Professional Documents
Culture Documents
a,b,*
Abstract
The removal of metals from metaliferous soil by living plants is termed phytoextraction. The technology can be used for remedial
purpose (phytoremediation), or potentially for economic prot (phytomining or phyto-reclamation). Gold has been suggested as a
likely candidate for phytomining. Plants do not normally accumulate gold; the metal must be made soluble before uptake can occur.
However some plants exude natural lixiviants that can mobilize gold in a soil. Laboratory and greenhouse research has shown that
uptake of gold can be induced using lixiviants such as cyanide and thiocyanate. Our preliminary modeling predicts that a harvested
crop of 10 t/ha biomass (dry) with a gold concentration of 100 mg/kg (100 g/t), which would yield 1 kg of gold per hectare, could be
economically viable. No study, however, has examined the practicality of this target in a eld environment. During 2003, a eld
demonstration study for gold phytoextraction was carried out in collaboration with Companhia Vale do Rio Doce at the Fazenda
Brasileiro mine in Bahia, Brazil. The plant species Brassica juncea (Indian mustard) and Zea mays (corn) were tested for their ability
to grow on an oxidized ore pile containing 0.6 g/t gold and to absorb mobilized gold after cyanide and thiocyanate treatment. Brassica juncea showed the best ability to concentrate gold giving an average of 39 mg/kg after sodium cyanide treatment. Correlation of
this result with a greenhouse plant-uptake model shows the eld trial results are in good accord with those obtained under controlled
conditions. Laboratory and greenhouse evidence therefore suggests that a target recovery of one kg of gold by plants from one hectare of land is a realistic achievement for a soil or ore resource with at least 2 g/t gold.
2004 Published by Elsevier Ltd.
Keywords: Gold ores; Leaching; Environmental; Reclamation
1. Introduction
The link between plants and mineralization has been
recognized since medieval time. The subject of biogeochemistry seeks to correlate metal concentrations in
plants with those in the soil as a tool for mineral exploration. Only in the 20th century, however, have analytical techniques become widely available to analyze
plant tissues for their metal concentration. Since the
turn of the 20th century, there have been many reports
of gold accumulation by plants, in particular trees.
*
Corresponding author. Tel.: +64 6 356 9099; fax: +64 6 350 5632.
E-mail address: c.w.n.anderson@massey.ac.nz (C. Anderson).
ARTICLE IN PRESS
2
content of 0.79% in the leaves of the Tuscan shrub Alyssum bertolonii (Brooks, 1998). These were two of the rst
widely available reports of signicant metal uptake by
plants.
In the 1970s, a New Zealand scientist formally named
the ability of plants to accumulate high concentrations
of metal. Robert Brooks and his colleagues coined the
term hyperaccumulation to describe the natural process
by which certain plant species could accumulate metals
to concentration levels more than 1000 mg/kg dry weight
(Brooks et al., 1977). Brooks denition was developed
with a focus on Ni-accumulating plants, but today,
hyperaccumulators have also been identied for the metals Cd, Cu, Co, Mn, Se, Tl and Zn. The current criterion
used to dene a hyperaccumulator is a plant that can
accumulate metal to a concentration that is 100 times
greater than normal plants growing in the same
environment.
Plants can be forced to accumulate metals for which
hyperaccumulators are not known, if the dissolution of
these metals is increased in the soil pore-water. Induced
hyperaccumulation is the term used to describe the
chemical amendment of a soil to make any plant species
accumulate a target metal. The rst report of induced
hyperaccumulation was for the uptake of lead by corn
(Zea mays), using the chelating chemical EDTA (Huang
and Cunnigham, 1996). Anderson et al. (1998a,b) reported induced hyperaccumulation of gold by Indian
mustard plants (Brassica juncea) after soil amendment
with the chemical, ammonium thiocyanate. They dened gold hyperaccumulation as a concentration above
1 mg/kg in the dry weight of plant tissues. Induced
hyperaccumulation was recently reported for mercury
(Moreno et al., 2004) and is also feasible for Ag, Pd
and Pt.
During the 1980s phytoremediation became recognized as a potential application for hyperaccumulators.
Phytoremediation is dened as the use of plants and
their associated root-bound microbial communities to
remove, contain, degrade or render harmless environmental contaminants (Robinson et al., 2001). It was
rst proposed by scientists in the USA (Chaney, 1983)
and later in Europe (Baker and Brooks, 1989; McGrath
et al., 1993). Phytoremediation using a hyperaccumulator involves cropping plants on a metaliferous or contaminated soil that will accumulate one or more
metals in their above-ground tissues during a growth cycle (phytoextraction). The plants are then harvested and
incinerated to generate a metal-rich ash for safe disposal. If the metals in question are relatively valuable,
it may be economic to recover them into a pure form.
An operation where metals are mined using plants is
known in the scientic literature as phytomining.
There are several misconceptions associated with this
term. First, the commercial recovery of metals by plants
is not mining but rather, it is farming. There is a
ARTICLE IN PRESS
C. Anderson et al. / Minerals Engineering xxx (2004) xxxxxx
Table 1
Description of lixiviant treatments
Treatment
Chemical
Application
Solution concentration
1
2
3
NH4SCN/peroxide
NaCN
KCN
Note. The chemical application rate is presented in two ways in Table 1. The total mass of chemical applied per treatment is recorded, as well as the
calculated mass of anion. Peroxide in combination with thiocyanate was shown to be a more ecient lixiviant for gold than thiocyanate alone at acid
pH levels (Massey University unpublished study).
ARTICLE IN PRESS
4
Table 2
Assay results for oxide ore used in the trial plot
pH
Au analysis
Ca
+Ca
8.9
0.64 g/t
9.5
0.66 g/t
4. Harvested biomass
Harvested biomass was unpacked on arrival in New
Zealand, re-dried at 70 C, and then weighed (Table 3).
The 6-week growing cycle used in the trial was insucient for the two species to attain maximum biomass.
Under ideal conditions, Brassica juncea yields 1015 t/
ha, while Zea mays yields up to 30 t/ha. Projecting the
biomass gures for the unamended ore plot to a 10-week
growth cycle indicates that a nal biomass of 10 t/ha
from the plot area would have been attained for B. juncea, while a 24-week growing period for Z. mays would
have been needed to achieve this production level. The
6-week period was adopted in consideration of the
schedules of both Massey University and CVRD sta
involved with the operation of the trial.
Table 3
Calculated biomass for the harvested plant material
Treatment
Ca
SCN
NaCN
KCN
+Ca
SCN
NaCN
KCN
Plant
Area (m2)
Brassica juncea
Zea mays
Brassica juncea
Zea mays
Brassica juncea
Zea mays
1.5
1.5
1.5
3
3
1.5
0.55
0.88
0.83
1.12
0.97
0.74
3.67
5.87
5.55
3.75
3.24
4.95
Brassica juncea
Zea mays
Brassica juncea
Zea mays
Brassica juncea
Zea mays
1.5
1.5
1.5
3
3
1.5
0.11
0.30
0.09
0.67
0.19
0.37
0.71
2.05
0.60
2.22
0.62
2.47
Note. Due to the trial design there were two dierent areas for treatment: 1.5 m2 corresponds to one row of treated biomass, 3 m2 corresponds to two
rows of treated biomass.
ARTICLE IN PRESS
C. Anderson et al. / Minerals Engineering xxx (2004) xxxxxx
5.3. Results
The results presented in Table 4 report average gold
and copper concentrations in the biomass harvested
across each treatment area. Accumulated metal concentrations were signicantly higher in Brassica juncea than
in Zea mays. For B. juncea, NaCN induced a slightly
greater gold uptake than did KCN, although no such
dierence was apparent for copper. The highest average
gold assay achieved was 39 mg/kg for B. juncea with unamended ore. The re assays from Acme conrm the results from the Massey University procedure as can be
seen in Table 4. For gold assays, this type of error is typical and acceptable.
Five individual Brassica juncea plants were harvested
and kept separate from the bulk biomass. These individual plants were not ground, but rather, were split into
5-cm leaf and stem intervals for atomic adsorption analysis at Massey University (Table 5). The gold concentrations show a variation that indicates that Brassica juncea
translocates gold to all plant organs when using CN
treatment. Higher concentrations were observed in the
upper stem and leaf tissues of these individual plant
samples relative to basal biomass. A similar study conducted in February 2003 on the distribution of gold
throughout a plant showed that when the more toxic thiocyanate treatment is used, gold is retained at the base
of the plant (Anderson, 2004). Gold concentrations reported in Table 5 are higher than the average of
39 mg/kg reported for B. juncea in Table 4, reecting
the selective harvesting of healthy plant materials for
this analysis that were presumed to have accumulated
increased levels of gold.
Variability in the plant-gold concentration is also a
function of variability of the ore-gold concentration.
The average Au concentration for the Ca plot was
0.64 mg/kg, however six replicates reported a range from
0.2 to 1.6 mg/kg. Individual plants collected from an
area with higher soil-gold concentration are expected
to have higher plant-gold concentrations than the average. Unfortunately, during harvesting no attempt was
made to correlate variations in gold concentrations in
the plant and soil samples.
Gold was not the only metal accumulated by the
plants after lixiviant treatment. Treated plants accumulated signicant and high concentrations of copper after
Table 4
Average metal concentrations for each plant and treatment combination
Treatment
Au mg/kg (sd) AA
Au mg/kg re assay
Cu mg/kg (sd) AA
Control
SCN
SCN
SCN
NaCN
NaCN
NaCN
KCN
KCN
KCN
<0.1
<1
<1
2 (0.5)
20 (1.5)
20 (2.7)
39 (1.1)
10 (2.9)
8 (0.7)
30 (3.4)
1.2
1.0
5.3
17.2
16.1
35.9
15.3
10.7
35.1
50 (36.0)
57 ( 6.3)
62 ( 8.7)
133 (11.0)
137 ( 7.3)
100 ( 2.2)
541 (14.0)
112 ( 4.8)
61 ( 5.7)
571 (36.0)
Zea mays
Zea mays
Brassica juncea
Zea mays
Zea mays
Brassica juncea
Zea mays
Zea mays
Brassica juncea
Ca
+Ca
Ca
Ca
+Ca
Ca
Ca
+Ca
Ca
Note. SCN indicates combined SCN/peroxide treatment. Insucient biomass was collected from the Brassica juncea +Ca plots to permit meaningful
analysis. AA denotes assay results using ame atomic adsorption at Massey University.
Table 5
Distribution of gold concentration through ve individual plants
Section of plant
A2
A3
Average
sd
Stem biomass
05 cm stem
510 cm stem
1015 cm stem
1520 cm stem
2025 cm stem
2530 cm stem
24.5
16.7
19.4
19.7
26.9
39.5
28.1
24.8
45.2
46.8
10.4
6.3
30.7
28.5
15.5
16.0
12.2
41.9
7.1
12.4
16.9
18.2
22.6
28.7
45.2
46.8
8.6
12.6
8.4
9.5
Leaf biomass
510 cm leaf
1015 cm leaf
1520 cm leaf
2530 cm leaf
43.7
63.1
36.4
30.0
24.1
30.6
45.2
45.2
36.8
39.3
36.4
9.7
20.9
Note. Plants A and C were treated with KCN, B with NaCN. All plants were harvested from the Ca plot.
ARTICLE IN PRESS
C. Anderson et al. / Minerals Engineering xxx (2004) xxxxxx
200
160
120
y = 51.314ln(x) + 62.882
80
R2 = 0.7042
40
The eld research conducted at the Fazenda Brasileiro site was the culmination of several years of research
performed in New Zealand. Previous work has consistently shown that plants accumulate gold in proportion
Table 6
Calculated gold recovery for all harvested biomass
Plant and treatment
Total mass
Au in plot (mg)
% Recovery by plants
Brassica juncea
NaCN Ca (1 row)
KCN Ca (2 rows)
39
30
0.83
0.97
32.4
29.1
176
354
18.4
8.2
Zea mays
NaCN Ca (2 rows)
NaCN +Ca (2 rows)
KCN Ca (1 row)
KCN +Ca (1 row)
20
20
10
8
1.12
0.67
0.74
0.37
22.4
13.4
7.4
3.0
354
354
176
176
6.4
7.6
4.2
0.8
ARTICLE IN PRESS
C. Anderson et al. / Minerals Engineering xxx (2004) xxxxxx
conditions. The model is able to predict the gold concentration in eld-harvested biomass, based on gold content
of the substrate.
The target of our gold phyto-reclamation research is
to harvest a crop with a gold concentration of 100 mg/
kg. Eq. (1) can also be used to calculate the concentration
of gold in a soil that might yield this plant concentration.
If y is set to 100, x calculates as 2.0. So, if Eq. (1) is a
proper description of the outcome of the eld trials, a
gold concentration of 2 mg/kg is required in the substrate
to yield a crop with a gold concentration of 100 mg/kg.
feasible technology. For the rst time, signicant induced gold accumulation into plant biomass is reported
outside a controlled laboratory or greenhouse environment. An average gold assay of 39 mg/kg was achieved
in Brassica juncea after a NaCN treatment of 0.6 mg/
kg gold ore. The highest individual gold concentration
determined through analysis of selected biomass was
63 mg/kg (NaCN treatment of B. juncea). B. juncea accumulated a signicantly higher gold concentration than
did Zea mays.
No advantage was gained through increasing the pH
of the plot area by amendment with lime. Although
higher pH increases stability of the AuCN complex,
the trade-o is signicantly reduced biomass production. Cyanide treatment showed limited toxicity to the
plants as illustrated by translocation of gold from plant
roots to the uppermost stem and leaf organs of individual plants. Although all treated plant material was dead
at the time of harvest, mortality is attributed to the accumulation of metals such as copper, that are more phytotoxic than is gold, and not to toxicity of the lixiviant
treatment.
Thiocyanate did not induce gold accumulation above
2 mg/kg. The oxide ore in Brazil was alkaline and so, it is
considered unsuitable for thiocyanate treatment. The
gold thiocyanate complex is stable only under acidic
pH conditions.
Although the target gold concentration of 100 mg/kg
was not obtained during the Brazilian eld trial, modeling studies indicate that this is due to low gold concentration in the ore. A gold concentration in the ore or
waste of 2 g/t should yield a gold content of 100 mg/kg
in the plants.
Acknowledgments
The authors acknowledge the generous support of
CVRD during the trial. Particular thanks is extended
to Mr. Alcides Palma and Mr. Jose Cerquiera, CVRD
management sta at the Fazenda Brasilieiro mine during 2003. The funding agencies for this research are also
acknowledged: CERM3 at the University of British
Columbia (through the Canada Foundation for Innovation Project Grant 2545); Akzo Nobel Chemicals Pte.
Ltd. (Singapore); the New Zealand Foundation for Research Science and Technology (Contract MAUX0020);
and the National Council for Scientic and Technological Development of Brazil (CNPq).
References
7. Conclusions
Fieldwork carried out at the Fazenda Braziliero mine
during 2003 illustrates that gold phyto-reclamation is a
ARTICLE IN PRESS
8