ETAAS method for the determination of Cd, Cr, Cu, Mn and Se in blood fractions and whole blood

An electrothermal atomic absorption method (ETAAS) for the direct determination of trace elements (Cd, Cr, Cu, Mn, Se) both in blood fractions (erythrocytes, plasma and lymphocytes) and whole blood was developed. Zeeman background correction and graphite tubes with L'vov platforms were used. Samples were diluted with HNO3/Triton X-100 and pipetted directly into the graphite tube. Ashing, pretreatment and atomization steps were optimized carefully for the different fractions and elements applying different matrix modifiers for each element. For the lymphocyte fraction a multi-fold injection technique was applied. Low detection limits of the ETAAS method (Cd 0.13 microgram/L, Cr 0.11 microgram/L, Cu 0.52 microgram/L, Mn 0.13 microgram/L, Se 0.7 microgram/L of whole blood) combined with small quantities of sample necessary for analysis allow determination of trace elements in this matrix. Verification of possible differences in the trace element status of humans was performed with statistical significance (P < 0.05). In addition, a contribution to the determination of normal values of essential elements was achieved. The method was applied for determination of trace elements in human blood and blood fractions of two groups (n = 50) different in health status.     

Determination of nonylphenol polyethoxylates in household detergents by high-performance liquid chromatography

The binding of metals to proteins in blood fractions was investigated applying hydrophobic interaction chromatography (HIC) for protein separation and graphite furnace atomic absorption spectrometry (GFAAS) as the element specific detector. For the semi-preparative separation of metalloproteins in erythrocytes and blood plasma, a HIC column (Fractogel EMD Phenyl I (S) 150 mm×10 mm I.D.) was adapted. The separation column was calibrated with the same four standard proteins as used in Pomazal et al. [Analyst 124 (1999) 657]. The sample injection volume and the ammonium sulphate gradient set-up were optimized: 20 or 200 μl, respectively, of blood plasma and of lysed erythrocytes were injected. The separated proteins were collected in 4-ml fractions and analyzed by GFAAS off-line. An optimization of the GFAAS measuring parameters for Cu, Mn, Fe, Zn, Co, Ni, and Cr was performed. For each element, a specific temperature program was optimized with respect to the matrix of the HIC eluate (0.02 M NaH₂PO₄, 1.8 M (NH₄)₂SO₄). The obtained metal profiles of the eluate were compared with the HIC chromatograms. The limits of detection (LOD) for the elements by GFAAS were: 0.5 ng Cu/ml; 0.2 ng Mn/ml; 1 ng Fe/ml; 0.2 ng Zn/ml; 0.12 ng Co/ml; 0.2 ng Ni/ml; 0.16 ng Cr/ml. The GFAAS method enabled the detection of the proteins of interest via the metals.     

ETAAS method for the determination of Cd, Cr, Cu, Mn and Se in blood fractions and whole blood

An electrothermal atomic absorption method (ETAAS) for the direct determination of trace elements (Cd, Cr, Cu, Mn, Se) both in blood fractions (erythrocytes, plasma and lymphocytes) and whole blood was developed. Zeeman background correction and graphite tubes with L’vov platforms were used. Samples were ¶diluted with HNO₃/Triton X-100 and pipetted directly ¶into the graphite tube. Ashing, pretreatment and atomization steps were optimized carefully for the different fractions and elements applying different matrix modifiers ¶for each element. For the lymphocyte fraction a multi-fold injection technique was applied. Low detection limits ¶of the ETAAS method (Cd 0.13 μg/L, Cr 0.11 μg/L, ¶Cu 0.52 μg/L, Mn 0.13 μg/L, Se 0.7 μg/L of whole blood) combined with small quantities of sample necessary for analysis allow determination of trace elements in this matrix. Verification of possible differences in the trace element status of humans was performed with statistical significance (P < 0.05). In addition, a contribution to the determination of normal values of essential elements was achieved. The method was applied for determination of trace elements in human blood and blood fractions of two groups (n = 50) different in health status.     

Speciation of Se,Fe and Zn in Human Milk Whey: The use of Instrumental Neutron Activation Analysis (INAA) to corroborate element profiles measured with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)

In human milk trace elements normally exist in a form which can easily be absorbed by the newborn infant. For investigations of the bioavailability of trace elements it is necessary to carry out a speciation analysis of the elements of interest. An independent analytical method has been used for the quality control of the shape of the element profiles obtained from the speciation analysis of Se, Fe and Zn in individual samples of human milk whey after chromatographic separation. For the element detection in the untreated milk fractions Instrumental Neutron Activation Analysis (INAA) was chosen as the reference method. Element distribution patterns have been obtained with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) using on-line digestion of the fraction, reduction and hydride formation of Se ("T"-mode). Prior results are compared with those obtained by means of element detection in the untreated fractions ("U"-mode) with ICP-AES. The elution profiles of Se, Fe and Zn in human milk whey obtained by means of ICP-AES detection using the "T"-mode show good agreement with the distribution patterns obtained with INAA. Recoveries of 103% for Fe, 86% for Zn and 87% for Se were obtained. The element distribution patterns of Fe and Zn obtained with ICP-AES speciation using the "T"-mode also show good agreement with those obtained by means of ICP-AES using the "U"-mode.     

血橙中微量元素的测定

采用电感耦合等离子体原子发射光谱仪(ICP-AES),对血橙果肉汁、皮、籽中10种微量元素进行了测定。结果表明,血橙果肉汁、皮、籽中含有Ca、Mg、Fe、Zn、Mn、Cu、Ni等丰富的人体必需微量元素,且血橙果皮、籽中的微量元素含量普遍高于果肉汁中的微量元素的含量,这为血橙药效功能的进一步研究和资源综合开发利用提供一定的科学依据。     

Direct determination of trace elements in niobium,tantalum and their oxides by inductively coupled plasma atomic emission spectrometry after microwave dissolution

Analytical schemes for the determination of trace elements in high-purity niobium, tantalum and their oxides are proposed. The schemes are based on microwave dissolution of the metals and oxides followed by inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of impurities in the solutions. The possibilities of interelement and off-peak background corrections in ICP-AES analysis are discussed. The accuracy of the results obtained is confirmed by the determination of trace elements after a matrix sorption separation procedure. For a number of elements, a comparison of the results obtained by ICP-AES without and with the matrix separation procedure and by electrothermal atomic absorption spectrometry (ETAAS) shows good agreement. The limits of detection for direct ICP-AES determination are in the range 0.4*1.0 μg g⁻¹ for Ba, Ca, Fe, Mg, Mn, Y and La; between 2.0 and 10.0 μ g⁻¹ for B, Cd, Co, Cr, Cu, Hf, Mo, Na, Nb, Ni, Pb, Sr, Ti, Zr and Ta; and for K, Sb and W a detection limit of 20 μ g⁻¹ is achieved. The schemes proposed are intended for rapid routine analysis.     

Determination of trace elements in olive oil by ICP-AES and ETA-AAS: A pilot study on the geographical characterization

The determination of trace elements in edible oils is important because of both the metabolic role of metals and possibilities for adulteration detection and oil characterization.The most commonly used techniques for the determination of metals in oil samples are inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectrometry (AAS). For this study, a microwave assisted decomposition of the olive oil in closed vessels using a mixture of nitric acid and hydrogen peroxide was applied as sample preparation.The low achievable LODs enable the determination by ICP-AES of even very low concentrations of most elements of interest. The proposed ICP-AES method permits the determination of Ca, Fe, Mg, Na, and Zn in olive oils. Elements present in small amounts (Al, Co, Cu, K, Mn, Ni) were measured by ETA-AAS in the same sample digest. The concentrations of Al, Co, Cu, K, Mn, and Ni were in the range from 0.15 to 1.5 μg/g and differ according to the geographical origin of the oils. For the amounts of Fe, Mg, Na, and Zn in the samples, no significant differences according to the geographical origin of the oils could be observed, the mean concentrations being 15.31, 3.26, 33.10, and 3.39 μg/g, respectively. The Ca content varies in the range of 1.3 to 9.0 μg/g.The dependency of the trace elemental content of olive oils on their geographical origin can be used for their local characterization.     

电感耦合等离子体原子发射光谱法测定马奶酒中的多种元素

电感耦合等离子体原子发射光谱法测定马奶酒中的多种元素嘎日迪,乌地（内蒙古师范大学化学系,配位化学研究所,呼和浩特,０１００２２）关键词电感耦合等离子体原子发射光谱,马奶酒,微量金属元素蒙古民族喜爱的传统饮料──马奶酒（蒙语“策格”）是用鲜马奶为原料发...     

Determination of Ca, Mg, Fe, Cu, and Zn in blood fractions and whole blood of humans by ICP-OES

Inductively coupled plasma – optical emission spectrometry (ICP-OES) was applied to the determination of the elements Ca, Mg, Fe, Cu, and Zn in blood plasma, erythrocytes, lymphocytes, and whole blood to obtain reliable data on their distribution in blood fractions. The samples were carefully collected to avoid contamination. Two different nebulizers (Babington and Meinhard) were tested and optimized for this analytical problem. Line selections for all elements of interest were performed (LODs were 0.8 μg/L for Ca, 1.7 μg/L for Cu, 3.0 μg/L for Fe, 1.1 μg/L for Mg, and 4.2 μg/L for Zn). Recoveries were determined as approx. 100%, and standard reference material was analyzed to obtain reliable data on element distribution. The optimized method was applied to the determination of Ca, Mg, Fe, Cu, and Zn in the course of a clinical study on blood and blood fractions of two groups of humans of differing health. The concentrations measured in blood fractions were verified by balancing with the values found in whole blood.     

Determination of Ca, Mg, Fe, Cu, and Zn in blood fractions and whole blood of humans by ICP-OES

Inductively coupled plasma-optical emission spectrometry (ICP-OES) was applied to the determination of the elements Ca, Mg, Fe, Cu, and Zn in blood plasma, erythrocytes, lymphocytes, and whole blood to obtain reliable data on their distribution in blood fractions. The samples were carefully collected to avoid contamination. Two different nebulizers (Babington and Meinhard) were tested and optimized for this analytical problem. Line selections for all elements of interest were performed (LODs were 0.8 microg/L for Ca, 1.7 microg/L for Cu, 3.0 microg/L for Fe, 1.1 microg/L for Mg, and 4.2 microg/L for Zn). Recoveries were determined as approx. 100%, and standard reference material was analyzed to obtain reliable data on element distribution. The optimized method was applied to the determination of Ca, Mg, Fe, Cu, and Zn in the course of a clinical study on blood and blood fractions of two groups of humans of differing health. The concentrations measured in blood fractions were verified by balancing with the values found in whole blood.     

PIXE analysis of human stones: Comparison with data from ICP-AES

25 human stone samples previously analyzed by inductively coupled plasma atomic emission spectroscopy /ICP-AES/ and the IAEA Animal Bone Standard Reference Material were used to evaluate trace element analysis by PIXE. Bombardment with 4 MeV protons was used for the determination of Mn, Fe, Cu, Pb, Br, Rb, Sr as well as Ca. PIXE and ICP-AES data gave correlation factors better than 0.97 for the elements Ca, Fe, Zn, Sr and Pb.     

Fractionation and speciation of Cu,Zn and Fe in wine samples by atomic absorption spectrometry

A scheme is presented for fractionation of wine components and Fe, Cu and Zn determination in different fractions. The charge of the metal species was established using cation and anion exchange separation based on solid phase extraction. The resin XAD-8 was used for the separation of wine polyphenols in complexes with wine proteins and polysaccharides. Dowex ion exchange resins were used for the separation of cationic and anionic species of Fe, Cu and Zn. Flame atomic absorption spectrometry and electrothermal atomic absorption spectrometry were used off-line for the quantitative determination of metals in the different fractions obtained.     

Flow injection flame atomic absorption determination of Cu, Mn and Zn partitioning in seawater by on-line room temperature sonolysis and minicolumn chelating resin methodology

A flow-injection system is developed for Cu, Mn and Zn partitioning in seawater by flame atomic absorption spectrometry. The first approach is where the trace metal species are fractionated in situ, but analysis is performed by using a flow injection manifold in the laboratory. This operational mode is used for the determination of the dissolved labile metallic fraction and is based on the elution of this fraction from a minicolumn packed with a chelating resin containing iminodiacetic acid groups (Serdolit Chelite Che) loaded in situ with the sample. The second is used for the determination of total dissolved concentrations of trace metals. This last mode is based on the retention/preconcentration of total dissolved metals on the chelating resin after on-line sonolysis of seawater samples acidified with diluted nitric acid to breakdown the metal-organic matter complexes. The figures of merit for Cu, Mn and Zn determinations in both fractions are given and the obtained values are discussed. The fractionation scheme is applied to the analysis of coastal seawater samples collected in Galicia (Northwest, Spain). The results of fractionation showed that Mn and Zn are mainly in the labile fraction, while Cu was mainly present in the organic fraction.     

Co-precipitative pre-concentration with sodium diethyldithiocarbamate and ICP-AES determination of Se, Cu, Pb, Zn, Fe, Co, Ni, Mn, Cr and Cd in water

Sodium diethyldithiocarbamate in the presence of a weak oxidizing agent is used as a co-precipitative agent for the pre-concentration of Se, Cu, Pb, Zn, Fe, Co, Ni, Mn, Cr and Cd. A procedure was developed for ICP-AES determination of these elements after pre-concentration in river and waste water (an enrichment factor of 40). The recovery of all the elements tested for was more than 98%. The limits of determination (mg l⁻¹) (10 S.D. blank) are 0.001 (Cu, Co, Cr, Mn), 0.0007 (Zn, Cd), 0.003 (Se), 0.004 (Fe), 0.007 (Ni), and 0.01 (Pb).     

Determination of trace metal ions Co,Cu, Mo,Mn, Fe,Ti, V in reference river water and reference seawater samples by inductively coupled plasma emission spectrometry combined with the third phase preconcentration

A combination of DAM-SCN^– third phase extraction and inductively coupled plasma emission spectrometry (ICP-AES) is used for the determination of trace metal ions in a river water and a seawater reference material. An implementation of the third phase extraction prior to ICP-AES allows a preconcentration of trace elements (Co, Cu, Mn, Fe, V, Ti, Mn) by a factor ranging from 33 to 45. A complete separation of these elements is accomplished from matrices, normally affecting the excitation characteristics of ICP and suppressing the elemental signals severely. Different factors, including pH of the solutions, amounts of reagents, matrix effects, have been investigated and optimized. Under the conditions selected, the limits of determination have been in the range of 0.02 to 0.6 g/L. The system has been successfully applied to the determination of Cu, Mn, V in the reference river water SLRS-3 and Mo in the reference seawater NASS-3. The results were in a good agreement with the certified values.     

阳江市健康儿童全血中六种元素含量分布研究

利用电感耦合等离子体原子发射光谱技术测定了广东省阳江市5134例健康儿童全血中Zn、Fe、Cu、Ca、Mn和Pb等六种元素的含量，并按男性和女性小于等于3岁和4—7岁年龄段共四种情况计算其平均值，标准偏差、各种百分位数值，应用标准差法和百分位数法求出各元素的正常值和正常范围值。文中还统计了上述六种元素的相关系数。     

血清六种微量元素与胃癌的相关性

为研究胃癌患者血清微量元素与胃癌的相关性 ,探讨其在胃癌诊断中的应用 ,取甘肃省武威市 2 0例胃癌患者血清作为胃癌组 (C组 ) ,3 0例当地健康志愿者血清作为对照组 (N组 ) ,用电感耦合等离子体原子发射光谱仪 (ICP -AES)进行了 6种微量元素的测定 ,并将结果用SPSS软件作统计分析。结果表明 ,胃癌组血清微量元素值高于对照组的元素有Cu、Cu/Zn、Fe (P <0 0 1 ) :低于对照组的元素有Zn、Mn (P <0 0 5 )。经Logistic回归分析 ,进入方程的为Zn元素 (P<0 0 5 )。多种微量元素联合诊断胃癌的准确率为 87% ,误诊率为 8%。提示 ,甘肃省武威市胃癌患者血清中Cu、Cu/Zn、Fe的升高以及Zn、Mn的降低与胃癌的发生具有相关性。其中Zn与胃癌的发生关系最为密切 ,且Zn降低可能为胃癌发生的癌前因素。测定血清微量元素值可以作为早期诊断胃癌的一种工具。     

四季柚微量元素的测定

采用电感耦合等离子体原子发射光谱仪(ICP-AES),对四季柚果肉、果皮、籽中10种微量元素进行了测定。结果表明,四季柚果肉、果皮、籽中含有Ca、Mg、Fe、Zn、Mn、Cu等丰富的人体必需微量元素,且四季柚果皮和籽中的微量元素含量普遍高于果肉中的微量元素含量,这为四季柚药效功能的进一步研究和资源综合开发利用提供一定的科学依据。     

Application of an on-line preconcentration system in simultaneous ICP-AES

A PC-controlled on-line preconcentration system (TRACECON) developed by Knapp et al. [11], was connected to a JY-70 Plus simultaneous ICP spectrometer to preconcentrate on-line seven trace elements (Cu, Fe, Zn, Cr, Ni, Mn, V) in biological and environmental samples. EDTrA-cellulose was used as column material. The elemental concentrations were determined by simultaneous ICP-AES. The effect of pH of the sample solution on the enrichment was studied. It was found that the recoveries of chromium and iron depend strongly on the pH of the sample solution. All the elements mentioned were recovered quantitatively at pH 4.0±0.1. The flow rates of sample solution and element solution were optimized. The enrichment factors for seven elements at 5 ml loading volume range from 3.9 for Cu to 7.9 for Zn. The detection limits of all seven elements were improved. The accuracy of the method was tested by the analysis of a number of CRMs of NIST, BCR and NIES. Most results are in good agreement with the certified values.On leave from Shanghai Institute of Metallurgy, Academia Sinica, Shanghai 200050, People's Republic of China     

Determination of metal-cofactors in enzyme complexes by total-reflection X-ray fluorescence spectrometry

The determination of metal-cofactors and their molar concentrations is an important requirement for the characterisation of metalloproteins and a challenge regarding the capabilities of trace analytical methods. In this respect, total-reflection X-ray fluorescence spectrometry offers many advantages for the determination of trace elements in enzymes, as compared to other well known analytical techniques such as flame atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry (ICP-AES), because of the significantly smaller amounts of sample required. Without any decomposition, elements like P, S, Fe, Ni, Cu, Zn, Mn and Mo could be determined with high accuracy, in spite of the large bio-organic matrix. The enzymes (polysulphide reductase and hydrogenase of the rumen bacterium Wolinella succinogenes, and the cytochrome c oxidase and quinol oxidase of the soil bacterium Paracoccus denitrificans) were transferred from their usual salt-buffer into a solution of 100 mmol l⁻¹ tris(hydroxymethyl)aminomethane (tris)-acetate containing an appropriate detergent. By this procedure, an improved signal-to-noise ratio is obtained. The polysulphide reductase was found to contain copper as a hitherto existing unknown cofactor. The enzyme contains a stretch of amino acids that are typical of copper proteins and thus confirm the presence of this element. Furthermore, the data concerning cytochrome c oxidase from Paracoccus denitrificans are in good agreement with published values obtained by ICP-AES. Also, results from measurements with the quinol oxidase from the same bacterium agree with the expected values. The investigations lead to the conclusion that the method is well suited to the quantitative determination of metals in enzymes, in particular their molar fractions, and requires only small amounts of the biological sample without any extensive pretreatment. © 1997 Elsevier Science B.V.