METHODS MANUAL VOLUME 1

GOLD ANALYSIS IN ALKALINE CYANIDE SOLUTIONS

Society of Mineral Analysts

COPIES OF THIS MANUAL MAY BE OBTAINED BY WRITING TO: Mr. Patrick Braun Managing Secretary Society of Mineral Analysts P.O. Box 50085 Sparks, Nevada 89435

Compiled under the review of the SOCIETY OF MINERAL ANALYSTS METHODS COMMITTEE

A SOCIETY OF MINERAL ANALYSTS PUBLICATION

GOLD ANALYSIS IN ALKALINE CYANIDE SOLUTIONS T.J. GILBERT - Topic Survey Editor TABLE OF CONTENTS

1.0.0 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.0.0 Applicable Documents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.0.1 General: Analytical References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.0.2 General: Health & Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.0 Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.0 Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.3.0 Inorganic Concentration (Fire Assay) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.0.0 Method Summaries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.1.0 Direct Spectroscopy (Method Group 1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.1.1 Atomic Absorption (AAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.1.2 Atomic Emission (AES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.1.3 Atomic Fluorescence - (AFS X-Ray) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 3.2.0 Organic Concentration Methods for Spectroscopy (Method Group 2) . . . . . . . . . . 10 3.3.0 Inorganic Concentration (Fire Assay) Methods (Method Group 3) . . . . . . . . . . . . . 11 3.3.1 Copper Sulfate Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 3.3.2 Chiddey Method (Composite) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3.3.3 Lead Acid Method (Composite) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3.3.4 Direct Assay Method (Newmont Method) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.0.0 Significance and Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 5.0.0 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 5.1.0 Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 5.2.0 Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 6.0.0 Interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.0 Interferences in Atomic Absorption Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.1 Physical interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.2 Chemical interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.3 Ionization interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.4 Spectral interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.5 Background interference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2.0 Survey: AAS Common Problem Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.0 Organic Concentration Methods (Extraction) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4.0 Inorganic Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 14 14 14 15 15 16 16 17 17

7.0.0 Apparatus (General) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

8.0.0 Hazards And Precautions (General) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 8.1.0 Cyanide Hazard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 9.0.0 Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 10.0.0 Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 10.1.0 Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 10.1.1 Atomic Absorption. Flame Composite Method . . . . . . . . . . . . . . . . . . . . . . . . 21 10.1.2 Procedure. Spectroscopy. Atomic Absorption. Furnace Gold in Solution: AAS, Graphite Furnace Atomization (Freeport Method) . . . . . . . . . . . . . . . . . . . . . . 23 10.1.3 Emission Spectrometry - DCP (Homestake Method): Gold and Silver . . . . . . . 26 10.1.4 Emission Spectrometry - ICP (Vegas Method): Determination of Noble Metals by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) . . . . . . 27 10.1.5 Atomic Fluorescence: Jumbo Mining Co. X-ray Fluorescence Spectrometry . . 33 10.2.0 Solvent Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 10.2.1 MIBK Extraction From Acidified Solution (Newmont Method) . . . . . . . . . . . . 37 10.2.2 DIBK/Aliquat 336 Extraction From Direct Solution (Freeport Method) . . . . . . 39 10.2.3 Butyl Sulfide Extraction (North American Laboratories) . . . . . . . . . . . . . . . . . . 43 10.3.0 Reference Fire Assay Procedure (Freeport/Newmont Composite) . . . . . . . . . . . 44 10.3.1 Procedure, Inorganic Concentration, Copper Sulfate (Pinson Method): Determination of Gold and Silver in Gold Plant Solutions by Fire Assay . . . . . . 48 10.3.2 Procedures. Inorganic Concentration. Copper Sulfate (Freeport Method): Gold Determination in Liquid by Fire Assay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 10.3.3 Procedures. Inorganic Concentration. Copper Sulfate (Golden Sunlight Method)52 10.3.4 Procedures. Inorganic Concentration: Chiddey . . . . . . . . . . . . . . . . . . . . . . . . . 53 10.3.5 Procedures. Inorganic Concentration: Lead - Acid . . . . . . . . . . . . . . . . . . . . . . 54 10.3.6 Procedures. Inorganic Concentration. Direct Assay: Fusion of High-grade Solutions for Gravimetric Assay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 11.0.0 12.0.0 13.0.0 14.0.0 15.0.0 General Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 Precision and Bias . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 Waste Disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 Contributing Organizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60 Disclaimer of Liability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

1.0.0 Scope This document is a collection based on a survey of analytical methodsin current or past use within the mining industry for the determination of gold in alkaline cyanide solutions. It may be used as an indicator of mining practice for discussion purposes, but should not be viewed as a collection of standardized methods. All method comparisons are of an approximate nature.

2.0.0 Applicable Documents Internal company documents listed as references are available from the listed companies on a limited basis at cost. Such references which are not available upon a postage-paid request have been deleted.

2.0.1 General: Analytical References C C C C C C 1979 Annual Book of ASTM Standards, Part 12, "Chemical Analysis of Metals and Metal Bearing Ores," American Society for Testing and Materials. C.H. Bucknam and D.M. Hausen, "Classification of Carlin Ores, Simple Diagnostic Tests," (memorandum) April 22, 1986. Newmont Gold. Frederick M. Garfield, Quality Assurance Principles for Analytical Laboratories, Association of Official Analytical Chemists, 1984. Handbook For Analytical Quality Control in Water and Waste Water Laboratories, USEPA, EPA-600/4-79-019, March 1979. Methods For Chemical Analysis of Water and Wastes, USEPA, EPA 600/4-79-020, Revised Edition, March 1983. Methods For Determination of Inorganic Substances In Water and Fluvial Sediments, U.S. Geological Survey, Open File Report No.85-495 by Marvin J. Fishman and Linda C. Friedman, Editors (1985). Test Methods For Evaluating Solid Wastes, USEPA, SW-846, Third Edition, November, 1986. USEPA Contract Laboratory Program, Statement of Work for Inorganic Analysis, Multi-Media, Multi-concentration, SOW No. 787, July, 1987.

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2.0.2 General: Health & Environment C C C.H. Bucknam and S.W. Nabbs, "Procedures to Ensure Compliance with State of Connecticut EPA. Regulations," (memorandum) Newmont Gold. Kraybill, Daniel D., Illinois Small Quantity Generators' Manual, Hazardous Waste Research and Information Center. Illinois Dept. of Energy and Natural Resources State Water Survey Division, HWRIC TN87-002, January 1987. OSHA Safety and Health Standards, General Industry, (29 CFR 1910), Occupational Safety and Health Administration, OSHA 2206, Revised January, 1976. Ralo, J. "Kids Leukemi~ from Parents Exposure" July 18, 1987 Science News. Randell C. Baselt, Ph.D. Biological Monitoring Methods for Industrial Chemicals Biomedical Publications, 1980. Tacket, Sandford L., "Lead in the Environment: Effects of Human Exposure, "July 1987 American Laboratory pg. 32-41. U.S. Dept of Health, Education & Welfare, Occupational Exposure to Inorganic Lead, Revised criteria, 1978. U.S. Environmental Protection Agency, "Understanding the Small Quantity Generator Hazardous Waste Rules: A Handbook for Small Business, EPA1530-SW-86-019, September 1986.

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2.1.0 Spectroscopy C V. Bennett, "Metallurgical Analysis by Plasma Emission Spectroscopy", pg. 27-44, Proceedings of the First Annual Conference of the Society of Mineral Analysts, Feb. 1987 C.H. Buckman, "Gold Check Assays by Graphite Furnace AAS," Newmont Gold (memorandum) August 19, 1986. G.D. Christian and M.S. Epstein, Atomic Absorption Spectroscopy, ACS Audio Course 1980. Scientific Apparatus Makers Association, Safety Procedures for Atomic Absorption Spectrophotometers, SAMA A 12-1970.

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Thermo Jarrell-Ash Corporation, IL Video 22 AAIAE Spectrophotometer Operator's Manual @ 1985. Thermo Jarrell-Ash Corporation, Atomic Absorption Methods Manual for Flame Operation @ 1986. Thermo Jarrell-Ash Corporation, Inductively Coupled Plasma Methods @ 1984. Perkin-Elmer Manuals: "Model 2380 Atomic Absorption Spectrophotometer," "Model 5000 Atomic Absorption Spectrophotometer," "Analytical Methods for Atomic Absorption Spectrophotometry," "Flame Autosampler for the Model 5000". R.K. Winge, V.A. Fassel, V. J. Peterson, and M.A. Floyd: Inductively Coupled Plasma Atomic Emission Spectroscopy: An Atlas of Spectral Information.

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2.2.0 Extraction C T. Gilbert, K. Smith, J. Anderson "An Examination of Some Techniques Performed at Freeport Gold," pg. 11-23. Proceedings of the First Annual Conference of the Society of Mineral Analysts, Feb. 1987. T. Groenwald "Determination of Gold (I) in Cyanide Solutions by Solvent Extraction and Atomic Absorption Spectrometry," pg. 863-866 Anal. Chem. May 1968. A. Parks and R. Mtirry Smith, "A Rapid Method for the Determination of Gold and Palladium in Soils and Rocks," pg. 57-59, Atomic Absorption Newsletter, March-April 1979. P.D. SewardlT.J. Gilbert, "DIBK Extraction," Freeport Interoffice Letter (Elko), July 20, 1984.

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2.3.0 Inorganic Concentration (Fire Assay) C C C C.H. Bucknam, "Analytical Procedure for Total Cold by Fire Assay - AAS," Newmont Gold (Memorandum). Beamish, F.E. and J.C. Van ~)on, Analysis of Noble Metals: Overview and Selected Methods, Academic Press, New York, 1977. E.E. Bugbee, A Textbook of Fire Assaying, (1940 edition) Colorado School of Mines Press, Golden, Colorado, 1984. Page 7

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N.H. Furman, (Ed.) Standard Methods of Chemical Analysis; VI Edition: D.VanNostrand Co., Inc., Princeton; pg. 870. Joseph Haffty, L.B. Riley, and W.D. Gross, A Manual on Fire Assaying and Determination of the Noble Metals in Geological Materials, Geological Survey Bulletin 1445, U.S. Government Printing Office, Washington D.C. (1977). South African Institute of Mining, Assay and Analytical Practice in the South African Mining Industry, Monograph Scores M6.

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3.0.0 Method Summaries

3.1.0 Direct Spectroscopy (Method Group 1)

3.1.1 Atomic Absorption (AAS) Direct atomic absorption is the most common means for determining gold in alkaline cyanide solutions. This choice is dictated by its relatively low cost for single element determinations, short analysis time and reasonable accuracy. With the exception of Battle Mountain Gold and the Bureau of Mines, labs in the method survey use background correction (continuum source, Smith-Hieftje, or Zeeman) for all determinations. Double beam optics are preferred, but several labs are comfortable with single beam instrument quality. Graphite furnace atomization is only used for samples which require lower detection limits. Organic concentration (see Method Group 2) or inorganic concentration (Method Group 3) is sometimes used to enhance sensitivity or accuracy for flame atomic absorption. The methods for atomic absorption consist of general operating parameters, a list of various blank/standard matrix solutions and a composite of operating suggestions from participating labs. Refer to Section 6.1.1 for a summary of interference types, appropriate action, and a comparative table of instrumental background correction methods.

3.1.2 Atomic Emission (AES) Emission equipment is relatively expensive to operate, but it is particularly cost-effective for multi-element analysis. A radio frequency generator (ICP) or a direct current (DCP) generates a plasma to stimulate atomic emission for analysis. Chromium (Cr), iron (Fe), Page 8

manganese (Mn) and vanadium (V) are listed as potential emission interference elements. The ICP method programs the interference patterns out. The DCP method dilutes samples until interference is insignificant. As in the atomic absorption method, exact operation instructions are left to the manufacturers' operating manual.

3.1.3 Atomic Fluorescence - (AFS X-Ray) X-Ray fluorescence does not currently have accurate direct sensitivity equivalent to AAS or AES, but field or benchtop instruments, which will continue to function under treatment hostile to AAS or AES equipment, have been attractive for some mine operations. A sealed radioisotope capsule or an X-ray tube is used as a source of high energy x-rays to excite inner shell electrons. An x-ray sensitive detector (scintillator, gas-proportional counter, solid state detector, etc.) is used to count the characteristic fluorescent x-rays which are emitted by the excited gold. Spectra are simple, but some corrections for spectral overlap (mercury, thallium, etc.) or background effects must be made. This is done with dispersing crystals in high resolution sophisticated instruments or Ross filters in benchtop models. Sample preparation is not normally required, but the method described in 10.l.3 uses preconcentration to obtain measurement precision and detection limits equivalent to flame AAS methods, Note: A Ross filter consists of two filters that transmit interfering x-rays equally while one limits analytical line transmission. The transmission difference is used to calculate "true" analyte fluorescence.

3.2.0 Organic Concentration Methods for Spectroscopy (Method Group 2) Extraction is a technique used to eliminate background interference or enhance absorbance for atomic absorption spectrophotometry. Gold is preferentially absorbed by an organic solvent which has been agitated with the sample solution. This organic phase is separated for AAS analysis. Absorbance is enhanced by using less extractant than sample, and interference is reduced when interfering elements are not extracted with the gold.

The first method uses MIBK as the organic extractant. MIBK affinity for the gold ions and complexes found in alkaline solution is limited, so the method requires that alkaline solutions be acidified in a hood prior to the addition of MIBK for extraction and separation. The second method uses a solution of DIBK and trialkyl ammonium chloride (Aliquat 336) to extract solutions over pH ranges of 1-l2.5. The method differs from 3.2.1 by adding salt solution to the sample to optimize extraction. Higher concentration ratios than Page 9

those in the MIBK extraction method are possible if quality standard solutions can be obtained. The extreme stability of gold in this extractant gives extracted samples a longer shelf life if this is required.

The third method uses a solution of xylene with dibutyl sulfide as the extractant. It is not in current mining use. Solutions require acidification before extraction and should be handled in a hood. The strong odor which is associated with dibutyl sulfide requires ventilation.

3.3.0 Inorganic Concentration (Fire Assay) Methods (Method Group 3) Fire assay methods are more labor intensive but are preferred for checking primary reference solutions or solutions which might contain uncorrected interference factors. These methods are considered to be relatively immune to chemical, elemental or physical interference factors which, in instrumental methods, can cause unrecognized false determinations. Reference standard solutions are not required, but control samples are recommended. A general fire assay method (10.3.0) has been included for reference. The fire assay practice outlined will produce accurate determinations for "fire assay as normal". It assumes that fusions will be with a fluid pouring, slightly acid fusion and cupellation will involve 25 or more grams of lead. Assay comparisons between analytical labs are recommended to detect errors in technique. Although the reference method and reference sources give a good basis in fire assaying, safe and accurate results depend on an experienced assayer. Note: Unless otherwise stated all chemicals are reagent grade.

3.3.1 Copper Sulfate Methods The Copper Sulfate Method uses a solution of copper sulfate and sulfuric acid to precipitate gold and silver from solution. This precipitate is filtered, dried and either scorified or fired to produce a lead button for cupellation. The Pinson assist the filtration Method uses potassium ferrocyanide and sodium sulfite to formation of the gold precipitate and flocculent to aid of the precipitate. The Freeport Method does not use fldcculent or potassium ferrocyanide. They believe ferrocyanide increases the amount of copper in the precipitate without an improvement in Page 10

gold values for their type of sample solutions. They do use sodium sulfite to assist precipitate formation. The Golden Sunlight Method combines copper sulfate, sodium hydroxide and sodium cyanide to make a precipitation solution. Potassium ferrocyanide is used to assist gold precipitation, and sodium sulfite is not used in the precipitation process. Flocculent is not used with filtration.

3.3.2 Chiddey Method (Composite) Chiddey is a term applied to a zinc precipitation method used to collect gold from solution for fLre assay cupellation. Three variations of this method were submitted which were essentially identical. This is a composite of all three methods.

3.3.3 Lead Acid Method (Composite) Gold ions from an HCl-adidified sample solution replace lead atoms granulated lead. The gold-loaded granulated lead is dried for cupellation by standard fire assay techniques. Three essentially identical methods were submitted. Battle Mountain Gold's method is the primary model for this composite.

3.3.4 Direct Assay Method (Newmont Method) The direct assay method is only used on high-grade solutions. A small aliquot of solution is dried in a crucible filled with standard flux and fire assayed by "normal" techniques. The procedure included here was submitted by Newmont Gold Company. No other labs are currently using direct assay.

4.0.0 Significance and Use In the primary metallurgical process used by the mineral processing industry on gold bearing ores, gold is extracted with alkaline cyanide solutions. Metallurgical accounting, process control, and ore evaluation procedures for this type of mineral processing plant depend on accurate, precise, and prompt measurements of gold concentration in alkaline cyanide solutions. It is assumed that all who use these methods will be trained analysts capable of performing common laboratory procedures skillfully and safely. A technician is assumed to have basic skills in fire assay methods and applicable instruments. It is expected that work will be Page 11

performed in a properly equipped laboratory. Since these are not necessarily standardized methods, it is assumed that all who use these methods will test their accuracy and safety before placing them in regular use.

5.0.0 Definitions 5.1.0 Terms C C C Atomic Absorption Spectroscopy: The analysis of the frequency-specific light absorbance characteristics of atomic elements to determine elemental concentration. Atomic Emission Spectroscopy: The analysis of the characteristic light frequencies emitted by atomic elements in a plasma to determine elemental concentration. Atomic Fluorescence: The analysis of characteristic light frequencies emitted by elemental atoms which have absorbed light at those frequencies from another light source to determine elemental concentration. Atomization: The process of converting a proportional amount of analyte element into an atomic state within a sample cell for absorbance analysis. Baseline: The concentration area where non-analyte or random fluctuations obscure analytical valves. Can also refer to the magnitude of these fluctuations. Detection Limit: A lab estimate which in this document is equivalent to the lowest concentration which can be separated from the baseline during average production conditions. Extraction: The selective chemical removal of an element from a sample solution into a solvent solution for spectrographic analysis. Fire Assay: A group of analytical techniques which use high temperature selective reduction of precious metals and lead from a molten solution (fusion). Precious metals are separated qualitatively by selective oxidation (cupellation) for gravimetric or instrumental analysis. Precision: A lab estimate of typical standard deviation in samples with analyte concentrations at the top of a method's analyte concentration range (definition limited to this document).

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5.2.0 Abbreviations

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AAS AFS DIBK FAAS GFAAS g lb/st MIBK m3 ug/ml mg/l oz/T ppm

Atomic Absorption Spectroscopy Atomic Fluorescence Spectroscopy Dusobutyl Ketone Flame Atomization Atomic Absorption Spectroscopy Graphite Furnace Atomization Atomic Absorption Spectroscopy grams pounds per short ton Methyl Iso-butyl Ketone cubic meters micrograms per milliliter milligrams per liter ounces troy per short ton parts per million (weight by weight)

6.0.0 Interference

6.1.0 Interferences in Atomic Absorption Analyses There are five types of interferences encountered in atomic absorption determinations: physical, chemical, ionization, spectral and background interferences. 6.1.1 Physical interferences: When there is a difference between samples and standards in the physical characteristics of the solutions (such as viscosity or density) it is possible for there to be a difference in aspiration rates or droplet size that causes a difference in response. Physical interferences can cause a determination to be either too high or too low. Correction techniques are: a) Matrix matching either by adding substances to the standards to match the physical characteristics of the samples or preparing the samples in such a way as to remove the interfering substance. b) Method or standard additions. c) Method of internal standardization (with a dual channel A.A. spectrophotometer). Physical interferences always affect the slope of the calibration curve. 6.1.2 Chemical interferences: The presence of certain chemical compounds in a sample matrix can suppress or enhance sensitivity causing a difference in response between samples and standards. This is often caused by the formation of refractory compounds in the flame. Correction techniques are: Page 13

a) Matrix matching. b) Matrix modification with a releasing agent such ad EDTA or lanthanum. c) Method of standard additions. d) Use of a hotter flame (Nitrous oxide/acetylene). Typical examples of chemical interferences include the formation of refractory phosphates when determining calcium or magnesium. The calcium phosphates do not melt in the flame, and the amount of free calcium available in the atomic state is reduced. 6.1.3 Ionization interferences: In some cases a flame can be hot enough to ionize the analyte element. When this occurs some of the atoms will be found in an ionized state and will not absorb light, giving a reduced response. Typically ionization interferences occur in the first column of the periodic table (Li, Na, K, etc.) in air/acetylene flames and the first two columns (Mg, Ca, Ba, etc.) in nitrous oxide/acetylene flames. Samples often will show less ionization suppression than standards. This is due to the free electrons and other ions which can be expected in chemically complex samples. Also ionization suppression occurs to a greater extent at low concentrations than in higher concentrations. As a result, ionization interferences will cause a difference in response between standards and samples and non-linear calibration curves at low concentrations. Correction techniques are limited to the use of ionization buffers. This usually consists of making all samples and standards in up in 0.1% cesium or 0.2% potassium. Since the method of standard additions is restricted only to chemical and physical interferences, no attempt should be made to correct for ionization interferences using the method of standard additions. 6.1.4 Spectral interference: When there is more than one absorbing line for more than one element in the spectral bandpass of the atomic absorption instrument, it becomes possible for the readings to be a function of the concentration of two elements independently rather than of a single analyte element. In this case it is impossible to tell if the reading is due to the presence of the analyte atom or some interference. Fortunately these interferences are extremely rare in atomic absorption. When encountered they can usually be eliminated by: a) Narrow the spectral bandpass of the instrument. b) If using a multi-element hollow cathode lamp, switching to a single element lamp. c) Using an alternate line. Again, when following the instrument manufacturer1 5 instructions for setup and operation of the spectrophotometer, these interferences are almost never encountered.

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6.1.5 Background interference: One of the most co~on interferences 15 background interference due either to the presence of salts in the flame which can scatter the light or molecular species which can absorb the light. In either case, the apparent concentration of analyte will be too high. Background interference is also called non-specific absorption. In graphite furnace determinations, background interferences become more significant because they are enhanced. A quick test for background interference is to run the sample with the background correction off and then again with it on. If the answers are comparable, there is no interference. Most instruments have some type of automatic background correction available. It is possible for a background interference to give a signal even when no analyte is present. Therefore, do not attempt to correct for background interference using the method of standard additions. Correction techniques are: a) Deuterium or tungsten continuum correctors. These are applicable to both flame and furnace. They may give over or under correction under certain conditions of “structured” background. For example, in the determination of arsenic by graphite furnace, sodium chloride will cause light scatter that can be corrected easily by the deuterium arc. However, if aluminum is present, a structured molecular absorbance that cannot be accurately corrected using a continuum corrector will interfere with an accurate determination. b) Zeeman Atomic Absorption. The Zeeman technique will correct for all kinds of background interferences, both structured and unstructured. Most instruments offer Zeeman background correction in a furnace-only configuration. Ed. Note: Hitachi offers Zeeman correction in flame mode. User references are not available, and Hitachi marketing appears limited in the U.S.A. at this date. • Smith-Hieftje (pronounced “Heef'-ya”) Atomic Absorption. This technique is applicable to both structured and unstructured background, and works on both flame and furnace determinations.

6.2.0 Survey: AAS Common Problem Summary C Iron has been reported in Australia as an interfering element for gold analysis by atomic absorption. The labs in this survey indicated that iron is not a problem. However, experience with problem iron concentrations may be limited. High salt concentrations (over 2%) affect nebulizer aspiration. This causes erroneous determinations if standards are not matrix matched.

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Background interference is a particular problem for process tailings/liquors. Tails solutions containing 0.1 ppm gold can have uncorrected values over 1 ppm. Non-routine problems (not listed above) are usually solved by applying Organic/inorganic concentration methods (6.3 or 6.4). Atomic Emission can require programmed elimination of interfering spectral emission lines or background elmination techniques. A method-specific discussion in method 10.1.2.2 can also be of use for non-ICP methods. Atomic Fluorescence (X-Ray) can suffer from heavy metal interferences (mercury thallium, etc.). Instrumental correction using matrix matched standards, Ross filters, dispersing crystals or instrument-specific methods are available and should be evaluated for each application.

C

6.3.0 Organic Concentration Methods (Extraction) Properly performed extractions eliminate most interferences to allow low detection limits. The increased sample handling does increase error risks. Extraction may be conbined with fire assay concentration if interference is suspected below the detection limits of direct fire assay checks. 6.4.0 Inorganic Concentration The potential for interference is considered to be lower for inorganic (Fire Assay) methods compared to spectroscopic methods. The primary risk lies in chemical interference or handling loss within the initial chemical precipitation or collection from the sample solution. Losses can also occur in fusion, cupellation and parting. The labs in the survey report that these problems are not significant within the precision limits of the various methods.

COMPARATIVE TABLE1 COMMERCIAL INSTRUMENTAL BACKGROUND CORRECTION (LINE SOURCE ATOMIC ABSORPTION SPECTROSCOPY)
TECHNIQUE ADVANTAGES DISADVANTAGES NOTES

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Continuum Source (D2 or equivalent)

C C C

Measures broadband or continuum background absorption Ready availability High sample rate correction available (200-240 measurements/second)2 on some instruments my reduce correction delay problems in graphite furnace applications

C C C

C C C Smith-Hieftje3 C C C C C C C Accurate correction for structural background Spectral interferences may be overcome for many cases Matches of two light sources is not required Visible and ultraviolet regions are corrected No double-valued analytical growth curves exist No light is lost due to polarizers Up to 3 absorbance units of correction4 Unaffected by structured background Spectral interferences may be overcome if lines are 0.02 nm apart Matching of two light sources is not required, which prevents problems of alignment, geometry, or differential drift Up to 3 absorbance units of correction4 C C

C C

Zeeman3

C C C

C C C

C

C C C C

C

2. 50-60 background measurements per second is the normal range of sampling rates for various correction techniques. in flame and many furnace applications, high rates do not Reduced Sensitivity (approx. improve correction quality. 40% for Au, less for other 3. The EPA has made a elements) preliminary recommendation that Special hollow cathode Lamps Smith-Hieftje and Zeeman are required to prevent gas correction techniques be pref er red Cleanup necessitated by over Continuum (D2) running lamps at high current correction techniques for graphite (even for a short pulse) furnace atomic absorption Cost spectrometry analysis. Not every hollow cathode Lamp will produce a usable 4. When extreme correction is self-reversal effect, particularly required, the signal-to-noise ratio of for refractory elements like an instrument is of primary molybdenum & titanium importance. For example, consider a sample requiring 2 absorbance Limited availability for flame units of correction. The background atomization applications in the matrix, in this case, absorbs 99% of United States the incident light and the analyte Direct overlap of Lines cannot absorbance be corrected must be measured in the remaining Analytical growth curves my 1% of light. Although correction by be dcuole-valued (two widely Zeeman and S-H methods would be different concentrations give accurate, the remaining signal is the same absorbance) dominated by the signal-to-noise Sensitivity Is reduced for some ratio of a particular analyte on each elements (10-20%) make and model instrument. Polarizers contribute to light loss Restriction of space due to the magnet Accuracy depends on background absorbance being unaffected by magnetic field strength and polarization of source Cost

Incorrect results in the presence of Structured background No correction for spectral interferences Difficult to match beams exactly because different geometries & optical paths between hollow cathode and continuum Lamp exist Potential drift Cost Most systems only correct up to 0.5 absorbance units

1. Table data from an article by Joseph Sneedon "Background Techniques in Atomic Absorption Spectrometry" Spectroscopy Vol. 2, No. 5, pg. 42, Table III). The table includes minor additions prompted by SMA member comments.

7.0.0 Apparatus (General) C Safety Equipment: Chemical-resistant lab aprons and gloves; safety glasses and chemical mask; emergency cyanide-poisoning first aid station; emergency eye-ash and shower; self-contained breathing apparatus and rescue contingency plan. Reagents: Unless otherwise noted, all chemicals are reagent grade. Refer to reagent lists of individual methods. Page 17

C

C C

Water: Deionized water or distilled water. Glassware pipets: Class A, sized as needed beakers: sized as needed, borosilicate, calibrated volumetric flasks: Class A, sized as needed glass stir rods auto-diluters assorted reagent dispensers Plastic Ware eyedroppers, disposable teaspoon, disposable (measure zinc powder, lead shot, etc.) Instrumentation Atomic absorption spectrophotometer equipped with background correction (graphite furnace or flame atomization), Autosampler (optional), Atomic Emission Spectrophotometer (ICP or DCP), Precision balance (accurate to .001 mg), Standard balance (accurate to .001 g)

C C

C

General Equipment Fire Assay Furnace equipped to fuse samples at 1950° F and cupel at 1650° F Hot Plate (set at less than 100° C), Annealing and parting trays, Cupel tongs, forks, etc., Porcelain Crucibles, MgO cupels, Crucibles (30g or 40g as preferred)

8.0.0 Hazards And Precautions (General) 8.1.0 Cyanide Hazard C The necessity, for both safety and sample preservation, of keeping the pH of cyanide solutions well into the alkaline range (10.5 to 14) by adding sodium hydroxide or calcium hydroxide The release of cyanide gas, a highly lethal poison, from any admixture of cyanide and acid (or, to a lesser extent, non-alkalinized water) -- cyanide to be mixed only under fume hoods The release of toxic cyanogen chloride from any admixture of cyanide and chlorine, hypochlorite, or aqua regia The necessity of following strict hygiene practices when handling cyanide An up-to-date cyanide safety program that includes a rescue contingency plan. Poisoning by fumes from solvents (MIBK, Aliquat 336), acids (nitric, hydrochloric, aqua Page 18

C C C C C

regia, sulfuric), and lead (during cupellation, fluxing, fusion) C C C C C C C Poisoning by ingestion or inhalation of lead (lead oxide dust in flux, lead acetate crystals) or of other chemicals Tissue destruction from acids (above) and alkalies (sodium and calcium hydroxide) Burns from furnaces, ovens, hot plates, tools, and from flame, torch, or electric-arc instruments Cuts from glassware Explosions (e.g., acetylene for atomic absorption instruments) Hazards related to improper housekeeping and hygiene Offsite hazards due to improper protective clothing or personal hygiene. (e.g. organic solvents, particularly chlorinated hydrocarbons, which are carried home on an employee's clothing or body are associated with a higher incidence of childhood leukemia within an employee's family).

9.0.0 Sampling C C C Samples should be taken in clean containers. Small gold residues or gold-precipitating chemical residues can be a significant problem Filter press samples should not be taken until flow has been established. Dilution or contamination by press residues can be significant

Samples should be preserved by adding an excess of cyanide and sufficient sodium hydroxide to maintain a pH 10 or above as soon as possible after collection. This will insure the stability of the gold in solution and prevent accidental toxic gas formative. CAUTION: All procedures which require sample acidification should be performed in an adequately ventilated hood 10.0.0 Procedures 10.1.0 Spectroscopy 10.1.1 Atomic Absorption. Flame Composite Method Reagents:

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C C

Primary Standard, 1000 ppm Au (Available from several vendors). Quality should be checked by Fire Assay Methods. Standards, Secondary: Prepared as needed to bracket samples with blank matrix solution. (see matrix table) (Battle Mountain Cold)

Example:

a) Prepare 1.0 lb./ton cyanide blank (0.5 g NaCN/l000 ml H20). b) Prepare 100 ppm Au Standard: pipette 10 ml of the stock 1000 ppm Au standard into a 100 ml volumetric flask. Bring to volume with H20. c) Prepare 0.015, 0.029, 0.058, and 0.116 oz/ton Au standards: C C C C Cut 0.5 ml of 100 ppm, bring to 100 ml with CN-Blank. Makes 0.015 oz/ton Cut 1.0 ml of 100 ppm, bring to 100 ml with CN-Blank. Makes 0.029 oz/ton Cut 2.0 ml of 100 ppm, bring to 100 ml with CN-Blank. Makes 0.058 oz/ton Cut 4.0 ml of 100 ppm, bring to 100 ml with CN-Blank. Makes 0.116 oz/ton

d) Standard and Blank Matrix: (table)
Lab Blank Notes

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Asamera Battle Mtn. Gold Bureau of Mines Dee Gold Freeport 1,3,4 FRM FMC Golden Sunlight Goldfields Newmont
2,3 1

2 Ib/st NaCN 0.5 g/l NaCN 0.25% NaCN, 0.1% NaOH 5 Ib/st NaCN, pH adjusted to 10.5 to 11 with NaOH 0.075 g/l Triton X-l00 (3 g/l NaCN, 0.1 g/l NaOH) Distilled water 1.5 g/l NaCN pH adjusted 2.6 g/l NaCN, adjusted above pH 10 with NaOH NaCN concentration and pH of Mill in last 24 hrs. 0.3% NaCN, pH adjusted above 10.5

1. These labs alter matrix as required when matrix interference become, apparent. Example: Dissolved salts greater than 2% require a similar viscosity matrix. 2. These labs do direct spectroscopic analysis on Aqua regia digested dore beads. This requires a 10% Aqua regia standard and blank matrix. 3. These labs use organic Concentration (extraction) to enhance detection limits. The organic extractant or the applicable method is wed for a blank and standards are extracted by the same method from appropriate aqueous standards. 4. Triton X-l00 (alkylaryl pelyelher alcohol) acts as a conditioner /cleanser for the burner chamber. The matrix absorbance is identical to deionized water when diluted to 0.075 g/l in deionized water.

Procedures: Set up the A.A. as required by the instrument manufacturer. AA Parameters: Wavelength: 242.8 nm Burner: Straight (no angle) Flame: Lean, blue @ maximum absorbance Integration: 1.0 Second (increase if jumpy) Slit: .7 nm Allow 10 minute AAS warmup if needed. Zero instrument with matrix-blank. Use two-or-more point calibration curve, and bracket the sample with a higher and lower standard. Operating Suggestions a) Use background correction unless verified as unnecessary (see section 6.1.1 comparison table for background correction options). b) Should be able to read samples to three significant places (.XXX oz.t/s.t., XXX oz.t./s.t., X. XXppm. XX.Xppm.). c) If results are excessively noisy, may want to increase integration time. d) Advise the use of a corrosion resistant nebulizer (Pt-Rh). e) Salt concentrations above 2% cause significant changes in aspiration rates. Standards for these types of samples should be matrix matched. f) Do not allow standards to stand open except during standardization. Evaporation Page 21

or contamination may change the concentration of the standard. g) Check standards and blank often. h) Do not aspirate directly from stock gold standard solutions. A portion of standard may be poured fresh for each standardization into a disposable test tube or a small, sealable working standard container may be used. Replace the solution or blank from the stock if contamination is suspected. i) Large production batches of samples should include control and duplicate samples of known concentration as an aid to maintaining quality control on precision and accuracy. j) Check all primary commercial gold standards by fire assay analysis. They are not always as accurate as vendors claim. CanMet or NBS standards are preferred for optimum accuracy. d) Solutions from unfamiliar sources should be checked by fire assay to eliminate the possibility of unexpected interference. See section 6.1.1 for a discussion of possible problems and corrective action.

10.1.2

Procedure. Spectroscopy. Atomic Absorption. Furnace Gold in Solution: AAS, Graphite Furnace Atomization (Freeport Method) Principle Liquor samples containing 0.02-3.0 mg/L Au are analyzed by furnace AAS. The samples are diluted with ammonium citrate-lanthanum nitrate buffer to decrease chemical and background interferences (see Note 2). If interferences are minimal (within the capability of the instrumental background correction), the buffering may be eliminated for direct readings. This will result in lower detection limits when standards have a matrix similar to the samples. Reagents C C C Ammonium citrate - (CH4)2HC6H507 Lanthanum nitrate - La(N03)3 -6H20 Ammonium citrate - Lanthanum nitrate buffer solution, 10 g/l Ammonium citrate and 5g/l Lanthanium nitrate - Using a large powder funnel, weigh 20 g of ammonium citrate and 10 g of lanthanum nitrate directly into a 2 liter volumetric Page 22

flask. Bring volume to the mark with distilled water. Add a magnetic stir bar to the flask and place flask on a mag mixer. Allow to stir overnight. Filter as needed just prior to use. C C C C Gold wire - Au - 99.99+ % pure Sodium hydroxide solution - Na0H, 1 N - Dissolve 40 g of NaOH in distilled water, cool, and dilute to 1 liter with distilled water. Sodium hydroxide solution - NaOH, 0.1 N - Dissolve 4 g of NaOH in distilled water and dilute to 1 liter with distilled water. l0g/l Sodium cyanide solution - Dissolve 10 g of NaCN in 500 ml of 0.1 N NaOH and dilute to 1 liter with distilled water. This solution should be made fresh as needed and in conservative quantities. Excess amounts should be properly treated and disposed of and NOT STORED. 1 g/l Sodium cyanide/sodium hydroxide solution - NaOH, 0.1 N; Dilute 100 ml of the 10 g/l NaCN solution above to 1 liter with 0.1 N NaOH. This solution should be made fresh as needed and in conservative quantities. Excess amounts should be properly treated and disposed of and NOT STORED. WARNING: Keep cyanide solutions separate from all acids. Note 1: Matrix problems can be complex for furnace atomization. See section 6.1.1 The La buffer method works for Au in typical solutions but must be tested on a case-by-case basis for alternate elements. Varian Associates (Palo Alto, Calif.) uses palladium in a universal matrix modifier method but none of the survey labs have tried the method.

C

Note 2:

Apparatus C C C C C Volumetric flasks, 10, 100, 1000, and 2000 ml Pipets, 5, 6 and 10 ml Eppendorf pipet, 100 uml Atomic Absorption Spectrophotometer, Perkin-Elmer Model No. 5000 with HGA-500 graphite furnace and AS-40 automatic sampler. Gold (Au) hollow cathode lamp (HCL)

Standards

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Au stock solution, 1,000 mg/L, (1000 ppm) (prepared when quality commercial standards are not available) - Dissolve 1 g (+ .0001 g) of pure gold wire or sponge in a minimum volume of aqua regia. Evaporate to approximately 2 ml. Dissolve the residue with 100 ml of concentrated hydrochloric acid. Heat gently to facilitate dissolution. Cool and transfer to a one liter volumetric flask, add 150 ml of concentrated hydrochloric acid and dilute to the mark with distilled water. Prepare the following Au-cyanide stock solutions: C Solution I. 0.100 g/l (100 mg/L) Au - Into a 100 ml volumetric flask, pipet 30 ml of 1 N NaOH and 10 ml of 10 g/l NaCN solution. Mix thoroughly, then pipet 10 ml of the g/l Au stock solution into the flask and dilute to the mark with distilled water. Solution II. 0.05 g/l (50 mg/l) Au - Into a 100 ml volumetric flask, pipet 15 ml of 1 N NaOH and 10 ml of 10 g/l NaCN solution. Mix thoroughly, then pipet 5 ml of the 1 g/l Au stock solution into the flask and dilute to the mark with distilled water. Solution III. 0.01 g/l (10 mg/l) Au - Into a 100 ml volumetric flask, pipet 10 ml of the 0.100 g/l Au (Soln. I) stock solution. Bring to volume with NaOH (.1 N) NaCN (1 g/l) solution. Solution. IV. 0.001 g/l (1 mg/l) Au - Into a 100 ml volumetric flask, pipet 10 ml of the 0.01 g/l Au (Soln. III) stock solution. Bring to volume with NaOH (.1 N) - NaCN (1 g/L) solution.

C

C

C

From these stocks prepare the following liquor standards given as actual concentrations: Au Concentration (mg/L)*: 0.02 0.05 0.1 0.5 1.0 3.0 Volume used of stock solution (ml): 2(a) 5(a) 10(a) 5(b) 10(b) 6(c) (a) Use a 1.0 mg/l Au stock solution (Soln. IV) (b) Use a 10.0 mg/l Au stock solution (Soln. III) (c) Use a 50.0 mg/l Au stock solution (Soln. II) Note: mg/l = ppm

*

Pipet the respective volume of each Au-cyanide stock solution into 100 ml volumetric flasks. Bring to volume with NaOH (.1 N)-NaCN (1 g/l) solution. Along with the sample preparations, dilute 100 ml of each standard to 10 ml with ammonium citrate-lanthanum nitrate buffer. The standards are now ready for analysis by furnace Page 24

AA. High Background Procedure Pipet 100 uml of sample into a 10 ml volumetric flask. Bring to volume with ammonium citrate-lanthanum nitrate buffer solution. Mix well. Use the graphite furnace atomic absorption table to set the parameters for Au in liquors and run against a set of correspondingly-prepared standards. Minimal Background Procedure (within background correction capabilities) When a comparison of determinations with and without buffering place the undiluted (no buffering) determinations within the accuracy limits of the buffer method, direct determinations are preferred. Sensitivity can improve by a factor of 100. Use the graphite furnace atomic absorption table to set the parameters for Au in liquors and run against a set of corresponding standards which have not been diluted with buffer solutions.

10.1.3

Emission Spectrometry - DCP (Homestake Method): Gold and Silver Method C Single element DCP mode.

Range C C 1000 ppm to 0.008 ppm for Au. 1000 ppm to 0.004 ppm for Ag.

Precautions Analyses affected by matrices which provide false gold signals. For high matrix interferences, make dilutions until signal is unaffected by matrix. Reagents C Gold &Silver Standards in 0.025% NaCN and 0.1% NaOH (100.0, 10.0, 1.0, 0.1, and 0.01 ppm)

Procedure

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C C C

50 ml Mill Solution Samples are centrifuged at a centrifuge setting of 35 for 20 minutes. Analyses are performed on the upper half of the tube. Calibrations are effected by running the following standards: 0, 0.01, 0.1, 1.0 ppm. DCP alignment is attained with 10 ppm Au and Ag standards. For enriched refinery samples, run calibration samples 0, 1, 10,100 ppm. Run samples. Make appropriate dilutions of samples so that analysis will fall between 0.1 and 2.0 ppm. Calibrate with 0, 0.01, 0.1, 1.0, 2.0 ppm standards. Run diluted samples.

Calculations C Adjusted ppm = Reading (ppm) x Dilution Factor

Some labs (not including Homestake) have encountered problems with Iron interferences. If instrumental background correction does not solve the problem, extract the sample with an organic solvent and back extract iron with HCl (see 10.2.2). For the 100 ppm preparation, add solution containing NaCN (2.5%) NaOH (10%) till solution turns pink to phenolphthalein indicator. Bring up to volume with solution containing 0.025% CN and 0.1% NaOH. Manganese represents a potential interfering element at 242.8 nm, but has not been encountered in problem concentrations.

10.1.4

Emission Spectrometry - ICP (Vegas Method): Determination of Noble Metals by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) Scope and Application The Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) technique is applicable for the determination of over 70 elements of the periodic table. The present discussion is limited to the precious metal elements namely, rhodium, palladium, iridium, platinum, gold and silver. The technique is applicable for samples dissolved in acidic solutions. A detailed description of the method is given in the references (2.0 General References Analytical: EPA 60014-79-020, Mar. 1983; USEPA SW-846, Nov. 1986: USEPA SOW No. 787, July 1987; U.S.G.S. Open File Report 85-495, pub. 1985). Table I gives the list of elements with their wavelengths, typical instrument detection limits (IDL), and possible interfering elements (2.1 Spectroscopy reference: R.K. Page 26

Winge and others, 1985). The interferences from other elements become very significant when their concentrations exceed 1000 mg/l. It is desirable to determine the IDLs and interference correction factors for each instrumental system and each new sample matrix prior to sample analysis. Description of Method The ICP-AES method is based on the measurement of atomic emission in the Ultraviolet-Visible (160-800 nm) spectral region by the optical spectroscopic technique. A sample in the form of a solution is fed to a nebulizer and the resulting aerosol enters the central channel of the plasma torch. A radio frequency (typically 27.12 or 40.0 MHz) Inductively Coupled Argon Plasma (ICAP) is made up of very hot (6000-100000 K) and highly ionized argon atoms. The donut-shaped flame-like ICAP has a cooler central channel where the sample aerosol enters. The sample aerosol is desolvated, dissociated, atomized, ionized and excited in the plasma. The radiation emitted by the excited sample atoms and ions is focused on to the entrance slit of the spectrometer. The atomic emission is dispersed by a grating spectrometer into individual spectral lines. The intensity of the spectral lines is measured by a photomultiplier tube (PMT). The entire system is controlled by a computer which converts the measured radiation into elemental concentration. There are two types of ICP-AES instrument, simultaneous and sequential. In a simultaneous ICP-AES system, several spectral lines are measured simultaneously (hence the name) by a photo-multiplier tube (PMT) for each element wavelength. This system offers the advantage of high speed and less consumption of sample. However, interferences and the high cost of individual PMT systems are the major disadvantages. With the sequential ICP-AES system, a computer-controlled diffraction grating points the correct wavelength of light towards one PMT. The advantage of this method is that when one wavelength is interfered by another element spectra, other wavelengths may be selected simply by telling the monochromator to turn to other positions. Sequential ICP-AES has the advantage of lower cost over the simultaneous. When you need to analyze the sample for many elements the sequential system will consume more samples as well as time. An alternative to the above systems uses two monochromators and two detector Systems. This allows for double the speed, and a wider range of spectral emission. Two examples of this type of ICP-AES are the Thermo Jerrell-Ash Plasma-200, Plasma-300, and the Perkin-Elmer Plasma II. Instrumentation The ICP-AES instrumentation system consists of 1) a radio frequency generator with Page 27

plasma torch assembly, 2) a sample introduction system consisting of a peristaltic pump, nebulizer, aerosol expansion chamber and a drain system, 3) computer-controlled atomic emission spectrometer with background correction, and 4) a supply of argon gas (welding grade or better) which should give 20 Llmin. @ 60 psig. Operating Conditions Since various makes and models of ICP-AES differ in their operation, it is difficult to provide a common operating procedure. It is important that the analyst follow the procedure given by the manufacturer of a particular instrument. Various operating parameters such as R.F. power, sample flow rate, argon flow rate, observation height in the plasma, integration time, standard concentrations, background correction, are to be set according to the manufacturer's instructions and experimental requirements. Instrument detection limits, linear dynamic range, sensitivity, precision and spectral interference correction factors are to be investigated and established for each spectral line on that specific instrument prior to the actual sample analyzation. Reagents And Standards C Deionized - distilled water. A supply of deionized - distilled water of ASTM Type II purity is essential for preparation of all blanks, standards and sample dilution. The purity of the water must be checked with a conductivity meter and also by actual analysis. C Concentrated acids. A supply of reagent grade (or better) acids including Hydrochloric, Nitric, and Sulfuric acids. C Standard solutions for calibration Primary standards: 1000 mgIL solutions of silver, palladium, rhodium, iridium, platinum and gold may be purchased commercially (from Spex, J.T. Baker, Inorganic Ventures etc.) or may be made by dissolving pure metals in appropriate acids. Use nitric acid to dissolve silver and aqua regia to dissolve other elements. Store in tightly capped glass or plastic bottles in a cool dark place. Check the concentration of these primary standards by comparing with known independent standards or a fire assay. Secondary working standards are prepared from these primary standards by diluting 1.0 ml of 100 mg/l standards to 100.0 ml with 1% nitric acid. Mixed Page 28

standards of several elements (except silver) may be prepared. All secondary standards should be prepared fresh at the time of analysis. Calibration blank solution contains the same acid as the standards and at the same concentration. Generally a 1 to 2% solution of nitric or hydrochloric acid will work as well. C Quality control standards: A) Initial Calibration Verification (ICV). ICV should be made from a different source than that of a primary standard. The ICV will identify any errors that were made while preparing secondary standards. Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB). A calibration blank may be used as ICB and CCB. The concentration of this standard should always read below the instrument dection limit (IDL). Continuing Calibration Verification (CCV). To ensure calibration accuracy during the analysis, a CCV should be analysed before and after the analysis of up to ten samples. The before and after concentrations of the CCV should not differ by more than 10%. The CCV'is prepared in such a way that the analyte concentrations are at one half of the maximum concentration of that analyte in the standard. Laboratory Control Sample (LCS). A ICS containing the elements of interest whose concentrations has been previously determined should be digested and analysed with each batch of twenty or less samples. The LCS analysis will ensure the accuracy of digestion and analysis procedures. Instrument Detection Limit Standard (IDLS). A solution containing the analyte element at a concentration equal to twice its detection limit should be analyzed prior to the sample analysis. This will ensure the accuracy of the calibration at the low end of the calibration curve.

B)

C)

D)

E)

A detailed quality assurancelquality control program described in references (2.0 General References, analytical: Garfield, 1984 or EPA-60014-79-019, March 1983) should be followed for the preparation and use of the quality control standards. Hence a separate detailed discussion on QAIQC program is not given here. An analyst may use any acceptable range for the various quality control standards. However, plus or minus ten percent is the normally acceptable range.

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Safety The toxicity or the carcinogenicity of the reagents used in this method has not been well defined. Each chemical reagent should be treated as a potential health hazard. Exposure to these chemicals should be kept at a lowest possible level. Extra care should be taken while handling cyanide solutions since they generate the deadly HCN gas even with mild acids. Good laboratory practice must be followed. Safety devices such as gloves, safety glasses and face mask should be used while handling these chemicals. Prepare all solutions in a fume hood with proper air flow. A reference file of materials handling data sheets should be available to all personnel involved in a chemical analysis. Additional references on laboratory safety are given at the end (2.0 General References, Health & Environment: OSHA 2206, Jan.1976; or 1979) for the information of the analysts. Operating Procedure Start the instrument according to the manufacturer's instructions. Allow sufficient time (about 15-30 minutes) for the system to become thermally stable. Make sure that the argon, colling water supply, exhaust system and other safety locks are satisfied before turning on the plasma. Most instruments will not allow the plasma to be ignited unless these requirements are met. Turn on the computer and call in the proper operating program. Profile the instrument's spectral lines in correct places using mercury alignment lamp. Calibrate the instrument according to the instructions using a mixed calibration standard solution and check the calibration using an initial calibration verification standard described earlier. Aspirate calibration blank solution between samples to avoid contamination. Begin analyzing samples after first analyzing CCV and CCB. After analyzing ten samples (or less), analyze CCV and CCB for the calibration check. If the CCV standard does not read within 10% of its original analysis value, check for the following problems. In any case, recalibrate the instrument, and recheck with ICV, CCB, and CCV prior to the actual sample analysis. Trouble-Shooting: C Change in the environmental temperature: It is important to have the ICP-AES system located in a room with constant temperature. Large fluctuations in the surrounding area temperature affect the optical alignment of the instrument resulting in a calibration drift. C Change in the sample uptake rate: A clogging of the nebulizer after running a sample containing high dissolved solids or suspended particles, will result in less and less sample injected in the plasma. Correct the problem by washing the Page 30

neublizer tip, and filtering and/or diluting the sample. C C C Argon pressure drop: Check the argon flow rates and pressure tank. Near the end of the tank, if the pressure is dropping, the argon tank. R.F. Power fluctuation: If you notice a significant change in the R.F. Power during the analysis, notify your instrument service department of the problem. If the CCB standard reads more than the IDL, check for any contamination. Prepare a fresh CCB and check again.

The procedure described here uses standards and samples made in acidic solutions. However, in the mining industries, cyanide solutions are commonly used to leach noble metals. A direct analysis of the solutions containing cyanides can be done if all standards and blanks are made up of similar matrix and pH. A sample introduction system including nebulizer, expansion chamber, drain introduction system including nebulizer, expansion chamber, drain line and drain container should be free from acids and be rinsed with deionized water followed by 0.1% NaOH solution. All standards, blank and solutions should be prepared with 0.1% NaOH solution. Interferences A) Spectral Interferences are caused by 1) overlap of a spectral line from other elements present in the sample, 2) unresolved overlap of molecular band spectra or 3) background contribution from continuous or recombination phenomena. The spectral overlap can be compensated by first determining interference correction factors (ICF) and using computer correction of the raw data to obtain the correct concentration. The ICFs are to be determined for each element present in the matrix. A 1000 mg/l solution of a pure interfering element is analyzed and a concentration read out for each analyte wavelength is recorded. The correction is made by using the amount of interfering element concentration and the ICFs. If all the operating conditions such as plasma power, argon flow, sample intake rate, observation height, etc. are same as they were at the time ICFs were determined, than a fairly good interference correction can be done. It is desirable to measure the ICFs every three months or whenever the operating conditions are changed. Table I. indicates possible interfering elements. This information is only for guidance; one should determine if any other elements are interfering or not. In a sequential ICP-AES, one can select an alternative spectral line or change in operating conditions to avoid or minimize spectral interferences. The problem of background contribution can be corrected by a background Page 31

correction adjacent to the analyte spectral line. B) Physical interferences are caused by sample transport and nebulization processes. A change in the viscosity and surface tension can cause significant change in the instrument response when analyzing solutions containing high dissolved solids or high concentration of acids. The problem can be reduced by diluting the solution and using a peristaltic pump, or by using a method of standard additions. A salt build-up on the nebulizer tip can also create problems. This can be corrected by using a tip washer and diluting the sample. The use of mass flow controllers to control the argon gas flow rates can also improve the instrument performance. Table 1 Spectral Lines of Noble Metals For Use in ICP-AES
Element Ag Ag Au Au Ir Pd Pd Pt Pt Rh Rh Wavelength 320.068 338.289 242.795 267.595 224.268 340.458 363.470 214.423 203.646 249.077 343.489 Relative Sensitivity 380 230 170 96 110 68 55 100 54 52 50 Detection Limit 0.007 0.013 0.017 0.031 0.027 0.044 0.054 0.030 0.055 0.057 0.060 Interfering Elements Fe, Mn, V Cr, Ti Fe, Mn Cr, Fe, Mg, Mn, V Cr, Cu, Fe, Ni Fe, Ti, V Ar, Fe, Ni, Ti Al, Fe Al, Cu, Fe Cr, Fe, Mn V

10.1.5

Atomic Fluorescence: Jumbo Mining Co. X-ray Fluorescence Spectrometry Principle Gold-bearing cyanide solution is passed thru a filter made of activated carbon. The carbon filter is then analyzed directly by the x-ray fluorescence (XRF) spectrometer. This approach offers several advantages over direct analysis of the solution: the gold is concentrated by several orders of magnitude, the background due to scattering of the excitation x-rays is greatly reduced because of the low mass of the sample, and because the sample is thin, matrix effects are virtually eliminated. Standards C C 1000 ppm Au standard, available from many vendors (Jumbo/ASOMA Method) This solution is diluted to simulate actual samples. The final volume of the Page 32

solution should be at 300-500 ml. C 20, 50, and 100 microgram/sq. cm. Au thin film standards. Available from: Micro-Matter, Seattle, WA

Reagents C Activated carbon cloth filter, 1.25 inch diameter, available from ASOMA Instruments, Inc. 12212-H Technology Blvd. Austin, TX 78727 (512) 258-6608

Special Equipment C A filter holder for the carbon disks and a pump for recirculating the solution thru the filter. A compact, hand operated device is available from ASOMA Instruments. This is a 500 ml syringe with fittings to hold the activated carbon filters. Instead of forcing the solution thru the filter, the filter may simply be placed in a jar of the solution and agitated for a few hours. This method is used when conducting bottle cyanidation tests.

C

Model 8620 )CRF analyzer (or equivalent) available from ASOMA Instrument Note: Many or all of the following instrument set up procedures may be automated by the on-board micro processors of the particular equipment being used. Procedure Configure the instrument for measurement of the Au L series x-rays and any other x-rays that might interfere due to spectral overlap. The Au L-beta x-ray is generally used for analysis since the carbon filters contain some zinc which interferes with the Au L-alpha x-ray. If necessary, use absorption edge filters to improve rejection of interfering x-rays (Reference: ASOMA Instruments, Inc. Model 8620 Operating Manual). Instrument Calibration C Run suitable blanks, such as fresh carbon filters to determine the instrument's background corrections.

Page 33

C

Run the MicroMatter standards to determine instrument sensitivity (S) in terms of counts per second (Au x-rays) per microgram Au per sq. cm. (Reference: ASOMA Instruments, Inc. Model 8620 Operating Manual).

Recovery Testing C The instrument itself is now calibrated. The following operations determine the recovery efficiency of carbon filters. The operations involved are the same as for analyzing unknown samples. Prepare standard solutions in the range of 0.5 to 2.0 ppm. Develop separate calibrations for samples that are agitated in the solution and those that are filtered.

C C

Agitated Samples C Place a known volume (300 to 500 ml) of a standard solution in a bottle. Enclose one carbon cloth filter in a mesh envelope and secure with a rubber band. The mesh will prevent the surface of the filter from fouling when this analysis is done as part of a bottle cyanidation test. Place the filter into the bottle and put the bottle on the agitator or roller. Recovery is usually complete after 6 to 8 hours, but to allow more complete extraction of gold from ore samples, the agitation is usually allowed to continue for 12 hours or more. After the allotted time, remove the filter, rinse off any ore that might be on the surface, dry the filter by pressing it between layers of paper towel, and present the sample to the XRF analyzer. Convert the gold x-ray intensity to micrograms of gold on the filter as follows: ug Au = net count rate * area of filter (sq. cm) S (defined as CPS per cmg/sq. cm) The concentration of gold in the solution is given by ppm Au = ug Au on filter volume of solution (ml) This value may be compared to the known concentration of the solution to find the recovery efficiency. With 8 hours agitation, the recovery is usually 95% or higher.

C

C

C

Filtered Samples C Take a known volume (approximately 400 ml) and pass it thru the filter 20 times or more. If the large syringe is used, prepare a stack of two filters and place them Page 34

in the holder on the syringe. Pour the sample into a large container (e.g. 1000 ml plastic beaker), insert the syringe tip into the beaker and operate the plunger 10 times, drawing the whole sample into the syringe and forcing it out each time. Remove the filters and dry them by pressing between layers of paper toweling. C Present the sample to the XRF analyzer and obtain the net count rate for the gold x-rays. Convert the intensity to micrograms of gold as follows: ug Au = net count rate * active area of filter S This value may be divided by the known amount of gold in the solution (mg Au = ppm* volume in ml) to determine the recovery efficiency. The efficiency will vary with technique, but should be at least 75%. Actual samples should be filtered in the same manner as the calibration samples. For routine analysis, the calculations are: ug Au on filter = net count rate * area of filter instrument sensitivity * recovery efficiency ppm Au = C ug Au on filter sample volume (ml)

C

C

For future analyses, the instrument sensitivity, the filter area and the recovery may be combined to obtain one overall calibration factor that will yield the total amount of gold in the solution. The reported concentration will be the weight of the gold divided by the sample volume. Actual samples should be filtered in the same manner as the calibration samples. Recovery efficiency should be checked routinely, especially when changing lots of the carbon filter material. If an ore sample was prepared, the concentration of extractable gold is given by ppm Au = ug Au on filter wt. of ore (grams) For future analyses, the instrument sensitivity, the filter area and the recovery may be combined to obtain one overall calibration factor that will yield the total amount of gold in the solution. Recovery efficiency should be checked routine, especially when changing lots of the carbon filter material.

C

C

Precision For XRF Analysis of Au in Solution C The measurement precision will depend greatly on instrument type and the analysis time used. For the Asoma Instruments Model 8620, the measurement precision is +1- 10 micrograms Au (1 sigma) for a 200 second analysis. This refers to the total Page 35

amount of gold in the filtered solution. If a 500 ml volume was filtered, the precision in ppm is ppm = 10 ug = 0.020 ppm 500 ml C The precision varies as a function of the square root of the count time. For example, a 50 second analysis would be four times quicker and have measurement precision two times higher than the 200 second measurement.

10.2.0

Solvent Extraction

10.2.1

MIBK Extraction From Acidified Solution (Newmont Method) Introduction C Gold-bearing solutions are acidified with aqua regia prior to extraction into methyl isobutyl ketone (MIBK) containing chelating agent (1% Aliquat 336). This preparation procedure assures dissolution of the gold contained in the solution and provides a universal matrix for presentation to the AAS for measurement.1 Alkaline cyanide solutions prepared using this procedure may be grouped with acid-fixed chlorination solutions, bottle test wash solutions, as well as dissolved dore beads, for instrumental analysis from 16 x 125 mm test tubes using the flame autosampler.

Reagents C C C Extractant: 1% Aliquat 336 (Trialki methyl ammonium chloride) in MIBK 1:1 Nitric acid: dilute concentrated nitric by 50%. Concentrated hydrochloric acid

Apparatus C C C C Pipets (Class A) sized as needed Culture tubes sized as needed Shaker table Centrifuge

Procedures

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C

Acidification Ten milliliter aliquots of each solution to be assayed, a solution of known value and a deionized water blank are transferred by pipet into clean test tubes in a numbered rack. the rack is placed into a sonic water bath at eighty degrees centigrade. A half milliliter portion of 1:1 nitric acid and a three quarter milliliter portion of concentrated hydrochloric acid are added to each of the tubes. After heating for ten minutes, the rack is removed from the bath and the solutions are coiled to room temperature.

C

Extraction Five milliliter portions of standards, in the range of one-tenth to five parts per million gold in ten percent aqua regia matrix, are transferred by pipet into clean test tubes in the rack and diluted with a five milliliter portion of deionized water. A five milliliter portion of MIBKcontaining one percent Aliquat 336 is dispensed into each test tube. They are capped, shaken for two minutes, centrifuged for five minutes, and transferred from the centrifuge, in the order of measurement on the AAS, to the flame autosampler carousel. Note1: Some labs would prefer to filter any undissolved gold solids prior to acidification. This is to insure that assay values reflect only dissolved gold when metullurgical balances are calculated.

C

Measurement The AAS instrument is optimized for gold with a lean flame in MIBK which is continuously burned during setup and measurement. Measurements are recorded in absorbance with deuterium arc background correction. Assays are calculated based on a linear regression of the known standard values, the concentration factor (2.00), and the conversion factor from parts per million to troy ounces per ton (0.02917). Samples which require higher sensitivity (below 0.0005 Au oz./ton) may be assayed by graphite furnace MS and samples above the high standard (above 0.075 Au oz./ton) may be assayed on another calibration or diluted. Extracts are stable for at least one week.

10.2.2

DIBK/Aliquat 336 Extraction From Direct Solution (Freeport Method) Principle

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C

This procedure uses solvent extraction followed by atomic absorption (flame atomization) to determine gold liquor values below .300 ppm. Gold is extracted from alkaline solutions by 1% trialkl methyl ammonium chloride (aliquat 336) and extracted from acid solution by diisobutyl ketone (DIBK).

Discussion C The standard 10:1 extraction is accurate to + .005 ppm with a detection limit of .001 ppm. A 50:1 extraction has been tested as accurate to + .001 ppm with a .0003 ppm detection limit. Concentration ratios up to 500:1 are possible, but accuracy is limited by the need for a quality standard. Extractions maintain accuracy limits from acid to base solutions for the 10:1 ratio, but this has not been verified for other ratios. Liquors of pH less than 1 or gre~ter than 12.5 have not been tested. MIBK may be substituted for DIBK. MIBK is more volatile and water soluble, therefore environmental risks are slightly higher. DIBK-and MIBK-extracted standards are not interchangeable. MIBK-based extractant may have a lower maximum concentration ratio than DIBK due to its higher solubility. The accuracy limits of this method were originally tested on a Perkin-Elmer model 5000 atomic absorption spectrometer with continuum (D2) background correction. They have also been verified on a Thermo Jarrell-Ash Video 22 atomic absorption spectrometer in both continuum and Smith-Hiefje background correction modes. The detection limits are slightly poorer on Perkin-Elmer model 2380 with continuum correction (.003) due to a poorer signal to noise ratio. In general, accuracy, detection limits and absorbance values may alter with the model of spectrometer.

C

C

C

Caution C C C Salt concentrations less than 10 g/l as NaCl affect gold extraction. All samples and standards should be adjusted above this level. Age can affect the quality of a DIBK/Aliquat 336 extractant solution. The extractant solution should be made every two weeks or less. Gold extracted from acid solution is not always stable. Do not allow an acid-extracted sample to stand more than twenty-four hours. A gold precipitate does form at the interface between the extractant and aqueous liquors if DIBK or MIBK alone (no Aliquat 336) is the extractant.

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C

Standards and extracted samples should not be left unsealed. Extractions from alkaline solution are stable, but all extractions are subject to contamination and evaporative concentration. Although sealed alkaline extractions may be accurate for several weeks, AA determination within five days is recommended. Dispose of all wastes in the tailings pond or as approved by the environmental department. Iron interference is a concern at some labs. Although iron will extract, alkaline solutions of up to 1% Fe as potassium ferrocyanide have been tested on background-corrected atomic absorption instruments without showing any effect. (Fe appears to reach its saturation point in this extractant from gold solutions with a 1% Fe conc.). If modern quality instrumental correction is not available, HCl back extraction (step 6, note C) may be employed for high Fe concentrations.

C C

Reagents / Equipment C C C C C C C C C C Diisobutyl ketone (2, 6-dimethyl-4-heptanone) Trialkl methyl ammonium chloride (aliquat 336, available from Aldrich chemical) Sodium Cyanide Sodium Hydroxide Sodium Chloride Acetone 500 ppm primary Au standard with + 1 ppm certified value 100 ml volumetric flasks (as needed) 50 ml volumetric cylinder 2 jet pipet dispenser (5 ml + .003 ml)

Prepared Reagents C Extractant (1% Aliquat 336 in DIBK): Weigh 20.Og Aliquat 336 into a 100 ml beaker. Dilute this with a small quantity of DIBK and pour into a two liter volumetric flask. Rinse the beaker with DIBK into the flask and bring to volume with DIBK. Matrix (.5 g/l NaCN, .1 M NaOH, 15 g/l NaCl): Dissolve 12.5g NaCN, 100 g NaOH, 375 g NaCl in 25 1 of deionized water. Stock gold standard (5.00 + .01 ppm) Calculate the weight of primary standard needed to make one liter of 5 ppm gold standard based on its certified concentration (liquors are weighed for stock standards to improve accuracy).

C C

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given: the primary standard is certified 495 ppm g primary = (intended stock conc.) * (intended stock volume) (certified primary conc.) g primary = 5 ppm * 1000 ml = 10.1 g 495 ppm Weight accuracy beyond + .005 g doesn't improve standard quality unless a better primary standard is available. Use a transfer pipet to weigh the primary standard into a tared 1000 ml volumetric flask. Bring to volume with matrix solution and mix contents. This solution should be sealed and protected from light over its six month lifetime. C Working Gold Standards (ppm Au): Prepare fresh each day in pre-equilibrated flasks (flasks which have held identical solutions for the previous 24 hrs). .100 + .0005 @ 200C: pipet (class A) 5 ml of 5 ppm stock into a 250 ml volumetric cylinder. Bring the flask to volume with matrix solution .300 + .001 @ 200C: pipet (class A) 15 ml of 5 ppm stock into a 250 ml volumetric cylinder. Bring the flask to volume with matrix solution. C Saturated salt solution: Dissolve 358 g of sodium chloride in one liter of hot deionized water. Allow the solution to cool and pour the saturated solution into a jet pipet dispenser. Atomic Absorption Gold Standards Extract the working standards by the same procedures and ratio used on samples submitted for analysis. Accuracy will vary with the extraction ratio. Normal multiple 10:1 extraction should match within .005 standardized ppm. The .100 ppm extraction will have an absorbance of approximately .06 (D2) or .02 (Smith Hieftje) and the .300 ppm extraction will be within .005 absorbance units of three times the .100 standard absorbance. If these conditions are not met, re-extract the standards. Procedure (10:1 Extraction Ratio) Page 40

C

1) Prepare the 100 ml volumetric flasks for extraction by dispensing 5 ml of saturated salt solution into each flask with the jet pipet. This prevents poor extraction and poor separation. Note: a) Check gold absorption and solvent interactions before substituting plasticware. b) Alternate glassware may be substituted, but at least 50% open space must remain in the container at step 4 for extractions of consistent quality. 2) Measure 50 ml of sample with a volumetric cylinder into each flask for each sample. 3) Squirt 5 ml of extractant solution into each flask using calibrated jet pipet or dispenser of equivalent accuracy (+ .003 ml). 4) Hand shake eight (or more if comfortable) extractions vigorously for 45 seconds. Note: a) Shaking should be vigorous enough to create a foamy appearance. b) If a machine shake is used, 2-5 minutes is required, depending on the pattern and vigor of agitation. 5) Add water to each flask to raise extractant into the glass neck. 6) Allow to separate for at least 45 minutes. Note: A) If the extractant is not given this time to clarify, the entrapped water can lower gold values during aspiration by as much as 6%. B) If iron interference is a concern, Fe may be back extracted with two washes of 10% HCl. Increasing iron concentration is marked by a darker yellow extractant. A green (iron) precipitate will form from extractions of 1% or more iron in alkaline solution. Interference is not a problem on equipment with quality background correction at 242.8 nanometers. C) Settling time may be decreased to two minutes if the extraction is performed in 100 ml centrifuge tubes and the tubes are centrifuged for two minutes. 7) Replace the burner assembly used for standard liquor determinations with the DIBK assembly. When separate assemblies are not used, standard liquor determinations will be affected. If the DIBK assembly is not cleaned ultrasonically at least once per week, determination quality can deteriorate. 8) Set the fuel/air ratio as lean as possible. Maximize absorbance with one of the standard extractions. Page 41

9) Use raw extractant as a blank. .100 ppm and .300 ppm working extractions serve as standards. Note: A) Samples with more than .300 ppm gold values must be extracted using less sample. Gold values may be calculated as follows: Calculated ppm = standardized value ppm * actual sample volume normal sample volume B) Burner slit deposits occur just before absorbance problems. Stop and clean the head ultrasonically when this appears. C) On P-E 5000 w/D2 correction .100 ppm, abs. approximately .06 w/D2; w/Smith-Heifje correction on TJA Video 22, abs approximately .02. Cleanup 10) Dump 100 ml flask contents into environmental department approved sinks (must drain into the tailings pond). Four or more flasks may be done at one time. Rinse with acetone until clear to remove DIBK. Rinse flasks with HCl to clean off any scale. Rinse flasks followed by three D.I. washes for the final cleaning. Rinse with acetone to speed drying and then set the flasks on the drying rack.

11) 12) 13) 14)

10.2.3

Butyl Sulfide Extraction (North American Laboratories) Reagents C C Conc. HCl Dibutyl sulfide extractant: 3,750 ml reagent-grade xylene with 100 g dibutyl sulfide

Procedure Measure 50 ml of sample & acidify w/HCl. Add 5.0 ml of butyl sulfide-xylene mixture, cap, and shake in an Eberbach or similar machine for 3 minutes. Allow the Page 42

phases to separate, and compare the gold absorbance from the organic solution against standards extracted from HCl solution in a similar manner. Atomic absorption conditions are those recommended by the manufacturer of the particular instrument to be used. The wavelength is 242.8 nm, and background correction is required. 1) If the sample contains organic material, it must be filtered prior to acidification. Organic material (i.e. carbon) may compete for gold during extraction. 2) Perform all steps in a ventilated hood. Butyl sulfide has a strong odor.

10.3.0

Reference Fire Assay Procedure (Freeport/Newmont Composite) Introduction Fire assay practice varies a great deal. This basic outline of one pattern is included to complete references to “fire assay as normal” in the collected methods. Depending on the method, begin with fusion or cupellation. It is recommended that anyone learning these methods obtain training and advice from an experienced fire assayer. While this method represents acceptable practice, it should not be regarded as universal practice. Reagents C Flux: Flux formulas are detailed in each individual method as needed. A respirator should be worn while handling soda ash, silica, borax and litharge (see lead control). Inquarts: silver wire, foil or Herman inquarts as required. Parting solution (1:4, Gravimetric Finish): measure four liters water for each liter of nitric acid. Parting solution (1:1, Instrument Finish): measure 1 liter nitric acid for each liter water. Aqua regia (Instrument Finish) measure 3 ml hydrochloric acid for each 1 ml nitric acid. Make fresh daily. Extractant (MIBK or DIBK w/5% Aliquat 336, Instrument Finish): weigh 50g Aliquat 336 into a 250 ml beaker. Dilute this with a small quantity of MIBK or DIBK. Pour into a one liter volumetric flask. Rinse the beaker into the flask with Page 43

C C C C C

the same organic solvent several times. Fill the flask to 1000 ml mark with the same organic. Equipment C C C C C C C C C C C Furnace equipped to fuse at 1950EF and cupel at 1650EF pour molds pouring tongs heat-protective gloves face shield (should stop U.V. and I.R. to avoid eye damage) 30g crucibles cupels (MgO preferred for gold) cupel fork parting trays (stainless steel preferred) parting china cups (sized to fit trays, hold about 10 ml) hotplate

Lead Control Lead is a toxic metal. TLV exposure level is .15 mg/m3. The general population has levels of 10-12 mg per deciliter1. Freeport-McMoRan Gold withdraws technicians from fire assay at levels as low as 20 mg/deciliter, but acceptable blood lead concentrations vary between labs. Note 1: Levels are higher in urban areas

1) Ventilation is recommended in any Fire Assay or flux exposure area. 2) A respirator should be worn while in any area with airborn lead concentrations above .15 mg/m3. 3) Wear disposable plastic gloves when handling lead in any form. 4) Wear lab coats or other protecting clothing which can be removed upon leaving the exposure area (don't wear lead home). 5) Maintain a clean work area. Procedure Fusion: 1) Prepare liquor sample as the chosen method indicates. Flux charges and treatment Page 44

are included in individual methods. Exact silver inquart values must be known if silver is also being assayed. Control assays of known grade are recommended. (Example: @ Freeport, #16 Fusion is always a blank or standard. #17 is always a refire of #20 from the previous fusion set). 2) Load charged crucibles in the furnace at 19500F. A standard order should be used to maintain sample identity. Fuse for 45 minutes. 3) Pour fusion in standard order. 4) Allow the slag to cool 5-10 minutes. The lead "button' at the bottom of the mold contains gold, silver and other precious metals. It should weigh about 25 g. 5) Break the slag and shape the lead button into a cube with a hammer. This shatters loose remaining slag. Cupellation: 1) Set furnace at 16500F (raise as required for MgO cupels) Note: If assaying for silver also, controls of known silver should be used to monitor silver volatilization losses. 2) Use a cupel fork and gloves to load the appropriate quantity of cupels (MgO cupels will give better and more consistent gold recovery. However silver assay temperature control is more difficult with these cupels) Draft damper (if so equipped) should be closed. 3) Preheat for 10 minutes 4) Load lead buttons in a consistent order. They should melt, then develop an open glowing surface. Raise the furnace temperature if cupels fail to open. (removing oxygen by burning objects in the furnace by the cupels will also help) Note: Higher temperatures increase silver volatilization losses. Cupellation is the process of 2 Pb+O2 ÷ 2PbO with the PbO draining into the cupel. 5) Once cupels are glowing ("driving"), the draft damper should be opened. 6) When glowing stops, leaving a round bead of silver and gold, remove the cupels using gloves and a cupel fork. Inorganic Concentration Finish (Parting) Of Dore' Bead:

Page 45

1) Pound the "dore'" beads flat and, using a consistent order, place them in china cups arranged on a metal parting tray. Weigh dore prior to parting if a silver assay is also being performed. 2) Fill each china cup with 1:4 parting solution. Over strength acid at this step will leave gold in a finely divided ("floured") state and cause poor assays. 3) Place parting tray on the hotplate. As the tray slowly warms, the acid will attack the silver in the beads with increasing vigor. When all effervescence stops, parting is complete (gold is not significantly attacked by the nitric). 4) Remove tray from the hotplate. 5) Decant the parting solution. A few drops of concentrated nitric may be used to ensure thorough parting at this point. 6) Decant again and rinse china cups with a 2% ammonia solution followed by distilled water. Incomplete rinsing will leave a dark stain in the China cup after rinsing and cause incorrect assays. 7) Return the tray to the hotplate for thorough drying. 8) Place the tray of china cups in a 19500F furnace for 1 minute to anneal the gold beads. 9) Cool to room temperature and weigh gold beads on a Micro balance to .001 mg. 10) Calculation: mg weight * 29.166 = Au ozt/st ml sample Silver oz/t is calculated using the difference between dore weight (less inquart's silver weight) and parted weight. Instrument Finish (Newmont Gold): 1) The bead is transferred with small tweezers from cupel to 16x126-mm (16-ml capacity) glass culture tube. 2) .5 ml of 1/1 nitric acid is dispensed into the tube and heated for 10 min at 90EC 3) .8 ml of fresh concentrated hydrochloric acid is added and heated at 90EC for 30 min. 4) 8.7 ml of deionized water is added.

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5) Depending upon the desired concentration factor, MIBK containing 5% Aliquat 336 is carefully dispensed into the culture tube -- for most l00-ml chiddeys, 5.0 ml of MIBK is adequate (factor 20.0). 6) The extraction is tightly capped and agitated for 2 mm. 7) The extraction is centrifuged for 5 mm., then transported to instrument room for atomic absorption spectroscopy.

10.3.1

Procedure, Inorganic Concentration, Copper Sulfate (Pinson Method): Determination of Gold and Silver in Gold Plant Solutions by Fire Assay Scope This method determines the gold and silver content in gold plant and heap leach solutions by fire assay. Equipment C C C C C C C C 500 ml conical beakers 100 mm funnels 20.5 cm fast filter paper assay furnace 30 gram crucibles cupels annealing cups bead balance

Standard Flux (blended in batches, used in 120 g charges. See standard flux survey for more information) C C C C PbO - 100 lb Soda Ash - 100 lb Silica - 4,4 lb Borax - 10.6 lb

Reagents 1) Potassium ferrocyanide - dissolve 50 grams/liter of distilled water. 2) 10% copper sulfate - dissolve 100 grams copper sulfate/liter distilled water. Page 47

3) 20% sodium sulfite - dissolve 20 grams/100 mls of distilled water. MAKE FRESH DAILY. 4) 10% sulfuric acid - add 100 mls of sulfuric acid to 500 mls of distilled water. Cool, make to one liter with distilled water. 5) Silver nitrate - dissolve 4.335 grams of silver nitrate in one liter of chloride-free distilled water. Store in an amber bottle (labeled as made-not a standardized normal solution). 6) Flocculent solution - disperse 2.0 grams of flocculent (Superfloc 16 or equivalent) in 10 mls of methanol, add to 900 mls of hot distilled water until dissolved. Note: Flocculent type works with typical solutions. A lab changing this method should test available commercial flocculents on their solutions to eliminate any possibility of introducing bias. Procedure 1) Measure a 5 assay ton (over .01 ozt/st Au expected) or 10 assay ton sample (150 or 300 mls) into a 500 ml conical beaker. 2) Add 1.0 ml of silver nitrate solution for inquart. 3) Add 1.0 ml of potassium ferrocyanide solution, stir briefly with a glass rod. 4) Add 40 ml of 10% copper sulfate solution, stir briefly with a glass rod. 5) Add 15 ml of 20% sodium sulfite, stir briefly with a glass rod. 6) Add 15 ml of 10% sulfuric acid, stir briefly with a glass rod. 7) Add several drops of flocculent solution and stir vigorously with a glass rod for a few seconds. 8) Allow precipitate to settle. 9) Filter precipitate through fast filter paper (VWR grade 615 or equivalent), wash with deionized water once. 10) Sprinkle small amount of assay flux on precipitate, transfer wet filter paper/precipitate to a 30 gram crucible containing 1/3 of a normal flux charge. Page 48

11)

Cover with remaining flux, do not stir. Total charge 120 g of flux. Add 1/4 tsp (3/4 gram) flour to obtain 25 g lead. Fire assay as normal (see 10.3.0 and references).

12)

10.3.2

Procedures. Inorganic Concentration. Copper Sulfate (Freeport Method): Gold Determination in Liquid by Fire Assay Reagents C C C C C C C C C NaCN Solid Copper sulfate solution (15% hydrated salt by weight in deionized H20) Sodium sulfite solution (10% anhydrous salt by weight in deionized H20) Sulfuric acid (20% by volume diluted in deionized H20) Borax glass Lead (granular test lead) - scorification method only Soda ash Litharge Flour or wood charcoal (flour preferred)

Note: Reagents mixed as a percent may vary plus or minus a percent without a problem (as opposed to normal solutions which must be exact). Procedure 1) Take 50 to 500 ml solution according to the probable amounts of gold and silver for barren solution and tails. 2) Add 25 ml copper sulfate solution and stir. 3) Add 25 ml sodium sulfite solution and stir. 4) Add 25 ml dilute sulfuric acid and stir. 5) If sufficient cyanide is present, a fairly heavy white precipitate of cuprous cyanide will form; otherwise, add 0.5 gram sodium cyanide dissolved in 50 ml and stir. An excess of cyanide is important to insure an accurate assay. The clear layer of this mixture should be blue. If not, add another 25 ml copper sulfate solution. 6) Filter through an 18 cm No. 40 Whatman filter paper. No washing is necessary. Fold filter paper (containing residue) in a 3-1/2 inch scorifier or in a fire assay Page 49

crucible. Dry and char until all carbon is destroyed. Charring should not produce a flame since it will carry off gold. With improper precipitation, gold may be present in the form of AuCl. This will volatilize with charring. 7) If you are using a scorifier, add 35 grams granular lead and 5 grams of borax. 8) Add 3 inquarts for tail solutions, 40 mg Ag for pregnant solutions, or add silver according to probable gold bead weight (Ag added = 3x expected wt of Au). Scorify at 1950EF. 9) If you are using DFC or A.P. Green fire clay crucible, add: C 35 8 litharge C 30 g Soda ash C 10 g borax C 1 g wood charcoal or 3/4 tsp. (about 2.5g) of flour C 3 pieces of herman inquart for barren and tail C 40 mg silver for pregnant solution 10) 11) Fuse, cupel, and part in the usual manner. (See 10.3.0) ppm Au = bead wt (mg) * 1000 ml sample

Note: Charge size and reagent balance can require some adjustment with different brands of fire clay crucibles. Note: Charcoal has a tendency to “spark" during the fusion reaction. Flour gives a more controlled reduction. Note: A concern was expressed about the inexact silver content of gold-free herman inquarts. Parting practice (1:4 nitric slowly warmed from cold to near boiling during parting) allows silver values between 2.5 and 4 times the expected gold content in dore beads without affecting gold assay quality. Of course, silver content must be exact if a silver assay is also being done by this method. 10.3.3 Procedures. Inorganic Concentration. Copper Sulfate (Golden Sunlight Method) Equipment / Reagents C C AgNO3 solution - 4.71g AgNO3/liter distilled H20. Potassium ferrocyanide - saturated solution 55 ml-300m1 H20.

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C

Precipitating solution - To a saturated solution of copper sulfate (75m1-400m1), slowly add a saturated solution of NaOH (5Om1-400m1) stirring constantly until a light precipitate is formed. Then carefully add a little more caustic solution until the color changes to a darker blue (still maintaining a heavy precipitate). To this mixture, slowly add a saturated solution of sodium cyanide (125-15Om1-400m1) stirring constantly until the blue formed with the NaOH solution is just dissolved and a yellow tea color is formed. Standard Flux: (70 grams), 46 g litharge, 12 g soda ash, 1 g borax glass.

C

Procedure 1) Measure 10 AT of sample solution into 450 ml beaker. Note: For low grade solutions, measure 20 AT in a 1000 ml beaker and add 1.5 times the additions in steps #3, #4, and #5. 2) Add 2 ml of AgN03 solution. 3) Add 4 drops ferrocyanide solution and stir. 4) Add 15 ml. of precipitating solution and stir well. 5) Add, carefully, 20m1 of concentrated sulphuric acid and stir well. 6) Allow precipitate to settle for 10 minutes and then filter through S & S 595 15 cm filter paper (or equivalent fast quantitative filter paper). 7) Wash three times with hot distilled water. 8) Transfer filter paper containing precipitate into 40 ml perforated bottom crucibles. Place crucibles in drying tray on a hot plate. Do not heat to burning temperatures. 9) Transfer dried paper with precipitate to a 20 g crucible. 10) Flux with a 70g charge of already-mixed flux plus 10 g silica - Do not stir. About 1.5 g flour may be blended into the surface. With the carbon contained in the filter paper, a minimum of 15 g of lead should form. Fire assay according to accepted practice (see 10.3.0 and references). Slag should be neutral or slightly acid (adjust flux if not).

11)

10.3.4

Procedures. Inorganic Concentration: Chiddey Page 51

Reagents C C C Lead Acetate Soution - 200 grams Lead Acetate/liter distilled or deionized H20. Zinc Dust Concentrated HCl

Procedure A spectroscopic finish is helpful when it is necessary to gain maximum measurement sensitivity on extremely low-grade solutions. Samples expected to measure above .010 oz/ton (e.g., mill pregnant solutions) are adequately concentrated by the gravimetric finish. 1) Assay by spectroscopic scan to determine appropriate sample volume and labeled labware: Sample (Newmont Format example) Aliquot l-L Beaker Under .010 oz/ton 300 ml Barren Under .010 oz/ton for AAS Finish 100 ml Barren .010 - .050 oz/ton 100 ml Preg Over .050 oz/ton 100 ml High Grade Limited Sample Available 100 ml (by grade) Instrument Calibration Standard 100 ml (by grade) 2) Pipet sample aliquot and transfer into l-L beaker. Use l00-ml pipet for all samples. Caution Note: Beaker must first be rinsed with concentrated HCl acid if it contains zinc from previous Chiddeys. Low-grade and high-grade glassware must be clearly marked and used for appropriate samples. 3) Place on hotplate and warm (approximately 40EC) solution then add 60 ml of lead acetate solution. Heat to just below the boiling point (steaming). Solid lead acetate may be dissolved directly in the sample instead of preparing a lead acetate solution for additions. 4) Add zinc dust until all lead is precipitated (approx. 5 gr). Complete precipitation can be checked by adding a few drops of concentrated HCl. If a white precipitate (PbCl2) forms, the lead is not completely precipitated. 5) Add concentrated HCl in excess to dissolve excess zinc (80 ml). Lower heat. (Note: some labs add HCl before adding zinc dust) step 4).

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Caution Note: If undissolved zinc is retained and HCl is not added in excess of zinc dissolution, low gold values will occur. Boiling temperatures will break up the lead sponge. This may result in low gold values due to lost lead particles. 6) When all action ceases, warm 5-15 minutes below boiling temperature (40-60EC). 7) Decant and wash lead sponge 3-4 times with deionized or distilled H2O. Press the water from the lead sponge by hand (fingers) until dry. CAUTION: Any "lost" lead represents a potential gold loss. 8) Wrap the dried lead sponge in 15g of lead foil. Put 2 herman Inquarts in with sponge. A hole should be punched in the lead foil so that any retained moisture may escape as steam. 9) Cupel and continue as in a standard fire assay (10.3.0, start with cupellation). Note: A concern was expressed for the exact silver content of herman inquarts. Herman inquarts are convenient. Parting practice (1:4 nitric warmed to near boiling during parting) allows silver between 2.5 and 4 times the gold content in the dore' without errors in gold analysis. Of course, silver addition must be known precisely if a silver determination is also being done. Note: (Historical) The chiddey method is named for Alfred Chiddey, who described the original version of this method (Bugbee, 1940, pg. 241).

10.3.5

Procedures. Inorganic Concentration: Lead - Acid Reagents C C C C Granulated lead: + 10 mesh - (screened test lead may be used) Concentrated HCl Lead Foil (7.5 cm x 7.5 cm) Ag for inquartation (AgNO3, solid inquart, etc.)

Procedure 1) Measure an appropriate aliquat of sample (typically 300 ml or 150 ml) of cyanide solution into a 600 ml beaker. 2) Add 1 ml AgN03 solution (6g/l) and mix well.

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3) Heat to just below boiling point. Add about 1/2 tsp (9 to 16 g) granulated lead. 4) Add 10 ml concentrated HC1 (CAUTION), cover with watch glass, and boil strongly for 10 to 15 minutes. 5) Cool solution, and carefully decant so as not to lose any lead. 6) Wash lead twice with deionized water by decantation and dry on a hotplate. 7) When dry, transfer the lead into a piece of prefolded lead foil. Wrap carefully, and cupel. Part dore , anneal, and weigh gold bead. Calculation Au in solution (oz/ton) = Bead weight (mg) * 29.166/sample volume (ml) C Notes (Battle Mountain Gold) Method has been compared to several others we have used, in particular the Copper Sulfate Collection method. With most solutions, assay results showed no significant bias. With foul solutions, the amount of HC1 added may have to be increased and reaction times may have to be increased as well. This also holds for high Au concentrations, though we have not made any detailed studies regarding this cutoff concentration. Note (Freeport) A minor amount of gold remained in waste solutions checked by AAS/DIBK methods. This did not affect the determination accuracy within precision limits. The method is ideal as a quick check for potential interference in higher (above .3 ppm) grade solutions.

C

10.3.6

Procedures. Inorganic Concentration. Direct Assay: Fusion of High-grade Solutions for Gravimetric Assay Scope When a gravimetric assay is required on alkaline cyanide solutions containing high concentrations of gold (e.g., refinery process samples), the chiddey assay is often rendered inappropriate by chemicals present in the solution; these solutions, however, may be fused by the following procedures and finished by gravimetric means. Procedure Page 54

1) 80 g standard (see topical survey on standard fluxes) fusion flux is placed into a used 40-g crucible (Caution: the glass lining in a used crucible is necessary to prevent sample from soaking into the porous ceramic.) 2) 15 ml of sample is transferred by class-A pipet into an indentation made by spatula in the center of the flux charge and covered with surrounding flux. 3) The sample is allowed to dry for 10 minutes, then microwave-dried for 2 minutes. 4) The sample is fired at 2000 degrees F for 45-60 minutes. 5) The fusion is poured and de-slagged, then cupeled. 6) The dore is weighed, and silver weighing approximately four times the dore weight is wrapped in lead foil with the dore. 7) The dore and inquarts are cupeled. 8) The bead is hammered flat and placed into a china cup to which nitric acid 1:4 parting solution is added. 9) The solution is heated on a hot plate until parting ceases; the solution is decanted and replaced, and several drops of pure nitric acid are added to ensure thorough parting. 10) The solution is decanted and the china cup is rinsed with ammonia solution, finally with distilled water. The cup is thoroughly dried on the hot plate, then inserted into the furnace for 1 mm to anneal the gold bead. After cooling to room temperature, the gold bead is weighed on a micro-balance (See Gravimetric Assay composite procedure for details on reagents, equipment). Calculation: mg weight * 1.944 = Au Troy oz/ton.

11)

12)

13)

11.0.0

General Calculations Dilutions

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1st Dilution Total Dilution Volume Aliquot Volume or Sample Weight x

2nd Dilution Total Dilution Volume x Aliquot volume

Each Additional Dilution Total Dilution Volume Aliquot volume

Dilution Factor x Diluted Sample Analysis = Original Sample Concentration Conversions ppm Concentration * .029167 = oz/t concentration oz/t Concentration * 34.285 = ppm concentration ppm = mg/l = ug/ml for solutions with a specific gravity of 1 (same as water): 1 g of solution = 1 ml of solution

12.0.0

Precision and Bias These methods are a result of a survey of mining practice. The precision reported is based on the rough estimates of participating labs. Interested parties should refer to contributing labs for details. The bias (absolute accuracy) has not been quantitatively verified. Most labs do indicate that bias is within precision limits as checked by Canadian, American, and commercial standards. Gold Precision Gold Detection Limit

Direct Spectroscopic Methods

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Atomic absorption with flame atomization 0.xxx bracketed range ±0.002 oz/t (±0.07 ppm) x.xx bracketed range ±0.01 oz/t (±0.3 ppm) With Graphite Furnace Atomization (w/o buffer) Atomic Emission (DCP) Atomic Emission (ICP) Atomic Fluorescence (X-Ray) w/500 ml preconcentration ±0.00020 oz/t (±0.005 ppm) Not Available Not Available ±0.0006 oz/t (±0.02 ppm) 0.001 oz/t (0.03 ppm) 0.01 oz/t (0.1 ppm) 0.00003 oz/t (0.001 ppm) 0.00003 to 0.0002 oz/t (0.001 to 0.005 ppm) 0.0006 to 0.0000 oz/t (0.02 to 0.03 ppm) 0.002 oz/t (0.06 ppm)

Organic Concentration Methods (Extraction)
MIBK from acidified solution Direct from sample 1:1 concentration ratio ±0.002 oz/t (±0.07 ppm) 3:1 concentration ratio ±0.001 oz/t (±0.04 ppm) 4:1 concentration ratio ±0.001 oz/t (±0.04 ppm) w/100 ml Chiddy 20:1 concentration ratio ±0.0005 oz/t (±0.02 ppm) w/300 ml Chiddy 60:1 concentration ratio ±0.0002 oz/t (±0.007 ppm) 0.0001 oz/t (0.003 ppm) DIBK/Aliquat 336 direct 10:1 concentration ±0.0001 oz/t (±0.005 ppm) 0.00003 oz/t (0.001 ppm) 50:1 concentration ±3x10-5 oz/t (±0.001 ppm) Dibutyl Sulfide from Acidified Solution Not Available 1x10-5 oz/t (0.0004 ppm) Not Available 0.0001 oz/t (0.003 ppm) 0.001 oz/t (0.03 ppm)

0.0005 oz/t (0.02 ppm) 0.0003 oz/t (0.01 ppm)

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Inorganic Concentration Methods (Fire Assay)
Copper Sulfate Pinson Freeport Golden Sunlight Chiddy 300 ml sample 100 ml sample Lead Acid 100 ml sample Direct Assay ±0.002 oz/t (±0.07 ppm) Not Available 0.0003 oz/t (0.01 ppm) Not Available ±0.0003 oz/t (±0.01 ppm) ±0.001 oz/t (±0.03 ppm) 0.0001 oz/t (0.003 ppm) 0.0003 oz/t (0.01 ppm) Not Available ±0.001 oz/t (±0.03 ppm) Not Available Not Available 0.0002 oz/t (0.005 ppm) Not Available

13.0.0

Waste Disposal All commercial and non-mine laboratories are required to meet EPA hazardous waste disposal regulations. Small and medium size labs (up to 2,200 lb/month hazardous waste or about five drums of waste with the density of water) are regulated as Small Quantity Generators (SQGs) under the Resource Conservation and Recovery Act (RCRA).1 Mining lab waste is exempt from hazardous waste designation by the Bevill Amendment to RCRA, but details should be confirmed with state and local EPA Jurisdictions. For example, the Nevada Department of Environmental Protection (NDEP) regulates certain mining and lab wastes and requires disposal in zero discharge tailings impoundments in conformance with the exemptions noted in Chapter 450.465 of the Nevada Revised Statutes (NRS) and the ensuing codes and policies. Hazardous wastes are generated in these gold analysis methods and are disposed as follows: Heavy Metals lead, silver, copper, selenium, etc.: Contact Jack Scott of Encycle, Inc. (An ASARCO subsidiary) at 801-262-2459. They may accept cupels and other metal waste for recycling. If this is not practical, locate an EPA-approved hazardous waste facility. In Nevada, call NDEP Solid Waste Division and Sierra Chemical Company in Reno. Organic Solvents MIBK, DIBK, Xylene, Acetone, etc.: Gibraltar Chemical Resources (subsidiary of Gilbraltor & Mobley Industries) in Kilgore, Texas (214) 983-2377 will recycle solvents. If recycling is not practical, use an EPA-approved hazardous waste dump, approved incinerator, or a zero discharge tailings pond. Ensure when placing wastes Page 58

in the tailings impoundment that it meets with federal, state and local approval. Sodium Cyanide Maintain cyanide solution pH above 10.5 prior to disposal. Destroy cyanide in a well-ventilated hood with a strong oxidizer, i.e., chlorine or peroxide solution, prior to disposal in sewer drains. Care is required due to toxic gas produced in this process. Excess alkalinity must be neutralized before offsite disposal. Acid/Base Reagents Alkaline or acid reagents must be neutralized before offsite disposal. Non Specific Waste Any waste-water can potentially be classified as hazardous. Consult the code of Federal Regulations, 40 CFR 261. This list should not be regarded as complete and other wastes or treatments may be significant depending on local jurisdiction. Don't avoid the waste disposal problem by storing waste. It may be illegal and could move a company into a more difficult category. Choose a waste management firm with care. Unless the waste is recycled, the original waste generator can retain permanent liability for any problems. This waste disposal section suggests the general nature of the waste problem. Detailed assistance is available from a number of sources. The EPA has published an excellent plain English handbook to assist the small business (EPA/53O-SW-86-019, Sept. 1986). The Illinois Hazardous Waste Research and Information Center (HWRIC) published a more detailed manual which includes tips on how to choose waste management firms and tips for staying out of trouble (Kraybill, January 1987). Although, these documents are difficult to obtain due to heavy demand, local regulatory officials may have copies. In addition, Ocal EPA jurisdictions will answer any general questions on compliance requirements. Note 1: SQG regulations became effective Sept. 22, 1986 and March 24, 1987

14.0.0

Contributing Organizations Methods listed under a company and underlined were the primary model for a composite or were included in entirety. Contributing companies and the types of methods they submitted are as follows (in alphabetic order) with Chief Chemists or contacts in parenthesis): Page 59

Asamera Minerals (Dave Potter) (509) 663-7313 1) Inorganic Concentration (Fire Assay) - Lead Acid 2) Direct Atomic Absorption - Flame Asarco Corp. (Steve McCann) (406) 227-7100 1) Commentary ASOMA Instrument~, Inc. (John Schindler) - 512-258-6608 1) Inorganic preconcentration (XRF) Battle Mountain Gold (Paul Corona) (702) 635-2465 1) Inorganic Concentration (Fire Assay) - Lead Acid 2) Direct Atomic Absorption - Flame Dee Gold (Lee Koch) (702) 738-6440 1) Direct Atomic Absorption - Flame FMC - Paradise Peak (Luis Acre) (702) 285-0060 1) Inorganic Concentration (Fire Assay) - Chiddy 2) Direct Atomic Absorption - Flame Freeport McMoRan Gold (Jim Anderson) (702) 738-9221, contribution compiled by T. Gilbert 1) Inorganic Concentration (Fire Assay) - Lead Acid, Chiddy, and Copper Sulfate Precip. Methods (indicated low usage) 2) Direct Atomic Absorption - Flame, Furnace (no longer used) 3) Extraction - DIBK/Aliquat 336, Dibutyl Sulfide/Xylene (not in use) 4) Reference Fire Assay Method 5) Waste Disposal FRM Corp. (Dave Maddox) (702) 635-5001 1) Direct Atomic Absorption - Flame Golden Sunlight Mine (John Stratton) (406) 287-3257 1) Gravimetric (Fire Assay) - Chiddy, Copper Sulfate 2) Direct Atomic Absorption - Flame Cold Fields Mining (Bob Gerteis) (303) 277-1378 1) Direct Atomic Absorption - Flame Homestake Mining (Wilson Tsu) (916) 446-1070 1) Direct Atomic Emission - DCP (Direct Coupled Plasma)

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Jumbo Mining Company (E.B. King) 1) Atomic Fluorescence (X-Ray) Newmont Gold (Gerry Scott) -- Contribution compiled by Jim Force (702) 738-7196 1) Direct Atomic Absorption - Flame 2) Inorganic Concentration (Fire Assay) - Chiddy, Direct Fire 3) Extraction - MIBK from Acidified Solution 4) Hazards & Precautions (section 8.0) 5) Fire Assay, Reference Method 6) Fire Assay, Instrument Finish Pinson Mining (Jack Simmons) (702) 623-5036 1) Inorganic Concentration (Fire Assay) - Copper Sulfate Skyline Labs (Edwin V. Post) (303) 424-7718 1) Final proof review (tech. spelling, punctuation, etc.) Spectroscopy (B. Jane Ellis, Associate Ed.) 1) Permission to use BC correction table Thermo Jarrell Ash Corporation (Jack Robert) (415) 327-5609 1) Comments on instrumental methods 2) General AAS Interference (section 6.1) U.S Bureau of Mines (Reno Office - Gene Elliot) (702) 784-5391 1) Direct Atomic Absorption University of Lowell, Mass., (Joseph Sneddon) (617) 452-5000 ext. 2552 1) Permission and review of the comparative table for instrumental background correction. Vegas Analytical Laboratory (B.M. Joshi) (702) 365-1201 1) ICP Emission

15.0.0

Disclaimer of Liability Neither the Editor, Society of Mineral Analysts nor the contributing organizations assume any liability for the 'use and application of the methods, procedures or other information contained in this document. The contents of this document should not be used without prior critical evaluation. The mention of any particular brandname, trademark, commercial service, or brand Page 61

name product herein does not imply any form of endorsement by the Society of Mineral Analysts.

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