Analytical techniques for the determination of precious metals in geological and related materials

Critical Review
G. S. Reddi and C. R. M. Rao Geochemistry Division, Geological Survey of India, Bandlaguda, Hyderabad-500 068 India. E-mail:; Received 17th June 1999, Accepted 25th August 1999

Summary of contents
1 2 2.1 2.2 2.3 2.4 2.4.1 2.4.2 3 3.1 3.1.1 3.1.2 3.2 3.3 3.4 3.4.1 3.4.2 4 5 6 Introduction Sample decomposition and preconcentration stage Lead fire assay Nickel sulfide fire assay Chlorination Wet chemical attack Gold Platinum group elements (PGE) Instrumental/measurement stage Atomic absorption spectrometry (AAS) Flame AAS Graphite furnace AAS Inductively coupled plasma atomic emission spectrometry (ICP-AES) Inductively coupled plasma mass spectrometry (ICP-MS) Neutron activation analysis (NAA) Instrumental neutron activation analysis (INAA) Radiochemical neutron activation analysis (RNAA) Conclusions Acknowledgements References

1 Introduction
Determination of the precious metals in complex geological and allied materials has always been a fascinating field of analytical

chemistry. Trace level occurrence, economic compulsions and the uncertainties in the world prices are the natural causes for the interest in their exploration and analysis. The renewed interest in the search for their deposits has led to improvements in the methodologies to determine the precious metals. The members of the platinum group elements (PGE) viz., platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir) and osmium (Os) and gold (Au) occur in nature as various mineral species chiefly as antimonides, arsenides, bismuthides, sulfides, tellurides and in the native state. The details of various minerals are described in Table 1. The precious metals possess some unique geochemical characteristics. They are very refractory, having high boiling points and a strong affinity for iron1 (siderophile) and for sulfur2 (chalcophile). They are normally present in silicate rocks at very low levels3 (Table 2). The precious metals often form discrete phases, such as alloys and therefore, unlike the rare-earth elements, they do not appear to partition themselves extensively between silicate phases. It is therefore a critical task to select a representative sample mass for analysis, since the presence or absence of one precious metal grain in the analyzed aliquot could have a significant effect on the analysis, particularly if small sample masses ( < 5 g) are chosen. The onus therefore is on the analyst to establish that his/her data are not affected by large sample inhomogeneity errors. The analytical chemistry of the noble metals has been reviewed extensively by Beamish and Van Loon,4 Yi5 and Barefoot.6 Procedures can normally be divided into two stages. The first is the sample decomposition and preconcentration step in which these elements are separated from the host matrix. In

Dr G. S. Reddi, a Geochemist working in the Geological Survey of India, Hyderabad, has over 30 international publications in analytical methods applied to rare, rare earth and precious metals. He is the recipient of the National Mineral Award of the Government of India and is an active member of the Indian Society of Analytical Scientists. His current research areas are in gold and platinum group metals in geological and environmental materials.

Dr C. R. M. Rao, a Senior Scientist at the Geological Survey of India, Hyderabad, has varied interests in different aspects of analytical geochemistry. He is a member of the ‘Technical Committee of Chemical Testing Laboratories’ under the Department of Science and Technology, and is a Principal Member of the ‘Noble Metal Sub Committee of the Bureau of Indian Standards’. Holder of the National Mineral Award from the Government of India, his present interests include analysis of precious and rare earth metals. C. R. M. Rao

G. S. Reddi

Analyst, 1999, 124, 1531–1540
This journal is © The Royal Society of Chemistry 1999.


Osmium is completely lost during cupellation as volatile oxide and ruthenium and iridium are partially lost as oxides into the cupel. In general terms Pb-FA suits the determination of Au. which still forms an important aspect of modern determinations of these elements. Fe) Tulameenite (Pt2CuFe) Platiniridium (Ir50Pt50) 1532 Analyst. (b) solubilizing the gold and PGE minerals. into this collector phase from which they may be subsequently separated for analysis. Pt. If the sample contains appreciable amounts of lead and sulfur then. Bi2) Braggite (Pt. S) Laurite (Ru. Pt. either determining the elements by NAA after appropriate radiochemical separations8 or in a solution obtained thereafter by AAS. litharge and a reducing agent such as flour or charcoal. Os. The molten lead and slag are poured into iron moulds and allowed to solidify. Te. (Ag. inductively coupled plasma mass spectrometry (ICP-MS) and neutron activation analysis (NAA).9 Hall and Pelchat10 reported an improved Pb-FA method to determine Au. Silver is normally added to the flux as powder or as a solution to collect the gold and the PGE. Pd and Rh. 1531–1540 . Te4 Certain sulfide and arsenide minerals also contain appreciable amounts of gold. and (c) complexing and or collecting the freed precious metals. Te2) (b) Arsenides (c) Bismuthides (d) Sulfides (e) Tellurides (f) Alloys Ruthenosmiridium (Ir. S2) Irsarite (IrAsS) Frodite (Pd. etc. The resultant melt separates into two immiscible phases. Pt)S Erlichmanite (Os.8 In this method all the precious metals are extracted from the sample by a reductive fusion and collected in a lead button. Most of the molten lead is absorbed (as PbO) by the cupel or is volatilized leaving a silver prill which contains Au. Pd)S Cooperite (Pt. Au)2. Au. lake 2 Sample decomposition and preconcentration stage Sample decomposition may involve three stages: (a) breaking open the matrix in which the precious metals are held. ICP-AES. Pb-FA and NiS-FA. Pt and Pd. fusion. In this we have various instrumental techniques such as flame atomic absorption spectrometry (FAAS). Te2.1 Lead fire assay7. The noble metals are strongly partitioned Table 1 Chemistry of the common minerals of gold and platinum group elements Gold— Free or native metal is the major source Other Minerals are (a) calverite. result in buttons of manageable proportions amenable for easy manipulation. usually composed of molten lead or nickel sulfide ‘button’. In the first instance fire assay techniques are discussed. (b) petzite. whereas the more dense ‘collector’ phase. The sign of a successful operation is a highly fluid melt indicating the complete solubilization of the PGE and gold in the molten lead. graphite furnace atomic absorption spectrometry (GFAAS). A suite of CRMs. 2. Platinum group elements— Free or native platinum and inter-metallic alloys of PGE occur in significant proportions. ICP-MS. The ratio of Ag+Au + PGE is about 20+1. The two dry assay procedures viz. 124. The wet chlorination is another important decomposition procedure for the determination of precious metals. Sulfide and arsenide bearing samples have to be roasted at 600–800 °C to oxidize and to volatilize the sulfur and arsenic in order to prevent the formation of a matte (base metal sulfide) during fusion which would otherwise retain the precious metals. potassium nitrate would be added to the flux to oxidize the sulfide. sinks to the bottom. nickel sulfide fire assay (NiS-FA) and wet chemical attack using acid mixtures like hydrofluoric acid–aqua regia (AR). S2) Merenskyite (Pd. Chromite samples are difficult to fuse and require increased amounts of sodium carbonate and borax along with silica and calcium fluoride. multi acid decomposition. sodium hydroxide and sodium peroxide. The second is the measurement stage. Sb) Stibiopalladinite (Pd3Sb) Holling worthite (Rh. S) Moncheite (Pt. borax. Ru) Isoferroplatinum (Pt3. As. accomplish only the first two steps necessitating another mechanism for ‘preconcentration’. instead of roasting. Te2) Michenerite (PdBiTe) Iridosmium Os80Ir20 Osmiridium Ir80Os20 Os Ir Pt Stumpflite (Pt. (c) sylvanite Au. Ag.. Most analytical methods proceed from the silver or gold prill stage.115 Other important minerals of PGE are: Ru (a) Antimonides Rh Pd Sudburyite (Pd.. The technique of fire assay. Pd and Rh. The slag is removed from the lead button by tapping and the lead button is then cupelled by placing it in a cupel made of bone ash or MgO and heating it to about 960 °C in an oxidative atmosphere.. The exact composition of the flux depends on the nature of the sample. Bi2 ) Vysotskite (Pd. etc. hydrobromic acid–bromine and cyanide leaching followed by solvent extraction and fusion with lithium borates.114. etc. Sb) Geversite (PtSb2) Sperrylite (PtAs2) Insiswaite (Pt.. When estimation of gold is not required the PGE are collected by gold instead of silver. 1999. The lighter glassy slag contains the aluminosilicates and base metals and is discarded. The fluxes used comprise sodium carbonate. followed by a preconcentration step.this we have lead fire assay (Pb-FA). The other decomposition methods viz. inductively coupled plasma atomic emission spectrometry (ICP-AES). after separation from the slag. involves fusing together a sample and flux at a temperature of about 1000 °C.

AR. However. 1531–1540 1533 .14 They concluded that recoveries are more Table 2 Elemental abundance of PGE and Au Element Platinum Palladium Rhodium Ruthenium Iridium Osmium Gold Range in unmineralized samples3/ng g21 1–10 0. (d) Large sample sizes can be handled since the flux to sample ratio is smaller.36. in the case of iron/sulfide ores an initial attack of the sample with HCl is necessary as this would dissolve any iron oxide coating on gold bearing particles and allow contact of such particles with AR in the second step. hornblendite and peridotite were reported.4 Wet chemical attack In this technique. The advantages of this method are: (a) All the PGE are collected including Os. Some of the reasons for this are particle size.16 and other workers17. The simplicity of either attack (AR or Br2–HBr) renders the method amenable to greater output.1 and 0. Digestion is carried out on a sample weight of about 10 g with heating to hasten the dissolution. after separation from matrix. Nickel manufactured by the carbonyl process is preferred for the purpose. After the gold is solubilized its separation from matrix elements is achieved by solvent extraction into methyl isobutyl ketone (MIBK).35 also reported methods suitable for batch analysis utilizing fusion techniques for variety of sample types. V.37 co-precipitation on tellurium38 or merAnalyst. the cupellation stage is absent thereby minimizing their losses. The technique (using Carius tube) has found wide application in Os/Re geochemistry. are used. Pt and Pd were seen in Pb-FA while all the PGE except gold were recovered quantitatively by NiS-FA.31 to effect complete dissolution of gold in siliceous materials. HClO4. Quantitative recoveries for Au. Strong and Murray-Smith32 demonstrated the importance of incorporating this step (heating in 6 M HCl) in some iron and sulfide ores and observed that recoveries of gold rose from 12% to 100%. Therefore an important prerequisite for obtaining reproducible data by the wet chemical attack is to ensure a uniform sample mesh size of 200–250 otherwise discrete noble metal minerals may be completely occluded within the grains of the host matrix and may not be effectively dissolved by acid attack.5 ppb for Au.18 have used the mini fusion technique involving buttons of around 0.1 Gold. HBr. 124. 2. In this preferred assay technique for the collection of all the precious metals. has been reported to be quite efficient for the solubilization of gold in geological materials. HNO3. (e) The NiS button may also be used directly for laser ablation studies.19 The NiS button has also been used by Silvester and Eggins20 for a detailed investigation for the direct determination of PGE and gold by the laser ablation technique. Practical detection limits of 2. Ir and Ru. Formation of different phases based on the flux composition and the distribution of different PGE in discrete NiS mineral phases has been the subject of a study by Urban et al. nickel (as metal or as oxide or carbonate) and sulfur is fused at 1000 °C for 1.1–3 < 0.24. Two oxidizing acid leaches are in use for the extraction of gold from rocks and sediments: AR (HCl + HNO3. 0. 1999.21. On the other hand the disadvantages of the NiS fire assay are: (a) The relatively high cost. Robert at the National Institute of Metallurgy. Further improvements in the detection limits of Pd have been suggested by purifying the flux components.29 Addition of HF along with AR and Br2–HBr has also been employed by some workers30. D. a medium often used for the dissolution of sulfides. however. Pt and Pd were reported. Serious problems.12 The effectiveness of NiS as a collector for precious metals has been known since the initial work of R. (b) The large quantity of hydrogen sulfide gas evolved during the treatment of the NiS button with hydrochloric acid requires an efficient fume and gas extracting system. The NiS formed during the fusion collects the gold and PGE. 2.5 <1 0. Of particular interest is the PGE impurity in the nickel salts. respectively. 2. For chlorination resistant minerals. natural alloys or sulfide minerals are attacked. The crushed NiS button.28. is treated with hot concentrated HCl and the insoluble precious metal sulfides along with the dissolved precious metals are then collected on tellurium.22 Analytes occurring as native metals.1 0. borax. mixtures of HCl. which forms an important and widely followed method for precious metal determinations.13 The effect of collector mass on the recovery of PGE and gold in a platinum ore grade sample and a komatiite sample which contained < 10 ng g21 of PGE were investigated in detail by Frimpong et al.3 Chlorination The technique involves conversion of precious metals into respective sodium salts by heating (at 580 °C) with sodium chloride in a current of chlorine.5% bromine in 9 M HBr). Roasting at 600 °C for an hour to volatilize sulfur and oxidize organic matter is preferable to effect complete dissolution of the noble metals. (c) Preliminary removal of nickel and sulfur in the sample is not required. CHR-Pt+ and 12 other samples from different ore types of the Keivitsa mafic layered intrusion in Northern Finland comprising quartz carbonate rock.23 The advantages of the method are very low blanks and the large sample masses that can be analysed.26 varying sample matrix and incomplete wetting27 as well as the different experimental conditions used. The black precipitate is filtered off and analysed either directly by NAA or dissolved in aqua regia or HCl + hydrogen peroxide and analysed by ICP or AAS.1–10 dependent on the sample type and PGE content rather than the collector mass. microwave digestion is adopted.sediments and humus materials has been investigated. South Africa.4.3–5 < 0.2 Nickel sulfide fire assay11. The sample and flux mixture consisting of sodium carbonate. beset the multi-acid digestion procedures. (b) Fewer modifications in the flux compositions are required for varying sample types. For the sake of convenience the available methods can be discussed under two headings. 3 + 1) and bromine–hydrobromic acid mixture (0.25 2. Comparison of the two assay procedures for the precious metal determination in SARM-7. (c) When dealing with low grade samples the PGE impurities in the relatively large weights of reagents used overshadow the analyte concentrations themselves.5 to 2 h. Asif and Parry15.. such as silicates.5 to 1 g mass for the quantitative recovery of precious metals. Separation of the precious metal chlorides is effected by water or weak acid dissolution and the insoluble and non-chlorinated matrix is separated by filtration.33 Recently some workers34. Br2. The tellurium co-precipitation step effectively collects all the PGE sulfides avoiding the H2S passing step at this stage. H2O2 etc.

PGE may occur as alloys or compounds which are insoluble in AR.42 microwave digestions43 and fusion with lithium borates. the ratio of sample weight to the volume of acid is also a significant factor in acid dissolution techniques. Hall et al.. The report deals with gold. separation by coprecipitation.. Rh.30 autoclave decompositions.cury39 to avoid interferences at the measurement stage and to effect preconcentration. Au) Direct estimation Sodium peroxide fusion (Pt. Table 3 Different methods such as digestion with multiple acids in open vessels. prolonged contact between the grains of the sample and the acid mixture is necessary for complete solubilization of gold. Pd. Pd. 1531–1540 .1 Atomic absorption spectrometry (AAS) 3. Rh. when the mineralogy of the sample is unknown. 199730 ICP-MS Jarvis et al.41 Reddi et al.. several workers suggested that addition of HF along with AR and. 1999. Rh. additional preconcentration steps are needed prior to the determination of the analytes after acid treatment. The drawbacks are: (a) limitations in handling large sample weights contributing to nonhomogeneity problems (nugget effect). Moreover.Pd.Ir) Ion exchange Sodium peroxide fusion (Pt. Au) Direct estimation HF–HNO3–HCl (Pt. More often the choice of the analytical technique depends on the availability and the level of occurrence of the precious metals. the proportion of gold leached by AR is dependent upon the sample matrix. HClO4 and H2O2 which is amenable for batch analysis.197847 Sighinolfi et al. Pd. Cyanide leaching of gold has been used commercially for many years. The reason lies in the poor sensitivity of the technique and the level of analyte concentrations sought.. Pd) HNO3–HF–HClO4/AR (Pt. 199844 the insoluble residue remaining after digestion is fused with 1534 Analyst. Rh) AR (Pt. 2.58 Beamish and Van Loon59 discussed the usage of this technique for the analysis of Pt..30 reported a rapid multi-acid digestion procedure utilizing mixtures of AR. Ir. inefficient mixing during digestion and also due to the protection of gold by unattacked gangue. In this technique if gold is to be extracted into MIBK prior to instrumental analysis. 198438 Branch and Hutchison. acid extractions do not result in complete recovery of the PGE. (c) does not attack refractory minerals such as chromite. (c) amenability for batch analysis. 198951 Reagents HBr–Br2 (Pt. (b) partial dissolution of PGE and gold when they occur as alloys or compounds in which case a fusion step is required. Pd) HF–AR/Na2O2a (Pt. Dissolution of PGE in AR may be limited because some proportion of the elements may be embedded within refractory chromite and/or silicate minerals.1 Flame AAS. The details of studies by various workers are furnished in Table 3. Often. (b) low blanks.2 Platinum group elements (PGE). Further. Ru. Usually. etc. 199535 ICP-MS Balaram et al. Ir. 3 Instrumental/measurement stage The solution obtained after the digestion/dissolution or preconcentration stage is presented to an analytical instrument for the measurement of the analytes. Ir) Tellurium co-precipitation AR. 199543 ICP-MS Enzweiler et al. major sources of error at the 10 g weight or greater are believed to be due to non-wetting of the samples. The method particularly suits placer samples.Rh. HClO4. sodium hydroxide and sodium peroxide44 prior to the determination of selected PGE have been the trivalent state with Br2–HBr or potassium permanganate.. Pd) LiBO2–Li2B4O7/AR (Pt. Pd and Ag in a suite of 12 CRMs. and particularly if the presence of chromite is suspected. The flame types used and the interferences encountered in the estimation of gold and PGE are described in Table 4 and the detection limits in Table 5. The results for a variety of samples have not always been quantitative and have depended upon the type of samples as well as the experimental conditions. 3. Therefore. HF. 196745 Stanton and Ramankutti.57. Further. it must first be oxidized from the mono. 197746 Fryer and Kerrich. 124. Extraction of PGE by acids have proved to be a more rapid and economical alternative to fire assay. Ru) Co-precipitation Extraction Co-precipitation Co-precipitation Ion exchange Ion exchange Extraction Ion exchange or coprecipitation HNO3–HCl–HClO4/AR (Pd) Extraction Sodium peroxide Co-precipitation HNO3–HCl–HF–HClO4 (Pt.. 198849 Brooks and Lee 198850 Sen Gupta. Results compared well with those obtained by Pb-FA. 199534 ICP-MS Totland et al.54–56 The flame version (air–acetylene or nitrous oxide–acetylene) of the AAS has found few applications in the precious metal determinations except possibly gold. Au) Se/Te carrier a The designation HF–AR/Na O means that the sample is first digested with HF–AR and 2 2 Na2O2. Pt. Br2.Ru. Evidently these elements normally require some separation and preconcentration prior to their determination. Br2–HF. 199753 ICP-MS Amosse. 198648 Chung and Barnes. the use of a fire assay decomposition procedure is preferred to a wet chemical procedure. 198952 RNAA Nogueira and Figueiredo. Pd. In their view. Ir. Further. and (d) it is ideal for semiquantitative data generation for exploratory work.1. GFAAS Wilson et al. Pd. Ru.4. Pd) HF–AR (Pt.45–53 It is evident from Table 3 that the choice of sample decomposition method depends on the particular elements to be determined and the sample matrix. Pd and Au in ores and concentrates.27 reviewed the various current methods used for the estimation of gold in geological materials. Sample preparation by means of acid digestion has been studied and used extensively. Using a 2 g sample Balaram et al. and (d) not comprehensive for a wide range of sample types as against fire assay techniques. In addition. Pd.40 more for rocks containing metallic gold at ‘ppm’ rather than ‘ppb’ levels. The solubilized gold metal was then coprecipitated on tellurium and measured by flame AAS. ion-exchange or extraction to preconcentrate the analytes may lower detection limits and remove or reduce interelement interferences to a tolerable level. H2O2 (Pt.33 reported a method where gold was extracted from a 20 g sample with HCl and HBr–Br2 mixture at room temperature with agitation. Pd) HBr–Br2 (Pt) Aqua regia (AR) (Pt. Thus it may be deduced that wet chemical attack has the following advantages: (a) low cost. Hall and Bonham-Carter58 discussed the flame AAS and its attributes in Sample decomposition for the determination of PGE (selected samples) Separated by Determined by Spectrophotometry FAAS GFAAS GFAAS GFAAS ICPAES GFAAS GFAAS Reference Thompson. intimate.

1531–1540 1535 . c By NiS– INAA (ref.g. Ru.03 ICP-AES 110 88 88 60 54 0.64 Hall.65 Simultaneous multi-element instruments overcome the problem of lower productivity to some extent. Table 6 Operating parameters for GFAASa Element Wavelength/nm Ashing temp. 3. 3.9 290. 1% lanthanum suppresses these effects Complex cationic interferences (suppressed by 1% lanthanum).9 1400 2700 Ir 208. Rh.5 1400 2600 Ru 349. 199642) Wavelength/ nm 265. Pd and Ag in another. with argon plasma as the excitation source (ICP-AES).5 Ideal solution detection limit is an estimate of the 6s detection limit of single element solutions. Pd and Au. Belskii et al. Matrix modification. The major disadvantages. Various operating parameters for the determination of precious metals by GFAAS are furnished in Table 6.. has gained world wide acceptance Table 4 Precious metal determination by flame AAS9 Element Pt Pd Rh Ru Ir Os Au Flame type Air–acetylene (lean flame) Air–acetylene (lean flame) Air–acetylene (lean flame) N2O–acetylene (reducing) Air–acetylene (reducing) N2O–acetylene (reducing) Air–acetylene (lean flame) Detection limit9/ ng mL21 100 20 10 100 600 100 20 as a versatile analytical technique for geological samples.9 1400 2700 a Literature values for the operating parameters vary depending on the instrument. Ir. Recently Kubrakova et al. In a study Sen Gupta31 analyzed the precious metals in two groups viz. However the limited use of ICP-AES in precious metal analysis.9 208.60 reported a modified flame AAS method for the determination of gold in ores. is mainly due to the large sample to volume ratio required (typically. The detection limits are thus lowered by at least one to two orders of magnitude depending on the element and sample volume./°C Atomization temp. are its inherently lower productivity and more severe interferences.2 Graphite furnace AAS. (for example see Zereini et al. Zhang et al. adding uniform amounts of magnesium to standards and analyte solutions to reduce the effect of magnesium contamination (from Mg adhering to the silver prill) the method is quite effective.3 0.5 6.9 244. 1999.. Thus GFAAS competes favourably in terms of detection limits with other sensitive techniques such as NAA and ICP-MS in precious metal determinations.67 and Schuster and Schwarzer68 have also used this technique for precious metal analysis.0 0.3 0. 1990.7 34 ICP-MS 2 1 2 8 4 2 1 INAAc 5 2 0. etc. The technique is characterized by low background emission hence superior detection limits. 95). 1994. graphite furnace AAS.64 A variant of the AAS technique.5 349.62 It is evident from Table 4 that the necessity of using suppressing agents and the poor sensitivity of Pt. are useful in overcoming some of the interferences.6 0. With precautions like adding scandium as internal standard to minimize the effect of the variations in acid concentrations. Minimal cationic interferences Minimal cationic interferences in dilute solutions Minimal cationic interferences Analyst. as evinced by the fewer publications.0 1800 2700 Pd 244.relation to other techniques in the estimation of Pt.6 1.2 Inductively coupled plasma atomic emission spectrometry (ICP-AES) Optical emission spectroscopy. Pt and Ir in one firing and Au.1 5. 3% sodium sulfate suppresses anionic interferences No significant cationic interferences in dilute solutions Diverse interferences. method of preconcentration.8 Interferences Complex cationic interferences (suppressed by 1% lanthanum) Several cationic interferences. 124. etc.1 1 0. three Canadian CRMs and four new Canadian candidate reference materials were studied. used the technique for the estimation of precious metals with dithiozone chelate forming resin61 and gold–Orange G chelate forming resin.9 1400 2700 Os 290. 20 g in 3 Table 5 Comparison of detection limits for PGE and Au (Average of literature and manufacturer’s suggested values) Limit of determination in ideal solutions26/ng mL21a Element Pt Pd Rh Ru Ir Os Au a FAAS 210 45 15 900 1500 300 30 GFAASb 0. 10 mL of 1000 mg L21 of iridium is used as a modifier. b Based on 100 mL injection volume. offers the unique advantage of enhanced sensitivity over the flame version.8 343.0 0.80 Torgov et al. Using polarized Zeeman correction... however.63.31 However for gold. The residence time of individual atoms in the optical path is approximately 1–2 s for the graphite furnace technique while in the flame atomization it is of the order of milliseconds. Recently Hoang et al./°C Au 242.1. The ICP-AES in conjunction with Pb-FA and AR dissolution of the silver prill has been recognized as a widely applied technique for the determination of Au. background correction using a continuum source (e. Pt and Pd in geological samples.8 1000 2500 Pt 266.65.58 When all the PGE are to be estimated NiS-FA and tellurium co-precipitation (Te-Coppt) are employed. high temperature ( ~ 10 000 K) leading to few chemical interferences and wide linear response range (5–6 orders of magnitude).66 has used this technique in conjunction with microwave decomposition followed by slurry nebulization for the determination of low levels of PGEs..8 1400 2600 Rh 343. deuterium lamp) or Zeeman and standard addition. For PGE mutual interferences appear to be more common especially at high concentrations where no specific modifiers are suggested. Ru and Os limits the applicability of flame AAS only to the estimation of precious metals in concentrates.9 242.

accuracy and freedom from contamination.3 Inductively coupled plasma mass spectrometry (ICP-MS) The ICP-MS technique combines advantages of the high temperature plasma source with the highly sensitive detection capabilities of the mass spectrometer.44 340.8 keV Au peak95).59 225. The main limitation of RNAA is the restriction on sample mass so as to limit the activity of irradiated samples that are then subjected to a radiochemical method. Due to lower background.268 225.36 Au I 242. Pt. 1531–1540 .74–94 The details of the isotopes.54 214.54 240. etc. 1999. a delay period of 5–7 d (half life = 64. The two variants of NAA viz.26 224. detection limits and potential interferences are furnished in Table 9.73 led the way in assessing the potential of ICP-MS for the estimation of precious metals and later various other workers for different types of samples. Hoffman et al. is Table 7 Operating parameters for the determination of precious metals by ICP-AES116 Emission Waveline length/nm II I 214. the NiS-FA/ICP-MS offers the advantage of eliminating the 5–7 d delay (for counting). Radiochemical separations have several advantages over other analytical techniques in particular the avoidance of contamination and the ability to add carrier to monitor and correct for losses. nugget effect becomes a major problem. have widened the applicability of the technique.73 242. fission product production of Pd and Ru from any uranium in the sample. Iridium of the PGE can also be determined by this method. The NiS-FA followed by ICP-MS.585 60 30 111 27 0. Ir and Os. Pd.60 242. A particular benefit of this technique is the possibility of isotope dilution calibration strategies which account for the few interferences and loss of analytes at the preparation stage. irradiation facilities should be available for handling such large sample masses. The nature of the sample.1 and 2 ppb respectively for Au..458 Detection limits116/ ng mL21 30 44 Interference and spectral lines/nm Al I Fe II Fe I V II Ti II WI V II Fe II Cu II Fe II Ni I Fe II Fe I Ni I Cr II Fe II Mn II Mn I VI V II W II Al I 214. with similar detection capabilities.26 224. Individual separation and counting schemes are necessary for each of the precious metals. more importantly.12 pioneered the technique and obtained detection limits of 0.4. Schramel and co-workers have used the technique for the determination of gold in soil by dithiol–cotton fibre column separation69 and its reliability and measurement uncertainty in environment samples.2. (b) inefficient control of neutron flux. With less sample weights.52 340.. Today most INAA results are derived after NiS fusion.18 224. in particular the mineralogical considerations. when Te-Coppt is to achieve a detection limit of 1. 1. electrothermal vaporization.4 Neutron activation analysis (NAA) Neutron activation analysis is also one of the preferred techniques for precious metal analysis. 3.894 224. Possible sources of error are due to: (a) nugget effect. which accomplishes separation of the analytes from the matrix.78 242. choice of the less sensitive 208 keV to remove the interference of Te on Pt are some of the noteworthy points.423 340. In this technique direct analysis of a sample is carried out after irradiation thus avoiding any separation or preconcentration. Jackson. i.44 214. This method is simple and sensitive reaching a detection limit of 5 ppb for a 10 g sample. Interference of Au on Pt (Compton scattering) and. involves neutron irradiation of the encapsulated sample. Gold.272 349. 5.1 Instrumental neutron activation analysis (INAA). With wide linear dynamic range. direct interference of calcium on Pt95 and. is not determined by RNAA. etc.83 242. Newer sample introduction methods such as laser ablation. Date et al. Parry97 and Artem’ev98 in their review articles discussed in detail the various radiochemical separation procedures employed for the precious Element Pt Pd Rh Ru Ir Os I II I II II 343. Ru. 124. after dissolution of the button in concentrated HCl and co-precipitation on tellurium. 3. determination of Au.489 240.75 197.8 h) and measurement of the 198Au nuclide at 412 keV.53 343. essentially simultaneous multi-element analytical capability due to rapid scanning facility and a fair degree of tolerance to interference free measurement of analytical signal the ICP-MS today is a widely used analytical tool for trace metal analysis.70 The technique has also been utilized for the determination of Au.e.50 340. respectively. For PGE a chemical separation prior to irradiation is necessary to obtain better sensitivities and or eliminate interferences. Pt and Pd after preconcentration separation by porous resin containing imidazoline group71 and for the determination of Pd and Rh in high purity alloys.819 38 1536 Analyst. on the other hand. 3. which has short-lived nuclides. better detection limits are obtained. The NiS/Te-Coppt method has also been studied by Shazali et al.1.83 242.. A popular application58 of the technique. However..59 225. Compared to NAA. Neutron activation analysis with radiochemical separation is a precise and accurate method for precious metal determination in certain type of samples. Rh. PGE. strongly influence the precision and accuracy. Table 8 describes the details of selected studies in precious metal analysis. The assay procedure also eliminates the problem of non-homogeneity in analyte distribution. In this technique the mass spectrometer receives ions from the plasma tail flame after a two-stage vacuum reduction interface. 3. have pioneered the technique in precious metal analysis. Pd and Pt.44 340.29 225.4.795 17 197.10 ppb for Au.2 Radiochemical neutron activation analysis (RNAA).1 keV Eu interferes on 411. Rhodium. This leaves no room for repeat analysis and the accuracy in diluting to such low volumes is difficult to achieve. (c) high europium concentration in the sample (411.96 3. and (d) variations in the sample/standard position relative to the detector. 0. 5. Jarvis. instrumental NAA and radiochemical NAA scores over other techniques due to their sensitivity.72 The operating parameters and possible interferences applicable to ICP-AES in precious metal analysis are given in Table 7.80 242.84 the most widely accepted method for precious metal determinations. slurry nebulization.58 225. Among them Hall.

Isobaric correction for NiAr.. 1996 77 Balaram et al. Pt and Pd Hall. Pt and Pd Au. Pd. Ir. PTM-1. GAu18 Pt. Pd. ores and heavy Pt. Ir and Os Au. and H2O2 in Teflon vessels Different acid mixtures comprising HF. Ru. insolubles Coedo et al. Pd. SARM-7.Table 8 Sl No.. Rh. 199543 Enzweiler et al. Ru and Ir Chromitite (2/77). 199075 calibration matched in silver concentration Analytes collected in Ag prill. Pt and Pd Au. HNO3. External calibration NiS fusion.. solubilized in AR after ashing. Pt. Ru. Os and Ir Au. Pd Au. Ultramafic rock (UM-1) 2 Hydrothermal fluids 3 Stream sediments.. SU-1a. SARM. (SARM-7. Pt. PCC-1 Sulfide ores (CH-1.. External Hall and Bonham-Carter. Isotope dilution Ashing at 870 °C. Pt. PTC-1) Geological and related materials SARM-7. Published methods to determine precious metals in geological materials by ICP-MS (selected examples) Matrix Elements determined Au. Pd. Pd and Ir Au. Wet chemical/water/fluids/fusion— 1 Water (surface. ores and other geological samples Komatiite (WITS-1). PTM-1. Ion exchange separation of combined solutions Roasted sample treated with mixture of HCl and HNO3 and the Rao and Balaram. 1999.. 199535 Tredoux and McDonald. HCl. NBM-6b Au. GXR-1. Rh. Pt. For AR leach 5 g sample + 10 ml AR Varying flux constituents. Rh. Pt and Pd Ru. calibration matched in Ag concentration 198858 Evaporation and Pb-FA of the residue. PCC-1 9 Many CRMs comprising ultra basic rock. Ru.199080 8 9 10 11 12 13 14 15 16 SARM-7. Os content calculated using isotope dilution. Pd. 124. PTM1. Ir and Os Au. HClO4 followed by Dowex 1-X8 based anion exchange separation Cidu et al. Rh. chromatite (OUCX) Fresh waters Au SARM-7. Pt and Pd Au. 199677 Sun et al. Pd. Ru. Precious metal sulfides Date et al. Rh. Os Pt. 199410 NiS fire assay— 1 Pyroxene (SARM-7.. Au. Ru fide concentrate (PTC-1) and Ir 2 Pyroxene (SARM-7).. Rh. Pt. 199485 Nowinski and Hodge. External calibration NiS-FA compared against Pb-FA and AR leach. Ar on Pd and TaO on Au NiS button dissolved in HCl–H2S and precious metal sulfides Simpson et al.. External calibration Frimpong et al. rocks. Ru and mineral concentrates Ir SARM-7. 198881 Sen Gupta and Gregoire. 199878 Slurry made out of standard solutions. Ru. Pt. Pd... 198773 dissolved in HCl–H2O2. Pt and Pd Au. Pd. External Simpson et al. automobile Pd catalysts 7 Ore grade sample (SARM7). Phase distribution study by electron Urban et al.. Pd. dissolved in 3 M HNO3 + 2. Pt. PTA-1. Ru. Pd Au. 199788 High pressure microwave digestion with HF and AR. Synthetic calibration solutions in matching acid and silver concentrations Hall and Pelchat. CH-3. SARM-7) Synthetic multi-element solutions.199084 Activated charcoal adsorption of the analytes. Cu. rocks. GXR-1. Ru. PTC-1.. Pt and Pd soils. residue fused with Na2O2 separation of the analytes by Te-Coppt. Ir. Isotope dilution for Pt and Pd et al. TeCoppt and dissolution in AR. 199487 Totland et al. Pt. Pd. NiCl on Ru. Pd. External calibration Concentration by evaporation. 199519 microprobe Effect of collector (NiS) mass and concentration of Ni. Pd. Internal standardization with Cd for Ru. sulAu. 199075 dissolved in HCl–H2O2. Te-Coppt. dissolved in HNO3/HCl. Ru and Ir Au. SARM-7. heavy mineral concentrates 4 Rocks. Pd and Tl for Os. Ru 7. Pt. solubilized in AR McKibben after ashing. fide concentrate (PTCIr and Os 1). NiS dissolved in HCl+Te-Coppt. Internal standardization with Tl for Pt and Ir and Tm for Rh. Pt. Pd. separation of analytes by Te-Coppt. Pd. Rh. brines) 2 3 4 5 6 7 Rocks and ores Vegetation Surface and ground waters Hydrothermal fluids Interstitial pore fluids Au.5 M HCl. 199890 dried residue treated with KMnO4 and HCl Table 8 continued over page— Analyst.GXR-4 and GAu-16. 199730 Jarvis et al. Ru and Ir Au.199183 AR leach followed by analysis of residue by energy despersive Gowing and Potts. Rh and Ir Au Wood and Vlassopoulos. 199076 under reflux with HNO3–HCl. External calibration McKibben et al. Pt. Au. NiS button Juvonen et al. isotope dilution for Pt and Pd et al. SU-1a. Pt. External calibration Cost effective NiS fusion.. Cu and Zn in the sample on the recovery of precious metals Low grade standard preparation using different techniques/laboratories NiS button dissolved in HCl/Te-Coppt. XRF and by INAA 199186 MIBK extraction AR–microwave digestion. Ir and Os NiS button dissolved in HCl–H2S. PTC-1. Rh. PGE Reddi et al. Au. S. chromitite... The objective of the study is to establish a low blank method for PGE and Os Analytes adsorbed on activated charcoal. Rh. HF–AR decomposition of the residue. Rh. CHR-Pt+ CHR-bkg Au. Filtered solution diluted (100+1) with HNO3 and analysed by ICP-MS Microwave acid dissolution followed by fusion of the residue with Na2O2–Na2CO3 or pure Na2O2 dissolving the melt in pure HCl Na2O2 fusion. for Pb-FA studies silver prill dissolved in AR. 1531–1540 1537 . 199474 sulfides in HCl–H2O2. Pd Notes on the method Reference Lead fire assay— 1 Sulfide (SU-1a).. Au/PGE dissolved Jackson et al. SU-1a and Ir Rocks. Rh. Isotope dilution Low grade ore standard preparation (WITS-1) using various methods Multi-acid digestion involving AR/Br2/HF/HClO4. Rh. NiS dissolved in HCl/Te-Coppt.Au.. 199082 Evaporation of the fluids. Pd HF–AR decomposition. sulfide (SU-1a) 3 4 5 6 Stream sediments. 199082 Analytes collected in Ag prill. Ru and Pd. Ir and Os Pt. 198979 Hall et al. Pt. GAu-17. Isotope dilution for Pt. sulAu. dissolved in HNO3/HCl. 199413 dissolved in HCl. heavy mineral concentrates Rocks. etc. Rh. Pt. soils. Cu–Ni ore. PM-1. Pt and Pd Au. soils. 199789 fused with Na2O2. Ru. Pt. ASK-3. Parkinson Te-Coppt. Rh. dissolution of the residue in HF–AR. 199514 Tredoux and McDonald. komatiite (BF-4) 8 Komatiite (WITS-1). Os and Ir GXR-4.. sediments and humus samples Analytes collected in Ag prill.

Ir.8 0. 199592 Standardization against NiS buttons of CRMs and synthetic buttons obtained by doping high purity quartz. Ir and Os Notes on the method Peroxide fusion in zirconium crucibles and Se/Te as carriers Reference Amosse. Pd. it is relevant to note that the reliability in precious metal data and the consequent bias is a point of concern.06 a Detection limit calculated as the concentration equivalent to 3s of the background signal in 1 M Aristar grade HCl. WMG-1. The dissolution of the NiS button in HCl accounts for a partial loss of precious metals. Ru. CHR-BKg Au.3 0. The technique also ideally suits RNAA measurements due to the complete separation from matrix (including uranium)..43 Isotope 101Ru 103Rh Detection limitsa/ Abundance (%) ng mL21 Potential interferences 84SrOH. Stone and Crocket99 described a RNAA technique with tellurium co-precipitation for the determination of Pd. On the other hand the traditional assay procedures score over other methods by presenting a mass of manageable size wherein the precious metals are concentrated. the NiS method may be well suited for the PGE analysis.0 0. but the sample throughput for the procedure remains low. The fusion methods place a restriction on the sample mass and increases salt content. The NiS fire assay has the advantage of being an efficient means of collecting all the PGE and perhaps is more easily adapted to handle refractory matrices. with reduction in the size of the nickel buttons without sacrificing the accuracy and the resultant lowering of blank levels.17 189Os 173YbO 16. WPR-1. Good recovery for all except Pt ( ~ 30% low) Flow injection incorporating alumina micro-column coupled Hidalgo et al. 3 mm torch injector tube. Both fire assay procedures (Pb. 124. automobile catalysts and common commercial analytical reagents UMT-1. and many types of material exhibit a chemical matrix dependence.110 Availability of well characterized CRMs of wide ranging analyte contents and their judicious use in routine analysis will help in reducing bias in reported values. When atomic absorption spectrometry is coupled with a graphite furnace atomisation cell (GFAAS). 199844 Alternative techniques— 1 PTA-1. Pd and Au in favourable matrices. a limiting factor is the contamination contributed during the preparation steps from reagents. 87SrO. the former has the ability to handle large sample masses. Rh. 65Cu40Ar 22. Although most instrumental techniques today require separation of the analyte from matrix components. Pt. 63Cu40Ar 100 0.58 1538 Analyst.. Pd.22 86SrOH. Pt and Pd. Pt.1 0. Ru and Ir Au. 64Ni37Cl 17. 199391 pyrophosphate as dispersive medium. The ICP-MS and NAA offer superior detection limits and are widely used presently all over the world for the estimation of gold and PGE. The elimination of the delay period prior to analysis. has been accepted to be a very good technique for the precious metals. UMT-1 Elements determined Au.102–108 have utilized the NAA technique for the precious metal analysis in different types of samples. Atomic absorption analysis is by far the most commonly used final measurement technique. However. Rh. NAA and GFAAS are such that the desirable determination limits for Au and PGE in rocks. increased forward power. nebulizer gas flow rate. chromitite (2/77) Natural waters. Hence. Pd.Table 8 Sl No.. Pt.g. Various experimental details in the NAA analysis of precious metals are described in Table 11. Ir and Os Pt 3 Slurry nebulization of samples ( < 5 mm) with AR+ tetrasodium Totland et al. Rh. which are collected by the Te-Coppt procedure. Ru. 4 Conclusions The wet chemical attack procedures comprising acid mixtures or fusion by strong alkalis have been widely applied for sample decomposition. Jarvis et al. Au in sulfur depleted rocks. Pt. LLD 4 ng L21 UV laser ablation of the NiS button. 199894 4 Au. soils and sediments are easily attained. 178HfOH 33. which does not involve a cupellation step. Pd. 180HfOH 100 0. The small sample volume precludes the second analysis and the high dissolved solid content of the solution is also a problem. 1531–1540 . 1999. PTC-1. The nickel sulfide assay process. Pt.17. GPt-1. the detection limits are higher than desirable for exploration work. Incomplete attack108 is the bane for multiacid procedures except for Pt. SARM-7 2 SARM-7. WGB-1. e. Indeed. Good agreement with certified values except Rh in UMT-1 and WMG-1 due to interference from Cu Jorge et al. Calibration using buttons prepared using doped quartz. 17 Continued— Matrix WMS-1.and NiS-) in common usage require the judicious balancing of flux components and Table 9 Isotopes generally used for analytical measurements.03 105Pd 88SrOH.PTM-1. WPR-1. An initial acid attack followed by fusion of the residue is a viable but more tedious method.27 193Ir 177HfO 62. 199693 with ICP-MS for online preconcentration (factor of 600). The implications arising out of such variations are discussed by McDonald. McDonald et al.11 197Au 181TaO. detection limits are improved significantly. Ir and Os metal determination.07 195Pt 179HfO. 89YO. Rh. 61Ni40Ar. detection limits and potential interferences in ICP-MS6. A brief review of the currently used final measurement techniques reveal that ICP-AES offers relatively poor sensitivity for the heavy elements and therefore requires a high sampleto-volume ratio to achieve reasonable detection limits. Another area of interest in the Pb-FA is the acid dissolution of the lead button without cupellation or scorification109 to eliminate the cupellation losses and contamination. Results (RSD 2–30%) tallied with published data Laser ablation of 1 g polished NiS button using Nd:YAG laser. Ru.. CHR-Pt+. The more practiced Pb-FA has been proved to be a good collector but the cupellation stage accounts for major losses except for Au. GPt-6. the inherent powers of detection of ICP-MS.. Finally. superior sensitivity and greater flexibility to manage interferences enjoyed by ICP-MS compared to NAA will probably ensure this technique a dominant role in this field when instrumentation becomes more widespread. WMG-1. Modified instrumental parameters.. Especially.7 0. The full details of the procedures are given in Table 10. experimental conditions by the assayer.100 Nguyen101 and other workers15.

shale. B. Rh. Sapozhnikov. MA-1b SARM-7. Explor... J. M. Quantitative recoveries were obtained Pt. 1995. G. Can. Mineral. A Text Book of Fire Assaying. R. 1995.. Os and Ir Au.. Ir. J. J.. Pd and Ir Thermal neutron irradiation of 250 mg sample. Palmer. E. 1989. Kallio and T. C... A.15 d 2. for their interest and suggestions in the present work. Ir and Os Notes on the method Reference Kolesov and Sapozhnikov. 1952. 1996104 Kong et al. R. 3rd edn.8 38.. L. Recent Advances in the Analytical Chemistry of the Noble Metals. Deputy Director General (Geochemistry). G. G. Pt. 44. pp. Barefoot. iron meteorites. 1971. R. direct irradiation to eliminate losses during dissolution Au. 1992.. Beamish and J. Ir. N. J. J. Chen and S. Beamish. Ag. Chicago. Very low detection limits reported Au. F. viz. Z. 1977. C. 1995. G.9 88. chromites. Cosmochim. Barefoot and J. Naldrett and D. Rh. etc. 1 2 3 4 Published methods to determine precious metals in geological materials by neutron activation analysis (selected examples) Matrix Ores. Pt. 1995.. Pd and Pt were estimated by GF-AAS Li et al. A. Acad.. R.6 d 74. H. Ir Irradiation of the precipitate. Chem. Vanwyk and R. 1996. Natl. P. 1997. A. Pd. Kolesov and D.2 d 3. Crocket. Jackson. Different decay and counting times for different elements Au. Geol. B. Pt.4 468. Chow and F. E. A manual on fire assaying and determination of the noble metals in geological materials.S. V. 115. 1675. University of Chicago Press. 1990. Pd. 5 B. 5 Acknowledgements The authors wish to thank Dr. Determination of Precious Metals. R. R. 120. Speller. P. S. Speller. Asif. C. Pt. D. Y. Pd. Anal. J. 3 I. Papanastassiou and G. A. 60. Newsl. M. 47. Zereini. D. J. and Dr. Frimpong. Spectrom. J. 1997. Africa. Rh. B. Urban. Lakomaa.. Pd Samples are irradiated for 10 h and allowed to decay for 24 h and then fused with Na2O2 in presence of added amounts of Au.. Siva Siddaiah and A. Eaton. 1993. 1996. Potts. B. J. 91–101. 139. D. button dissolved in 6 M HCl and Te-Coppt. Chim. Q. 1351. Ru NiS button crushed and extracted with 500 ml of HCl and Os (37%). J. Metall. Insoluble PGE sulfides collected on filter paper and dried in desiccator before irradiation using thermal neutron flux. ed. Os Combination of scanning proton microprobe and NAA. Coope and E.3 129. 1995103 Nguyen. A.. V. J. Halliday and R. Appl. E. 1999. 688–694. Weiland. V. 199215 Nogueira and Figueiredo.69 min 13. New York. M. Pd. F. Eggins. D. J. R. 219. 17. A. Van Loon. London. B. Shen. J. M. Hoffman. Analyst. Geochem. Vaive. Authors are also thankful to the unknown referees for their valuable comments which have improved the quality of the paper. 42. Pergamon. Chem. Anal. Oxford. Holland and A. 1997107 Table 11 Experimental details for neutron activation analysis of precious metals15. soil and lunar rocks SARM-7.. 1978. Barefoot. A. New York. chondritic metals Copper nickel sulfides South African kimberlites Elements determined Au. P. Mineral. 1967. 120. 1998. 139. L. J. 361. Wentz. 199517 Asif et al. 157. M. Sreenivasa Rao. Geochemistry.. Spiking technique to overcome the standardization of the button mass Au. Masuda. 157. 119. S. USGS standards GSP-II for comparison. J. 537. M. 34. Hancock and A. B.1 158. E. Van Loon. Acta. A Handbook of Silicate Rock Analysis. 245. Skerstupp and M. Geostand. 617. 1971. Report No. J.1 51. Ir. 1992. Pt. Explor. Juvonen. Chem. Geochem. Van Loon. Chim. 73. 391 and 889. 2 K.003 (Ir) to 1. Pelchat. Chem. Riley and W. Van Loon. Sahama. H. Naldrett.9 d 4. E. 1957. J. 1972. Bugbee.. Haffty. Analyst. S. Spectrosc. Geochem. Ru. Ser. J. 321. D. pp. Hall. Analyst. J. 1979.41 min 4. chemical separation of the analytes by Te-Coppt utilizing AR leach and sodium peroxide sintering Au. J. Asif and S. 38. M. Van Loon. Hall and J. Tarkian.. 2887. Ru. Longerich. E. 61. Rehkaemper. 1461.0 (Pt) (ng mL21) Au. Proc. V. 1994. 1531–1540 1539 . Os. R. Very low detection limits ranging from 0. 1371. R. 1997106 McDonald et al. V. 215. 117.. 14. Non-destructive determination of meteoritic metal Ir and Pt samples. 1994. C. Wasserburg. CHR-Pt+ Geological and other related materials Marine sediments (GSMS-2 and GSMS-3) and Mn nodules (GSPN-2 and GSPN-3) Iron meteorites. F. Jarvis. 13. 124. Barefoot. C.. 1994100 Lahiri et al. R.4 188. Anal. E. 352. Parry. Goss. 1991. C. 1987.. 13. Petrol. Pd. Interferences and neutron flux gradients among multiple samples discussed Pt. Talanta. 25 26 27 28 29 R. M. Geological Survey of India. 131. Robert. Perry. Jpn. T. in Applications of Plasma Source Mass Spectrometry II. Rh. Barefoot. A. 1993. R. G. Ru. Yi. E. Royal Society of Chemistry. Blackie & Sons. Cambridge. sediment. 102. K. Concentration of the noble metals by a fire assay technique using NiS as the collector. Anal.70 d 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Preparation of series of CRMs. At. Fresenius’ J. Perry.4 411. Pd. and Ru Variable irradiation times. Manson. E. E. 21. E. A. Ru and NiS-FA. Can. Malik. Anal. J. H. 124. U.5 h 14. Chemical Division. Inst. 1996105 Li et al.. Hildon and G. J..5–1 g NiS button. Analyst. Parry and H. 1998. Sylvester and S. 1077. 121. Geol. 217. soil. Perry. 1445. M. Van Loon and R. Speller. N.Table 10 Sl No. J. Os. 54. Acta. C. R. Sully. Fresenius’ J. E. Jarvis and K. Fryer. Wiley. B. Geological Survey Bull. nodules. Analyst. Pt and Pd Pb-FA preconcentration.. Acta. 24 6 References 1 J.111–113 and availability of other low grade precious metal containing CRMs would help in reducing the inconsistency in data. 1994101 5 6 7 8 9 Proterozoic Dalma rocks of Eastern India NAA with micro fire assay involving NiS fusion with varying masses of fluxes 0. Halder. John Wiley.26 Element Ru Rh Pd Os Ir Pt Au Isotope 101Ru 104mRh 109mPd 109Pd 191Os 192Ir 199Au 198Au 6 7 8 t⁄ 1 2 Energy/keV 497. Analyst. Rankama and T. J. G. 4 F.

Rao and V. Sect. Radiat. Gijbels. Geol. Murray-Smith. 22. 1977. Crocket. W. Jezowska. Newsl. Stokking. 1979. 348. 20. K. A. Bertalan. A. Juvonen and E. G. I. C. Fresenius’ J. Zhang. 67. Hall. Geol. L. K. J. Talanta. Y.. A. S. 489. T. Shulman. M. M. Mao. Vijayalakshmi. 289. Nebol’sina. L. Hall. 1. 1967. 2. 4130. 17.. C. Geostand. 24. Ilangovan. Res. 1990. E. C. Spectrosc.. J. I. Anjaiah. Newsl. Dunn. Mahalingam. E. G. 1983. L. 44. Strong and R. 1988. E. Verlag Chemie. E. V. O. 1999. Explor. Geostand. Chim.. 1997. Min. U. 1989. Li. N. J. Amsterdam. Van’t Dack and R. 124. J.. E. 93. B: Appl. Horskey. Williams. K. 18. Zh. 307. Newsl. 187. 1127. Gu. Price. I. 267. Geostand. P. K.. Longerich and D.. F. A. John Wiley. J. 1980. 1986. 1997. 340. Mohamed. 1441. X. Newsl. Dorado. Talanta. M. Chim. C. 342. M. Fryer. M. 1987. P. Geol. 773. G. Philadelphia. X. 92.. Fryer and R. Robotham and G. J. M. E. Prof. 126. B. Sen Gupta. Erzmetall. Sci. Atomic Absorption Spectroscopy.. R. Vlassopoulos. Y. Anal. G. 651. M. Wood and D. ICP Inf. 255.. Bernhard. Jarvis. PA. At. A.. V. K. 8. A. 1997. Amosse. Zhu and Y. Talanta. 333. Hoffman. M. Hu.. TX. Metall. Prabhu and T. Geostand. Gregoire. J. 1995. 179. Anal. D. The Rare Elements Occurrence and Technology. J. R. 1987. Newsl. 37. K. M. Z. Acta. Fanfani. A.. A. Skoog. 1. 65. C. Chem. Mullings. 22. T. Anal. Newsl. Instrum. Grebnova and Yu. Fryer. Gowing and P. Isot. 21. M. G. Inductively Coupled Plasma Atomic Emission Spectroscopy. Chem. S. J. R. Chem. 85. Hall and G. 60. R. 354. 1998. Geol. J. K. Diamantatos. 1997. Chim. Geol. Chen. ICP Inf. Cidu. 19. Stanton and S. 24. 169. Sarkis and A. Tredoux and I. S. Basu and N. L. G. 111. 1995. Niskavaara and E. 334. Geol.. C.S. Virtasalo. M. 1998. 1926. Brooks and R. J. Ramanan. M.. Amsterdam. 27. K. Wilson. Palacios. Absorp. 29. M.. Zhang. S. Healey. T. At. Phillips and I. Radioanal. Li. 791. D. 121. Sighinolfi. 207. J. 116. 231. Spectrom. Xu and P. Floyd. Kubrakova. C. I. Elsevier. J. A. F. 104. New York. 549. 350. Ramankutti. 1976. 25. Geochem. Pearce and L. C. Spectrosc. Newsl. Phys.. 4. Geostand. 544.. Nogueira and A. Xi-Jun. Newsl. M. M. D. 30. At. J. Talanta... F. Peterson and M. H. K. 1994. 1998. Padilla and F. 48. Radioanal. Schramel. 183. 196. Branch and D. J. An Atlas of Spectral Information. Tredoux. Fletcher and S. Newsl. Schramel and W. Jarvis. S. 19. Geol. M.. V. 659. Analyst. 1996. 1996. 124.S. Jackson. 143. G. Torgov. Newsl. 5. Shazali.. F. Anal. Principles of Instrumental Analysis. E.. X. E.30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 V. 12. S. Z. Q. W. A. 187. J. 219. Nucl... K. J. Feng-Zhi. H. N. Stockman. J. J. Explor. T. Acta. 24. Li. B. J. B.. S. Analyst. Bonham-Carter. 1994. Z. 18. 1990. M. 1994. H. J. A. S. Geostand. N. 7. T.. Anal. 1997. 1441. Schwarzer. Wu and Y. T. 1079. 45. M. 85. H. R. Guang and F. 1996. E. Zhu. A. 1996. T. Anal. 120. 20. 1995. Tian and C. P. J. Chem. R. P. McDonald. Luschow. Shibuya. Geostand. E. Geochem. Analysis of Noble Metals. Paper 9/04839A 1540 Analyst. L. S. Geostand. Thompson. 47. P. Newsl. L... H. 321. Stone and J. Spectrom. Enzweiler. I. 1974. Nogueira and A. Zhi-Xing. Geostand. 1995. Elsevier. Chem. J.. 119. Explore. Belskii. G. 1984. Uday Raj. E. C.. Academic Press. 420. Kalish and R. Fassel. W. J. Radioanal. X. Wegscheider. S. 663. Acta. 75. ICP Inf. H. Davis and Y. E.. Geol. E. At. A. 109. Chai. P. W. Jorge. Zolotov. Hussain. 98. Ebihara and H. Balaram. 1993. Plessen and J. Barnes. Wang. Xing-Yin. Nowinski and V. 1991. 31. Anal. B. Spectrosc. 22. 237. K. M. J. Baidya. 25. College Station. B. Riley. A spectrophotometric method for the determination of traces of platinum and palladium in geological materials. 1999. R. Circ. F. Jarvis. P. J. 1998. I. Fresenius’ J. P. 1997. Cheung. Acta. S. 1999. Explor. Zolotov. Chem. A. Ramanaiah. E. Rao. At. Saunder’s College. S. 1981. 1996. M. At. Brooks and B.. Geochem. Dey. 1990. G. R. Strong. M. Pap.. V. Li. Sen Gupta. G. 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 G. 1986. Geochem. Determination of gold in geological materials by solvent extraction and atomic absorption spectrometry. 173. 121. Chem. 404. R. Kontas. Qiao-Sheng. M. Mukulski. J. M. Geostand. Chem. Potts and K. 15. Shand. 1253. B. S. 1997. R. Abs.. E. 1989.. Ramesh and S. 1998. X. Edmunds. Parry and E. C. W. Chem. Acta. Sills. At. Kudinova. P.. M. Zereini. Jarvis. 25. C. Explor. L. I. 131. 49. S. Geol. L. 1988. R. 22. M. 1998. 1217. Jarvis. 19. Hutchison. Li and X. J. Geochem. M. Jarvis. J.. G. Gu. Acta. 1990. E. Zhong. D. I.. 125. 3. Hidalgo. J. Huffman. Kong. Hart and M. 78. ICP Inf. 305. Anal. S. Surv. Du. Chim. Goose. R. 1993. 575-D. D. 1993. Bao. Hodge. Gomej and M. G. C. 1992. M. 1990. pp. M. Earth Sci. Geochem. M. Beamish and J. G. Simpson. Analyst. Nandy. Pearce. Balaram. J. A. Demidova. D. Parry. Newsl.. Geol. Sen Gupta. P. Q. 1967. C.. G. A. Econ. R. H. E. A. Guang-Yao and R. S. Malhotra. Fenxi Huaxue. E. E. Acta. Newsl. 1990. Trysin and Yu. Fenxi Huaxue. Sun. 1391. V. Newsl. T. Figueiredo. C. At.. 125. Totland and K. 296.. 23. Jarvis. E. 68. 1977. 37. B130. Q. T. Analyst. R. M.. R. Guan and A. 13. 204. 1997. At. Oksenoid. V. Chem. M. K. Lahiri. 1995. Analyst. Meier. Yan. D. G. E. J. 20. Analyst. Anal. 1997. Urban and H. 263. Chim. M. S. B. Gorgoni and A. L. E. 1998. Kontas. Miner. Totland. 122. Anal. Pelchat and C. U. Acta. Inst. M. 64. N. A. S. 120. Chi and Z. A. P. Li and S. 195. 124. Methods. 1992. Subba Rao. Analyst. H.. M. M. 1992. L. S. 1988. 1531–1540 . 260. C. S. in Proceedings ODP Scientific Results. X. Lu. 1998. T. Zischka. Potts. 44. 13. A. 132. 273. D. R. Nucl. 175. Anal. G. Spectrosc. 295. New York. 77. Chung and R. 1994. Gijbels. Korda. M. K. ed. Niskavaara and J. G. Jarvis and K. L. McDonald. 167. G. 1989. Reddi. Williams and G. Dong. I. Eng. Nguyen. S. 1991. A. 1995. 120. W. Rao. C. 52. 10. 1988. 1973. 213. Analyst.. Anal. M.. Alguacil. R. Spectrosc. 1993. London. E. 17. New York. Figueiredo. Reddi. Figueiredo. Kontas. K. 617. H. Explor.. Trans. I. Kovalev. 73. Tong. Jarvis and K. E. V. Surv. Mensik and L. Hall and J. 114. Totland. D236-D238. R. G. 22. Kopacz and T. Das. At. 1992. 40. Khim. H. 1996. 1984. Ganesh. O. Y. J. H. Artem’ev. 22. Kontas. 1978. N. 1983. C. 1998. Spectrochemical Analysis by Atomic Absorption. Chem. Geostand. L. 235. A. Schuster and M.. 1998. Y. 1994. McDonald. S.. Geochem. M. Y. 10.. Explor. Anal. Overview and Selected Methods. M. 36. Van’t Dack and R. Coedo. 1998. V. Totland and K. Newsl. W. Nucl. I. Hall. J. J. 433. Kerrich. R. 649. 1998. 59. Explor. D. C. 197. Erzinger. Hoang. L. Date. Sen Gupta and D. Rao and V. Jarvis. Satyanarayana and G. 47. Chim. Newsl. 1990. Parkinson. B. C. Enzweiler. Newsl. J. 1993. 112... I. Lee. Anal. Chem. Hall. Chem. Explor. A.. J. Charan. R. 28. Mineral. Hall. I. Z. Van Loon. Q. Fresenius’ J. Geochem. I. Hoashi. N. Sun. J. K. 297. Zhang. Nakahara. Chim. McKibben. 106. E. Appl. 83. K. Spectrosc. M. Can. 21. J. 1986. J. Wang. Winge. 219.. M. 1994. Kuzmin. H. 30. H. Anal. G. 42... Chim. Reeves. 1988.. S. 99. W. Chem. M.

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