Identical flow injection spectrophotometric manifold for determination of protein, phosphorus, calcium, chloride, copper, manganese, iron, and zinc in feeds or premixes

A simple procedure using an identical manifold was developed for determination of nitrogen (protein) phosphorus, calcium, chloride, copper, manganese, iron, and zinc in feeds and feedstuffs. By changing appropriate reagents and detection wavelength, these 8 elements were determined successively with a simple identical double-line flow injection (FI) manifold. Fl spectrophotometric determinations were made by the blue indophenol reaction for ammonium, the molybdenum blue method for phosphate, the cresolphthalein complexone procedure for calcium, and the mercuric thiocyanate procedure for chloride. The chromogenic reagents for copper, iron, manganese, and zinc determination were bis(cyclohexanone)oxalydihydrazone (Cuprizone), 1,10-phenanthroline, formaldoxime, and xylenol orange, respectively. Sample digestion catalyst, Fl manifold, and some chemical parameters were optimized. The proposed procedure had a sampling rate of 90/h for each analyte. The determination ranges (mg/L) were 10-60 for N, 1-15 for P and Ca, 540 for Cl, and 0.5-15 for Cu, Fe, Mn, and Zn, respectively. Results of the analyses of animal feed and feedstuff samples by this procedure did not differ significantly from those obtained by proven manual methods.     

微波消解/ICP-OES法同时测定发菜中Fe、Cu、Mn、Zn

采用微波消解处理样品,电感耦合等离子体发射光谱(ICP-OES)测定了发菜中微量元素Fe、Cu、Mn、Zn含量。结果表明,各元素检出限分别为1.58、0.79、0.52、0.67μg.mL1;相对标准偏差均小于2.2%;回收率为92.7%~101.3%。该法精密度高、准确度好,所测数据可为发菜的合理利用提供依据。     

流动注射在线分离富集-MPT全谱仪测定饮用水中的微量金属元素

建立了流动注射进样法结合717型阴离子树脂富集柱在碱性条件下同时富集饮用水中的Al,Cu,Fe,Mn和Zn等5种微量金属元素的MPT全谱仪原子发射光谱测定的新方法.本法简单快捷,成本低,而且可消除Na,Ca和K等基体元素的干扰(包括光谱干扰).取8mL水样时,对Al,Cu,Fe,Mn和Zn的检出限(3σ)分别为17,0.27,2.0,4.3和9.8μg/L;相对标准偏差均小于5%(n=7);在检测范围内各元素测量线性良好.本法已成功应用于自制水样和实际自来水样的分析.     

New sorbents and indicator powders for preconcentration and determination of trace metals in liquid samples

Two approaches to immobilize complex-forming analytical reagents (PAN, PAR, Xylenol orange, Brombenzothiazo, Crystal violet, Cadion, and Sulfochlorophenolazorhodanine) for the preparation of new sorbents and indicator powders are suggested: on-line coating of reversed-phase silica gel by reagents or doping of porous sol-gel silica with reagents. The retention of Ag, Cd, Cu(II), Co(II), Fe(III), Mn(II), Ni, Pb, and Zn on the sorbents developed was investigated. Quantitative sorption and desorption conditions were optimized. Procedures for the determination of Cd, Cu(II), Fe(III), Pb, and Zn with flame atomic absorption, spectrophotometric, and diffusion scattering spectrometric detection were elaborated. Detection limits for Cd, Cu(II), Fe(III), Pb, and Zn were 3 μg/L, 6 μg/L, 5 μg/L, 40 μg/L, and 1 μg/L, respectively. The procedures were used for the analysis of various real samples, e.g., natural and waste waters, and food.     

Direct Analysis of Beer by ICP-AES: A Very Simple Method for the Determination of Cu, Mn and Fe

A very simple method for determination of trace amount of Cu, Mn and Fe in beer by inductively coupled plasma spectrometry (ICP-AES) was developed. The beer was directly introduced into the plasma, without dilution or adding of reagents, via a conventional V-groove nebulizer. The only sample preparation used was degassing of the beer to remove CO₂. By optimizing the ICP-AES parameters (RF power and Nebulizer gas flow rate) and by the appropriate choice of wavelengths for measurements, sufficient accuracy for the determination of the trace metals was obtained. Various types of beers were analysed by the direct ICP-AES method and for comparison, also with two other methods: by GFAAS and ICP-AES after decomposition. No significant difference was found for Cu and Mn (ANOVA, 95% confidence level) using the three methods. This was normally also the case for Fe; only in one case did the result of Fe by the direct method deviate from the other methods (10% lower results). The limit of detection for the direct method was estimated to 1.1, 0.3, and 1.1 ng mL⁻¹ for Cu, Mn, and Fe, respectively.     

高效液相色谱光度法测定痕量铜、锌、铁、锰的磺化四苯基卟啉配合物

本文用磺化四苯基卟啉作柱前衍生试剂,研究了试剂与铜(Ⅱ)、锌(Ⅱ)、铁(Ⅲ)及锰(Ⅱ)的络合反应。在ODS柱上,用乙腈-水(40:60,V/V)作流动相,溴化四丁基铵作离子对试剂,在420nm波长处进行光度检测。提出了离子对反相高效液相色谱快速分离及测定痕量铜、锌、铁及锰的新方法。检测下限为(×10^-3ppm):Mn 3.6、Fe 1.8 、Zn 0.93、Cu 0.70。应用于植物样品中痕量铜、锌、铁及锰的测定,分析结果与标准参考值相符。     

Electrospray ionisation with selected reaction monitoring for the determination of Mn‐citrate,Fe‐citrate,Cu‐citrate and Zn‐citrate

Citrate complexes of Mn and Fe, and potentially those of Cu and Zn, are considered as important low molecular mass species in human serum and cerebrospinal fluid (CSF). For example, Mn is supposed to enter the brain under excess exposure as Mn‐citrate leading to neurotoxic effects. Mn‐citrate has been characterised in human CSF using chromatography and electrophoresis online with inductively coupled plasma mass spectrometry, but not yet with molecular mass spectrometry. Therefore, this study explores the potential of electrospray ionisation (ESI) with selected reaction monitoring (SRM) for the detection of metal‐citrate complexes, in particular Mn‐citrate. The collision‐induced dissociation of precursor ions with various metal:citrate stoichiometries was studied for Mn‐citrate, Fe‐citrate, Cu‐citrate and Zn‐citrate. High selectivity was achieved for Mn(II)‐citrate even in respect to Fe(III)‐citrate which forms isobaric precursor ions. The limit of detection for Mn‐citrate was estimated to be around 250 µg L^?1 (referring to the total Mn content in the standard) using flow injection. The sensitivity was sufficient for the determination of Mn‐citrate in standard solutions and in an extract of an Mn‐citrate‐containing supplement. An improved ESI source design is expected to reduce the limits of detection significantly. The developed ESI‐SRM method has the potential to provide complementary data for the quality control of current separation methods for metal citrates using element‐selective detection, with application to biomedical samples and further matrices. Copyright © 2009 John Wiley & Sons, Ltd.     

A double-line sequential injection system for the spectrophotometric determination of copper, iron, manganese, and zinc in waters

A double-line sequential injection system was developed for the spectrophotometric determination of several metal ions in waters. The proposed double-line configuration was used to enable adding sample and chromogenic reagents as merging zones. The methodology was applied to the spectrophotometric determination of copper, iron, manganese, and zinc in samples of diverse origins at the range of 0.15-5.00, 0.10-10.0, 0.48-4.00, and 0.11-5.00 mg/L, respectively. Different chromogenic reagents and detection wavelengths were used. The chromogenic reagents for iron and manganese were 1,10-phenanthroline and formaldoxime, respectively. Copper and zinc were both determined using the analytical reagent zincon. Analytical characteristics of the methodology, such as manifold parameters, buffer pH, and reagent concentrations were optimized, and interference of some of the metal ions commonly present in water sample was assessed. Results of the analysis were in agreement with those obtained by atomic absorption spectrometry. Repeatability, expressed as the relative standard deviation for 10 consecutive injections of water samples, was lower than 6%. The determination rate was approximately 36/h.     

New sorbents and indicator powders for preconcentration and determination of trace metals in liquid samples

Two approaches to immobilize complex-forming analytical reagents (PAN, PAR, Xylenol orange, Brombenzothiazo, Crystal violet, Cadion, and Sulfochlorophenolazorhodanine) for the preparation of new sorbents and indicator powders are suggested: on-line coating of reversed-phase silica gel by reagents or doping of porous sol-gel silica with reagents. The retention of Ag, Cd, Cu(II), Co(II), Fe(III), Mn(II), Ni, Pb, and Zn on the sorbents developed was investigated. Quantitative sorption and desorption conditions were optimized. Procedures for the determination of Cd, Cu(II), Fe(III), Pb, and Zn with flame atomic absorption, spectrophotometric, and diffusion scattering spectrometric detection were elaborated. Detection limits for Cd, Cu(II), Fe(III), Pb, and Zn were 3 μg/L, 6 μg/L, 5 μg/L, 40 μg/L, and 1 μg/L, respectively. The procedures were used for the analysis of various real samples, e.g., natural and waste waters, and food. Received: 17 July 1997 / Revised: 20 January 1998 / Accepted: 5 February 1998     

在线的离子交换预富集流动注射──原子吸收光谱法测定铁、锰、铜和镉的研究

本文使用大孔弱酸阳离子交换树脂Ｄ—１５２微型柱预富集，将流动注射与原子吸收光谱法相结合测定了Ｆｅ、Ｍｎ、Ｃｕ和Ｃｄ等离子。讨论了溶液酸度、采样速率及沈脱剂等对上述四元素灵敏度的影响。在采样频率４０次／ｈ、采样体积７ｍｌ时，Ｆｅ、Ｍｎ、Ｃｕ和Ｃｄ增敏１６～２４倍，检出限分别为０．９、０．４、０．４和０．１ｎｇ／ｍｌ。     

等离子体原子荧光光谱法测定碳酸锂中钠、钾、钙、镁、铜、铁、钴、镍、锰、锌、镉

建立了用ICP-AFS同时测定碳酸锂中11种微量金属杂质元素的方法。加入甲烷可改善检出限,方法简便,样品分析结果与AAS法结果一致。     

An intelligent flow analyser for the in-line concentration, speciation and monitoring of metals at trace levels

An intelligent and versatile flow system is proposed for the in-line speciation and/or concentration of metal ions at a wide range of concentrations without requiring manifold reconfiguration. On one hand, sample enrichment strategies are accomplished using packed-bed reactors, on the other hand speciation procedures are readily performed exploiting the selective complexation of the different oxidation states with the appropriate chromogenic reagents.

The potentials of the automated methodology were evaluated using the spectrophotometric monitoring of iron as a model of chemistry. Under the optimised physical and chemical variables, linear analytical curves over the ranges 0.025–0.5 or 2.0–40 mg l⁻¹ Fe were attained. The 3σ detection limit, the repeatability at the 0.5 mg l⁻¹ level, the enrichment factor for a sampling volume of 10 ml, and the maximum injection throughput were 8.4 ng ml⁻¹ Fe, 2.5%, 58.6 and 22 h⁻¹, respectively. The flowing system was applied to the speciation analysis of iron in waters, pharmaceutical formulations and agricultural products, using ICP-OES detection as an external reference method for total iron determination.

A remarkable feature of the expert system hereby presented is the ability to decide by itself if the pre-concentration and/or oxidation of the sample zone is required.     

The application of an argon/nitrogen inductively-coupled plasma to the analysis of organic solutions

A 4-kW argon/nitrogen inductively-coupled plasma (ICP) is used for multielement trace determinations in organic solutions. After optimization of the pneumatic nebulizer and ICP parameters, trace determinations at sub-mug/ml concentrations with relative standard deviations of 1% are possible. The first application described is the determination of a series of metals (Cd, Cu, Fe, Mn, Zn) after their isolation from the sample matrix by extraction of the ammonium pyrrolidinedithiocarbamate complexes into methyl isobutyl ketone. Alkali and alkaline-earth metal salts at 50-g/l. concentrations do not affect the method, which can be applied to trace determinations in industrial waste waters having high salt contents. The second application is the multielement analysis of oils. The samples are diluted 1:10 with xylene, and the detection limits for Al, Cu, Fe, Mg, Mn, Si and Zn are in the sub-mu/g range. The superior detection power of spectrographic ICP methods in comparison with photoelectric techniques using a monochromator and a polychromator is discussed. Oils of different viscosities can be analysed with use of the same calibration graphs. From experiments with a computer-controlled polychromator with background measurement facilities, it is concluded that the accuracy is improved if background measurements are made at wavelengths near the analytical lines, for each sample independently.     

Die gleichzeitige Bestimmung von Cu,Fe, Mn,Zn, Pb und Cd in Pflanzengewebe mittels Differential-Puls-Polarographie

Zusammenfassung Die Ionen des Cu, Pb, Cd, Zn, Fe und Mn in Pflanzenmaterial können mittels Differential-Puls-Polarographie ineinem Analysengang bestimmt werden, wenn man eine erste Grundlösung ohne Wechsel des Meßgefäßes durch Zusatz so variiert, daß jeweils eine andere Gruppe aus den genannten Ionen störungsfrei bestimmbar ist. Nach Veraschung und Lösung in Weinsäure lassen sich Cu, Pb, Cd und Zn, nach Zusatz von Ammoniak Cd, Zn und Fe, nach weiterem Zusatz von Kaliumcyanid Mn bestimmen. Benötigte Probenmenge 0,2–0,5 g, untere Bestimmungsgrenze um 1g/g. Die Methode eignet sich besonders für Serienanalysen. Ein Analysenbeispiel ist angegeben.

---

Simultaneous assay of Cu, Fe, Mn, Zn, Pb and Cd in plant tissue by means of differential pulse polarography

Summary Cu, Pb, Cd, Zn, Fe and Mn ions in plant material can be assayed by means of differential pulse polarography in one analysis operation if the first basic solution is varied without changing the measurement vessel by addition in such a way that in each case one other group of the named ions can be assayed without interference. After incineration and dissolution in tartaric acid, Cu, Pb, Cd and Zn can be assayed. After addition of ammonia Cd, Zn and Fe, and after further addition of potassium cyanide, Mn can be determined. Required sample amount: 0.2 to 0.5 g; lower limit of detection is around 1g/g. The method is especially suitable for serial analyses. An analysis example is given.

     

18种中药中微量元素铁锌锰铜的含量研究

为研究治疗黄褐斑常用中药中Fe、Zn、Cu、Mn的含量与药效的关系,测定了18种中药材中Fe、Zn、Cu、Mn含量,并用主成分分析法进行分析.结果表明,Fe含量最高,Zn、Mn次之,Cu最少;Zn和Cu的相关系数最大,且Zn与Cu比均大于1.说明补充Zn可以抑制Cu与酶结合,防治色斑.     

Determination of Cu, Fe, Mn, and Zn in blood fractions by SEC-HPLC-ICP-AES coupling

The binding of Cu, Fe, Mn, and Zn to proteins in blood and in blood fractions was investigated, since their interactions in free radical metabolism in humans is of great interest. An HPLC-ICP-AES technique was developed allowing adequate separation of metalloproteins and of inorganic and organic metal species. For the separation of metalloproteins in erythrocytes and blood plasma a Merck Superformance Fractogel EMD BioSEC 650 (S) column was used. Size exclusion chromatography (SEC)-HPLC was hyphenated to ICP-AES both on-line and off-line for the detection of trace elements in the fractions resulting from HPLC separations. HPLC parameters, pH, temperature, flow rate and salt concentration were optimized for the protein separation and the optimal conditions were applied for the hyphenation to the ICP-AES detector. The separation column was calibrated with five standard proteins. For the element determination by ICP-AES a line selection with respect to the sensitivity was performed. Three different methods were used for the determination of trace elements in blood: direct determinations, on-line and off-line SEC-HPLC-ICP-AES measurements. For the optimizing experiments blood samples of one female subject were used. The direct determination by ICP-AES of the elements was performed in blood and blood fractions of ten different subjects to obtain the average concentration ranges. From the results the identification of the protein Cu/Zn superoxide dismutase in erythrocytes was possible. The LOD were 0.03 microgram mL-1 for Cu, 0.026 microgram mL-1 for Fe, 0.8 ng mL-1 for Mn, and 0.09 microgram mL-1 for Zn in a synthetic blood matrix.     

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.     

Determination of inorganic elements in animal feeds by NIRS technology and a fibre-optic probe

In the present work we study the use of near infra-red spectroscopy (NIRS) technology together with a remote reflectance fibre-optic probe for the analysis of the mineral composition of animal feeds. The method allows immediate control of the feeds without prior sample treatment or destruction through direct application of the fibre-optic probe on the sample.The regression method employed was modified partial least squares (MPLS). The calibration results obtained using forty samples of animal feeds allowed the determination of Fe, Mn, Ca, Na, K, P, Zn and Cu, with a standard error of prediction (SEP(C)) and a correlation coefficient (RSQ) of 0.129 and 0.859 for Fe; 0.175 and 0.816 for Mn; 5.470 and 0.927 for Ca; 2.717 and 0.862 for Na; 4.397 and 0.891 for K; 2.226 and 0.881 for P; 0.153 and 0.764 for Zn, and 0.095 and 0.918 for Cu, respectively.The robustness of the method was checked by applying it to 10 animal feeds samples of unknown mineral composition in the external validation.     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

几种药渣中铁、锌等元素含量的测定及再利用讨论

用原子吸收分光光度法测定几种药渣中铁、锌、铜、锰元素含量,为药渣再利用提供依据。实验表明,不同药渣中铁、锌、铜、锰元素含量不同,同一药渣中各元素含量也不同,且药渣中铁元素含量均高于其它几种元素;实验所测的药渣中平均含铁318.3mg/kg,锌、锰平均含量为34.31和39.13mg/kg。药渣中含有较为丰富的Fe,Zn,Cu,Mn元素,具有再利用价值。