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An eco-friendly chemistry for gold extraction using supercritical carbon dioxide

Jeremy D. Glennon*, Josephine Treacy, Anne M. OKeeffe, Mark P. OConnell, Conor
C. McSweeney, Stephen J. Harris and Andrew Walker
Analytical Chemistry and Supercritical Fluid Centre, Department of Chemistry,
University College Cork, Ireland.
Email: j.glennon@ucc.ie

Introduction
A number of exciting challenges, opportunities and unanswered questions remain
concerning the chemistry, geochemistry, medical, industrial and analytical applications of
gold and its compounds.1 Among the challenges presented is the need for extraction
methods for gold, at process and indeed analytical scales, that avoid the use of organic
solvents or hazardous reagents. Extensive environmental contamination has occurred in
the Brazilian Amazon from the mercury-gold amalgamation process. Major problems
with the cyanidation process are the relatively slow dissolution kinetics and the health
and environmental problems associated with it. With innovation and technical changes, a
cleaner way for solubilising and extracting this versatile precious metal can be found.
This cleaner future may lie in supercritical fluid science. Interestingly, geochemical
studies of gold solubility and speciation in hydrothermal solutions have highlighted the
importance of supercritical conditions and sulphur species in the deposition of gold in
natural environments. Gold solubility in supercritical brines is far higher than previously
supposed while interest in the high content of carbon dioxide in the mineralizing fluids is
growing. 2,3 In recent years, also, there has been a tremendous amount of attention paid in
analytical chemistry and in industry, to the area of supercritical fluid extraction (SFE) of
organic and metallic species. 4 This interest has been fuelled by the introduction of more
stringent environmental control and the subsequent need for cleaner solvents and
processes to replace established ones. Carbon dioxide is the substance of choice for SFE
because of its moderate critical parameters (Tc = 31oC, Pc = 73atm), inertness and
availability in pure form. It is an excellent extraction medium for non-polar and
moderately polar species, and with careful ligand design, it can be used for analytical and

process scale metal extraction from solution and solid phases. In general, the dissolution
of a metal in supercritical CO2 (sc-CO2) requires that the charge on the metal ion be
neutralised on complexation by the ligand or through a form of ion pairing (analogous to
the situation where metal ions are extracted into organic solvents, such as methyl isobutyl
ketone or toluene). In this way, then, many chelating agents such as dithiocarbamates
and hydroxamic acids have been utilised to extract metal ions such as Cu and Fe into scCO2, the process greatly enhanced by the use of fluorinated ligand derivatives. 5-7
In this review paper, we show that supercritical conditions and complexation with
sulphur donor atoms, important in the natural deposition of gold, can form the basis of a
clean, eco-friendly chemistry for gold extraction. Analytical scale extractions of gold
from a variety of matrices can be conveniently used to assess the efficiency of any new
proposed ligand.
Supercritical Fluid Extraction.
Extractions were performed using an Isco SFX supercritical fluid extraction system (Isco
Inc., USA, supplied by Jones Chromatography, UK). The SFE system is controlled by a
260D series pump controller and consists of a syringe pump and heated extractor block,
into which a 2 or 10 ml stainless steel extraction cell is placed. A heated variable
restrictor was used at a flow rate of 1.0 ml min-1, with all extracts collected in MIBK or
MeOH, for analysis of metal content by FAAS or ICP. Unmodified CO2, i.e. without the
addition of an organic modifier such as methanol, was used for all extractions. Operating
temperatures and pressures above the critical point of carbon dioxide were used.
An examination of the efficiency of extraction of gold using selected chelating reagents,
in the presence or absence of diverse metal ions, is readily carried out using Au(III)
spiked cellulose filter paper, prepared using L additions onto the paper from a 1000 ppm
gold atomic absorption solution. Alternatively, weighed quantities of a Au(I) salt, gold
powder or gold bearing solid can be used. Both the reagent (on this scale, mg quantities
are used) and gold containing matrix were loaded into the cell, and maintained for a static
period in supercritical CO2, before being dynamically extracted into the collecting
solution. Supercritical fluid extraction was generally carried out at 250 atm and 60C, 35
min static and 15 min dynamic, all extracts being collected in 10 ml of methanol and
analyzed using FAAS. Larger 3-5g quantities of an ore reference material (OXM16)

containing a certified gold content of 15.15 g/g Au (Rocklabs Ltd., Auckland, New
Zealand) were also extracted with n repeated additions (35mg) of fluorinated thiourea
ligand (T3) reagent. The residue ore reference material after supercritical fluid extraction
was also prepared by fire assay prior for flame atomic absorption spectroscopic analysis.

Selective Chemical Reagents

Metal solubilisation and extraction has been achieved in pure supercritical carbon dioxide
by utilizing fluorinated reagents.

Among the selective reagents synthesised in our

laboratory for SFE are macrocyclic calix[4]arene derivatives of the general structure
shown in Figure 1(a). The incorporation of fluorinated groups at the upper rim (R)
greatly enhances the solubility of these molecular baskets, while lower rim
functionalisation (R`) can be used to shape the host cavity with suitable donor atoms for
selective guest metal complexation. 8 In this way, the SFE of Fe(III) using a fluorinated
calix[4]arene tetrahydroxamate has been demonstrated, and more recently, Au(III) has
been shown to be complexed and carried in sc-CO2 using a thiourea-functionalised
calix[4]arene, without recourse to the use of an organic modifier. 9
More recently, the synthesis of novel fluorinated thiourea reagents of varying chain
lengths (n) has been carried out and their enhanced solubilities in supercritical carbon
dioxide observed (Figure 1(b)). 10 Efficiency of extraction has been optimised for gold
extraction from a variety of matrices including a geological ore reference material by
varying temperature and pressure.

CF3

H S H H
N C N C (CF2)n CF3
H

CF3

Figure 1 Chemical structures of ligands synthesised for SFE: general structures of

(a) calix[4]arene and (b) fluorinated thiourea derivatives (T3 n = 2).

Selectivity of Supercritical Fluid Extraction

We demonstrate that gold, in a variety of matrices, can be effectively complexed and
extracted by supercritical carbon dioxide containing new fluorinated linear thiourea
ligands. With reagent solubilities greater than 0.1 mol

L-1

at 60

and 250 atm, the

extraction of Au(III) from spiked cellulose paper and from Au(0) powder, following
addition of oxidant, is demonstrated using atomic absorption spectrometric analysis of
extracts. Selectivity of extraction has been studied and the effects of diverse ions graphed

% Au Extraction

as shown below in Figure 2.

100
95
90
85
80
75
70
65
60
55
50

Pb(II)
Ag(I)
Ni(II)
Cu(II)
Mn(II)
Zn(II)
Fe(II)
Cu(II)
Ni(II)

Fe(II)
Zn(II)
Mn(II)

Ag(I)

1:

1:2

Pb(II)

1:4

Mole Ratio
Au:Interferant

8 1:8

Figure 2 Plot of % gold extraction from spiked cellulose paper versus mole ratio
Au:interferent metal ion.
The results indicate interference from selected diverse ions Ag(I), Cu(II) and Fe(II) only
under excess mole ratio conditions.
Furthermore, the extraction of gold from ore reference material using supercritical CO2 is
demonstrated, and proposed as a clean, eco-friendly chemistry for gold extraction. The
extraction of gold from the geological ore reference material by SFE, using added oxidant
FeCl3, was carried out exhaustively using repeated additions of ligand T3. Failure to add
excess oxidant or ligand resulted in no gold extraction, when collected extracts were
analysed by FAAS. Analysis of residue ore samples a-c after SFE, by fire-assay FAAS,
yielded preliminary data as shown in Table 1.

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Table 1. Preliminary results from Fire Assay-FAAS of ore reference material.

Ore Reference Material

Found residual Au

Au extracted

analysed after n* SFE

(ppm)

OXM16 a, (n = 7)

4.5

70.4

OXM16 b, (n = 6)

7.7

49.2

OXM16 c, (n = 5)

5.7

62.4

OXM16 d, (control)**

14.7

*where n is the number of extractions with fresh additions of T3.

**Control-no supercritical fluid extractions performed.

The lower residual gold levels in the ore reference material after SFE confirm the
extraction levels found by FAAS in collected extracts using this green chemistry
approach but further investigations of this process are currently underway.

Acknowledgements
Research grant support from Enterprise Ireland through the Basic and Strategic Research
Programmes, and travel support from the Organising Committee Gold2003 are gratefully
acknowledged. The support of the Industrial Liaison Office (UCC) and of Mr. Robert
Gogan is also acknowledged, as are helpful discussions with Dr. Barry Foley (DIT) and
OMAC laboratories on aqueous based gold extraction methods and analysis.

References
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John Wiley & Sons (Chichester, England) 1999, ISBN 0-471-97369-6.
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2931-2947.
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and deposition using supercritical carbon dioxide, paper in preparation (2003).