Zeeman Graphite Furnace Atomic Absorption Research Articles

Determination of arsenic in edible oils by direct graphite furnace atomic absorption spectrometry

A direct analytical method of arsenic content in edible oil with graphite furnace atomic absorption spectrophotometer was studied. Edible oil was diluted with n-heptane followed by the determination of arsenic with Zeeman graphite furnace atomic absorption spectrophotometer and transverse heated graphite atomizer (THGA). The arsenic organic AAS standard solution was used as calibration standard, and bis (benzonitrile) dichloro palladium solution was used as a matrix modifier. The results showed that the optimal ashing and atomizing temperatures were 1200°C and 2300°C, respectively. The detection limit was estimated to be 0.010 ppm, and the percentages of recovery for the spike of 0.05, 0.10 and 0.20 ppm arsenic to salad oil, fish oil, palm oil, and lard were 91.2-94.3%, 94.7-95.6%, 94.2-96.7% and 93.3-94.1%, respectively. With the use of this method, thirty edible oils were analyzed and the arsenic contents were found to be below the detection limits.

Determination of copper in edible oils by direct graphite furnace atomic absorption spectrometry

A simple method for determination of copper in edible oils was developed, using a polarized Zeeman graphite furnace atomic absorption spectrophotometer and a pyro graphite tube. Edible oils were diluted with 2% lecithin-cyclohexane and analyzed directly by the standard addition method. The optimal ashing and atomizing temperatures were 900°C and 2700°C, respectively. A standard solution diluted with 2% lecithin-cyclohexane was superior to salad oil or cyclohexane. Results were best measured when the concentration of lecithin in cyclohexane was higher than 2%. The detection limit of this method was 2.0 ng/mL. The respective range of recovery of copper was 85.5-90.0% and 86.0-93.0% in salad oil and lard which were fortified with 10, 20 and 40 ng Cu/mL respectively using the standard addition method.

Optimisation of Direct Copper Determination in Human Breast Milk Without Digestion by Zeeman Graphite Furnace Atomic Absorption Spectrophotometry with Two Chemical Modifiers.

Milk is an important food in the human diet, and copper (Cu) in human milk is indispensable to children's normal growth and development. It is consequently important that Cu deficiency, occurring in malnourished women or in malabsorption following bariatric surgery, be prevented. The objective of this work is to provide hospital-based paediatricians with a tool enabling rapid measurement of Cu in human breast milk through a technique that biology laboratories can easily apply. Using electrothermal atomic absorption spectrophotometry with Zeeman correction, we have optimized this method with two chemical modifiers and without digestion for analytical procedure. Detection limits and quantification limits for Cu in human milk were found to be 0.077 and 0.26 μmol/L, respectively. Within-run (n = 30) and between-run (n = 15) variations in a pool of human milk samples were 1.50 and 3.62%, respectively. Average recoveries ranged from 98.67 to 100.61%. The reliability of this method was also confirmed by analysing certified reference material (10%). In breast milk samples collected from 100 lactating mothers, Cu mean (±1 SD) was 7.09 ± 1.60 μmol/L. In conclusion, with minimal preparation and quick determination, the method proposed is suitable for measurement of Cu in human breast milk.

Transformation of tributyltin in zebrafish eleutheroembryos (Danio rerio).

Organotin compounds are highly versatile group of organometallic chemicals used in industrial and agricultural applications. Their endocrine-disrupting effects are well known and their extensive uses as biocide materials, e.g., in antifouling paints, for many years have led to serious environmental problems. So far, attention has mainly been given to tributyltin pollution in water, sediments, and marine organisms because of its highly toxic effects and high accumulation levels at very low concentrations. In this study, we will focus on the conversion of tributyltin after it is absorbed by zebrafish eleutheroembryos, presented here as an alternative model to adult fish for describing bioconcentration. A simplified analytical extraction procedure based on the use of an assisted ultrasonic probe and derivatization by ethylation, followed by gas chromatography with a flame photometric detector (GC-FPD) is proposed. This classical methodology for organotin determination has been validated by inductively coupled plasma mass spectrometry (ICP-MS) and Zeeman graphite furnace atomic absorption spectrometry (ZGF-AAS) in terms of total tin content. The speciation analysis results show that zebrafish eleutheroembryos absorb high amounts of tributyltin and convert it into monobutyltin and likely in inorganic tin.

Estimating ink mileage of dry toners in electrophotography

This work investigates the ink mileage of dry toners in electrophotography (EP). Four different substrates were printed on a dry-toner color production Xerox iGen3 EP press. The print layout contained patches with different cyan, magenta, yellow, and black tonal values from 10% to 100%. Toner amounts on cyan patches were measured using an analytical method. Printed patches and unprinted paper samples, as well as dry toners, were dissolved in concentrated nitric acid. The copper concentrations in the dissolved solutions were analyzed by a Zeeman graphite furnace atomic absorption spectrometer. Analytical results were calculated to determine the toner amounts on paper for different tonal values. Their corresponding reflection densities were also measured. All data were plotted with OriginPro® 8 software, and four mathematical models were used for curve fitting. It was found that the C-S model fitted the experimental data of the two uncoated papers better than the other three models. None of the four models fitted the experimental data of the two coated papers, while the linear model was found to fit the data well. Linear fitting was the best in the practical density region for the two coated papers. Ink mileage curves obtained from curve fitting were used to estimate how much ink was required to achieve a target density for each paper; hence, the ink mileage was calculated. The highest ink mileage was 3.39 times the lowest ink mileage. The rougher the paper surface, the higher the requirement for ink film weight, and the lower ink mileage. No correlation was found between ink mileage and paper porosity.

Determination of Chromium in Biological Material by Electrothermal Atomic Absorption Spectrometry Method

Abstract Procedure for determination of chromium in biological materials by Zeeman graphite furnace atomic absorption spectrometry method using a Perkin-Elmer spectrometer equipped with hollow-cathode lamp at 357.9 nm was developed. The samples of animal tissues, food, and feed were digested in muffle furnace at 450ºC. The ash was dissolved in 1 N hydrochloric acid and the final solution was diluted in 0.2% nitric acid. Magnesium nitrate (1%) was used as a matrix modifier. The method was validated in terms of basic analytical parameters. The mean recoveries of chromium was 84.4% for muscle, 79.0% for canned meat, and 80.2% for feed, and analytical detection limit was 0.003 μg/g. Certified reference materials were used for analytical quality assurance. The proposed analytical procedure is well adapted for monitoring chromium content in food and feedstuffs. Content of total chromium in the tested samples (animal muscles and liver) was low and was situated in the range of 0.031-0.101 mg/kg (muscles) and 0.047-0.052 mg/kg (liver).

Application of Zeeman Graphite Furnace Atomic Absorption Spectrometry with High-Frequency Modulation Polarization for the Direct Determination of Aluminum, Beryllium, Cadmium, Chromium, Mercury, Manganese, Nickel, Lead, and Thallium in Human Blood

Determination of aluminum (Al), beryllium (Be), cadmium (Cd), chromium (Cr), mercury (Hg), manganese (Mn), nickel (Ni), lead (Pb), and thallium (Tl) concentrations in human blood using high-frequency modulation polarization Zeeman graphite furnace atomic absorption spectrometry (GFAAS) was performed. No sample digestion was used in the current study. Blood samples were diluted with deionized water or 0.1 % (m/v) Triton X-100 solution for Tl. Dilution factors ranged from 1/5 per volume for Be and Tl to 1/20 per volume for Cd and Pb. For Tl, Cd, and Hg, noble metals (gold, platinum, rhodium, etc.) were applied as surface modifiers. To mitigate chloride interference, 2 % (m/v) solution of NH(4)NO(3) was used as matrix modifier for Tl and Ni assessment. The use of Pd(NO(3))(2) as oxidative modifier was necessary for blood Hg and Tl measurement. Validation of the methods was performed by analyzing two-level reference material Seronorm. The precision of the designed methods as relative SD was between 4 and 12 % (middle of a dynamic range) depending on the element. For additional validation, spiked blood samples were analyzed. Limits of detection (LoDs, 3σ, n = 10) for undiluted blood samples were 2.0 μg L(-1) for Al, 0.08 μg L(-1) for Be, 0.10 μg L(-1) for Cd, 2.2 μg L(-1) for Cr, 7 μg L(-1) for Hg, 0.4 μg L(-1) for Mn, 2.3 μg L(-1) for Ni, 3.4 μg L(-1) for Pb, and 0.5 μg L(-1) for Tl. The LoDs achieved allowed determination of Al, Cd, Cr, Mn, Ni, and Pb at both toxic and background levels. Be, Hg, and Tl could be reliably measured at toxic levels only. The methods developed are used for clinical diagnostics and biological monitoring of work-related exposure.

Zeeman graphite furnace atomic absorption spectrophotometric determination of urine vanadium

目的 建立石墨炉原子吸收光谱法测定尿钒的方法.方法 以氟化钡作为基体改进剂,进样30μl,用石墨炉原子吸收光谱法测定.结果 方法的特征浓度为1.11×10-3μg/L,3倍空白测定标准偏差的检出限为0.38μg/L,相对标准偏差为0.45%～1.29%.样品加标回收率为90.0%～101.2%;该法与ICP发射光谱法比较,测定结果差异无统计学意义(P>0.05).结论 该方法简便、快速、灵敏度高,适用于不同人群尿中钒的测定。

Serum Selenium Level and Prostate Cancer: A Case-Control Study

Selenium is a potential chemopreventive agent against prostate cancer. This study sought to evaluate and compare the serum selenium level in men with newly diagnosed prostate cancer and noncancerous patients. Between 2005 and 2006, this prospective case-control study was performed on patients referred to Sina and Imam University hospitals, Tehran, Iran; it included 62 men with clinicopathologically confirmed diagnosis of prostate cancer (case group) and 68 men with no detectable prostate cancer [normal digital rectal examination and prostate-specific antigen (PSA) level] or any other malignant disease (control group). The serum selenium level was assessed using Zeeman graphite furnace atomic absorption spectrometer (Varian Company, Australia). The mean serum selenium level in the case and control group was 66.3 ± 17.7 μg/l and 77.5 ± 22.5 μg/l, respectively (P = 0.002). Serum selenium was inversely associated with prostate cancer risk. After adjustment for age, body mass index (BMI), and smoking, the odds ratio was 0.16 and 95% confidence intervals were 0.06 to 0.47 (P trendq = 0.001) comparing the highest with the lowest tertile (≥ 89.3 μ g/l). No correlation was observed between serum selenium level and age, BMI, or PSA level. In conclusion, serum selenium levels in prostate cancer cases were lower than in controls, which supports the hypothesis that selenium may protect against prostate cancer.

Determination of metal partitioning in porewater extracted from the Seine River Estuary sediment (France).

Total dissolved trace and major metals and their partitioning in porewater sediment have been investigated at two sites in the Seine River estuary (France). For this purpose, solid phase extraction (SPE) has been employed using specific chelating resins for the separation and preconcentration of organic and inorganic forms of studied metals under controlled (N2) inert atmosphere. In fact, the study is focused on the development of a method for sample collection and handling under inert atmosphere in order to avoid some potential artefacts of the extracted porewater, to preserve the samples from possible chemical oxidation changes and to determine metals partitioning between organic and inorganic forms. For this point, a separation and preconcentration method using two columns in series (chelamine and C18 columns) was used. The trace and major metals fixed on the two resins for all determinations were stripped by nitric acid (2 M) and analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Zeeman Graphite Furnace Atomic Absorption Spectroscopy (ZGF-AAS). The relationship between the distribution of metals and physico-chemical parameters such as pH and Eh (redox potential) as a function of depth was discussed. Some tendency in the distributions and seasonal variability of these traces and major metals are improved. The concentrations for all studied metals decreased as a function of depth where iron and manganese were found at mg L(-1) levels and other metals were found at [micro sign]g L(-1) levels, as well as there were significant fractions of all metals (except of manganese) which were complexed by organic matter. The comparison of data for the major elements (Fe and Mn), obtained by direct determination (without preconcentration) and preconcentration, show a very good recovery.

Prion protein suppresses perturbation of cellular copper homeostasis under oxidative conditions

Prion protein (PrP) binds copper and exhibits superoxide dismutase-like activity, while the roles of PrP in copper homeostasis remain controversial. Using Zeeman graphite furnace atomic absorption spectroscopy, we quantified copper levels in immortalized PrP gene ( Prnp)-deficient neuronal cells transfected with Prnp and/or Prnd, which encodes PrP-like protein (PrPLP/Dpl), in the presence or absence of oxidative stress induced by serum deprivation. In the presence of serum, copper levels were not significantly affected by the expression of PrP and/or PrPLP/Dpl, whereas serum deprivation induced a decrease in copper levels that was inhibited by PrP but not by PrPLP/Dpl. The inhibitory effect of PrP on the decrease of copper levels was prevented by overexpression of PrPLP/Dpl. These findings indicate that PrP specifically stabilizes copper homeostasis, which is perturbed under oxidative conditions, while PrPLP/Dpl overexpression prevents PrP function in copper homeostasis, suggesting an interaction of PrP and PrPLP/Dpl and distinct functions between PrP and PrPLP/Dpl on metal homeostasis. Taken together, these results strongly suggest that PrP, in addition to its antioxidant properties, plays a role in stabilizing cellular copper homeostasis under oxidative conditions.

Investigation of trace level binding of PtCl 6 and PtCl 4 to alfalfa biomass ( Medicago sativa) using Zeeman graphite furnace atomic absorption spectrometry

Batch laboratory experiments were performed to investigate the effects of pH, chemical modification, time dependency, and interference studies on the binding of trace concentrations of hexachloroplatinate(IV) and tetrachloroplatinate(II) to alfalfa biomass. The pH profiles were measured between pH 2.0 and 6.0. It was found that the binding of trace concentrations of platinum(IV and II) to alfalfa biomass was dependent on pH with a maximum binding occurring at pH 3.0 and a minimum at pH 6.0. When the alfalfa biomass was chemically modified (esterified), maximum binding occurred at pH 6.0 for both oxidation states of platinum. From the batch time dependency experiments, it was found that binding took at least 20 min to level off for both platinum oxidation states. Batch experiments were performed with various concentrations of calcium, magnesium, and sodium (0.1, 1.0, 10, 100 and 1000 ppm) and it was found that calcium affected the binding of platinum(II and IV) to the alfalfa biomass. It was determined that magnesium and sodium did not interfere appreciably with the binding of platinum in either of the oxidation states studied. Finally, batch experiments were performed with Mg 2+, Ca 2+ and Na + in solutions at various concentrations, and it was observed that the binding was affected similarly to that by calcium alone.

Evaluation of a tunable bandpass reaction cell for an inductively coupled plasma mass spectrometer for the determination of chromium and vanadium in serum and urine

A Dynamic Reaction Cell™ inductively coupled argon plasma mass spectrometer (DRC-ICP-MS) was evaluated for the determination of chromium and vanadium in serum and urine. Reaction cell conditions were evaluated for the elimination of ArC + and ClOH + interferences on chromium at mass 52 and OCl + on vanadium at mass 51. A diluent containing only 1% nitric acid and internal standards (Y and Ga) was used to prepare serum and urine for analysis. Instrument response calibration was achieved by using aqueous acidic standards spiked into pooled sera or urine matrices. The slopes of the calibration curves prepared in urine and serum matrices were nearly identical. On average, chromium detection limits are 2.5 times lower using the DRC than Zeeman graphite furnace atomic absorption spectrometry (ZGFAAS). Vanadium detection limits are approximately 50 times lower. Average detection limits achieved with DRC-ICP-MS are 0.075 μg Cr/l and 0.028 μg V/l. Average results for the analysis of National Institute of Standards and Technology Standard Reference Material (NIST SRM) 1598 Bovine Serum (attained over 22 days) are: 0.14 μg Cr/l and 0.068 μg V/l. The reference concentrations for vanadium and chromium in NIST SRM 1598 are (0.06) μg V/l and 0.14±0.08 μg Cr/l, respectively. Results for chromium and vanadium determinations on ICP-MS survey samples from the Toxocologie du Quebec are equivalent to those reported by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for the same survey samples.

Exposure of cadmium from infant formulas and weaning foods

Cadmium levels were determined in 59 baby food samples, including milk-based, cereal and milk-based and soy-based formulas, recommended from 0 to 18 months of age. Determinations were performed by Zeeman graphite furnace atomic absorption spectrophotometry, after dry ashing, with parallel determinations of certified reference samples. Mean cadmium levels were found to range from 1.10 to 23.5 μg / kg fresh weight concentrated formulas. L evels were related to the composition of the diets. Formulas based on cow's milk had the lowest concentrations. Soy formulas contained approximately six times more cadmium than cow's milk formulas, and diets with a cereal content had 4–21 times higher mean levels. The mean weekly intakes of dietary cadmium were estimated to vary between 0.10 and 3 : 05 μg / kg body weight of the child, if the recommended amount of formula were to be consumed at the recommended age, and if the child were of average weight. This estimation however does not include the contribution of cadmium from drinking water. The highest intake on a body weight basis was found in 6-month-old children, consuming the recommended amount of wheat-, oat- and milk-based formulas. This intake is below the provisional tolerable weekly intake (PTW I) of 7 μ g / kg body weight, established by a W HO/FAO expert group. However, the risk assessment is based on renal effects in adults. Furthermore, preparations of a formula by adding water with cadmium concentrations at the W HO guideline level could lead to intakes at the PTW I level. Compared to breast-fed children, the exposure of dietary cadmium from weaning diets can be up to 12 times higher in children fed infant formula.

The determination of selenium in serum and urine by inductively coupled plasma mass spectrometry: comparison with Zeeman graphite furnace atomic absorption spectrometry

An inductively Coupled Plasma Mass Spectrometric (ICPMS) method for the determination of selenium in both serum and urine is described. 78Se is used analytically in spite of 38Ar40Ar isobaric interference at mass 78. Initially 82Se was monitored but, limited isotope abundance and therefore limited detection capability for urine selenium precluded continued use. An ethanol–Triton X-100-nitric acid diluent was used to dilute serum and urine and enhance selenium ionization so that both serum and urine can be analyzed with the same calibration curve. Results derived by the ICPMS method were compared with Zeeman Graphite Furnace Atomic Absorption Spectrometry (ZGFAAS) using nickel as the matrix modifier. Detection limits for ZGFAAS and ICPMS using mass 78 are 2.9 and 0.25 μg/l, respectively. ICPMS and ZGFAAS instrument responses were recorded for additions of inorganic selenium, trimethylselenonium iodide, seleno-dl-methionine, and seleno-dl-cystine to urine and serum. ICPMS slopes for all compounds added to urine and serum were found to be nearly identical. ZGFAAS response for each compound was more variable than ICPMS. ZGFAAS response for trimethylselenonium iodide was approximately 3-fold lower than for the other compounds. ZGFAAS regression slopes and correlation coefficients were 0.72 and 0.8139 for reference urine samples. ICPMS regression slope and correlation coefficient vs. the reference target values were 0.95 and 0.9700 for the same urines. Regressions slopes and correlation coefficients for reference sera were 1.01 and 0.9912 for ICPMS and 1.12 and 0.9648 for ZGFAAS. We conclude that ICPMS produced more accurate results than ZGFAAS for selenium in serum and urine.

Determination of transition metals in wine by IC, DPASV-DPCSV, and ZGFAAS coupled with UV photolysis.

In the present work ion chromatography (IC), differential pulse anodic (DPASV) or cathodic stripping voltammetry (DPCSV), and Zeeman graphite furnace atomic absorption spectroscopy (ZGFAAS) were applied to the determination of heavy and transition metals in wine. The matrix is degraded by oxidative UV photolysis in a digester equipped with a high-pressure mercury lamp. The temperature of the sample is maintained at 85 +/- 5 degrees C by a combined air/water cooling system. This procedure has decisive advantages if compared with other sample pretreatment techniques. Most organic wine constituents degrade in <1 h, whereas metals quantitation remains unaffected by UV radiation, with the exception of manganese. The clear solution is directly analyzed for most common heavy and transition metals such as cadmium, cobalt, copper, iron, lead, nickel, and zinc. In the absence of standards, the results obtained by different techniques are compared and are found in good agreement. All of the considered techniques appear to be equivalent, but ZGFAAS is more time-consuming because it does not permit multielement analyses.

Background correction errors for lead in the presence of phosphate with Zeeman graphite furnace atomic absorption spectrometry

Background overcorrection problems with lead in the presence of phosphate in Zeeman graphite furnace atomic absorption spectrometry are investigated. Results show that the overcorrection is not affected by changing the atomization temperature in the furnace program, but is significantly reduced by decreasing the strength of the magnetic field. This observation further supports the assumption that the background overcorrection is caused by the presence of a molecular species (such as PO) formed during the heating process having molecular absorption bands which are subject to Zeeman-effect splitting. The overcorrection error can be diminished by deceasing the amount of phosphate or by replacing the standard transverse-heated graphite atomizer (THGA) tube with an end-capped tube. An accurate method for the determination of Pb in bone using a transverse heated furnace (a P-E 4100ZL) is described.

Urinary homovanillic acid (HVA) and vanillymandelic acid (VMA) in workers exposed to manganese dust

The neurotoxicity of manganese (Mn) is well known, however, the neurochemical effect caused by this metal is less well investigated. In this study, urinary homovanillic acid (HVA) and vanillymandelic acid (VMA), two end products of catecholamine metabolism, were measured in 39 workers chronically exposed to Mn in a manganese smelting plant. The average duration of Mn exposure was 17.4 yr. Nineteen nonexposed workers were also studied. Concentrations of Mn in serum (MnS) and in urine (MnU) were measured by Zeeman graphite furnace atomic absorption spectrophotometry (ZAAS), and HVA and VMA determined by high performance liquid chromatography (HPLC). For Mn-exposed workers, the concentration of MnS was nearly 2.8 times (1.61 +/- 0.16 mg/L vs 0.56 +/- 0.16 mg/L) and MnU about 4.5 times higher (7.62 +/- 0.17 mg/L vs 1.69 +/- 0.16 mg/L) than the nonexposed. Although the geometric mean concentration of HVA in exposed workers was similar to that of the nonexposed (3.09 +/- 1.39 mg/g cre. vs 2.99 +/- 1.40 mg/g cre.), the VMA concentration was significantly higher (3.02 +/- 1.43 mg/g cre. vs 2.49 +/- 1.58 mg/g cre., p = 0.033). Multiple regression analysis showed that although there were no correlations between any of these parameters with the duration of exposure to Mn, both HVA and VMA showed significant correlations with increase in MnS and MnU. These data provide evidence that exposure to Mn was associated with measurable increase in catecholamine metabolites. This finding is compatible with recent observations in laboratory animals that Mn interferes with neurochemical metabolism.

Trace Metals in Urine of United States Residents: Reference Range Concentrations

We measured 13 metals in the urine of 496 United States residents to establish reference range concentrations using inductively coupled argon plasma mass spectrometry and Zeeman graphite furnace atomic absorption spectrometry. We frequently found 8 of these analytes at detectable concentrations in urine specimens: molybdenum (in 99.8%); lead (98.8%); tin (89%); thallium (77%); antimony (73.5%); manganese (73%); cesium (71%); tungsten (70%); and platinum (69.7%). The 95th percentile concentration for molybdenum was 168 μg/L; concentrations ranged up to 688 μg/L. Lead concentrations ranged up to 67 μg/L, and the 95th upper percentile was 6.4 μg/L. Tin had 95th upper percentile of 20.1 μg/L. Other analytes measured at detectable concentrations included barium (in 67% of the specimens); beryllium (67%); chromium (54%); thorium (44%); and cobalt (43%). In almost every case, the 95th upper percentiles of these analytes were less than 15 μg/L.

Determination of manganese and chromium in foods by atomic absorption spectrometry after wet digestion

Wet digestion procedures using acid mixtures of HNO 3/H 2SO 4/HClO 4 and HNO 3/H 2SO 4 were investigated for their effectiveness for decomposition of food samples prior to determination of manganese (Mn) and chromium (Cr) by flame and Zeeman graphite furnace atomic absorption spectrophotometry. The addition of hydrofluoric acid (HF) to the mixture of HNO 3/H 2SO 4 was also investigated for determination of Cr. All the acid mixtures tested were found to be satisfactory, but, for reasons of safety, HNO 3/H 2SO 4 was the method of choice. No apparent matrix interferences or losses of analytes were encountered with the method used. Analysis of selected food samples found relatively high levels of Mn and Cr in most cereal products. Meats, dairy products (except for Cr in cheese), vegetables and fruits contained relatively low levels of both elements.