Fuel 89 (2010) 481493

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Chemical forms of ash-forming elements in woody biomass fuels

Johan Werkelin *, Bengt-Johan Skrifvars, Maria Zevenhoven, Bjarne Holmbom, Mikko Hupa
bo Akademi Process Chemistry Centre, Piispankatu 8, FI-20500 TURKU, Finland

a r t i c l e

i n f o

Article history:
Received 30 June 2008
Received in revised form 28 August 2009
Accepted 3 September 2009
Available online 20 September 2009
Keywords:
Biomass
Ash
Fuel characterization

a b s t r a c t
Advanced fuel characterization helps to predict ash fouling and slagging. Chemical fractionation analysis,
i.e. sequential leaching in H2O, NH4Ac(aq), and HCl(aq), was applied to the biomass of spruce, pine, birch,
and aspen. All of the Cl in the samples and most of the K, Na, and P were water-soluble; most of the Mg
and Mn, and some of the Ca were leached in NH4Ac; most of the Ca was leached in HCl; and most of the Si
and S remained insoluble in the biomass. Ion Chromatography found the water-soluble Cl, P, and S pres2
2
ent as Cl, PO3
4 , and SO4 , respectively, and equimolar concentrations of C2 O4 as leached Ca in the acid
fraction. The biomass solids were determined for anionic groups by methylene blue sorption. The
contents were lowest in the wood samples (22118 mmol/kgD.S.) and highest in the bark samples
(130453 mmol/kgD.S.). The closing of the ion charge balance led to a quantitative model for the ashforming matter: water-soluble salts (KCl, K2HPO4, and K2SO4), acid-soluble minerals (CaC2O4), non-soluble minerals (SiO2), and organically associated ash-forming elements (ionically bonded Ca2+, Mg2+, Mn2+,
and K+, and covalently bonded P and S).
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Biomass is a renewable energy source and replaces fossil fuels
in existing heat and power plants. Biomass comprises all kinds of
matter derived from living organisms, including animals, plants,
trees, crops, and algae. Woody biomass is here dened as the biomass derived from lignied plants, like trees and bushes, of which
the main components are cellulose, hemicelluloses, lignin, and
extractives.
Woody biomass is burned in the whole range of heat-producing
applications from small-scale stoves to large-scale heat and power
generation plants. The pulp and paper industry and wood manufacturing industries have a long tradition of utilizing their by-products: sawdust, wood spill, bark residues, and spent cooking liquors.
There is a signicant potential for use of the fraction that remains
after the outtake of timber: the tree top and branches make up 20
30% of the aboveground biomass in trees.
Ash is a serious concern in biomass combustion, for it causes
slagging, bed agglomeration, fouling, and corrosion in the combustion device, which degrade its performance and severely damage
the ring equipment. Such problems are coupled to the high-temperature chemistry of ash; i.e., its melting and volatility at different
combustion temperatures (8501400 C). The understanding of
these phenomena requires detailed information about the fuel, in
particular, the amount and composition of its ash-forming matter
[1]. It is essential to know the concentrations of the main ash* Corresponding author. Tel.: +358 2 215 4554; fax: +358 2 215 4962.
E-mail address: johan.werkelin@abo. (J. Werkelin).
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.09.005

forming elements (Si, Al, Fe, Ca, Mg, Mn, Na, K, P, S, and Cl) and
the ways they are associated in the fuel as a part of different salts,
minerals, and organic structures [2,3].
In a review from 1996 [3], Bryers summarized the occurrence of
ash-forming matter in biomass fuels, mainly with reference to the
biological literature [4]. Sulphur (S) occurs in two different forms:
as sulphates in salts, or as reduced sulphur in various organic compounds. Chlorine (Cl) is present as chloride in soluble salts. Phosphorus (P) occurs as phosphate, either in inorganic salts or in
organic compounds such as esters and pyrophosphates. Silicon
(Si) is present in oxidized form as silica, whereas the metals aluminium (Al), iron (Fe), calcium (Ca), magnesium (Mg), manganese
(Mn), sodium (Na), and potassium (K) occur as positive metal ions.
These can be present in minerals and precipitated salts and can occur in solution as free ions or complexes. Metal ions may also be
organically associated with biomass bres.
The ash-forming matter in coal is typically studied by X-ray diffraction (XRD) and computer-controlled scanning electron microscope (CCSEM) [5]. These methods are not appropriate for woody
biomass due to its low degree of mineralization. An advanced
method for characterizing biomass is chemical fractionation analysis (CFA) [3,610]. It was developed for analysis of coal in the
1970s [11] and 1980s [12,13], and introduced [14] and standardized [15] for biomass at the end of the 1990s. In CFA, the fuel is leached step-wise in increasingly aggressive solvents: water,
ammonium acetate (a buffer solution), and hydrochloric acid to
classify the ash-forming matter with respect to solubility.
There are no clear guidelines for how to determine and quantify
the modes of ash-forming matter using CFA. For coal, the general

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J. Werkelin et al. / Fuel 89 (2010) 481493

interpretation is that the water step leaches easily soluble salts like
alkali chlorides, sulphates, and carbonates. The buffer step leaches
metal ions that are organically associated in the fuel matrix, and
the acid step leaches acid-soluble salts and minerals like earth alkali carbonates and sulphates. Insoluble silicates are left in the
remaining fraction. Insoluble alkali is bound to them and this fraction of alkali is considered less reactive in combustion, i.e. they do
not contribute to the fouling processes in the boiler [16] or bed
agglomeration problems in uidized bed combustion [6]. An ongoing discussion concerns whether the soluble alkali is released to
the gas phase [17]. So far, there are no generally agreed guidelines
for quantifying this issue with respect to biomass.
The objective of this work is to study woody biomass fuels and
their ash-forming matter: water-soluble salts, organically associated elements, and minerals. This is done by studying 18 selected
samples of woody biomass. The samples represent different types
of biomass (wood, bark, twigs, and foliage) in four different species
(spruce, pine, birch, and aspen) and cover a wide range of concentrations of the main ash-forming elements (Si, Al, Fe, Ca, Mg, Mn,
Na, K, P, S, and Cl). The goal is to identify the various forms of
ash-forming matter present and to quantify them in the studied
samples.
Firstly, the solubility of the main ash-forming elements is
determined by CFA. This results in a water-leached, buffer-leached, acid-leached, and non-leached fraction of each element.
Secondly, the chemical form of the leached elements is investigated by ion chromatography. A distinction was made between
metals and non-metals based on the ability to form positively
and negatively charged ions, respectively. The three liquid fractions from the CFA (the water-, buffer-, and acid-leachates) were
analysed on the expected anionic forms of the non-metals P, S,
2

and Cl: phosphate (PO3
4 ), sulphate (SO4 ), and chloride (Cl ). An2
other anion of interest is oxalate (C2 O4 ). Nitrogen (N) is not an

ash-forming element, but nitrate (NO

3 ) and ammonium (NH4 )
may be associated with the ash-forming matter. Finally, the negative charge of the biomass bres is measured. The untreated and
treated solids from CFA were analysed in terms of their contents
of anionic groups (AG) using the methylene blue sorption method
(MB). The purpose was to balance the charge from the leached
metal ions with the anionic charge in the biomass solids to quantify the presence of organically associated ash-forming elements,
i.e., metal ions that are ionically bonded to the combustible part
of the fuel.

2.1. Chemical fractionation analysis (CFA)

Fig. 1 shows the step-wise leaching procedure of CFA. The procedure in this work was scaled down (1:20) from the standardized
method [15]. About 5 g of dry sample was transferred to a 50 ml PE
ask and sequentially leached:
(1) once in 3050 ml ultra-pure H2O for 24 h under stirring
(65 rpm); and
(2) three times in 3  25 ml 1.0 M NH4Ac(aq) for 3  24 h under
stirring; and
(3) twice in 2  25 ml 1.0 M HCl(aq) for 2  24 h under stirring
and heating (80 C).
After each leaching step (in water, buffer, and acid), the solids
were rinsed two times for 2  10 min with 2  25 ml ultra-pure
H2O and dried for 24 h at 105 C to determine the remaining dry
solids in the sample and some of the solids were removed after
leaching for future analyses of anionic groups. The combined
leaching solvent and rinsing water from each step (hereafter called
leachates) were analysed for element concentrations. The measured pH in the water solutions was between 4.4 and 5.0 for all

Table 1
Generalized results of CFA for all samples.

2. Experimental
a

In a previous work [18], 140 carefully selected samples of different tree parts from four adult trees were collected and analyzed to
determine their main ash-forming elements: Si, Al, Fe, Ca, Mg, Mn,
K, Na, P, S, and Cl. Each tree was of a different species: spruce (Picea
abies), pine (Pinus sylvestris), birch (Betula pubescens), and aspen
(Populus tremula). The sample preparation included drying
(105 C for 2 h) and grinding (1 mm). After the project was completed, the samples were placed in sealed PE bags in dark storage.
For this work, 18 samples were chosen to represent the different
types of biomass present in the four trees:
4 samples of wood: stemwood of spruce, pine, and birch; branch
wood of aspen
4 samples of bark: stembark of spruce, pine, and birch; branch
bark of aspen
4 samples of twigs: the outermost branches of all four species,
<0.4 cm in diameter
2 samples of needles: old foliage (>1 year) of spruce and pine
2 samples of shoots: young foliage (<1 year) of spruce and pine
2 samples of leaves: young foliage (<1 year) of birch and aspen.

Acid-leached
(%)

Non-leacheda
(%)

Metals, leached according to ionic charge

K
75
25
Na
65
b.d.f
Mg
40
60
75
Mnb 25
25
70
Cab
10
0
Alc
Fe
5
0

0
b.d.
<5
<5
5
30
60

0
0
0
0
0
60
35

Metals, exceptions
Cad
5
Mnd 20
e
70
Al

25
65
0

60
15
30

10
0
0

Non-metals
Cl
90
P
65
S
15
Si
5

10
10
5
10

n.a.g
25
15
10

0
0
65
75

Water-leached
(%)

b
c
d
e
f
g

Buffer-leached
(%)

Insoluble fraction was calculated, not measured.

Stemwood.
Samples of spruce, birch, and aspen.
Bark, twigs, and foliage of all four tree species.
Bark, twigs, and foliage of the pine tree.
b.d. = below detection limit.
n.a. = not analysed.

Fig. 1. Chemical fractionation analysis.

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J. Werkelin et al. / Fuel 89 (2010) 481493

Table 2
Original K contents in the samples and leached amounts in the water, buffer, and acid
step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

100000

Acid
ppmD.S.

Wood

Spruce
Pine
Birch
Aspen

215
407
315
1370

173
354
276
1150

60
63
49
235

<11
<10
<10
13

Bark

Spruce
Pine
Birch
Aspen

2030
3180
1710
4730

1360
2840
1100
3380

674
832
334
1230

29
20
21
254

Spruce
Pine
Birch
Aspen

3560
3040
3020
5870

2380
2230
2090
3810

978
594
715
1400

96
30
45
303

Needles

Spruce
Pine

4270
4770

3640
3350

490
592

13
13

Shoots

Spruce
Pine

14,600
8790

12,500
6690

2490
2170

59
77

Leaves

Birch
Aspen

9420
24,000

6680
18,200

2430
6360

76
136

Twigs

Leached K [ppm D.S.]

in water
y = 0.77x

in buffer
y = 0.24x

R2 = 0.99

R2 = 0.95

in acid

10000

1000

100

10
100

1000

10000

100000

Original K content in the samples [ppm D.S.]

Fig. 2. Leached fractions vs. original K contents.

samples. The theoretical pH was 7.0 in the ammonium acetate and

0.0 in the hydrochloric acid.
The analyses of the three liquid fractions (the water-, buffer-,
and acid-leachates) were performed by an accredited laboratory:
20 ml solution was treated with 2 ml concentrated HNO3(aq) and
heated in a microwave oven. The treated solutions were analysed
by induced coupled plasmaatomic emission spectrometry (ICP
AES). The Cl concentrations were determined without acid treatment, after ltration (35 lm), by sector eld mass spectroscopy
(ICPSFMS).
2.2. Ion chromatography (IC)
The CFA yielded three liquid fractions (leachates) from each
sample. The anions in these leachates were analyzed in a Metrohm
Ion Chromatograph using conductivity detection after chemical
suppression. A standard [19] was applied for the determination

of chloride (Cl), sulphate (SO2
4 ), nitrate (NO3 ), phosphate

2
(PO3
4 ), and oxalate (C2 O4 ). To this standard was added acetate

(Ac ). The column (6.1006.530 Metrosep A SUPP 5-250) contained
polyvinyl alcohol with quaternary ammonium groups that separated the ions in the injected sample volume (20 ll). The eluent
ow (0.7 ml/min) contained 1.0 mM NaHCO3(aq) and 3.2 mM Na2CO3(aq) to buffer to pH 10. Before detection, the sodium ions in the
eluent were removed by chemical suppression in a cation exchange column (regenerated with 50 mM H2SO4(aq)).
For the identication and quantication of the six anions, standard solutions of the six anions were prepared from the respective
sodium salts of high purity (pro analysis). The retention times for
the ions in the standards were used for the identication of the
ions in the leachates, and the known concentrations were used
for the quantication. This was achieved by linear correlation with
the peak area.
The analyses were performed in two batches: samples (16)
and samples (718). The sample preparation was identical for both
batches: each leachate was ltrated (35 lm) and diluted in order
to not exceed the maximum concentrations of the calibration

Table 3
Original Na contents in the samples and leached amounts in the water, buffer, and
acid step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Acid
ppmD.S.

Wood

Spruce
Pine
Birch
Aspen

6
15
4
15

<10
17
7
12

<16
<16
<16
<15

<16
<15
<15
<16

Bark

Spruce
Pine
Birch
Aspen

26
22
14
12

17
21
11
<8

<16
<16
<17
<16

<17
<15
<16
<15

Twigs

Spruce
Pine
Birch
Aspen

97
40
43
19

49
24
41
18

34
<17
21
<16

22
18
<15
<16

Needles

Spruce
Pine

48
28

42
28

<18
<19

18
<16

Shoots

Spruce
Pine

13
36

<9
18

<15
34

<17
31

Leaves

Birch
Aspen

32
9

18
<8

<17
<16

18
<13

Leached Na [ppm D.S.]

100

in water
y = 0.78x
R2 = 0.67

in buffer

in acid

10
10

100
Original Na content in the samples [ppmD.S.]

Fig. 3. Leached fractions vs. original Na contents.

484

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 4
Original Mg contents in the samples and leached amounts in the water, buffer, and
acid step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Spruce
Pine
Birch
Aspen

95
189
92
286

26
90
36
141

75
111
60
166

<5
<5
<5
6

Bark

Spruce
Pine
Birch
Aspen

865
874
323
1370

184
328
46
542

701
682
227
827

48
32
13
64

Twigs

Spruce
Pine
Birch
Aspen

909
715
448
644

331
295
148
199

559
386
266
373

51
30
24
31

Needles

Spruce
Pine

1050
804

758
413

303
268

18
10

Shoots

Spruce
Pine

907
1020

504
255

586
747

23
43

Leaves

Birch
Aspen

2030
2940

702
1280

1260
1890

130
171

(100 ppm) or the maximum load of the column. The dilution factor
was 2100.
The water leachates from the second batch were analysed for
ammonium ions (NH
4 ). The samples were sent to an external laboratory, where the concentrations were determined by ion chromatography. The N content of the biomass was also analysed by
an external laboratory: the samples were combusted in oxygen,
and the nitrogen content (N2) of the product gas was measured
to quantify the released N.

2.3. Methylene blue sorption (MB)

A small amount of solids (0.20.5 g) was taken aside from the
samples after each leaching step in CFA (after leaching in water,
ammonium acetate, and hydrochloric acid, respectively). These
solids and the original untreated samples were determined for
AG using the methylene blue sorption method (MB).

Table 5
Original Mn contents in the samples and leached amounts in the water, buffer, and
acid step of CFA.

Wood

Water
ppmD.S.

Buffer
ppmD.S.

10000

Acid
ppmD.S.

10

1
10
100
1000
10000
Original Mg content in the samples [ppmD.S.]
Fig. 4. Leached fractions vs. original Mg contents.

The procedure followed a method developed for pulp bres

[20]. After vacuum drying, 20200 mg of sample was transferred
to a 50 ml mixing ask and mixed with the appropriate volume of
0.4 mM methylene blue, which was prepared in a 0.60 mM barbital buffer (pH 7.8). The volume of added solution was adjusted to
the amount of AG in the samples so that the concentration of free
methylene blue in solution after reaction was 0.10.2 mM. After
20 min with continuous stirring, the solids were removed from
the solution by ltering the mixture through a lter paper in a
Bchner funnel. The resulting solution was diluted (25 times)
with the 0.60 mM barbital buffer and determined for the methylene blue concentration using UVvisible spectroscopy at a wavelength of 664 nm. The concentration was determined by
comparison with a calibration curve prepared from the 0.4 mM
solution diluted at a ratio of 25:250 with the barbital buffer.
The amount of methylene blue absorbed by the biomass solids
was calculated, and the concentration of AG in the dry sample
was determined based on a 1:1 M ratio of the absorbed methylene blue. A blank determination without a sample was performed for each batch of samples, and the loss of methylene

10000

80
57
76
31

3
2
2
3

Spruce
Pine
Birch
Aspen

714
343
534
256

71
76
33
54

486
234
366
143

99
45
82
36

100

Spruce
Pine
Birch
Aspen

496
244
354
183

122
64
66
36

277
135
198
110

105
33
60
21

10

Needles*

Spruce
Pine

1390
839

668
361

434
345

53
44

Shoots*

Spruce
Pine

245
193

98
32

130
127

35
27

Birch
Aspen

1600
667

288
131

715
280

362
146

in water

Leached Mn [ppm D.S.]

16
28
27
16

Leaves*

R2 = 0.85

100

98
81
102
49

Twigs*

R2 = 0.93

in acid
y = 0.05x

1000

Spruce
Pine
Birch
Aspen

Bark*

R2 = 0.87

Acid
ppmD.S.

Wood

Original
ppmD.S.

in water
in buffer
Leached Mg [ppm D.S.]
y = 0.41x
y = 0.62x

in buffer

in acid

y = 0.26x
*y = 0.21x

y = 0.75x y = 0.03x
*y = 0.63x *y = 0.14x

R2 = 0.58

R2 = 0.96

R2 = 0.52

1000
*
*
*

1
10

100

1000

10000

Original Mn content in the samples [ppmD.S.]

Fig. 5. Leached fractions vs. original Mn contents.

485

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 6
Original Ca contents in the samples and leached amounts in the water, buffer, and
acid step of CFA.
Original
ppmD.S.
Wood

Water
ppmD.S.

Buffer
ppmD.S.

Acid
ppmD.S.

100000

Spruce
Pine
Birch
Aspen

724
641
636
998

142
189
156
262

628
484
483
596

39
44
34
182

Spruce
Pine
Birch
Aspen

8350
6350
7860
11,700

359
448
134
849

2960
1910
2010
2870

4260
2830
4430
6660

1000

Spruce
Pine
Birch
Aspen

4320
5300
4730
10,400

403
404
338
501

1730
1170
1450
2020

2500
3640
2380
6610

100

Needles*

Spruce
Pine

8030
4140

261
342

514
595

6572
2508

Shoots*

Spruce
Pine

1670
2370

24
54

200
831

1374
1457

Birch
Aspen

9120
9800

575
747

2240
2360

6050
5440

Bark*

Twigs*

Leaves*

blue in the blank was subtracted from the amounts absorbed by

the samples.
The determination of a batch of samples was repeated the following day, each time with a new blank and a new calibration
curve. Some samples were analyzed 68 times, but the typical repetition frequency was 34 times, and some samples were analyzed
only twice. The results from all analyses were included in the calculation of the average AG content and the standard deviation for a
sample. Instead of using the calibration curve and the blank for
each batch, the average calibration curve and the average blank
were used for all samples.

3. Results
The CFA divides the element contents of the samples into four
fractions: the water-leached fraction, the buffer-leached fraction,
the acid-leached fraction, and the non-leached fraction. The non-

Table 7
Original Al contents in the samples and leached amounts in the water, buffer, and acid
step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Acid
ppmD.S.

Spruce
Pine
Birch
Aspen

2
4
2
6

<2
<3
<3
<2

<3
<3
<3
<3

<3
<2
<2
<3

Spruce
Pine*
Birch
Aspen

98
908
19
20

35
792
<3
2

5
23
<3
<3

43
230
5
7

Spruce
Pine*
Birch
Aspen

221
332
23
35

12
171
<0
5

<4
8
<3
<3

53
105
8
11

Needles

Spruce
Pine*

83
374

23
198

<3
14

37
98

Shoots

Spruce
Pine*

27
331

8
106

<3
<4

10
143

Leaves

Birch
Aspen

40
20

<2
1

<3
<3

9
11

Wood

Bark

Twigs

in water

Leached Ca [ppmD.S.]

in buffer
y = 0.71x

in acid

y = 0.25x
*y = 0.06x

*y = 0.24x

y = 0.06x
*y = 0.60x

R2 = 0.58

R2 = 0.58

R2 = 0.88

10000

*
*
*

10
100

1000

10000

100000

Original Ca content in the samples [ppm D.S. ]

Fig. 6. Leached fractions vs. original Ca contents.

leached fraction is calculated by subtracting the leached fractions

from the original contents. The IC identies and quanties the anions in the liquid fractions and the MB measures the concentrations of anionic groups in the solid fractions. The total anionic
charge from the anions and the anionic groups is then compared
with the cationic charge from the leached metals.

3.1. Leached elements

Table 1 shows the generalized results of the CFA for all 18 samples: the typical percentages of the water-, buffer-, and acid-leached fractions of each element. The water step leached most of
the K (75%) and Na (65%), some of the Mg (40%), Mn (25%), and
Ca (25%), and only a small fraction of the Al (10%) and Fe (5%);
the buffer step leached the remainder of K (25%), Mg (60%), Mn
(75%) and Ca (70%); and the acid step leached a large part of the
Fe (60%) and Al (30%). Exceptions comprised the bark, twigs and foliage of all four species: the acid step leached most of the Ca (60%)
and some of the Mn (15%); and the water and buffer step leached

Leached Fe [ppm D.S.]

10000

in water in buffer in acid

*y = 0.75x y = 0.03x y = 0.32x
R2 = 0.85 R2 = 0.88 R2 = 0.90

1000

*
100

10

10

100
1000
10000
Original A1 content in the samples [ppmD.S.]

Fig. 7. Leached fractions vs. original Al contents.

486

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 8
Original Fe contents in the samples and leached amounts in the water, buffer, and
acid step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Acid
ppmD.S.

Spruce
Pine
Birch
Aspen

4
8
6
5

<0
1
<1
<0

<1
<1
<1
<1

2
9
8
6

Bark

Spruce
Pine
Birch
Aspen

39
52
24
27

3
14
<1
1

<1
3
<1
1

36
57
16
20

Twigs

Spruce
Pine
Birch
Aspen

167
73
40
35

2
5
2
1

2
4
<1
<1

75
36
27
26

Needles

Spruce
Pine

45
40

2
3

<1
<1

32
19

Shoots

Spruce
Pine

43
113

4
2

<1
<1

35
53

Leaves

Birch
Aspen

83
56

1
3

1
1

60
50

Wood

smaller fractions of Ca (5% and 25%, respectively) and Mn (20% and

65%, respectively). The high Al contents in the pine samples were
readily leached in the water step (70%). The leaching of non-metals
in CFA showed a consistent trend for all 18 samples: both Cl and P
were completely soluble in the CFA, whereas S and Si were mainly
insoluble (70% and 75%, respectively). The water step leached almost all Cl (90%), most P (65%) and some S (15%) and Si (5%). All
four non-metals were sparsely leached in the buffer step (5
10%), whereas the acid step leached the remaining P (25%), some
S (15%), and Si (10%).
Each of Tables 212 shows individual results for the 18 samples
from the leaching of one element: the original concentration in the
samples and the leached fraction in the three leaching steps. All
numbers, original contents and leached fractions, are given in mg
of element per kg of dry biomass solids (ppmD.S.). Adjacent to the
tables are gures (Figs. 212) showing a loglog diagram, wherein
the leached amounts are plotted versus the original contents in the

Table 9
Original Cl contents in the samples and leached amounts in the water, buffer, and acid
step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Acid
ppmD.S.

Leached Fe [ppm D.S.]

in buffer

1000

in acid
y = 0.57x
R2 = 0.68

100

10

1
1

10
100
1000
Original Fe content in the samples [ppmD.S.]

Fig. 8. Leached fractions vs. original Fe contents.

samples (also the insoluble fractions are plotted for Si and S). A
trend line is drawn that shows the correlations between the leached amounts and the original contents, which was used to generalize the results shown in Table 1. The equation of the trend line is
given in the diagrams together with the squared correlation coefcient (R2).
The 18 samples represent a large variety of biomass: the
element contents in the samples range over several orders of
magnitude. The major ash-forming elements are Ca and K, and
the minor elements are Na and Fe. The concentrations of P, K, S,
Cl, and Mg increase according to the order wood < bark < twigs < old foliage (needles) < young foliage (shoots and leaves). Also
the concentrations of Ca, Mn, Si, and Al are lowest in the wood
samples, but the highest concentrations are as follows: Al in pine
bark; Mn in birch leaves; Si in spruce needles; and Ca in aspen
bark.
The leaching of the metals correlates with their ionic charge in
the biomass: the more aggressive solvents are needed for leaching
metal ions with higher valences. Tables 2 and 3 and Figs. 2 and 3

in water
y = 0.91x
R2 = 1.00

Leached Cl [ppmD.S.]
10000

Wood

Spruce
Pine
Birch
Aspen

51
85
40
35

39
26
10
59

9
15
21
14

n.a.
n.a.
n.a.
n.a.

1000

Bark

Spruce
Pine
Birch
Aspen

260
147
149
40

303
192
45
188

39
211
23
27

n.a.
n.a.
n.a.
n.a.

100

Twigs

Spruce
Pine
Birch
Aspen

317
200
120
87

388
195
183
206

45
24
27
16

n.a.
n.a.
n.a.
n.a.

10

Needles

Spruce
Pine

504
407

465
248

77
41

n.a.
n.a.

Shoots

Spruce
Pine

1090
538

1090
686

89
73

n.a.
n.a.

Leaves

Birch
Aspen

181
511

149
471

105
62

n.a.
n.a.

n.a. = not analysed.

in water

in buffer
y = 0.12x
R2 = 0.57

1
10

100

1000

10000

Original Cl content in the samples [ppmD.S.]

Fig. 9. Leached fractions vs. original Cl contents.

487

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 10
Original P contents in the samples and leached amounts in the water, buffer, and acid
step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Spruce
Pine
Birch
Aspen

4
41
49
191

<3
31
32
138

<5
9
7
12

<5
10
15
19

Bark

Spruce
Pine
Birch
Aspen

452
1260
428
663

160
697
243
385

26
147
24
46

135
293
73
115

Twigs

Spruce
Pine
Birch
Aspen

1080
848
820
708

460
428
397
496

150
64
57
30

270
275
211
132

Needles

Spruce
Pine

1540
1270

773
392

125
110

383
429

Shoots

Spruce
Pine

3830
2590

2230
1940

262
274

892
448

Leaves

Birch
Aspen

3140
5140

1710
4140

313
485

878
273

show that the monovalent ions of alkali metals (K+ and Na+) are
leached primarily in the water step (75%) and secondarily in the
buffer step (25%). Tables 46 and Figs. 46 show that the divalent
ions of earth alkali metals (Mg2+ and Ca2+) and the transition metal
Mn (probably as Mn2+) are readily leached in the buffer step (60%,
75%, and 70%, respectively), but that Ca and Mn in the bark, twigs
and foliage are exceptions from this rule. A large portion of the Ca
and some of the Mn in the bark, twigs and foliage are leached in the
acid step (some 60% and 15%, respectively), and the buffer-leached
fractions are consequently smaller (some 25% and 65%, respectively). Tables 7 and 8 and Figs. 7 and 8 show that the trivalent ions
of the group-3 metal Al (Al3+) and the transition metal Fe (probably
as Fe3+) are leached primarily in the acid step (30% and 60%, respectively), but that the pine samples are exceptions from this rule. The
high Al contents in the pine bark, twigs and foliage are mainly leached in the water step (70%).

Table 11
Original S contents in the samples and leached amounts in the water, buffer, and acid
step of CFA.

Wood

Water
ppmD.S.

Buffer
ppmD.S.

10000

Acid
ppmD.S.

Wood

Original
ppmD.S.

Leached P [ppmD.S.]

Acid
ppmD.S.

10

1
10

100

1000

10000

Original P content in the samples [ppmD.S.]

Fig. 10. Leached fractions vs. original P contents.

Tables 912 and Figs. 912 show that both Cl and P are completely soluble in the CFA, whereas S and Si are mainly insoluble
(70% and 75%, respectively). All four non-metals are sparsely leached in the buffer step (510%). The Cl was almost completely leached in the water step (90%), and the P was mainly leached in the
water step (65%) and the remaining fraction in the acid step (25%).
The S was equally leached in the water step (15%) and the acid step
(15%).
A signicant fraction of the dry solids was lost in the leaching.
This fraction of the biomass was dissolved in the liquids. Below
is a summary of the loss of dry mass in the three leaching steps
(average standard deviation):
Loss in the water step:
 3 1% of the dry mass in the wood samples;
 16 8% of the dry mass in the bark samples;
 10 4% of the dry mass in twigs (both wood and bark material); and
 18 5% of the dry mass in the foliage.

S [ppm D.S.] in water in buffer in acid insoluble

y = 0.15x y = 0.04x y = 0.15x y = 0.71x
10000
2
R2 = 0.69 R = 0.82 R2 = 0.94 R2 = 0.96

<3
5
<4
28

<5
<5
<5
<5

15
11
9
33

1000

Spruce
Pine
Birch
Aspen

367
311
329
520

68
62
19
143

16
13
<6
25

47
46
29
103

100

Spruce
Pine
Birch
Aspen

776
587
493
479

118
111
62
83

44
16
13
12

101
111
64
65

Needles

Spruce
Pine

704
845

139
94

26
25

94
101

Shoots

Spruce
Pine

1320
1250

152
208

47
66

193
182

Birch
Aspen

1690
2560

69
888

32
144

219
553

Leaves

in acid
y = 0.24x
R2 = 0.94

100

50
94
82
125

Twigs

in buffer
y = 0.09x
R2 = 0.94

1000

Spruce
Pine
Birch
Aspen

Bark

in water
y = 0.67x
R2 = 0.93

10

1
10

100

1000

10000

Original S content in the samples [ppm D.S.]

Fig. 11. Leached and insoluble vs. original S contents.

488

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 12
Original Si contents in the samples and leached fractions in the water, buffer, and acid
step of CFA.
Original
ppmD.S.

Water
ppmD.S.

Buffer
ppmD.S.

Si [ppm D.S.]

in water

10000

Acid
ppmD.S.

Wood

Spruce
Pine
Birch
Aspen

59
123
77
63

3
<1
<1
5

5
<1
<1
6

7
5
4
5

Bark

Spruce
Pine
Birch
Aspen

171
60
114
94

12
7
2
7

38
4
<1
9

24
5
9
10

Twigs

Spruce
Pine
Birch
Aspen

982
312
69
188

18
10
3
12

35
5
2
3

63
34
15
13

Needles

Spruce
Pine

6640
549

40
10

702
136

800
108

Shoots

Spruce
Pine

300
747

96
37

70
29

26
64

Leaves

Birch
Aspen

318
133

13
71

28
186

23
39

in buffer in acid insoluble

y = 0.11x y = 0.12x y = 0.76x
R2 = 0.91 R2 = 0.99 R2 = 1.00

1000

100

10

1
10

100

1000

10000

Original Si content in the samples [ppm D.S.]

Fig. 12. Leached and insoluble vs. original Si contents.

(0.35 lm) to remove the suspended particles before analysis. The

comparison showed that all leached elements were dissolved in
the solution.

Loss in the buffer step:

 3 4% of the dry mass in all 18 samples.
Loss in the acid step:

3.2. Leached anions

 22 4% of the dry mass in all 18 samples.

The loss of dry solids in the water step was due to wood extractives being dissolved. Wood extractives are organic compounds
with low molecular weight, some of which are water-soluble.
Wood extractives account for up to 5% of the dry solids in wood
[22] and around 30% of the dry solids in bark [23]. The foliage
can contain even larger amounts. The loss of dry solids in hydrochloric acid was due to hydrolysis of the hydrocarbons, which
causes a fraction of the biomass polymers to dissolve in the liquid.
The dissolved wood extractives in the water step formed a suspension upon storing. To investigate if the suspension contained
ash-forming elements, 12 parallel water-samples were ltrated

Leached PO43
[mmol/kgD.S.]

Table 13
Leached PO3
4 in the water, buffer, and acid step of CFA.
Water
mmol/kgD.S.

Buffer
mmol/kgD.S.

Acid
mmol/kgD.S.

Wood

Spruce
Pine
Birch
Aspen

n.d.
1.0 0.0
0.7 0.1
5.7 0.3

n.d.
n.d.
n.d.
0.6 0.0

n.d.
n.d.
n.d.
n.d.

Bark

Spruce
Pine
Birch
Aspen

4.5 0.3
16 0.9
6.1 0.8
13 1.0

0.4 0.0
2.3 0.0
n.d.
1.8 0.0

0.4 1.0
4.0 0.0
n.d.
n.d.

Twigs

Spruce
Pine
Birch
Aspen

17 0.9
11 1.4
9.2 1.0
5.6 1.7

2.9 1.0
n.d.
n.d.
3.9 1.0

4.3 0.0
n.d.
2.4 1.0
n.d.

Needles

Spruce
Pine

21 1.0
9.4 1.3

n.d.
2.9 0.0

3.5 0.0
3.9 0.0

Shoots

Spruce
Pine

64 4.1
50 0.1

5.6 0.0
5.3 0.0

4.5 1.0
5.0 3.0

Leaves

Birch
Aspen

41 6.3
113 3.0

5.8 1.0
13 0.0

6.2 0.0
n.d.

n.d. = not detected.

Tables 1316 show the measured amounts of the leached anions from all 18 samples (mmol/kgD.S.) and the standard deviations
in the measurements. Adjacent to the tables are for comparison
Figs. 1316, which show diagrams where the measured amounts
of leached anions are plotted versus the measured amounts of leached elements (data from Part 1) in the same leachates: chlorine
2
(Cl) for Cl, phosphorus (P) for PO3
4 , and sulphur (S) for SO4 .
2
The amount of leached C2 O4 was compared with the amount of
leached calcium (Ca) to determine the leaching of calcium oxalate
minerals (CaC2O4). No NO
3 was detected in the leachates, and the
detected Ac did not originate in the biomass. The NH
4 was compared with the nitrogen (N) content of the solid, untreated sample.

1000.0

in water
y = 0.83x
R2 = 0.99

in buffer
y = 0.70x
R2 = 0.85

in acid

100.0

10.0

1.0

Leached P
[mmol/kgD.S.]
0.1
0.1

1.0

Fig. 13. Leached

10.0
PO3
4

100.0

vs. P in the three leachates.

1000.0

489

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 14
Leached SO2
4 (mmol/kgD.S.) in the water, buffer, and acid step of CFA.
Water
mmol/kgD.S.

Buffer
mmol/kgD.S.

Acid
mmol/kgD.S.

Wood

Spruce
Pine
Birch
Aspen

0.1 0.0
0.3 0.0
0.1 0.0
2.6 0.1

0.2 0.0
n.d.
0.4 0.0
0.3 0.0

0.4 0.0
n.d.
n.d.
0.8 0.0

Bark

Spruce
Pine
Birch
Aspen

2.0 0.1
2.4 0.0
1.1 0.2
13 0.3

0.4 0.0
n.d.
6.8 2.0
1.3 0.0

2.0 0.0
0.8 0.0
1.8 1.0
5.5 1.0

Twigs

Spruce
Pine
Birch
Aspen

6.3 0.1
2.6 0.1
1.0 0.0
7.9 0.2

1.5 2.0
n.d.
n.d.
n.d.

1.8 0.0
0.6 0.0
0.5 0.0
n.d.

Needles

Spruce
Pine

4.3 0.1
3.0 0.1

n.d.
0.3 0.0

0.8 0.0
0.6 0.0

Shoots

Spruce
Pine

1.3 0.9
3.4 0.1

0.8 0.0
0.8 0.0

1.2 0.0
1.6 2.0

Leaves

Birch
Aspen

1.8 0.4
15 0.4

6.1 2.0
17 24

0.3 0.0
2.2 1.0

Leached SO42
[mmol/kg D.S.]
100.0

in water
y = 0.64x
R2 = 0.42

in buffer

in acid

10.0

1.0

Leached S
[mmol/kgD.S.]
0.1
0.1

1.0

10.0

100.0

Fig. 14. Leached SO2

4 vs. S in the three leachates.

n.d. = not detected.

All or most of the Cl, P, and S in the water and buffer leachates
was present as chloride (Cl), phosphate (PO3
4 ), and sulphate
(SO2
4 ). A much smaller fraction of the P and S in the acid leachates
2
was present as phosphate (PO3
4 ) and sulphate (SO4 ). The water
leached ammonium (NH4 ) constituted only 0.11.4% of the total
N in the original samples, and its inuence on the overall charge
balance is small.
Large amounts of oxalate were present in the acid leachates,
and the amounts correlated on a 1:1 ratio with the amounts of
leached Ca. The concentrations were high from the samples of
bark, twigs, and foliage, and they were low from the samples of
wood. Only small amounts of oxalate (C2 O2
4 ) were present in the
water and buffer leachates compared to the amount of leached Ca.
Fig. 17 shows chromatograms for the three leachates of spruce
twigs. These exhibit typical peaks observed for all samples. The
identied peaks are labeled, but unidentied peaks are present in
all three leachates. The water leachates had several unidentied

Table 15
Leached Cl (mmol/kgD.S.) in the water, buffer, and acid step of CFA.
Water
mmol/kgD.S.

Buffer
mmol/kgD.S.

Acid
mmol/kgD.S.

Wood

Spruce
Pine
Birch
Aspen

1.2 0.0
0.9 0.0
0.5 0.0
1.7 0.0

n.d.
b.d.
b.d.
n.d.

n.a.
n.a.
n.a.
n.a.

Bark

Spruce
Pine
Birch
Aspen

9.6 0.1
6.6 0.0
2.5 0.1
6.2 0.0

n.d.
b.d.
b.d
n.d.

n.a.
n.a.
n.a.
n.a.

Twigs

Spruce
Pine
Birch
Aspen

5.2 0.0
3.9 0.1
3.0 0.0
2.8 0.0

b.d.
b.d.
b.d.
b.d.

n.a.
n.a.
n.a.
n.a.

Needles

Spruce
Pine

11 0.0
7.6 0.0

b.d.
n.d.

n.a.
n.a.

Shoots

Spruce
Pine

33 0.7
13 0.0

2.4 1.0
b.d.

n.a.
n.a.

Leaves

Birch
Aspen

6.8 0.0
20 0.2

b.d.
1.4 0.0

n.a.
n.a.

n.d. = not detected; b.d. = below detection limit; and n.a. = not analyzed.

peaks around 57 min. The unidentied peaks were larger and

more frequent in the water leachates from the foliage than in those
from the wood, bark, and twigs. The acetate and acid leachates had
peaks around 4 min, before the dip in the baseline, and a broad
peak at 1015 min. These leachates were strongly dominated by
the acetate and chloride ion, respectively, which caused a heavy
load on the column.
3.3. Anionic groups
Table 17 shows the concentrations of AG in the 18 samples of
woody biomass before and after the water-, buffer-, and
acid-leaching steps in CFA. The concentrations are expressed in
terms of mmol AG per kg of dry solids, which corresponds to
meq (milli equivalents) of negative charge per kg of dry biomass.
The concentration of AG in the biomass was lowest in the wood
samples (22118 mmol/kgD.S.) and highest in the bark samples
(130453 mmol/kgD.S.). The concentrations after water-, buffer-,

Leached Cl
[mmol/kgD.S.]
100.0

in water

in buffer

y = 0.98x
R2 = 0.86

10.0

1.0

Leached Cl
[mmol/kgD.S.]
0.1
0.1

1.0

10.0


Fig. 15. Leached Cl vs. leached Cl.

100.0

490

J. Werkelin et al. / Fuel 89 (2010) 481493

Table 16
Leached C2O42 (mmol/kgD.S.) in the water, buffer, and acid steps.
Water
mmol/kgD.S.

Buffer
mmol/kgD.S.

Acid
mmol/kgD.S.

Wood

Spruce
Pine
Birch
Aspen

0.4 0.0
0.5 0.1
0.3 0.0
0.7 0.1

0.2 0.0
n.d.
1.3 1.0
1.0 0.0

0.4 0.0
0.4 0.0
0.9 0.0
4.3 1.0

Bark

Spruce
Pine
Birch
Aspen

1.7 0.1
1.7 0.1
0.4 0.1
1.4 0.2

1.6 0.0
3.8 1.0
1.6 1.0
3.2 0.0

88 7.0
61 1.0
90 3.0
190 2.0

Twigs

Spruce
Pine
Birch
Aspen

0.3 0.0
0.9 0.1
0.9 0.1
2.0 0.3

6.6 2.0
2.4 0.0
2.1 0.0
3.8 2.0

58 0.0
79 4.0
49 1.0
137 2.0

Needles

Spruce
Pine

2.0 0.1
2.1 0.1

2.1 1.0
6.6 0.0

154 1.0
60 1.0

Shoots

Spruce
Pine

2.1 0.9
10 0.1

24 0.0
12 3.0

51 5.0
33 3.0

Leaves

Birch
Aspen

1.0 0.2
3.2 0.7

5.5 2.0
3.5 0.0

122 1.0
111 10

n.d. = not detected.

in water

in buffer

in acid
y = 0.90x
R2 = 0.95

1000.0

100.0

10.0

1.0

Leached Ca2+
[mmol/kgD.S.]
0.1
0.1

1.0

10.0

100.0

1000.0

2+
Fig. 16. Leached C2 O2
in the three leachates.
4 vs. Ca

and acid-leaching were not signicantly different from those in the

untreated biomass, indicating that.
1. The associated metal ions were effectively exchanged for methylene blue.
2. Treatment in the water, buffer, or acid did not destroy or create
any AG, and
3. The leached dry solids in the water and acid steps (see Part 1)
contained amounts of AG similar to those in the non-leached
fraction of the samples.
The above effects may perhaps compensate for one another, but
the key result was that different types of biomass, i.e., wood, bark,
twigs, and foliage of the four species, showed signicant differences in AG contents, which has signicant implications for the total charge balance of the leached ash-forming matter.

Table 17
The charge from anionic groups (AG) in the samples (meq/kgD.S.) before leaching and
after each leaching step.
Before
leaching
(meq/kgD.S.)
Wood

Leached C2O42
[mmol/kgD.S.]

After waterleaching
(meq/kgD.S.)

After bufferleaching
(meq/kgD.S.)

After acidleaching
(meq/kgD.S.)

3.4. Charge balance

The metals are present in oxidized form in the biomass, and the
charge of each can be calculated from the corresponding ions (K+,
Na+, Mg2+, Mn2+, Ca2+, Al3+, and Fe3+). This charge may be balanced
2
2

by the negative charge from the anions (PO3
4 , SO4 , Cl , and C2 O4 )
and the AG content of the biomass. The pH is a key parameter in
the calculation of the charge from ionic species in the biomass
and leachates. The free oxonium H3O+ and hydroxide OH concentrations do not inuence the charge balance other than in very
acidic (pH < 2) or saline (pH > 12) solutions, but they have a significant inuence on the charge of other ionic species by protonation
of anions and hydration of metal ions.
The phosphate is monovalent (H2 PO
4 ) in the water leachate at
)
in
the
eluent
at pH 10 used for deterpH 4.55.0, divalent (HPO2
4
mination by ion chromatography, and without charge (H3PO4) in
the acid leachate at pH 0. In the neutral pH of the buffer leachate,
the monovalent and divalent forms coexist at a ratio close to 1:1.
The average charge of the phosphate ion in neutral pH is around
1.5.
The P contents in the woody biomass of the four investigated
species were correlated to the presence of living cells in different

2-

C2O4

Spruce
Pine
Birch
Aspen

86 7
38 18
52 4
91 6

90 8
22 13
54 9
115 3

93 17
53 3
49 16
107 1

77 9
52 16
51 17
118 8

Spruce
Pine
Birch
Aspen

448 33
253 39
145 72
397 18

368 99
125 21
134 48
321 17

453 37
299 52
130 28
375 11

387 63
239 90
177 66
372 19

Spruce
Pine
Birch
Aspen

171 12
172 39
185 42
179 55

87 48
156 38
121 39
149 45

193 62
221 14
170 4
225 34

188 60
182 28
164 34
221 33

Needles

Spruce
Pine

167 11
147 17

128 38
129 23

164 38
195 40

118 51
164 20

water-leachate

Shoots

Spruce
Pine

140 18
165 97

167 10
109 65

103 31
125 32

118 17
127 56

Retention time (min)

Leaves

Birch
Aspen

201 18
505 31

110 93
502 28

217 51
328 99

202 68
416 42

Bark

Twigs

Ac

3PO4

Cl

2-

SO4
Ac

acid-leachate

3PO4

2-

Cl

C2O4

buffer-leachate

3-

Cl

PO4

10

15

2SO4

20

2-

C2O4

25

30

Fig. 17. Chromatograms of leachates from spruce twigs.

491

J. Werkelin et al. / Fuel 89 (2010) 481493

tree parts [18]. In the solution inside living cells, which has high P
concentrations [27], the pH is close to neutral, and the average
charge of the phosphate ion in the biomass is therefore 1.5. The
K and S contents in all samples were strongly correlated to the P
contents (R2 = 0.92), as were the Cl contents (R2 = 0.64). All these
elements are strongly coupled to the living cells [27], as is oxalate
2
2

[26]. The anions PO3
4 , SO4 , Cl , and C2 O4 , are present as watersoluble salts with the metal ion K+ in the biomass. The negative
charge of these anions in the neutral pH of the cell solution is
1.5, 2, 1, and 2, respectively, and an equivalent amount of K is
bound in these salts. The anionic groups in woody biomass originate in the carboxylic groups (R-COO) in hemicelluloses, pectines,
and tannins (in bark). Their afnity to different metals increases
with the charge of the metal ion so that a higher charge creates a
stronger bond to the AG [21]. The acid-leached Al and Fe may also
have been ionically bound to the AG. Their presence as trivalent
ions (Al3+, and Fe3+) and their insolubility in neutral pH may explain why these metals were leached mainly in the acid step.
Fig. 18 shows the charge balance for the ash-forming matter in
the three leached fractions of CFA. The 18 samples in this work represent the large variety of biomass present in trees. Their concentrations of ash-forming elements range over several orders of
magnitude. However, the closing of the charge balance for the leached elements makes it possible to quantify the different forms of
ash-forming matter.

1400
1200
1000
800
600
400
200
0

4. Discussion
The balance between negative and positive charge for the
water- and buffer-leached fractions of ash-forming elements is explained by the presence of water-soluble metal salts of chlorides,
phosphates, sulphates, oxalates, and non-identied, probably organic, anions. The unidentied peaks in the water leachates may
originate in organic anions from the leached wood extractives.
Since these anions were not identied, the charge could not be
quantied.
The small amounts of Cl, P, and S in the buffer leachates were in
the same form as in the water leachates, which strengthened the
hypothesis that the buffer-leached fraction of these elements resulted from traces of a water-soluble fraction. Their presence could
be due to insufcient leaching in the rst step or non-ideal mixing
in the washing between the rst and the second leaching steps.
The balance between the negative and positive charge for the
acid-leached and non-leached fractions of ash-forming elements
is explained by the presence of the following ash-forming matter:
calcium oxalate dihydrate (acid-soluble mineral), organically associated P and S (insoluble, covalently bonded elements), and polymerized silicic acid (insoluble mineral).
The non-metal Si was mainly in the insoluble fraction. The Si in
trees originates in polymerized silicic acid [24], i.e., opal, which is
an amorphous mineral of silica with varying amounts of crystal
water (SiO2nH2O(s)). According to Van Lier [25], the solubility of
quartz (SiO2(s)) in pure water at 25 C is 6 mg Si per litre (ppm).
Quartz has lower solubility than amorphous silica, and the Si concentrations in the water, buffer, and acid solutions were at most 8,
32, and 51 ppm, respectively.
Calcium oxalate (CaC2O4) is a mineral that forms in many types
of plants [26]. In this work, CFA proved to be a successful tool for
quantifying this mineral in different samples of woody biomass.
Although a fraction of the total Fe (3/5), Al (1/3), and Mn (1/6)
and trace amounts of the total Mg (1/20) and K (<1/20) were also
leached in the acid step, the dominating counter-ion for the oxalate
was Ca2+. The small amounts of oxalate (C2 O2
4 ) leached in the
water and acetate steps did not correlate with the amount of leached Ca in these fractions. Its negative charge, however, balanced
some of the positive charge from the leached metals in these
fractions.
According to the mass balance for the leached Ca and the original contents in the samples, a fraction of the Ca in the bark, twigs,

meq/kg D.S.
Leached ions in water
Leached ions in acetate
Anionic groups in solids
Leached ions in acid

++++++++++++++++++
W B Tw N S W B Tw N S W B Tw L W B Tw L
Spruce

Pine

Aspen

Birch

Fig. 18. Charge balance in the ash-forming matter of the 18 samples expressed as
meq/kgD.S. (W = wood, B = bark, Tw = twigs, N = needles, S = shoots; L = leaves).

ash-forming
elements

Si

Al

water-soluble
salts

70%

Fe

Ca

Mg

Mn

Na

70%

15%

P
75%

K2HPO4
KH2PO4

Al(OH)3

organically
associated
ion-exchangable
metal ions

Mg2+
Ca2+

2+

Al3+ Fe3+
included
minerals
excluded
minerals

(Ca,Mn)C2O42H2O
SiO2

Cl
25%

K2SO4 KCl
organically
associated
covalently
bonded
non-metals

Na+ K+
Mn

Org-P

Org-S

quartz, feldspar, clays, earth minerals

Fig. 19. Ash-forming elements and their chemical forms in woody biomass fuels. The colours indicate the solubility in the CFA: water-soluble (blue), buffer-soluble (yellow),
acid-soluble (red) or insoluble (grey). The dashed lines apply to only certain fuel types ( = bark and forest residue of pine; * = bark and forest residue of all four species). The
dotted line applies to fuel impurities, of which the amounts may vary and for which the solubility is unknown (but typically insoluble).

492

J. Werkelin et al. / Fuel 89 (2010) 481493

and foliage remains in the non-leached fraction. This fraction, however, corresponds to less than 10% of the acid-leached fraction, and
unless a fraction is bound in the biomass silicates, it may be calcium oxalate that did not dissolve in the acid treatment. The latter
possibility seems more likely, and the non-leached fraction of Ca
was regarded as non-leached calcium oxalate.
The acid-leached P and S may originate in an organically bound
fraction, for these non-metals form strong covalent bonds with organic molecules in the biomass. Since the acid-leached P and S
2
were generally not present as PO3
4 and SO4 , and since the leached
amounts correlated with the loss of dry mass in the acid step, the
likely source of these fractions is in the organic matrix. The acidleached P and S were therefore assigned to the same class as the
non-leached fraction of these elements: insoluble, organically
associated elements (covalently bonded).
Fig. 19 shows a model for the ash-forming matter in woody biomass fuels based on the results in this work. Of the ash-forming
elements in woody biomass, all the Cl, three quarters of the P,
and one quarters of the S occur in a portion of the water-soluble
potassium salts: KCl, KH2PO4, and K2SO4. In bark and forest residue
fuels, 70% of the total Ca is present as calcium oxalate minerals:
CaC2O4, which perhaps contain small amounts of Mn in solid solution. Furthermore, 70% of the Al content in the biomass of pine may
be present as water-soluble Al(OH)3. The remaining metals are
organically associated: the major fraction is dispersed in ionexchangeable form with the anionic groups in the fuel matrix,
but a minor fraction could be in dissolved form with organic anions. The remaining fractions of P and S (one quarter and three
quarters, respectively) are organically associated by strong covalent bonds to the organics in the fuel matrix. Finally, all the Si is
present as silica (SiO2). However, Si of biological origin is amorphous silica [24], while Si from impurities occurs in the form of
crystalline silicates.
5. Conclusions
The results from this work were combined into a quantitative
model for the ash-forming matter in woody biomass fuels. This
new information allows better ash predictions in biomass combustion systems. Based on the element concentrations in a fuel, the
ash-forming matter can be described in terms of water-soluble
salts: KCl, KH2PO4, and K2SO4; minerals (acid- and non-leachable):
CaC2O4 and SiO2; and organically associated ash-forming elements
(ionically bonded metal ions: K+, Na+, Mg2+, Mn2+, Ca2+, Al3+, and
Fe3+, and covalently bonded non-metals: P and S).
The work comprised the use of three different analytical tools to
study pure samples of wood, bark, twigs (small branches), and foliage (needles, shoots and leaves) of four different wood species:
spruce, pine, birch, and aspen:
Chemical fractionation analysis (CFA) classied the solubility of
11 ash-forming elements by step-wise leaching in water, ammonium acetate and hydrochloric acid.
Ion chromatography (IC) determined the concentrations of dissolved anions; and
Methylene blue sorption (MB) determined the concentration of
anionic groups (AG) in the samples and in the solid residues
after each leaching step in the CFA.
These tools are not new; they are standardized methods for
analysis of different materials. However, the use of the last two
methods in fuel research is novel, and the results give new insights
to the chemical forms of the ash-forming matter in woody biomass
fuels.
The results in this paper may be applied for advanced ash predictions. The contents of ash-forming elements are determined in

different fuel compartments and critical levels may suggest measures for fuel pre-treatment. The speciation and quantication of
ash-forming matter in woody biomass fuels open the door to kinetic modelling. This may render new insights in the predictions
of ash-related problems in combustion systems. In combination
with CFD modelling, kinetic predictions are the basis for a sound
universal model for ash behaviour.
Acknowledgements
Pia Leppsalo, Ben Ohran and Rama Jampana are thanked for
their laboratory work with CFA; Luis Bezerra and Pramod Jangaon
are thanked for their laboratory work with IC, and Jonas Konn and
Seelam Prem Kumar are thanked for their laboratory work with
MB. Debby Repka of WISEonline has helped to improve the language in this paper. This project was part of the activities of the
bo Akademi Process Chemistry Centre, funded by the Academy
of Finland through its Centre of Excellence program. We gratefully
acknowledge the nancial support of the Finnish Graduate School
of Chemical Engineering and the TEKES project ChemCom and its
industrial partners.
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