Trace metals in raw cows’ milk and assessment of transfer to Comté cheese

As part of a program to assess the transfer of metals from soil to dairy products, the transfer of metal trace elements to milk and cheese was studied. Concentrations of non-essential (Cd and Pb) and essential elements (Cu and Zn) were determined by atomic absorption spectrometry in 61 samples of raw milk and 21 of the corresponding cheese. While metal concentrations (dry weight) in raw milk were very low (Cd: 0.34–1.01 ng/g; Pb: 0.009–0.126 μg/g; Cu: 0.28–1.71 μg/g; Zn: 20.62–30.96 μg/g), concentrations in the corresponding cheese were significantly higher (Cd: 0.68–11.37 ng/g; Pb: 0.020–0.925 μg/g; Cu: 5.35–21.34 μg/g; Zn: 33.66–63.41 μg/g). The retention factor R_t suggests a concentration effect during the cheese making process, especially in the case of Cu, due to the use of large copper vats. Concentrations of non-essential elements (Cd and Pb) in cheese largely remained below those considered as dangerous for consumers. Finally, Comté cheese may constitute a useful source of Cu and Zn in human diet.     

Simultaneous determination of ultra trace amounts of lead and cadmium in food samples by adsorptive stripping voltammetry

A selective and sensitive method for simultaneous determination of lead and cadmium by adsorptive differential pulse cathodic stripping voltammetry is presented. The method is based on adsorptive accumulation of the complexes of Pb (II) and Cd (II) ions with 2-mercaptobenzothiazole onto hanging mercury drop electrode (HMDE), followed by the reduction of the adsorbed species by differential pulse cathodic stripping voltammetry. Optimal conditions were obtained at pH 8.0, 2-mercaptobenzothiazole concentration of 1.0 × 10⁻⁴ M, the accumulation potential of −0.4 V (vs. Ag/AgCl), the accumulation time of 160 s, and the scan rate of 100 mV/s. Under optimised conditions, linear calibration curves were established for the concentration of Pb (II) and Cd (II) in the range of 0.5–70 and 0.2–30 ng/ml, respectively, with detection limit of 0.017 ng/ml for Pb (II) and 0.01 ng/ml for Cd (II). The procedure was successfully applied to the simultaneous determination of both ions in food samples (rice, soya and sugar).     

Role of transition metals,Fe(II), Cr(II), Pb(II), and Cd(II) in lipid peroxidation

Cod liver oil was oxidized with Fenton-like systems containing transition metals Fe(II), Cr(II), Pb(II), and Cd(II). Malonaldehyde (MA) formed from 10 μl cod liver oil oxidized by a Fenton-like system containing each metal at levels of 0.25, 0.5, 1 and 4 μmol was analyzed by a gas chromatograph equipped with a nitrogen phosphorus detector. The MA production exhibited dose response and the greatest amount (837.0 ± 19.1 nmol) was obtained by the Fe(II) system at the level of l μmol. Generally, higher MA formation is observed in the lower the third ionization potential of the metal. The decreasing order of MA formed in the metal systems at the level of 1 μmol is Fe(II) > Cr(II)(274.1 ± 20.1 nmol) > Pb(II)(150.7 ± 13.0 nmol) > Cd(II)(95.4 ± 6.7 nmol). The amounts of MA formed in Cr(II), Pb(II), and Cd(II) systems were considerably lower than those in the Fe(II) system. The relative formations of MA in the Cr(II) and Pb(II) systems were similar to those in the Fe(II) system. The results suggest that trace amounts of metals contribute oxidative effects to lipid peroxidation followed by various diseases.     

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.     

Monitoring of Zn(II), Cd(II), Pb(II) and Cu(II) During Refining of Some Vegetable Oils Using Differential Pulse Anodic Stripping Voltammetry

In this study, a novel approach has been developed using differential pulse anodic stripping voltammetry (DPASV) for the simultaneous determination of Zn(II), Cd(II), Pb(II) and Cu(II) in edible oils at hanging mercury drop electrode. The microwave digestion of oil samples was carried out with concentrated HNO₃ and H₂O₂. KNO₃ was used as a supporting electrolyte. The experimental conditions optimized such as deposition time, stirring rate and size of mercury drop were 300 s, 600 rpm and 10 mm², respectively. The method was applied to quantify Zn(II), Cd(II), Pb(II) and Cu(II) in crude and refined hazelnut, corn, sunflower and olive oils. During refining of different vegetable oils, the removal efficiencies of Zn(II), Cd(II), Pb(II) and Cu(II) were calculated as 98.20–99.91, 98.50–99.90, 95.26–99.76 and 95.93–99.92 %, respectively. The limits of detection for Zn(II), Cd(II), Pb(II) and Cu(II) were 2.1?×?10^?8, 8.7?×?10^?10, 7.1?×?10^?9 and 3.4?×?10^?9 and the limits of quantification were 6.8?×?10^?8, 2.9?×?10^?9, 2.3?×?10^?8 and 1.1?×?10^?8 M with linear regression coefficients (R ²) of 0.9930, 0.9928, 0.9893 and 0.9931, respectively. It was observed that the above metals in crude and refined vegetable oils could be determined simultaneously by the DPASV method.     

Voltammetric determination of ultra-trace total mercury and toxic metals in meals

This paper reports the sequential voltammetric determination of Hg(II) and Cu(II) at the gold electrode (GE), and of Cu(II), Pb(II), Cd(II), Zn(II) at the hanging mercury drop electrode (HMDE) by square wave anodic stripping voltammetry (SWASV).     

Potential of Sawdust as a Green and Economical Sorbent for Simultaneous Preconcentration of Trace Amounts of Cadmium,Cobalt, and Lead from Water,Biological, Food,and Herbal Samples

Application of treated sawdust with NaOH as a green and economical sorbent for simultaneous preconcentration of trace amounts of Cd(II), Co(II), and Pb(II) ions from liver, lettuce, fish, and water as test samples with complicated matrices was investigated. Various parameters, such as effect of pH and contact time, breakthrough volume, type, and concentration of eluent and interference of ions were studied. The sorption was quantitative in the pH of 5.0 to 7.0 and desorption occurred instantaneously with 5.0 mL of mixed solutions of ethanol and 2.0 mol/L HNO₃–HCl and the amount of ions was measured by using flame atomic absorption spectrometry. Linearity was maintained at 3 to 500 μg/L for cobalt, 5.0 to 800 μg/L for lead, and 2.0 to 300 μg/L for cadmium in the original solution. The relative standard deviation was less than 1.80% (n = 6, with concentration of 0.3 mg/L for cadmium and 0.5 mg/L for lead and cobalt). Detection limits and maximum capacity of the sorbent for Co (II), Cd (II), and Pb (II) in the original solution were 0.86, 0.50, and 1.7 μg/L and 28.5, 30.6, and 47.3 mg/g, respectively. The results for spiked real samples, effect of interfering ions, and adsorption capacity indicated that the applicability of this method for lead preconcentration is better than cadmium and cobalt preconcentration from complicated matrices. Practical Application : Sawdust can be applied as a green and economical sorbent for simultaneous preconcentration and solid‐phase extraction of metal ions from food and environmental samples with complicated matrices.     

Effect of canned tuna fish processing steps on lead and cadmium contents of Iranian tuna fish

The contents of Pb and Cd in two species of Iranian tuna fish (yellowfin and skipjack), which were caught from the Persian Gulf and Oman Sea, and the effects of canning processing steps on their contents were assessed by electrothermal atomic absorption spectrometry. The results revealed that the levels of lead and cadmium throughout the processing steps in yellowfin were in range of 0.154 ± 0.019–0.441 ± 0.025 μg/g and 0.029 ± 0.002–0.084 ± 0.0005 μg/g, respectively. Pb and Cd concentrations from received fish to final product in skipjack were found to be in range of 0.072 ± 0.031–0.218 ± 0.031 μg/g and 0.016 ± 0.001–0.062 ± 0.002 μg/g, respectively. The limit of detection for lead and cadmium were 0.058 μg/g (11.6022 μg/l) and 0.0007 μg/g (0.1485 μg/l), respectively. Results from paired sample t-test analysis showed that defrosting, cooking, and sterilisation by autoclave would reduce the contents of lead and cadmium, considerably.     

Comparison of chemical modifiers for direct determination of Cd, Cu and Zn in food stuffs by solid-sampling-ETAAS

In this work, the capability of different chemical modifiers (Pd, Pd/Mg(NO₃)₂, Pd/NH₄NO₃, NH₄H₂PO₄, NH₄H₂PO₄/Mg(NO₃)₂) to eliminate the matrix effects in the direct determination of Cd, Cu and Zn in food-stuffs by solid sampling-electrothermal atomic absorption spectrometry was compared. The alternative analytical lines were used for determination of Cu (327.4 nm) and Zn (307.6 nm) in order to allow the introduction of reasonably high sample mass into the furnace. Mixed modifiers containing palladium were useful to eliminate the matrix effect in Cd determination. For Cu and Zn determination the application of Pd shows satisfactory analytical performance. In the determinations of Cd and Zn the phosphate containing modifiers shows elimination of matrix effects only when applying them to a partially pyrolysed sample (at 400 °C). The achievable limits of detection for Cd, Cu and Zn in solid samples were 0.279 ng g⁻¹; 0.020 μg g⁻¹ and 2.04 μg g⁻¹, respectively.     

Determination of heavy metals (Cd,Pb) and trace elements (Cu,Zn) in sediments and fish of the Southeastern Aegean Sea (Turkey) by atomic absorption spectrometry

The Bay of Güllük in Southeastern Aegean Sea (Turkey) is very important by the potential of marine product in the Aegean Sea. There are various polluting elements in Güllük Bay. The current situation of the bay and impact of pollutants have became necessity. Dicentrarchus labrax are frequently used for human consumption. In this study, heavy metals (Pb, Cd) and trace elements (Cu, Zn) were analyzed in fish (D. labrax) and sediments in the Bay of Güllük by atomic absorption spectrometry. The average metal concentrations in the fish varied in the following ranges: Pb; <0.02–0.4, Cd; <0.01–0.04, Cu; <0.1, Zn; <0.5–7.2 mg kg⁻¹. In addition, seven sediment samples were analyzed and avarage concentrations of them were found as Zn; 80.8 ± 0.45, Cu; 25.2 ± 0.14, Pb; 20.0 ± 2, Cd; 0.560.08 mg kg⁻¹. The accuracy and precision of our results were checked by using International Certified Reference samples (fish: DORM-2, sediment: HISS-1).     

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.     

Trace element content of fish feed and bluegill sunfish (Lepomis macrochirus) from aquaculture and wild source in Missouri

Trace element content of fish feed and bluegill sunfish muscles (Lepomis macrochirus) from aquaculture and natural pond in Missouri were determined using the inductively coupled-plasma optical emission spectrometer (ICP-OES) and the direct mercury analyzer (DMA). Dietary intake rates of trace elements were estimated. Dogfish muscle (DORM-2) and lobster hepatopancreas (TORT-2) reference standards were used in trace element recovery and method validations. The average elemental concentrations (mg/kg diet, dry wt.) of fish feed were: As 1.81, Cd 2.37, Co 0.10, Cr 1.42, Cu 8.0, Fe 404, Mn 35.9, Ni 0.51, Pb 9.16, Se 1.71, Sn 20.7, V 0.09, Zn 118 and Hg 0.07. The mean elemental concentrations (μg/kg wet wt.) in bluegill muscles from both aquaculture and wild (in parenthesis) sources were: As 0.36 (0.06), Cd 0.28 (0.01), Co 0.0 (0.0), Cr 0.52 (0.05), Cu 0.38 (0.18), Fe 17.5 (2.43), Mn 0.18 (0.24), Ni 0.18 (0.04), Pb 1.03 (0.04), Se 0.34 (0.30), Sn 0.66 (0.42), V 0.02 (0.01), Zn 6.97 (9.13) and Hg 0.06 (0.24). Kruskal–Wallis chi square indicated significant differences in As, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sn, V, Zn and Hg (P < 0.001), Se (P < 0.01) and Mn (P < 0.05) across the sampling locations. Dietary intake rates, estimated from weekly consumption of 228 g of aquaculture and wild bluegills, posed no health risks for approximately 85% of all samples.     

Ultra trace quantification of chromium(VI) in food and water samples by highly sensitive catalytic adsorptive stripping voltammetry with rubeanic acid

A simple and highly selective and sensitive catalytic adsorptive stripping voltammetric procedure for determination of ultra trace levels of chromium(VI) on hanging mercury drop electrode is reported. The method is based on the adsorptive preconcentration of the Cr(III)–dithiooxamide (rubeanic acid) complex and the utilization of the catalytic reaction in the presence of nitrate. At optimized conditions the calibration graph is linear from 0.01 to 6 ng/ml and detection limit is 0.002 ng/ml for accumulation time of 50 s. The interference of some common ions was studied and this method has been applied to the determination of chromium in food and waste water samples with satisfactory results.     

Voltammetric method using a lead film electrode for the determination of caffeic acid in a plant material

This paper deals with development of an adsorptive stripping voltammetric method for determination of caffeic acid (CA) at a lead film electrode (PbFE). The working electrode was prepared in situ on a glassy carbon substrate as a “mercury-free” electrochemical sensor. The method is based on the accumulation by adsorption of caffeic acid on PbFE and then the oxidation of CA during the stripping step. In a acetate buffer based supporting medium the oxidation signal for caffeic acid was found to be proportional to the CA concentration in the range from 1 × 10⁻⁸ to 5 × 10⁻⁷ mol/L with the limit of detection equal to 4 × 10⁻⁹ mol/L (with preconcentration for 30 s). The method, operated in the square-wave voltammetric mode, was successfully applied to the determination of CA in a plant material (herbs of Plantago lanceolata). The content of caffeic acid received by the proposed method was in close agreement with that obtained by high performance thin-layer chromatography (HPTLC) combined with densitometry. This appears to be the first application of a lead film electrode to the determination of an organic compound in such complicated matrix.     

Separation‐preconcentration of Cu,Cd, Pb and Ni in various water and food samples on Sepabeads SP‐207

This study presents a solid phase extraction (SPE) procedure for preconcentration and separation of Cu(II), Cd(II), Pb(II) and Ni(II), as their diethyldithiocarbamate chelates on Sepabeads SP‐207 resin using flame atomic absorption spectrometry. The parameters, including pH, sample volume, eluent type and volume etc., were optimised. The influences of the some alkali, alkali earth and transition metal ions on the involvement of copper(II), cadmium(II), lead(II) and nickel(II) were also examined. The preconcentration factor was calculated as 50. The limit of detections of the analyte ions (k = 3, N = 21) were 0.18 μg L^?1 (Cu), 0.17 μg L^?1 (Cd), 0.55 μg L^?1 (Pb) and 1.67 μg L^?1 (Ni). GBW 07605 Tea and NRCC‐DORM‐2 Dogfish Muscle certificated reference materials were used for confirm of method. The method was successfully performed for determination of Cu(II), Cd(II), Pb(II) and Ni(II) ions in water and food samples. The relative standard deviation was found to be lower than 7%.     

Multi-element determination of Cu,Fe, Ni and Zn content in vegetable oils samples by high-resolution continuum source atomic absorption spectrometry and microemulsion sample preparation

The aim of this work was to evaluate the microemulsification as sample preparation procedure for determination of Cu, Fe, Ni and Zn in vegetable oils samples by High-Resolution Continuum Source Flame Atomic Absorption Spectrometry (HR-CS FAAS). Microemulsions were prepared by mixing samples with propan-1-ol and aqueous acid solution, which allowed the use of inorganic aqueous standards for the calibration. To a sample mass of 0.5 g, 100 μL of hydrochloric acid and propan-1-ol were added and the resulting mixture diluted to a final volume of 10 mL. The sample was manually shaken resulting in a visually homogeneous system. The main lines were selected for all studied metals and the detection limits (3σ, n = 10) were 0.12, 0.62, 0.58 and 0.12 mg kg⁻¹ for Cu, Fe, Ni and Zn, respectively. The relative standard deviation (RSD) ranged from 5% to 11 % in samples spiked with 0.25 and 1.5 μg mL⁻¹ of each metal, respectively. Recoveries varied from 89% to 102%. The proposed method was applied to the determination of Cu, Fe, Ni and Zn in soybean, olive and sunflower oils.     

Statistical study of the influence of fungicide treatments (mancozeb, zoxamide and copper oxychloride) on heavy metal concentrations in Sicilian red wine

The aim was to assess the influence of mancozeb, zoxamide and copper oxychloride fungicide treatments on Mn, Zn, Cu, Cd and Pb concentrations in Sicilian red wines, grapes, marcs and grape stalks. The experimentation was carried out over two crop years: 2003 and 2004. Trace metals analysis was performed by derivative stripping chronopotentiometry, which allowed detection of concentrations lower than 1 ng g^-1. The data obtained gave evidence that the levels of Mn and Zn in wines from plots treated with zoxamide-mancozeb were about threefold higher than those observed in the control. Wines treated with Cu oxychloride had a significant increase in Cu(II) concentrations with respect to the control; in particular, samples from 2004 showed a 50% increase in Cu levels. Furthermore, as shown in a previous paper, the fungicides treatments studied led to a moderate increase in Pb(II) and Cd(II) levels in treated samples with respect to the control. Wines from 2004 had higher Cu and Pb amounts than wines from 2003; but the concentrations of all the other metals were similar. Statistical analysis of the data by linear discriminant analysis (LDA) and the Kruskal-Wallis test confirmed that both zoxamide-mancozeb treatments and copper oxychloride treatments exerted a significant influence on Mn(II), Zn(II) Cu(II), Pb(II) and Cd(II) concentrations in wines, grapes, marcs and grape stalks samples from both the studied vintages.     

Minor and trace elements in different honey types produced in Siena County (Italy)

The concentrations of 23 chemical elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Th, Tl, U, Zn) were determined in 51 honey samples of different botanical origin produced in Siena County (Italy). K, Ca, Na and Mg were the most abundant elements, with mean contents of 1195, 257, 96.6 and 56.7 mg/kg, respectively. The Fe, Zn and Sr contents generally ranged from 1 to 5 mg/kg. Except for Ba, Cu, Mn and Ni, the trace element contents were below 100 μg/kg. The analytical data indicated a good level of quality of the honeys, especially with regard to the concentrations of toxic trace elements, such as As, Cd, Pb and Sb, and suggested a significant influence of the botanical origin on the element composition. Some local geological and geochemical features also seemed to affect the chemistry of the honey.     

Statistical study of the influence of fungicide treatments (mancozeb,zoxamide and copper oxychloride) on heavy metal concentrations in Sicilian red wine

The aim was to assess the influence of mancozeb, zoxamide and copper oxychloride fungicide treatments on Mn, Zn, Cu, Cd and Pb concentrations in Sicilian red wines, grapes, marcs and grape stalks. The experimentation was carried out over two crop years: 2003 and 2004. Trace metals analysis was performed by derivative stripping chronopotentiometry, which allowed detection of concentrations lower than 1 ng g^?1. The data obtained gave evidence that the levels of Mn and Zn in wines from plots treated with zoxamide–mancozeb were about threefold higher than those observed in the control. Wines treated with Cu oxychloride had a significant increase in Cu(II) concentrations with respect to the control; in particular, samples from 2004 showed a 50% increase in Cu levels. Furthermore, as shown in a previous paper, the fungicides treatments studied led to a moderate increase in Pb(II) and Cd(II) levels in treated samples with respect to the control. Wines from 2004 had higher Cu and Pb amounts than wines from 2003; but the concentrations of all the other metals were similar. Statistical analysis of the data by linear discriminant analysis (LDA) and the Kruskal–Wallis test confirmed that both zoxamide–mancozeb treatments and copper oxychloride treatments exerted a significant influence on Mn(II), Zn(II) Cu(II), Pb(II) and Cd(II) concentrations in wines, grapes, marcs and grape stalks samples from both the studied vintages.     

Determination of zinc,cadmium, lead and copper in pellets and pulp of sugar beet

Pulp is a residual product of the sugar industry resulting from the total extraction of sugar contained in the root of sugar beet and is normally used in the form of pulp or pellets as food in the cattle industry. The objective of this work was the simultaneous determination of zinc, cadmium, lead and copper in pellets and dried pulp. For this we have developed a method of analysis using anodic stripping voltammetry in the differential pulse mode (DPASV) at a hanging mercury drop electrode (HMDE) and compared the results with those obtained by means of electrothermal atomic absorption spectrometry (ETAAS). We conclude that DPASV can be used as an alternative method to ETAAS to determine low concentrations of Zn, Cd, Cu and Pb in such samples, having the advantage of allowing the determination of all four metals simultaneously. From the analysis of real samples it can be concluded that Zn is present in the highest concentration, ranging from 3 to 30 mg kg^?1, while Cd, Pb and Cu concentrations were always lower than 1, 8 and 8 mg kg^?1 respectively. Copyright © 2005 Society of Chemical Industry