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By I. Ruiz Bustinza, L. F. Verdeja, Daniel Sbarbaro, R. Parra, J. Mochón

The oxidation of sulfides is a complex process involving gaseous products and intermediate species given rise to emission and absorption spectra which carry out important information about the reaction process. This information could be used for on line monitoring of pyrometallurgical reactor if the appropriate sensors were available. We present in this paper an analysis of the concept that has been successfully applied in iron and steel making industry, as well on fuel combustion control, where the spectra measurement gives the possibility for online monitoring and automatic control of high temperature processes. This concept has not been widely applied in the nonferrous pyrometallurgical primary production. The design of new sensors is discussed from the analysis of spectra measurements during flash combustion of copper concentrates at laboratory scale.

Jan 1, 2015

By Ronald W. Marrs

Kimberlite contains a unique assemblage of minerals and exhibits a characteristic pattern of spectral reflectance in the visible and near-infrared wavelength region. This spectral pattern is readily discerned in well-exposed kimberlite outcrops, but becomes increasingly difficult to identify when outcrops are partially covered by vegetation or soils derived from non-kiaberlitic materials. Detection of poorly exposed kimberlite diatremes is possible using multispectral imaging techniques in which spectral bands are chosen to optimize contrast between he kimberlitic soils, non-kimberlitic soils and vegetation. Careful processing of the multi-spectral data is also essential in order to separate the spectral signature of kimberlite from the signatures of other components of the scene.

Jan 1, 1984

By Lifeng Li, Jhon Silva-Castro

"Signature Hole Technique is one method to assess the vibration waveform of a production blast.Methematically, it is the convolution between a prior measured waveform of a single blast hole (signature) and a given time delay sequence (comb function). Being an advantage, the inverse operation of convolution, known as deconvolution, can be used to estimate the signature."

Jan 1, 2017

By J. N. Baloyi

"In atomic emission and atomic absorption spectrophotometry, the sample is heated to a high temperature and thereby decomposed into atoms and ions that absorb or emit visible or ultraviolet electromagnetic radiation at energies characteristic of the elements involved. The flame test is a very simple form of this technique. The yellowing of a flame by the addition of salt, for example, occurs because the sodium in salt emits strongly in the yellow portion of the visible spectrum. These methods are especially useful for low concentrations of metallic elements in both qualitative and quantitative analysis.Interference on Iep-OES has not always been considered a serious problem, especially in the beginning, when compared with Atomic Absorption Spectroscopy. This was due to the euphoria created by the new technique. It meant that criticism was subdued. The Iep was vastly superior to the Atomic Absorption technique, that the interferences suffered by the Atomic Absorption technique dwarfed the little interferences suffered by the rep-OES technique. This is how rep-OES has had a reputation as an interference free technique."

Jan 1, 2014

By E. F. Paski

Geological materials are likely the most complex and challenging substances to quantitate by ICPOES (inductively coupled plasma optical emission spectroscopy). For complex materials having widely varying compositions, spectral overlap interferences govern detection and quantitation limits attained by ICPOES based analytical methods.

Jan 1, 1993

By P. Kolettas

The development of novel methods for the investigation of the subsoil contributes to the improvement of geotechnical research, enhances the obtained geotechnical characterization and may reduce the investigation cost by reducing the number of required tests. Non-destructive testing methods, performed either in situ (i.e. electrical tomography, seismic refraction, etc) or in the laboratory can provide initial data and perhaps estimates of rock/soil properties. This study focuses on the development of rock material properties and/or characteristics based on non-destructive laboratory testing of a number of stones, ranging from porous (bioclastic) limestones to impervious marbles. Seismic velocity measurements as well as attenuation signals were digitally recorded using a digital oscilloscope. Data were processed using a novel technique of spectral analysis available through special Matlab packages employing Fourier transform methods. More specifically, the NFFT (Non Equispaced Fourier Transform) transformation was applied to seismic waves traveling through the subsoil using the Autosignal program (by Seasolve) and the Specgramdemo program included in the Signal Analysis toolbox of Matlab 6.5 (Mathworks). Results indicate a definite relationship between the frequency content of the signal and the rock type as well as the degree of saturation of the specimen.

Jan 1, 2008

By J. E. Hawley

Abstract Spectrographic methods for the analysis of minor constituents such as platinum-group metals, gold, silver, and silica in palladium and platinum refinery sponge are described. These involve the conversion of the sponge metals to the black form by reduction with high purity aluminum filings in either acid or alkaline media. Standards of known composition are prepared in the same manner from either refinery or spectrographically standardized sponge metals. Samples of the black metals are mounted in pellet form and a multisource spark discharge used for excitation. The range of concentrations of impurities studied are those common to refinery samples. Excellent reproducibility of intensity ratios using major constituents as internal standards, is demonstrated and two methods have noted by which the accuracy of the procedures are shown to be of the order of 3 per cent, on the basis of synthetic preparations. Introduction During the past two years an investigation has been carried out in the Spectrographic Laboratory, Queen's University, to determine the suitability of modern spectrographic techniques for the precise analysis of the platinum-group metals palladium, platinum, rhodium, iridium, and ruthenium in the form of refinery sponge analyzing about 99 per cent of the major constituent.

Jan 1, 1951

By W. L. Ott, C. L. Lewis

"AbstractA technique is described for preparation of palladium sponge and for spectrochemical analysis of the metal in this form. The precision and accuracy of the method are discussed. Analyses are compared with previous spectrochemical analyses of palladium in the black form. Good agreement was found in the two sets •of results and it is concluded that they are more reliable than wet chemical .analyses of the same material.IntroductionFOR SEVERAL YEARS the problem of platinum metal analysis by spectrochemical methods has been under investigation at the Spedtrographic Laboratory, Department of Geological Sciences, Queen's University. The problem, briefly -stated, is as follows: Samples of platinum, palladium,-rhodium, ruthenium, and iridium are received as fine metal powders, called sponge. Direct spectrographic analysis of this material has not been found satisfactory due to its heterogeneity •as regards contaminant metals, which may be present up to a total of one per •cent or more. Further-more, spectrographic standards are difficult to obtain and difficult to prepare accurately by adding weighed portions of contaminant metals to the sponge. The fact that •contaminant metals in original samples are probably alloyed with the major constituent is a further difficulty since complete fusion of these refractory metals proved impractical in the present case as a means of standard preparation. It •has, therefore, been found most satisfactory to dissolve the metals, prepare standards by addition of solutions of contaminant metals, and to reduce both standards and samples to a homogeneous form. A previous paper, by Hawley, Wark, Lewis and Ott (2) dealt with a method for spectrochemical analysis of platinum and palladium in their black form. Since completion of research on the black technique, the possibility of analyzing palladium accurately in its sponge form has• been investigated."

Jan 1, 1953

By W. L. Ott, J. E. Hawley, C. L. Lewis

"IntroductionTHE APPLICATION of spectrochemical analysis to metals of the platinum group was advocated by Harvey (3) as follows: ""The spectra of the platinum group metals have been studied less than many of the more common metals. The rarity of occurrence of these elements makes the analysis relatively unusual. Potentially, the analysis of this group is an excellent application of spectrographic methods, particularly in contrast to the tedious chemical procedure"".Wichers (8) divides platinum-metal analysis into three broad divisions as follows :( 1) The detection and estimation of these metals in other materials, e.g., ores, where the amounts present are very small.(2) The detection and estimation of impurities in the refined metals themselves ....(3) The analysis of alloys of the platinum metals .....The present paper deals with the second division: analysis of refined rhodium.Research on spectrochemical techniques for determination of trace contaminants in refined platinum metals was begun at Queen's University in 1949, under the supervision of Professor J. E. Hawley. Since 1953, the work has been continued in the Metallurgical Laboratories of Falconbridge Nickel Mines, Limited. Techniques for spectrochemical analysis of refined platinum and palladium have been published ( 4, 5). A technique for analysis of refined iridium has been developed but not yet published."

Jan 1, 1955

By A. G. Scobie

THE research laboratory of this Company was recently faced with the problem of determining trace amounts of tungsten in a series of classifier sands. A spectrographie survey revealed the feasibility of using this instrument in the final evaluation, but a check of the common methods in use for the isolation of tungsten (3, 4) showed these methods to give incomplete separation for trace amounts. An investigation into the possibility of modifying these procedures, or developing others, was thus indicated. ASSAY PROCEDURE Weigh 10 grams of 200-mesh ore or concentrate into a 400-ml. beaker, wet the sample well with about 20 ml. of water, and add 100 ml. of hydrochloric acid. Cover, digest at 60° to 70° C. for about 1 hour, and then boil down to approximately 25 ml. Cool, add 25 ml. of hydrochloric acid and 10 ml. of nitric acid, and again boil to former volume. Add 20-ml. portions of nitric acid with successive boiling clown until chemical action is complete. Then add 20-ml. portions of hydrochloric acid until all nitric acid is removed. Take nearly to dryness on a law-temperature hot plate, but do not bake. Take up in 10 ml. of hydrochloric acid and 20 ml. of water and heat on a law-temperature hot plate until all iron goes into solution. Dilute to 200 ml. and heat to just below boiling. Stir in pulp of about half of a No. 41 Whatman filter paper (12.5-cm.) and continue digestion on plate with occasional stirring for 15 to 20 minutes.

Jan 1, 1943

By Paul Giesecke

SINCE most modem metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. PRINCIPLES OF SPECTROCHEMICAL ANALYSIS In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1944

Spectroelectrochemical Investigation of Hydroxamate Reagents on Copper Oxide Minerals

Sep 13, 2010

By K M. Watling, F M, G K. Parker

Surface enhanced Raman scattering (SERS) spectroscopy at surfaces under electrochemical control has been applied to elucidate the adsorption of thiol collectors. SERS spectroelectrochemical studies at coinage metal electrodes have been carried out on ethyl xanthate and three iso-xanthates, O-isopropyl-N-ethylthionocarbamate, 2-mercaptobenzothiazole, diisobutyl- dithiophosphinate and butylethoxycarbonylthioura. For each collector, adsorption occurs via charge transfer to form a metal-sulfur bond and, in situations for which the reversible potential of the formation of the bulk phase is known, at underpotentials.

Jan 1, 2005

By R. N. Gow

The presence of enargite (Cu3AsS4) is problematic in gold processing because it is environmentally hazardous due to its arsenic content but also because it is double refractory causing both cyanide and oxygen consumption to increase. Selective leaching and treatment of the arsenic would prove advantageous prior to applying conventional gold leaching methods. The reactivity of enargite samples from Butte, Montana and Quiruvilca, Peru were spectroelectrochemically studied under alkaline conditions, pH range of 8-13, using Raman spectroscopy and cyclic voltammetry. Raman spectra of the surface were collected during and after voltammograms were potentially cycled in order to determine and compare surface species against theoretical EH-pH diagrams determined from mass-balanced thermodynamic calculations using StabCal software. Under slightly oxidizing conditions, covellite (CuS) peaks were found in a short matter of time, above ~100mV vs SHE for pH 9-13, suggesting arsenic leaching specifically occurred. At longer conditioning times, elemental sulfur was observed and tended to passivate the surface. The presence of sulfur suggests that copper was eventually leached. By operating above pH 12, under slightly reducing conditions near -300mV vs SHE, arsenic can be selectively leached as thioarsenate (AsS43-) or thiosulfate (AsO43-) without sulfur formation.

Feb 27, 2013

By H. Huang, Y. Takasaki, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing not only because it is environmentally hazardous due to its arsenic content but also because it is refractory, causing both cyanide and oxygen consumption to increase. Selective leaching and treatment of the arsenic would prove advantageous prior to applying conventional gold leaching methods. The reactivity of enargite samples from Butte in Montana and Quiruvilca in Peru were spectroelectrochemically studied under alkaline conditions – pH range of 8-13 – using Raman spectroscopy and cyclic voltammetry. Raman spectra of the surface were collected during and after potentially cycled voltammograms in order to determine and compare surface species against theoretical EH-pH diagrams constructed from mass-balanced thermodynamic calculations using STABCAL software. Under slightly oxidizing conditions, covellite (CuS) peaks were found in a short matter of time, above ~100mV vs. SHE for pH 9-13, suggesting arsenic leaching specifically occurred. At longer conditioning times, elemental sulfur was observed and tended to passivate the surface. The presence of elemental sulfur suggests that copper was eventually leached from the surface. By operating above pH 12, under slightly reducing conditions near -300mV vs. SHE, arsenic can be selectively leached as thioarsenate (AsS4 3-) or thiosulfate (AsO4 3-) without sulfur formation.IntroductionEnvironmental limitations on the pyrometallurgical processing of ores and concentrates bearing arsenic and other hazardous elements often outweigh those in hydrometallurgical processing, particularly when minerals like enargite (Cu3AsS4) are present. The hydrometallurgical processing of enargite-bearing materials can be broken down into two categories: the co-dissolution of arsenic and copper under acidic conditions, and the selective leaching of arsenic under alkaline conditions. The selective leaching of arsenic would preferably leave behind copperrich sulfide phases, typically chalcocite (Cu2S) and covellite (CuS), which then become more amenable to conventional copper (and gold) processing. Furthermore, selective leaching often employs sulfide (S2-), bisulfide (HS-) or polysulfides (Sx 2-) to first extract the arsenic as AsS4 3- and AsS3 3- (Delfini et al., 2003; Anderson and Twidwell, 2008; Tongamp et al., 2010a,b). However, hypochlorite leaching (Viñals et al., 2003; Curreli et al., 2005; Mihajlovic et al., 2007), ammoniacal leaching (Gajam and Raghavan, 1983), and finegrinding to mechanically activate the enargite surface (Balaz and Achimovicova, 2006) have been investigated to increase the normally slow reaction kinetics. Because gold ores are becoming more refractory due to increasing arsenic contents as a result of enargite, these methods are being examined more closely by the gold-mining industry."

Jan 1, 2015

By H. Huang, R. N. Gow

Acidic treatment of enargite (Cu3AsS4) dissolves both arsenic and copper from the mineral and then attempts to separate them in the leach solution. The reactivity of enargite was examined in acidic to neutral solutions, over the pH range 1-7, to determine a potential range for co-dissolution. Enargite mineral samples from Butte, MT and Quirivilca, Peru were used as working electrodes in a cyclic voltammetry corrosion cell setup, which were then cycled multiple times over -1000 to 1000 mV. Surface reactions and transitions were characterized using in-situ Raman spectroscopy, which were then compared to updated EH-pH diagrams for the copper-arsenic-sulfur-water system from a previous study done under alkaline conditions. The region of co-dissolution is limited to > 600 mV vs. SHE and pH < 1 under the proposed diagram.

Jan 1, 2014

By R. N. Gow

Acidic treatment of enargite (Cu3AsS4) dissolves both arsenic and copper from the mineral and then attempts to separate them in the leach solution. The reactivity of enargite was examined in acidic solutions, over the pH range 1-7, to determine a potential range for co-dissolution.. Enargite mineral samples from Butte, MT and Quirivilca, Peru were used as working electrodes in a cyclic voltammetry corrosion cell setup, which were then cycled multiple times over -1000 to 1000 mV. Surface reactions and transitions were characterized using in-situ Raman spectroscopy, which were then compared to updated predominance diagrams for the copper-arsenic-sulfur system from a previous study done under alkaline conditions. The region of co-dissolution is limited to > 600 mV vs. SHE and pH < 1 under the proposed diagram.

Feb 23, 2014

By H. Huang, R. N. Gow

"The reactivity of an enargite mineral electrode was investigated spectroelectrochemically under conditions typically found in alkaline sulfide leach solutions, with pH 11-13 and Na2S additions of 50 and 250 gL-1. A bulk enargite electrode was cycled between 0 and -1,000 mV for each set of solution conditions. Raman spectroscopy was used to determine and compare surface formations against species in mass-balanced EH-pH diagrams generated using STABCAL. Previously, it was determined that arsenic could be selectively leached under alkaline conditions at an average solution potential of -300mV, across the pH range 11-13. Operating under such conditions allowed for the selective leaching of arsenic with elemental sulfur formation. From several of the voltammograms obtained during this current testing, the formation of elemental sulfur appeared at increasingly reducing conditions with increasing sulfide concentration. At high concentrations, copper started to dissolve, possibly as a bisulfide complex, reducing the selectivity of the leach, unlike previous studies. However, the presence of the higher sulfide concentration is also anticipated to prevent passivation by consuming any surface formation of elemental sulfur. This study provides insight into the operating parameters of alkaline sulfide leaching in regards to the selectivity of arsenic leaching, as well as guidance for control of reagents and solution potential and, of course, the need for water treatment afterwards.IntroductionEnvironmental limitations on the pyrometallurgical processing of arsenic-bearing concentrates have forced operations to consider other solutions. Attempts to hydrometallurgically process enargite (Cu3AsS4) fall into two categories: the co-dissolution of arsenic and copper under acidic conditions, and the selective leaching of arsenic under basic conditions. The authors believe that the selective leaching of arsenic is more amenable because it produces a solid copper phase, preferably chalcocite (Cu2S) or covellite (CuS) that could then be processed using conventional methods already in place in the copper and gold industries. Potential leaching methods include alkaline sulfide leaching (Achimovicovica et al., 1999; Anderson and Twidwell, 2008a,b; Tongamp et al., 2009 and 2010), hypochlorite leaching (Vinals et al., 2003; Curreli et al., 2005; Mihaljovic et al., 2007), ammoniacal leaching (Gajam and Raghavan, 1983), and acid leaching (Gow et al., 2014b) with or without fine grinding to mechanically activate the enargite surface and increase normally slow leach reaction kinetics (Achimovicova et al., 1999; Balaz et al., 2000; Balaz and Achimovicova, 2006). In this study, the reactivity of enargite under alkaline sulfide leach conditions was examined."

Jan 1, 2015

By W. W. Schmittroth, A. Y. Bethune

THE commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc .are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "superpurity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,1 it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon was not desirable. The use of Special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1946

By A. G. Scobie

A spectrographic method for the determination of small amounts of gold and the platinum metals in ores has been developed. By means of this method, an assay of 0.001 ounce per ton on one assay ton samples is possible, and by seecrrographic adjustments the sensitivity may be increased to 0.0001 ounce per ton. All the prec10us metals may be determined from one spectrographic arcing with an accuracy of about 5 per cent average deviation from absolute values, and the complete analysis of an ore or similar product may be reported five or six hours after receipt of sample.

Jan 1, 1945