Single Step Extractions of Metals in Coal Fly Ash: Lokeshappa B, Anil Kumar Dikshit
Single Step Extractions of Metals in Coal Fly Ash: Lokeshappa B, Anil Kumar Dikshit
Single Step Extractions of Metals in Coal Fly Ash: Lokeshappa B, Anil Kumar Dikshit
DOI: 10.5923/j.re.20120202.01
1
Centre for Environmental Science and Engineering, Indian Institute of Technology Bombay, 400076, India
2
Department of Civil Engineering, University BDT College of Engineering, Davangere, 577004, India
3
School of Civil Engineering, Survey and Construction, University of KwaZulu-Natal, Durban, 4041, South Africa
4
School of Civil and Environmental Engineering, Nanyang Technological University, 639798, Singapore
Abstract There is an increasing use of coal and subsequently large amounts of fly ash is generated in the thermal power
plants in India and elsewhere in the world. Hence it becomes increasingly important to be able to assess the environmental
risks involved in the management and disposal of fly ash materials. The fly ashes contain toxic metals that can be released
into the environment through the coal combustion processes and through the leaching during disposal/ wet storage/ reuse of
fly ash. The evaluation of the optimum time for leaching of the toxic metals and metalloids present in the three fly ashes was
determined using the single step extraction procedure. The optimum time of 4 hours agitation was determined for the water
soluble step as well as that for ion exchangeable step while the optimum time was 24 hours agitation in the acid soluble and
reducible steps.
Keywords Coal Fly Ash, Extraction Procedure, Leaching, Metals
* Corresponding author:
dikshit@iitb.ac.in (Anil Kumar Dikshit)
2. Materials and Methods
Published online at http://journal.sapub.org/re
Copyright © 2012 Scientific & Academic Publishing. All Rights Reserved 2.1. Materials
2 Lokeshappa B et al.: Single Step Extractions of Metals in Coal Fly Ash
Figure 1. Toxic metals transformation in the coal fly ash to the environment
Three coal fly ash materials named as CFA1, CFA2 and 2.3. Determination of Metals Concentrations
CFA3 were collected from dust hoppers of electrostatic Concentrations of trace metals in samples from SSEP
precipitators of three full-scale Indian power plants in and were obtained using Jobin Yvon Horib ICP-AES (ULTIMA
around Maharashtra. The power plants are using bituminous 2000, France). Prior to analysis, the samples were diluted
and sub-bituminous coals from India and from imported with 2% HNO3 solution. Dilution factor was kept as 1:10 for
Indonesia. The coal fly ash materials were characterized for the water soluble step, 1:20 for the acid-soluble step and 1:50
their ash contents, calcium oxide contents and mineralogy for the other two steps. Calibration standards were analyzed
using X-ray diffraction. in the same matrices as the samples.
Ultra pure water produced by TWF EDI UV TM, Water
Kit (Semens, Singapore) was used for washing of glassware Table 1. Steps of SSEP
and preparation of reagents. Ammonium nitrate, acetic acid,
Steps Phase for Leaching Leaching Solution
sodium dithionite, sodium citrate, sodium bicarbonate,
concentrated nitric and hydrochloric acids were used to 1 Water Soluble (WS) Ultrapure Water
prepare extractants for the single step extraction. The acetic 2 Ion Exchangeable (IE) 1.0 M Ammonium Nitrate
acid, nitric and hydrochloric acids were trace metal grades. 3 Acid Soluble (AS) 0.11 M Acetic Acid
All chemicals were purchased from Merck chemical 0.158 M Dithionite, 0.3 M
(Mumbai, India). The 25 element aqueous custom standard 4 Reducible (RD)
Citrate and 1.0 M Bicarbonate
in 5% HNO3 (ZOASIS 1004) from VHG Labs, Manchester,
USA was used for calibration of ICP-AES. An aliquot of the
standard was also used as control for the extraction tests.
3. Results and Discussion
2.2. Single Step Extraction Procedure
3.1. Properties of Coal Fly Ashes
Single step extraction procedure (SSEP) was developed
The properties of coal fly ashes are shown in the Table 3.
to optimize the leaching time to achieve optimum leaching
Coal fly ashes are classified based on their calcium oxide
of elements. The following extractions were carried out: (1)
contents. Coal fly ash CFA2 is class C ash being cal-
Ultrapure water was used to extract metals that were water
cium-rich with greater than 10% calcium oxide while CFA1
soluble; (2) 1.0 M NH4NO3 was used to remove ion ex-
and CFA3 are silica-rich class F having less than 10% cal-
changeable metals; (3) 0.11 M acetic acid targeted acid
cium oxide.
soluble metals; (4) a solution of 0.128 M sodium dithionite,
0.3 M sodium citrate, and 0.1 M NaHCO3 (DCB) was used Table 3. Properties of Coal Fly Ash
to remove reducible metals. In all experiments, a solid to
Properties CFA1 CFA2 CFA3
liquid ratio of 5.0 g ash/500 mL (10 g/L) extractant was
Average ash content
used and contents were stirred in a magnetic stirrer at 500 25.0 1.9 38.6
in coal (%)
rpm. 10 mL samples were drawn after leaching time inter-
Loss on ignition (%) 1.4 1.11 1.6
vals of 1 hr, 2 hr, 4 hr, 8 hr, 12 hr, 24 hr, 30 hr, 36 hr, and
Coal fly ash classes* F C F
48 hr, respectively. Each sample was centrifuged for 10
Quartz and
minutes at 10000 rpm and the extractant was filtered with Quartz and Quartz and
Minerals in fly ash magnesium and
the 0.2 µm PTFE filter and analyzed for major and minor mullite mullite
iron oxides
metals using ICP-AES as given in section 2.3. The various
steps are shown in the Table 1. * C-calcium rich and F-Silica rich ash
Resources and Environment 2012, 2(2): 1-8 3
Concentration (µg/g)
17500
5
Optimum Leaching Time
7500
Concentration (µg/g)
4
5000
3
2500
2
0
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr 1
Time (hrs)
0
(a)
As Cr Mn Ni Cu 1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
Time (hrs)
Zn Se Cd Pb
6.00 (b)
Optimum Leaching Time Figure 3. Leaching of water soluble fractions for CFA2, (a) Major metals,
5.00 (b) Minor metals
Concentration (µg/g)
Concentration (µg/g)
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr 35000
Time (hrs) 30000
(a) 25000
As Cr Mn 20000
Ni Cu Zn 15000
4 10000
Optimum Leaching Time
5000
Concentration (µg/g)
3 0
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
2
Time (hrs)
1 (a)
As Cr Mn Ni Cu
0 Zn Se Cd Pb
50
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr Optimum Leaching Time
Time (hrs)
(b) 40
Concentration (µg/g)
Figure 4. Leaching of water soluble fractions for CFA3, (a) Major metals,
(b) Minor metals 30
Ca Fe Mg 20
6000 Optimum Leaching Time 10
5000
Concentration (µg/g)
4000 0
3000 1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
1000 (b)
Figure 6. Leaching of ion exchangeable fractions for CFA2, (a) Major
0 metals, (b) Minor metals
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30hr 36 hr 48 hr
Time (hrs) Trends observed for CFA3: Among major metals, Ca and
(a) Mg exhibited peak leaching concentrations at 4 hours, Na
As Cr Mn and Si leached about 90% and 95% of their maximum
Ni Cu Zn
Se Cd Pb leaching concentration respectively at 4 hours, while Fe
4.00
Optimum Leaching Time leached about 66% of its peak leaching concentration at 4
hours as shown in Figure 7(a). Among minor metals, Cu and
Concentration (µg/g)
3.00
Zn leached less than 70% of their maximum leaching con-
2.00
centration at 4 hours, while Mn and Ni leached about 85% of
their peak concentration at 4 hours. The remaining metals
1.00 showed their maximum concentration at 4 hours as shown in
Figure 7(b).
0.00
3.2.3. Acid Soluble Fractions
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
Time (hrs)
Trends observed for CFA1: Among major metals, Ca and
(b) Fe exhibited peak leaching concentrations at 24 hours, while
Figure 5. Leaching of ion exchangeable fractions for CFA1, (a) Major
metals, (b) Minor metals
Mg and Si leached about 95% and Na leached about 85% of
its peak leaching concentration at 24 hours as shown in
Trends observed for CFA2: Among major metals, Ca and Figure 8(a). Among minor metals, all metals exhibit more
Resources and Environment 2012, 2(2): 1-8 5
than 80% of their peak leaching concentrations at 24 hours, Trends observed for CFA2: Among major metals, Mg and
except Mn which leached about 70% of its maximum Si exhibited peak leaching concentrations at 24 hours, while
leaching at 24 hours as shown in Figure 8(b). Fe and Na leached between 90% and 95% of their maximum
leaching concentration at 24 hours and Ca leaches about 85%
Ca Fe Mg
8000
of its peak leaching concentration at 24 hours as shown in
Optimum Leaching Time Figure 9(a). Among minor metals, all metals exhibit their
6000 peak leaching concentrations at 24 hours, except Mn and Cr
Concentration (µg/g)
Concentration (µg/g)
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
Time (hrs) 80000
(a)
As Cr Mn 60000
Ni Cu Zn
30 Optimum Leaching Time 40000
20000
Concentration (µg/g)
20
0
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
10 Time (hrs)
(a)
0 As Cr Mn Ni Cu
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr Zn Se Cd Pb
Time (hrs) 500
Optimum Leaching Time
(b)
Concentration (µg/g)
Figure 7. Leaching of ion exchangeable fractions for CFA3 (a) Major 400
metals, (b) Minor metals
300
Ca Fe Mg Na Si
7000 200
Optimum Leaching Time
6000
100
Concentration (µg/g)
5000
4000 0
3000 1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
2000 Time (hrs)
1000 (b)
Figure 9. Leaching of acid soluble fractions for CFA2 (a) Major metals, (b)
0
Minor metals
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 32 hr 48 hr
Time (hrs) Trends observed for CFA3: Among major metals, Ca and
(a) Na exhibited peak leaching concentrations at 24 hours, while
As Cr Mn
Ni Cu Zn Mg, Na and Si leached about 90% of their maximum leach-
Se Cd Pb ing concentration at 24 hours as shown in Figure 10(a).
150
Optimum Leaching Time Among minor metals, all metals exhibit their peak leaching
concentrations at 24 hours, except Mn and Cr which leached
Concentration (µg/g)
about 90% of their maximum leaching at 24 hours as shown Trends observed for CFA2: Among major metals, Mg, Ca
in Figure11(b). and Fe exhibited peak leaching concentrations at 24 hours,
Ca Fe Mg
while Si and Na leached more than 90% and 95% respec-
10000 tively of their maximum leaching concentration at 24 hours
Optimum Leaching Time
as shown in Figure 12(a). Among minor metals, all metals
8000 exhibit their peak leaching concentrations at 24 hours, except
Concentration (µg/g)
Concentration (µg/g)
As Cr Mn
Ni Cu Zn 2000000
40
Optimum Leaching Time
1500000
Concentration (µg/g)
30
20 1000000
10 500000
0
0
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
Time (hrs) 1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
(b) Time (hrs)
Figure 10. Leaching of acid soluble fractions for CFA3 (a) Major metals,
(a)
(b) Minor metals
As Cr Mn
Ca Fe Mg Ni Cu Zn
2500000 Se Cd Pb
Optimum Leaching Time 50 Optimum Leaching Time
2000000 45
Concentration (µg/g)
Concentration (µg/g)
40
1500000
35
1000000 30
500000 25
20
0
15
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
Time (hrs) 10
(a) 5
As Cr Mn 0
Ni Cu Zn
Se Cd Pb 1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
20
Optimum Leaching Time Time (hrs)
Concentration (µg/g)
15 (b)
Figure 12. Leaching of reducible fractions for CFA2 (a) Major metals, (b)
Minor metals
10
Trends observed for CFA3: Among major metals, Ca ex-
5 hibited its peak leaching concentration at 24 hours, Si
leached about 95% of its peak leaching concentration while
0 Na, Mg and Fe leached more than 90% of their maximum
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr leaching concentration at 24 hours as shown in Figure 13(a).
Time (hrs)
(b)
Among minor metals, all metals exhibit their peak leaching
Figure 11. Leaching of reducible fractions for CFA1 (a) Major metals, (b) concentrations at 24 hours, except Cr, Cu, Mg and Ni which
Minor metals leached about 90% of their maximum leaching concentra-
Resources and Environment 2012, 2(2): 1-8 7
20
15 REFERENCES
10 [1] Sahu, S. K., Bhangare, R.C., Ajmal, P.Y., Sharma, S., Pandit,
G.G., and Puranil, V.D., 2009 , Characterization and quanti-
5 fication of persistent organic pollutants in fly ash from coal
0 fueled thermal power stations in India., Journal of Micro-
chemical, 92, 92-96.
1 hr 2 hr 4 hr 8 hr 12 hr 24 hr 30 hr 36 hr 48 hr
Time (hrs) [2] Lokeshappa B., and Dikshit, A.K., 2011, Disposal and man-
(b)
agement of coal fly ash, Proc. ICLST, 11-14
Figure 13. Leaching of reducible fractions for CFA3, (a) Major metals, (b) [3] Adriano, D. C., Page, A. L., Elseewi, A. A., Chang A. C., and
Minor metals Straughan, I., 1980, Utilization and disposal of fly ash and
other coal residues in terrestrial ecosystems: a, review.,
Journal of Environmental Quality, 9, 333–344.
5. Conclusions [4] Aitken, R.L., and Bell, L.C., 1985, Plant uptake and phyto-
Water Soluble Fractions: Most of the metals exhibit toxicity of boron in Australian fly ash., Journal of Plant and
Soil, 84, 245-257.
more than 90% of their peak leaching concentrations at 4
hours, except Si, Na, Ni, Mn, Cr, which show divergence in [5] Mattigod, S. V., Rai, D., Eary, L. E., and Ainsworth, C. C.,
behaviour for some ashes. Thus, 4 hours can be taken as the 1990, Geochemical factors controlling the mobilization of
optimum leaching time for water soluble metals. inorganic constituents from fossil fuel combustion residues:
Ion Exchangeable Fractions: Many metals leach more review of the major elements., Journal Environmental Qual-
ity,19, 188–201.
than 80% of their peak leaching concentrations after 4 hours,
many of them even leaching more than 90% of their peak [6] Yuan, C. C., Fang, W. C., Mui, D.T., and Chiang., H.L., 2009,
values. Mn shows low leaching at 4 hours for two ash sam- Application of methods (sequential extraction procedures and
ples, so it will not be correctly estimated at 4 hours. Cu, Fe, high pressure digestion method) to fly ash particles to deter-
mine the elements: a case study of BCR 176., Journal of
Mg Ni and Zn exhibit moderate leaching for some ash sam- Hazardous Materials, 163, 578-587.
ples. Thus, 4 hours can be asserted as the optimum leaching
time for ion exchangeable conditions. [7] Carlson, C.L., and Andriano, D. C., 1993, Environmental
Acid Soluble Fractions: All major metals exhibit more impacts of coal combustion residues, Journal of Environ-
mental Quality., 22, 227-247.
than 90% of their maximum leaching concentrations at 24
hours, although Ca and Na exhibit about 85% of their [8] Turiel, F.J.L., Carvacho, W., Cabanas, M., Querol, X., and
maximum leaching concentrations for some ash samples at Soler, L.A., 1994, Mobility of heavy metals from coal fly ash.,
24 hours. All minor elements show maximum leaching at 24 Environmental Geology, 23, 264-270.
hours except Mn and Cr which show about 70% to 80% and [9] Worathanakul, P., Kongkachuichay, P., Noel, J.D., Suriya-
90% respectively of their maximum leaching concentrations wong, A., Giammar, D.E. and Biswas, P., 2008, Evaluation of
at 24 hours. Thus, the optimum leaching time for acid soluble nanostructured sorbents in differential bed reactors for ele-
8 Lokeshappa B et al.: Single Step Extractions of Metals in Coal Fly Ash
mental mercury capture., Environmental Engineering Science, fly ash as a function of the acidity of the contact solution and
25, 1061-1070. the liquid/solid ratio. In Environmental aspects of stabiliza-
tion and solidification of hazardous and radioactive wastes;
[10] Groot, D. G.J., Wijkstra, J., Hoede, D., and vander Sloot, H., Côté, P., Gilliam, T. M., Eds.; American Society for Testing
1989, Leaching characteristics of selected elements from coal and Materials: Philadelphia, PA, pp 170-183.