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A R T I C L E I N F O A B S T R A C T
Article history: Bioleaching of a low-grade Indian silicate-apatite uranium ore containing 0.024% U3O8 and 10.6% iron with
Received 29 October 2007 minor amounts of base metals has been reported. The studies involved extraction of uranium using enriched
Received in revised form 18 March 2008 culture containing Acidithiobacillus ferrooxidans (A. ferrooxidans) derived from the source mine water
Accepted 27 April 2008
employing bio-chemically generated ferric ion as an oxidant. Parameters such as particle size of the ore, pulp
Available online 3 May 2008
density, and pH of lixiviant media were optimised. Maximum uranium bio-dissolution of 98% was achieved
Keywords:
using ore of mixed particles of b 76 μm size. Uranium bio-recovery was found to be 96% at the pulp density
Acidithiobacillus ferrooxidans (PD) of 10% (w/v) and 20% (w/v) with the particles of b 76 μm size in 40 days at 2.0 pH and 35 °C temperature.
Uranium bio-recovery At 1.7 pH and 20% (w/v) PD, 98% uranium bio-recovery was achieved with a rise in redox potential from
Ferric ions 595 mV to 715 mV in 40 days. Uranium bio-dissolution may be correlated with the generation of ferric ions
Indirect leaching through the bio-chemical action on the ore. The work illustrated the efficacy of leaching of uranium by the
involvement of bacteria by indirect mechanism.
© 2008 Elsevier B.V. All rights reserved.
0304-386X/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.04.013
Abhilash et al. / Hydrometallurgy 95 (2009) 70–75 71
% Component Uranium ore collected in the form of lumps from Turamdih mine
was crushed, ground and sieved to get different size fractions. A
U3O8 Fe Cu Ni Co SiO2 CaO TiO2 S Al2O3
representative sample was prepared by coning and quartering for
0.024 10.64 0.093 0.048 0.056 47.40 1.085 0.383 0.168 15.445
chemical analysis (Table 1). The uranium content (U3O8) in different
size fractions were found as: 0.016% in 150–76 μm, 0.024% in 76–45 μm
and 0.013% in b45 μm. The phase identification by XRD as in Table 2
shows that quartz, apatite, alumina and magnetite were the major
et al., 2005; Anderson and Lovley, 2002; Bonk et al., 1997; Devasia and phases while kyanite (aluminium silicate), ferrosilite (ferro-silicate),
Natarajan, 2004) in which the bacteria generate ferric sulfate—a pyrite and hematite being the minor phases. Uranium was present as
lixiviant which chemically oxidises the small amount of pyrite present uraninite in the ore. The ore was in partially oxidised state with 40%
in the ore. uranium in +4 oxidation state while remaining 60% in +6 state.
At:f Water samples collected from different uranium mines (Jaduguda,
2FeS2 þ 2H2 SO4 þO2 Y 2FeSO4 þ2H2 Oþ4S- ð1Þ
Narwapahar and Turamdih) were the source of A. ferrooxidans which
At:f
2FeSO4 þH2 SO4 þ 1=2O2 Y Fe2 ðSO4 Þ3 þH2 O ð2Þ were isolated in 9K media [(NH4)2SO4: 3.0 g/L, KCl: 0.1 g/L, K2HPO4:
0.5 g/L, MgSO4·7H2O: 0.5 g/L, Ca(NO3)2: 0.01 g/L, FeSO4·7H2O: 44.2 g/L] at
As the amount of pyrite is often small, addition of sulfuric acid for 2.0 pH (Mehta et al., 2003). The oxidation of Fe2+ to Fe3+ by A.
maintaining pH leads to dissolution of iron from the magnetite ferrooxidans was considered as an indication of its growth. Growth was
present in ore (reaction 3) also monitored through cell count which was determined in a Petroff-
Hauser counter using Leica™ Biological Microscope. Uranium was
Fe3 O4 þ 4H2 SO4 →FeSO4 þ Fe2 ðSO4 Þ3 þ 4H2 O: ð3Þ
analysed by Flourimetry [Fluorimeter-Model-FL-6200™] whereas other
2+
Sufficient iron as Fe in the solution is thus available because of metals were analysed by Atomic Absorption Spectrometer [Model-GBC
chemical oxidation of iron sulfide and solubilisation of magnetite in an 908BT™]. The enriched culture of A. ferrooxidans was subjected to three
acid environment at 1.7–2.0 pH (Dutrizac and MacDonald, 1974). The times adaptation on 5% (w/v) ore at 35 °C temperature and 2.0 pH in
ferrous iron is oxidised to ferric iron by A. ferrooxidans which takes incubator shaker and adapted cultures were used for bioleaching.
part in the oxidation process. In the pH range 1.5–2.5, bacterial The leaching experiments were carried out in Erlenmeyer flasks in
oxidation of ferrous oxidation is about 105–106 times faster than the an incubator shaker. A 200 mL of slurry containing ore (40 g) was
chemical oxidation (Muňoz et al., 1995a). inoculated with 10% (v/v) of enriched adapted culture with
The sulfur obtained above (reaction 1) may simultaneously be 8.8 × 109 cells/mL. Conditions such as 35 ± 0.2 °C temperature, 2.0 pH,
oxidised to sulfuric acid by A. ferrooxidans (Tuovinen and Hsu, 1984). 20% (w/v) pulp density (PD) with shaking at 120 rpm were maintained
for leaching unless otherwise stated. A known amount of sample was
At:f drawn at 5 days interval for analysis of metals leached out. All the
2S-þ3O2 þ2H2 O Y 2H2 SO4 ð4Þ
inoculated sets had their corresponding sterile control sets prepared
3+
The role of Fe in the bioleaching of uranium from its ore is to oxidise under the same condition with 0.2 g/L HgCl2 added as bactericide.
tetravalent uranium to water-soluble hexavalent uranium (Tuovinen Ferrous ion concentration was analysed by titration against N/20
and Hsu, 1984): potassium dichromate solution. The pH of the leach solution was
maintained daily with 5 M sulfuric acid. Redox potential was
At:f
UO2 þFe2 ðSO4 Þ3 Y UO2 SO4 þ2FeSO4 : ð5Þ measured against SCE. On completion of the leaching experiment,
the slurry was filtered on Whatman Filer Paper (No. 42) and solid
Ferrous sulfate produced in the process is re-oxidised to ferric residue was dried. The representative sample of the residue was
sulfate by bacteria. There are however, some reports on oxidation of U chemically analysed and the phases were identified by XRD (Table 2).
(IV) to U(VI) enzymatically by A. ferrooxidans which uses energy of this
reaction for the assimilation of CO2 (Tuovinen and Kelly, 1974; 3. Results and discussion
DiSpirito and Tuovinen, 1982; Hutchins et al., 1986), but indirect
mechanism is mostly accepted in the bio-recovery of uranium. The 3.1. Isolation of A. ferrooxidans and microbial cell count
acidic ferric sulfate could replace environmentally undesirable
pyrolusite as an oxidant in conventional leaching. To optimise the parameters for recovery of uranium from the
Bioleaching of uranium was studied earlier by Mathur and Turamdih ore, the strains of A. ferrooxidans were isolated from
Dwivedy (1994), Mathur et al. (2000) and Dwivedy and Mathur different mine waters such as Jaduguda, Narwapahar and Turamdih
(1995) for testing the dissolution efficiencies of some ores in East mines, which were situated within 10 km distance. The microorgan-
Singhbhum Belt (Jharkhand) of India. The use of biogenically isms were isolated in 9K media at 2.0 pH and 35 °C. The culture in
generated ferric sulfate in uranium leaching was proposed, which 10 days from the Turamdih mine water had 7.2 × 107 cells/mL whereas
showed reduction in acid consumption also. The low-grade ores/
tailings of uranium from different mines are owned and developed by
Table 2
Uranium Corporation of India Limited (UCIL), Jaduguda. In order to XRD Phase Analysis of Ore and Leach Residue
augment the supply of uranium in India, efforts are being made to
recover uranium using bioleaching approach. In this endeavour, the Sample Phases
low-grade ore of Turamdih area which is friable in nature and Major Minor
produced from open cast mining may be considered for its Ore Quartz, apatite, alumina, Kyanite, ferrosilite, pyrite, hematite
amenability to bioleaching. This ore contains partially oxidised magnetite
uraninite embedded in the closely compact matrix of quartz and
Leach residue
high amount of apatite and magnetite. The present paper discusses At 1.7 pH Quartz, alumina Kyanite, villamaninite, hydronium
the results of bench scale work on optimisation of parameters for jarosite, magnetite
uranium bioleaching from Turamdih ore with enriched culture of At 2.5 pH Quartz, alumina, hydronium Kyanite, villamaninite, magnetite,
A. ferrooxidans derived from the mine water sample. jarosite pyrolusite
72 Abhilash et al. / Hydrometallurgy 95 (2009) 70–75
Fig. 3. Recovery of uranium at 20% and 30% PD with enriched culture at 35 °C, 2.0 pH
with b76 μm particles (BL: bioleaching, CL: chemical leaching).
Fig. 1. Change in pH, ferrous ion concentration, and consumption of 5 M H2SO4 during
isolation of A. ferrooxidans from Turamdih mine water (volume of solution: 200 mL).
culture containing A. ferrooxidans from Turamdih mine water was
the counts were 6.8 × 107 and 6.1 × 107 cells/mL from the mine waters taken for investigating the bio-recovery of uranium. Use of such a
of Narwapahar and Jaduguda mines respectively. Subsequent sub- culture may be further beneficial for leaching because of its natural
culturing of the microbes showed the presence of 8.8 × 109, 7.4 × 109 adaptation to the native ore, although the enriched culture was
and 7.8 × 109 cells/mL for the mine waters of Turamdih, Narwapahar inoculated after three times adaptation to the ore in the laboratory
and Jaduguda mines respectively. The growth of A. ferrooxidans was conditions as previously mentioned.
measured by the iron oxidation rate (Fe2+ to Fe3+) as shown in Fig. 1.
There was a sharp decrease in the concentration of Fe2+ as the bacteria 3.2. Effect of pulp density
(A. ferrooxidans) present in the system utilised Fe2+ as energy source to
convert it to Fe3+. The bacteria from Turamdih mine water were found Pulp density (PD) for the bioleaching of uranium was varied in the
to be most potent for oxidation of Fe2+ as its concentration decreased range 5–30% (w/v) using ore particles of b76 μm (mixed) size using
from 2.65 g/L to zero in 7 days of incubation. The redox potential 10% (v/v) adapted enriched culture, while shaking at 120 rpm at 2.0 pH
during growth of A. ferrooxidans from Turamdih mine water at 2.0 pH and 35 °C temperature. Data presented in Figs. 2 and 3 show increase
and 35 °C in 7 days varied from 275 to 424 mV. The increase in redox in dissolution of uranium with time in both chemical and bioleaching
potential may be attributed to the improved oxidation of Fe2+ present experiments. At 5% pulp density, uranium recoveries of 58% and 68%
in the solution because of bacteria present in it. The most suitable pH were obtained in 40 days in chemical and bioleaching respectively. On
for isolation of A. ferrooxidans was observed to be 1.7–2.0 and further increasing the pulp density to 10% and 20%, the uranium bio-
therefore, the pH of the growth medium was maintained at 2 by recovery was found to be the same (96%) with corresponding chemical
adjusting it with 5 M H2SO4 daily. After 5–6 days, the pH of inoculated control leaching of 60% and 71%. The rise in E was observed from
sample remained close to 2 and very less H2SO4 (0.0015 M sulfuric 590 mV to 697 mV in bioleaching and 357 mV to 398 mV in control
acid in 200 mL working solution) was consumed for pH maintenance leaching for 20% PD in 40 days. At still higher pulp density of 30% (w/v)
as shown in Fig. 1. High acid consumption during 0–2 days was to under the above conditions, the bio-recovery decreased to 84% (Fig. 3)
oxidise Fe(II) to Fe(III) as in reaction 6 and to control the rising pH. The because of lower ratio of inoculum to substrate. Uranium leaching in
lower acid consumption beyond 3 days may be the result of sterile set (control) was also lower at higher pulp densities. Thus, in
precipitation of Fe(OH)3 with the release of protons (reaction 7) further experiments, 20% pulp density was maintained.
(Daoud and Karamanev, 2006).
3.3. Effect of pH
2Fe2þ þ 1=2O2 þ 2Hþ →2Fe3þ þ H2 O ð6Þ
The effect of varying pH from 1.3 to 2.5 at 20% (w/v) PD, 35 °C
Fe3þ þ 3H2 O→FeðOHÞ3 þ 3Hþ ð7Þ temperature with b76 μm size particles on control leaching and
bioleaching of uranium was examined and results are presented in
Total sulfuric acid consumed in 7 days was worked out to 0.036 M
Figs. 4 and 5. An appreciable increase in bio-recovery of uranium (98%)
(for 200 mL working solution). In view of similar growth patterns of
at 1.7 pH with an increase in redox potential from 595–715 mV in
different isolate cultures from the mine water samples, the enriched
40 days was observed as compared to the bio-recovery of 70% and 77%
Fig. 2. Recovery of uranium at 5% and 10% PD using adapted culture at 35 °C, 2.0 pH and Fig. 4. Bio-recovery of uranium at varying pH against Redox Potential with 20%PD with
particles of b 76 μm (BL: bioleaching, CL: chemical leaching). b76 μm particles at 35 °C in 40 days.
Abhilash et al. / Hydrometallurgy 95 (2009) 70–75 73
Fig. 6. Uranium recovery and Fe(II) concentration at pH 1.7 (20% PD, b76 μm, 35 °C). Fig. 7. (a–c): Effect of particle size on bio-recovery of uranium at pH 1.7, 35 °C and 20% PD.
74 Abhilash et al. / Hydrometallurgy 95 (2009) 70–75
high (7.2 × 107 cells/mL) for the Turamdih mine water as compared to
other mine water samples. The sub-culturing of the isolate of the
Turamdih mine water at 2.0 pH increased the bacterial population to
8.8 × 109 cells/mL. The enriched culture was adapted three times on
the uranium ore at 2.0 pH and its inoculation in the bioleaching
experiment at 1.7 pH, 20% PD and 35 °C temperature in 40 days time
with the mixed particles of b76 μm size gave 98% uranium recovery.
Effect of particle size variation showed higher uranium dissolution
(91%) with the medium size particles in the range 53–45 μm at 1.7 pH
in 35 days as compared to the coarser (76–53 μm) and finer size
(b45 μm) fractions. High metal recovery with the mixed size particles
(b76 μm) may be attributed by the better permeability of ferric ions in
iron silicate matrix to dissolve uranium. Recovery of uranium may be
correlated with the values of redox potential acquired during the
experiments. Under the optimum condition at 1.7 pH and 35 °C
temperature, rise in redox potential was recorded to be 595–715 mV
in 40 days. Bioleaching of uranium appeared to follow the indirect
mechanism with the involvement of Fe(III) biogenically generated by
the bacteria.
Acknowledgements
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