International Journal of Coal Geology 60 (2004) 57 72

www.elsevier.com/locate/ijcoalgeo

Characterization of Candiota (South Brazil) coal and

combustion by-product
Marcal Pires a,*, Xavier Querol b
a

Faculty of Chemistry, Pontifical Catholic University of Rio Grande do Sul, Av. Ipiranga 6681 Predio 12B, 90619-900 Porto Alegre-RS, Brazil
b
Institute of Earth Sciences Jaume Almera, CSIC, c/Mart i Franque`s s/n, E-08028 Barcelona, Spain
Received 8 October 2003; accepted 30 April 2004
Available online 28 July 2004

Abstract
Elemental composition and mineralogy of a high ash feed coal (ash: 49.7 wt.%), and its bottom and fly ash from a Brazilian
power plant (Presidente Medici Power Plant or UTPM-446 MW) was determined using ICP-MS, ICP-AES, X-ray diffraction
(XRD) and scanning electron micrography (SEM). Most trace elements in coal fall in the usual range determined for world coals.
However, concentrations of some elements were higher than the expected for coals, including Cs Rb and heavy rare earth
elements (REEs). This might be due to the high content of detrital minerals of the studied coal, given that these elements are
usually associated with clay minerals. Elements were classified into three groups based on the analysis of trace element
concentrations in fly and bottom ashes, and enrichments or depletions of these concentrations in relation to the coal: Group I
(volatile elements with subsequent condensation): As, B, Bi, Cd, Ga, Ge, Mo, Pb, S, Sb, Sn, Tl and Zn; Group II (no volatile
elements enriched in bottom ash vs. fly ash): Ca, Fe, Mn, P, Ti and Zr; Group III (low volatile elements with no partitioning
between fly and bottom ashes): Al, Ba, Be, Co, Cr, Cs, Hf, K, Li, Mg, Na, Ni, Rb, Sr, Th, U, W, Y and most of REE. The mass
balance for trace elements obtained demonstrated that the volatile emission of the trace elements studied is very low. According to
the leachable proportion obtained, the elements may be classified as follows: B (40 50%)>Mo>Cu>Ge = Li = Zn = As>, Ni, Sb,
Tl, U>Ba, Cd, Sr, V (0.3 2%). For the other elements studied, the leachable fraction is in most cases < 1% of the bulk content.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Candiota coal; Fly ash; Trace elements; Leaching; Brazil

1. Introduction
Coal was first mined in Brazil 140 years ago
(BRAZIL, 1987), but the sector has not developed
as fast as other segments of Brazils economy because
Brazilian coal has low caloric value and high ash

* Corresponding author. Fax: +55-51-3320-3612.

E-mail address: mpires@pucrs.br (M. Pires).
0166-5162/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2004.04.003

contents, thus requiring expensive processing treatment hampering its competitiveness. These limitations
may become less significant with the development
and introduction of new technologies which favor
direct burn, thus dispensing with phases of processing
which had to be used in the past when the coal used
for thermoelectric power generation was a by-product
of the coal for steel production.
Until 1975, coal contributed no more than 3.2% of
Brazils energy requirements, and its main use (80%

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M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

of the total) was in iron and steel production (Carrisso

and Possa, 1995). Since 1975, industrial use of coal
increased as a consequence of the price advantage it
offered in comparison to fuel oil and also as a result of
transport subsidies, which were reduced after 1986
with the reduction in cost of fuel. Currently (2000),
coal provides 5.3% of Brazils energy requirements,
of which 1% is Brazilian coal and 4.3% imported coal
and coke (Gomes et al., 1998). In 1997, 78% of the
over 6 Mt of nationally produced coal was consumed
by thermoelectric plants and 22% by industry
(BRAZIL, 2001a). In the year 2000, coal-consuming
power plants with capacity of 1.4 GW, produced
7.4 TWh of electricity (85% increase in relation to
1996), using 6.1 Mt of coal. Current plans for the
electrical sector foresee an increase in capacity of
1.1 GW (four plants, two with 350 MW and two with
200 MW capacity) by the year 2005.
The prospects for thermoelectric generating plants
in Brazil will most certainly receive a boost from
privatization of the Electric Power Sector; however,
competitiveness dictates that in order to be successful
they must use clean-coal technologies with locations
close to the mines. Although such technologies have
proven to be effective, even for the combustion of
low-rank coal, none of them has been applied in
Brazil. Under the Expansion Plan 1998/2007 of the
Brazilian Government (BRAZIL, 2001b), the countrys electricity production will grow from 59.3 to
95.7 GW. The contribution of thermoelectric power
generation will grow from 8% to 17% during this
period, with a corresponding decline of hydroelectric
power (BRAZIL, 2001a). The projected power plants
will consume mainly natural gas, but coal will also be
used at a large scale.
1.1. Candiota area
The region of Candiota, located 380 km from Porto
Alegre in the southwest of Rio Grande do Sul, has an
area of 430 km2. The largest coal reserves in Brazil, as
well as a coal-fired power station (Presidente Medici
Power Plant or UTPM-446 MW) are located in this
area approximately 50 km from the border with
Uruguay. The Candiota coal is Permian Gondwanan,
belonging to the Tubarao subgroup of the Parana
Basin (Alves and Ade, 1996). This coal, as most of
the Brazilian coals, is a high bituminous class C

volatile coal with high ash content, as classified

according to ASTM (1996a).
Environmental aspects from the combustion of
fossil fuels, mainly coal, have been reported in certain
areas of Rio Grande do Sul, the southernmost state of
Brazil (JICA, 1996). Thus, Teixeira (1997) detected
contamination problems due to the disposal of coal
wastes and combustion by-products in area of Baixo
Jacu, affecting the quality of surface and underground
water, as well as of air quality, mainly from suspended
particulate matter (Sanchez et al., 1995).
The purpose of this work is the physico-chemical,
mineralogical, and morphological characterization of
Candiota coal and combustion by-products produced
at UTPM. The aim of this characterization is to assess
further studies on the environmental impact due to
coal combustion (atmospheric emissions) and the
consequent waste disposal (fly ash and bottom ash
leaching).

2. Methods
2.1. Sampling and sample preparation
The present work was performed with a sample of
feed coal ( f 50 kg) used at UTPM, located in
Candiota, state of Rio Grande do Sul in the south of
Brazil (446 MW, Fig. 1). The combustion by-products
from this power station were sampled simultaneously
with feed coal. To this end, samples of 30 kg of
bottom ash and 50 kg of fly ash, from the hoppers of
electrostatic precipitator (EP), were collected following ABNT (1983) and ASTM (1996b) procedures.
The coal and bottom ash samples were ground to
pass a < 63-Am sieve. The fly ash, due to its homogeneity and finer grain size, was used as received in
most of the subsequent analysis. The only exception
was the grain size separation with the cascade impactor, which needed the separation of the coarser fraction (>63 Am). Subsamples of coal and ashes were
dried at 105 jC, and used in subsequent characterization analysis.
2.2. Immediate and elementary analysis of the coal
The moisture, ash (HTA), volatile matter and fixed
carbon contents of the coal were measured according

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

59

Fig. 1. Location of the Candiota area, in the southern state of Rio Grande do Sul, Brazil (adapted from Migliavacca, 2001).

to ASTM standards (ASTM, 1996c). Major and trace

elements content in the coal, the fly and bottom ashes,
and the different grain size fractions of the fly ashes

obtained in the cascade impactor were determined

using ICP-MS and ICP-ES according to methodology
of Querol et al. (1995). After acid digestion (HF/

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M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

Table 1
Characterization of Candiota coal
Proximate analysis
Moisture (%)
Ash (%)
Volatile matter (%)
Fixed carbon (%)
Gross calorific
value (MJ kg
1)
Sulphur (%)

Mineral content (wt.%)

16.4
49.7
23.1
27.2
14.3
0.96

Quartz
Kaolinite
Illite
K-feldspar
Calcite
Pyrite/marcasite

30.9
16.0
2.0
0.5
< 0.5
0.3

HNO3/HClO4) of bulk samples, the contents of major

and trace elements were determined by ICP-MS and
ICP-AES. Reference materials of coal (SARM 19)
and ashes (NIST 1633b) were analyzed with the same
procedure to check the analysis quality.
The mineralogical composition of the bulk coal
and ashes, as well as of ashing products, was characterized by X-ray diffraction (XRD) using similar
methods to those described by Ward (2002) and
Vassilev and Tascon (2003).
The grain size distribution of fly ash sample was
characterized by a laser analyzer using ethanol as
dispersing agent. A cascade impactor was used to
obtain seven grain size fractions (0.4 0.8; 0.8 1.7;
1.7 3.3; 3.3 6.6; 6.6 13; 13 26; and 26 63 Am)
from the < 63-Am fractions of the bulk fly ash. The
subsamples were recovered from the impactor units in
an ultrasound bath. The insoluble fraction was recovered by filtration (membrane filter 0.45 Am) and
analyzed by ICP-MS and ICP-AES. The efficiency
of the grain size cut off was checked by SEM.
2.3. Leaching tests
Room temperature leaching tests using open and
closed systems were carried out for the fly ash. For
bottom ashes, only closed leaching was performed.
Three different procedures were used in the closed
system: (a) DIN-38414-S14 procedure with a fly ash/
water ratio of 100 g/l with mechanical agitation for 24 h,
followed by centrifugation; (b) a 20 g/l ratio with
mechanical agitation for 24 h; (c) a 20 g/l ratio with
mechanical agitation for 2 h, followed by centrifugation.
Conductivity and pH were measured immediately, and
the major and trace elements contents were determined
in the leachates using ICP-AES and ICP-MS. Previously
cleaned polyethylene flasks were used in all tests.

The open system leaching test is based on the

passage of a continuous flow of water through a
column containing the ashes. In the first test, a water
flow of 50 ml h
1 was put through the column
containing 2 g of ash. Samples of leachates were
collected at intervals of 10 ml ( f 8 min) and the
pH and conductivity were determined. The test was
performed for 20 h, with total water volume of 1000
ml, when low (10 AS cm
1) and constant conductivity
values were observed. In a second test, performed in
the same conditions, continuous 10 ml leachate samples were periodically collected and analyzed by ICPMS and ICP-AES.

3. Results and discussion

3.1. Chemical and mineralogical characterization of
coal
Tables 1 and 2 show the results of ultimate,
proximate, chemical and mineralogical analyses of
the studied coal and combustion by-products. The
high ash yield and the relative low sulfur content
obtained for this coal confirm literature data (BRAZIL, 1987; Fiedler, 1987). The main mineral phases
present in the coal are quartz, kaolinite, illite, Kfeldspar and pyrite. The mineralogy of HTA (750
jC) ash consists of meta-kaolinite, hematite and
microcline.
The fly and bottom ashes were characterized by
relatively high contents of SiO2 (56 59%) and Al2O3
Table 2
Major oxide contents in Candiota coal HTA, fly ash and bottom ash,
on dry basis (wt.%)

SiO2
Al2O3
Fe2O3
CaO
MgO
Na2O
K2 O
P2O5
TiO2
MnO
SO3
SiO2/Al2O3

HTA

Fly ash

Bottom ash

70.6
24.3
2.9
0.7
0.2
0.03
0.50
0.01
0.8
0.01
4.7
2.9

56.7
38.4
2.5
1.1
0.2
0.04
0.6
0.02
0.5
0.02
0.2
1.5

58.9
36.0
2.4
1.3
0.2
0.04
0.6
0.02
0.6
0.02
< 0.1
1.6

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

Table 3
Trace and major elements contents in coal and in fly and bottom
ashes (% from Al to Ti, other elements in mg kg
1 on a dry basis)
Coal
%
Al
Ca
Fe
K
Mg
Na
P
S
Ti
mg kg
1
Li
Be
B
V
Cr
Mn
Co
Ni
Cu
Zn
Ga
Ge
As
Rb
Sr
Y
Zr
Nb
Mo
Cd
Sn
Sb
Cs
Ba
La
Ce
Nd
Sm
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Tl

Fly ash

Bottom ash

3.24
0.42
2.01
0.92
0.21
0.06
0.01
0.96
0.23

10.16
0.77
4.63
1.74
0.46
0.12
0.02
0.08
0.41

9.54
0.90
7.68
1.67
0.47
0.12
0.025
0.01
0.49

14
2.5
9.2
55
26
410
10.1
17
20
45
9.1
2.1
4.4
50
42
24
128
16.1
1.4
0.5
3.2
1.4
9.1
152.3
24.9
53.7
25.4
4.2
6.8
0.8
5.3
0.7
3
0.31
3.2
0.9
4.4
7.4
3.2
0.8

29
4.9
23.9
78
51
614
16.2
29
33
77
19.3
3.8
11.5
119
103
49
215
22
4.8
1.2
5.4
3.2
16.8
283.9
52.7
113.3
55.2
9
12.1
1.8
10.5
1.7
5.7
0.74
6.3
1.3
10.2
13.9
4
2.1

28
4.3
15.3
93
47
991
17.5
30
32
47
11.8
1.3
1.8
107
100
46
218
25.1
3.6
0.3
3.5
2.6
14.8
278.9
49.7
109.4
53.6
8.9
10.7
1.6
10.5
1.6
5.2
0.78
6.3
1.3
9.1
14.3
3.4
0.4

61

Table 3 (continued )
Coal
mg kg
1
Pb
Bi
Th
U

20.5
0.8
9.5
3.3

Fly ash
41.1
1.6
21.0
6.0

Bottom ash
19.2
1.1
22.0
6.1

(36 38%) and low contents of alkaline oxides (Table

2). This fact has great influence on the leaching
processes discussed later, and on the potential application of these materials. For comparison, most of the
European fly ashes have < 55% SiO2 and < 30%
Al2O3 (Moreno et al., 2002).
The main components of the fly ash are the glassy
aluminium silicate matrix, mullite, quartz and magnetite. A similar composition was obtained for bottom
ash, with a higher content of magnetite. Calcination
(1000 jC) of fly ash resulted in the oxidation of the
magnetite into hematite.
3.1.1. Concentration of trace elements in coal
Table 3 shows the concentrations of major and
trace elements in the feed coal and fly and bottom
ashes from UTPM. Table 4 shows typical concentration values of several trace elements of subbituminous
coals of different countries and the worldwide concentration range for coal. The results of 17 studies on
Brazilian coals, among them the coal of Candiota,
compiled by Pires et al. (2002) are also presented in
this table, together with more recent data on the coals
from Santa Catarina, feed coal of the Jorge Lacerda
Power Plant (Pereira, 1996), the largest coal-burning
utility in Brazil (860 MW).
In general, the concentration of (a) Cu, Mo, Se and
Zn is lower than other Brazilian coals; (b) Be, Bi and
Ba are within the range, and similar to the coal from
Santa Catarina; (c) concentration of Mn is greater than
the other Brazilian coals.
The concentrations of most of the trace elements in
the Candiota sample are within the range for world
coals (Swaine, 1990).
3.2. Concentration of the trace element in fly and
bottom ashes
As indicated previously, the measured concentrations of major and trace elements present in fly and

62

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

Table 4
Typical trace element concentrations (mg kg
1) in the world coals (Swaine, 1990) and coals from selected countries
Worlda

Specific coals
USAb

Canadab

Australiab

Brazilc
JL-SCd

As
B
Ba
Be
Bi
Cd
Ce
Cl
Co
Cr
Cs
Cu
Dy
Er
Eu
F
Ga
Gd
Ge
Hf
Hg
Ho
La
Li
Lu
Mn
Mo
Nb
Nd
Ni
P
Pb
Rb
Sb
Sc
Se
Sm
Sn
Sr
Tb
Th
Tl
Tm
U
V
W
Y
Yb
Zn
Zr

0.5 80
5 400
20 1000
0.1 15
2 20
0.1 3
2 70
50 2000
0.5 30
0.5 60
0.3 5
0.5 50
0.5 4
0.5 3
0.1 2
20 500
1 20
0.4 4
0.5 50
0.4 5
0.02 1
0.1 2
5 300
1 80
0.03 1
5 300
0.1 10
1 20
3 30
0.5 50
10 3000
2 80
2 50
0.05 10
1 10
0.2 10
0.5 6
1 10
15 500
0.1 1
0.5 10
< 0.2 1
no data
0.5 10
2 100
0.5 5
2 50
0.3 3
5 300
5 200

0.1 420

4 53
5 32

0.05 32

< 0.1 36
1 14
< 0.5 12

0.03 3.7

1.3 12
36 230
30
5 73
9
0.024 2.2

0.06 70
0.54 70

1.1 31
5.7 64

< 5 321
< 5 117

100 8000
6 43
9 74

0.16 120

14 80

< 1 741

9 71

126 1287
23 28

0.01 8.0

0.02 0.44

35.14
49.48
98.13
3.49
1.41
2.6
110.73
10.29
73.2
10.59
33.39
6.13
3.53
1.64

Candiota-RS
Rangec

This work

Ratioe

1.3 2.6
36
30
73
9
2

4.4
13.7
152
2.7
0.8
0.1
54
na
10.1
24
9.1
4.4
5.3
3.0
ni
na
9.1
6.8
2.3
4.4
0.1
0.6
25
14.2
0.9
452
1.4
16.1
25
17.1
166
20.5
50
ni
ni
ni
4.2
3.4
42
0.8
8.5
0.7
0.3
3.3
50
3.2
23.7
3.2
11.4
128

0.05
0.03
0.15
0.18
0.04
0.04
0.77
0.00
0.34
0.40
1.81
0.09
1.33
1.01
0.00
0.00
0.46
1.70
0.05

169 1287
6 21
27 73
24 71

110 560
18.35
8.46
9.49
8.87

0.05 0.8

0.1 0.8
1.24
56.22
42.2
0.49

1.4 3500
0.13 41

1.6 1000
< 0.8 9

0.32 69

< 2 667
< 0.1 6

2 161

0.7 76

1.9 19

0.04 43

0.1 2.4

0.10 16

0.5 2.0

0.08 54

< 0.1 9

< 1 595

31 240
2.6 10

15 64
2 95

1.5

< 0.4 26

0.06 76
0.14 370

0.2 2.4
23 300

< 1 58
2 279

0.88 910

7.6 83

< 2 273

23 86

30 217
110 127

5.9
20.57
42.05
24.05
49.64
69.59
5.88
19.44
2.57
8.51
8.79
56.32
1.16
8.9
4.21
3.8
187.25
6.59
37.25
3.64
473.53
857.82

31 240
4

22 34
4 50

1.5

23 60

80 98
110

0.06
0.30
0.62
0.18
0.90
1.50
0.14
0.80
0.85
0.34
0.06
0.26
1.00
0.00
0.00
0.00
0.70
0.34
0.08
0.84
0.85
0.67
0.33
0.50
0.63
0.47
1.08
0.04

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

63

Fig. 2. Ratio of major, minor and trace elements content in fly and bottom ashes. Reproduced with permission of the editor from: Pires, M. et al.
Caracterizacao do carvao de Candiota e de suas cinzas. Geochimica Brasiliensis, 15 (1 2): 113 130.

bottom ashes are shown in Table 3. The contents of

trace elements in fly and bottom ashes depend on
several factors related to the concentration and the
geochemical distribution of the elements in the coal
and to the combustion and pollution control technologies used (Davidson and Clarke, 1996; Meij, 1994;
Ratafia-Brown, 1994; Davidson, 2000; Huggins,
2002; Huggins et al., 2004). Fig. 2 shows element
concentration ratios in fly ash (FA) and bottom ash
(BA). Through the analysis of these results, it is
possible to classify the elements to the following
groups:
(a) Elements enriched in fly ash (FA/BA 1.3 9.7):
As, B, Bi, Cd, Ga, Ge, Mo, Pb, S, Sb, Sn, Tl and
Zn.
(b) Elements enriched in bottom ash (FA/BA < 1): Ca,
Fe, Mn, P, Ti and Zr.

(c) Elements present in similar concentrations (FA/

BA f 1,0): Al, Ba, Be, Co, Cr, Cs, Hf, K, Li,
Mg, Na, Nb, Ni, Rb, Sr, Th, U, V, W, Y and most
of rare earth elements (REEs).
The first class of elements (a) partially volatilise
(especially As, Cd, Tl, Pb and mainly S) during coal
combustion, condensing as temperature decreases,
mainly on the finest and coolest particles, or are
emitted, in different proportions, as gaseous species.
The relatively low proportion of volatile B is due
mainly to the association with detrital minerals instead
of the organic matter (Boyd, 2002).
On the other hand, the low-volatile elements (c)
present a weak segregation and the non-volatile elements (b) may be found in higher concentrations in
bottom ashes. In general, it is observed that the
segregation of the trace elements in fly ash/bottom

Notes to Table 4:
a
Swaine (1990).
b
Swaine and Goodarzi (1995).
c
Pires et al. (2002).
d
Pereira (1996).
e
Ratio between the element concentrations in Candiota coal and maximum observed level by Swaine (1990) for the World coals. nilower
than detection limit. naelement not quantified.

64

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

ash is not very strong at UTPM. This fact could be

related to the low efficiency of the burning conditions,
due to the high mineral matter contents of the Candiota coal (>50%).
To elucidate the behavior of the trace elements
during the coal combustion, their concentrations in fly
and bottom ashes can be normalized using a nonvolatile element, whose concentrations both in the
coal and in the ashes are accurately known. Such
procedure allows calculating an enrichment factor EF
(Gordon and Zoller, 1973) as follows:
EF XS =YS =XC =YC
where [X]S and [X]C are the concentrations of the X
element in the fly ash or bottom ash, and in the coal,
respectively. [Y]S and [Y]C are the contents of a nonvolatile element taken as reference. The non-volatile

elements most frequently selected for calculation of

EF are Al, Ce, Fe, La, Si and Ti (Ratafia-Brown,
1994; Smith, 1987). Most REEs, such as Ce and La,
present the additional advantage of being present in
constant concentrations in all particle sizes of the fly
ashes. Consequently, cerium was chosen as the
reference element in the calculation of the enrichment
indices of elements. Considering that around 80% of
the produced waste is fly ash and the remaining 20%
is bottom ash, the total enrichment factor based on
mass can be calculated as: EFtotal = EFFA  0.8 +
EFBA  0.2. It is assumed that this is an approximation and not an accurate calculation of the flow mass
balance into the power plant.
Fig. 3 shows the Ce-normalized EF for studied
elements, calculated for the fly and bottom ashes, in
relation to Ce.
The partially volatile elements such as As, B,
Cd, Ga, Ge, Mo, Pb and Tl (EFFA>1) are enriched

Fig. 3. Enrichment factors for major and trace elements in fly (EFFA), bottom ash (EFBA) and total EF (EFtotal = EFFA  0.8 + EFBA  0.2.)
normalized to Ce and coal.

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

in the fly ash samples. These elements are associated with organic and sulfide affinities, and are
similar to the elements classified previously as
group (a).
Ba, Be, Co, Cr, Cs, Hf, K, Li, Mg, Na, Ni, Rb, Sr,
Th, U, W, Y and most of REE presented similar
EF f 1 in both fly and bottom ashes.
Although a precise mass balance is difficult to
obtain with the data obtained in this study, the
calculation of EFtotal demonstrated that the volatile
emission of the trace elements studied is very low
since most EFtotal are close to 1 (Fig. 3). The data
show that volatilization of many elements occur
(EFfly ash>EFbottom ash) but most of them condense
on fly ash particles (Fig. 3).

65

3.3. Grain size separation of fly ash

Fig. 4 shows the results of the grain size classification of the fly ashes. Two different characterization
methods are used: laser analyzer (LA) and cascade
impactor (CI). The CI results were recalculated, for
the sample of the analyzed fly ash was previously
fractioned through sieving ( < 63 Am). In spite of the
differences between these two methods, the results
obtained are similar, as it can be observed by the
accumulated distribution of particle sizes (Fig. 4B).
The continuous interval of particle sizes estimated
in the LA was between 0.5 and 600 Am, and an average
diameter of 49.30 Am was obtained. These values are
within the expected diameter for the Candiota fly ash

Fig. 4. (A) normal and (B) accumulated fly ash particle distribution measured by a laser analyser (bulk sample) and a cascade impactor ( < 63 Am
fraction, recalculated). Reproduced with permission of the editor from: Pires, M. et al. Caracterizacao do carvao de Candiota e de suas cinzas.
Geochimica Brasiliensis, 15 (1 2): 113 130.

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M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

(Andrade, 1995). Ninety percent of the particles have

diameters smaller than 232 Am, while the finest
particles ( < 5 Am) correspond to f 1% of the total
mass of the sample.
Fig. 5 shows scanning electron micrographs of the
grain size fractions separated from the fly ash with the

CI. It is observed that CI presents good separation

efficiency, with most of the particles of each fraction
being within the range of expected aerodynamic
diameters. It also observed different morphologies of
ash particles size, with the predominance of cenospheres in the intermediate fractions (1.7 13 Am).

Fig. 5. SEM photomicrographs of size fractions of Candiota fly ash. Reproduced with permission of the editor from: Pires, M. et al. Caracterizac
ao do carvao de Candiota e de suas cinzas. Geochimica Brasiliensis, 15 (1 2): 113 130.

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

67

Fig. 6. Mass percent of major and trace elements during ultrasound water extraction, of grain size fractions of fly ash sample ( < 63 Am).

The percent solubility of the elements in the

different grain size fractions is shown in Fig. 6. Some
elements present remarkable increasing solubility
(>40%) as grain size decreases (As, Co, Sr, Ba, Zn
and Ni). The same behavior was observed to the
elements Zr, Cr, V, Tl and Hf but with small solubility
(5%). On the other hand, the elements Fe, Nb, REE,
Cs, Li and W showed low solubility in all grain size
fractions. Sulfur and Mo presented very different
solubility profiles with higher values in coarse grain
size fractions.
3.4. Leaching tests
3.4.1. Closed system
Table 5 shows that the fly ash leachate is slightly
acidic pH in all tests, while bottom ash yielded a
slightly alkaline leachate. This behaviour was also
pointed out for the Candiota coal ashes by other
authors (Sanchez et al., 1994; Fernandez-Turiel
et al., 1994), and it is possibly due to the low

concentration of alkaline oxides in these ashes

(CaO < 1.3%), especially in the light fraction, Low
conductivity values ( < 100 AS/cm) are observed
when compared to other leachates for fly ash
(Querol et al., 2001), reflecting the low solubility
observed for most major species. The highest conductivity value was measured in the test with fly
ash with agitation of 2 h. This may be due to the
re-precipitation of slightly soluble elements in the
Table 5
pH and conductivity of the leachates measured for the closed system
using fly and bottom ashes

Fly ash

Bottom ash

Test
code

L/S ratio
(ml g
1)

Agitation
time (h)

pH

Conductivity
(AS cm
1)

1
2
3
4
5
6

10
50
50
10
50
50

24
24
2
24
24
2

3.90
3.94
4.03
8.30
8.42
7.90

105
105
130
30
30
30

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M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

24-h test. Any influence was detected on the

percentage of element leached by changing the
liquid/solid ratio from 10 to 50 ml g
1.
The concentration of trace elements in the leachates from bottom ash in closed system showed very
low concentrations for all elements.
As shown in Table 6, B, Ni, Cu, Zn, Mo and Sb
were leached from fly ash using ultra sound in
appreciable proportions (55%, 8%, 9%, 13%, 18%
and 8% of the bulk content, respectively), and only B
and Ge were leached in appreciable levels using a
shaker in a closed system (57% and 8%, respectively). The rest of extractable yields for the other
elements in this table reached values < 5%. Although
these second group reach extraction yields are
close to the analytical error determined for these
elements in the bulk sample (Finkelman et al.,
1990; Gentzis and Goodarzi, 1999; Seames et al.,
2002; Wang et al., 2004), the leachable proportion is
clearly lower than the one obtained for the first group
of elements.
3.4.2. Open system
In the open system, it was possible to follow the
time evolution of the pH and conductivity as well as
the concentrations of the leachable elements. Fig. 7
shows the profiles of the pH and the conductivity
obtained in the leaching tests of fly ash using a L/S
ratio of 50 ml g
1. A rapid increase of the pH from
4.2 to 7.0 is observed in the first 100 ml water, with
stabilization and slow decrease with the increase of
the L/S ratio, reaching a pH of f 6.0 after a 1000 ml
leaching. This behavior is associated to the fast initial
extraction of acidic components, concentrated in the
surface of the particles (Swaine, 1990), with subsequent slower extraction of alkaline elements (Querol
et al., 1996, 2001), less soluble or linked to the matrix
of the ash. The initial pH, measured in the first aliquot
of 10 ml, is similar to that found in the closed system
test (pH 4.0), performed in the same conditions.
Recalculating pH values after the passage of
100 ml, using the identical volume in the closed
system, a relatively higher value is obtained (pH
4.9), which can indicate that the processes/kinetics
of solubilization of the two systems are different.
The time evolution of the conductivity corroborates with a rapid extraction of the mobile elements,
predominantly with acidic character in that ash,

Table 6
Trace element extraction yields (% of bulk concentration) obtained
in open and closed leaching tests applied to fly ash
Closed

Li
Be
B
Ti
V
Cr
Mn
Co
Ni
Cu
Zn
Ga
Ge
As
Rb
Sr
Y
Zr
Nb
Mo
Cd
Sn
Sb
Cs
Ba
La
Ce
Nd
Sm
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
Tl
Pb
Th
U

Open

Ultrasound,
30 ml

Shaker,
100 ml

100 ml

1000 ml

4.6
< 0.1
55.2
< 0.1
0.2
1.1
1.5
0.5
8.3
8.7
13.2
< 0.1
3.6
1.4
0.5
1.8
0.8
0.1
1.0
18.1
< 0.1
< 0.1
8.1
< 0.1
2.0
0.4
0.4
< 0.1
1.4
1.0
< 0.1
< 0.1
1.1
< 0.1
< 0.1
1.2
< 0.1
2.5
2.1
2.6
4.5
1.1
0.8

3.8
0.2
57.3
< 0.1
2.2
0.4
0.9
1.0
2.9
3.4
1.4
0.1
7.8
2.5
0.4
1.5
0.5
< 0.1
< 0.1
3.3
2.1
< 0.1
1.0
0.5
0.4
0.4
0.3
0.3
0.1
0.6
< 0.1
0.3
< 0.1
0.1
< 0.1
0.4
1.7
0.2
0.6
1.4
1.4
0.0
0.6

3.9
0.4
42.9
< 0.1
0.2
0.2
0.7
0.6
0.9
3.5
2.7
0.1
5.0
2.4
0.4
1.4
0.6
< 0.1
0.1
20.2
0.3
0.6
2.5
0.3
0.4
0.4
0.4
0.4
0.5
0.4
0.7
0.5
0.7
0.4
2.1
0.5
0.8
0.1
0.1
1.1
0.3
0.1
1.2

5.2
0.5
43.0
< 0.1
0.2
0.6
0.9
1.2
12.4
9.3
18.9
0.6
9.3
9.6
1.0
2.2
0.6
0.2
0.7
52.4
0.3
8.4
14.3
1.0
2.1
0.4
0.4
0.6
0.9
0.8
2.0
1.2
1.2
0.4
16.0
0.9
6.2
0.1
0.1
11.9
2.5
1.9
9.5

Experiments made using 0.08 g (ultrasound) and 2.0 g of sample

ash (mechanical agitation) and different water volumes (30 and 100
ml for closed system using ultrasound and mechanical agitation,
respectively; 100 and 1000 for open system).

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

69

Fig. 7. Temporal evolution of pH and conductivity of the leaching tests using Candiota fly ash in open system.

reaching high ionic concentrations ( f 500 AS/cm) in

the first 10 ml of water, and accentuated decrease
with the increase of the L/S ratio (30 AS/cm to 100 ml
and 10 AS/cm to 1000 ml). Recalculating these
values, as was previously done with pH values, a
conductivity of 117 AS/cm for an accumulated leachate volume of 100 ml is obtained. This value is within
the range obtained for the conductivity in closed
system tests performed with the same L/S ratio
(105 130 AS/cm). In fact, the pH and conductivity
profiles observed are similar to those obtained by
Querol et al. (2001) for the ashes from Puertollano,
which had similar composition to the Candiota ashes
(high SiO2, Al2O3 and low CaO contents).
Fig. 8 shows the time evolution of the concentration of some trace elements (Li, Cu and Mo) in
leachates from fly ash. These elements represent
typical profiles of three time evolution trends (elements in between brackets, less evident):
A: As, Li, Mn, Sb (Ba, Co, Cs, Dy, Eu, Ge, Ho,
Nb, Pr, Rb, Sm, Sr, Tb, Tm and Yb)
B: B, Cu, Lu, Ni, Pb, Ti, Tl, U, (Zn V, Y, Be, Ce,
Cr, Er, Gd, La, Nd, Sc, Th and Zr)
C: Mo and Sn (Ga)
It has to be pointed out that the results on a number
of elements in brackets are of a lesser significance due
to the fact that the extractable fraction is < 5%.
The elements classified in groups A and B present
the highest concentrations in the first aliquot of
leachate (10 ml), with a rapid decrease with the
increase of the solid to liquid ratio. The differences
between these groups can be seen in leachate volumes

>50 ml. While the elements of Group A present low

concentrations (100 times lower than the initial one)
but measurable until the end of the test (1000 ml),
Group B elements present behavior quite similar to
Group A elements, differing only for a small concentration increase in the last leaching stage.
The elements from Group C (Ga, Mo and Sn)
presented atypical behaviors and could not be classified in any of the previous groups. The highest Mo
concentrations are not observed in the first leachate
fractions, but after the passage of some milliliters.
This maximum is followed by a slight concentration
decrease up to 800 ml when a pronounced concentration decrease is evident in the last leached fractions.
Swaine and Goodarzi (1995) classify the behavior
of trace elements during the leaching processes in
three categories:
Type IElements that dissolve immediately and
do not form slightly soluble compounds. In closed
system tests, the concentration of these elements
reaches a plateau that corresponds to the total
dissolution of the soluble fraction on the ash
particle surface. In the open system, these elements
are present in high concentrations in the initial
stages of the leaching with rapid decline with the
increase of the L/S ratio.
Type IIElements present in constant leaching
concentrations with the increase of the L/S ratio in
open system. In this case, there is dissolution of
slightly soluble superficial phases and/or desorption of the element linked to the matrix phases.
This type of behavior is also the result of the
dissolution of the matrix itself and of the migration,

70

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

proposed by Swaine and Goodarzi (1995). On the

other hand, Group B presents a concentration increase
with the increase of the L/S ratio, like Type III
elements, but with high initial concentrations.
3.5. Comparison among leaching systems

Fig. 8. Temporal evolution of the A, B and C class types, using as

example the concentrations of the Li, Cu and Mo, respectively.
Concentrations in the leachates of Candiota fly ash in open system
are expressed in microgram per liter versus water volume, in ml.

limited by the diffusion, of the element contained

inside the fly ash particles.
Type IIICorresponds to low initial leaching
concentrations, followed by a concentration increase with the increase of the L/S ratio. This
behavior occurs due to solubility limitations
mainly due to the pH.
The behavior of the elements classified in Group A
could be correlated to Type I leaching categories

Table 6 shows the results obtained from the closed

system fly ashes leaching tests with mechanical agitation or ultrasound assistance, and from open system
in a column with a constant water flow. The results are
expressed in percentage values of the extraction in
relation to the total content of each element in the
ashes in order to facilitate a comparison between the
different tests performed.
Comparing the tests performed in closed systems,
ultrasound and shaker, it is observed that the ultrasound stirring contribute to a more efficient leaching
of most elements (25 of 47 studied). However, these
differences may be in part attributed to the fact that the
sample submitted to the ultrasound stirring was the
< 63-Am fraction of the bulk sample. Unfortunately,
data on ultrasound leaching was not found to compare
with our results.
The tests performed in open system best simulate
the mobilization of the trace elements in the environmental conditions. Comparing the data from the open
and closed systems, similar extraction rates are
obtained for most elements for the same L/S of
50 ml.g
1. However, some elements, such as Mo
and Sb, among others, presented notably higher extraction yields in the open system when compared
with the closed one (20% and 3%, and 3% and 1% for
the open and closed systems of Mo and Sb, respectively). B, V, Ge, Cd, Pb and Ni yielded lower or
similar extraction rates in the open systems. For some
elements that are present in concentrations close to the
detection limit, this behavior could be attributed to a
low analytical precision. With the increase of the L/S
ratio (50 500 ml g
1) in the open system, a extraction yield increase is verified for the following elements: Li, Cu, Zn (3 19%), Ge, As (2 10%), Mo
(20 52%), Sb (2 14%), Sn, Ni (1 12%), Cs, Ba, Th,
Tl, Pb, V, U, and most REEs. Thus, higher extraction
yields for Mo, Sb, Ni and As can only be reached with
the use of large water volumes.
According to the leachable proportion obtained in
open and closed systems, the elements may be clas-

M. Pires, X. Querol / International Journal of Coal Geology 60 (2004) 5772

sified as follows: B (43 57%), Mo (3 52%), Cu (3

9%), Ge (4 9%), Li (4 5%), Zn (2 19%), As (1
10%), Ni, Sb, Tl, and U (1 14%). For the other
elements studied, the leachable fraction is in most
cases < 1% of the bulk content.

4. Conclusion
The present results indicate that:


The elemental concentration of the Candiota high

ash coal is within the range of the world coals.
However, the concentration of some elements, such
as Cs, Rb and heavy REEs, are higher than those
element concentrations indicated in the literature.
This might be due to the high content of detrital
minerals of the studied coals.
 Three groups of elements can be recognized based
on the partitioning between coal and fly and
bottom ashes: Group I (volatile elements with
subsequent condensation): As, B, Bi, Cd, Ga, Ge,
Mo, Pb, S, Sb, Sn, Tl and Zn; Group II (no volatile
elements enriched in bottom ash vs. fly ash): Ca,
Fe, Mn, P, Ti and Zr; Group III (low volatile
elements with no partitioning between fly and
bottom ashes): Al, Ba, Be, Co, Cr, Cs, Hf, K, Li,
Mg, Na, Ni, Rb, Sr, Th, U, W, Y and most of REE.
 The leachability of elements is as follows: B (43
57%), Mo (3 52%), Cu (3 9%), Ge (4 9%), Li
(4 5%), Zn (2 19%), As (1 10%), Ni, Sb, Tl,
and U (1 14%),). For the other elements studied,
the leachable fraction is in most cases < 1% of the
bulk content.

Acknowledgements
The present study was supported by FAPERGS,
AECI and IJA-CSIC. We would like to express our
gratitude to Dr. J. Alastuey and Dr. F. Plana for their
valuable comments and expert technical assistance
and to CGTE and Dr. E.C. Teixeira for supplying the
samples. We are especially grateful to Ms. Silvia Rico,
Ms. Merce Cabanas and Mr. Josep Elvira for their
invaluable collaboration in the analytical work, and to
C.A. Palmer and another anonymous reviewer for
their valuable comments and suggestions.

71

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