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.     

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.     

Quantification of lactose using ion-pair RP-HPLC during enzymatic lactose hydrolysis of skim milk

The correct labelling of dairy foods as “lactose-free” requires a suitably sensitive and valid analytical method for the quantification of lactose in complex food matrices. Thus, an ion-pair RP-HPLC method for the simultaneous determination of lactose, glucose and galactose in original skim milk was investigated. The samples derived from an enzymatic lactose hydrolysis approach (0.5 L) using the commercial β-galactosidase Godo-YNL2. After derivatisation with p-aminobenzoic acid and sodium cyanoborohydride, the samples were injected on a RP-C₁₈ column. Tetrabutylammonium hydrogen sulphate was used as the ion-pair reagent in the eluent system. The sugars were quantified using photometric- (UV; 303 nm) and fluorescence-detection (λ_ex 313 nm, λ_em 358 nm). The overall run time was 27 min. The limits of detection (LOD) were estimated at 2 mg L⁻¹ (UV detection) and at 0.13 mg L⁻¹ (fluorescence detection). The limits of quantification were 6 mg L⁻¹ (UV detection) and 0.45 mg L⁻¹ (fluorescence detection). Thus, this analytical method is suitable for sensitive lactose quantification in milk systems of less than 10 mg L⁻¹.     

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.     

Weight loss of frozen bread dough under isothermal and fluctuating temperature storage conditions

Evaporative weight loss from food leads to both loss of saleable weight and quality deterioration so it need to be minimized. The effect of isothermal and fluctuating conditions on frozen dough weight loss was measured and compared with kinetic, physical and artificial neural network (ANN) models. Frozen dough samples were regularly weighed during storage for up to 112 days in loose-fitting plastic bags. The storage temperatures were in the range of −8 to −25 °C with fluctuations of ±0.1 °C (isothermal), ±1, ±3 or ±5 °C about the mean. For each combination of temperature and fluctuation amplitude, the rate of dough weight loss was constant. The rate of weight loss at constant temperature was nearly proportional to water vapour pressure consistent with standard theories for evaporative weight loss from packaged foods but was also accurately fitted by Arrhenius kinetics. Weight loss increased with amplitude of temperature fluctuations. The increase could not be fully explained by either the physic model based on water vapour pressure differences or the kinetic model alone. An ANN model with six neurons in the input layer, six neurons in hidden layers and one neuron in the output layer, achieved a good fit between experimental and predicted data for all trials. However, the ANN model may not be accurate for product, packaging and storage systems different to that studied.     

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.     

A multi-residue method for fast determination of pesticides in tea by ultra performance liquid chromatography–electrospray tandem mass spectrometry combined with modified QuEChERS sample preparation procedure

A multi-residue method was developed for rapid determination of pesticide residues in tea by ultra performance liquid chromatography–electrospray tandem mass spectrometry (UPLC/MS/MS). The QuEChERS method was used for sample preparation. In order to minimise the matrix effects from tea, a solid phase extraction (SPE) cartridge layered with graphite carbon/aminopropylsilanized silica gel was applied as complementary to QuEChERS method. For accurate quantification, representative matrix-matched calibration curves were applied to compensate matrix effects. Limits of quantification varied with different pesticides but all can be measured at 0.01 mg kg⁻¹ level in a 5 g tea sample except dichlorvos (0.02 mg kg⁻¹). Recoveries ranged from 70% to 120% and relative standard deviation (RSD) met the European United Quality Control guideline. Efficiency and reliability of this method were investigated by the analysis of both fermented and unfermented Chinese tea samples.     

Kinetic-spectrophotometry method for determination of ultra trace amounts of aluminum in food samples

A simple and sensitive kinetic-spectrophotometry method is developed for the determination of trace amounts of aluminum in food samples based on its catalytic effect on the oxidation of Nile Blue A by potassium bromate in sulfuric acid medium. The absorbance is measured at 595.5 nm with the fixed-time method. The optimization of the operating conditions regarding concentrations of the reagents, temperature and interferences are also investigated. The calibration curve is linear over the concentration range 0.07–0.9 μg ml⁻¹ of aluminum with good precision and accuracy and the detection limit was down to 0.034 μg ml⁻¹. The relative standard deviation for a standard solution of 0.4 μg ml⁻¹ of aluminum is 1.73% (n = 10). The proposed method proved highly sensitive, selective and relatively rapid for the assay of aluminum at ultra trace level without any pre-concentration and separation step. The method was applied to the determination of aluminum in food samples (rice, tea and potato). The analytical results of the real samples were in good agreement with the standard method.     

Decaffeination of fresh green tea leaf (Camellia sinensis) by hot water treatment

Hot water treatment was used to decaffeinate fresh tea leaf in the present study. Water temperature, extraction time and ratio of leaf to water had a statistically significant effect on the decaffeination. When fresh tea leaf was decaffeinated with a ratio of tea leaf to water of 1:20 (w/v) at 100 °C for 3 min, caffeine concentration was decreased from 23.7 to 4.0 mg g⁻¹, while total tea catechins decreased from 134.5 to 127.6 mg g⁻¹; 83% of caffeine was removed and 95% of total catechins was retained in the decaffeinated leaf. It is considered that the hot water treatment is a safe and inexpensive method for decaffeinating green tea. However, a large percentage of tea catechins was lost if rolled leaf and dry tea were decaffeinated by the hot water treatment and so the process is not suitable for processing black tea.     

Experimental and theoretical study of LDPE versus different concentrations of Irganox 1076 and different thickness

This work presents a theoretical and experimental study on the specific migration process, describing the mass transfer of a model migrant Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (I-1076), an antioxidant commonly used in the polyolefins processing. Film samples (LDPE), with initial concentration of Irganox between 1000 and 6000 (mg/kg), and thickness of 50-190 ??m, were placed in contact with fatty (EtOH 95%) and aqueous (EtOH 10%) food simulants at 40 °C for 20 days, in order to obtain the concentration evolution in the food simulant which was measured by HPLC. On the other hand, a phenomenological model based on a resistances-in-series approach was developed considering the diffusion through the polymer film, natural convection in the food simulant and the thermodynamic equilibrium between the polymer and the liquid simulant phase. For the thickest films, the diffusion coefficient of I-1076 through the polymer phase was estimated varying between 1.95·10^− 13 (m² s^− 1) and 2.0·10^− 13 (m² s^− 1) at 40 ºC. On the contrary, the thinnest one shows a significant decrease of the diffusion coefficient value, which was evaluated in 1.0·10^− 14 (m² s^− 1). This modification can be explained by means of a crystal distribution and size in the thinnest polymer film prepared by CAST extrusion. The mathematical model developed is a tool for prediction and analysis which can be used to facilitate the characterization of polymers, and it could predict the response as packaging for food in a specific application.     

Thin layer drying characteristics of rapeseed (Brassica napus L.)

This study was performed to determine the most appropriate thin layer drying model and the effective moisture diffusivity of rapeseed. The thin layer drying tests were conducted at three different combinations of drying air temperature levels of 40, 50, and 60 °C and relative humidity levels of 30, 45, and 60%. The thin layer drying characteristics of rapeseed were determined. The Page (1949) model was the most adequate model for describing the thin layer drying of rapeseed. Drying occurred in the falling rate period and the rate of moisture removal from rapeseed was governed by the rate of water diffusion to the surface of the seed. Effective moisture diffusivities were calculated based on the diffusion equation for a spherical shape using Fick’s second law. Effective moisture diffusivity during drying varied from 1.72 × 10⁻¹¹ to 3.31 × 10⁻¹¹ m² s⁻¹ over the temperature range. The dependence of moisture diffusivity on temperature was described by an Arrhenius-type equation. The activation energy for moisture diffusion during drying was 28.47 kJ mol⁻¹.     

Quantitative analysis of acrylamide in tea by liquid chromatography coupled with electrospray ionization tandem mass spectrometry

An effective sample preparation procedure was optimized and a liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed for the quantitative analysis of acrylamide in tea. [¹³C₃]-acrylamide was used as internal standard. Acrylamide was extracted at 25 °C for 20 min by 10 ml water followed by 10 ml acetonitrile, and then 4 g of magnesium sulfate and 0.5 g of sodium chloride were added to the above mixture under stirring thoroughly. In order to increase the response of acrylamide, 9 ml acetonitrile layer was taken and concentrated to 0.5 ml. Solid-phase extraction with an Oasis MCX cartridge was carried out for clean-up. The limit of detection (LOD) and limit of quantification (LOQ) were 1 and 5 ng/ml, respectively. The recovery efficiency of the extraction procedure ranged between 74% and 79%. The levels of acrylamide in 30 tea samples were less than 100 ng/g. Black, oolong, white and yellow tea samples had quite low acrylamide contents (<20 ng/g). Higher acrylamide levels occurred in baked, roasted, and one sun-dried green tea samples (46–94 ng/g).     

Process optimisation for recovery of carotenoids from tomato waste

Carotenoids constitute an important component of waste originating from tomato processing plants. Studies were carried out to assess the extraction yield of tomato waste carotenoids in different solvents and solvent mixtures and to optimise the extraction conditions for maximum recovery. A mixture of ethyl acetate and hexane gave the highest carotenoid extraction yield among the others examined. Extraction conditions, such as percentage of hexane in the solvent mixture of ethyl acetate and hexane, ratio of solvent to waste and particle size were optimised using a statistically designed experiment. A regression equation for predicting the carotenoid yield as a function of three extraction variables was derived by statistical analysis and a model with predictive ability of 0.97 was obtained. The optimised conditions for maximum carotenoid yield (37.5 mg kg⁻¹ dry waste) were 45% hexane in solvent mixture, solvent mixture to waste ratio of 9.1:1 (v/w) and particle size 0.56 mm.     

Quantitative analysis of lincomycin and narasin in poultry, milk and eggs by liquid chromatography-tandem mass spectrometry

This study presents the simultaneous extraction and determination of lincomycin (LCM) and narasin (NAR) by using liquid chromatography-electrospray ionisation tandem mass spectrometry (LC-MS/MS) on samples from poultry, milk and eggs (n = 196). The homogenised samples are extracted with acetonitrile and the extract is further cleaned using C₁₈ solid-phase extraction cartridges. The recoveries of the analytes in different matrices were found ranging from 90% to 101% and 85% to 95% for LCM and NAR, respectively. The corresponding limits of detection were 0.6 and 1.5 ng g⁻¹ for LCM and NAR, respectively. As a result of monitoring, NAR was not detected in any samples and LCM was detected in one egg with a concentration of 25 ng g⁻¹. The method was relatively simple to perform and therefore could be used for food safety surveillance activities.     

Artificial intelligence in predicting extraction of anti-cancer compounds

Saponins from the particulate Saponaria vaccaria L. seeds (0.29–0.84 mm, 15.35–61.40 g H₂O/100 g dry mass) were extracted for methanol concentrations (MeOH) of 30, 50, 70, and 90 mL/100 mL H₂O and temperatures (T) of, 30, 45, and 60 °C at ten extraction intervals (t) between 1 and 180 min. A calibration equation was developed from the liquid-chromatogram–mass spectroscopy peaks to quantify the extract yields (mg mL⁻¹) for various types of saponins. An artificial neural network (ANN) with three inputs, MeOH, T, and t predicted the extraction kinetics and the yields with less than ca. 12% error. The ANN model not only slightly outperformed the numerical diffusional model, but it also made the prediction simple and faster eliminating the use of the partition coefficient and the effective diffusivity. Therefore an ANN model can be a right approach to predict the yields of saponins and similar products.     

Artificial neural network modeling and optimization of ultrahigh pressure extraction of green tea polyphenols

In this study, the ultrahigh pressure extraction of green tea polyphenols was modeled and optimized by a three-layer artificial neural network. A feed-forward neural network trained with an error back-propagation algorithm was used to evaluate the effects of pressure, liquid/solid ratio and ethanol concentration on the total phenolic content of green tea extracts. The neural network coupled with genetic algorithms was also used to optimize the conditions needed to obtain the highest yield of tea polyphenols. The obtained optimal architecture of artificial neural network model involved a feed-forward neural network with three input neurons, one hidden layer with eight neurons and one output layer including single neuron. The trained network gave the minimum value in the MSE of 0.03 and the maximum value in the R² of 0.9571, which implied a good agreement between the predicted value and the actual value, and confirmed a good generalization of the network. Based on the combination of neural network and genetic algorithms, the optimum extraction conditions for the highest yield of green tea polyphenols were determined as follows: 498.8 MPa for pressure, 20.8 mL/g for liquid/solid ratio and 53.6% for ethanol concentration. The total phenolic content of the actual measurement under the optimum predicated extraction conditions was 582.4 ± 0.63 mg/g DW, which was well matched with the predicted value (597.2 mg/g DW). This suggests that the artificial neural network model described in this work is an efficient quantitative tool to predict the extraction efficiency of green tea polyphenols.     

Determination of caffeine content in tea based on poly(safranine T) electroactive film modified electrode

Safranine T was electropolymerised on a glassy carbon electrode and then characterised by scanning electron microscope (SEM), X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). This uniform electropolymerised film was crystallisable and showed a high electrocatalytic ability towards the oxidation of caffeine. To avoid the interferences of the anions, Nafion was covered on the surface of poly(safranine T) film modified glassy carbon electrode. As a new voltammetric sensor, this modified electrode is sensitive, selective and stable to determine caffeine content in tea. The peak current increased linearly with the concentration of caffeine in the range of 3 × 10⁻⁷–1 × 10⁻⁴ M, with a detection limit of 1 × 10⁻⁷ M. All of these make it a useful tool for determining caffeine content in tea. What’s more, it produces much less organic waste compared with other analytical techniques.     

Mathematical modeling of the heat and mass transfer in a stationary potato sphere impinged by a single round liquid jet in a hydrofluidization system

The hydrofluidization (HF) is a method of chilling and freezing of foods which consists in a circulating system that pumps a refrigerating liquid upwards through orifices or nozzles, creating agitating jets. The objectives of this work were to develop a mathematical model to represent the combined heat and mass transfer between a food and a refrigerant liquid medium in a HF system and to validate the model using a single stationary sphere of food impinged by a single round jet of liquid. The food domain consisted of a rigid solid matrix, a liquid phase and the ice phase. Transport equations were applied to each phase and solved by a control-volume approach. The transport phenomena in the fluid domain were studied by computational fluid dynamics. The surface heat transfer coefficients obtained from fluid flow simulations were used to model the heat and mass transfer inside the food. Experimental central temperature and average solute uptake profiles were obtained when potato spheres were placed in a HF system using a NaCl-water as refrigerant and considering different temperatures (−10 and −15 °C), flow rates (1 and 3 L min⁻¹), and orifice-sphere distances (1 and 5 cm). The predicted values agreed well with the experimental ones, the maximum root mean square errors being 3.3 g NaCl kg⁻¹ potato and 2.9 K for the average solute concentration and temperature profiles studied, respectively. The simulations improved the understanding of the HF process and it may help to study and control different operation scenarios.     

Detection of irradiated black tea (Camellia sinensis) and rooibos tea (Aspalathus linearis) by ESR spectroscopy

Detailed ESR investigation on irradiated black and rooibos tea was carried out in the dose range of 0.5–10 kGy. Unirradiated black and rooibos tea samples exhibit a weak, symmetric ESR (electron spin resonance) singlet centered at g = 2.0043 ± 0.0010 with peak-to-peak line widths (ΔH_pp) of 1.00 ± 0.05 and 0.64 ± 0.05 mT, respectively. Irradiation caused a significant increase in ESR signal intensity of both samples without any changes in spectral patterns and these increases were found to be explained by a quadratic and/or an exponentially varying functions. Variation of ESR signal intensity, for the irradiated samples, at room temperature (295 K) with time in a storage period of 39 days showed that free radical responsible from the ESR spectrum of black tea is more stable than that of the rooibos tea. However, variable temperature and annealing studies show that the free radical responsible from the ESR spectrum of rooibos tea, with activation energy of 46.0 ± 3.5 kJ mol⁻¹, is more resistant to the temperature than that of the black tea with activation energy of 33.8 ± 3.1 kJ mol⁻¹.     

Determination of polycyclic aromatic hydrocarbons in edible oils and barbecued food by HPLC/UV–Vis detection

Determination of nine polycyclic aromatic hydrocarbons in corn, sunflower, olive oils and barbecued meat and fish by HPLC/UV–Vis method is described. The extraction procedure included a saponification, liquid–liquid extraction and finally purification of PAHs through a house-made silica–alumina column. Chromatographic determination was based on separation of PAHs on ODS column and measurement at 254 nm. All polycyclic aromatic hydrocarbons were separated and analyzed in 12 min on reversed phase ODS column with acetonitrile/water mobile phase at 1.5 mL min⁻¹ flow rate. The detection limits of nine polycyclic aromatic hydrocarbons ranged from 0.26 to 1.15 μg L⁻¹ at a signal/noise ratio of 3. The linearity of the method was between 0.9951 and 0.9996. Oil samples contain different PAHs ranging from 0.44 to 98.92 μg L⁻¹. Barbecuing process increased the concentration (in the range of 2- to 8-fold) and caused the formation of PAHs in food samples.