J.G. Sen Gupta

Determination of yttrium and rare-earth elements in rocks by graphite-furnace atomic-absorption spectrometry☆

With use of synthetic solutions and several international standard reference materials a method has been developed for determining traces of Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in rocks by electrothermal atomization in a pyrolytically-coated graphite furnace. Depending on the element, the sensitivity is of the order of 10(-9)-10(-12) g at 2500 degrees . To avoid matrix interferences the lanthanides are separated from the common elements by co-precipitation with calcium and iron as carriers. The data for Canadian reference rock SY-2 (syenite), U.S.G.S. reference rocks W-2 (diabase), DNC-1 (diabase) and BIR-1 (basalt), and South African reference rock NIM-18/69 (carbonatite) obtained by graphite-furnace atomization are compared with the values obtained by flame atomic-absorption. The results are in good agreement with literature values.

Determination of trace and ultra-trace amounts of noble metals in geological and related materials by graphite-furnace atomic-absorption spectrometry after separation by ion-exchange or co-precipitation with tellurium

Two methods for determining mug/g and ng/g levels of the noble metals, except for osmium, in ores, concentrates, mattes, and silicate and iron-formation rocks are described. After sample decomposition with hydrofluoric acid and aqua regia, followed by fusion of any insoluble residue with sodium peroxide, the noble metals are separated from the matrix elements by either cation-exchange or co-precipitation with tellurium. The resulting eluate, or the solution obtained after dissolution of the tellurium precipitate, is evaporated to dryness and the noble metals are ultimately determined in a 1M hydrochloric acid medium by graphite-furnace atomic-absorption spectrometry. The ion-exchange method is recommended for the determination of mug/g levels of gold, silver and platinum-group elements, whilst the tellurium co-precipitation method is recommended for ng/g levels of platinum-group elements. The latter method is not recommended for the determination of ng/g levels of silver and gold in rocks, because of interference from tellurium during atomization in the furnace. Results obtained by these methods for 15 international reference samples, including four Canadian iron-formation rocks, are compared with other published data.

Direct determination of traces of Ag, Cd, Pb, Bi, Cr, Mn, Co, Ni, Li, Be, Cu and Sb in environmental waters and geological materials by simultaneous multi-element graphite furnace atomic absorption spectrometry with Zeeman-effect background correction☆

A method was developed for direct determination of minor and trace amounts of Cr, Mn, Cu, Ni, Co, Li, Pb, Cd, Bi, Sb, Be and Ag in silicate rock, lake and stream sediments using a microwave oven dissolution method and a multi-element graphite furnace atomic absorption spectrometer equipped with a Zeeman-effect background correction device. The measurement technique was also suitable for direct determination of trace and ultra-trace amounts of these elements in drinking and seawater samples. A rock or sediment sample was brought into solution in a Teflon vessel by heating in a microwave oven with a mixture of hydrofluoric acid and aqua regia, followed by a further heating with a mixture of boric acid and ethylenediaminetetraacetic acid. The specified elements were directly determined in a group of four elements in one firing and eight elements in two firings from this solution or from a diluted solution using the optimum operating parameters developed in this work. The method, tested with 23 international reference rocks and sediments and seven international quality control and reference water samples, showed good to excellent agreement with the recommended values.

Determination of lanthanides and yttrium in rocks and minerals by atomic-absorption and flame-emission spectrometry

Abstract The sensitivity of atomic-absorption and flame-emission determination of lanthanides and yttrium is improved by a factor of 2–5 when an absolute ethanol solution of the perchlorate of the metal (instead of an aqueous solution) is aspirated into a nitrous oxide-acetylene flame. Based on this, a method has been developed for accurate determination of small amounts of certain rare earths and yttrium. Lanthanum (1%) is used as a spectroscopic buffer to eliminate interferences and to enhance the sensitivities in certain determinations. Where the use of lanthanum is not practicable because of interferences (such as in the determination of praseodymium and samarium by flame emission), sodium (2000 ppm) is used as the spectroscopic buffer. Studies with synthetic solutions indicate that yttrium and most lanthanides can be directly determined in minerals without any chemical separation. With rock samples it is necessary to preconcentrate the traces of the rare earths by fluoride or oxalate precipitation with calcium as the carrier, followed by removal of calcium by hydroxide precipitation using mg amounts of iron as the carrier. The method developed has been applied to the determination of certain lanthanides and yttrium in a variety of rocks, including the Canadian reference rocks, syenites SY-1, SY-2 and SY-3, and some minerals such as britholite, cenosite, chevkinite, allanite, apatite and sphene.

Determination of scandium, yttrium and lanthanides in silicate rocks and four new canadian iron-formation reference materials by flame atomic-absorption spectrometry with microsample injection.

Enhancement of sensitivity by factors of up to 1.5 by use of the microsampling technique, coupled with the advantage of using small samples in small solution volumes, permits rapid flame AAS determination of traces of Sc, Y, Nd, Eu, Dy, Ho, Er, Tm and Yb in ultramafic and most other rocks of low rare-earth content, which would be either impossible or very difficult to analyse by direct aspiration because of the need for much larger sample weights and solution volumes. The rare-earths are separated by a modified ion-exchange or a double calcium oxalate and single hydrous ferric oxide co-precipitation procedure, and ultimately determined in an ethanolic perchlorate solution, buffered with 1% lanthanum, by the flame microsample injection technique, with a nitrous oxide-acetylene flame. The results obtained by this technique for six international reference rocks SY-2 (syenite), BCR-1 (basalt), BHVO-1 (Hawaiian basalt), SCo-1 (cody shale), MAG-1 (marine mud) and STM-1 (syenite) are compared with those obtained previously by the direct aspiration method and with other reported data. Results are given for four new Canadian iron formation reference materials FeR-1 to FeR-4.

Determination of noble metals in silicate rocks, ores and metallurgical samples by simultaneous multi-element graphite furnace atomic absorption spectrometry with Zeeman background correction☆

A new method has been developed for rapid determination of mug/g and ng/g amounts of noble metals in silicate rocks, ores and metallurgical samples by attacking with hydrofluoric acid and aqua regia, preconcentration by ion-exchange chromatography and measuring in a simultaneous multi-element graphite furnace atomic absorption spectrometer equipped with a polarized Zeeman background correction device which eliminated interferences from any incompletely separated common elements. The method was tested for Ru, Rh, Pt, Ir, Pd, Ag and Au with three Canadian certified reference materials, and then applied to the determination of ng/g amounts of these elements in four new Canadian candidate reference materials.

Determination of fluorine in silicate and phosphate rocks, micas and stony meteorites

Abstract By making certain modifications to a published procedure for fluorine in rocks, it has been possible to improve stability and extend the range of the method. The modified method has been successfully applied to silicate and phosphate rocks, micas, glass and stony meteorites, containing from 60 p.p.m. to 8% fluorine. Some precautions are recommended for reliable determination of chlorine.

Determination of the rare earths, yttrium and scandium in silicate rocks and four new geological reference materials by electrothermal atomization from graphite and tantalum surfaces

Abstract An improved graphite furnace atomic-absorption method has been developed for the determination of Sc, Y and the rare-earth elements in silicate rocks and related materials. The method, which involves the separation of the lanthanides by ion-exchange followed by their determination by electrothermal atomization, with use of an automatic sampling device, is more rapid than a previous method based on separation by co-precipitation with calcium oxalate and hydrous ferric oxide followed by normal injection of the solution into the furnace. Greater sensitivity (~ 10–40-fold) for La, Ce, Pr, Gd, Tb and Lu is also achieved by using a tantalum foil-lined graphite furnace instead of a pyrolytically-coated furnace. Results obtained for five international reference rock samples, NIM-G, SCo-1, MAG-1, SDC-1 and BHVO-1, are compared with those obtained previously by the oxalate-hydrous oxide co-precipitation method and with other published values. Results are given for four new Canadian iron-formation reference materials, FeR-1 to FeR-4.

The determination of noble and base metals in osmiridium, native platinum and sperrylite by atomic absorption spectrophotometry

Abstract Atomic absorption spectrophotometric methods for determining the noble and base metals in osmiridium, native platinum and sperrylite have been developed and applied to the analysis of some naturally occurring samples. The sample is decomposed by dry chlorination at 700° in the presence of sodium chloride, or by treatment with aqua regia (native platinum) or Br 2 -KBr (sperrylite) followed by dry chlorination of the insoluble residue. Osmium and ruthenium are separated by distillation with perchloric acid and collected in hydrobromic acid. From different aliquots the noble metals are determined in the presence of 0.5% Cu–0.5% Cd buffer and the base metals in the presence of 1% lanthanum or strontium buffer.

Determination of cerium in silicate rocks by electrothermal atomization in a furnace lined with tantalum foil: Application to 19 international geological reference materials

A 40-fold increase in sensitivity obtained by using a tantalum foil lining in a pyrolytically-coated graphite furnace permitted determination of low ppm levels of cerium in most silicate rocks. A preliminary preconcentration by oxalate and hydroxide co-precipitations was used before determination by use of a Varian GTA-95 atomizer coupled with an AA-475 spectrometer. The results for 3 synthetic and 19 international reference materials, including 4 new Canadian iron-formation reference materials, showed good recovery and satisfactory agreement with other published values.