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Immobilization of heavy metals from mining waste

Conference Paper · May 2015

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 Slovak Society of Chemical Engineering
Institute of Chemical and Environmental Engineering
Slovak University of Technology in Bratislava

PROCEEDINGS
nd
42 International Conference of Slovak Society of Chemical Engineering

Hotel Hutník
Tatranské Matliare, Slovakia
May 25–29, 2015

Editor: prof. Jozef Markoš

ISBN: 978-80-89475-14-8, EAN: 9788089475148

Gardić, V., Markovic, R., Obradović, L., Stevanovic, J., Gvozdenovic, M., Grgur, B., Jugovic, B.:
Immobilization of heavy metals from mining waste, Editor: Markoš, J., In Proceedings of the 42nd
International Conference of Slovak Society of Chemical Engineering, Tatranské Matliare, Slovakia,
910–913, 2015.
42nd International Conference of SSCHE
May 25–29, 2015, Tatranské Matliare, Slovakia Po-Th-4, 200.pdf

IMMOBILIZATION OF TOXIC METALS FROM MINING WASTE

V.Gardić1, R.Marković1, Lj.Obradović1, J.Stevanović2, M.Gvozdenović3, B. Grgur3, B.Jugović4

1
Mining and Metallurgy Institute Bor, Zeleni bulevar 35, Bor, Serbia
2
Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12,
Belgrade, Serbia
3
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, Belgrade, Serbia
4
Institute of Technical Sciences of the Serbian Academy of Science and Arts, Knez Mihailova
35/IV, Belgrade, Serbia

Key words: mining waste, immobilization, heavy metals

ABSTRACT

Chemical immobilization treatment technique was evaluated using wood ash to determine his
ability to reduce toxic metal transport in copper flotation tailing samples. Copper flotation tailing
sample was mixed with wood ash in the weight ratio of 1.0:0.5. The results of laboratory leaching
testing demonstrate that relatively small additions of wood ash to the copper flotation tailing sample
drastically reduces the mobility of toxic metal and increase pH value of waste leaching solution
from 3.38 to 6.66. The results show that wood ash can be effectively applied as an agent for
immobilizing the toxic metals and stabilize the mine waste. Also, the results indicate the possibility
of applying this technique as the best available technology at acceptable costs, because the wood
ash is low cost treatment agens.

1. INTRODUCTION

The main sources of metal pollutants in soils and surface water are mining and smelting activities,
fossil fuel combustion, agricultural practices, industrial activities and waste disposal [1]. The
disposed flotation tailing represents the potential risks to human health and the environment,
particularly in the area there is the possibility of occurrence acid rain and acid mine drainage water.
Toxic element present in flotation tailing, Zn, Cd, Pb, Cu, As, Sb and etch., are becoming mobile
and polluted surrounding environment of the mining sites.
Under acidic conditions, zinc, unlike lead and copper, is one of the most soluble and mobile of the
trace metal cations. Cadmium is even more soluble than zinc in acidic conditions. The precipitation
mechanisms responsible for heavy metal immobilization, being all them favored at higher pH.
Above pH 6, these ions precipitated as hydroxide, oxide or hydroxy carbonates [2].
Several options can be pursued for cleaning up contaminated area. The choice of the technique is
depending on technical, economic and legislative parameters. Current legislative regulation the
rehabilitation of contaminated sites generally prescribes the use of the best available technology at
acceptable costs. Because of that, it is necessary to develop immobilizing techniques based on the
use o appropriate low cost agens [3-5].
This paper presents the results of immobilization of heavy metals from mining waste by different
stabilization agens.

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May 25–29, 2015, Tatranské Matliare, Slovakia Po-Th-4, 200.pdf

2. EXPERIMENTAL

Materials and methods

Copper flotation tailing from the old copper flotation tailings RTB Bor, Serbia belongs to mining
waste. Disposal of this waste without prior treatment has a negative impact on the environment
(quality of surrounding soil, groundwater, surface water and air). Chemical composition of copper
flotation tailings is shown in the table 1.

Table 1. Chemical composition of copper flotation tailings

Parameter Measure unit Content Analitical method
Cu % 0.2 AAS
Fe % 4.11 AAS
Fe 3 O 4 % 0.06 A- Fe 3 O 4
Cu ox % 0.112 AAS
S % 5.08 S
SO 4 2- % 7.21 NTU
Al 2 O 3 % 14.89 PT
SiO 2 % 62.83 G
MgO % 0.16 AAS
As % 0.0082 ICP-OES
Pb % <0.03 AAS
Zn % 0.0030 AAS
Hg g/t 0.1 AAS
Mn % 0.005 AAS
Cr % 0.16 ICP-OES
Cd % <0.0025 AAS
Ag g/t 0.9 FA/AAS
Au g/t 0.1 FA/AAS
Analytical methods:
- The content of Cu, Fe, Cu Ox , MgO, Pb, Zn, Hg, Mn and Cd were determined by atomic absorption
spectrophotometry (AAS) on Perkin Elmer 2380th
- Sulphate content was determined by turbidimetry method (NTU).
- The sulfur content was determined by the gas volumetry, incineration (S).
- The content of Fe 3 O 4 was determined on the magnetite analyzer (A -Fe 3 O 4 -) – produced by Satmangan.
- The content of arsenic and chromium was determined by optical emission spectrometry method with Induction
Coupled Plasma (ICP-OES) on the Spectro Ciros Vision.
- The content of silicon dioxide is determined by the gravimetric method (G) and the content of aluminum oxide by
using the potentiometric titration (PT) on the potentiometer Mettler 50T.
- The content of silver and gold was determined by a combination of cupellation and atomic absorption
spectrophotometry (FA / AAS).

The impact of flotation tailings on the environment was carried out by leaching test carried out
according to standard methods EN 12457-2 (Characterization of waste - Leaching - Compliance test
for leaching of granular waste materials and sludges - Part 2: One stage batch test at a liquid-solid
ratio of 10 l / kg for materials with a high content solids and particle size of less than 4 mm (with
decreasing particle size, or without decreasing).
The results of waste testing were compared with limits given in Annex 10 of the Regulation on
categories, testing and classification of waste (Office Gazette RS 56/2010.) and indicate an
increased copper content in the effluent. Copper flotation tailing shows a H8-corrosiveness
characteristic, because of leach solution pH values that is significantly lower (3.38) than the limit
value (6.0) and indicates the acidity eluate generated during the leaching test.
The results indicated the potential risks to human health and the environment that may arise due to
disposal of the flotation tailings without treatment.

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May 25–29, 2015, Tatranské Matliare, Slovakia Po-Th-4, 200.pdf

As a immobilization agens for toxic metals and waste stabilization was used wood ash. The
chemical characteristics of wood ash are shown in Table 2. The immobilization and stabilization
process was carried out with ratio of flotation tailings to stabilization agens at 1.0: 0.5.

Table 2. Chemical composition of wood ash

Parameter Measure unit Content Analytical method
CaO % 39.00 AAS
MgO % 4.93 AAS
Na 2 O % 0.17 AAS
K2O % 11.82 AAS
Analytical method: The content of the components listed in the table was determined by atomic absorption
spectrophotometry (AAS) using a Perkin Elmer 2380

Based on the chemical composition of the wood ash it is clear that the ash has a large capacity as an
stabilization agens, particularly in cases of hazardous wastes, that as a characteristic that makes him
dangerous manifested H8-corrosiveness. Study was performed at lab scale.

3. RESULTS AND DISCUSSION

Testing and verification of the stabilization immobilization method effectiveness based on treated
copper flotation tailings was carried out of leaching test on treated samples of flotation tailing. The
results are shown in Table 4.

Table 4. The results of immobilization method effectiveness testing by leaching standard test
method EN 12457-2 on stabilized copper flotation tailing sample
Limit
Analytical testing
Parameter Measure unit Content value
standard method
**
SRPS Z1
pH - 6.66 6-13
111:1970
SRPS EN ISO
mg/kg dm* 0,149 10
Pb 11885
SRPS EN ISO
Cd mg/kg dm* 0,008 1
11885
SRPS EN ISO
Zn mg/kg dm* 0,439 50
11885
SRPS EN ISO
Cu mg/kg dm* 0,708 50
11885
SRPS EN ISO
Ni mg/kg dm* <0,05 10
11885
SRPS EN ISO
Cr total mg/kg dm* 0,019 10
11885
Hg mg/kg dm* 0,046 0.2 SRPS EN 1483
As mg/kg dm* 0,072 2 *
Sb mg/kg dm* <0,02 0.7 *
Ba mg/kg dm* 2,653 100 *
Ag mg/kg dm* - *
The rest of the
mg/kg dm* 22,96 60,000.00 APHA 2540B
annealing at 105 oC
Cl- mg/kg dm* 0,2479 15,000.00 *

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May 25–29, 2015, Tatranské Matliare, Slovakia Po-Th-4, 200.pdf

SO 4 2- mg/kg dm* 20,234 20,000.00 EPA 375.4

F- mg/kg dm* 0,0096 150 SRPS H.Z1.142
mg / kg dm * - mg / kg dry weight
** Appendix 10 of the Rules on categories, testing and classification of waste (RS 56/2010).

The results are within the permitted limits for the disposal of nonhazardous waste to the landfill, in
accordance with applicable laws and regulations of the Republic of Serbia, which are in full
compliance with applicable EU legislation in this area.
The results also represent the new verification procedure applied in order to immobilizing toxic
metals and stabilizing the copper flotation tailings by wood ash as a low cost agens.

4. CONCLUSION

Application of wood ash like low cost immobilization and stabilization agens increases waste pH
and decreasing toxic metals mobility.
Waste pH increased from 3.38 to 6.66 by addition of wood ash in copper flotation tailing in ration
1.0:0.5.
The obtained results demonstrate that relatively small additions of wood ash resulting in reducing of
toxic metal mobility and decreasing pH waste value.
The chemical immobilization method represents the new verification procedure applied in order of
the immobilization of Cu in mine waste-copper flotation tailing and reducing metal transport.

Acknowledgment: This paper is result of Project No. 37001, „The impact of mining waste from
RTB Bor on the pollution of surrounding water systems with the proposal of measures and
procedures for reduction the harmful effects on environment“, funded by the Ministry of Education
and Science the Republic of Serbia.

REFERENCES

[1] Basta N.B., McGowen S.L., Evaluation of chemical immobilization treatments for reducing
heavy metal transport in a smelter-contaminated soil, Environmental Pollution 127 (2004)
73–82
[2] Garcia y Alvarez, Macla, Conferencia Soil Remediation in Mining Polluted Areas, 10
(2008) 76-84
[3] R.Marković, J.Stevanović, Z.Stevanović, M.Bugarin, D.Nedeljković, A.Grujić, J.Stajić
Trošić, Using the Low-Cost Waste Materials for Heavy Metals Removal from the Mine
Wastewater, Material Transactions JIM, Vol. 52, No. 10 (2011) 1849-1852
[4] Ciccu R., Ghianu R., Serci A., Zucca A., Heavy metal immobilization using fly ash in soils
contaminated by mine activity, International ash symposium, Kentucky (2001) 9
[5] Ciccu R., Ghiani M., Serci A., Fadda S., Peretti R., Zucca A., Heavy metal immobilization
in the mining-contaminated soils using various industrial wastes, Minerals Engineering 16
(2003) 187–192

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