Preconcentration of trace amounts of cobalt (II) ions in water and agricultural products samples using of 5-(4-dimethylaminobenzylidene) rhodanin modified SBA-15 sorbent prior to FAAS determination

In the present study, the ?5-(4-dimethylaminobenzylidene)rhodanin-modified SBA-15? was applied as stable solid sorbent for the separation and preconcentration of trace amounts of cobalt ions in aqueous solution. SBA-15 was modified by ?5-(4-dimethylaminobenzylidene)rhodanin reagent. The sorption of Co²⁺ ions was done onto modified sorbent in the pH range of 6.8–7.9 and desorption occurred in 5.0 mL of 3.0 mol L^?1 HNO₃. The results exhibit a linear dynamic range from 0.01 to 6.0 mg L^?1 for cobalt. Intra-day (repeatability) and inter-day (reproducibility) for 10 replicated determination of 0.06 mg L^?1 of cobalt was ±1.82% and ?±1.97%?. Detection limit was 4.2 µg L^?1 (3S_b, n = 5) and preconcentration factor was 80. The effects of the experimental parameters, including the sample pH, flow rates of sample and eluent solution, eluent type and interference ions were studied for the preconcentration of Co²⁺. The proposed method was applied for the determination of cobalt in standard samples, water samples and agricultural products.     

Determination of Total Arsenic in Wastewater and Sewage Sludge Samples by Using Hydride-Generation Atomic Fluorescence Spectrometry Under the Optimized Analytical Conditions

In this work, an improved hydride-generation atomic fluorescence spectrometry (HG-AFS) method for the determination of total arsenic (As) in wastewater and sewage sludge samples was applied. The samples were digested completely with mixtures of HNO₃ and HClO₄. Analytical conditions were studied and optimized through uniform experimental design U*₁₀(10⁸) combined with a single factor test. A mathematical model was established, and a quadratic polynomial stepwise regression analysis by using the DPS software was employed to obtain the factors that impact the fluorescence intensity. This technique is then combined with a single factor test. The optimized experimental conditions were obtained as follows: PMT voltage was 305 V, lamp current was 70 mA, KBH₄ concentration was 2.0% (m/v), carrier liquid (HCl) concentration was 5% (v/v), carrier gas (Ar) flow rate was 300 mL min^?1, and reaction acidity was 10% (v/v) HCl. The pre-reduction of all forms of As to As(III) was performed by using a mixed solution of 1% thiourea and 1% ascorbic acid. The content of total As was determined under the optimized experimental conditions. The detection limits for total As in wastewater and sewage sludge were 0.09 µg L^?1 and 0.01 mg kg^?1, respectively. The linear ranges were 0.24–100 µg L^?1, and the recovery was 91.0–102.0%. The relative standard deviation (RSD, n = 5) for eleven replicate measurements of the certified reference materials containing 60.6 ± 4.2 µg L^?1 As (certified sample of water) and 10.7 ± 0.8 mg kg^?1 As (certified sample of soil) were 3.1% and 1.6%, respectively. The proposed method was validated by the analysis of certified reference materials and was successfully applied to the determination of total As in real samples of wastewater and sewage sludge with satisfactory results.     

Bioequivalence evaluation of Florfenicol pharmaceutics in pigs using liquid chromatography-tandem mass spectrometry

The bioequivalence of two Florfenicol (FF) products in pigs was evaluated. A 2?×?2 crossover trial with a 14 days wash-out period was performed. The pigs were orally administered in a single dose (2?mg/kg b.w of FF). Serum samples were analyzed using a liquid chromatography-tandem mass spectrometry method. The limit of quantification was 0.1?ng/mL, and the calibration range was 1.0–100.0?ng/mL. Furthermore, intraday and interday were 5.43–9.09% and 6.23–9.68%, respectively. The areas under the curve (AUC_0–48) for the test product B of FF and reference product A were 7289.61?±?1750.44 and 6545.01?±?2766.25?h?×?ng/mL, respectively. The highest concentrations of FF in the serum (C_max) were 726.05?±?211.77 and 641.97?±?117.94?ng/mL. The mean retention times (MRT) was 7.91?±?1.98 and 7.76?±?2.89?h while the half-lives (T_1/2) were 4.07?±?1.71 and 4.99?±?3.30?h. From the analysis of variance results, the p values of C_max and AUC_0–∞ for the 90% confidence interval were 0.492 and 0.320 (p?>?0.05), respectively. A comparison between the test product and the reference product showed no significant difference. Both products showed bioequivalence after being administered in pigs.     

Preconcentration of beryllium via octadecyl silica gel microparticles doped with aluminon, and its determination by flame atomic absorption spectrometry

A simple and sensitive method is presented for solid phase extraction (SPE) and preconcentration of trace quantities of beryllium using octadecyl silica gel modifed with aurin tricarboxylic acid (aluminon). Beryllium is then determined by flame atomic absorption spectroscopy. Parameters affecting SPE such as pH, sample solution and eluent flow rate, type, concentration and volume of eluent, interfering ions and breakthrough volume, were investigated. Under optimal conditions, the beryllium ions were retained on the sorbent at pH 6–6.7, while 3.0 mL of 0.05 mol L^?1 HNO₃ is sufficient to elute the ions. The limit of detection (LOD) based on 3σ was 0.8 µg L^?1 for 250 mL sample solution and 5 mL 0.05 mol L^?1 HNO₃ as eluent. The LOD can reach 0.1 µg L^?1 for 1 L sample solution and 3 mL of 0.05 mol L^?1 HNO₃. The accuracy and precision (RSD %) of the method is >90% and <10%, respectively. The method was applied to the determination of beryllium in aqueous samples.     

Application of double-spike isotope dilution for the accurate determination of Cr(III), Cr(VI) and total Cr in yeast

A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate at 95±2 °C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na₂CO₃ for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO₃ and H₂O₂ was used for the determination of total Cr. Concentrations of 2,014±16, 1,952±103 and 76±48 mg kg⁻¹ (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III) to Cr(VI) (24.2±7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6±6.5% Cr(VI) reduced, n=3 ) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition, mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3, 2 and 30 mg kg⁻¹ were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample.     

Determination of hydration numbers of acids in organic phase by IR spectrometry

By the precision infrared spectrometry the hydration numbers n were determined for a series of acids in 0.64 M tributyl phosphate (CCl₄) and acetonitrile at a concentration of free water 0.01–0.1 M. In tributyl phosphate n = 3.1±0.3 (HAuCl₄); 2.9±0.3 (HFeCl₄); 1.9±0.2 (HClO₄); 1.0±0.2 (HNO₃); 1.0±0.1 (HCl). In acetonitrile n = 3.1±0.7 (HAuCl₄); 1.1±0.4 (HFeCl₄); 2.1±0.2 (HClO₄), 0±0.05 (HNO₃); 0.1±0.15 (HCl).     

Quantification of homoegonol in rat plasma using liquid chromatography–tandem mass spectrometry and its pharmacokinetics application

Homoegonol is a biologically active neolignan isolated from Styrax species with cytotoxic, antimicrobial, anti‐inflammatory and anti‐asthma activities. For the quantification of homoegonol in rat plasma, a selective and sensitive liquid chromatography–tandem mass spectrometric method was developed and validated for the first time using protein precipitation with methanol as a sample clean‐up procedure. The analytes were separated in an Atlantis dC₁₈ column using a gradient elution of methanol and 0.1% formic acid, and mass‐to‐charge ratios were determined in selective reaction monitoring mode using tandem mass spectrometry with m/z 343.12 > 296.97 for homoegonol and m/z 517.30 > 282.90 for udenafil (internal standard). The standard curve was linear over the concentration ranges of 1 ? 500 ng/mL using a 30 μL rat plasma sample. The coefficient of variation and relative error for intra‐ and inter‐assay at four quality control levels were 3.9–10.0 and ‐3.3–2.7%, respectively. The overall recovery of homoegonol from rat plasma using protein precipitation was 99.7 ± 7.7%. The pharmacokinetics parameters of homoegonol were dose‐independent after both intravenous (1, 2.5 and 5 mg/kg doses) and oral (5, 10 and 20 mg/kg doses) administration in male Sprague–Dawley rats. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of a new analytical method for Pb preconcentration and its further determination in water and foodstuffs using relatively low-sensitivity flame atomic absorption spectrometry

The present study describes chelation of Pb(II) with ascorbic acid and formation of a charge-transfer sensitive ion-pair in the presence of Rhodamine 6G at pH 5.5, and then its extraction to the micellar phase of non-ionic surfactant, PONPE 7.5 by an ultrasound-assisted cloud point extraction method before analysis by FAAS. The various variables affecting ion-pair formation and extraction efficiency were studied and optimised. Under the optimised conditions, the good linear relationships in the ranges of 0.4–150 μg L^?1 and 0.8–120 μg L^?1 for solvent-based calibration and matrix-matched calibration curves, respectively, were achieved with a pre-concentration factor of 71.4 from pre-concentration of 50-mL sample. Moreover, the limits of detection with good sensitivity enhancements of 124 and 114.5 were 0.13 and 0.24 μg L^?1, respectively, while the intra-day and inter-day precision (as RSD%, for five replicate measurements of 5 and 100 μg L^?1 in the same day and three succeed days) were in range of 2.8–5.4% and 3.7–6.3%, respectively. The matrix effect on triplicate determination of 50 µg L^?1 Pb(II) was also investigated. The accuracy of the method was statistically verified by the analysis of two certified reference materials (CRMs) after digestion with acid mixtures (HNO₃-H₂O₂-HF and HNO₃-H₂O₂) and dilution at suitable ratios. It has been observed that there is statistically not a significant difference between the certified- and found-values. The accuracy was also controlled using the pre-treated sample solutions spiked at different concentration levels, and the good spiked recoveries were obtained in range of 90–102.8%. The method was successfully applied to the determination of trace amounts of lead in water and food matrices with satisfactory results.     

Application of Ni(II)-imprinted cross-linked poly(methacrylic acid) synthesised through double-imprinting method for the on-line preconcentration of Ni(II) ions in aqueous media

The present paper describes the feasibility of on-line preconcentration of nickel ions from aqueous medium on Ni(II)-imprinted cross-linked poly(methacrylic acid) (IIP) synthesised through a double-imprinting method and their subsequent determination by FAAS. The proposed method consisted in loading the sample (20.0 mL, pH 7.25) through a mini-column packed with 50 mg of the IIP for 2 min. The elution step was performed with 1.0 mol L^?1 HNO₃ at a flow rate of 7.0 mL min^?1. The following parameters were obtained: quantification limit (QL) – 3.74 µg L^?1, preconcentration factor (PF) – 36, consumption index (CI) – 0.55 mL, concentration efficiency (CE) – 18 min^?1, and sample throughput – 25 h^?1. The precision of the procedure assessed in terms of repeatability for ten determinations was 5.6% and 2.5% for respective concentrations of 5.0 and 110.0 µg L^?1. Moreover, the analytical curve was obtained in the range of 5.0–180.0 µg L^?1 (r = 0.9973), and a 1.64-fold increase in the method sensitivity was observed when compared with the analytical curve constructed for the NIP (non-imprinted polymer), thus suggesting a synergistic effect of the Ni(II) ions and CTAB on the adsorption properties of the IIP. The practical application of the adsorbent was evaluated from an analysis of tap, mineral, lake and river water. Considering the results of addition and recovery experiments (90.2–100 %), the efficiency of this adsorbent can be ensured for the interference-free preconcentration of the Ni(II) ions.     

Micro-homogeneity studies of boron carbide powders

We have studied the micro-homogeneity of boron carbide powders by inductively coupled plasma optical emission spectrometry (ICP-OES) and total reflection X-ray fluorescence spectrometry (TXRF) using slurry sampling. To get information on the particle size distributions of the powders, the stabilized slurries of boron carbide powders were nebulized, the aerosols were transported into a Batelle impactor and the droplets were collected on the impactor stages bearing TXRF sample holders. In a first series of measurements, parameters of the impaction like the duration of the impaction and the use of glutinous substance on the sample holders were optimized. The different mass size fractions for industrial boron carbide powders were determined by weight measurements of the fractions collected on the different stages. The established particle size distributions were in the range of 0.5 to >16 μm and found similar to those determined by laser diffraction reported elsewhere. Analyses of the mass fractions by slurry sampling TXRF showed that Ca, Ti, Cr, Mn, Fe, Ni and Cu within the measurements errors were homogeneously distributed over the mass fractions between 0.5 and 4 μm and that their concentrations agreed with the bulk composition, as determined with ICP-OES subsequent to digestion. However, light underestimates were found at the 5 (Mn) up to 150 μg g^?1 (Fe) level. Finally, boron carbide powders were washed out with nitric acid with different concentrations and leaching solutions and the residues were analyzed by ICP-OES and TXRF respectively. It is shown that up to 60% of the residual trace impurities in the powder studied can be removed by leaching with 34% (v/v) of nitric acid.

Analysis of nickel-niobium alloys by inductively coupled plasma optical emission spectrometry

Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO₃. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%.     

Magnetic solid-phase extraction to preconcentrate trace amounts of gold (III) using nickel ferrite magnetic nanoparticles

In this research, nickel ferrite (NiFe₂O₄) magnetic nanoparticles were synthesised by a simple method and applied as sorbent for magnetic solid-phase extraction of trace amounts of Au(III) from water samples. Detection in this technique was performed by flame atomic absorption spectrometry. The effects of sample pH, amount of sorbent, extraction time, desorption solvent and its volume on the extraction process were optimised. The effects of interfering ions on the recovery of the analyte were also evaluated in model solutions. The best results were obtained at pH 6.5 with 5 mL of eluent solution (0.1 mol L^?1 sodium thiosulphate) and an extraction time of 30 min. Under optimal conditions, the sorption capacity was 34.6 mg g^?1. Also, enhancement factor (for 100 mL of sample solution) was found to be 19.3. The calibration graph was linear in the range of 4.4–800.0 µg L^?1 gold concentration and the limit of detection was 1.32 µg L^?1. The relative standard deviation of the method (for n = 8) was 1.57%. The method was successfully applied to the extraction of Au(III) from water samples.     

Investigation of four digestion procedures for multi-element determination of toxic and nutrient elements in legumes by inductively coupled plasma-optical emission spectrometry

A simple and reliable multi-element procedure for determination of essential (Cr, Cu, Fe, Mg, Mn, Zn) and toxic (Al, Cd, Pb) elements in legumes by inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed. In this contribution, four different digestion procedures were thoroughly investigated and accurately evaluated with respect to their affect on the analysis of legumes. These included wet digestion with HNO₃/H₂SO₄ and HNO₃/H₂SO₄/H₂O₂, and dry ashing with Mg(NO₃)₂ and Mg(NO₃)₂/HNO₃. Two calibrations (aqueous standard and standard addition) procedures were studied, and proved that standard addition was preferable for all analytes. ICP-OES operating parameters, such as radio-frequency (RF) incident power, sample uptake flow rate and nebulizer argon gas flow rate were optimized. The precision as repeatability, expressed as relative standard deviation (R.S.D.) for aqueous standard containing 250 μg l⁻¹ of each analyte was in the range1.5-8.0%. The accuracy, expressed as relative error was generally varied in the range of 0.5-10% for all analytes, while the quantification limits were lower than 2.5 μg g⁻¹. Although, acceptable results were obtained from all developed procedures, wet digestion method with HNO₃/H₂SO₄/H₂O₂ is recommended for better recovery. The good agreement between measured and certified concentrations with respect to IAEA-331 and IAEA-359 (CRM's supplied by IAEA, International Atomic Energy Agency) indicates that the developed analytical method is well suited for determination of toxic and nutrient elements in legumes and possibly similar matrices.     

Heated Slurry Sampling for the Determination of Cadmium in Food by Electrothermal Atomic Absorption Spectrometry

A heating procedure is reported with slurry sampling electrothermal atomic absorption spectrometry to improve the accuracy of cadmium determination in food. In comparison to conventional slurry sampling, the heating significantly increased cadmium recovery and improved the precision. For the optimized procedure, 25–250 mg of food were treated with 2% HNO₃ and 1% H₂O₂ with heating at 120°C for 20 min, followed by the addition of 50 µL of 10% Triton X-100, and homogenization in an ultrasonic bath prior to analysis. Tungsten and rhodium were employed as a permanent modifier with optimum pyrolysis and atomization temperatures of 500°C and 1500°C. Calibration with aqueous standards resulted in good agreement between certified or information values and measured results at the 95% confidence level. A characteristic mass of 0.8 ± 0.1 pg and a detection limit of 0.7 ng g^?1 for a 2% slurry were obtained. The method was employed for the direct determination of cadmium in food certified reference materials.     

LC‐MS/MS profiling of polyphenol‐enriched leaf,stem and root extracts of Korean Humulus japonicus Siebold & Zucc and determination of their antioxidant effects

Polyphenols from ethyl acetate extracts from the leaves, stems and roots of Korean Humulus japonicus were comprehensively profiled using liquid chromatography–electrospray ionization–tandem mass spectrometry. A total of 36 polyphenols were detected, of which 26 were structurally characterized based on their [M − H]⁻ peak, tandem mass spectrometry fragmentation pattern, UV–vis absorption and published data. Validation data provided satisfactory results for the evaluated parameters. The determination coefficients were ≥0.9812. The limits of detection and quantification were 0.017–0.573 and 0.056–1.834 mg/L, respectively, indicating good performance limits. The accuracy (expressed as percentage recovery) at 50 and 100 mg/L was 71.4–99.7 and 75.1–105.1%, with precisions (expressed as relative standard deviation) of 1.5–7.3 and 0.8–4.1%, respectively, indicating acceptable accuracy and precision values. The leaves were rich in total polyphenols (3089.9 ± 6.4 mg/kg of fresh sample) followed by the stems (1313.9 ± 6.4 mg/kg of fresh sample) and roots (655.2 ± 2.7 mg/kg of fresh sample). Antioxidant activity, determined by α,α‐diphenyl‐β‐picrylhydrazyl, 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) scavenging activity and ferric reducing antioxidant power assay, revealed the lowest EC₅₀ value for the leaf extracts, indicating a higher scavenging activity in this tissue followed by the roots and stems. Overall, the results indicated that H. japonicus is rich in polyphenols and could be a potential alternative to Humulus lupulus (hop plant) in the brewery industry.     

Determination of bakkenolide A in rat plasma using liquid chromatography/tandem mass spectrometry and its application to a pharmacokinetic study

A sensitive rapid analytical method was established and validated to determine the bakkenolide A (BA) in rat plasma. This method was further applied to assess the pharmacokinetics of BA in rats receiving a single dose of BA. Liquid chromatography tandem mass spectrometry in multiple reaction monitoring mode was used in the method, and costundide was used as internal standard. A simple protein precipitation based on methanol was employed. The combination of a simple sample cleanup and short chromatographic running time (2.4 min) increased the throughput of the method substantially. The method was validated over the range of 1–1000 ng/mL with a correlation coefficient > 0.99. The lower limit of quantification was 1 ng/mL for BA in plasma. Intra‐ and inter‐day accuracies for BA were 93–112% and 103–104%, respectively, and the inter‐day precision was less than 15%. After a single oral dose of 20 mg/kg of BA, the mean peak plasma concentration (C_max) of BA was 234.7 ± 161 ng/mL at 0.25 h. The area under the plasma concentration–time curve (AUC_{0–24 h}) was 535.8 ± 223.7 h·ng/mL, and the elimination half‐life (T_1/2) was 5.0 ± 0.36 h. In case of intravenous administration of BA at a dosage of 2 mg/kg, the area under the plasma concentration–time curve (AUC_{0–24 h}) was 342 ± 98 h?ng/mL, and the elimination half‐life (T_1/2) was 5.8 ± 0.7 h. Based on the results, the oral bioavailability of BA in rats at 20 mg/kg is 15.7%. Copyright © 2012 John Wiley & Sons, Ltd.     

A new acylated flavonol from the aerial parts of Asteriscus maritimus (L.) Less (Asteraceae)

Phytochemical investigation of the flowering aerial parts of Asteriscus maritimus (L.) Less (Asteraceae) led to the isolation of a new compound: patuletin 7-O-β-D-[(2″′S) 6″(3″′-hydroxy-2″′-methyl-propanoyl)] glucopyranoside, together with five known metabolites; β-sitosterol 2, chlorogenic acid 3, P-hydroxy -methylbenzoate 4, luteolin 5 and protocatechuic acid 6. The structures of the isolated compounds were determined by comprehensive analyses of its 1D and 2D NMR, HRMS and compared with previously known analogues. The ethanolic extract of the flowering aerial parts of A. maritimus was found to be safe (LD₅₀ = 4.6 mg/kg) and possess significant antioxidant and anti-inflammatory activities and this was in accordance with its high phenolic content (107.36 ± 0.051 mg GAE/g extract).     

A matrix effect and accuracy evaluation for the determination of elements in milk powder LIBS and laser ablation/ICP-OES spectrometry

Laser ablation coupled to inductively coupled plasma optical emission spectrometry (LA-ICP-OES) and laser-induced breakdown spectroscopy (LIBS) were investigated for the determination of Ca, Mg, Zn and Na in milk samples. The accuracy of both methods was evaluated by comparison of the concentration found using LA-ICP-OES and LIBS with classical wet digestion associated with ICP-OES determination. The results were not fully acceptable, with biases from less than 1% to more than 60%. Matrix effects were also investigated. The sample matrix can influence the temperature, electron number density (n _e) and other excitation characteristics in the ICP. These ICP characteristics were studied and evaluated during ablation of eight milk samples. Differences in n _e (from 8.9 to 13.8 × 10¹⁴ cm⁻³) and rotational temperature (ranging from 3,400 to 4,400 K) occurred with no correlation with trueness. LIBS results obtained after classical external calibration procedure gave degraded accuracy, indicating a strong matrix effect. The LIBS measurements clearly showed that the major problem in LA-ICP was related to the ablation process and that LIBS spectroscopy is an excellent diagnostic tool for LA-ICP techniques.     

Solid phase extraction of Pb(II) and Cd(II) as 2,9 dimethyl-4,7-diphenyl-1,10-phenanthroline chelates on activated carbon cloth in environmental samples and their determination by flame atomic absorption spectrometry

A solid-phase extraction procedure for Pb(II) and Cd(II) as 2,9 dimethyl-4,7-diphenyl-1,10-phenanthroline complexes on activated carbon cloth (ACC) has been established. In the determination step, flame atomic absorption spectrometry (FAAS) was used. The optimum conditions for pH, type and volume of eluent, volume of sample solution, flow rates of eluent, sample solution and matrix effect were determined. For quantitative recovery of the analyte ions, refereed optimum values are as follows: amount of ACC, 0.4 g; pH, 6.0 and eluent, 10 mL 3 M HNO₃. To test the accuracy of the method, a certified reference material (CRM) analysis and add-recovery methods were performed. The developed method was applied for the determination of the analyte elements in water and vegetable samples.     

Determination of Cu(II), Fe(III), Mn(II) and Zn(II) in various samples after preconcentration with Rhizopus oryzae loaded natural cellulose (almond bark)

A procedure for the pre-concentration of Cu(II), Fe(III), Mn(II) and Zn(II) is described utilising a minicolumn of natural cellulose (almond bark) modified with fungus (Rhizopus oryzae) prior to their determination by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS). The optimum pre-concentration conditions such as pH and flow rate for the analytes have been investigated. The analytes were quantitatively retained on the column between pH 6 and 8. Elution was made with 10 mL 1 M HCl solution. Under the optimum conditions, recoveries were found as 97 ± 3%, 96 ± 3%, 98 ± 3% and 94 ± 2% for Cu(II), Fe(III), Mn(II) and Zn(II), respectively, at 95% confidence level. The detection limits obtained from preconcentration of 50 mL of blank solutions (n = 11) were 1.6, 1.8, 2.8 and 1.2 µg L^?1 for Cu(II), Fe(III), Mn(II) and Zn(II), respectively. Relative standard deviations (RSD) of the recoveries for five replicate analyses were lower than 3%. The proposed method was validated by analysing certified reference materials (Peach Leaves SRM 1547 and Fish Tissue IAEA-407). Determination of the Cu(II), Fe(III), Mn(II) and Zn(II) in K?z?l?rmak River water, green beans, beans leave and tomato leaves and fish (Tinca tinca) tissue samples was performed by the proposed method.