Chapter28

Gold

Gold (Au, atomic weight 196.97, melting point 1063C, d = 19.3 g cm -3 ) is a noble, easily malleable, yellow lustrous metal. It occurs in the earth's crust with an average abundance of 3.5 fg gl. Gold mostly occurs as native metal in lode and placer deposits often in association with quartz. Gold is also present as a minor component of base-metal ores, especially those of copper obtained as a by-product in the electrolytic refining of copper and nickel. The metal is used in electronic industry and in jewellery. Gold compounds are used in medicine because of their antitumour and antirheumatoid activity. Gold normally resists corrosion by a single mineral acid but dissolves in aquaregiawith formation of chloroauric acid, HAuCl 4. Gold dissolves (at ambient temperature) in alkali cyanide solution in the presence of atmospheric oxygen to form a stable Au(CN) complex. It is also attacked by fused alkali containing an oxidizing agent to produce soluble aurates. The most common valence states of gold are I and III giving origin to aurous and (more stable) auric compounds, respectively. The Au(I) and Au(III) ions do not exist in aqueous solutions; analytical chemistry of Au is based on chloride and bromide complexes of Au(III). Gold(III) forms relatively stable nitrate complex which often makes it necessary to eliminate nitrate from solutions obtained on dissolving Au in aqua regia. The hydroxide, Au(OH)3 , is amphoteric. When Au solutions are treated with NH 3 aq an explosive fulminate may be formed. The gold in chloride solution is readily reduced to the colloidal metal by many organic (e.g. ascorbic acid, oxalic acid, hydrazine, hydroquinone) and inorganic reducing agents (e.g. Zn, SnCl 2 , H202), some of which do not precipitate the Pt-group metals. The analytical chemistry of Au has been reviewed [1-3].

439

28.1 SEPARATION AND PRECONCENTRATION

Extraction

Gold(III) is readily extracted from 4-8 M HCl or HBr as AuC14 or AuBr4, respectively, into oxygen containing organic solvents, e.g. DIPE, MIBK, ethyl or amyl acetate. The interference of Fe(III) is removed by its reduction to Fe(II) [4] or by stripping of Fe(III) with 0.5 M HCl [5]. Extraction ofAu(III) halide complexes or Au(I or III) cyanide complexes as ion pairs with quaternary ammonium salts is less popular [6-8]. Trace amounts of gold can be extracted with DIPE from 7 M HN0 3 [9]; only U(VI) and Th are partly co-extracted. Although extraction of Au(III) is often claimed to be quantitative, the degree of extraction of Au from real matrices may be dependent on the composition of the solution. It is therefore recommended to match the sample matrix with standards as closely as possible.
Coprecipitation

Gold may be concentrated by precipitation on reduction to the metal, in the presence of a collector, usually Hg [10,11], Te [12-15] and mixed Se-Te [16]. Copper is used as a collector for the coprecipitation of gold as sulphide using thiourea and thioacetamide. 2-Mercaptobenzothiazole and thiobarbituric acid are common group regents for noble metals [17]. Trace amounts of gold can be enriched by flotation using dimethylaminobenzylidenerhodanine [18], 2-phenylethylenephosphonic acid [19] or basic dyes [20,21], or by accumulation by bacterial cells [22]. Separation of Au on Nb cathode has been reported [23].
Sorption and ion exchange

Activated charcoal is the most frequently used sorbent as it retains ionic and colloidal gold quantitatively at pH < 5, is readily adaptable to field sampling and can be easily handled for NAA and AAS determinations [26,271. Anion exchange resins which bind strongly gold(III) chloride complex are a viable approach [26-34]. Various chelating resins, polyDDTC [35], dehydrodithizone [36,37], thiol cotton fibre [38], silica gel modified with y-aminopropyltriethoxysilane [39] and poly(vinylthiopropionamide) [40], di(methylheptyl)methyl phosphonate loaded resin [41], usually of transient importance, have been proposed. Cation exchange resins are convenient to separate base metals since Au chloride complexes are not sorbed. In contrast to charcoal, the resins allow a quantitative recovery of ionic gold whereas the retention of colloidal gold which is trapped mechanically in the resin voids is often not quantitative.
440

28.2 DETERMINATION TECHNIQUES Spectrophotometry Spectrophotometry of Au is based either on complexes with organic S-donor reagents (usually thio-Michler's ketone and rhodanine) or on ion associates of an anionic gold halide complex with basic dyes (usually Rhodamine B). Thio-Michler's ketone reduces Au(III) and forms with Au(I) colour ( = 1-2 x 105) complexes of different composition. Rhodanine forms in a 0.1 M HCl medium a sparingly soluble pink-violet complex which remains dispersed in the aqueous phase ( = 5.8 x 104 at 515 nm in H 2 0-pyridine medium). The most popular is the ion associate of AuC14 with Rhodamine B which is extracted with benzene or DIPE ( = 8.7 x 10 4 at 565 nm). Sb(V), Tl(III), Fe(III), Ga and Hg(II) interfere and must be separated beforehand. In flotation-spectrophotometric methods an adduct of a simple ion associate of the AuBr 4 complex with a basic dye and several molecules of the salt of the dye precipitates on the wall of a separating funnel during the shaking of the aqueous phase with a nonpolar solvent. The precipitate is dissolved in a polar solvent and the solution obtained is the basis for the sensitive determination of gold ( = 11.4 x 105) [20,21]. The methods, however, lack precision unless in the hands of an experienced analyst. Spectrofluorimetry In spectrofluorimetric methods blue fluorescence exhibited by the extract of the ion-associate of AuC14 (or AuBr 4) with Rhodamine B or Butylrhodamine B is measured. Flame atomic absorptionspectrometry Flame AAS offers a sensitivity of 2 g ml-l in the recommended N 20-C 2 H 2 flame at the most sensitive 242.8 nm line. A 1% solution of LaC13 is commonly used to control the interferences although the use of triethanolamine has been reported [42]. Flame AAS of the organic phase after extraction with MIBK is popular. Silver, Se(IV), Te(IV), Fe(III), Tl(III), Cr(VI), Mo(VI), As(V), Sb(V) and Sn(IV) are partially co-extracted but do not interfere with the measurement. Graphitefurnace atomic absorption spectrometry Graphite furnace AAS offers a characteristic mass of ca 10 pg. It is plagued by interferences which are difficult to remove by optimization of the GF programme. The maximum allowable char temperatures of 441

800-900C are just below the char temperature of the carbonaceous material and the volatilization temperature of common salts such as NaCl or MgC12 which interfere with the formation of Au atoms. The char temperature can be increased by 300-400C by the use of a matrix modifier, most often nickel or a Pd-Mg mixture. Interferences and matrix modifiers in ETA AAS of Au have been critically discussed [43,44]. L'vov platform atomization, Zeeman effect background correction and peak area absorbance measurements are a must for a successful analysis.
Inductively coupled plasma atomic emission spectrometry

Inductively coupled plasma AES offers detection limits of 0.02 and 0.03 tg ml-l at the two most sensitive Au lines, 242.795 nm and 267.595 nm, respectively. The former is interfered by Fe, Mn whereas the latter by Fe, Cr, Mg, Mn and V. In practice the determination of Au requires separation and preconcentration [35].
Neutron activation analysis

Gold is an element with one of the best sensitivities in NAA. It is subject to the activation reaction: 1 97Au(n,y)19Au producing 1 98Au nuclide (t1 /2 = 2.7 d, EY = 0.413 MeV) which is counted, usually after a 3-10 day decay. The interferents include Ag (the "l'Ag -photopeak at 0.455 MeV) and Pt, Pt (owing to the interference of the 3.15-day 99Au daughter isotope) as well as 76As and 8 lBr which might be critical for the determination of Au at the ng/g level. Simultaneous determination of Au and Pt is possible but should be considered for each material and the Pt/Au ratio in the sample must be taken into account. Radiochemical NAA allows the detection limits at the low ng/g and the sub-ng/g level to be obtained for most of the samples [26,45-48].
Mass spectrometry

Gold is monoisotopic and cannot be determined reliably by TI MS. ICP MS analysis for gold offers high sensitivity (DL 0.06 ng ml-l) [49,50]. The few possible isobaric interferences at mass 197 include a hydride of ' 9 6 Pt and l 1Ta oxide [51]. To date, ICP MS coupled to HPLC is the only technique capable of the speciation analysis of gold metabolites in biological samples [52].
Fluorescence techniques

The direct XRF analysis is hampered by the high content of admixtures that give energetically similar K and L series X-rays and by the strong absorption of gold X-ray fluorescence by the base elements in the
442

samples [53]. Gold sorbed on organic support may be analyzed [53]. Non-dispersive AFS allows a low detection limit of ca 0.5 ng ml-1 or 0.01 ji g g-1 in the solid sample. Large scatter signals due mainly to Al and refractory metals make separation necessary [7]. A detection limit of 10 fg was obtained by ETV LE AFS [54]. 28.3 ANALYSIS OF REAL SAMPLES 28.3.1 Geological materials Gold is always extremely dispersed in the raw material (the nugget effect) so large sample weights are required for a representative sample. The malleability of gold makes it difficult to grind, and there may be some losses on the grinding surfaces. Samples to be analyzed should have a particle size below 200 mesh. The most common approaches to transfer gold into solution include the fire assay (cf. Section 2.2.3.) followed by the button dissolution or acid leaching. Alkali fusions which are used in post-irradiation decomposition of samples are considered unsuitable for other techniques unless removal of a salt matrix is included. Methods for the spectrometric analysis for Au in geological samples are summarized in Table 28.1. The classical fire assay enables the quantitative collection of gold in the lead button which is then dissolved, usually in aqua regia, to produce a solution for an instrumental determination. Fire assay suffers from loss of accuracy when low levels of gold (<400 ng gl) are present. Losses of gold can be caused by boiling over and spitting during fusions, non-recovery from slag and loss into the cupels. Low recoveries can be encountered from some sample types. If the Cu, Fe or Zn content of the sample is fairly high, slag retention and cupel adsorption of Au are appreciable. The lead fire assay is inadvisable for samples containing osmiridium owing to spitting during cupellation resulting in losses of Au and the risk of contamination. Second fusion is necessary to recover gold from the silicate glass. Nickel sulphide [13,17] and copper fire assays [71] have alternatively been proposed. The most frequently used is the halide acid leach, using aqua regia but a preliminary attack by Br 2 and HBr has been advocated [72]. Roasting of samples containing sulphides and organic matter at carefully optimized conditions is necessary to eliminate S and As. Below 500"C the decomposition of sulphides and some carbonaceous material
443

TABLE 28.1 Determination of gold in geological materials Material (amount) Ores (1-50 g) Sample decomposition roasting, lead fire Separation technique pptn. with HCHO, dissoln. in aqua regia Detection DL technique (ng/g) GF AAS n.g. Ref.

17

assay, the bead dissolved in HC10 4 -AcOH Rocks, ores (20-50 g) CRM (4 g) NiS fire assay; the bead dissolved in HCI dissoln. in aqua
regia, fusion with Na 202

copptn. with Te

NAA

0.2

13

copptn. with Te

DCP AES n.g.

55

Sand, rocks, ores (25 g)

NiS fire assay

INAA FAAS

2 n.g.

56 10

(leaching)
Rocks, ores aqua regia

FAAS

18

57

(25 g)
Rocks (10 g) Ores (25 g)

(leaching)
aqua regia (leaching) HNO 3 (leaching), roasting, dissoln. in aqua regia HF-aqua regia (leaching); fusion with Na 2 02 HPO 4-HCIO,4 (leaching); HBr-Br2 HCI-Br 2 (leaching) aqua regia aqua regia

ICP MS

n.g.

58

sorption on TBP modified support cation exchange

XRF

10

53

Rocks (5 g), ores (2 g) Ores

GF AAS

n.g.

12

extrn. into AmAc upon redn. of Fe(III)

GF AAS

Rocks and placers Rocks Ores (10 g)

AAS GF AAS Fl FAAS

n.g. 0.3 10

59 60 61

444

Material (amount)
Ores (5-9 g) Ores (0.5-1 g)

Sample decomposition HNO 3, aqua regia HNO3 -HF (bomb)

Separation technique

Detection technique

DL (ng/g) 1000 n.g.

Ref.

extrn. with N, N'VIS diphenylbenzamidine anion exchange as AuCl4, extrn. with RhB anion exchange of
AuCl4

VIS

Ores CRMs (10 g) HNO 3-HCI (microwave assisted) aquaregia-Br2 HF-aqua regia HF-aqua regia (bomb) HF, HNO 3, aqua regia HCI-HNO3 HCI, HNO 3 , HF roasting, aqua regia roasting, HCI-HNO 3 roasting, HBr-Br2 roasting, aqua regia

WD XRF FI FAAS

200 2.2a

sorption on Cellex T anion exchange

Rrocks (10 g), ores (5 g) Ores, concentrates Rocks (5 g) Ores (- 5 g)

FAAS
GF AAS

1000 100 0.5 600

anion exchange

GF AAS

extrn. with amidine AAS (CHC13), back-extrn. with thiourea copptn. with Hg sorption on activated charcoal GF AAS GF AAS

Geo CRMs (0.5 g) Sulphide ore (25 g) Ore (10 g)

n.g. 2 10

GF AAS extrn. into MIBK after pptn. of Fe(III) with NH3(aq) extrn. with Aliquat-336 in DIBK copptn. with Te sorption on a foamed plastic, ashing, dissoln. in aqua regia ND AFS

Rocks (30 g)

10

Rocks (5-10 g) Rocks (2-8 g)

FAAS Arc ES

15 0.3

14 68

continued 445

TABLE 28.1 (continuation) Material (amount) Ores (10 g) Ores (2.5 g) Sample decomposition Separation technique Detection DL technique (ng/g) FI FAAS 50 Ref.

roasting, aqua regia on-line sorption roasting, aqua regia (leaching), fusion with Na 2 02 roasting, H2 SO4 HF (leaching), fusion of with Na20 2-NaKCO 3 fusion with NaOHNa2 0 2 fusion with Na2O2, lead fire assay, fusion with NaOHNa2 02 fusion with LiBO 2, dissoln. in HNO 3 dissoln. in HNO 3 HCI with KBrO 3 aqua regia (leaching), HC1HC10 4 leaching with aqua regia for strongly bound Au and dil. HCI for weakly bound Au SPE on polyDDTC resin, dissoln. in 50% H2 02 extrn. into MIBK

27 36, 37

sorption on dehydro- DCP AES n.g. dithizone column, elution with thiourea copptn. with Se-Te GF AAS 0.5

Rocks (5 g)

16

CRMs coal and rock Rock (-0.5 g)

anion exchange

NAA

lb

26

NAA

0.008

45

Pt ore (0.5 g)

ICP AES

620

35

Soils Soil and sludge (1-2 g)

GF AAS

n.g.

69 38

sorption on thiolICP AES cotton fibre column,

n.g.

Humus soil (3 g)

(0.2 -16)

70

SPE = solid phase extraction. a In the reduction fed, ng/ml; b ADL, pg

may be incomplete whereas above this temperature volatilization of gold may occur especially when large amounts of As and Sb are present. In addition, trapping of the gold present may occur owing to the sintering of certain clays. For some types of samples the recovery of Au can be low because of the inability of these acids to liberate gold occluded in silicates, spinels and refractory minerals. Hydrofluoric acid facilitates
446

release of Au grains but requires the use of expensive platinum or PTFE crucibles. Typical problems include the formation of emulsions during solvent extraction, the co-extraction of Fe(III) and losses of Au due to CO 2 evolution and frothing as the reaction with carbonates is very vigorous. Cyanide or thiourea leaching is slow and fails to liberate gold enclosed in gangue and sulphides. 28.3.2 Other materials Water The analysis of waters is affected by contamination and the uncertainty about gold speciation. Analytical methods for ionic gold may not be adequate for the measurement of total gold. Checking the recoveries by means of ionic standards often leads to false conclusions. In oxic seawater Au is predicted to be in the monovalent state as the neutral Au(OH)(H 2 0) or AuCl2 species but if the equilibrium is not attained soluble Au(III) complexes and Au colloids are common. Under anoxic conditions, in the presence of sulphide Au(HS)2 and Au are predicted to dominate [73]. In fresh waters dissolved organic acids (able to reduce gold to Au ) play an important role. Speciation of Au is further complicated by the formation of soluble auriferous humate and fulvate complexes and/or adsorption on particulate matter. To avoid the loss of gold by adsorption on the wall of a sample container, samples should be acidified immediately after collection with HCl and some Br 2 should be added. In spite of acid additions, amorphous Si and sulphide minerals (hydrothermal fluids) rapidly precipitate and take up Au. A minimum amount of Br 2 -HF-HNO 3 should be added to resolubilize the material [51]. Further, indiscriminate acid additions can promote Au losses in glass and polyethylene containers. An alternative to Br 2 addition is the adsorption of gold on charcoal just after the sample has been filtered. Because of very low concentration of Au in natural waters (in open sea 1-100 pg 1-1, in surface waters 0.1-1 ng -1) a preconcentration step is always required. Ion exchange resins are well suited for the determination of gold from seawater but charcoal sorption has a more universal character. The methods for the determination of Au in water are summarized in Table 28.2. Biological materials Dry ashing is not recommended as some plants are cyanogenic and all or part of the Au contained may be lost by volatilization. In wet digestion 447

TABLE 28.2 Methods for the determination of gold in water Water (amount) Natural (1 1) Natural (2 1) Preconcentration sorption on activated charcoal, ashing, the residue dissolved in HC1 anion exchange, elution with acetone-HNO 3 , extn. of AuBr4 (MIBK) extrn. as AuCl4 (MIBK) anion exchange, upon elution resorption on a single anion exchange bead anion exchange, elution with hot coned. HNO3 SPE on TBP saturated with chlorine, ashing or elution with thiourea anion exchange; elution with acetone-HNO3, evaporation, dissolution in HBr/Br 2, extrn. into MIBK UV irradiation, evaporation with HF, redissoln. in aqua regia, anion exchange, elution with hot concd. HNO 3 evaporation, dissoln. in HCI-HNO 3 , extrn. into MIBK Detection technique GF AAS GF AAS DL (ng/ml) 0.5 0.4 Ref. 24 74

Natural (2 1) Sea

ICP MS GF AAS

0.2 <0.100

74 75

Ssea (4 1) Rriver, mineral (11) Natural (1 1)

FI ICP MS NAA GF AAS

0.002 0.2 1

51 76 29

Sea

ICP MS

80

30

Lake (0.1 1)

GF AAS

few

77

with a mixture of H 2SO4 , HC10 4 and HNO3 plant materials may yield
some insoluble white precipitates (which appear to be metal oxides) occluding gold and making the addition of HF necessary. In addition, gold complexes can be reduced readily by chemicals such as amino acids to colloidal gold, which is adsorbed on the walls of vessels. In most oxidizing media: HC10 4 -HNO3 , concentrated HNO3 , fuming HN0 3 and HN0 3 H 2 SO4 incomplete recoveries are observed above 100 C. Addition of aqua 448

TABLE 28.3 Methods for the determination of gold in biological and clinical materials Material (amount) Plant (1 g) Digestion Separation Detection technique GF AAS DL (ng/g) 0.2 Ref.

fuming HNO 3

extrn. into MIBK from HCl-Br 2 medium copptn. with Te

Plant (1-2 g ash) Plant, animal CRMs Plant, animal CRMs Animal tissue (2 g) Intraocular fluid, animal tisue (<0.2 g) Animal serum Blood, serum Urine (25 ml) Human bone (0.1 g)

dry ashing, dissoln. in aqua regia-HF HNO 3 -H2SO4 HC1 (HF added for plants) (??) H2 SO4-HC10 4 HNO 3, then with aqua regia HNO 3 -H2 02

GF AAS, ICP MS RNAA

0.5

15

pptn. as Au

10 fg/g

46

extrn. with DDTC extrn. into MIBK none

RNAA GF AAS

few 0.10

47 78

GF AAS

n.g.

79

Triton X-100 added none none

GF AAS GF AAS

80

160 (plasma) 81 64 (blood) 12 40 6 82

extrn. of AuI4 GF AAS with TOA (n-BuAc HNO 3 (microwave assisted) extrn. into MIBK GF AAS

regia and gentle heating over a water bath prevent losses [5]. Methods for the analysis of biomaterials for Au are summarized in Table 28.3.
Industrialmaterials

The methods for the determination of Au in industrial materials (concentrates, sweeps and jewellery) are summarized in Table 28.4.
449

TABLE 28.4 Methods for the determination of gold in industrial materials Material (amount) Concentrates, mattes (2.5 g) Concentrates Bauxite residue Slime Sample decomposition roasting, aqua regia (leaching), fusion with Na2 02 HF-aquaregia HF-HCI-HNO 3 (microwave assisted)
aqua regia

Separation sorption on dehydrodithizone column, elution with thiourea

Detection technique DCP-AES

DL (ig/g) n.g.

Ref. 36, 37

GF AAS none GF AAS

100 .la

83 84

(leaching) Blister copper, Speiss products (5 g) Steel Pt-powder, Pt-chloride Cyanide process solutions Wastewater (2 ml)
H2SO 4-aqua regia

extrn. with Aliquat 336 into DIBK amalgamation with Hg

FAAS

AAS

85

HCl-HF, HNO 3
aqua regia

anion echange of AuCl4 anion exchange

RNAA GF AAS

10 24 b 5a

48 32 86

extrn. as Au(CN)j FI FAAS on a liquid membrane sorption on a TOPO modified tungsten wire GF AAS

0.2 a

87

a In the solution fed, ng/ml; b ADL, pg. 28.3.3 Accuracy considerations Standardsolutions The stability of Au solutions is affected by exposure to bright sunlight and by base exchange reactions and adsorption on glass containers. Gold standard solutions (1 or 10 mg ml-1 ) are available from reputable chemical suppliers. These solutions when stored in clean containers at 450

2-4 0C in darkness should be stable for up to a year. Working solutions of 1 ,ig ml-l or less are stable for short periods and should be prepared daily.
Contamination

The contamination hazard is mainly associated with the earlier handling of samples containing high Au levels, such as sweeps and alloys. Contamination of the trace level fire assays by residues from high level gold assays is common unless separate pots, moulds, grinders are used for each of these operations. Measures to eliminate contamination problems have been discussed [88]. Special precautions to avoid contamination are necessary in the analysis of water and biological materials owing to the very low Au concentrations present.
Losses

The handling of traces of gold is hampered by different oxidation states, the tendency towards formation of coordination compounds and by kinetic indifference of many compounds. In all wet procedures the speciation of gold must be carefully considered as only active species can undergo the expected reactions. Care should always be taken to avoid the reduction of gold compounds to the metal which might occur, e.g. by overheating during evaporation or exposure to sunlight in glass containers. NaCl is added to form chlorocomplexes of Au to prevent the loss during the evaporation step [12]. The use of flexible tubing in peristaltic pumps was reported to adsorb Au in an uncontrolled manner [51].
Certified reference materials

A variety of CRMs are available for geological samples from the US Geological Survey and the Canada Centre for Mineral and Energy Technology (CANMET). For biological materials there are very few reliable data for gold in SRMs. The gold content in NBS Orchard leaves is estimated at 1.640.10 ng g-1 and that in the Bowen's kale at 2.20+0.25 ng g'. Seawater standards with certified gold values do not exist. The ng/kg levels of gold are still not reliably determinable with any currently available method. REFERENCES
1 2 3 F.E. Beamish and J.C. Van Loon, Analysis of Noble Metals. Overview and Selected Methods. Pergamon, Oxford, 1977. S. Kallmann, in: Anal. Chem., 56 (1984) 1021A. J.C. Van Loon, R.R. Barefoot, Determinationof the Precious Metals. Se451

lected InstrumentalMethods. Wiley, Chichester, 1991. J. Vermeulen, J. Anal. At. Spectrom., 4 (1989) 77.

5 6 7 8 9 10 11 12 13 14 15 16 17
18

R.R. Brooks and S.D. Naidu, Anal. Chim. Acta, 170 (1985) 325. J. Flanjak and A.E. Hodda, Anal. Chim. Acta, 207 (1988) 283. P.L. Larkins, Anal. Chim. Acta, 173 (1985) 77. R.A. Curra-Lava and J.A. Jimenez-Prieto, At. Spectrosc., 12 (1991) 210. Z. Marczenko and T. Kowalski, Anal. Chim. Acta, 156 (1984) 193. R.K. Tewari, V.K. Tarsekar and M.B. Lohande, At. Spectrosc., 11 (1990) 125. H. Niskavaara and E. Kontas, Anal. Chim. Acta, 231 (1990) 273. J.G. Sen Gupta, Talanta, 36 (1989) 651. I. Shazaki, L. Van't Dack and R. Gijbels, Anal. Chim. Acta, 197 (1987) 49. P. Chattopadhyay and B.N. Sahoo, Analyst, 117 (1992) 1478. G.E.M. Hall, J.C. Pelchat and C.E. Dunn, J. Geochem. Explor., 37 (1990) 1. J. Amosse, W. Fischer, M. Allibert and M. Piboule, Analusis, 14 (1986) 26. Analyst, 111 (1986) 213. A. Diamantatos,
X. Wu and S. Liang, Fresenius'J.Anal. Chem., 336 (1990) -120.

U. Dietze, J. Braun and H.J. Peter., Fresenius'Z.Anal. Chem., 322 (1985) 17. 20 K. Jankowski and Z. Marczenko, Anal. Chim. Acta, 176 (1985) 185. 21 K. Jankowski and Z. Marczenko, Talanta, 32 (1985) 291. 22 L.C. Robles, C. Garcia-Olalla and A.J. Aller, J. Anal. At. Spectrom., 8 (1993) 1015. 23 B. Rietz and K. Heydorn, J. Radioanal. Nucl. Chem., 174 (1993) 49. 24 G.E.M. Hall, J.E. Vaive and S.B. Ballantyre, J. Geochem. Explor., 26 (1986) 191. 25 F. Me, R. Sera, R. Enne, I. Trudu and E. Contini, At. Spectrosc., 11 (1990) 128. 26 A. Rivoldini and T. Haile, At. Spectrosc., 10 (1989) 89. 27 S. Xu, L. Sun and Z. Fang, Anal. Chim. Acta, 245 (1991) 7. 28 M. Oddone, S. Meloni and R. Vannucci, J. Radioanal. Nucl. Chem., 142 (1990) 489. 29 J.B. McHugh, Talanta, 33 (1986) 349. 30 E. Bakowska, K.K. Falkner, R.M. Barnes and J.M. Edmond, Appl. Spectrosc., 43 (1989) 1283. 31 K. Brajter and K. Slonawska, Fresenius'Z.Anal. Chem., 328 (1987) 128. 32 K. Brajter and K. Slonawska, J. Anal. At. Spectrom., 2 (1987) 167. 19
33 34 K. Pyrzyhska, J. Anal. At. Spectrom., 9 (1994) 801. K. Kritsotakis and H.J. Tobschall, Fresenius'Z. Anal. Chem., 320 (1985)

35 36 452

15. Y.S. Chung and R.M. Barnes, J. Anal. At. Spectrom., 3 (1988) 1079. M. Grote and A. Kettrup, Fresenius'Z. Anal. Chem., 327 (1987) 11.

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

M. Grote and A. Kettrup, Anal. Chim. Acta, 201 (1987) 95. L. Xu and P. Schramel, Fresenius'J. Anal. Chem., 342 (1992) 179. A. Tong, Y. Akama and S. Tanaka, Anal. Chim. Acta, 230 (1990) 179. Z. Su, X. Chang, K. Xu, X. Luo and G. Zhan, Anal. Chim. Acta, 268 (1992) 323. P. Di and D.E. Davey, Talanta, 41 (1994) 565. S.E. Ghazy, M.A. Kabil and M.A. Mostafa, J. Anal. At. Spectrom., 9 (1993) 857. J. Egila, D. Littlejohn, J.M. Ottaway and X. Shan, J. Anal. At. Spectrom., 2 (1987) 293. B. Welz, G. Schlemmer and R. Mudakavi, J. Anal. At. Spectrom., 7 (1992) 1257. H.T. Millard jr, J. Radioanal. Nucl. Chem., 113 (1987) 125. R. Zeisler and R.R. Greenberg, J. Radioanal.Nucl. Chem., 75 (1982) 27. E. Taskaev, M. Karaivanova and T. Grigorov, J. Radioanal. Nucl. Chem., 120 (1988) 75 X.L. Wang, Y.L. Chen, X.Y. Wang and Y. Sun, J. Radioanal.Nucl. Chem., 147 (1991) 377. A.R. Date and A.L. Gray, Spectrochim. Acta, 40B (1985) 115. E. Denoyer, R. Ediger and J. Hager, At. Spectrosc., 10 (1989) 97. K.K. Falkner and J.M. Edmond, Anal. Chem., 62 (1990) 1477. S.G. Matz, R.C. Elder and K. Tepperman, J. Anal. At. Spectrom., 4 (1989) 767. S.M. Dmitriev, T.V. Shishkina, E.L. Zhuravleva and J. Chimeg, Anal. Chim. Acta, 252 (1991) 97. B. Remy, L. Verhaeghe and P. Mauchien,Appl. Spectrosc., 44 (1990) 1633. M. Tripkovi, M. Todorovi and I. Holclajtner-Antunovi, Anal. Chim. Acta, 296 (1994) 315. M. Asif, S.J. Parry and H. Malik, Analyst, 117 (1992) 1351. K. Jakubec, Z. Sir and J. Vilimec, Anal. Chim. Acta, 173 (1985) 97. C.J.B. Gowing and P.J. Potts, Analyst, 116 (1991) 773. G.S. Reddi, S. Ganesh, C.R.M. Rao and V. Ramanan, Anal. Chim. Acta, 260 (1992) 131. S. Terashima, Geostand. Newsl., 12 (1988) 57. W. Qi, X. Wu, C. Zhou, H. Wu and Y. Gao, Anal. Chim. Acta, 270 (1992) 205. C. Agrawal, M. Shrivastava, R.K. Mishra and K.S. Patel, Anal. Chim. Acta, 237 (1990) 491. H. Koshima and H. Onishi, Anal. Sci., 6 (1990) 421. V. Cojocaru and S. Spiridon, J. Radioanal.Nucl. Chem., 170 (1993) 259. C. Garcia-Olalla and A.J. Aller, Anal. Chim. Acta, 252 (1991) 97. K.S. Patel and K.H. Lieser, Fresenius'Z.Anal. Chem., 323 (1986) 494. T. Stafilov and T. Todorovski, At. Spectrosc., 8 (1987) 12. 453

67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82

83 84 85 86 87 88

T. Stafilov and T. Todorovski, At. Spectrosc., 8 (1987) 12. P. Xu, J. Anal. At. Spectrom., 7 (1992) 775. V.K. Jain, P.M. Hall and J.S. Tiwari, At. Spectrosc. 8 (1987) 77. B.J. Perry, J.C. Van Loon in: G. Holland and A.N. Eaton (Eds), Applications of Plasma Source Mass Spectrometry. RSC, Cambridge, 1991, pp. 38-47. A. Diamantatos, Talanta, 34 (1987) 736. P. Chattopadhyay and B.N. Sahoo, Analyst, 117 (1992) 1481. D. Vlassopoulos and S.A. Wood, Cosmochim. Geochim. Acta, 54 (1990) 3. R. Cidu, L. Fanfani, P. Shand, W.M. Edmunds, L. van't Dack and R. Gijbels, Anal. Chim. Acta, 296 (1994) 295. M. Koide, D.S. Lee and M.O. Stallard, Anal. Chem., 56 (1984) 1956. T.V. Shishkina, S.N. Dmitriev and S.V. Shishkin, Anal. Chim. Acta, 236 (1990) 483. R. Hahn and M. Ikramuddin, At. Spectrosc., 6 (1985) 77. D.F. Kehoe, D.M. Sullivan and R.L. Smith, J. Assoc. Off. Anal. Chem., 71 (1988) 1153. D.O. Matthews and M.C. McGahan, Spectrochim. Acta, 42B (1987) 909. L. Thunus and J.F. Dauphin, Anal. Chim. Acta, 235 (1990) 393. X. Shan, J. Egila, D. Littlejohn and J.M. Ottaway, J. Anal. At. Spectrom., 2 (1987) 299. C. Minoia, E. Sabbioni, R. Pietra, A. Ronchi, F. Poggio and A. Salvades, in: C. Minoia and S. Caroli (Eds.), Applications of Zeeman GraphiteFurnace AAS in the Chemical Laboratory and in Toxicology, Pergamon Press, Oxford, 1992. G. Lu, J. Xu, T. Xu, L. Jin and Y. Fang, Talanta, 39 (1992) 51. J. Alvarado and A. Petrola, J. Anal. At. Spectrom., 4 (1989) 411. N. Likhareva, S. Ganeva and P. Kosturkova, FreseniusZ. Anal. Chem., 331 (1988) 599. M.J.C. Taylor, D.E. Barnes and G.D. Marshall, Anal. Chim. Acta, 265 (1992) 71. A.M.E. Balaes,Appl. Spectrosc., 40 (1986) 1190. M. Asif and S. Parry, Analyst, 114 (1989) 1057.

454