Determination of trace elements by inductively coupled plasma mass spectrometry of biomass and fuel oil reference materials using milligram sample sizes

Most of the analytical techniques used to quantify elements associated with solid samples suffer from high detection limits and cannot be used for trace elements in biomass samples, particularly when only 20 mg are available for analysis. Inductively coupled plasma mass spectrometry (ICP-MS) can achieve detection limits of parts-per-trillion with liquid sample introduction by solution nebulisation. This technique was therefore tested with two standard biomass reference materials: oriental tobacco leaves and cabbage leaves. Two preparations successfully used on coal standards were used to digest the solid samples: a total digestion method (wet ashing digestion) and a partial leaching (microwave extraction). The concentrations of up to seventeen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn) were measured after the two preparations. The accuracy and sensitivity of the measurements improved when the dilution factor decreased from 5000 to 1000 and to 500. Since the proportion of mineral matter in biomass samples is small (5%), the microwave digestion extracted elements that are generally not completely extracted from coal samples (e.g. Sb). However, some trace element concentrations were below the limit of quantification after microwave extraction, even with a reduced dilution factor (As, Se and Mo) and could not be quantified. A fuel oil was also digested. The trace element concentrations were very low (between 28 and 0.1 microgram g(-1)) but acceptable results were obtained by applying a dilution factor of 100. Only six elements in the fuel oil (As, Ba, Co, Ni, Se and V) had certified or indicated values. Factors affecting the accuracy and sensitivity of the analyses are discussed. The reproducibility of analysis of the tobacco leaf standard was checked over a period of nine months by both digestion methods. The wet ashing method gave acceptable reproducibility for Ba, Cd, Co, Cu, Ga, Mn, Mo, Ni, Pb, V and Zn but poor precision for Cr, Se and Sn and showed evidence of residual chloride interference for As. The microwave extraction gave good reproducibility for As, Ba, Cd, Co, Cr, Cu, Mo, Ni and Zn but poor precision for Se and low recoveries for Ga, Mn, Sn and V. In spite of the small quantities of material analysed, it proved possible to determine the trace elements at levels down to 0.1 microgram g(-1) in the reference materials.     

煤中痕量元素在循环流化床锅炉中的迁移行为与富集特性

对天津市某电厂循环流化床(CFB)锅炉燃用的原煤及燃烧产物底灰、飞灰、细飞灰(≤50 μm)进行痕量元素含量的测定,分析了Be、Zn、Hg、V、Cr、Mn、Co、Ni、Cu、As、Se、Cd、Pb 13种痕量元素在燃烧过程中的迁移行为,揭示了痕量元素在CFB锅炉中的分配、富集特性。结果表明,CFB锅炉中,较低的炉温对于痕量元素的迁移富集产生了较大的影响。由相对富集系数得知,Be、V、Co、Se在底灰中耗散,在飞灰中富集,Zn、Mn倾向于在底灰中富集,元素Cd、Pb、Ni、Cu挥发性较强,在底灰和飞灰中均是耗散。As受钙氧化物影响,挥发性表现并不明显。Hg在底灰和飞灰中相对富集系数均很低,表明Hg在整个燃烧过程中以气态形式排放;Hg、As、Se、V、Cr、Mn、Co、Ni、Cu、Zn、Pb均有向小颗粒物中富集的趋势。根据相对富集系数以及研究的13种元素在低温CFB锅炉中的迁移行为,将这些元素分为三类:A类(E_R<0.1),主要是以气态形式排放元素Hg;B类(0.1R≤0.85),较易挥发元素As、Be、Ni、Cu、Se、Cd、Pb、Co、V;C类(E_R>0.85),主要残留在固体产物中元素Zn、Mn、Cr。     

Polarographic determination of cadmium, lead, nickel, thallium and uranium(VI) in isoquinoline formate

Summary The polarographic behaviour of Cd, Pb, Ni, Tl and U(VI) has been described in 0.1 M isoquinoline formate as base electrolyte. In all cases well defined reversible waves were obtained and determinations are possible in the presence of Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg and Cu.

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Polarographische Bestimmung von Cadmium, Blei, Nickel, Thallium und Uran(VI) in Isochinolinformiat

Zusammenfassung Das polarographische Verhalten von Cd, Pb, Ni, Th. und U(VI) in 0,1 M Isochinolinformiatlösung wird beschrieben, Bestimmungsmöglichkeiten werden aufgezeigt. In allen Fällen werden gut definierte reversible Stufen erhalten. Folgende Elemente stören nicht: Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg, Cu.

     

Summary of preparation and homogeneity characterization of ten agricultural food reference materials for elemental composition

Summary Preparation and development has been completed of ten agricultural/food reference materials (RMs): bovine muscle powder, corn starch, hard red spring wheat flour, soft winter wheat flour, whole milk powder, wheat gluten, corn bran, durum wheat flour, whole egg powder and microcrystalline cellulose. Homogeneity tests for 14 elements, Al, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr and Zn were performed by the initiating laboratories by application of precise and reliable analytical methods based on flame atomic absorption spectrometry and graphite furnace atomic absorption spectrometry. An extensive set of analytical results obtained from the interlaboratory cooperative characterization campaign was assessed to provide homogeneity estimates for other elements. Estimates of homogeneity from within-laboratory precision indicated that all materials exhibited acceptable homogeneity for virtually all 29 elements (Al, As, B, Ba, Br, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg, I, K, Mg, Mn, Mo, N, Na, Ni, P, Pb, Rb, S, Se, Sr, V, Zn) for which best estimate concentration values are available. Two thirds of all homogeneity coefficients of variation were below 5%.     

Pure graphite as a reference material for the determination of trace elements — an interlaboratory collaborative study

Seven synthetic graphite powders of different grade of purity were analyzed by means of INAA, WDXRF, EDXRF, DC-OES directly and using ICP-MS, ICP-OES, ETAAS and FAAS in combination with various sample preparation techniques. On the basis of a statistical evaluation of the results obtained, for the trace elements Al, Ca, Cr, Cu, Fe, Mn and Ni, reference values were established and, for the elements As, Co, Mg, Mo, Pb, Sb, Si, Sr, Ti, V, Zn and Zr, informative values are given. The analyzed reference materials are commercially available.     

Über eine allgemein anwendbare Methode zur Bestimmung von Aluminiuni in Stahl

The method has been worked out for Al contents from 0.01 to 1.1% in iron, steels and alloy steels, and tested with standard reference materials. Aluminium is separated by 8-hydroxy-quinoline at pH 9 after Hg-electrolysis and step-wise pre-extraction of interfering constituents as Fe, Mo, Cr, Cu, Co, Cd, Mo, Pb, Ni, Sb, Zn, Sn, Mn. Finally the 8-hydroxy-quinoline extract is digested with nitric/sulphuric acid and aluminium is determined spectrophotometrically by the Aluminon method.     

Comparative PGAA and NAA results of geological samples and standards

Concentrations of major and trace elements in volcanic rock and soil samples, including geological standard reference materials, were determined by neutron activation analysis (NAA) and prompt gamma activation analysis (PGAA), both using the k ₀-standardization method. The paper highlights the different experimental procedures, such as sample preparation, data collection and spectrum evaluation. In geological samples, PGAA gives precise results for major elements (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K and—as a unique method—for H), for some of the light trace elements as B and Cl, as well as for Sc, S, Cr, Co, Ni, Cd, Nd, Sm and Gd. NAA is sensitive for the rare earth elements, and for many major (Ti, Al, Fe, Mn, Mg, Ca, Na, K) and trace elements (e.g.: Sc, V, Cr, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Zr, As, Sb, Ce, Ba, Hf, Ta, W). For most major elements the results obtained by the two methods show good agreement. The comparison of the results obtained for trace elements is not always possible, since PGAA is less sensitive and concentrations are often below its detection limits. Nevertheless, the complementarity of NAA and PGAA allows nearly panoramic analysis of geological materials.     

Preparation of the Bovine Kidney and Bovine Muscle reference materials and the certification of element contents from interlaboratory comparisons

Results obtained in interlaboratory comparisons on candidate reference materials Bovine Kidney and Bovine Muscle, in which more than 32 laboratories participated employing atomic spectrometry, electrochemical, and nuclear analytical techniques, have been evaluated using combined statistical and analytical considerations. Certified and/or information values for the elements Br, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, P, Pb, Rb, Se, and Zn have been established. Information on contents of the elements Al, As, Au, Cs, Li, Ni, Sb, Sn, Sr, and V is also presented.     

前列舒通胶囊中26种无机元素的分析

目的：明确造成前列舒通胶囊不同批次间差异的标志性无机元素,并进行安全性评价。方法：采用ICP-MS测定制剂中Al、As、B、Ba、Ca、Cd、Co、Cr、Cu、Fe、K、Mg、Mn、Mo、Na、Ni、Pb、Sb、Se、Sn、Sr、Ti、Tl、V、Zn和Hg元素含量并进行数据分析。运用主成分及综合评分结合聚类分析手段,确定制剂的特征性元素;进行元素含量和相关性分析,明确不同批次各元素的差异及元素之间的关系;以多元素含量为指标,绘制无机元素谱图。结果：19批样品中均未检测出Se、Mo、Sn、Sb、Tl和Hg,且Pb、Cd、As、Cu、Hg均符合限量标准,无机元素含量谱图趋势一致。主成分分析提取了4个主成分,确定元素B、K、Al、V、Cr、Ca、Ti、Na、Co和Mn可作为特征元素。主成分得分图将19批样品分为两类,聚类分析及综合评分结果与其一致,两类样品中各元素含量存在差异性。相关性分析中,明确了B与K、Al、Cr正相关,K与Cr、Co正相关,V与Cr、Mn正相关,Mn与Co正相关,Ca、Ti、Na两两正相关。结论：通过分析前列舒通胶囊中无机元素含量,确定了特征元素,为前列舒通胶囊质量全面控制研究提供科学依据。     

Multielemental Analysis of Human Serum by Dynamic Reaction Cell–Inductively Coupled Plasma Mass Spectrometry

The selection of the most suitable dilution methods for determination of trace elements in human serum using inductively coupled plasma mass spectrometry is reported. The trace elements were Al, V, Cr, Fe, Mn, Co, Cu, Zn, As, Cd, Sn, Tl, and Pb. The performance of various dilution methods was assessed by precision, linearity, detection limits, quantification limits, fortified recoveries, and the analysis of reference materials. The results demonstrate that diluted solution containing only nitric acid is most suitable for As, Cr, Mn, and Co in serum. Dilute solutions containing nitric acid and Triton X-100 were most appropriate for Cu, Zn, Cd, and Tl. The optimum conditions for Al, V, Mn, Fe, Cr, Co, Sn, and Pb used tetra-n-butylammonium hydroxide, Triton X-100, and ethylenediamine tetraacetic acid.     

Preconcentration by dithiocarbamate extraction for determination of trace elements in natural waters by inductively-coupled plasma atomic emission spectrometry

Preconcentration by dithiocarbamate extraction into 2-ethylhexyl acetate for simultaneous determination of trace elements in natural water is described. After 250-fold concentration, the organic phase is used directly for inductively-coupled plasma atomic emission spectrometry. Thirteen elements (As, Se, Mo, Zn, Cd, Ni, Co, Sn, Fe, Cr(VI), Pb, V and Cu) are simultaneously concentrated at pH 4.3 with the combination of ammonium tetramethylenedithiocarbamate and dibenzylammonium dibenzyldithiocarbamate and are determined in the extract; Mn and Cr(III) are also determined after preconcentration at pH 6.9 with the same chelating agents. Lake waters are analyzed by this method.     

Elemental analysis of special materials by X-ray fluorescence spectrometry

The special materials like phosphor bronze for P, Fe, Ni, Cu, Zn, Sn and Pb; mild steel for P, S, V, Cr, Mn, Co, Ni, Cu, As, Nb, Sb and W; special alloys for Ti and Mo, zircaloy and zirconium oxide for Hf; and zircon ore for Zr have been analyzed by X-ray fluorescence spectrometry (XRFS). The measured values along with certified values, precision and accuracy have been given for all the elements analyzed. Some of these materials have also been analyzed by atomic absorption spectrometry (AAS), neutron activation analysis (NAA) and inductively coupled plasma emission spectrometry (ICP-ES). The analytical data of XRFS are in agreement with the results obtained by AAS-ICP-ES and NAA. In most cases the precision is within ±2% and accuracy is ±4%. The precision and accuracy for S, P, Ni and Hf are poor at low concentrations. Practical low detection limit of about 40 g/g of Hf in zirconium matrix has been achieved. It is established that precise and accurate determination of Ti and Mo in special alloys is possible using XRFS.     

Certification of the contents of some heavy metals (Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn) in three types of sewage sludge

Summary The element contents of Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn of three different types of sewage sludge were certified. The preparation, the homogeneity and the stability are reported. The certified contents as well as values for Cr and Se and for the aqua regia soluble contents of Cd, Cr, Co, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn) in drei Klärschlammproben

Zusammenfassung In drei verschiedenen Klärschlammproben wurden die Elementgehalte an Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Herstellung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt von Cr, Se und der Gehalt an königswasserlöslichem Cd, Cr, Co, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Challenges and successes in the use of neutron activation analysis procedures for value assignment of animal serum and bovine liver Standard Reference Materials

Analyses for value assignment in the renewal Standard Reference Materials^® SRM 1598a Animal Serum and SRM 1577c Bovine Liver included extensive characterization by neutron activation analysis (NAA). Conventional instrumental NAA procedures were complemented by pre-irradiation chemical separations for the determination of Al, V, Mn, and Cu, radiochemical separations for the determination of Ag, As, Cd, Cr, Cu, Mo, Sb, and Se, and the use of (anti-) coincidence gamma-ray spectrometry systems for the instrumental determination of Ag, Cr, and Hg. The previous materials, SRMs 1598, 1577, and 1577b, were analyzed together with the new materials for quality control.     

Simultaneous on-line preconcentration and determination of trace metals in environmental samples by flow injection combined with inductively coupled plasma mass spectrometry using a nanometer-sized alumina packed micro-column

A flow injection (FI) on-line preconcentration procedure by using a nanometer-sized alumina packed micro-column coupled to inductively coupled plasma mass spectrometry (ICP-MS) was described for simultaneous determination of trace metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in the environmental samples. The effects of pH value, sample flow rate, preconcentration time, and interfering ions on the preconcentration of analytes have been investigated. Under the optimized operating conditions, the adsorption capacity of the nanometer-sized alumina for V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb were found to be 11.7, 13.6, 15.7, 9.5, 12.2, 13.3, 17.1, 17.7 and 17.5 mg g⁻¹, respectively. With 60 s preconcentration time and 60 s elution time, an enrichment factor of 5 and the sampling frequency of 15 h⁻¹ were obtained. The proposed method has been applied to the determination of trace metals in environmental certified reference materials and natural water samples with satisfactory results.     

Preparation and homogeneity characterization of ten agricultural/food reference materials for elemental composition

Summary Ten agricultural/food reference materials (RM): bovine muscle powder, corn starch, hard red spring wheat flour, soft winter wheat flour, whole milk powder, wheat gluten, corn bran, Durum wheat flour, whole egg powder and microcystalline cellulose, were prepared by milling, irradiation, sieving, blending and packaging procedures. Homogeneity tests for 14 elements in randomly selected units were performed by the initiating laboratories by application of various analytical methods. Al, Ca, Cu, Fe, K, Mg, Mn, Na, Sr and Zn were determined by acid digestion flame atomic absorption spectrometry, and Cd, Co, Ni and Pb using acid digestion graphite furnace atomic absorption spectrometry after separation/preconcentration of the analytes by co-precipitation. In addition, the extensive set of analytical results obtained from the interlaboratory cooperative characterization campaign was assessed to provide homogeneity estimates for other elements. Measures of homogeneity were estimated from the within-laboratory precision from the more precise laboratories. All materials exhibited acceptable homogeneity for virtually all 29 elements (Al, As, B, Ba, Br, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg, I, K, Mg, Mn, Mo, N, Na, Ni, P, Pb, Rb, S, Se, Sr, V, Zn) for which best estimate concentration values were available, an essential pre-requisite in establishing reference values for these materials. Sixty-two percent of all homogeneity coefficients of variation (CV) were below 5%, with Br, Ca, Cl, Mg, Na, P, Zn and especially K and N exhibiting very high homogeneity CV less than 1% in some cases.Contribution no. 92–148 from Centre for Land and Biological Resources Research     

Analysis of marine biological certified reference material by various non-destructive neutron activation methods

By the use of non-destructive neutron activation analysis (NAA) twenty-four trace (Ag, As, Br, Cd, Ce, Cr, Co, Cu, Eu, Fe, Hf, I, La, Mn, Ni, Rb, Sb, Sc, Se, Sm, Sr, U, V and Zn) and six minor (Ca, Cl, Mg, K, Na and S) elements were determined in a certified marine tissue standard reference material. Four non-destructive methods including thermal, epi-thermal, prompt-gamma ray and delayed neutron counting activation analyses were performed. Results when compared to the certified values showed the reliability of employing these methods in such standards program.     

Certification of the contents of some heavy metals (Cd, Cu, Hg, Ni, Pb and Zn) in three types of soils

Summary The element contents of Cd, Cu, Hg, Ni, Pb and Zn of three types of soil were certified. The preparation, homogeneity and stability are reported. The certified contents as well as values for Co, Cr, Mn and Se and for the aqua regia soluble contents Cd, Cr, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Cu, Hg, Ni, Pb und Zn) in drei Bodenproben

Zusammenfassung In drei verschiedenen Bodenproben wurden die Elementgehalte an Cd, Cu, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Bereitung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt an Cr, Co, Mn und Se und der Gehalt an königswasserlöslichem Cd, Cr, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Certified reference materials—Hay Powder (CRM 129) and Rye Grass (CRM 281)—for the quality control of analysis of animal feed

Analyses of nutritive elements are routinely performed in grass or hay for animal feed in order to improve the state of health and growth of domestic animals. To control the quality of such determinations, the Community Bureau of Reference (BCR) so far has produced two certified reference materials: Hay Powder (CRM 129) and Rye Grass (CRM 281). After a careful preparation procedure of the materials, a homogeneity study and a long-term stability study, the contents of the elements Ca, K, Mg, P, S, Zn, I, N and Kjeldahl-N were certified in CRM 129, whereas CRM 281 was certified for As, B, Cd, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se and Zn. This paper presents the certification exercise and especially concentrates on the elements I, B and Mo as examples of analytical work. Indicative values for Co, Cr, Fe, Cl and Na were also obtained.