INAA of toxic elements in coal and their transfer into environments

An instrumental neutron activation analytical (INAA) technique is described for the determination of 26 toxic and other trace elements in Eastern Coal (NBS SRM-1632a), local coal and its ash. The coal ash was produced by heating coal at 750°C in a muffled furnace. The transfer of these elements to the environment on the complete compustion of coal is estimated from the difference between the elemental concentration of coal and its ash.     

New Data on Sixteen Reference Materials Obtained by INAA

We report instrumental neutron activation analysis results for 15 elements (K, Fe, Sc, Cr, Co, Zn, As, Rb, Sb, Cs, Ba, Hf, Ta, Th, and U) in 16 geochemical reference samples, namely SDC-1, SCo-1, SGR-1, STM-1, RGM-1, BIR-1, MAG-1 and BHVO-1 from USGS (United States Geological Survey, Reston), Soil-5, Soil-7 and SL-1 from IAEA (International Atomic Energy Agency, Vienna), and GSS-1, GSS-4, GSS-7, GSR-2 and GSR-3 from IGGE Institute of Geophysical and Geochemical Prospecting, People's Republic of China), The results are compared with literature values. In general our results agree well with recommended or proposed values.     

Application of the k0 standardization method in reactor nuetron activation analysis of standard steels and fly ash

The method of k₀ standardization is suitable for routine multi-element determinations by reactor neutron activation. Investigation of NBS steel standards showed the systematic error of the method to be less than 3%. Numerical evaluation of the spectra was found to be fast and convenient. Fourteen elements in the steel samples were determined; for nine, the standard deviation was less than 4%. Thirty seven elements were determined in NBS SRM-1663a Coal Fly Ash; agreement with certified values was again very good.     

Trace elemental composition of Nigerian coal measured by neutron activation analysis

The instrumental neutron activation analysis (INAA) technique has been used to determine 17 major, minor, and trace elements in samples of the three major sources of Nigerian coal. The NBS Standard Reference Material, Coal SRM 1632, was also analyzed, for the purpose of verifying the accuracy of the method. The results obtained with it were in good agreement with the NBS certified values. The concentrations of the major elements determined for the Nigerian coal were found to be much lower than the mean values of those reported for coal samples from other parts of the world.     

Multielement analysis of Chinese Biological Standard Reference Material by monostandard instrumental neutron activation analysis

A procedure for monostandard INAA of 21 elements (Hg, As, Br, Cr, Sb, Se, Ba, Zn, Ca, Ce, Co, Cs, Eu, Fe, Hf, K, La, Rb, Sc, Sr, Ta) in Chinese Biological Standard Reference Material (peach leaves) is described. The accuracy of the procedure was checked by analyzing the U.S. NBS Standard Reference Materials SRM-1571 and SRM-1632a.     

Determination of multielement in optical waveguide and standard reference materials by instrumental neutron activation analysis

Trace amounts of transition elements (Co, Cr, Cu, Fe, Mn and V) and other seven elements in optical waveguide samples were determined by INAA. The contents of impurities in ultra-pure materials are less than those of high-purity materials and of G.R. grade. The increase of contamination of trace transition elements and iridium from furnace or crucible are observed in the production of optical glass fibers. Up to seventeen elements were determined in five NBS biological standard reference materials: Oyster Tissue: SRM-1566, Brewers Yeast: SRM-1569, Spinach: SRM-1570, Orchard Leaves: SRM-1571 and Tuna Fish, and in four Japanese biological standard reference materials: Tea Leaves B&C, Pepperbush and Shark Meat. The analytical results in NBS and Japanese standard reference materials are in good agreement with published values and certified values by NBS.     

Simultaneous determination of sixteen major and minor elements in river sediments by energy-dispersive x-ray fluorescence spectrometry after fusion in lithium tetraborate glass

Fluvial sediments, including the NBS SRM-1645 Standard River Sediment, were fused in lithium tetraborate to form glass discs on which determinations of 16 elements (K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr and Pb) were obtained simultaneously at a single set of x-ray conditions by energy-dispersive x-ray fluorescence spectrometry (e.d.x.r.f.). Relatively high sample-to-flux ratios of 1:3 were employed to obtained determinations of several minor as well as major elements on a single disc. Lower sample concentrations 1:6 and 1:10 were also used with the NBS SRM-1645. Inter-element corrections for absorption by iron were significant for detectable elements heavier than iron. In the NBS SRM-1645 samples, corrections were made for the fluorescence of chromium by the Fe K lines as well as the absorption of the Fe K lines by chromium. A background correction was also necessary for manganese in NBS SRM-1645. At the lowest sample-to-flux ratio (1:10) good agreement was obtained between the e.d.x.r.f. determinations and the NBS values for all quantifiable elements except zinc. At higher sample-to-flux ratios, agreement with the NBS values was generally poorer with increasing sample concentration. The relative standard deviation (RSD) of the eight quantifiable major and minor elements (K, Ca, Ti, Mn, Fe, Zn, Sr and Zr) determined under a single set of x-ray conditions ranged from 2 to 9% (RSD) with a mean RSD of 4.4% for a set of replica discs fused with Lake Pueblo/Arkansas River sediment samples.     

Application of laser-excited atomic fluorescence spectrometry to the determination of iron

A frequency-doubled, flashlamp-pumped tunable dye laser is used to excite the Stokes direct-line atomic fluorescence transition of iron (296.7 nm/373.5 nm). Limits of detection are determined with single (0.6 ng/ml) and multipass (0.2 ng/ml) and with a l s time constant (a 0.06 ng/ml limit detection is obtained with an 8 s time constant). Noise sources limiting precision at both low (background flame emission shot and flicker noise) and high concentrations (laser pulse to pulse variability) concentrations are investigated and the technique is used for the determination of iron in simulated fresh water NBS SRM-1643), unalloyed copper (NBS SRM-394) and fly ash (NBS SRM-1633).     

Instrumental neutron activation analysis of trace elements in quartz

A scheme for INAA of 32 elements (As, Au, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Eu, Fe, Hf, Hg, Ir, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, W. Yb, Zn) in quartz glass is proposed. The accuracy of the procedure is evaluated by the analysis of two NBS standard reference materials (SRM-1571 and SRM-1632-a). The method is convenient for routine work. The method was used for the determination of impurities in laboratory quartz glass. Dedicated to the 60th birthday of acad. prof. g. bliznakov     

Geological reference materials for standardization and quality assurance of instrumental neutron activation analysis

Results are presented from the INAA of 34 elements in NIST and USGS geological reference materials that were analysed relative to multielemental SRM-1633a Coal Flyash standards. The data compare favorably with works reported by other investigators. The application of historical control charts for continuous monitoring of quality assurance and detection of systematic errors is demonstrated.     

Improvements in repetitive scanning techniques for reducing spectral interferences in flame emission spectrometry

This paper describes several improvements in the use of the repetitive optical scanning (wavelength modulation) technique applied to the correction for spectral interferences due to line, band, and continuum radiation in flame emission spectrometry (FES). A simple and easily constructed mechanical device for performing the repetitive scan is described, and the procedures for optimizing experimental conditions are discussed. A new technique for the correction for spectral line interferences is introduced. Repetitive scanning FES is used for the analysis of several trace elements in NBS SRM-1633 (fly ash), and the precision and accuracy of results are compared to analysis by normal flame emission techniques.     

Determination of 34 elements in Chinese geochemical standard reference materials by instrumental neutron activation analysis

Thirty four elements (Al, As, Ba, Br, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Gd, Hf, Ho, K, La, Lu, Mg, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, Ti, U, V, W, Yb) were determined by instrumental neutron activation analysis in the second set of Chinese geochemical standard reference materials (sediments from GSD-9 to GSD-12, soils from GSS-1 to GSS-8, rocks from GSR-1 to GSR-6) using both thermal and epithermal irradiations. Irradiation schemes designed to utilise short, medium and long-lived nuclides were employed in order to analyse major, minor and trace elements with different half-lives. The gamma-ray spectra were measured by Ge(Li) and HP(Ge) detectors. Relevant nuclear data and possible interferences are listed, and analytical results are presented and discussed.     

Homogeneity tests and certification analyses of coal fly ash reference materials by instrumental neutron activation analysis

The instrumental neutron activation analysis technique (INAA) was used for homogeneity tests and certification analyses of coal fly ash reference materials ENO, ECH, and EOP prepared at the Institute of Radioecology and Nuclear Techniques (IRANT), Koice, Czechoslovakia. Quantitative estimation of a degree of inhomogeneity was suggested. The relative standard deviations due to inhomogeneity were found to be <1% for macroconstituents and <3% for minor and trace elements for sample weights about 25 mg. The results of determination of the elements Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, In, K, La, Mn, Na, Nd, Ni, Rb, Sb, Sc, Sm, Sr, Ta, Th, Ti, U, V, W, and Zn were compared with the IRANT certified or information values. NBS SRM 1633a Trace Elements in Coal Fly Ash was also analyzed as a control sample and the results for the above elements were compared with the NBS certified, information or literature available values. From these comparisons, inference was made on the quality of the IRANT specified values for the element contents.     

Substoichiometric extraction of chromium

Substoichiometric extraction of chromium with tetraphenylarsonium chloride (TPACl), tri-n-octylamine (TNOA), diethylammonium diethyldithiocarbamate (DDDC) and ammonium pyrrolidinedithiocarbamate (APDC) was examined in detail. Chromium can be extracted substoichiometrically in a pH range, which is 1.1–2.6 for the TPACl compound, 0.6–2.3 for the TNOA compound, 5.1–6.4 for the DDCC chelate and 3.9–4.9 for the APDC chelate. Chromium in high-purity calcium carbonate, Orchard Leaves (NBS SRM-1571) and Brewers Yeast (NBS SRM-1569) was determined by neutron activation analysis combined with substoichiometric extraction by DDDC and APDC. The values of 2.0±0.02 ppm and 2.6±0.2 ppm were obtained for Brewers Yeast and Orchard Leaves, respectively. These values were in good agreement with the values reported by NBS. The reaction mechanism and the reaction ratio between hexavalent chromium and dithiocarbamate were also discussed.     

Development of an accurate,sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine,sulfur, and heavy metals) in coal samples

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for ³⁵Cl⁺ to more than 6 × 10⁵ cps for ²³⁸U⁺ for 1 μg of trace element per gram of coal sample. Detection limits vary from 450 ng g⁻¹ for chlorine and 18 ng g⁻¹ for sulfur to 9.5 pg g⁻¹ for mercury and 0.3 pg g⁻¹ for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis. Figure LA-ICP-IDMS allows direct multi-element determination in powdered coal samples     

Determination of Fluorine in NBS Coal and Coal Fly Ash by Proton Induced Gamma Ray Emission and Spark Source Mass Spectrometry

Abstract

Fluorine concentrations in US National Bureau of Standards standard reference materials 1632a (coal) and 1633a (coal fly ash) have been determined by proton induced gamma ray emission (PIGME) and spark source mass spectrometry (SSMS) using the method of standard additions. Good agreement was obtained between the two techniques with no significant bias. The mean values for 1632a and 1633a were ± 18 mg kg^?1 and 109 ± 11 mg kg^?1 respectively.     

Determination of selenium with solid sampling and direct Zeeman-AAS

Summary It is demonstrated by analysis of four standard reference materials (NBS 1632 a coal, NBS 1633 a coal fly ash, NBS 1648 urban particulate matter and BCR 176 city waste incineration ash) that the selenium determination by Solid Sampling ZAAS works well, if fine grained elemental nickel is used as matrix modifier. Optimum nickel-to-sample ratios are in the range of 21 to 81. Admixture of graphite powder is necessary in some cases in addition. The detection limit is about 0.1 g/g. If the matrix is well-known, the described method is a convenient and fast alternative to conventional trace analytical techniques.

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Selenbestimmung aus festen Proben mit direkter Zeeman-AASTeil 1

Zusammenfassung Durch die Analyse von vier Standardreferenzmaterialien (NBS 1632 a Kohle, NBS 1633 a Kohleflugasche, NBS 1648 Stadtstaub und BCR 176 Stadtmüllverbrennungsasche) wird gezeigt, daß die Selenbestimmung mittels Feststoff-ZAAS zu guten Ergebnissen führt, wenn feinkörniges elementares Nickelpulver als Matrixmodifizierer eingesetzt wird. In der Regel ist ein zwei- bis achtfacher Nickelüberschuß erforderlich, ggf. auch eine Beimischung von Graphitpulver. Die Nachweisgrenze des Verfahrens liegt bei etwa 0,1 g/g. Bei gut bekannter Matrix ist die beschriebene Methode eine bequeme und schnelle Alternative zu konventionellen spurenanalytischen Techniken.

     

A comparison of two separation techniques using NaI(Tl) and Ge(Li) spectrometry for trace element determination in biological materials by neutron activation analysis

A comparison of two group separation techniques using either NaI(Tl) or Ge(Li) spectrometry is presented for trace element determination in biological materials by neutron activation analysis. The capabilities of both procedures are described in terms of detection limits, precision and accuracy for the determination of the elements As, Cd, Co, Cr, Cu, Fe, Hg, Mo, Ni, Sb, Se, Sn, and Zn in various types of biological samples. For this purpose the (standard) reference materials NBS SRM-1577 Bovine Liver, Bowen's Kale, IAEA Pig Kidney H-7 and IAEA Milk Powder A-11 were analyzed. An attempt was also made to minimize blank values for several elements.     

Stripping voltammetry of tellurium(IV) in 0.1 M perchloric acid at rotating gold disk electrodes

The stripping voltammetry ofteIlurium(IV) in 0.1 M perchloric acid at gold electrodes is described. Detection limits for solid gold, in situ gold-plated and externally gold-plated rotating glassy carbon disk electrodes are presented. There is no significant increase in sensitivity for the use of solid gold electrodes; 0-25 ppm teIIurium(IV) can be determined by anodic stripping voltammetry at an in situ gold-plated rotating glassy carbon disk electrode. The determination of tellurium in NBS SRM 1632a (Trace Elements in Coal) is described.     

Determination of Essential Elements in Ayurvedic Medicinal Leaves by k0 Standardized Instrumental Neutron Activation Analysis

Elemental concentrations of a few medicinal leaves are determined by instrumental neutron activation analysis using the single comparator (k ₀) method. Data obtained for neem leaves, collected from two different places, have been used to see the effect of soil condition. The applicability of the method particularly for the simultaneous determination of Ca, Mg, V and Al in biological matrices has been evaluated in terms of the detection limit, precision and accuracy. The method was validated by analysing the NIST Standard Reference Material (SRM-1571) and it was found that the elemental concentrations measured in SRM-1571 are within ±10% of the reported values.