-bis(1-hydroxy-2-naphthylazo)pyridine as spectrophotometric reagent. At pH 7.8, in 50% (v/v) ethanol–water medium, the complex is found to obey Beer’s law up to 1.3 mg/L with an optimum concentration range between 0.19 and 1.0 mg/L. Sandell’s sensitivity of the color reaction was calculated to be 0.0011 μg cm⁻² with molar absorptivity of 6.0 × 10⁴ L mol⁻¹ cm⁻¹ at 560 nm. The optimum conditions for the determination of Zn(II) with the reagent were ascertained. The complexation at different pH was studied in water–ethanol medium. The composition of the complex is 1:2. The action of some interfering ions was verified, and the developed method applied successfully for the estimation of zinc levels in food and milk samples, and the results were then compared with those obtained by using AAS.     

Micelle-Mediated Extraction and Flame Atomic Absorption Spectrometric Method for Determination of Trace Cobalt Ions in Beverage Samples

A new method has been developed for preconcentration of cobalt at trace levels in beverage samples using calcon carboxylic acid as chelating agent and cetyl pyridinium chloride as an auxiliary ligand and entrapped into Triton X-114 prior to its determination by flame atomic absorption spectrometry (FAAS). The main parameters affecting cloud point extraction (CPE) efficiency such as pH, concentration of the complexing agent, cationic and nonionic surfactant concentration, salt effect, the equilibrium time, and temperature were investigated and optimized. After optimization of the CPE conditions, a preconcentration factor of 60, an enhancement factor of 106, and a detection limit of 0.20 μg L⁻¹ by (R ² = 0.9978) were obtained from a calibration curve constructed in the range of 0.7–100 μg L⁻¹. The proposed preconcentration procedure was successfully applied to the determination of cobalt ions in some real samples including natural drinking water, tap water, and beer and wine samples. The accuracy and validity of the proposed CPE/FAAS method was tested by means of five repeated analysis of reference standard materials (TM-253, a low level fortified water standard for trace elements). A good agreement between analytical results (28.8 and 28.5 μg L⁻¹ with calibration curve and standard addition curve method, respectively) and certified value (27.9 μg L⁻¹) for Co (p < 0.05) were obtained and verified by means of calibration curve and standard addition curve method using CPE procedure.     

Optimization of the Production of Total Carotenoids by Sporidiobolus salmonicolor (CBS 2636) Using Response Surface Technique

This work aimed at evaluating the conditions of growth and the recovery of total carotenoids produced by Sporidiobolus salmonicolor (CBS 2636). Optimization of carotenoid production was achieved by experimental design technique. A Plackett–Burman design was used, followed by a complete second-order design, to optimize the concentration of total carotenoids in a conventional medium. Maximum concentration of 1,019 μg l⁻¹ of total carotenoids was obtained in a medium containing 40 g l⁻¹ glucose, 10 g l⁻¹ malt extract, and 14 g l⁻¹ peptone, at 180 rpm, 25 °C, and initial pH of 4.0. So far, no previous systematic study using microorganisms of the genus Sporobolomyces (formerly Sporidiobolus) for production of carotenoids has been reported. In this study, very good yields of carotenoids (1 mg l⁻¹) could be obtained after optimization of fermentation medium and operation conditions.     

Optimization of Solid-Phase Microextraction Procedure Coupled to GC-ECD for Triazole Fungicides Determination in Juice Samples

A solid-phase microextraction (SPME) procedure followed by gas chromatography electron capture detection (GC/ECD) for the determination of triazole residues was developed. An experimental design with two steps was done. Firstly, a 2⁶⁻² fractional factorial design for screening several experimental variables (fiber-coating type, extraction temperature, extraction time, stirring rate, desorption temperature, and desorption time) was done. After, a two-factor central composite design for optimizing, the experimental conditions were carried out. The chosen experimental conditions were: fiber, PDMS/DVB; extraction time, 45 min; extraction temperature, 60 °C; desorption time, 3 min; desorption temperature, 260 °C, and stirring speed, 500 rpm. Using those conditions the limits of detection obtained for tetraconazole, myclobutanil, and diniconazole were in the order of few μg L⁻¹ in grape and apple liquid extracts. Recoveries were from 93.6% to 112.1%. Relative standard deviation ranged from 1.2% to 11.6% (apple) and 6.7 to 18.0% (grape). The method was applied to five grape samples and 13 apple samples collected in Navarra, Rioja, and Basque Country. Quantification was performed by the standard addition method. Three standard additions by duplicate covering adequate range concentration were used. Myclobutanil was found in three apple samples (110–122 μg L⁻¹) and diniconazole in one grape sample (9.4 μg L⁻¹).     

Occurrence of aflatoxin M1 in raw, pasteurized and UHT milk commercialized in Esfahan and Shahr-e Kord, Iran

Between September 2006 and September 2007, 236 samples of raw (n = 140), pasteurized (n = 48) and UHT (n = 48) milk were collected from supermarkets and from bulk milk tanks of eight dairy plants in the cities of Esfahan and Shahr-e Kord, Iran. All samples were analyzed for aflatoxin M₁ (AFM₁) contamination by ELISA and 213 (90.3%) were positive with mean concentrations 65 ng.l⁻¹. These concentrations are lower than the standards of Codex Alimentarius and FDA (500 ng.l⁻¹), but 119 samples (55.9%) had higher concentrations than the maximum tolerance accepted by some European countries (50 ng.l⁻¹). Mean concentrations of AFM₁ in raw, pasteurized and UHT milk were 68, 56, and 65 ng.l⁻¹, respectively. Mean concentrations of AFM₁ in autumn and winter samples were significantly higher (P < 0.05) than those of spring and summer but differences between AFM₁ concentrations of spring and summer samples were not significantly different. Concentrations of AFM₁ in milk from Shahr-e Kord were significantly lower (P ≤ 0.05) than those from Esfahan.     

Development of an Analytical Method Based in the Slurry Sampling for Iron Determination in Fortified Milk Powder by HR-CS FAAS

The use of slurry sampling as the procedure for sample preparation provides simplicity, speed, and low consumption of reagents in analytical methods. In this paper, a method based on slurry sampling for the determination of iron in samples of fortified milk powder by high-resolution continuum source flame atomic absorption spectrometry was developed. Multivariate design techniques were applied for the optimization of experimental conditions of the method for a sample mass of 100 mg, final volume of slurry of 10 mL, and using the absorbance signal as response. Initially, a two-level full factorial design was used for the preliminary evaluation of the variables involved in slurry preparation: concentration hydrochloric acid, Triton X-100 concentration, and sonication time. Then, the Doehlert matrix was applied for the determination of the critical conditions: 2.5 mol L⁻¹ hydrochloric acid and sonication time of 20 min. External calibration technique with aqueous standard was used for the quantification of iron. This way, the method allowed iron determination with limits of detection and quantification of 0.9 and 3.0 μg g⁻¹, respectively. The precision expressed as the relative standard deviation was evaluated under repeatability and reproducibility conditions, being 3.2% and 4.0%, respectively. Addition/recovery test was used for assessing the accuracy of the method, and the recovery values achieved were in the range of 90–110%. The method was applied for iron determination in eight samples of fortified milk powder, and the obtained concentrations varied from 95.4 to 295.6 μg g⁻¹. The results were compared with those obtained after acid digestion, and no significant difference was observed applying t test at the 95% confidence level.     

Sensitive determination of parabens in soy sauces by capillary zone electrophoresis with amperometric detection

A high-performance capillary zone electrophoresis with amperometric detection (CZE-AD) method has been developed for the separation and sensitive determination of the preservatives methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP) in soy sauce samples. The effects of several factors such as the pH and concentration of running buffer, the separation voltage, the applied potential and the injection time on CZE-AD were investigated. Under the optimum conditions, four preservatives can be well separated within 16 min at the separation voltage of 16 kV in a 80 mmol/L borax running buffer (pH 9.94), and adequate extraction was obtained with ethanol for the determination of the above four parabens. Satisfactory recovery (95.0–102.0%), repeatability of the peak current (≤2.4%) and migration time (≤0.5%) of four analytes, as well as detection limits (5.7 × 10⁻⁸–4.4 × 10⁻⁸ g/mL) for the method, were achieved. This proposed procedure has been successfully used for the analysis of paraben preservatives in soy sauce samples, and the content of EP was from 0.08 to 0.14 mg/mL in the tested samples.     

Quantitation of the homocysteine content in wine

Alcohol consumption has been previously shown to correlate with elevated plasma homocysteine levels, but investigations have not been carried out on the possible availability of this compound in alcoholic beverages such as wine or spirits. Therefore, in this study we investigated the levels of homocysteine in various Bulgarian wines. A total of 36 different Bulgarian wines with known origins were studied. The measured values were in the range of 0.09–0.64 mg l⁻¹ for the tested white wines and in the range of 0.10–1.37 mg l⁻¹ for the red wines. The method used for homocysteine determination was based on RP-HPLC with fluorescent detection after derivatization with N-(2-acridonyl)maleimide. The method was linear in the range of 0.0070–1.35 mg l⁻¹ homocysteine and showed low limits of detection and quantification (LOD = 6 fmol, LOQ = 68 fmol). The within-run precision expressed as relative standard deviation (RSD, %) was 2.2–2.4% and the between-run precision was 2.6–3.9%. Enzyme immunoassay and LC-MS ⁿ analyses were used for confirmation of presence of homocysteine in wine.     

An Automated Single Interface Flow System for the Spectrophotometric Determination of Ethanol in Beverages Based on Schlieren Effect

A new and expeditious automated procedure for the determination of ethanol content in alcoholic beverages (distilled liquors and wine) by using a single interface flow analysis (SIFA) system with spectrophotometric detection is presented. The developed approach was simply based on refractive index gradient measurements, known as Schlieren effect, produced when acidified beverages samples were introduced in a single-line SIFA system that used deionized water as carrier (trailing) stream and a computer-controlled spectrophotometer as detector. In the implemented SIFA system, no chromogenic reagent is used, being the refractive index gradient a consequence of the mutual interdispersion of sample and carrier zones at the formed single interface, and no predefined volumes of both sample and carrier are required, which greatly simplifies system operation and optimization. The proposed methodology allowed the determination of ethanol concentrations between 4% and 24% (v/v) with good precision (RSD < 5.2%, n = 3) and a sampling frequency of about 58 h⁻¹ with consumption of 400 μl of sulfuric acid 0.5 mol l⁻¹ and 400 μl of sample per measurement. The developed procedure was applied to whisky, gin, rum, vodka, the sugar cane-based beverage “cacha?a,” and white wine, and the obtained results were in a good agreement with those provided by the reference method (RD < 5.0%). Recovery values acquired in the analysis of spiked ethanol samples (between 90.0% and 111.0% of the added amount) were also satisfactory.     

The Influence of Oxygen Volumetric Mass Transfer Rates on Cyclodextrin Glycosyltransferase Production by Alkaliphilic Bacillus circulans in Batch and Fed-Batch Cultivations

In this work, the influence of oxygen mass transfer rates on the production of cyclodextrin glycosyltransferase (CGTase) by the alkaliphilic bacterium Bacillus circulans ATCC 21783 was investigated. Experimental design and response surface methodology were applied to optimize agitation speed and air flow rate in batch cultivations, in order to identify their significant effects and interactions with the synthesis of CGTase. Results were expressed as the volumetric mass transfer rates of oxygen (k_la, [per hour]). The maximal CGTase productivity of 155 U mL⁻¹ h⁻¹ was achieved with k_la of 48 h⁻¹. CGTase production was also studied in fed-batch cultures using the optimized parameters obtained in the batch experiments. The maximal CGTase productivity on fed-batch cultivations was 137 U mL⁻¹ h⁻¹ with feeding rates of starch at 0.17 g L⁻¹ h⁻¹.     

Evaluation of W-Rh permanent modifier for lead determination in sugar by graphite furnace atomic absorption spectrometry

An alternative procedure that improves the performance of graphite atomizers for the determination of Pb in sugar by electrothermal atomic absorption spectrometry is described. The procedure is based on the injection of 10 μl of an acidified aqueous solution containing 8% w/v sugar and 0.2% v/v HNO₃ into integrated graphite platforms. Either transversely (THGA) as well as longitudinally heated graphite atomizers (LHGA) were evaluated by using conventional co-injection of 0.03% Pd + 0.05% Mg(NO₃)₂ or thermally treated platforms with 250 μg W + 200 μg Rh and co-injection of 5 μg l⁻¹ Rh solution. With W-Rh under the same analytical conditions, the lifetimes of THGA and LHGA reached up to 1110 and 900 firings, respectively. With Pd + Mg the LHGA tube lifetime was limited to approximately 500 firings, but for THGA up to 1020 firings were made with a single tube. Characteristic masses were 11 and 29 pg Pb for LHGA and THGA, respectively. Detection limits (3 s) based on sugar blank solution and on integrated absorbance were 5.0 mg kg⁻¹ with LHGA and 9.3 mg kg⁻¹ Pb for THGA. In general, the coefficients of variation of 20 consecutive measurements of a solution containing 50 μg l⁻¹ Pb were lower than 5%. The obtained detection limits are in consonance with the Codex Alimentarius recommendation for the maximum Pb content in the sugar.     

Square-Wave Adsorptive Stripping Voltammetry for Trace Determination of Dimoxystrobin and Azoxystrobin in Potatoes and Grapes

Square-wave voltammetry was used for trace determination of azoxystrobin and dimoxystrobin in potatoes, grapes, and grape juice. Experimental conditions have been optimized to achieve simultaneous determination of these analytes using the hanging mercury drop electrode. Supporting electrolyte was HCl 0.1 mol L⁻¹, and other optimized conditions were deposition potential (−300 mV), deposition time (30 s), amplitude (150 mV), frequency (150 Hz), and step height (2 mV). Azoxystrobin and dimoxystrobin redissolution peaks presented their maxima, respectively, at −928 mV and around −650 mV. Linear and homoscedastic analytical responses (r ² > 0.99) have been observed. Limits of quantification as low as 119 μg L⁻¹ (in grape juice) and 45 μg kg⁻¹ (in potatoes and grapes) were found. A previous solid-phase extraction was necessary to eliminate interferences from potato and grape samples. For grape juice, no sample treatment was required. Satisfactory recoveries (from 72.3% to 96.7% for dimoxystrobin and from 81.7% to 102.3% for azoxystrobin) were found. Interferences from other strobilurins (piraclostrobin and picoxystrobin) were evaluated.     

Determination of Copper,Cobalt, Lead,and Iron in Table Salt by FAAS After Separation Using Violuric Acid and Multiwalled Carbon Nanotubes

A separation–enrichment technique for the determination of trace amounts of copper(II), cobalt(II), lead(II), and iron(III) as violuric acid chelates on multiwalled carbon nanotubes at pH 6.0 was established. Analytes were determined by flame atomic absorption spectrometry. The effects of some analytical parameters like pH, amounts of violuric acid, flow rates, eluent type, and sample volume were investigated. The influences of the matrix ions were also investigated. The relative standard deviations for analyte elements were below 10%. The quantification limits of the analyte ions were found as 0.36 μg g⁻¹ for copper, 0.43 μg g⁻¹ for lead, 0.15 μg g⁻¹ for cobalt, and 0.38 μg g⁻¹ for iron. The accuracy of presented method was checked by the analysis of TMDA 54.4 fortified lake water, NIST SRM 1515 apple leave, and HR-1 Humber river sediment certified reference materials. The method was applied to analyte contents of table salt samples from different origin. The levels of iron in the analyzed table salt samples were found in the range of 1.6–6.4 μg g⁻¹, while lead was found in only one sample as 5.0 μg g⁻¹. In all other samples, cobalt, lead, and copper were found below the quantification limits of the analytes.     

Benzyloxybenzaldehydethiosemicarbazone: Extractive Spectrophotometric Reagent for the Determination of Cu(II) in Food and Water Samples

Benzyloxybenzaldehydethiosemicarbazone (BBTSC) was prepared and developed a new method for the simple, highly selective, and extractive spectrophotometric determination of copper(II) with BBTSC at wavelength 370 nm. The metal ion formed a bluish green colored complex with BBTSC in acetate buffer of pH 5.0, which was easily extractable into n-butanol with 1:1(metal/ligand) composition. The method obeys Beer’s law in the range of 0.5–5.2 ppm. The molar absorptivity and Sandell’s sensitivity were found to be 1.5 × 10⁴ l mol⁻¹ cm⁻¹ and 0.00412 g cm⁻², respectively. The correlation coefficient of the Cu(II)–BBTSC complex was 0.998, which indicated an excellent linearity between the two variables. The repeatability of the method was checked by finding the relative standard deviation (RSD; n = 10), which was 0.377% and its detection limit 0.0204 μg ml⁻¹. The interfering effect of various cations and anions were also studied. The proposed method was successfully applied to the determination of copper(II) in food and water samples. Comparing the results with those obtained using an atomic absorption spectrophotometer tested the validity of the method.     

Spectrophotometric Determination of Trace Nitrite with Brilliant Cresyl Blue Using β-Cyclodextrin as a Sensitizer

A simple and sensitive spectrophotometric method for determination of nitrite has been described. The method is based on the oxidation of brilliant cresyl blue (BCB) by nitrite in acidic medium, which results in the decrease in absorbance at 636 nm. The decrease in absorbance is directly proportional to nitrite concentration obeying Beer’s law. The sensitivity is largely enhanced in the presence of β-cyclodextrin (β-CD) because of inclusion complexation. It was calculated that β-CD and BCB could form 1:1 inclusion complexation with a formation constant of 546.6 L/mol. Linear calibration graphs were obtained for 0.02 × 10⁻³–0.8 × 10⁻³ g/L sodium nitrite at 636 nm. The detection limit for the analytical procedure was 4.0 × 10⁻⁶ g/L sodium nitrite. The relative standard deviation for determination of 0.1 × 10⁻³ g/L and 0.5 × 10⁻³ g/L sodium nitrite were 0.69% and 0.38%, for ten determinations, respectively. Twenty-two coexistent ions or species were examined, and no serious interference for most of ions was observed. The method has been applied to determine nitrite in water and vegetable samples with satisfactory results.     

Quantitative Determination and Confirmation of Five Synthetic Glucocorticoid Residues in Milk Powder by Gel Permeation Chromatography–Liquid Chromatography–Tandem Mass Spectrometry

A new method for multi-residue determination of five synthetic glucocorticoids (betamethasone, dexamethasone, prednisone, prednisolone, and hydrocortisone) in milk powder is developed. The glucocorticoids in the samples were extracted with tert-butyl methyl ether under ultrasonication incubation, and then cleaned up through gel permeation chromatography. After C18 LC gradient elution separation using acetonitrile with 0.1% formic acid as a mobile phase, the eluents were determined by liquid chromatography–tandem mass spectrometry with multiple reaction monitoring and positive ionization modes. The effective separation for the five glucocorticoids was achieved. The limit of quantification of the method for testing five glucocorticoids in milk powder was in the range from 0.2 to 0.5 μg kg⁻¹, which was lower than the maximum residue limits established by European Union for glucocorticoids in foods. Experiments on spiked samples of milk powder showed that the mean recoveries at addition level of 1.0, 3.0, and 5.0 μg kg⁻¹ were in the range of 71.2% and 103%, and the relative standard deviation ranged from 4.7% to 16.8%. The calibration curves for these drugs between 1.0 and 100 μg l⁻¹ showed good linearity, with correlation coefficient (r) more than 0.999. The real sample test showed that this method is sensitive and accurate. It can be used for qualitative and quantitative determination of studied glucocorticoid residues in milk powder samples.