Fuel 105 (2013) 40–76

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Fuel
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Review article

An overview of the composition and application of biomass ash. Part 1.

Phase–mineral and chemical composition and classification
Stanislav V. Vassilev a,b,⇑, David Baxter a, Lars K. Andersen a, Christina G. Vassileva b
a
Institute for Energy and Transport, Joint Research Centre, European Commission, P.O. Box 2, NL-1755 ZG Petten, The Netherlands
b
Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Sofia 1113, Bulgaria

a r t i c l e i n f o a b s t r a c t

Article history: An extended overview of the phase–mineral and chemical composition and classification of biomass ash
Received 18 July 2012 (BA) was conducted. Some general considerations related to the composition of BA and particularly prob-
Received in revised form 13 September lems associated with this issue were discussed initially. Then, reference peer-reviewed data including
2012
phase–mineral composition and properties of BAs plus own investigations were used to describe and
Accepted 17 September 2012
Available online 4 October 2012
organise the BA system. It was found that BA is a complex inorganic–organic mixture with polycompo-
nent, heterogeneous and variable composition. The phase–mineral composition of BA includes: (1)
mostly inorganic matter composed of non-crystalline (amorphous) and crystalline to semi-crystalline
Keywords:
Biomass ash
(mineral) constituents; (2) subordinately organic matter consisting of char and organic minerals; and
Phase and mineral composition (3) some fluid matter comprising moisture and gas and gas–liquid inclusions associated with both inor-
Chemical composition ganic and organic matter. Approximately 229 forming, major, minor or accessory phases or minerals were
Classification identified in BA. These species have primary, secondary or tertiary origin in the combustion residue and
they are generated from natural (authigenic and detrital) and technogenic phases or minerals originally
present in biomass. Common topics related to BA such as: terminology clarification; chemical composi-
tion; contents and concentration trends; correlations and associations; formation and behaviour; fusion
temperatures; and leaching; were discussed and compared to coal ash. A general characterization of the
phase–mineral composition and description of the occurrence and origin for common constituents in BA,
namely: (1) silicates; (2) oxides and hydroxides; (3) sulphates (plus sulphides, sulphosalts, sulphites and
thiosulphates); (4) phosphates; (5) carbonates (plus bicarbonates); (6) chlorides (plus chlorites and chlo-
rates); (7) nitrates; (8) glass; (9) other inorganic phases; (10) organic phases; and (11) organic minerals;
were also conducted and compared to coal ash. Finally, certain major associations related to the occur-
rence, content and origin of elements and phases were identified in the BA system and they include:
(1) Si–Al–Fe–Na–Ti (mostly glass, silicates and oxyhydroxides); (2) Ca–Mg–Mn (commonly carbonates,
oxyhydroxides, glass, silicates and some phosphates and sulphates); and (3) K–P–S–Cl (normally phos-
phates, sulphates, chlorides, glass and some silicates and carbonates). It was found that these systematic
associations in BA have a key importance in both fundamental and applied aspects, namely their poten-
tial application for classification and indicator purposes connected with innovative and sustainable pro-
cessing of BA. The potential utilization, technological and environmental advantages and challenges
related to BA using the above classification approach are described in Part 2 of the present work.
Ó 2012 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
1.1. General considerations about biomass composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.2. Common issues concerning the composition of biomass ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2. Materials, methods and data used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.1. Common observations about biomass ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

⇑ Corresponding author at: Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Sofia 1113, Bulgaria. Tel.: +359
2 9797055; fax: +359 2 9797056.
E-mail address: vassilev_stan@yahoo.com (S.V. Vassilev).

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.09.041
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 41

3.1.1. Definition, specification and terminology clarification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

3.1.2. Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.1.3. Content and concentration trend. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1.4. Correlation and association . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.1.5. Formation and behaviour . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.1.6. Fusion temperatures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.1.7. Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.1.7.1. Water leaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.1.7.2. Leaching by different solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.1.7.3. Sequential leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.2. General comments about phase–mineral composition of biomass ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.3. Phase–mineral composition of biomass ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.3.1. Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.3.2. Oxides and hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3.3. Sulphates, sulphides, sulphosalts, sulphites and thiosulphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3.4. Phosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3.5. Carbonates and bicarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3.6. Chlorides, chlorites and chlorates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.7. Nitrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.8. Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.9. Other inorganic phases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.10. Organic phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.3.11. Organic minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4. Chemical and phase–mineral classifications of biomass and biomass ash and their potential applications . . . . . . . . . . . . . . . . . . . . . . . . . 70
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

Nomenclature

A ash yield LTA low-temperature ash (100–250 °C)

AFT ash-fusion temperature M moisture
BA biomass ash MA medium acid
BC beech wood chips MM marine macroalgae
CC corn cobs MS mass spectrometry
Daf dry, ash-free basis OM organic matter
DAI SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2/ PP plum pits
CaO + MgO + MnO + K2O + P2O5 + SO3 R2 correlation coefficient
Db dry basis RH rice husks
DT initial deformation temperature SG switchgrass
DTA differential-thermal analysis SS sunflower shells
DWR dry water-soluble residue SSA specific surface area
EDF enrichment/depletion factor ST spherical temperature
FC fixed carbon TGA thermo-gravimetric analysis
FT fluid temperature VM volatile matter
HT hemispherical temperature WS walnut shells
HTA high-temperature ash (>500 °C) XRD X-ray powder diffraction
ICP inductively coupled plasma % weight%
LA laser ablation

1. Introduction
It is widely accepted that biofuels combustion does not contrib-
ute to the greenhouse effect due to the CO2 neutral conversion
thanks to the renewability of biomass. The focus on bioenergy as
an alternative to fossil energy has increased tremendously in re-
cent times because of global warming problems originating mostly
from fossil fuels combustion. Therefore, extensive investigations
have been carried out worldwide recently to enhance biomass
use instead of fossil fuels for energy conversion ([1,2] and refer-
ences therein).
The global growth of biomass is estimated between 112 and
220 billion tonnes per year [3–8]. However, the annual world pro-
duction of biomass with potential energy application at present is
estimated to be about 3 billion tonnes for forest residues [9], be-
tween 1.1 and 3.1 billion tonnes for agricultural residues [9–11],
about 1.1 billion tonnes for municipal solid wastes [3] plus sewage
sludge and other biomass resources [9,12]. Biomass currently con-
tributes between 8% and 15% of the world energy supplies as heat,
electricity and fuels for transportation [5,8,9,13–18]. By 2050, up to
33–50% of the world’s current primary energy consumption could
be met by biomass [3,8,18,19]. In total about 95–97% of the world’s
bioenergy is produced by direct combustion of biomass [16,20–22].
Hence, approximately 476 million tonnes of biomass ash (BA) may
be generated worldwide annually if the burned biomass is as-
sumed to be 7 billion tonnes with 6.8% mean ash yield on dry
basis [1]. This quantity is comparable to that of coal ash,
namely 780 million tonnes produced per year at present [23]. The
42 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

perspective of increasing large-scale combustion of natural bio-
mass and its co-combustion with semi-biomass (contaminated
biomass such as municipal solid waste, refuse-derived fuel, sewage
sludge, demolition wood and other industrial organic wastes) and
solid fossil fuels (coal, peat, petroleum coke) seems to be one of the
main drivers for biofuel promotion by many countries worldwide
in the near future. Therefore, some of the major open questions re-
lated to extensive biomass combustion are what we are going to do
with this huge amount of BA and if there are any environmental
risks related to BA. The present overview will cover such topics.
1.1. General considerations about biomass composition
Two fundamental aspects related to the use of BA are:
(1) To extend and improve the basic knowledge on composition
and properties and
(2) To apply this knowledge for the most innovative and sus-
tainable utilization and/or an environmentally safe disposal.
The composition of BA depends on various factors; however, it
is directly related to the biomass used as feedstock because the ori-
ginal constituents in biomass are the precursors for the newly
formed components in BA (Tables 1 and 2). Therefore, detailed
knowledge of the biomass composition is also required for the reli-
able characterization of BA. The systematic identification, quantifi-
cation and characterization of chemical and phase composition of a
given solid fuel and its conversion products are the initial and most
important steps for their proper utilization. The composition of
biomass and BA define properties, quality and application perspec-
tives, as well as technological and environmental problems or
advantages related to any fuel and its products [1,2].
As first and second steps, two extended overviews of the bulk
chemical composition [1] and organic and inorganic phase compo-
sition [2] of biomass, respectively, were conducted recently. Exten-
sive reference peer-reviewed data for numerous biomass varieties
(86 for chemical composition and 93 for phase composition) plus
own investigations of eight varieties of biomass were used to de-
scribe the composition of the biomass system. In these previous
overviews it was found that:
(1) Biomass, similar to solid fossil fuels, is a complex heteroge-
neous mixture of organic matter and, to a lesser extent, inor-
ganic matter, containing various intimately associated solid
and fluid phases with different contents and origin. The
phases in biomass originate from natural (authigenic and
detrital) and anthropogenic (technogenic) processes during
pre-syngenesis, syngenesis, epigenesis and post-epigenesis
of biomass according to the main formation process and
place, time and mechanism of phase formation. The main
structural organic components in biomass are cellulose,
hemicellulose and lignin and these matrices contain in addi-
tion various major, minor or accessory organic and inorganic
phases.
(2) The chemical and phase differences among the specified nat-
ural and anthropogenic biomass groups and sub-groups are
significant and they are related to diverse biomass source
and origin, namely from plant, animal and manufactured

Table 1
Phase composition of biomass ash.

Matter State and type of constituent
Inorganic matter Solid, non-crystalline
(amorphous)
Solid, non-crystalline
(amorphous)
Solid, crystalline to semi-
crystalline (mineral)
Organic matter Solid, crystalline (mineral)
Solid, non-crystalline
(amorphous) to semi-crystalline
Fluid matter Fluid, liquid, gas
Phase, mineral and particle morphology
Spherical and spheroidal glass particles (massive, vesicular, cenospheres, plerospheres, dermaspheres,
ferrospheres, ferrispheres, others)
Angular, irregular and other aspherical glass particles (massive, hollow, vesicular, fibres, needles, cylinders,
discs, slabs, sheets, lacy, spongy, porous, elongated, rounded, agglomerates, others)
Crystals, grains, aggregates, clusters, ferrospheres, ferrispheres, skeletal spheres and spheroids,
agglomerates and others of various minerals or poorly crystallized mineraloids (silicates, oxides and
hydroxides, sulphates, sulphides, sulphosalts, sulphites, thiosulphates, phosphates, carbonates, chlorides,
chlorites, chlorates, nitrates, native elements, pure metals, metallic alloys, others)
Crystals, grains and aggregates of organic minerals (whewellite-weddelite and other groups)
Char including semi-coked, coked, soot and tar particles (angular, irregular, rounded, massive, hollow,
vesicular, spongy, porous, skeleton, needles, whiskers, fibres, scaly, flaky, sheets, clusters of rosettes,
cylinders, discs, slabs, spherical, spheroidal, agglomerates, others)
Moisture and gas and gas–liquid inclusions associated with both inorganic and organic matter

Table 2
Origin of phases in biomass ash.

Origin Formation Place of formation Time of formation Formation mechanism

process
Primary Natural Biomass Before and during plant Original phases or minerals that have undergone no phase transformations during
growing, and after plant combustion
died
Secondary Anthropogenic Combustion During combustion New phases generated by solid, liquid and gas reactions among pre-existing and
(technogenic) installation newly formed compounds (amorphization, carbonation, carbonization, coalescence,
crystallization, decarbonation, decomposition, dehydration, dehydroxylation,
destruction, desulphation, dissolution, evaporation, fragmentation, hydration,
hydroxylation, melting, nucleation, oxidation, polymorphic transformation,
precipitation, recrystallization, reduction, softening, solid-state reactions,
sulphation, vitrification, volatilization, combined conversions, others)
Tertiary Natural Transportation During transport and New minerals or phases originated by wheathering (amorphization, carbonation,
facility and storage of combustion crystallization, decarbonation, decomposition, dehydration, dehydroxylation,
disposal site residues destruction, desulphation, dissolution, evaporation, hydration, hydroxylation,
oxidation, polymorphic transformation, precipitation, recrystallization, solid-state
reactions, sulphation, vitrification, others)
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
products. The composition of semi-biomass is more complex
and quite complicated compared with natural biomass as a
result of incorporation of various non-biomass materials
through processing steps.
(3) Biomass has highly variable composition and properties,
especially with respect to moisture, structural components
and inorganic constituents. These characteristics are more
changeable and differ significantly in comparison with those
of coal and a good understanding is critical for proper use of
biomass and/or co-processing with coal and other fuels. The
major and minor elements in biomass, in decreasing order of
abundance, are commonly C, O, H, N, Ca, K, Si, Mg, Al, S, Fe, P,
Cl and Na, plus Mn, Ti and other trace elements. In compar-
ison with coal, natural biomass is normally: (1) highly
enriched in Mn > K > P > Cl > Ca > (Mg, Na) > O > moisture >
volatile matter; (2) slightly enriched in H; and (3) depleted
in ash, Al, C, Fe, N, S, Si and Ti.
(4) The organic matter (54–99%, mean 93%, on dry basis) in bio-
mass has: non-crystalline character and only limited crystal-
linity with larger d-spacings (between 0.33 and 0.88 nm) in
comparison with carbonised fuels such as coal, char and
coke (between 0.26 and 0.59 nm); and characteristic inter-
molecular distances at about 0.59 nm and 0.40 nm related
to complex cellulose – hemicellulose – lignin – oxalate –
opal associations.
(5) The structural components in biomass belong to six orders
(or types) as the most common orders include: cellu-
lose > hemicellulose > lignin; cellulose > lignin > hemicellu-
lose; and hemicellulose > lignin > cellulose. Hemicellulose
tends to be abundant in annual and fast-growing plants or
plant parts and this constituent plays a role of conducting
and concentrating tissue for mineralized solutions abundant
in sulphates, chlorides, nitrates and silicic acid in plants. Cel-
lulose, lignin and extractives show associations with differ-
ent non-mobile and mobile elements in biomass.
(6) Bulk extractives (1–87%, mean 10%, on dry, ash-free basis) in
biomass consist of various organic and inorganic compo-
nents and their contents are normally higher in herbaceous
and agricultural biomass than in wood and woody biomass.
(7) The fluid matter (3–63%, mean 14%, normally on as received
and air-dried basis) in biomass is a mineralized aqueous
solution associated with both inorganic and organic matter.
These water solutions have slightly acidic to neutral charac-
ter with salty, sea salty to brine total mineralization and var-
iable electrical conductivity. These three characteristics
correlate positively with one another and commonly with
inorganic matter and mobile S, Cl, Na and N components.
(8) The inorganic matter (0.1–46%, mean 7%, on dry basis) in
biomass includes various minor and accessory mineral spe-
cies and poorly crystallized mineraloids from various min-
eral groups and classes, as well as some amorphous
inorganic phases. The most mobile water-soluble phases in
biomass are chlorides, sulphates, oxalates and nitrates plus
some carbonates and amorphous material with both organic
and inorganic character.
(9) Certain major associations related to the occurrence, content
and origin of elements and phases were identified in natural
biomass and they include: (1) C–H (mainly as authigenic cel-
lulose, hemicellulose, lignin and organic extractives); (2) Si–
Al–Fe–Na–Ti (mostly as detrital silicates and oxyhydroxides,
excluding authigenic opal); (3) Ca–Mg–Mn (commonly as
authigenic oxalates and carbonates); and (4) N–K–S–P–Cl
(normally as authigenic phosphates, sulphates, chlorides
and nitrates). These systematic associations are important in
both fundamental and applied aspects, namely their potential
43
application for classifications and indicator purposes con-
nected with innovative and sustainable processing of
biomass.
(10) The occurrence, content, origin and association of different
inorganic matter types and mineral classes, groups and spe-
cific species are likely to be the major reasons for many tech-
nological problems (combustion efficiency, low-temperature
eutectics, agglomeration, slagging, fouling, corrosion, abra-
sion-erosion, partitioning, ash utilization) and environmen-
tal concerns (water, soil and plant contamination, leaching,
alkalinity, emission, inhalation, ash disposal) during biomass
processing (see below and Part 2).
(11) Biomass ashes (500 °C) have highly crystalline character
with limited occurrence of inorganic amorphous material
and organic matter. Various species of carbonates, sulphates,
silicates and phosphates were identified in these ashes and
most of them are newly formed minerals during biomass
combustion.
(12) Energy from biomass cannot only be carbon–neutral, but
carbon-capture and storage is also possible due to fixation
of CO2 in the combustion residues as newly formed carbon-
ates. Some biomass is highly enriched in alkaline-earth and
alkaline constituents (see below and Part 2) and this favour-
able composition can contribute significantly to the capture
of volatile C, S, Cl and trace elements in combustion residues.
Hence, there are potential possibilities for reduction of
harmful emissions by modification of the feed fuel composi-
tion through tailored and self-cleaning fuel mixtures during
co-firing or co-gasification of biomass with fossil fuels.
Both previous overviews concluded that future detailed and
systematized data on the phase–mineral composition of BA are re-
quired as a third step to explain some leading trends and associa-
tions connected with biomass and its conversion products.
Therefore, the main purposes of this subsequent work presented
here are: (1) to perform an overview of the chemical and especially
phase composition of BAs and (2) to indicate the potential applica-
tions of BAs based on the composition and properties of these com-
bustion products.
1.2. Common issues concerning the composition of biomass ash
A detailed review of the scientific literature, including more
than 600 mostly peer-reviewed references and data compilations
has been conducted to systematise the results obtained for compo-
sition and properties of biomass and BA. It was found that numer-
ous studies on phase composition of BA have been performed
worldwide and data for ashes of different biomass varieties have
been generated and published [10,13,14,18,24–141]. As a result,
significant information for inorganic matter (various phases and/
or minerals) and, to a lesser extent, organic matter (char, others)
identified in BA has been collected and arranged systematically
(Table 3). These results provide a sound foundation for an initial
database that can be used for phase characterization and subse-
quent classification and sustainable exploitation of BA. It was also
found that serious problems related to phase investigations of BA
occur and some of them are similar to those determined for chem-
ical and phase studies of biomass [1,2]. Therefore, an attempt to
summarize the problems related to phase investigations of BA
was initially undertaken and is described below:
(1) There is a huge amount of data on the phase composition of
BA on the Internet and numerous scientific reports from pro-
jects, conference proceedings and workshop presentations,
as well as in many publications; however, such information
is unreliable because the data are not peer-reviewed.
44 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Table 3
Phases and minerals identified in biomass ashes.

Phase, mineral Chemical formula Reference used

1. Inorganic matter
1.1. Silicates
Afwillite Ca3(SiO3OH)22H2O or [24a]
Ca3(Si2O4)(OH)6
Akermanite Ca2MgSi2O7 [24–34b]
Albite NaAlSi3O8 [18,33,35c–47]
Amorphous silica SiO2 [18,30,48–53]
Anorthite CaAl2Si2O8 [34b,37d,38,47,54,55]
Augite (Ca, Na)(Mg, Fe, Al, Ti)(Si, Al)2O6 [30,56]
Bredigite Ca7Mg(SiO4)4 [33]
Ca aluminosilicates [35,47,57,58]
Ca chlorosilicate Ca2SiO3Cl2 [59]
Ca–Fe–Mg silicate Ca(Fe,Mg)Si2O6 [18]
Ca–Mg silicates [25]
Ca silicate hydrate CaO.SiO2.H2O [24a,39,60,61]
Ca silicates CaSiO4, CaSi2O5, Ca4Si2O8, [25,26,57,62–65]
Ca8Si5O18, others
Cd silicate CdSiO3 [66,67]
Chlorite (MgFe)5Al2Si3O10(OH)8 [27b]
Clay minerals [36,68]
Clinochlore (MgFe)5Al(Si3Al)O10(OH)8 [45]
Cordierite (MgFe)2Al3(Si5AlO18) [27b]
Cristobalite SiO2 [13,18,25,27b,31,33,38,46,47,49,53,56,69–73, present study]
Diopside CaMgSi2O6 or CaMg(SiO3)2 [25,30,33,46,74]
Enstatite MgSiO3 [75]
Faujasite Na2Al2Si3.3O10.67H2O [38d]
Fayalite Fe2SiO4 [47,74]
Fe gehlenite Ca2FeAlSiO7 [26]
Feldspars NaAlSi3O8–CaAl2Si2O8, KAlSi3O8 [24,33,45,75]
Ferrosillite FeSi2O6 [74]
Forsterite Mg2SiO4 [34b,74]
Garnet (andradite, pyrope, grossular) Ca3Fe2Si3O12, Mg3Al2Si3O12, [26,28,30,53]
Ca3Al2Si3O12
Gehlenite Ca2Al2SiO7 [24,27b,34b,38,43,47,65,76]
Gismondite Ca2Al4Si4O169H2O [65a,77]
Hatrurite Ca3SiO5 [78,79]
Hedenbergite CaFeSi2O6 or Ca(FeMg)(SiO3)2 [36,45]
Illite (KH2O)Al2(AlSi)Si3O10(OH)2 [27b,55]
Kalsilite KAlSiO4 [26,29,33,65,78,80]
K aluminosilicates [58,81]
Kaolinite Al2Si2O5(OH)4 [27b,40,82]
K–Ca aluminosilicate [83]
K–Ca silicates K2CaSiO4, K4CaSi3O9, others [13,25,64,65,74,78,83–86]
K feldspars KAlSi3O8 [24,25,27b,33,38,46,57,61,64,65,87,88, present study]
K–Mg silicate K2MgSi3O8 [89]
K silicates K2Si4O9, others [26,84,85,90–92]
Larnite Ca2SiO4 [13,24,25,27b,30,31,33,34b,53,59,60,62,78–80,89,111]
Leucite KAlSi2O6 [18,30,33,46]
Makatite Na2Si4O8(OH)24(H2O) [38d]
Melilite (akermanite–gehlenite) Ca2MgSi2O7–Ca2Al2SiO7 [26,28,30,53]
Merwinite Ca3Mg(SiO4)2 [24,25,29,33,46]
Metakaolinite Al2Si2O5 [55]
Mg silicate [57]
Microcline KAlSi3O8 [13,39,45]
Monticellite CaMgSiO4 [29,30]
Mullite Al6Si2O13 [27b,47,82,93, present study]
Muscovite KAl2AlSi3O10(OH,F)2 [27b,37,41,42]
Na–Ca silicate Na2CaSiO4 [89]
Na melilite NaCaAlSi2O7 [26]
Na silicate (water glass) Na2Si3O7 or Na2SiO3 [59]
Na tremolite (Ca,Na)23Mg5Si8O22 (OH)2 [86]
Orthoclase KAlSi3O8 [26,74]
Paranatrolite Na2Al2Si3O103H2O [38d]
Plagioclases NaAlSi3O8–CaAl2Si2O8 [24,25,27b,35c,e,55,57,61,65, present study]
Quartz SiO2 [13,14,18,24,25,27b,30,31,33–36b,c,e,38–47,55–57,59,61,62,64,65,68,71,72,74–
78,80,82,84–87,94c–99,111, present study]
Rankinite Ca3Si2O7 [25–27b]
Riebeckite Na2Fe3Fe2Si8O22(OH)2 [60]
Sanidine KAlSi3O8 or (K, Na)(Si, Al)4O8 [43]
Sepiolite Mg4Si6O15(OH)26H2O [27b]
Serandite Na(MnCa)2Si3O8(OH) [60]
Silica SiO2 [26,28,29,35,37,44,59,60,63,74,79,90,100]
Suolunite Ca2Si2O5(OH)2(H2O) [77]
Talc Mg3Si4O10(OH)2 [27b,45]
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 45

Table 3 (continued)

Phase, mineral Chemical formula Reference used

Tridymite SiO2 [13,33,47,49,53, present study]
Vermiculite (MgFeAl)3(SiAl)4O10(OH)24H2O [27b]
Wollastonite a-Ca3Si3O9 or a-CaSiO3 [25,27b,30,31,33,38,63,79,89,101,111]
Zeolites (Ca, Sr, Ba, Na2, K2)Al2Si2–10O8– [27b,38d]
242–8H2O
Zn-bearing silicates [65]
1.2. Oxides and hydroxides
Alumina c-Al2O3 [63,82]
Ca–Al oxides Ca3Al2O3, Ca3Al2O6 [24,38,61,75]
Ca–Fe oxide CaXFeYOZ [102]
Ca–Mn oxides Ca2MnO4, Ca4Mn3O10 [89]
Cd-bearing oxides [67,103]
Corundum Al2O3 [27b,39,86,99]
Cr-bearing oxides [103]
Cr–Fe oxide (Cr, Fe)2O3 [102]
Fe oxide [13,58]
Gibbsite Al(OH)3 [57]
Goethite a-FeOOH [27b,45,102]
Hematite a-Fe2O3 [13,24,25,27b,33,34b,36–42d,44–46,55,75,82,86,96,98,99,103,104]
Hydrocalumite Ca2Al(OH)6[Cl1x(OH)x]3(H2O) or [34b]
Ca4Al2Cl2O610H2O
K–Al oxides K2Al2O4 or K2Al19O29.5 [64,65a]
K–Fe oxide K3FeO2 [80]
K hydroxide KOH [105]
K oxide K2O [26,105]
Lime CaO [24,25,27b,33,35,37,41,42,45,46,55,57,58,60–
63,65,79,89,90,92,96,98,101,104,106,107]
Macedonite PbTiO3 [73]
Maghemite c-Fe2O3 [33,44]
Magnetite FeFe2O4 [27b,34b]
Mg–Cr–Fe oxide Mg(Cr, Fe)2O4 [102]
Mg–Fe–Al oxide MgFeAlO4 [75]
Mg–Mn oxide Mg6MnO8 [89]
Monteponite CdO [67]
Na hydroxide NaOH [105]
Na oxide Na2O [105]
Pd oxide PdO [108]
Periclase MgO [13,24,25,27b,30,32,33,35–37,39–42,45,46,53,55,57,62,79,80,89,96,98,99,101,102,
present study]
Plattnerite PbO2 [102]
Portlandite Ca(OH)2 [24a,27b,34b,37,38,42,46,57a,58,60–62a,65,75,77,79,89,96,98,106, present study]
Rutile TiO2 [24,26,27b,36–38d,45]
Srebrodolskite Ca2Fe2O5 [39]
Wustite FeO [109]
Zincite ZnO [31,66]
Zn–Al oxide [65]
Zn ferrite (Zn, Fe)Fe2O4 [102]
Zn–Ti oxide ZnXTiYO4 [102]
1.3. Sulphates, sulphides, sulphosalts, sulphites and thiosulphates
Amorphous K, Na, Ca and Mg sulphates [74]
Anhydrite CaSO4 [24,27b,36–39,41–47,55,61,64,65,74,75,77,87,94c,96,98,99,104,106,110,112,113,
present study]
Aphthitalite (KNa)3Na(SO4)2 [33,41,42,62,98]
Arcanite K2SO4 [13,24,25,33,35c,37,38,42,45,46,57–
59,62,65,74,77,79,80,84,85,87,89,94c,98,101,103,104,110–118, present study]
Bassanite CaSO40.5H2O [44a,65a]
Ca–K sulphates [58,92]
Ca langbeinite K2Ca2(SO4)3 or K2CaMg(SO4)3 [25,74,79,89,104,118]
Ca–Mg sulphate CaMg3(SO4)4 [94]
Ca sulphate [58,92]
Cd sulphate [66]
Ettringite Ca6Al2(SO4)3(OH)1226H2O [24a,57a,61a,65a]
Glaserite K3Na(SO4)2 [24,31,37,46,79]
Gypsum CaSO42H2O [24a,57a,61a,65a, present study]
Kieserite (dehydrated) MgSO4 [37]
K sulphide K2S [112f]
Langbeinite K2Mg2(SO4)3 [86]
Mg thiosulphate MgS2O3 [94]
Millosevichite Al2(SO4)3 [13]
Na thiosulphate Na2S2O3 [94]
Oldhamite CaS [35,77,112f,119]
Picromerite K2Mg(SO4)26H2O Present study
Sulphides Compounds with sulphide anion [109,120]
(S2)

(continued on next page)

46 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Table 3 (continued)

Phase, mineral Chemical formula Reference used

Sulphites Compounds with sulphite anion [120]
ðSO2
3 Þ
Syngenite K2Ca(SO4)2H2O [24a,57a,77]
Syngenite (dehydrated) K2Ca(SO4)3 [25]
Thenardite Na2SO4 [37,117]
Xanthoconite Ag3AsS3 [100]
1.4. Phosphates
Al phosphates [38d,121]
Apatite Ca(PO4)3(Cl, F, OH, CO3) or [27b,33,44,48,56,57,74, present study]
Ca5(PO4)3(Cl, F, OH, CO3)
Apatite (Ca deficient) Ca10x(HPO4)x(PO4)6x(OH)2x [44,56]
Berlinite AlPO4 [75,104]
Ca–Fe phosphate (similar to whitlockite) Ca9FeH(PO4)7 [44]
Ca–K phosphate CaKPO4 [101]
Ca–Mg–K phosphate Ca9MgK(PO4)7 [38d]
Ca phosphates Ca3(PO4)2, Ca3P2O8, others [26,32,37,44,53,54,56,57,84,92,104,113]
Chloroapatite Ca(PO4)3(Cl) or Ca5(PO4)3(Cl) [56]
Durapatite Ca5HO13P3 [104]
Fe phosphates FePO4, Fe7(PO4)6 [38a,44]
Hydroxylapatite Ca(PO4)3(OH), Ca5(PO4)3(OH) or [24,33,37,41,42,44–46,56,57,62,79,98,101,122,65]
Ca10(PO4)6(OH)2
K–Ca phosphate KCa(PO4) [79,94]
K hydrophosphate KH2PO4 [94]
K phosphates K3PO4, K5P3O10, others [32,59,92,101,123]
K pyrophosphate hydrate K4P2O73H2O [94]
Mg–Ca phosphate MgCaPO4 [94c]
Mg phosphates [92]
Mg pyrophosphate Mg2P2O7 [94]
Na–K phosphate [44]
Na phosphates Na6P2O8, others [13,26,92]
Whitlockite Ca9Fe(PO4)7 or Ca3(PO4)2 [33,38d,44,75d, present study]
Zn phosphate [44]
1.5. Carbonates and bicarbonates
Ankerite Ca(MgFe)(CO3)2 [40]
Arterite Mg2CO3(OH)23H2O [37]
Baylissite K2Mg(CO3)24H2O [37]
Butschliite (dimorphous with fairchildite) K2Ca(CO3)2 [13,111]
Ca–K carbonate Ca2K2(CO3)3 [33,46,58]
Calcite CaCO3 [13,24,25,27b,30,33–38b,40–47,53,55–
62,64,65,68,71,75,76,79,80,87,89,90,92,94c,98,105–108,111,112,118,124, present
study]
Cr-bearing carbonates [103]
Dolomite CaMg(CO3)2 [36,42,45,80,94,98,108, present study]
Eitelite Na2Mg(CO3)2 [37]
Fairchildite K2Ca(CO3)2 [24,25,33,35,37,45,46,62,79,80,89,94, present study]
Hydrocalcite CaCO3H2O [24a,57a]
Hydrotalcite Mg6Al2CO3(OH)164H2O [60]
Kalicinite KHCO3 [37, present study]
K carbonate (potash) K2CO3 [13,33,37,57–59,89,105,112,113,117,124,125]
Magnesite MgCO3 [103,124]
Natrite Na2CO3 [105,117,124, present study]
Natrofairchildite Na2Ca(CO3)2 [94, present study]
Nesquehonite MgCO33H2O [94]
Nyerereite (Na0.82K0.18)2Ca(CO3)2 [37]
Paraalumohydrokalcit CaAl2(CO3)2(OH)46H2O [24a]
Siderite FeCO3 [40,45]
1.6. Chlorides, chlorites and chlorates
Ca chloride CaCl2 [38]
Ca chlorite hydrate Ca(ClO)23H2O [60]
Ca hydroxylchloride CaOHCl [38]
Ca–K chlorides Chlorocalcite type (KCaCl3) [92]
Cd chloride CdCl2 [67]
Cotunnite PbCl2 [126]
Fe chloride [127d]
Halite NaCl [24,37,38,56,68,94c,99,113,117,126, present study]
K halite K0.2Na0.8Cl or K0.4Na0.6Cl [24,75]
K perchlorate KClO4 [68c]
Sylvite KCl [13,24,25,30,31,33,35–38,45–47,53,56–59,62,64,65,77,79,80,84–
87,92,94c,96,99,100,103,111–118,125, present study]
Zn chloride ZnCl2 [126,128]
1.7. Nitrates
Nitrates [94c]
Nitre (niter) KNO3 [35c,68c]
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 47

Table 3 (continued)

Phase, mineral Chemical formula Reference used

1.8. Glass Various elements [13,24–27b,29–31,33–35b,46–48,55–57,65,69,71,74,76,88,97,101,110,116,129–
131, present study]
1.9. Other inorganic phases
Amorphous (non-glass) inorganic material [24,35c,48,53,65,86,94,111, present study]
Elemental Al Al [27b,38b]
Elemental Pb Pb [109]
K-Mo selenide K2Mo3Se18 [100]
Margaritasite (CsKH3O)2(UO2)2V2O8H2O [73]
Metallic alloys and pure metals Various elements [27b,108]
2. Organic matter
2.1. Organic phases
Char (unburned organic matter, semi-coke, [13,14,18,24,27b,31,35,40,55,58,60,63,73,76,84,86,95,97,106,114,126,129,130,132–
coke, soot, tar, others) 136, present study]
Chlorobenzene C6H5Cl [132]
Chlorophenol C6H5ClO [132]
Cyanides Salts of CN- [137]
Na cyanate NaOCN [128]
Polychlorinated dioxins Chlorinated hydrocarbons [10,14,95,121,126,132,138,139]
Polychlorinated furans Halogenated organic compounds [10,14,95,126,132,138–140]
Polycyclic aromatic hydrocarbons Polyaromatic or polynuclear [14,132,137,141]
hydrocarbons
2.2. Organic minerals
Weddelite (Ca oxalate dihydrate) Ca(CO2)2(H2O)2 or CaC2O42H2O [94c]
Whewellite (Ca oxalate dehydrate) CaC2O4 [94c]
Whewellite (Ca oxalate monohydrate) CaC2O4H2O [35c]
3. Fluid matter [28,53,102]
a
Hydrated or leached ash.
b
Municipal solid waste ash.
c
Low-temperature ash produced in oxygen plasma (100–250 °C).
d
Sewage sludge ash.
e
From soil.
f
In char.

(2) The long term experience and knowledge achieved for the
phase composition of the most studied ashes, namely from
coal, peat, petroleum coke and municipal solid waste or
refuse-derived fuel ([27,142–146] and references therein)
have not been implemented very successfully in the field
of BA. Therefore, the use of unsuitable scientific approaches,
models and procedures, incomplete data or unusual and
sometimes inappropriate terms and interpretaions is com-
mon in many investigations of BA (see below).
(3) A serious omission is the limited description of the specific
type, place and manner of BA collection, as well as storage
and processing conditions. This is a serious problem for the
reliable identification and characterization of phases in BA.
Representative sampling problems associated with BA also
occur and some of them have been discussed [14,95,147].
(4) The phases in BA are a result of combustion of biomass orig-
inating from natural and anthropogenic formation processes
and a significant fraction in BA can contain other non-bio-
mass phases ([1,2,27,144] and references therein). Therefore,
BA produced from contaminated biomass (semi-biomass)
should always be considered separately from BA generated
from natural biomass due to the different origin, composi-
tion and potential use.
(5) The lack of generally accepted terminology, classification
systems and standards worldwide for the phase composition
of BA leads to very serious misunderstanding during the
investigations. The biggest problem seems to be the absence
of appropriate phase classifications for BA in contrast to
some other ashes. For example, there are systematic and rel-
atively strict phase specifications for coal ash (which can
also be applied to BA) including: (1) inorganic matter (crys-
talline and non-crystalline) such as mineral classes, groups
and species and amorphous phases and (2) organic matter,
namely chars produced from different lithotypes, microlith-
otype groups and macerals; and which are well recognized
worldwide and relatively well characterized ([142,143,148]
and references therein).
(6) Detailed and complete data sets from simultaneous chemi-
cal and phase–mineral analyses for various BAs are scarce.
Thus, limited systematic interpretations can be made from
investigations [89,131,149].
(7) Most studies used the data from ash yield or the bulk chem-
ical composition of ash to explain mineral matter, mineral
composition, inorganic matter or inorganics in biomass
and BA, which is not fully correct and can lead to confusion
in many cases (see below and [1,2]).
(8) The common scientific approach used is to study the concen-
tration and behaviour of individual elements (Ca, Cl, K, Na, P,
S, Si and trace elements) for explaining and evaluating dif-
ferent technological and environmental problems related
to BA. However, the actual reasons for such problems in a
multicomponent system like that for BA are most likely con-
nected with modes of element occurrences, namely specific
phases and minerals that contain such elements, similar to
coal ash (see Part 2 and [143,150,151] and references
therein).
(9) The methods for phase and mineral investigations of BA
have not been developed and implemented very well.
Extraction procedures are dominantly used for the identifi-
cation and quantification of the inorganic and organic phase
composition of BA. Unfortunately, the direct methods for
determination of phases in BA are not common (see below).
Some analytical concerns associated with BA have been dis-
cussed ([14,95,147] and references therein).
(10) Sequential chemical fractionation is mostly used to distin-
guish the speciation (modes of occurrence or chemical forms
of combination) of elements in BAs. However, this indirect
procedure cannot be applied to identify the actual modes
48 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
of occurrence of elements in a multicomponent system.
Leaching alone has many limitations and can be used only
to provide preliminary information for some possible associ-
ations of elements in phases (see below). Other direct meth-
ods commonly applied for coal and coal products ([145,146]
and references therein) provide better information and they
should always be used additionally for such a purpose.
(11) Many findings about the behaviour of organic and inorganic
matter during biomass heating are based only on theoretical
equilibrium and stoichiometric calculations of chemical
data. These indirect investigations may be quite unrealistic
for actual predictions of phases in a multicomponent system
under non-equilibrium conditions (see for example [46]).
Such calculations can be used only to provide a subsidiary
or preliminary prediction procedure of the real and direct
(input, output) phase studies of the systems.
(12) The variable ash-melting points of biomass fuels have been
discussed in numerous studies. However, it should be stated
that melting points occur only for pure (monocomponent)
systems, while biomass ash (similar to coal ash) is a multi-
component system of powder material and cannot have a
specific melting point (see for example [152]). Therefore,
BA has three or four characteristic and measurable ash-
fusion temperatures because ash melting occurs over a wide
temperature range (see below).
(13) The challenges and advantages related to BA utilization are
only at an initial stage of investigation and they need further
clarification by extensive and detailed studies (see Part 2).
(14) There is a strange acceptance that BA does not contain toxic
metals like in the case of coal ash [13,153]. However, certain
results for BAs [41,95,108,127,154–158] concerning the con-
centrations of elements such as Ag, As, Ba, Cd, Cl, Cr, Cu, Hg,
Mn, Mo, Ni, Pb, S, Sb, Se, Sn, Th, Tl, U, V and Zn are very dis-
turbing (see below and Part 2). Systematic studies about
trace elements in biomass and BA are only at an initial stage
of investigation and more work is needed.
(15) Washing to remove water-soluble phases prior to use of BAs
may reduce some technological and environmental problems.
However, such future large-scale leaching may create new
environmental concerns related to the fate of mobile phases
containing alkali metals, Cl, S, P and some hazardous trace
elements associated with these phases (see below and Part 2).
(16) Regulations exist in some countries which specify the limit-
ing and guiding values for the contents of some elements
(Ca, Cd, Cl, Co, Cr, Cu, K, N, Ni, Pb, S, V, Zn) in biomass fuels
and their BAs in respect of their unrestricted use. However,
the bulk concentrations of these elements are less informa-
tive than the abundance and behaviour of the forms in
which they are present (see below and Part 2).
The above listed problems show that additional, systematic and
detailed chemical and phase–mineral studies of BA based on
proved, improved or new approaches are required to reduce uncer-
tainties. There are thus ample opportunities for new research in
this area. Here, based on a critical review of publications and some
own investigations an attempt will be undertaken to:
(1) Compile and systematize a reliable database related to the
composition of BAs.
(2) Describe the basic findings and clarify some of the problems
associated with the composition of these combustion
residues.
(3) Supply additional results related to composition and proper-
ties of BAs.
(4) Indicate the potential applications and environmental risks
connected with BAs.
(5) Understand how the fundamental knowledge on the compo-
sition and properties may be exploited for the most innova-
tive and sustainable utilization of these combustion
residues.
The present overview includes the composition and application
of BA and it was split in two parts for better systematisation and
presentation. Part 1 comprises the phase–mineral and chemical
composition and classification of BAs, while Part 2 incorporates po-
tential utilization, technological and ecological advantages and
challenges related to BAs.
2. Materials, methods and data used
The results in this overview are obtained from: (1) reference
peer-reviewed investigations and (2) reference peer-reviewed data
including our own new data and studies with novel interpretation
from both previous overviews [1,2] plus additional own data in the
present overview. For better differentiation, they are referred to as:
(1) ‘‘reference investigations’’ and (2) ‘‘present study’’ throughout
the text, respectively.
The phases and minerals identified or assumed (with uncertain
identification) in BAs are given in Table 3 using mostly peer-re-
viewed investigations [10,13,14,18,24–141] plus own data. Eight
biomass samples were collected and studied for additional clarifi-
cation of the phase composition of BAs in the present work (Ta-
ble 4). They include beech wood chips (BC), corn cobs (CC),
marine macroalgae (MM), weathered plum pits (PP), rice husks
(RH), switchgrass (SG), sunflower shells (SS) and walnut shells
(WS). The majority of investigations up to now have been concen-
trated dominantly on woody biomass and wheat straw as solid bio-
fuels. Most of these eight samples are herbaceous and agricultural
residues and algae (sea lettuces) and much less is known about
them. The selection of these samples is also based on their highly
variable: (1) structural composition and especially (2) inorganic
chemical composition (Table 4 and Fig. 1) according to the refer-
ence data [1,2,159,160]. Another big advantage of these samples
for comparative investigations is that they belong to all four inor-
ganic chemical types of biomass (‘‘S’’, ‘‘C’’, ‘‘K’’, and ‘‘CK’’ types) and
different sub-types (Fig. 1) that have been specified recently [1].
Additionally, five samples from them belong to the low acid ‘‘K’’
and ‘‘CK’’ types and sub-types, which are among the most problem-
atic biomass resources from technological and environmental
points of view [2]. The samples collected were between 2 and
5 kg in weight and they were air dried under ambient conditions
during a period of over 12 months. After that, visible contaminants
such as sand, soil or shell particles were eliminated manually from
RH and MM. Then the samples were cut/crushed (CC, PP, WS) and
ground (BC, CC, MM, PP, RH, SS, SG, WS) to a particle size of
<500 lm (BC, MM, RH, SG, SS) or <1000 lm (CC, PP, WS). Finally,
they were investigated using light microscopy, powder X-ray dif-
fraction (XRD), differential-thermal (DTA), thermo-gravimetric
(TGA) and chemical analyses, as well as some leaching, precipita-
tion, ashing and other procedures.
An ordinary stereomicroscope under transmitted and reflected
light was used for optical observations. XRD patterns of finely
ground samples were recorded by D2 Phaser Bruker AXS and DRON
3 M diffractometers, and collected at 10–70° 2h using Cu and Co Ka
radiations, respectively. The high-temperature ashes (HTAs) of bio-
mass samples were produced in an electric oven (Carbolite) with
static air at 500 ± 10 °C for 2 h with a heating and cooling rate of
about 5 °C min1. The above temperature and holding time were
selected as the lowest ones for gentle and successful incineration
of biomass prior to intensive decomposition (above 500 °C) of car-
bonates and some sulphates which are typical minerals for bio-
mass and BA.
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 49

Table 4
Data for eight biomass samples (air-dried basis) additionally studied, wt.% (indicated otherwise).

Characteristic Beech wood Corn cobs Marine macroalgae Plum pits Rice husks Switchgrass Sunflower Walnut
chips shells shells
Code BC CC MM PP RH SG SS WS
Source JRS Rosenberg, Debnevo, Tsarevo, Bulgaria Debnevo, Kovachevo, Bulgaria Mead, Nebraska, Billa Sofia, Debnevo,
Germany Bulgaria Bulgaria USA Bulgaria Bulgaria
Collection time 01.2009 08.2008 08.2009 08.2008 08.2007 2003 08.2008 08.2008
Note Produced size Cleaned from sand Weathered Cleaned from sand Two mixed
is 1–4 mm and shell grains for 1 year and soil grains harvests
(50:50 vol.%)
Size reduction (mm) <0.5 <1 <0.5 <1 <0.5 <0.5 <0.5 <1
Bulk density (loose) 454 412 954 889 451 263 250 833
(kg m3)
Bulk density (shaken) 479 435 1250 1000 476 286 275 883
(kg m3)
pH of leachate (solid– 5.15 5.32 6.75 5.57 6.66 5.20 5.12 5.28
liquid = 1:10 mass
ratio)
Electrical conductivity 0.70 1.60 19.81 0.67 2.12 1.63 3.47 0.88
of leachate (mS/cm)
DWR 1.4 0.8 15.1 0.3 1.5 7.8 2.9 0.9
Ash (500 °C/2 h) 1.31 2.14 28.24 0.66 18.50 5.14 2.97 0.90
Ash (700 °C/1 h) 0.94 1.70 23.58 0.52 17.48 4.23 2.36 0.77
Ash (900 °C/1 h) 0.86 1.47 20.50 0.51 17.41 4.17 1.95 0.57
Ash (1100 °C/1 h) 0.84 1.44 17.17 0.50 17.37 4.14 1.86 0.52
Ash (1300 °C/1 h) 0.80 11.69 0.47 17.37 1.67 0.51
Ash (1500 °C/1 h) 17.22
Fluid AFT 61300 61100 61300 61300 >1500 61100 61300 61300
Ash (500 °C/2 h) bulk 170 200 430 130 270 80 120 150
density (loose)
(kg m3)
Reference data
VM (db) 82.0 81.2 50.5 80.8 62.8 80.4 76.0 59.3
FC (db) 17.2 16.8 25.9 17.8 19.2 14.5 20.9 37.9
A (db) 0.8 2.0 23.6 1.4 18.0 5.1 3.1 2.8
Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
C (daf) 47.2 47.8 41.7 49.9 49.3 49.6 50.4 49.8
O (daf) 46.6 45.6 44.3 42.4 43.6 43.4 42.9 42.4
H (daf) 6.1 5.9 6.0 6.7 6.1 6.1 5.5 6.2
N (daf) 0.1 0.5 2.1 0.9 0.8 0.7 1.1 1.4
S (daf) 0.01 0.01 2.51 0.08 0.08 0.11 0.03 0.09
Cl (daf) 0.01 0.23 3.34 0.01 0.12 0.08 0.10 0.15
Sum 100.02 100.04 99.95 99.99 100.00 99.99 100.03 100.04
Cel (daf) 45.2 48.1 28.5 23.7 43.8 48.7 56.5 28.1
Hem (daf) 32.7 37.2 65.5 22.0 31.6 38.4 28.0 26.6
Lig (daf) 22.1 14.7 6.0 54.3 24.6 12.9 15.5 45.3
Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Ext (daf) 1.1 7.0 15.1 5.4 6.6 8.0 2.6 2.7
HTA (550–600 °C)
SiO2 12.33 27.65 1.44 3.59 94.38 66.09 23.46 23.29
CaO 67.80 13.19 10.79 14.65 0.97 10.19 15.18 16.70
K2O 2.59 35.49 13.37 44.88 2.29 9.62 28.29 32.99
P2O5 2.29 6.96 8.50 20.12 0.54 3.91 7.07 6.20
Al2O3 0.12 2.49 0.74 0.11 0.21 2.21 8.67 2.40
MgO 11.43 2.05 10.89 11.62 0.19 4.70 7.27 13.49
Fe2O3 1.09 1.55 1.63 0.68 0.22 1.36 4.23 1.50
SO3 0.80 7.14 22.42 2.47 0.92 0.83 4.03 2.20
Na2O 0.89 1.26 17.32 0.46 0.16 0.58 0.79 1.00
TiO2 0.10 0.13 0.01 0.02 0.02 0.28 0.15 0.10
Cl2O 0.16 2.01 12.86 1.35 0.08 0.16 0.85 0.12
MnO 0.40 0.08 0.03 0.05 0.02 0.07 0.01 0.01
Sum 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
DAI 0.2 0.5 0.3 0.1 19.0 2.4 0.6 0.4
Ref. [1,2] [1,2] [1,2,159,160] [1,2] [1,2] [1,2] [1,2] [1,2]

Abbreviations: A, ash yield; AFT, ash-fusion temperature; Cel, cellulose; daf, dry ash-free basis; DAI, detrital/authigenic index (Si + Al + Fe + Na + Ti oxides/
Ca + Mg + Mn + K + P + S + Cl oxides); db, dry basis; DWR, dry water-soluble residue; Ext, extractives; FC, fixed carbon; Hem, hemicellulose; HTA, high-temperature ash; Lig,
lignin; VM, volatile matter.

The thermal experiments include a gradual heating of HTAs
produced at 500 °C/2 h via 200 ± 5 °C intervals in the electric oven
under atmosphere of static air. The heating was conducted at 700,
900, 1100, 1300 and 1500 °C or up to the fluid ash-fusion temper-
atures of the samples (excluding only RH), namely 1100 °C (CC,
SG), 1300 °C (BC, MM, PP, SS, WS) and 1500 °C (RH). The sample
RH has a fluid ash-fusion temperature higher than 1500 °C. Initial
portions of HTA samples (0.1–0.9 g) spread out in a layer (about
1–3 mm thickness) at the bottom of ceramic crucibles (5  3 cm
in diameter and 3.5 cm height) were heated up to the respective
temperature for each experiment. The heating and cooling rate
was about 10 °C min1. A holding time at the fixed temperature
50 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Fig. 1. Positions of eight biomass varieties in some classification systems based on data from: (a) proximate; (b) ultimate; (c) structural; and (d) ash analyses [2], wt.%.
Abbreviations: B, bituminous coal; BC, beech wood chips; CC, corn cobs; daf, dry, ash-free basis; db, dry basis; FC, fixed carbon; L, lignite; MM, marine macroalgae; P, peat; PP,
plum pits; RH, rice husks; S, sub-bituminous coal; SG, switchgrass; SS, sunflower shells; VM, volatile matter; WS, walnut shells.

was 1 h and then gradual cooling to ambient temperature was car-
ried out. This holding time is based on the former investigations
[25,161–164] that found a time interval of P30 min to be entirely
sufficient to achieve equilibrium in the system. Breaking of the
ceramic crucibles and gentle handpicking under a binocular micro-
scope were applied to separate the fused material (slag) that was
formed at the maximum temperatures. Despite that, a few and fine
ceramic particles from the crucibles were observed microscopically
to occur as contaminants in BC, MM, PP and SS slags. These con-
taminants were identified as mullite, plagioclase and quartz by
XRD for these four samples heated at 1300 °C. Additionally, DTA
and TGA analyses were conducted using a Stanton Redcroft STA
760 apparatus. These experiments were carried out for 10–20 mg
of biomass samples and their HTAs produced at 500 °C/2 h. The
samples were gradually heated in corundum crucibles from ambi-
ent temperature to 1400 °C under oxidising conditions as the flow
rate of air was 30 ml min1 and the heating rate was 10 °C min1.
The thermally treated HTAs are defined below as ashes and slags.
Dry, water-soluble residues (DWRs) were isolated from the bio-
mass samples by evaporation and precipitation of the water-solu-
ble solutions leached. The leachates from this extraction procedure
were generated from 10 g of biomass samples placed in glass con-
tainers with 100 ml of distilled water and soaked for 24 h at ambi-
ent temperature. The suspensions were periodically stirred and
finally decanted and filtered. The pH and electrical conductivity
values were measured in the generated water solutions by a bench
pH-mV-conductivity meter PC 5000L (VWR International Ltd.).
Then the leachates were placed in a drying oven at 80 °C for evap-
oration and crystallization giving DWRs. These leaching and pre-
cipitation procedures are similar to those applied for coals
[165,166] and refuse-derived fuels [27].
The contents of trace elements (Ag, Au, B, Be, Cd, Cr, Cu, Mn, Ni, Rb,
Se, Zn) in biomass ashes (500 °C/2 h) were determined by induc-
tively coupled plasma - mass spectrometry (ICP-MS) and laser abla-
tion ICP-MS (LA-ICP-MS), respectively, following: (1) acid digestion
of the samples by HCl, HNO3 and HF and subsequent measurement
of the solutions (for B and Mn) by Perkin Elmer ELAN DRC-e mass
spectrometer and (2) preparation of discs after fusion of the samples
with Li2B4O7 at 1000 °C and subsequent measurement of the glass
discs (for other elements) by the above apparatus combined with
New Wave UP193FX excimer laser ablation system. NIST SRM
glasses 610 and 612 were used as external calibration standards.
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
3. Results and discussion
3.1. Common observations about biomass ash
3.1.1. Definition, specification and terminology clarification
An initial clarification of certain terminology, definitions and
specifications is useful due to some misunderstandings and un-
clear interpretations in the literature about the terms used during
characterization of biomass ashes. The proposed description below
related to the composition, content and origin of phases and min-
erals in BA is based on detailed investigations of other solid fuel
ashes, particularly coal ashes [27,148,150,163,164,166–168], as
well as some data for biomass and BA (Table 3 and [1,2]).
Biomass ash is the solid residue that results from the combus-
tion of biomass. This combustion residue is a complex inorganic–
organic mixture with polycomponent, heterogeneous and variable
composition and contains intimately associated solid, liquid and
gaseous phases (Table 1) with different origin (Table 2).
BAs can be laboratory and industrially generated combustion
products. The laboratory-produced BAs include:
(1) Low-temperature ash (LTA) prepared in oxygen plasma at
100–250 °C;
(2) High-temperature ash (HTA) produced in air normally above
500 °C; and
(3) Slag generated from completely molten ash; at regulated
temperatures.
On the other hand, the industrial BAs consist of.
(1) Bottom ash (from dry-ash discharge boilers) or slag (from
melt discharge boilers).
(2) Fly ash (from flue gas discharge systems); produced in
industrial combustion and gasification installations at tem-
peratures commonly between 800 and 1600 °C.
The chemical composition of BA comprises: (1) major (>1%); (2)
minor (1–0.1%); and (3) trace (<0.1%) elements; according to their
elemental concentrations, where the major and minor elements
are mostly expressed as oxides (see Section 3.1.2).
The phase–mineral composition of BA includes:
(1) Mostly inorganic matter composed of non-crystalline (amor-
phous) and crystalline to semi-crystalline (mineral)
constituents.
(2) Subordinately organic matter consisting of char and organic
minerals.
(3) Some fluid matter comprising moisture and gas and gas–
liquid inclusions associated with both inorganic and organic
matter (Table 1 and Sections 3.2 and 3.3).
The phases and minerals in BA can be divided into: (1) forming
(>10%); (2) major (1–10%); (3) minor (0.1–1%); and (4) accessory
(<0.1%); based on their contents (see Section 3.2).
BA is composed of original (primary) or newly formed (second-
ary and tertiary) inorganic and organic solid phases generated from
natural (authigenic and detrital) and technogenic inorganic, organ-
ic and fluid matter during biomass combustion. Therefore, the
phases and minerals in BA can be classified in origin as:
(1) Primary, namely pre-existing or original minerals and
phases in biomass that have undergone no phase transfor-
mations during combustion.
(2) Secondary such as new phases formed during combustion
process.
51
(3) Tertiary, namely new minerals or phases formed during
transport and storage of BA (Table 2 and Sections 3.2 and
3.3).
Ash is one of the most studied characteristics of biomass, but
unfortunately still with relatively poor understanding. The reason
for this problem is the complex character of this term. Therefore,
the differentiations and specifications of terms such as ash yield
or ash content (A), ash, inorganic matter and mineral matter re-
lated to biomass (they are also valid to BA) are a necessity. It
should be stated that these terms are not synonymous because
they comprise constituents with different composition, quantity
and origin, similar to coal [1,2,145,146,169,170].
BA is the solid residue that results from the complete or incom-
plete combustion (or occasionally low-temperature oxidation) of
the organic matter in biomass. Hence, the term biomass ash com-
prises the inorganic residue without or with some amount of un-
burnt organic matter resulting from the combustion of biomass
at laboratory or industrial conditions, as specified above. The ash
yield of biomass or BA is just the measured quantity of the incom-
bustible inorganic residue resulting from the complete combustion
(or oxidation) of biomass or BA at laboratory conditions.
The inorganic matter of biomass or BA comprises inorganic and
solid crystalline, semi-crystalline and amorphous phases (Table 1
and [2]). The actual mineral matter of biomass or BA, as a part of
inorganic matter, excludes inorganic amorphous matter and in-
cludes only minerals and mineraloids that belong to mineral clas-
ses, groups and species strictly divided, defined and characterized
in the mineralogical sense (Tables 1 and 3 and [2]). Hence, constit-
uents such as organic matter, char and inorganic elements (Al, Ca,
Cl, Fe, K, Mg, Mn, Na, Si, Ti, trace elements) associated with organic
matter, namely:
 Covalently and ionically bound in the organic matter (for exam-
ple, organometallic compounds).
 Combined in ion-exchangeable forms and as salts of carboxylic
acids in organic matter.
 Present as discrete organic minerals; are not included in the
inorganic matter of biomass or BA [2], which is similar to coal
[145] and coal ash [146].
It should be stated that the ash yield itself brings relatively lim-
ited information when the composition, abundance and origin of
the biomass and BA constituents are not considered. Hence, the
ash yield should always be interpreted together with the composi-
tion, content and origin of constituents in biomass or BA. Such
interpretations have a great importance for elements and phases
in biomass or BA because their modes of occurrence are related
mostly to both organic and inorganic forms and mixed natural
and technogenic origin. The ash yields can be measured routinely,
while the actual determination of bulk inorganic and mineral con-
tents, as well as the complete isolation of inorganic and mineral
constituents from biomass or BA, are a complex procedure and
cannot be quickly and routinely achieved. Even the LTA yield of
biomass is not the actual inorganic or mineral matter of biomass,
as also observed for coal [145]. Despite the above limitations, the
ash yield is still an important parameter for approximating:
 Bulk inorganic matter.
 Predominant affinity of elements and compounds to inorganic
or organic matter.
 Possible contamination of biomass.
3.1.2. Chemical composition
The composition of BA depends on many factors including:
52 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
(1) Biomass resource (type of biomass, plant species or part of
plants, growing processes and conditions, age of the plants,
fertilizer and pesticide doses used, harvesting time, collec-
tion technique, transport, storage, pollution, processing, oth-
ers) [1].
(2) Biomass combustion (fuel preparation, combustion technol-
ogy and conditions, collection and cleaning equipments).
(3) Transport and storage of BA.
The elements in biomass and BA can be classified into major,
minor and trace elements according to their elemental concentra-
tions, as mentioned above. The decreasing order of abundance of
major and minor elements in biomass is variable. For example,
the reference investigations show that the major elements in
angiospermous and gymnospermous plants are C > O > H > N >
Ca > K, whereas the minor elements are normally
S > Mg > P > Cl > Na [159]. Another study reveals that this order is
C > O > H > N > K > Ca for major elements and S > (Cl, Mg, P) > Si
for minor elements in plants [108]. The chemical data from the
present study related to the composition of 86 varieties of biomass
and their groups and sub-groups specified have been reported re-
cently [1]. This study reveals that in decreasing order of abun-
dance, the major elements are commonly C > O > H > N > Ca > K,
the minor elements normally include Si > Mg > Al > S > -
Fe > P > Cl > Na, and the trace elements are Mn and Ti plus other
elements in biomass. There are many individual cases among bio-
mass varieties, where the above orders for certain elements are
interchanged. The organic-forming elements in biomass are nor-
mally C, O, H, N and S, whereas the inorganic-forming elements
are commonly the other elements. However, some proportions
from the organic-forming elements also occur in inorganic matter,
whereas parts of the inorganic-forming elements are also present
in organic matter, as also observed for coal [1].
The reference investigations show that in decreasing order of
abundance the contents of major and minor elements in plant
ashes are commonly Si > (Mg, P) > S > (Ca, K) > Na > Al > (Fe,
Cl) > Mn > Ti [171]. The chemical data from the present study (10
oxides normalized to 100% plus Mn contents) related to the tradi-
tional ash analyses of 86 varieties of biomass and their groups and
sub-groups specified have been reported recently [1]. This study
reveals that the major and minor elements in BA, in decreasing
order of abundance, are commonly O > Ca > K > Si > Mg > Al > Fe >
P > Na > S > Mn > Ti plus some Cl, C, H, N and trace elements.
The oxide contents in BAs are normally SiO2 > CaO > K2O > P2O5 > -
Al2O3 > MgO > Fe2O3 > SO3 > Na2O > MnO > TiO2. BA from natural
biomass is commonly enriched in Mn > K > P > Cl > Ca > Na > Mg
and depleted in Al > Ti > Fe > Si > S in comparison with coal ash.
Similar to biomass, there are many individual cases among BAs,
where the above orders for certain oxides and elements are inter-
changed. The major and minor elements in BA (or the so called ash-
forming elements) can be all elements listed above represented as
elemental contents or more commonly as oxides in BA. The data
also demonstrate that the chemical composition of BAs has extre-
mely large variations and this is due to the highly variable contents
of bulk inorganic matter and different genetic classes of inorganic
matter in biomass varieties.
The chemical ash composition of the specified biomass groups
and sub-groups as well as four solid fossil fuel types from the pres-
ent study are given herein (Table 5). This ash composition for ma-
jor and minor elements has been reported and described in detail
recently [1]. Additionally, only the contents of 12 trace elements
enriched in eight BAs are provided in Table 6. The specific prob-
lems related to the concentrations and modes of occurrence of
trace elements in biomass and BA are beyond the subject of the
present study and they will be characterized in further publica-
tions. Here, it is interesting to note that Ag, Au, B, Be, Cd, Cr, Cu,
Mn, Ni, Rb, Se and Zn in some of these BAs can show higher con-
tents than the respective Clarke values (worldwide average con-
tents) for coal ashes (Table 6). This comparison is evaluated by
the enrichment/depletion factor (EDF) defined as a ratio of the ele-
ment content in BA to the respective Clarke value in coal ash [172].
For example, the decreasing order of trace elements with over
Clarke concentrations based on the mean EDF values for the eight
BAs (Table 6) is: B (23.5) > Au (18.2) > Cd (4.9) > Cr@Mn (3.8) > Ag
(3.5) > Zn (2.6) > Be@Cu@Se (2.5) > Ni (2.0) > Rb (1.8). It can be
seen that the above listed elements belong mostly to chalcophile
and siderophile groups and, to a lesser extent, noble, lithophile
and non-metal groups according to the mineralogical classification
of elements [173]. Despite the limited BAs studied such a prelimin-
ary geochemical comparison indicates elements that may have
some environmental impacts and/or industrial potential for BA.
For instance, the data (Table 6) point out that some regulated toxic
and potentially toxic trace elements [174,175] in BA such as Ag, Be,
Cd, Cr, Cu, Mn, Ni, Se and Zn might cause some environmental pol-
lution of the air, water, soil and plants during BA utilization. On the
other hand, the concentrations and modes of occurrence of some
trace elements such as Ag, Au, B, Cr, Mn and others may have a re-
source recovery potential from certain BAs (see Part 2). Hence, the
enriched and/or hazardous elements in BA should have a more de-
tailed environmental concern and economical assessment.
Finally, the bulk chemical composition of biomass and BA is an
important characteristic; however, it is quite insufficient for a reli-
able explanation of elemental behaviour during biomass and BA
utilization. The abundance, origin and performance of modes of
element occurrence (minerals and phases) in biomass and BA are
needed to fully understand this elemental behaviour (see Sections
3.2-3.4 and Part 2).
3.1.3. Content and concentration trend
The present study shows that the ash yield (dry basis) deter-
mined at 550–600 °C for 86 varieties biomass is in the interval of
0.1–46% (mean 6.8%) [1]. It is interesting to note that some sea-
weeds can even have more than 50% ash content [108]. The ash
yield normally decreases in the order: animal biomass > aquatic
biomass > contaminated biomass > herbaceous and agricultural
biomass > wood and woody biomass [1]. For coal (dry basis), the
ash content (815 °C) is in the relatively more narrow range of 6–
52% (commonly 6–30% and mean about 21%) and normally shows
much higher value than in biomass [1].
The reference investigations also reveal that wood and woody
biomass has lower ash content compared with herbaceous and
agricultural biomass [95,126,176,177]. The ash yield in wood and
woody biomass commonly decreases in the order: foliage, leaves
or needles P bark > branches or twigs > wood stems or stumps
[108,178–182]. It was also found that:
 Temperate-climate woods yield less ash than tropical and sub-
tropical woods [132].
 Hard wood has higher ash content than soft wood [5,14,183].
 The ash yield of wood is reduced with age [178].
On the other hand, herbaceous and agricultural biomass
(straws, grasses, cereals and fruits) has higher ash content than
wood and woody biomass because the former biomass has differ-
ent organic structure, rapid metabolism and takes up much more
nutrients during the growing periods [95,126,176,177]. The ash
yields of herbaceous biomass also vary within the parts of the
plant, namely: leaves > reproductive organs > stems [131,177].
The annual species and especially grasses contain high ash con-
tents [184] and the ash yields decrease with increasing lignin
contents in grasses [185]. It was identified that the ash contents
in grasses decline during late summer and then rise again during
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 53

Table 5
Chemical ash composition of biomass groups and sub-groups (86 varieties of biomass) plus algae and four solid fossil fuel types based on high-temperature ash analyses
(normalized to 100%), wt.%. The Mn contents are additionally given (based on [1]).

Biomass group and sub-group SiO2 CaO K2O P2O5 Al2O3 MgO Fe2O3 SO3 Na2O TiO2 Sum Mn Samples
1. Wood and woody biomass (WWB)
Mean 22.22 43.03 10.75 3.48 5.09 6.07 3.44 2.78 2.85 0.29 100.00 1.32 28
Minimum 1.86 5.79 2.19 0.66 0.12 1.10 0.37 0.36 0.22 0.06 0.08 28
Maximum 68.18 83.46 31.99 13.01 15.12 14.57 9.54 11.66 29.82 1.20 3.57 28
2. Herbaceous and agricultural biomass (HAB)
Mean 33.39 14.86 26.65 6.48 3.66 5.62 3.26 3.61 2.29 0.18 100.00 0.13 44
Minimum 2.01 0.97 2.29 0.54 0.10 0.19 0.22 0.01 0.09 0.01 0.02 44
Maximum 94.48 44.32 63.90 31.06 14.60 16.21 36.27 14.74 26.20 2.02 0.46 44
2.1. Grasses (HAG)
Mean 46.18 11.23 24.59 6.62 1.39 4.02 0.98 3.66 1.25 0.08 100.00 0.31 10
Minimum 8.73 2.98 2.93 3.14 0.67 1.42 0.58 0.83 0.09 0.01 10
Maximum 84.92 44.32 53.38 20.33 2.59 8.64 1.73 9.89 6.20 0.28 10
2.2. Straws (HAS)
Mean 43.94 14.13 24.49 4.13 2.71 4.66 1.42 3.01 1.35 0.16 100.00 0.09 9
Minimum 7.87 2.46 12.59 0.98 0.10 1.67 0.41 1.18 0.16 0.02 0.02 9
Maximum 77.20 30.68 38.14 10.38 5.57 14.10 2.82 4.93 3.52 0.33 0.28 9
2.3. Other residues (HAR)
Mean 24.47 16.58 28.25 7.27 4.90 6.62 4.84 3.80 3.05 0.22 100.00 0.16 25
Minimum 2.01 0.97 2.29 0.54 0.11 0.19 0.22 0.01 0.12 0.01 0.02 25
Maximum 94.48 44.13 63.90 31.06 14.60 16.21 36.27 14.74 26.20 2.02 0.46 25
3. Animal biomass (AB)
Mean 2.90 49.04 7.67 28.17 1.69 2.75 0.35 3.91 3.50 0.02 100.00 0.05 2
Minimum 0.02 41.22 3.16 15.40 1.01 1.38 0.25 3.59 0.60 0.01 0.01 2
Maximum 5.77 56.85 12.19 40.94 2.37 4.11 0.45 4.24 6.41 0.03 0.09 2
4. Mixture of biomass (MB)
Mean 44.19 17.48 6.00 5.72 10.82 3.52 6.34 2.66 2.53 0.74 100.00 0.16 4
Minimum 34.75 11.51 3.11 1.08 9.77 2.31 4.19 1.88 1.25 0.52 4
Maximum 57.83 25.70 7.76 18.07 11.35 4.77 10.44 4.62 3.18 0.95 4
5. Contaminated biomass (CB)
Mean 35.73 18.30 3.45 3.64 15.41 3.60 9.78 3.45 1.90 4.74 100.00 0.15 8
Minimum 3.39 7.63 0.16 0.20 3.08 1.57 0.82 0.99 0.54 0.32 0.02 8
Maximum 60.10 26.81 9.70 15.88 53.53 6.45 22.18 10.55 4.06 27.58 0.23 8
All varieties of biomass (AVB)
Mean 29.76 25.27 17.91 5.71 5.51 5.42 4.00 3.28 2.48 0.66 100.00 0.75 86
Minimum 0.02 0.97 0.16 0.20 0.10 0.19 0.22 0.01 0.09 0.01 0.01 86
Maximum 94.48 83.46 63.90 40.94 53.53 16.21 36.27 14.74 29.82 27.58 3.57 86
Natural biomass
Mean 29.14 25.99 19.40 5.92 4.49 5.60 3.41 3.27 2.54 0.24 100.00 0.81 78
Minimum 0.02 0.97 2.19 0.54 0.10 0.19 0.22 0.01 0.09 0.01 0.01 78
Maximum 94.48 83.46 63.90 40.94 15.12 16.21 36.27 14.74 29.82 2.02 3.57 78
Aquatic biomass
Marine macroalgae 1.65 12.39 15.35 9.76 0.85 12.50 1.87 25.74 19.88 0.01 100.00 0.03 11
Solid fossil fuels
Peat 37.53 9.97 1.12 2.75 20.14 2.14 13.83 12.11 0.10 0.31 100.00 0.08 1
Lignite (mean) 44.87 13.11 1.48 0.20 17.11 2.50 10.80 8.64 0.48 0.81 100.00 0.07 5
Sub-bituminous coal (mean) 54.74 7.05 1.67 0.08 22.86 2.14 5.30 4.07 1.09 1.00 100.00 0.05 10
Bituminous coal (mean) 56.14 4.90 1.61 0.22 24.82 1.55 6.68 2.16 0.77 1.15 100.00 0.05 22
Coal (mean) 54.06 6.57 1.60 0.50 23.18 1.83 6.85 3.54 0.82 1.05 100.00 0.05 37
Coal (minimum) 32.04 0.43 0.29 0.10 11.32 0.31 0.79 0.27 0.09 0.62 0.02 37
Coal (maximum) 68.35 27.78 4.15 1.70 35.23 3.98 16.44 14.42 2.90 1.61 0.18 37

the late winter [131]. Additionally, grass produced on a clay soil
contained almost five times as much ash yield as a crop from a hu-
mus-rich soil, mainly due to differences in Si content [186]. It was
also found that elements such as Si plus Al, Ti and Fe normally rep-
resent inorganic matter of soil origin [70]. Finally, the ash yields of
finer fractions (<420 lm or < 180 lm) of biomass are substantially
larger than of coarser fractions (420–850 lm or 180–2000 lm)
[7,48].
The combustion temperature also significantly affects the yield
of ash from biomass. For example, the reference investigations
show that ash yields determined at 1000–1300 °C are 10–70% low-
er than those produced by LTA at 100–150 °C or HTA at 500–575 °C
[48,60,68,89,94,183]. The present study (Table 4) confirmed the
above observations and reveals that the ash yields determined at
1100–1500 °C are 7–59% lower than those produced at 500 °C,
namely MM (59%) > SS (44%) > WS (43%) > BC (39%) > CC
(33%) > PP (29%) > SG (19%) > RH (7%). This order shows that mini-
mum losses occur for the biomass varieties highly enriched in silica
and silicates (RH and SG), while maximum losses are typical for
biomass varieties abundant commonly in Ca, Cl, Fe, K, Mg, Na, P,
S, chlorides, sulphates, carbonates and phosphates (Table 4 and
[2]). These weight losses for biomass are normally higher than
for coal and such differences are a result of some more intensive
phase transformations (loss of adsorbed and combined water, com-
bustion of volatile matter, decomposition of less stable minerals)
and probably higher volatilization behaviour of mobile elements
(Br, C, Cl, H, Hg, K, N, Se, S and other trace elements) from biomass
phases in the high temperature ranges [163,164].
54 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Table 6
Contents of some trace elements in eight biomass ashes (500 °C/2 h), ppm.

Element Coal ash Beech wood Corn Marine Plum Rice Switchgrass Sunflower Walnut Mean EDFb
Clarkea chips cobs macroalgae pits husks shells shells
Sample BC CC MM PP RH SG SS WS
code
Non-metal elements
B 335 10,257 6619 8653 11,311 4101 7106 5900 8908 7857 23.5
Lithophile elements
Be 9.4 20.9 23.4 8.7 13.0 33.6 31.7 25.1 27.4 23.0 2.5
Rb 79 453 233 25 19 35 54 278 64 145 1.8
Siderophile elements
Cr 100 24 750 66 160 348 49 1504 167 384 3.8
Mn 490 10,595 404 167 466 1825 872 365 202 1862 3.8
Ni 76 36 286 42 64 107 37 574 60 151 2.0
Chalcophile elements (metals and semi-metals)
Cd 1.2 4.9 5.1 5.0 3.5 8.2 9.8 4.4 5.9 5.9 4.9
Cu 92 98 139 36 636 76 66 331 477 232 2.5
Se 8.8 16.4 15.7 9.8 10.5 35.3 37.1 19.0 28.9 21.6 2.5
Zn 140 213 1232 52 779 103 103 338 110 366 2.6
Noble elements
Ag 0.61 1.08 1.91 0.90 1.00 4.13 3.37 1.98 2.57 2.12 3.5
Au 0.022 0.37 0.32 0.16 0.20 0.62 0.73 0.30 0.52 0.40 18.2

Note: The mineralogical classification of elements [173] was used.

a
Clarke for coal ashes worldwide [172].
b
Enrichment/depletion factor (EDF) is defined as a ratio of the element content in biomass ash to the respective Clarke value in coal ash.

Finally, it should be stated that the abnormally high ash yields
of biomass are commonly an indication of increased amounts of
contamination such as:
 Soil added by heavy rainfall, dry and windy conditions mobiliz-
ing dust [177].
 Soil added during harvesting processes and other biomass han-
dling activities [177,184].
 Mineral and metallic impurities and other contaminants due to
later manufacturing processes [1,2].
3.1.4. Correlation and association
The reference investigations show that there are some strong
correlations between ash yield and other characteristics,
namely:(1) Positive correlations with contents of Cl, N and S for
straws (consistent with a predominantly authigenic inorganic mat-
ter) [70]; Si [133]; N and S [187]; bark [180]; and Ca, P, S and Si
[131]; and(2) Negative correlations with concentrations of C, H,
O, N, Cl and S for woods (consistent with inorganic matter of
increasing detrital origin, namely greater levels of dirt) [70]; and
C, Cl and Na [131].
The present study (Figs. 2 and 3) shows that biomass ash yield
correlates:
(1) Positively and significantly (at 95% confidence level) with
pH, ash bulk density, electrical conductivity, dry water-solu-
ble residue, S, N, Cl, hemicellulose, P2O5 and C; and posi-
tively and insignificantly with SiO2, extractives, cellulose, H
and SO3.
(2) Negatively and significantly with volatile matter, Mn, O and
MgO; and negatively and insignificantly with lignin, fixed C,
Fe2O3, K2O, Na2O, TiO2, Al2O3 and CaO according to the cor-
relation analyses [1,2].
mass varieties belonging to the specified inorganic biomass types
and sub-types. Hence, some important associations can be identi-
fied for indicator purposes according the above correlations. For
example, natural biomass commonly enriched in hemicellulose,
water-soluble salts and silicic acid (authigenic phosphates, sul-
phates, chlorides, nitrates and opal) tends to produce higher ash
yields. Certainly, high ash yields in some non-biomass materials
can also be a result of incorporation of: (1) detrital (terrigeneous)
sand, soil or shell particles in natural biomass and (2) mineral
and metallic contaminants in semi-biomass (as mentioned above
and described in [1,2]).
The present study also shows that there are some interesting
relationships between the ash yield and detrital/authigenic index
(DAI), which is the ratio between the sum of Si + Al + Fe + Na + Ti
oxides and sum of Ca + Mg + Mn + K + P + S + Cl oxides (Fig. 3). It
should be noted that the common detrital position of Si and Na
in biomass (as quartz and acid plagioclases) can be changed to
the authigenic position in some biomass varieties due to enrich-
ment of authigenic opal (rice husks, some grasses and straws)
and halite (olive husks and pits, algae or sea transport of biomass),
respectively [1]. Additionally, the two trends between the ash yield
and DAI specified in Fig. 3 illustrate the very high contents of authi-
genic inorganic matter for some biomass varieties highly enriched
in Si-bearing compounds (such as rice straw, rice husks, reed can-
ary grass, coconut shells for the line up) and Ca- and P-bearing
components (namely, chicken litter and meat-bone meal for the
line below). On the other hand, some general and very strong po-
sitive correlations between Al, Fe and Ti in BA also occur (Fig. 3).
They indicate that most biomass varieties probably exhibit the ef-
fects of a general uptake of these elements as has been mentioned
earlier [108]. Therefore, such elements can be used as an indicator
of minerogenic contamination (by rock minerals in soil), while the
uptake of major nutrients (Ca, K, Mg, P and S) is closely related to
an optimal growth of the plant [188].

Additionally, sub-trends following dominantly the major posi-

tive or negative trends between ash yield and many characteristics 3.1.5. Formation and behaviour
(particularly, N, S, Cl, cellulose, hemicellulose, extractives, SiO2, The numerous processes related to ash formation are listed in
CaO, K2O, P2O5, MgO, Al2O3, Na2O) can also be seen (Figs. 2 and Table 2. The detailed phase transformations during biomass com-
3). The reason for such sub-trends is mostly associated with bio- bustion are beyond the subject of the present study and they will
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 55

% 100 % 40 % 80

80

C (daf)
VM (db)

FC (db)
20 60
60

40 0 40
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
Ash (db) % Ash (db) % Ash (db) %

% 15 % 100
% 50

40 10 10

N (daf)
O (daf)

H (daf)
30 5 1

20 0 0.1
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
% Ash (db) %
Ash (db) % Ash (db)

% 10 % 10 % 60

Cellulose (daf)
50
1 1
Cl (db)
S (daf)

40
0.1 0.1 30

0.01 20
0.01
0 10 20 30 40 0 5 10 15 20 25
0 10 20 30 40
Ash (db) % Ash (db) % Ash (db) %

% %
40
% 60 30
Hemicellulose

Extractives (daf)
35
Lignin (daf)

40 20
(daf)

30
20 10
25
0 0
20
0 5 10 15 20 25 0 5 10 15 20 25
0 5 10 15 20 25
Ash (db) % Ash (db) %
Ash (db) %

% 100 % 100 % 80
80 80
60
60 60
CaO

K2O
SiO2

40
40 40
20 20
20
0 0 0
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40

Ash (db) % Ash (db) % Ash (db) %

% 20 % 100
% 100
15
10 10
MgO

Al2O3
P2O5

10
1 1
5

0.1 0 0.1
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
Ash (db) % Ash (db) %
Ash (db) %
% 100 % 100 % 100

10 10
10
Na2O
Fe2O3

1 1
SO3

1 0.1 0.1

0.1 0.01 0.01

0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
Ash (db) % Ash (db) % Ash (db) %

Fig. 2. Some correlations among the characteristics of 78 and 28 varieties of natural biomass based on [1,2], wt.%. Abbreviations: daf, dry, ash-free basis; db, dry basis; FC,
fixed carbon; VM, volatile matter.
56 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

% 10 % 100 100
10 10
1

DAI
1

Mn
1
TiO2

0.1
0.1 0.1

0.01 0.01 0.01

0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
Ash (db) % Ash (db) % Ash (db) %

% 100 % 10 % 10

10 1 1

TiO2

TiO2
Fe2O3

1 0.1 0.1

0.1 0.01 0.01

0 5 10 15 20 0 5 10 15 20 0.1 1 10 100
Al2O3 % Al2O3 % Fe2O3 %

7 100 % 20
EC (mS/cm)

6.5 15
10

DWR
pH

6 10
1
5.5 5

5 0.1 0
0 10 20 30 0 10 20 30 0 10 20 30
Ash (db) % Ash (db) % Ash (db) %
Ash density (kg/m3)

500
400
300
200
100
0
0 10 20 30
Ash (db) %

Fig. 3. Some correlations among the characteristics of 78 and 8 varieties of natural biomass based on [1,2], wt.%. Abbreviations: DAI, SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2/
CaO + MgO + MnO + K2O + P2O5 + SO3; db, dry basis; DWR, dry water-soluble residue; EC, electrical conductivity.

be characterized in a further publication. The present study only
addresses some general observations on the ash formation and
behaviour of inorganic and organic matter during heating. These
preliminary observations are based on data obtained by optical
microscopy, XRD and DTA-TGA for eight biomass varieties and they
are summarised below.
Some processes such as: (1) fragmentation of particles (500 °C);
(2) initial (700–900 °C), significant (700–1100 °C) and extensive
(700–1300 °C) agglomeration of particles; (3) initial (700 °C),
extensive (900–1100 °C) and complete (1100–1500 °C) melting of
particles; (4) various new phase crystallizations (500–1500 °C);
and (5) glass formation (700–1500 °C); were observed microscop-
ically in BAs.
The DTA-TGA profiles of the biomass varieties studied show
very similar combustion behaviour for organic matter (OM) despite
their highly variable chemical and phase composition (Table 4). For
example, they reveal some common and similar transformations
such as: (1) loss of adsorbed water (57–92 °C); (2) OM oxidation
(200–650 °C); and (3) burning of some residual char (650–800 °C).
In contrast to biomass samples, the DTA-TGA profiles of BAs
produced at 500 °C/2 h show very distinct and complex transfor-
mation behaviour due to their highly variable inorganic composi-
tion (Table 4). For instance, they reveal: (1) loss of adsorbed
water (69–129 °C); (2) burning of the residual char (300–850 °C);
and (3) complex phase transformations related to decomposition
of various carbonates, sulphates and phosphates, formation of sil-
icates and melting of phases up to 1300 °C.
Typical XRD patterns (Fig. 4) of BC, water-soluble residue of BC
and BC ash treated up to 1300 °C, as well as DTA-TGA profiles
(Fig. 5) of BC and BC ash are given just for an initial illustration
of the future investigations. Different phase transformations re-
lated to organic matter, oxalates, calcite, quartz, whitlockite, port-
landite, lime, periclase, apatite, glass and other phases and
minerals in biomass ashes can be seen on XRD patterns (Figs. 4
and 6).
As a result of biomass combustion, volatilization of elements
forming OM (C, H, N, S, O) or associated with OM (Ca, Mg, Na, K,
Fe, Si, Al, P, Ti, Mn, others) as covalently or ionically bound ele-
ments, organic-metal components, adsorbed ions or metal ions in
ion-exchanged forms bound to specific functional groups [2] oc-
curs. These elements can: (1) escape the system as volatile compo-
nents; (2) form discrete inorganic phases in ash; (3) react with
each other; or (4) react with original or newly formed inorganic
matter [163,164]. For example, the highly variable values of ele-
ments emitted during biomass combustion are listed in Table 7
based on reference investigations. It can be seen that elements
such as Hg > (Cd, Sb, Se, V) > Br > Cr > Pb > Zn > Cl > As > S > K > Na
show the highest volatilization potential (based on mean values)
[14,89,108,110,114,123,189–192].
The reference investigations show that the size of biomass fly
ash particles varies from 10–50 nm to more than 1–2 mm, but
these powder materials are commonly very fine as their median
size is dominantly below 10–100 lm [14,33,47,107,113,114,118,
126,191]. It was found in the above studies that the alkali chlorides
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 57

Fig. 4. XRD patterns of beech wood chips (BC), dry water-soluble residue (DWR) from BC and high-temperature ashes (HTAs) of BC generated at 500 °C/2 h, 700 °C/1 h,
900 °C/1 h 1100 °C/1 h and 1300 °C/1 h. Abbreviations: Ap, apatite (Ca(PO4)3(Cl,F,OH)); Arc, arcanite (K2SO4); CaNH, Ca nitrate hydrate (Ca(NO3)2.2H2O); Cc, calcite (CaCO3);
Cps, counts per second; Ha, halite (NaCl); L, lime (CaO); Mu, mullite (Al6Si2O13); Op, opal (SiO2.nH2O); Peri, periclase (MgO); Port, portlandite (Ca(OH)2); Q, quartz (SiO2); Sy,
sylvite (KCl); Wd, weddelite (Ca(CO2)2.(H2O)2); Wh, whewellite (Ca(CO2)2.H2O); Wl, whitlockite (Ca3(PO4)2). The occurrence of Mu and Q in the sample BC-HTA-1300 is a
result of contamination from the broken ceramic crucible.

and sulphates and some trace elements (for example, Pb and Zn)
were normally enriched in the finest fly ash fraction (<1 lm) orig-
inated from volatilized elements that nucleate to form new parti-
cles or condense on existing particles during the flue gas cooling.
On the other hand, the coarser ash fraction (>1 lm) is dominated
by components containing non-volatile elements such as Ca, Si,
Mg, Al, Fe, P and Mn that have remained in the solid and/or liquid
phases during the combustion process [14,118,191]. It was also
identified that Ca-bearing minerals seemed to be enriched com-
monly in the size range 1–50 lm, while Si-bearing minerals were
normally found in the largest particles (>10–50 lm) [47,107].
Finally, the present study indicates some important combustion
trends. It was found that the organic matter of different biomass
varieties tends to show similar combustion behaviour, whereas
the inorganic matter of these biomass varieties has a tendency to
reveal variable performance during burning. The preliminary
observations also indicate that the thermal behaviour of different
biomass ashes tends to be similar among the inorganic ‘‘S’’, ‘‘C’’,
‘‘K’’ and ‘‘CK’’ types and probably some sub-types specified recently
[1,2]. The interesting behaviour of inorganic and organic matter
during combustion will be characterized in a further publication.
3.1.6. Fusion temperatures
The ash-fusion temperatures (AFTs), namely initial deformation
(DT), spherical (ST), hemispherical (HT) and fluid (FT) tempera-
tures of 87 varieties of biomass are given in Table 8 based on
numerous references [10,14,25,29,30,35,41,45,48,62,68,69,77,80,
81,86,90,99,129,133,177,181,193–201]. AFTs of coals with differ-
ent rank [170] are also provided in Table 8 for comparison. These
data show that biomass ashes have more variable AFTs in compar-
ison with coal ashes (Table 8). Therefore, the AFTs values for 77
varieties of biomass were subjected to a correlation test to calcu-
late correlation coefficient (R2) values among these four character-
istic temperatures. Ten biomass varieties (samples 5, 12, 18, 24, 31,
48, 52, 53, 80 and 81) were excluded from the database due to
incomplete data for the most important DT, HT and FT (Table 8).
58 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
Fig. 5. DTA and TGA profiles of beech wood chips (BC) and high-temperature ash
(HTA) of BC generated at 500 °C/2 h.
It was found that there are significant, positive and very strong R2
values among AFTs, namely for:
(1) DT with ST (0.78) > HT (0.53) > FT (0.50).
(2) ST with HT (0.84) > FT (0.82).
(3) HT with FT (0.97); as the significant R2 values at 95% confi-
dence level are P0.22 and P0.27 for 77 and 51 variables,
respectively.
Hence, there is an almost perfect fit for both HT and FT, while ST
and especially DT show more individual behaviour probably due to
some different processes responsible for the specific AFTs. It should
be noted that such very similar correlations were also identified for
coal AFTs [202,203]. These observations indicate that the major
processes responsible for the characteristic AFTs seem to be similar
for both biomass and coal ashes.
The present study shows that the DT value of biomass ashes
(Table 8) varies over the large interval of 670–1565 °C (mean
1111 °C). In contrast, DT value of coal ashes (Table 8) is in the rel-
atively more narrow range of 1105–1525 °C (mean 1251 °C). The
mean DT value decreases in the order: bituminous coal > sub-bitu-
minous coal > wood and woody biomass > contaminated bio-
mass > lignite > herbaceous and agricultural biomass (Table 9).
Hence, DT mostly has a much lower value in biomass ash than in
coal ash. The low DT is characteristic of some biomass sub-groups
such as herbaceous and agricultural shells, straws, grasses, stalks
and other residues, as well as wood and woody stumps. The extre-
mely low DT is typical of some biomass varieties, namely eupato-
rium and xanphium stumps, alfalfa, safflower and wheat-barley
straw. In contrast, the high DT is characteristic of some biomass
sub-groups such as agricultural husks and wood and woody barks
and stems. The exceptionally high DT is typical of some biomass
varieties, namely balsam, hemlock, poplar and maple (hard) barks,
rice husks, willow stems and reed canary grass.
The present study reveals that the ST value of biomass ashes
(Table 8) varies over the large interval of 795–1571 °C (mean
1277 °C). The mean ST value decreases in the order: wood and
woody biomass > herbaceous and agricultural biomass (Table 9).
The low ST is characteristic of some biomass sub-groups such as
herbaceous and agricultural shells, straws, grasses, stalks and other
residues, similar to DT. The extremely low ST is typical of some bio-
mass varieties, namely almond shells, wheat straw, thistle and
miscanthus. In contrast, the high ST is characteristic of some bio-
mass sub-groups such as wood and woody barks, twigs, stems
and leaves. The exceptionally high ST is typical of some biomass
varieties, namely balsam, maple (hard), beech, poplar and hemlock
barks, as well as spruce and willow stems and reed canary grass.
The present study shows that the HT value of biomass ashes
(Table 8) varies over the large interval of 975–1665 °C (mean
1322 °C). In contrast, HT value of coal ashes (Table 8) is in the rel-
atively more narrow range of 1200–1575 °C (mean 1388 °C). The
mean HT value decreases in the order: bituminous coal > wood
and woody biomass > sub-bituminous coal > contaminated bio-
mass > lignite > herbaceous and agricultural biomass (Table 9).
Hence, HT normally has a lower value in biomass ash than in coal
ash. The low HT is characteristic of some biomass sub-groups such
as herbaceous and agricultural straws, stalks, pits, grasses, shells
and other residues. The extremely low HT is typical of some bio-
mass varieties, namely wheat-barley, barley, oat and rye straws,
corn cobs and grass. In contrast, the high HT is characteristic of
some biomass sub-groups such as agricultural husks and wood
and woody barks and twigs. The exceptionally high HT is typical
of some biomass varieties, namely spruce stems, rice husks, balsam
and maple (hard) barks, tree pruning, alfalfa and reed canary grass.
The present study reveals that the FT value of biomass ashes
(Table 8) varies over the large interval of 1000  >1700 °C (mean
1353 °C). In contrast, FT value of coal ashes (Table 8) is in the rel-
atively more narrow range of 1205–1585 °C (mean 1411 °C). The
mean FT value decreases in the order: bituminous coal > wood
and woody biomass > sub-bituminous coal > lignite > herbaceous
and agricultural biomass > contaminated biomass (Table 9). Hence,
FT normally has a lower value in biomass ash than in coal ash. The
low FT is characteristic of some biomass sub-groups such as herba-
ceous and agricultural straws, stalks, shells, grasses, pits and other
residues, similar to HT. The extremely low FT is typical of some
biomass varieties, namely corn cobs, stalks and fodder, banagrass,
wheat-barley and barley straws, paper pellets, grass and cynara
grass. In contrast, the high FT is characteristic of some biomass
sub-groups such as agricultural husks and wood and woody barks
and twigs, similar to HT. The exceptionally high FT is typical of
some biomass varieties, namely spruce and willow stems, balsam,
beech, hemlock, maple (hard), pine, poplar and spruce barks, as
well as tree pruning, rice husks, reed canary grass, alfalfa, sugar
cane baggase and paper sludge.
The present study shows that AFTs of biomass are more variable
than of coal and they are normally lower (excluding some lignites
and certain biomass varieties from ‘‘S’’ and ‘‘C’’ ash types). For com-
parison, BAs can be divided initially into five melting types accord-
ing to HT (the most informative AFT), namely:
(1) Very low (<1000 °C).
(2) Low (1000–1200 °C).
(3) Moderate (1200–1400 °C).
(4) High (1400–1600 °C).
(5) Very high (>1600 °C) types; similar to coal ashes [152].
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 59

Fig. 6. XRD patterns of high-temperature ashes (HTAs) generated from eight biomass varieties at 500 °C/2 h. Abbreviations: A, anhydrite (CaSO4); Ap, apatite (Ca(PO4)3
(Cl,F,OH)); Arc, arcanite (K2SO4); BC, beech wood chips; Cc, calcite (CaCO3); CC, corn cobs; Cps, counts per second; Cr, cristobalite (SiO2); F, fairchildite (K2Ca(CO3)2); G,
gypsum (CaSO42H2O); Ha, halite (NaCl); K, kalicinite (KHCO3); KF, K feldspars (KAlSi3O8); MM, marine macroalgae; N, natrite (Na2CO3); NF, natrofairchildite (Na2Ca(CO3)2);
Pm, picromerite (K2Mg(SO4)26H2O); Pl, plagioclases (NaAlSi3O8–CaAl2Si2O8); PP, plum pits; Q, quartz (SiO2); RH, rice husks; SG, switchgrass; SS, sunflower shells; Sy, sylvite
(KCl); Tr, tridymite (SiO2); Wl, whitlockite (Ca3(PO4)2); WS, walnut shells.

Table 7
Mean and range values of elements volatilized during biomass combustion, wt.%.

Element Mean Minimum Maximum Samples Reference used

Hg 99 95 100 5 [108,192]
Cd 95 1 [108]
Sb 95 1 [108]
Se 95 1 [108]
V 95 1 [108]
Br 85 80 90 2 [108]
Cr 75 70 80 2 [108]
Pb 71 40 100 5 [190,191]
Zn 70 3 95 7 [190,191]
Cl 66 15 100 9 [14,114,123,189–191]
As 58 25 90 2 [108]
S 57 7 90 15 [14,89,108,114,123,190,191]
K 36 5 90 8 [89,110,190,191]
Na 13 2 24 2 [191]
60 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Table 8
Ash-fusion temperaturesa of 87 varieties of biomass and coals with different rank, °C.

Ash DT ST HT FT Typeb Samplesc Reference used

1. Wood and woody biomass (WWB)
Mean 1192 1328 1380 1407 M 50
Minimum 670 1105 1190 1207 L 50
Maximum 1565 1571 1665 >1700 VH 50
1.1. Stems (WWS)
1. Beech wood 1140 1260 1310 1340 M 1 [14]
2. Citrus tree wood 1210 1240 1295 1335 M 1 [62]
3. Cork oak 1190 1200 1220 1280 M 1 [197]
4. Eucalyptus 1155 1200 1215 1245 M 2 [197]
5. Eucalyptus stems 1430 PH 1 [35]
6. Fir-pine chips 1236 1244 1246 1249 M 1 [30]
7. Manzanita chips 1080 1400 >1400 M, H 1 [68]
8. Olive tree wood 1225 1270 1325 1360 M 1 [62]
9. Pine 1190 1200 1220 1280 M 1 [197]
10. Pine chips 1125 1210 1250 1275 M 1 [196]
11. Pine sawdust 1215 1241 1252 1271 M 2 [77,196]
12. Poplar >1400 PH 1 [197]
13. Rockrose 1360 1360 1370 1390 M 1 [197]
14. Sida rhombifolia stumps 1170 1310 1398 1439 M 1 [201]
15. Spruce 1320 1525 1600 1650 H 1 [198]
16. Spruce sawdust 1120 1150 1200 1270 L, M 1 [195]
17. Spruce wood 1225 1525 1665 >1700 VH 3 [14]
18. Spruce-pine pellets 1241 PM 7 [29]
19. Willow 1453 1518 1528 1550 H 3 [194,196,198]
20. Wood chips 1050 1190 >1190 L 1 [68]
Mean 1227 1297 1334 1366 M 20
1.2. Barks (WWBA)
21. Balsam bark 1565 1571 1574 1576 H 1 [68]
22. Beech bark 1360 1538 1541 1543 H 1 [68]
23. Birch bark 1309 1392 1440 1487 H 3 [68,196]
24. Coniferous bark-wood chips 1100 1475 H 1 [25]
25. Eucalyptus bark 1200 1250 1275 M 1 [90]
26. Hemlock bark 1471 1515 1521 1526 H 1 [68]
27. Maple (hard) bark 1454 1548 1551 1554 H 1 [68]
28. Maple (soft) bark 1387 1465 1468 1471 H 1 [68]
29. Pine bark 1231 1425 1519 1527 H 3 [68,196]
30. Poplar bark 1471 1537 1540 1543 H 1 [68]
31. Sawmill bark 1160 PL 1 [35]
32. Spruce bark 1345 1474 1520 1530 H 6 [14,68,196]
33. Tamarack bark 1232 1260 1274 1287 M 1 [68]
Mean 1330 1473 1473 1483 H 13
1.3. Stumps (WWST)
34. Anisomales stumps 740 1250 1412 1441 H 1 [181]
35. Eupatorium stumps 670 1109 1233 1242 M 1 [181]
36. Sida stumps 760 1360 1460 1490 H 1 [181]
37. Vinca rosea stumps 1191 1314 1421 1462 H 1 [201]
38. Xanphium stumps 670 1105 1191 1207 L 1 [181]
Mean 806 1228 1343 1368 M 5
1.4. Leaves (WWL)
39. Parasol tree leaves 1126 1292 1294 1295 M 1 [77]
40. Sida rhombifolia leaves 1081 1245 1330 1388 M 1 [201]
41. Vinca rosea leaves 1182 1327 1429 1471 H 1 [201]
42. Vine shoots 1268 1280 1353 1380 M 2 [45,62]
Mean 1164 1286 1352 1384 M 4
1.5. Twigs (WWT)
43. Sida rhombifolia branches 1157 1335 1434 1474 H 1 [201]
44. Vinca rosea branches 1180 1320 1409 1456 H 1 [201]
Mean 1169 1328 1422 1465 H 2
1.6. Roots (WWR)
45. Sida rhombifolia roots 1073 1196 1305 1354 M 1 [201]
46. Vinca rosea roots 1155 1280 1390 1435 M 1 [201]
Mean 1114 1238 1348 1395 M 2
1.7. Others (WWO)
47. Forest residue 1320 1380 1395 M 1 [45]
48. Olive tree prunings 1280 >1400 PM 1 [197]
49. Tree pruning 770 1550 >1550 H 1 [68]
50. Wood residue chips 1175 1205 1230 1250 M 1 [196]
Mean 1136 1205 1387 P1399 M 4
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 61

Table 8 (continued)

Ash DT ST HT FT Typeb Samplesc Reference used

2. Herbaceous and agricultural biomass (HAB)

Mean 979 1112 1241 1285 M 34
Minimum 700 795 975 1000 VL 34
Maximum 1472 1513 1605 P1620 VH 34
2.1. Grasses and flowers (HAG)
51. Alfalfa 700 1550 >1550 H 1 [68]
52. Banagrass 1000 VL 4 [193]
53. Brassica 1005 >1400 PM 2 [197]
54. Cynara grass 1060 1130 1180 L 1 [177]
55. Grass 953 1023 1090 1165 L 4 [14,198]
56. Miscanthus 940 990 1168 1240 L 2 [14]
57. Reed canary grass 1453 1513 1549 P1586 H 14 [129,133]
58. Safflower 700 1430 >1430 H 1 [68]
59. Thistle 945 980 1240 P1275 M 2 [197]
Mean 970 1127 1308 P1314 M 9
2.2. Straws (HAS)
60. Barley straw 845 1025 1125 L 2 [10,68]
61. Bean straw 920 1205 >1205 M 2 [68]
62. Oat straw 800 1050 1200 L 1 [10]
63. Rice straw 991 1180 1266 1369 M 9 [30,48,68,77,90,197]
64. Rye straw 825 1100 1350 L 1 [10]
65. Wheat straw 915 941 1111 1226 L 9 [10,14,48,80,99,194,197,200]
66. Wheat-barley straw 700 975 1025 VL 1 [25]
Mean 857 1061 1105 1214 L 7
2.3. Stalks (HAST)
67. Corn stalks 973 1155 >1155 L 3 [68]
68. Cotton stalks 1019 1159 1288 1335 M 2 [68,80]
69. Pepper stalks 1154 1202 1224 1241 M 1 [80]
Mean 1049 1181 1222 P1244 M 3
2.4. Shells (HASH)
70. Almond shells 775 795 1395 >1400 M 4 [68,197]
71. Walnut shells 820 1225 >1225 M 1 [68]
Mean 798 798 1310 >1313 M 2
2.5. Husks (HAH)
72. Rice husks 1472 1605 P1620 VH 5 [68,69,86,90]
2.6. Pits (HAP)
73. Olive pits 1132 1265 1303 1328 M 6 [41,45,62,68,197]
2.7. Other residues (HAR)
74. Cocoa (shea) meal 1140 1310 1330 M 1 [81]
75. Corn cobs 900 1020 >1020 L 1 [68]
76. Corn fodder 1010 1180 >1180 L 1 [68]
77. Cotton gin trash 1010 1380 >1380 M 1 [68]
78. Cotton residue 1120 1180 1190 L 1 [45]
79. Olive residue 1260 1280 1310 1325 M 2 [197]
80. Palm kernel expellers 1070 PL 1 [199]
81. Sugar cane baggase 1500 H 6 [193]
82. Sunflower 740 1360 1390 M 1 [197]
83. Wheat cereals 990 1020 1145 1200 L 3 [14]
84. Wheat straw-corn stalks 985 1260 >1260 M 1 [68]
Mean 1023 1150 1238 P1278 M 11
3. Contaminated biomass (CB)
85. Demolition wood 1195 1205 1210 M 1 [45]
86. Paper pellets 890 1130 >1130 L 1 [68]
87. Paper sludge 1438 1505 1510 H 1 [45]
Mean 1174 1280 P1283 M 3
Minimum 890 1130 >1130 L 3
Maximum 1438 1505 1510 H 3
All varieties of biomass (AVB)
Mean 1111 1277 1322 1353 M 87
Minimum 670 795 975 1000 VL 87
Maximum 1565 1571 1665 >1700 VH 87
Natural biomass (NB)
Mean 1109 1277 1323 1356 M 84
Minimum 670 795 975 1000 VL 84
Maximum 1565 1571 1665 >1700 VH 84
Coal
Lignite (mean) 1147 1261 1286 M 5 [170]
Subbituminous coal (mean) 1218 1365 1389 M 10 [170]
Bituminous coal (mean) 1280 1404 1423 H 22 [170]
Coal (mean) 1251 1388 1411 M 37 [170]

(continued on next page)

62 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
Table 8 (continued)
Ash DT ST HT
Coal (minimum) 1105 1200
Coal (maximum) 1525 1575
a
DT, initial deformation temperature; ST, spherical temperature; HT, hemispherical temperature; FT, fluid temperature.
b
Melting types based on HT: VL, very low (<1000 °C); L, low (1000–1200 °C); M, moderate (1200–1400 °C); H, high (1400–1600 °C); VH, very high (>1600 °C) types.
c
Some of these data are mean values from numerous determinations for a given biomass variety.
Some indicative inorganic trends of natural biomass in compar-
ison with coal were found recently [2], namely the potential of bio-
mass to have normally:
(1) Higher values of Ca, Cl, H, K, Mg, Mn, Na, O, P, carbonates,
chlorides, phosphates, organically bound inorganic elements
and water-soluble components.
(2) Lower values of Al, C, Fe, N, S, Si, Ti, ash (inorganic matter),
oxyhydroxides, silicates and sulphates-sulphides.
These differences could be the reason for the lower AFTs of bio-
mass in comparison with coal (Tables 8 and 9). For example, it is
widely accepted that high contents of Si-, Al- and Ti-bearing min-
erals are responsible for increased AFTs of coal [152]. An under-
standing of such differences, in particular for the various
inorganic and AFT types and sub-types, is important for trouble-
free combustion and co-combustion of biomass with coal and
other fuels (see Part 2). The phase transformations responsible
for the specific AFTs during biomass combustion are beyond the
subject of the present study and they will also be characterized
in a future publication.
3.1.7. Leaching
3.1.7.1. Water leaching. The reference investigations show that the
content of water-soluble fraction in BA is high [14,69] and can be
up to 61.0% [103], while the same value for coal ashes is much less,
namely 0.2–7.2% (mean 1.6%) [150]. The pH values of the different
BA leachates (dominantly produced from woody and straw bio-
mass) vary in the range 4.5–13.4 (mean about 10.7)
[14,24,39,41,45,47,57,60,105,121,132,204], while the values of
water leachates from coal ashes fall in a more narrow range,
namely 6.2–12.5 (mean 10.0) [150]. The pH values of woody BAs
are normally higher than straw and cereal BAs due to the higher
Ca and lower S and Cl concentrations in the former ashes [14]. It
is well known that in comparison with coal and peat, biomass
has significantly higher levels of water-soluble material abundant
in K, Cl, Ca and Mg [14,69]. Therefore, the loss of organic acids dur-
ing biomass burning and the production of soluble Ca, Mg, K and
Na oxides, hydroxides, carbonates and bicarbonates in BA are the
major reasons for increasing pH in BA [60,105,121]. The pH of
BAs is also largely influenced by the combustion temperature
and the storage time, as the alkalinity decreases with increasing:
(1) combustion temperature and (2) period of storage [121]. The
decreasing trend for pH with storage time can be caused by trans-
formation of hydroxides to carbonates in BA [24]. It was also found
that the total dissolved solids from wood BA increased by 500% as
the pH decreased from 13 to 5, while their extraction rate was
essentially independent of pH [60].
The reference investigations also reveal (Table 10) that the
mean contents of the water-soluble elements leached from differ-
ent BAs (produced mainly from woody and straw biomass) are:
Cl > S > K > Na > Sr > Ni > Mn > Cd > Cr > Zn > Co > Si > Mo > -
Li > (Mg, Pb) > Ca > Cu > Ba > P > Se > Sb > Al > Fe > (Br, Hg) > (As, B,
Sn, Ti, V) [18,24,35,41,45,57,60,65,67,70,95,121,122,137,157]. It is
widely accepted that the solubility (hence, environmental mobil-
ity) of most elements contained in BAs and coal ashes is markedly
FT Typeb Samplesc Reference used
1205 L, M 37 [170]
1585 H 37 [170]
pH sensitive and a more alkaline character depresses the release of
a large number of elements (Al, Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb, Sn Ti,
Zn among others) but enhances the release of oxyanionic-forming
species of As, B, Cr, F, Mo, Sb, Se, V and W [23,204–206].
The data from Table 3 show that the water-soluble phases in BA
mostly include phases of alkali and alkaline earth elements such
as:
(1) Highly soluble chlorides (sylvite, halite), sulphates (arcanite,
syngenite, ettringite, gypsum), oxides (lime), hydroxides
(portlandite), nitrates, carbonates and bicarbonates.
(2) Certain less soluble carbonates (calcite) and phosphates
(phosphorites).
(3) Some slightly soluble phosphates (apatite) and silicates (Ca
silicates, feldspars).
It should be stated that some precipitation of minerals such as
ettringite, portlandite, calcite, gypsum and Ca silicate hydrate from
water leachates of BAs at alkaline pH (typical for BA) was also ob-
served [57,60]. It is well known that there is transformation of ele-
ments from water-soluble forms in the biomass itself to more
stable acid soluble and insoluble forms (silicates and oxides) in
BAs [18]. Hence, the conditions under which the biomass is burned
are also important for the amount and properties of the water-sol-
uble fraction in BA. For example, carbonates and bicarbonates pro-
duced at combustion temperatures below 500–800 °C are
common, while oxides and silicates are most prevalent at higher
temperatures (at or above 800–1000 °C) and longer heating times
[25,60,62,107,207].
Finally, the dry residues obtained by the evaporation of water-
soluble extracts from solid fuels and their ashes are quite impor-
tant for the definitive identification of various chlorides (sylvite,
halite, carnallite), sulphates (gypsum, bassanite, anhydrite, hexa-
hydrite, barite, alunite, jarosite, szomolnokite, kieserite, polyha-
lite), carbonates (calcite, dolomite, ankerite), silicates (opal,
zeolite), hydroxides (portlandite), organic minerals (Ca oxalates),
phosphates and amorphous matter that may be originally present.
These water-soluble residues can be highly enriched in some mo-
bile minerals and minor and trace elements (B, Cl, Cs, Cu, Li, Mn,
Mo, Ni, P, Rb, Sb, Se, Sn, Sr, Ti, Zn, others) and most of them may
have resource potential and/or be of environmental concern during
the transport, storage and processing of solid fuels and their ashes
(see Part 2 and [145,146] and references therein). Some initial
investigations about the composition and significance of water-
soluble residues produced from biomass have been described re-
cently [2].
3.1.7.2. Leaching by different solvents. In contrast to the simple and
highly informative water leaching of BA, the leaching of BA by
other solvents is accompanied by serious problems and some elu-
cidation of this method is required. Therefore, a short summary of
leaching of solid fuels and their ashes by different solvents is in-
cluded herein, based on ([145,146] and references therein). There
are numerous more or less successful leaching procedures using
open or closed systems for dissolving (or etching) organic matter
and inorganic matter from solid fuels and their ashes. The digestion
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 63

Abbreviations: AVB, all varieties of biomass; B, bituminous coal; C, coal; CB, contaminated biomass; DT, initial deformation temperature; FT, fluid temperature; HAB, herbaceous and agricultural biomass; HAF, herbaceous and
agricultural fibers; HAG, herbaceous and agricultural grasses and flowers; HAH, herbaceous and agricultural husks; HAP, herbaceous and agricultural pits; HAR, other herbaceous and agricultural residues; HAS, herbaceous and

wood and woody biomass; WWBA, wood and woody barks; WWL, wood and woody leaves; WWO, other wood and woody biomass; WWR, wood and woody roots; WWS, wood and woody stems; WWST, wood and woody stumps;
agricultural straws; HASH, herbaceous and agricultural shells; HAST, herbaceous and agricultural stalks; HT, hemispherical temperature; L, lignite; NB, natural biomass; S, sub-bituminous coal; ST, spherical temperature; WWB,
of organic constituents is commonly performed in hydrogen perox-

HAH(1605) > WWBA(1473) > WWT(1422) > B(1404) > C(1388) > WWO(1387) > WWB(1380) > S(1365) > WWL(1352) > WWR(1348) > WWST(1343) > WWS(1334) > NB(1323) > AVB(1322) > HASH(1310) > HAG(1308)
ide, concentrated nitric acid, alkaline hydroxides and organic sol-

WWBA(1473) > WWB = WWT(1328) > WWS(1297) > WWL(1286) > AVB = NB(1277) > HAP(1265) > WWR(1238) > WWST(1228) > WWO(1205) > HAST(1181) > HAR(1150) > HAG(1127) > HAB(1112) > HAS(1061)
vents (for example, benzene and many others [2]). On the other
hand, the leaching of inorganic matter, specific mineral classes
and occasionally (for more simple systems) mineral groups and

HAH(1620) > WWBA(1483) > WWT(1465) > B(1423) > C(1411) > WWB(1407) > WWO(1399) > WWR(1395) > S(1389) > WWL(1384) > WWST(1368) > WWS(1366) > NB(1356) > AVB(1353) > HAP(1328)
species, is mostly carried out in acids. This demineralization is car-
HAH(1472) > WWBA(1330) > B(1280) > C(1251) > WWS(1227) > S(1218) > WWB(1192) > CB(1174) > WWT(1169) > WWL(1164) > L(1147) > WWO(1136) > HAP(1132) > WWR(1114) > AVB(1111)
ried out mainly with hydrochloric, nitric and hydrofluoric acids, to
a lesser extent, sulphuric, citric and acetic acids, and occasionally
other solvents such as ammonium acetate, Na acetate, Na hydrox-
ide and hydroxylamine hydrochloride or their combination. How-
ever, the interpretation of such chemical leaching should always
be approached with much caution because the results obtained
are indirect. Additionally, this method is unselective and unreliable
for characterization of phases in multicomponent systems such as
solid fuels and their ashes because the solvents leach assumed and
preliminary unidentified components (various phases of Al, C, Ca,
Fe, K, Mg, N, Na, P, S, Si, Ti and trace elements) associated with both
Decreasing orders of mean values for the ash-fusion temperatures (AFT) of the biomass groups and four solid fossil fuel types (bold font), as well as biomass sub-groups, °C.

organic matter and inorganic matter. Most of the unstable minerals

and phases in the samples treated by the specific solvents are nor-
mally easily leached, destroyed or altered during this procedure
(chlorides, sulphates, sulphides, carbonates, oxyhydroxides, phos-
phates and some silicates, glass and organic matter). Therefore,
the leached species are not available or actual for any future direct
phase study of the samples. On the other hand, there is a formation
of new artificial and stable minerals and phases (some chlorides,
fluorides, nitrates, oxalates, sulphates, oxyhydroxides, others), as
well as sorption phenomena (re-adsorption) of elements on some
stable phases in the system during this leaching and they can re-
main in the solid residue. Furthermore, portions of different origi-
nal phases (quartz, clays, carbonates, oxides, phosphates, accessory
minerals, organic matter, others) treated by the above solvents
may remain insoluble in the solid residue. This is due to the lower
solubility of these phases or less accessability of other phases,
> HAG(1314) > HASH(1313) > L(1286) > HAB(1285) > CB(1283) > HAR(1278) > HAST(1244) > HAS(1214)
> NB(1109) > HAST(1049) > HAR(1023) > HAB(979) > HAG(970) > HAS(857) > WWST(806) > HASH(798)

namely when the solvents cannot make contact with phases

encapsulated in other more stable organic and inorganic matrices
(in particular glass and certain silicates and oxides). There are also
many additional problems related to the appropriate selection of
conditions (time, temperature, agitation, batch or column test),
> HAP(1303) > CB(1280) > L(1261) > HAB(1241) > HAR(1238) > HAST(1222) > HAS(1105)

solvents, sample volume and particle size, solid/liquid ratio and

concentration and performance of the reagents because this selec-
tion can be different for each sample or type of samples due to var-
iable composition. Finally, it should be stated that there are no
universal solvents and procedures for all solid fuels and their ashes
because each have distinct composition and behaviour during
leaching. Hence, the assumed dissolution of inorganic matter, or-
ganic matter and specific mineral classes, groups and species with
subsequent determination of the element contents in the leachates
should always be accompanied by phase–mineral investigations on
the solid residues after chemical leaching. Unfortunately, such par-
allel investigations are not common in the literature.

3.1.7.3. Sequential leaching. A short summary of sequential chemi-

cal leaching (also known as sequential speciation, fractionation,
selective extraction and stepwise or successive leaching) of solid
Order for groups and sub-groups

fuels and their ashes by different solvents is also included herein,

based on ([145,146,208–210] and references therein). This sequen-
tial leaching, using also open or closed systems, is commonly con-
WWT, wood and woody twigs.

ducted by distilled, redistilled or deionised water (occasionally

plus acetic acid), hydrogen peroxide, acetic acid, ammonium ace-
> HASH(795)

tate, hydrochloric acid, hydrofluoric acid and nitric acid under dif-
ferent leaching schemes. These batch or column procedures use
sequential solubility in increasingly aggressive solvents for isola-
tion of water-soluble, adsorbed and ion-exchangeable compo-
nents, chlorides, sulphates, carbonates, oxides, phosphates,
Table 9

AFT

HT
DT

ST

FT

silicates, glass, sulphides and organic matter. However, it was con-

cluded that the utilization of sequential leaching methods without
64 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Table 10
Mean and range contents of water-soluble elements leached from biomass ashes, wt.%.

Element Mean Minimum Maximum Samples Reference used

Cl 67.9 8 99 17 [18,95,122,157]
S 58.2 16 97 14 [95,122,157]
K 44.0 2 98.1 26 [18,24,35,57,60,65,95,121,122,157]
Na 35.5 0 100 22 [24,35,57,60,95,122,157]
Sr 15.0 1 [157]
Ni 9.8 0 18 4 [41,45,157]
Mn 9.6 0 46 7 [41,45,57,65,157]
Cd 8.3 0 48.9 6 [57,65,67,121,157]
Cr 8.0 0 30 5 [41,45,121,157]
Zn 7.9 0 44 8 [41,45,57,65,121,157]
Co 7.8 0 15 4 [41,45,157]
Si 6.2 0 74 13 [70,122,157]
Mo 6.1 Trace 12 2 [137,157]
Li 5.0 1 [157]
Mg 3.8 0 39 17 [35,57,65,122,157]
Pb 3.8 Trace 15 5 [41,57,65,121,157]
Ca 3.4 0 19.7 19 [57,65,95,122,157]
Cu 3.1 0 10 8 [41,45,57,65,121,157]
Ba 3.0 1 [157]
P 2.3 0 15 15 [18,95,122,157]
Se 2.0 1 [157]
Al 0.9 0 9 13 [65,122,157]
Sb 0.6 Trace 1 2 [137,157]
Fe <0.1 0 1 14 [57,122,157]
Br Trace 1 [137]
Hg Trace 1 [57]
As 0 1 [157]
B 0 1 [157]
Sn 0 1 [157]
Ti 0 12 [122,157]
V 0 1 [157]

significant phase–mineral information for the bulk samples and
each residue obtained, might be quite confusing in the interpreta-
tion of assumed leachates (see also Section 3.1.7.2). Unfortunately,
such combined investigations are not common in the literature.
Similarly, sequential chemical leaching of BA and biomass in-
volves the treatment with a series of progressively more severe
chemical reagents in order to determine the speciation (chemical
forms, modes of occurrence) of elements. The chemical fraction-
ation techniques of BA and biomass is normally performed by
deionised (or distilled) water, acidified water, ammonium
acetate, hydrochloric acid and occasionally other solvents
[14,18,35,36,38,39,48,64,65,67–69,75,90,92,93,100,107,109,110,122,
177,179,190,204,205,211–226]. Unfortunately, this approach is
mostly used to distinguish the speciation of elements in BA and
biomass. For example, as a result of this sequential solubility in
three increasingly aggressive solvents (water, ammonium acetate
and hydrochloric acid), the following speciation of elements was
identified in BA and biomass:
(1) Water soluble: salts; alkali salts; K, Cl and P; alkali material;
alkali metal salts; salts and loosely bound material; alkali
metal salts, S and Cl compounds; alkali chlorides, sulphates
and carbonates; chlorides and alkali sulphates and carbon-
ates; alkali and alkaline earth chlorides and alkali sulphates;
alkali chlorides, sulphates and carbonates, and alkaline earth
chlorides.
(2) Ammonium acetate soluble: alkali material; ion-exchange-
able material; organically associated metals; organically
associated components; ion-exchangeable elements and
organic acids; organic fraction present as cations and che-
lates; ion-exchangeable alkali and alkaline earth compo-
nents; inorganic elements ionically bound to organic
structure; ion-exchangeable Ca, Na and K directly bound to
the organic groups; ion-exchangeable S and Ca and more
organically associated K and Na; ion-exchangeable inorganic
part represented by organically associated metal ions; and
organically associated ion-exchangeable Na, Ca and Mg,
and part of calcite.
(3) HCl soluble: carbonates and clays; carbonates and sul-
phates; Ca carbonates and sulphates; Ca and Fe carbonates
and Ca oxalates; carbonates, sulphates and mono-sulphides;
carbonate, sulphate and alkali chloride minerals; alkaline
earth carbonates, sulphates and sulphides; and inorganic
salts or organically associated non-metals like P or S.
(4) Solid residue with insoluble: silicates; silicate minerals;
principally silicates; quartz, clays and rutile; silicates, oxides
and sulphides; silica, silicates and other mineral species; sil-
icates, oxides, sulphides and other minerals; silicates and S,
Cl and P covalently bound to the organic structure; and sili-
cates and elements that are bound to organic matrix with a
covalent bond [14,36,38,48,90,92,109,190,211,215,220–
222,225].
The above investigations obviously show that there was no one
real speciation among thousands of mineral species and phases or
even among a group of mineral species and phases. Hence, this
procedure cannot be applied to identify the actual modes of ele-
ment occurrence in a multicomponent system and its advanced
role is highly overestimated in the literature. This was evident even
after the application of an improved six-stage sequential leaching
procedure (by distilled water, hydrogen peroxide and acetic,
hydrochloric, hydrofluoric and nitric acids) of coal ashes with pre-
liminary well known bulk chemical and phase–mineral composi-
tion [209,210]. The sequential leaching and digestion by different
solvents as mentioned above (see also Section 3.1.7.2) have numer-
ous limitations and these subsidiary procedures cannot be used as
basic techniques unaccompanied by other indispensable methods
of investigations such as light microscopy, electron microscopy,
XRD, physical separations and others. Hence, this indirect, rather
unselective and maybe unreliable sequential leaching procedure
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
cannot be applied to identify the actual modes of element occur-
rence in a multicomponent system such as biomass ash and the
interpretation should always be approached with much caution.
The results from the leaching procedures of muticomponent sys-
tems such as solid fuels and their ashes could be used mostly to
provide:
 Determination of elemental proportions leached by specific sol-
vents or their combination.
 Preliminary information for some possible associations of ele-
ments in some mineral classes or group of phases.
 Specification of some limiting and guiding values for certain
hazardous elements in leachates.
 Simulations of some probable release of elements and assumed
components in time during weathering.
 Experiments related to recovery or concentration of elements
and compounds for industrial purposes; as the results should
be interpreted very carefully and only together with data from
more secure methods.
Other preferably direct methods commonly applied for coal and
coal products ([145,146,208] and references therein) provide much
better information for such a speciation purpose and they should
always be used additionally before and after the supplementary
leaching procedures. Unfortunately, such parallel investigations
are almost absent among the extensive investigations related to
sequential leaching of solid fuels and their ashes.
3.2. General comments about phase–mineral composition of biomass
ash
The reference investigations and present study show that the
identified minerals and phases in BA include approximately 229
species and groups of species, which are arranged systematically
and alphabetically (Table 3). In contrast, the minerals and phases
found in coal ash are totally about 188 species and groups of spe-
cies [146] and most of them are listed in Table 11 (based on
[148,150,166,167]). The identified minerals in BA (in decreasing
number of species) belong to the mineral classes: silicates > oxides
and hydroxides > sulphates (plus sulphides, sulphosalts, sulphites
and thiosulphates) > phosphates > carbonates > chlorides (plus
chlorites and chlorates) > nitrates (Table 3). The common phases
found in BAs (in decreasing number of identifications) comprise:
(1) Mostly quartz, calcite, sylvite, arcanite, anhydrite, char,
glass, lime, periclase and hematite.
(2) Subordinately portlandite, cristobalite, hydroxylapatite, lar-
nite, albite, Ca phosphates, fairchildite, K carbonate, K feld-
spars, halite and K–Ca silicates.
(3) More rarely akermanite, plagioclases, wollastonite, dolo-
mite, apatite, Ca langbeinite, dioxins, furans, gehlenite, K sil-
icates and rutile.
(4) Occasionally glaserite, kalsilite, K phosphates, oldhamite,
amorphous inorganic matter, anorthite, aphthitalite, Ca–Al
oxides, diopside, ettringite, gypsum, melilite, merwinite,
muscovite, natrite, tridymite; plus a number of uncommon
(accessory) phases (Table 3).
In contrast to coal ashes (Table 11), there are not enough data
for the concentration of minerals and phases for different BAs to di-
vide them into forming, major, minor and accessory phases despite
some quantitative determinations by XRD and computer con-
trolled scanning electron microscopy [40,46,55,59,68,84,106]. Nev-
ertheless, some minerals and phases in BAs produced only from
woody biomass, straw and switchgrass can be divided preliminary
and roughly, in decreasing order of concentration, into:
65
(1) Forming (>10%) such as glass, sylvite, calcite, leucite, anor-
thite, K–Ca silicate, char and quartz.
(2) Major (1–10%), namely albite, anhydrite, ankerite, kaolinite,
siderite, cristobalite, arcanite, hematite, illite, lime, Na sili-
cate, fairchildite, hydroxylapatite, merwinite, periclase, Ca
chlorosilicate, diopside, glaserite, K feldspar, larnite, and
portlandite.
(3) Minor (0.1–1%) such as K silicate, K phosphate and K carbon-
ate; and
(4) Some accessory phases (<0.1% or only traces) according to
their mean contents.
The present study shows that most of the BAs produced at
500 °C/2 h (Fig. 6) have a highly crystalline character with limited
occurrence of inorganic amorphous material and organic matter at
this temperature. Only a few individual char particles were recog-
nized by light microscopy in these ashes as black porous particles
particularly encapsulated by silicates. The XRD data reveal the
occurrence of different minerals in the BAs studied (Fig. 6). Most
of them seem to be newly formed minerals in BAs and they belong
to carbonate, sulphate, silicate and phosphate classes. Some of
them are very interesting species from technological and environ-
mental points of view (see Part 2 and [150,151]) because they are
not typical of coal ashes ([148,150,166,167,227] and references
therein). The BC sample thermally treated in air up to 1300 °C
(Fig. 4) is just given for an illustration of some phase transforma-
tions and formations (see Section 3.1.5), and certain contamina-
tions (mullite and partly quartz) occurring in BA with gradual
increasing of temperatures above 500 °C.
The reference investigations and present study reveal that
phases in BA are mostly secondary, to a lesser extent tertiary and
occasionally primary in origin. For example, the mineral species
found in biomass ([2] and references therein) and belonging to
classes such as oxalates, silicates, oxides, hydroxides, sulphates,
sulphites, sulphides, phosphates, carbonates, chlorides, nitrates,
amorphous inorganic matter and others can be primary inorganic
species in BA. On the other hand, various silicates, oxides, hydrox-
ides, carbonates, sulphates, sulphides, sulphosalts, sulphites, thio-
sulphates, phosphates, chlorides, chlorites, chlorates, nitrates,
oxalates, char, amorphous inorganic matter and glass can be newly
formed secondary phases in BA. Additionally, minerals mostly from
silicate, hydroxide, sulphate and carbonate classes, to a lesser ex-
tent phosphates and chlorides, and probably some nitrates can also
have tertiary origin (Table 3 and see Section 3.3 for details). These
observations are similar to those for coal ash (Table 11).
Finally, it can be seen that most of the minerals and phases
identified in coal ashes (Table 11) were also found in BAs (Table 3).
However, many mineral species among Ca–K–Mn silicates, Ca–Al–
Mn oxides, K–Na–Ca chlorides and K–Ca–Mg–Na carbonates, sul-
phates and phosphates were normally not identified in coal ashes.
The reason for that could be the enrichment of elements such as Ca,
Cl, K, Mg, Mn, Na and P in BAs compared to coal ashes. In contrast,
many Al-, Fe-, Si- and Ti-bearing minerals, typical for coal ashes,
were not identified in BAs probably due to limited contents of
these elements in BAs [1,2].
3.3. Phase–mineral composition of biomass ash
The phase and mineral composition of BA includes various spe-
cies and groups of species that belong to different mineral classes,
organic phases, organic minerals and other phases identified in
various BAs worldwide (Table 3). A short summary of the mineral
classes and other common phases based on reference investiga-
tions and present study is provided below, while the general and
specific phase transformations during biomass combustion are
66 S.V. Vassilev et al. / Fuel 105 (2013) 40–76

Table 11
Occurrence, abundance and origin of minerals and phases in coal fly ashes from 37 power plants of Bulgaria, Greece, Italy, Spain, The Netherlands and Turkey (based on
[148,150,166,167]).

Mineral, phase Formula Quantity Origin

P S T
Silicates
Amphibole NaCa2(Mg, Fe, Al)5(Si, Al)8O22(OH)2 A ⁄
Andalusite Al2SiO5 A ⁄ 
Ca–Fe aluminosilicate A 
Ca–Fe–Mg aluminosilicate A 
Ca–Fe silicate A 
Ca–Mn silicate A 
Celsian BaAl2Si2O8 A  ⁄
Chloritoid (Mg, Fe)2Al4Si2O10(OH)4 A 
Chlorite (Mg, Fe)5Al2Si3O10(OH)8 A–Mi  ⁄
Cristobalite SiO2 A–M ⁄ 
Fe–Mg aluminosilicate A 
Illite-metaillite (K,H2O)Al2(Al, Si)Si3O10(OH)2 A–M  ⁄
Kaolinite-metakaolinite Al2Si2O5(OH)4 A–M ⁄ 
K feldspars KAlSi3O8 A–M  ⁄
Larnite b-Ca2SiO4 A–M 
Melilite (akermanite-gehlenite) Ca2MgSi2O7–CaAl(Si, Al)2O7 A–M 
Mica K, Na, Mg, Fe, Li aluminosilicates A–M  ⁄
Monticellite CaMgSiO4 A–M 
Mullite Al6Si2O13 Mi–F ⁄ 
Muscovite KAl2AlSi3O10(OH, F)2 A–M  ⁄
Olivine Mg, Fe, Ni, Mn silicates A–Mi ⁄ 
Opal SiO2nH2O A 
Plagioclases NaAlSi3O8–CaAl2Si2O8 Mi–M  ⁄
Pyroxene Mg, Fe, Ca, Mn, Na, Li silicates A–Mi ⁄ 
Quartz SiO2 M–F  ⁄
Rankinite Ca3Si2O7 A–Mi 
Talc Mg3Si4O10(OH)2 A ⁄  ⁄
Tridymite SiO2 A–M ⁄ 
Vermiculite (Mg, Fe, Al)3(Si, Al)4O10(OH)24H2O A ⁄ 
Wollastonite a-Ca3Si3O9 A–M 
Zeolites (Ca, Sr, Ba, Na2, K2)Al2Si2–10O8–242–8H2O A 
Zircon ZrSiO4 A  ⁄
Oxides and hydroxides
Alumina c-Al2O3 A 
Anatase TiO2 A 
Ba–Ca oxyhydroxide A  ⁄
Baddeleyte ZrO2 A 
Ba hydroxide A  ⁄
Boehmite c-AlOOH A–Mi ⁄ ⁄ ⁄
Brookite TiO2 A 
Brucite Mg(OH)2 A–Mi ⁄ ⁄ 
Ce oxide A 
Chalcophanite ZnMn3O7.3H2O A ⁄ 
Chromite FeCr2O4 A  ⁄
Chromspinel CrFe2O4 A 
Corundum Al2O3 A–M ⁄ 
Cuprite Cu2O A 
Diaspore a-AlOOH A–Mi ⁄ ⁄ ⁄
Fe spinel Mg(Al, Fe)2O4 A ⁄ 
Gibbsite Al(OH)3 A–Mi ⁄ ⁄ ⁄
Hematite a-Fe2O3 Mi–M ⁄  ⁄
Hercynite FeAl2O4 A 
Ilmenite FeTiO3 A  ⁄
Jacobcite MnFe2O4 A 
Lime CaO A–M 
Limonite Fe products A–Mi ⁄ ⁄ 
Maghemite v-Fe2O3 A–Mi ⁄  ⁄
Magnesioferrite MgFe2O4 A–Mi ⁄ 
Magnetite FeFe2O4 Mi–M ⁄ 
Periclase MgO A–Mi 
Portlandite Ca(OH)2 A–M ⁄ ⁄ 
Pyrolusite b-MnO2 A 
Rutile TiO2 A  ⁄
Spinel MgAl2O4 A–Mi ⁄ 
Tenorite CuO A 
Ulvospinel TiFe2O4 A 
W–Nb–Pb oxide A ⁄ 
Zincite ZnO A 
Sulphates
Anglesite PbSO4 A 
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76 67

Table 11 (continued)

Mineral, phase Formula Quantity Origin

P S T
Anhydrite CaSO4 A–F ⁄  ⁄
Alunite KAl3(SO4)2(OH)6 A ⁄ ⁄ 
Barite BaSO4 A–Mi ⁄  ⁄
Bassanite CaSO40.5H2O A 
Ettringite Ca6Al2(SO4)3(OH)1226H2O A–M ⁄ 
Fe sulphates A–Mi ⁄  ⁄
Gypsum CaSO42H2O A–F ⁄ 
Jarosite KFe3(SO4)2(OH)6 A–M ⁄ ⁄ 
Mg sulphates A–Mi ⁄  ⁄
Na–K sulphates A–Mi ⁄  ⁄
Carbonates
Ankerite Ca(Mg, Fe)(CO3)2 A–M ⁄ ⁄ 
Calcite CaCO3 A–M  ⁄ 
Cerussite PbCO3 A ⁄ ⁄ ⁄
Dolomite CaMg(CO3)2 A–M  ⁄ 
Manganocalcite CaMn(CO3)2 A  ⁄ 
Witherite BaCO3 A  ⁄ ⁄
Phosphates
Apatite Ca(PO4)3(Cl, F, OH) A  ⁄
Goyazite Al2Sr(PO4)2(OH)5H2O A  ⁄
Monazite (Ce, La, Y, Th) (PO)4 A  ⁄
Ningyoite CaU(PO4)22H2O A  ⁄
Svanbergite SrAl3(PO4)(SO4)(OH)6 A  ⁄
Vivianite Fe3(PO4)28H2O A  ⁄
Sulphides and sulphosalts
Chalcocite Cu2S A ⁄ 
Pb–Sb sulphosalt A ⁄
Pyrrhotite Fe1xS A ⁄ 
Tungstates
Scheelite CaWO4 A  ⁄
Carbides
Fe carbide A ⁄ 
Native elements
Graphite C A ⁄ ⁄
Chlorides
Halite NaCl A 
Organic minerals
Ca–K–Na oxalate Ca, R, Na(C2O4)nnH2O A 
Others
Char A–F ⁄ 
Glass F ⁄ 

Abbreviations: F, forming (>10%); M, major (1–10%); Mi, minor (0.1–1%); A, accessory (<0.1%); P, primary; S, secondary; T, tertiary; , dominant; ⁄, subordinate.

beyond the subject of the present study and they will be character-
ized in a further publication.
3.3.1. Silicates
The numerous silicates identified in BA are listed in Table 3.
They can be mostly secondary, to a lesser extent primary, and occa-
sionally tertiary phases in BA. These minerals have both detrital
and authigenic occurrence in/on plants because:
(1) Quartz, cristobalite, feldspars, clay and mica minerals, and
some pyroxenes and olivines are typical soil minerals
[24,25,35,56,57,62,68,98,105,228] and they can have some
detrital uptake from the soil during plant growth.
(2) Opal is a characteristic authigenic mineral in plants and orig-
inates from syngenetic and epigenetic evaporation and pre-
cipitation of water, namely mineralized aqueous solution
enriched in non-charged silicic acid ([2] and references
therein).
Hence, some silicates can be primary phases in BA due to their
possible presence as unchanged relics having relatively high
decomposition and/or melting temperatures during heating. Addi-
tionally, some technogenic silicate impurities as additives or con-
taminants in semi-biomass (clay minerals, zeolites, talc and other
silicates in Table 3) generated from processing of natural biomass
can also be primary as a result of their occurrence as unaltered
minerals in BA [37,38,45]. However, the secondary silicates are
dominant in BA and these newly formed phases originate from
the alteration of pre-existing silicates, melt crystallization and
mostly from the complex reactions among silica and oxyhydrox-
ides of Al, Ba, Ca, Cd, Fe, K, Mg, Mn, Na, Sr and Ti (Table 3) gener-
ated commonly from the decomposition of organic matter,
oxalates, carbonates, phosphates, sulphates, chlorides and nitrates
during biomass combustion. For example, crystallization of various
newly formed silicates (grains and crystals with size between 1 lm
and 1 mm) within the glass matrix originated from the melt and in
wollastonite matrix was observed in some BAs [28,30,48]. The ori-
gin of these secondary silicates in BA is similar to that in coal ash
and their formation mechanisms have been described in detail ear-
lier ([163,164] and references therein). Finally, the tertiary silicates
can include minerals containing water molecules and/or hydroxyl
groups (for example, afwillite, Ca silicate hydrate, gismondite,
68 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
some clay minerals and zeolites), which are a result of hydration
and hydroxylation of other less stable silicates by water and mois-
ture in the air during transport and storage of BA [24,60,65].
3.3.2. Oxides and hydroxides
The various oxides and hydroxides found in BA are listed in Ta-
ble 3. They can be mostly secondary, to a lesser extent tertiary, and
occasionally primary phases in BA. These minerals have commonly
detrital and occasionally authigenic accessory occurrence in/on
plants because:
(1) Fe, Al and Ti oxyhydroxides are typical soil minerals
[62,98,228] and they can have some relatively low detrital
uptake from the soil during plant growth [43].
(2) Some authigenic hydroxides in plants may originate from
syngenetic and epigenetic evaporation and precipitation of
mineralized aqueous solution enriched in different cations
and hydroxide anion ([2] and references therein).
Hence, some oxyhydroxides can be primary phases in BA due to
their possible presence as unchanged relics having relatively high
decomposition and/or melting temperatures during heating. Addi-
tionally, the occurrence of some technogenic Fe-, Al-, Mg-, Ca- and
Ti-bearing oxyhydroxides (Table 3) in semi-biomass as impurities
(additives or contaminants) generated from processing of natural
biomass can also be primary as a result of their presence as unal-
tered minerals in BA [37]. However, the secondary oxyhydroxides
of Al, Ca, Cd, Cr, Fe, K, Mg, Mn, Na, Pb, Pd, Ti and Zn (Table 3) are
dominant in BA and these newly formed phases originate mostly
from the decomposition and oxidation of organic matter, oxalates,
carbonates, phosphates, sulphates, chlorides and nitrates, and, to a
lesser extent, melt crystallization during biomass combustion. The
origin of these secondary oxyhydroxides in BA is similar to that in
coal ash and their formation mechanisms have been described in
detail earlier excluding the phases containing some trace elements
([163,164] and references therein). Finally, the tertiary hydroxides
can include minerals containing hydroxyl groups and water mole-
cules (for example, gibbsite, goethite, portlandite, brucite, hydro-
calumite and K and Na hydroxides), which are a result of
hydration and hydroxylation of other less stable oxides by water
and moisture in the air during transport and storage of BA
[24,34,57,60,62,89].
3.3.3. Sulphates, sulphides, sulphosalts, sulphites and thiosulphates
The various sulphates identified in BA are listed in Table 3. They
can be mostly secondary, to a lesser extent tertiary, and occasion-
ally primary phases in BA, which is identical to oxyhydroxides. Sul-
phates are highly mobile during weathering and they are not
typical soil minerals [228]. These minerals have authigenic occur-
rence in plants because they originate from syngenetic and epige-
netic evaporation and precipitation of mineralized aqueous
solution enriched in different cations and sulphate anion, as well
as probably sulphide anion ([2] and references therein). Hence,
some sulphates can be primary phases in BA due to their possible
presence as unchanged relics having relatively moderate to high
decomposition and/or melting temperatures during heating. Addi-
tionally, the occurrence of some technogenic Al, Ca and Fe sul-
phates (Table 3) in plants from fertilizers and in semi-biomass as
impurities (additives or contaminants) generated from processing
of natural biomass can also be primary as a result of their presence
as unaltered minerals in BA [38]. However, the secondary sul-
phates of Al, Ca, K, Mg and Na (Table 3) are dominant in BA and
these newly formed phases are commonly attributed to interaction
between acidic SOX (SO2 and SO3) gases and oxides of the above
elements generated mostly from organic matter during biomass
combustion. The origin of these secondary sulphates is similar to
that in coal ash and their formation mechanisms have been de-
scribed in detail earlier ([163,164] and references therein). Finally,
the tertiary sulphates can include minerals containing water mol-
ecules and/or hydroxyl groups (for example, gypsum, bassanite,
ettringite, picromerite, syngenite), which are a result of hydration
and hydroxylation of other less stable sulphates by water and
moisture in the air during transport and storage of BA [24,57,65].
The less stable sulphides, sulphosalts, sulphites and thiosulphates
(Table 3) are not characteristic phases of BA in contrast to sul-
phates, and their accessory occurrence can be a result of some
reducing and unstable conditions in the system during biomass
combustion. For example, this statement is evidenced by the asso-
ciation of sulphides with char in BA [112].
3.3.4. Phosphates
The various phosphates found in BA are listed in Table 3. They
can be mostly secondary, to a lesser extent primary, and occasion-
ally tertiary phases in BA, which is identical to silicates. These min-
erals have both detrital and authigenic occurrence in/on plants
because:
(1) Some phosphates (such as the group of apatite) are typical
soil minerals [228] and they can have some relatively low
detrital uptake from the soil during plant growth; and
(2) Phosphates are characteristic authigenic minerals in plants
and animals and originate from syngenetic and epigenetic
evaporation and precipitation of mineralized aqueous solu-
tion enriched in different cations and phosphate and hydro-
gen phosphate anions ([2] and references therein).
Hence, some phosphates can be primary phases in BA due to
their possible presence as unchanged relics having relatively high
decomposition and/or melting temperatures during heating. Addi-
tionally, the occurrence of some technogenic phosphates (Table 3)
in plants from fertilizers and in semi-biomass as impurities (addi-
tives or contaminants) generated from processing of natural bio-
mass can also be primary as a result of their presence as
unaltered minerals in BA [24,38,41,42,45,62,104]. However, the
secondary phosphates of Al, Ca, Fe, K, Mg, Na and Zn (Table 3)
are dominant in BA and these newly formed phases are attributed
to interaction between oxides of the above-listed elements and P
generated mostly from organic matter, as well as melt crystalliza-
tion during biomass combustion. For example, evidence of apatite
crystallization within the Si–K glass formed from melt was ob-
served in BA [48]. The origin of these secondary phosphates is
probably similar to that in coal ash and this has been suggested
elsewhere [94]. Finally, the tertiary phosphates can include miner-
als containing water molecules and/or hydroxyl groups (for exam-
ple, hydroxylapatite and K pyrophosphate hydrate), which are a
result of hydration and hydroxylation of other less stable phos-
phates by water and moisture in the air during transport and stor-
age of BA [57]. The less stable pyrophosphates (Table 3) are not
characteristic phases of BA in contrast to phosphates, and their
accessory occurrence could be a result of some unstable conditions
in the system during biomass combustion.
3.3.5. Carbonates and bicarbonates
The various carbonates and bicarbonates identified in BA are
listed in Table 3. They can be mostly secondary, to a lesser extent
tertiary, and occasionally primary phases in BA, which is identical
to oxyhydroxides and sulphates. These minerals have both detrital
and authigenic occurrence in/on plants because carbonates are:
(1) Typical minerals for some soils [62,98,228] and they can
have some relatively low detrital uptake from the soil during
plant growth.
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
(2) Characteristic authigenic minerals in plants and animals and
originate from syngenetic and epigenetic evaporation and
precipitation of mineralized aqueous solution enriched in
different cations and carbonate, hydrocarbonate and hydro-
bicarbonate anions ([2] and references therein).
Hence, some carbonates can be primary phases in BA due to
their possible presence as unchanged relics despite their relatively
moderate decomposition and/or melting temperatures during
heating. Additionally, the occurrence of some technogenic carbon-
ates in semi-biomass as impurities (additives or contaminants)
generated from processing of natural biomass can also be primary
as a result of their presence as unaltered minerals in BA (Table 3).
However, the secondary carbonates of Al, Ca, Cr, Fe, K, Mg and Na
(Table 3) are normally dominant in BA and these newly formed
phases originate from the decomposition and oxidation of organic
matter, oxalates and carbonates and subsequent carbonation (and
recarbonation) of the secondary oxyhydroxides during biomass
combustion [65,94,107]. Hence, the origin of these secondary car-
bonates in BA is similar to that in coal ash and their formation
mechanisms have been described in detail for some carbonates
([163,164] and references therein). On the other hand, tertiary car-
bonates can be formed from secondary Ca and Mg hydroxides dur-
ing transport and storage of BA due to reactions of the former
minerals with CO2 occurring in air and water [24,57,60,65]. Finally,
other tertiary carbonates can also include minerals containing
water molecules and/or hydroxyl groups (for example, arterite,
baylissite, hydrocalcite, hydrotalcite, nesquehonite, paraalumohy-
drokalcit), which are a result of hydration and hydroxylation of
other less stable carbonates by water and moisture in the air dur-
ing transport and storage of BA.
3.3.6. Chlorides, chlorites and chlorates
The chlorides identified in BA are listed in Table 3. They can be
mostly secondary, to a lesser extent primary, and occasionally ter-
tiary phases in BA, which is identical to silicates and phosphates.
Chlorides are highly mobile during weathering and they are not
typical soil minerals [228], similar to sulphates. These minerals
have authigenic occurrence in plants because they originate from
syngenetic and epigenetic evaporation and precipitation of miner-
alized aqueous solution enriched in different cations and chloride
anion ([2] and references therein). Hence, some chlorides can be
primary phases in BA due to their possible presence as unchanged
relics despite their relatively low to moderate decomposition and/
or melting temperatures during heating. Additionally, the occur-
rence of some technogenic chlorides in plants from fertilizers and
in semi-biomass as impurities (additives or contaminants) gener-
ated from processing of natural biomass can also be primary as a
result of their presence as unaltered minerals in BA (Table 3).
The secondary chlorides of Ca, Cd, K, Na, Pb and Zn (Table 3) are
dominant in BA and these newly formed phases are commonly
attributed to interaction between Cl gases and the above elements
(generated mostly from organic matter) during biomass combus-
tion. The origin of these secondary chlorides is probably similar
to that in coal ash. Finally, the tertiary chlorides can include min-
erals containing water molecules and/or hydroxyl groups (for
example, Ca chlorite hydrate, Ca hydroxylchloride), which are a re-
sult of hydration and hydroxylation of other less stable chlorides
by water and moisture in the air during transport and storage of
BA. The less stable chlorites and chlorates (Table 3) are not charac-
teristic phases of BA in contrast to chlorides, and their accessory
occurrence can be a result of some unstable conditions in the sys-
tem during biomass combustion. For example, potassium forms
perchlorates during low-temperature oxidation (100–250 °C) and
these compounds decompose between 200–700 °C releasing Cl
[68].
69
3.3.7. Nitrates
The nitrates identified in BA are listed in Table 3. They can be
secondary and probably primary and tertiary phases in BA; how-
ever, the available information for them is very limited. Nitrates
are highly mobile during weathering and they are not typical soil
minerals [228], similar to sulphates and chlorides. These minerals
have authigenic occurrence in plants because they originate from
syngenetic and epigenetic evaporation and precipitation of miner-
alized aqueous solution enriched in different cations and nitrate
anion ([2] and references therein). Hence, some nitrates may be
primary phases in BA due to their probable presence as unchanged
relics despite their relatively low decomposition and/or melting
temperatures during heating. Additionally, the occurrence of some
technogenic nitrates in plants from fertilizers and in semi-biomass
as impurities (additives or contaminants) generated from process-
ing of natural biomass may also be primary as a result of their pres-
ence as unaltered minerals in BA (Table 3). The secondary nitrate of
K (Table 3) is probably dominant in BA and this newly formed
phase can be attributed to interactions between acidic NOX (NO
and NO2) gases and K (generated mostly from organic matter) dur-
ing biomass combustion. The origin of this secondary nitrate is
probably similar to that in coal ash [94]. For example, potassium
forms nitrates during low-temperature oxidation (100–250 °C)
and these compounds decompose between 200 and 700 °C releas-
ing N [68]. Finally, the tertiary nitrates may include minerals pre-
cipitated from water solutions (enriched in nitrate anion) and
generated during transport and storage of BA.
3.3.8. Glass
Glass is mostly newly formed secondary phase in BA resulted
from fusion of inorganic material in biomass and abrupt cooling
of the melt produced during combustion. Some unchanged glass
particles may also be primary in BA if there is pre-existing detrital
(from volcanic rocks in soil and their uptake) and technogenic
(impurities from additives or contaminants) occurrence of glass
with relatively high melting temperatures in biomass and semi-
biomass, respectively. It was found that glass in BA contains pri-
marily Si, K, Ca and Na, and, to a lesser extent, Mg, S, P, Fe, Mn
and Al [30,33,48,69]. It forms rock-like, ribbon-like, hair-like and
other morphological types [69]. Glass agglomerates also occur in
BA, composed of different sintered or melted ash particles bound
by glassy materials [57,69]. It was identified that some high silica
BAs (especially rice straw ash) produce highly vesicular glass prod-
ucts from bubble formation and expansion. These products occa-
sionally form hollow spherical particles of 5–10 lm in diameter,
which entrap gases [28,53,102]. This is similar to coal ash ceno-
spheres [229]. In contrast to silica enriched BA, high Ca wood BA
normally produces massive glass beads without quench crystals
and vesicles [28,53]. The observations above are identical or simi-
lar to those identified for various glass morphologies in coal ash
[148,167].
3.3.9. Other inorganic phases
The other inorganic phases identified in BA are listed in Table 3.
The newly formed amorphous (non-glass) inorganic material rep-
resents particles composed of non-fused phases and they were
identified in BA produced from different biomass varieties
[24,35,48,53,65,74,86,94]. It is well known, that phases such as
clay, mica and silica minerals, zeolites and some hydroxides, sul-
phates and phosphates lose their crystallization water at 300–
1100 °C, resulting in structural collapse and consequent amorph-
ization in this temperature range ([151,164] and references there-
in). For example, the presence of amorphous sulphate phases [74],
poorly crystallised hydrohylapatite [56] and non-crystalline nee-
dle-shaped silica grains or rounded to irregular shaped grains com-
posed mostly of Si, K and Ca [53] were observed in some BAs.
70 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
Additionally, the formation of hydrated silicate phases and port-
landite with amorphous, disordered or poorly crystallised struc-
tures during hydration of BA is also common [24,65].
Finally, different metallic alloys and pure metals are typical
minor and accessory phases in municipal solid waste ashes
[27,38], other industrial ashes [109], and even some plants [108].
Hence, these metallic alloys and pure metals can occur as un-
changed relics or impurities (additives or contaminants) in BA if
they have relatively high melting temperatures. The presence of
some unusual phases such as K–Mo selenide [100] and margarita-
site ((Cs,K,H3O)2(UO2)2V2O8(H2O)) [73] in ashes produced from
incomplete combustion of oil palm biomass waste (fibers from
empty fruit bunches) and rice husks, respectively, has also been
reported.
3.3.10. Organic phases
The organic phases identified in BA are listed in Table 3. They
include mostly secondary semi-coked and coked char particles
and associated with them other minor organic phases in BA origi-
nated from incomplete biomass combustion. Additionally, the
presence of some technogenic organic phases in semi-biomass as
impurities (additives or contaminants) generated from processing
of natural biomass can also occur in BA. The char contents in BA
are highly variable (0.3–79%), but the most common values are
in the range 1–20% [35,47,63,73,76,97,114,129,136]. The char par-
ticles have various morphologies (Table 1), but the original tex-
tures and structures of biomass are often maintained in char
particles [47,123,230–232]. It was found that the coarser grain
fractions of BA normally contain increased contents of unburned
matter [47,133,134]. An association of organic pollutant species
(polychlorinated dioxins and furans and polycyclinc aromatic
hydrocarbons) with char when the unburned organic levels in BA
are high is also possible [14,95]. Finally, Na cyanate is formed from
biomass combustion; however, cyanate is only stable under reduc-
ing conditions and decomposes to other alkali salts and gaseous N
compounds at oxidizing conditions [128].
3.3.11. Organic minerals
Weddelite (Ca oxalate dihydrate), whewellite (Ca oxalate
monohydrate) and dehydrated whewellite were identified in
low-temperature BA, but not in high-temperature BA (Table 3).
Oxalates are minerals, but they are specified to a special group
because they are organic species, which is one of the exceptions
in a mineralogical sense [228]. They can be secondary and proba-
bly primary phases in BA. Oxalates are typical authigenic minerals
in plants because they originate from syngenetic and epigenetic
evaporation and precipitation of mineralized aqueous solution
enriched in different cations and oxalate anion ([2] and references
therein). Hence, some oxalates may be primary phases in BA due
to their possible presence as unchanged relics despite their
relatively low to moderate decomposition temperatures during
heating. Additionally, the occurrence of some technogenic oxa-
lates in semi-biomass as impurities generated from processing
of natural biomass may also be primary as a result of their
presence as unaltered minerals in BA (Table 3). However, the
secondary oxalates of Ca, K, Mg, Mn and Na are probably domi-
nant in BA (Table 3 and [2]) and these newly formed phases
may be a result of decomposition of organic matter under some
unstable and lower temperature conditions in the system during
biomass combustion [94].
3.4. Chemical and phase–mineral classifications of biomass and
biomass ash and their potential applications
The characterization of phase–mineral and chemical composi-
tion of biomass and BA has a key importance in both fundamental
and applied aspects of biomass fuels and their combustion prod-
ucts, similar to coal and coal ash [150,151,170]. Further, the chem-
ical and phase–mineral classifications of biomass and BA can assist
directly or indirectly in:
(1) Establishment of a uniform nomenclature and standards.
(2) Characterization of composition and prediction of
properties.
(3) Elucidation of the behaviour of organic and inorganic matter
during processing.
(4) Identification of appropriate or potential modes of
utilization.
(5) Prediction, assessment, reduction or elimination of techno-
logical, ecological and health problems or benefits such as:
 Economically valuable or environmentally hazardous
components.
 Innovative (effective, muticomponent, wasteless) and sustain-
able utilization.
 Biological, physical, chemical and thermo-chemical perfor-
mance in industrial installations.
 Global and local environmental contamination of the air,
water, soil and plants by toxic and potentially toxic compounds
[2].
It has been evidently demonstrated that the inorganic composi-
tion of biomass and BA is highly variable [1,2]. Therefore, the
assignment of various biomass varieties to different inorganic
types and sub-types could have primary significance when predict-
ing the behaviour of a particular fuel during processing and poten-
tial applications of biomass conversion (combustion, pyrolysis and
gasification) products. Therefore, some chemical and phase ap-
proaches for initial and preliminary classification and prediction
purposes related to biomass and BA has been introduced or sug-
gested recently (Figs. 1 and 7 and others in [1,2]). They are similar
to those that have been earlier applied for coal and coal ash
[150,151,170]).
There is a big advantage when the biomass and BA classification
systems are based on the identification and implementation of sig-
nificant relationships between elemental concentrations, com-
bined chemical and phase–mineral associations and especially on
an application of genetic approaches for specification of the phases.
In this case the reasons for different problems or benefits during
biomass processing can be systematically identified. Therefore,
the specified oxide associations based on the correlation analysis
in BA [1] are also informative for the preferable occurrence and
possible origin of inorganic elements in BA and this is demon-
strated below. For instance, the chemical classification of BAs
(Fig. 1) is extended (Fig. 7) including the dominant phase–mineral
composition of BAs (Table 3) as:
(1) The upper corner (SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2) in
Fig. 7 mostly represents the occurrence of glass, silicates
and oxyhydroxides of these elements in BA.
(2) The left corner (CaO + MgO + MnO) in Fig. 7 commonly
includes carbonates, oxyhydroxides, glass, silicates and
some phosphates and sulphates of such elements in BA.
(3) The right corner (K2O + P2O5 + SO3 + Cl2O, as N also belongs
to this association, see [1]) in Fig. 7 normally represents
phosphates, sulphates, chlorides, glass and some silicates
and carbonates of these elements in BA. Certainly, some of
the phases or minerals have mixed contributions to the dif-
ferent corners because of their complex composition.
The above three systematic associations related to the occur-
rence, content and origin of elements and phases divide BAs
(Fig. 7) to:
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
WWB - Wood and woody biomass
HAB - Herbaceous and agricultural biomass
HAG - Herbaceous and agricultural grass
HAS - Herbaceous and agricultural straw
HAR - Herbaceous and agricultural residue
AB - Animal biomass
MB - Mixture of biomass
CB - Contaminated biomass
AVB - All varieties of biomass
P - Peat
L - Lignite
S - Sub-bituminous coal
B - Bituminous coal
A - Algae
Fig. 7. Position areas of 86 biomass varieties and 38 solid fossil fuels in the chemical classification system of biomass ash based on [1,2,170], wt.%.
 Four ash types (‘‘S’’, ‘‘C’’, ‘‘K’’ and ‘‘CK’’).
 Six ash sub-types (‘‘S-HA’’, ‘‘S-MA’’, ‘‘C-MA’’, ‘‘C-LA’’, ‘‘K-MA’’ and
‘‘K-LA’’).
Additionally, the concept of dividing inorganic matter into: nat-
ural (authigenic, detrital) and technogenic classes for biomass [2];
and primary, secondary and tertiary classes for BA in the present
work; has also both fundamental and applied importance. For
example:
(1) The authigenic minerals in biomass are opal, oxalates, car-
bonates, phosphates, sulphates, chlorides and nitrates (char-
acteristic of inorganic ‘‘C’’, ‘‘K’’ and ‘‘CK’’ types of biomass).
Such minerals are normally highly mobile (water-soluble)
and reactive, and with low decomposition or melting tem-
peratures. Therefore, they can be responsible for enhanced
leaching behaviour, low-temperature transformations, parti-
tioning behaviour and emission (or capture) of many volatile
elements and hazardous components, corrosion, agglomera-
tion, deposits formation, slagging, fouling, bed defluidization
and composition of residues during biomass combustion [2].
Some of these authigenic minerals can occur as primary
(unchanged) phases in BA, but they commonly form second-
ary and tertiary Ca-, K-, Mg-, Na- and Mn-bearing carbon-
ates, oxyhydroxides, phosphates, sulphates, chlorides, glass
and some silicates in BA (Fig. 7) as a result of subsequent
reactions with: detrital minerals; inorganic and organic
components released from organic matter during biomass
combustion; and with air and moisture during BA storage.
(2) The detrital minerals in biomass are silicates and oxyhy-
droxides, excluding opal (typical of inorganic ‘‘S’’ type of bio-
mass). Such minerals are commonly stable, less mobile
(water-insoluble), less reactive and with high-melting tem-
71
peratures during combustion. Therefore, they can be impor-
tant for enhanced abrasion-erosion, formation of some low-
temperature eutectics, partitioning element behaviour and
for decreasing combustion efficiency and increasing operat-
ing costs for the handling of such inert material during bio-
mass combustion [2]. Many of these detrital minerals can
occur as primary (unchanged) phases in BA, but they mostly
form secondary Si-, Al-, Fe-, Na- and Ti-bearing glass, sili-
cates and oxyhydroxides (Fig. 7) due to subsequent reactions
with: authigenic minerals; inorganic and organic compo-
nents released from organic matter during biomass combus-
tion; and with air and moisture during BA storage (similar to
authigenic minerals).
(3) The technogenic minerals in biomass include various
anthropogenic species with highly variable properties and
behaviour (characteristic for different inorganic types). They
can also be responsible for many of the above listed prob-
lems plus enhanced pollution by trace elements because
most semi-biomass fuels contain high levels of such ele-
ments [2]. The technogenic minerals in biomass can also
be primary, secondary and tertiary phases in BA.
Furthermore, it should be stated that biomass fuels with sim-
ilar bulk chemical composition may behave quite differently and
may generate distinctly different solid products during biomass
conversion. This is due to different modes of element occurrence
in biomass and BA. For example, the organic phases and mineral
classes, groups and species occurring in biomass [2] and BA
(Table 3) have different behaviour during processing. Hence,
their actual identification, quantification and associations in a
specific biomass and BA can be used to predict the behaviour
of fuel during conversion and potential applications of BA.
Additionally, the knowledge of phase, mineral and element
72 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
occurrences in biomass and their transformations during bio-
mass thermal treatment is important for determining formation
mechanism of BA, as also demonstrated for coal and coal ash
[150,151,163,164,170].
Finally, it is suggested that the inorganic chemical types and
sub-types classified [1] and the specified origin of inorganic matter
in biomass [2] and BA (as Fig. 7) may also play a leading role in
many technological and environmental problems, similar to coal
and coal ash [150,151,170]). Therefore, the specified inorganic
types and sub-types, and genetic mineral classes, as well as struc-
tural organic types of biomass ([1,2]; Tables 2, 4, 5, 8 and 9; and
Figs. 1–7) will be used for some prediction of potential utilization,
technological and ecological advantages and challenges related to
BA. These topics will be discussed in Part 2.
4. Conclusions
Some conclusions based on the present overview of the phase–
mineral and chemical composition of biomass ash (BA) can be
made:
(1) BA is the solid residue that results from the combustion of
biomass. It is a complex inorganic–organic mixture with
polycomponent, heterogeneous and variable composition,
containing intimately associated solid, liquid and gaseous
phases with different origin. The phase–mineral composition
of BA includes (1) mostly inorganic matter composed of non-
crystalline (amorphous) and crystalline to semi-crystalline
(mineral) constituents; (2) subordinately organic matter
consisting of char and organic minerals; and (3) some fluid
matter comprising moisture and gas and gas–liquid inclu-
sions associated with both inorganic and organic matter.
(2) The chemical elements present in BA (in decreasing order of
abundance) are commonly O > Ca > K > Si > Mg > Al >
Fe > P > Na > S > Mn > Ti, plus some Cl, C, H, N and trace ele-
ments. BA from natural biomass is commonly enriched in
Mn > K > P > Cl > Ca > Na > Mg and depleted in Al > Ti >
Fe > Si > S in comparison with coal ash. Trace elements such
as B > Au > Cd > (Cr, Mn) > Ag > Zn > (Be, Cu, Se) > Ni > Rb in
different BAs can show higher contents (2–24 times) than
the respective worldwide average values for coal ashes.
(3) The minerals and phases found in BAs (229 identified)
include more species and groups of species in comparison
with coal ashes (188 identified). The minerals identified in
BAs (in decreasing number of mineral species) belong to
the mineral classes: silicates > oxides and hydroxides >
sulphates (plus sulphides, sulphosalts, sulphites and thio-
sulphates) > phosphates > carbonates > chlorides (plus chlo-
rites and chlorates) > nitrates. The common phases found
in BAs (in decreasing number of identifications) comprise:
(1) mostly quartz, calcite, sylvite, arcanite, anhydrite, char,
glass, lime, periclase and hematite and (2) subordinately
portlandite, cristobalite, hydroxylapatite, larnite, albite, Ca
phosphates, fairchildite, K carbonate, K feldspars, halite
and K–Ca silicates.
(4) The minerals and phases in BA can be divided into: (1) form-
ing (>10%); (2) major (1–10%); (3) minor (0.1–1%); and (4)
accessory (<0.1%); based on their contents. The forming
and major phases (in decreasing order of abundance) in
BAs include glass, sylvite, calcite, leucite, anorthite, K–Ca sil-
icate, char, quartz, albite, anhydrite, ankerite, kaolinite, sid-
erite, cristobalite, arcanite, hematite, illite, lime, Na silicate,
fairchildite, hydroxylapatite, merwinite, periclase, Ca chlo-
rosilicate, diopside, glaserite, K feldspar, larnite and
portlandite.
(5) BA is composed of original or newly formed inorganic and
organic solid phases generated from natural (authigenic
and detrital) and technogenic inorganic, organic and fluid
matter during biomass combustion. Therefore, the phases
and minerals in BA can be classified in origin as: (1) primary,
namely pre-existing or original minerals and phases in bio-
mass that have undergone no phase transformations during
combustion; (2) secondary such as new phases formed dur-
ing combustion process; and (3) tertiary, namely new min-
erals or phases formed during transport and storage of BA.
The phases found in BA are mostly secondary, to a lesser
extent tertiary and occasionally primary in origin.
(6) Most of the minerals and phases identified in coal ashes
were also found in BAs. However, many mineral species
among Ca–K–Mn silicates, Ca–Al–Mn oxides, K–Na–Ca chlo-
rides and K–Ca–Mg–Na carbonates, sulphates and phos-
phates identified in BA were normally not found in coal
ashes. The reason for that could be the enrichment of ele-
ments such as Ca, Cl, K, Mg, Mn, Na and P in BAs compared
to coal ashes. In contrast, many Al-, Fe-, Si- and Ti-bearing
minerals, typical for coal ashes, were not indentified in BAs
probably due to limited contents of these elements in BAs.
(7) The ash yield from biomass (animal > aquatic > contami-
nated > herbaceous and agricultural > wood and woody) is
normally much lower than the ash yield from coal. Natural
biomass commonly enriched in hemicellulose, water-solu-
ble salts and silicic acid (authigenic phosphates, sulphates,
chlorides, nitrates and opal) tends to produce higher ash
yields. The unusually high ash yields of biomass are com-
monly an indication of increased amounts of contamination
with detrital or technogenic origin.
(8) Organic matter of different biomass varieties tends to show
similar combustion behaviour, whereas the inorganic matter
of these biomass varieties has a tendency to reveal very var-
iable performance during burning. The ash-fusion tempera-
tures of biomass are more variable than of coal and they
are normally lower. The preliminary observations also indi-
cate that the thermal behaviour of different biomass ashes
tends to be similar among the inorganic ‘‘S’’, ‘‘C’’, ‘‘K’’ and
‘‘CK’’ types and probably some sub-types specified.
(9) The content of water-soluble fraction in BA is high and can
be up to 61.0%, while the values of this characteristic for coal
ashes are much less, namely 0.2–7.2% (mean 1.6%). The pH
values of BAs vary in the range 4.5–13.4 (mean about
10.7), while for coal ashes these values are in more narrow
range, namely 6.2–12.5 (mean 10.0). The water-soluble ele-
ments leached from BAs are commonly Cl > S > K > Na >
Sr > Ni > Mn > Cd > Cr > Zn > Co > Si > Mo > Li > (Mg, Pb) > Ca >
Cu > Ba > P > Se > Sb > Al > Fe > (Br, Hg) > (As, B, Sn, Ti, V).
The water-soluble phases in BA mostly include phases of
alkali and alkaline earth elements such as: (1) highly soluble
chlorides (sylvite, halite), sulphates (arcanite, syngenite,
ettringite, gypsum), oxides (lime), hydroxides (portlandite),
nitrates, carbonates and bicarbonates; (2) certain less solu-
ble carbonates (calcite) and phosphates (phosphorites);
and (3) some slightly soluble phosphates (apatite) and sili-
cates (Ca silicates, feldspars).
(10) Sequential chemical fractionation is mostly used to distin-
guish the speciation of elements in BAs. However, this indi-
rect, rather unselective and maybe unreliable procedure
cannot be applied to identify the actual modes of element
occurrence in a multicomponent system such as biomass
ash and the interpretation should always be approached
with much caution. In preference, other direct methods
should be used for such a purpose.
 S.V. Vassilev et al. / Fuel 105 (2013) 40–76
(11) The inorganic composition of biomass and BA is highly var-
iable and the assignment of various biomass varieties to dif-
ferent inorganic types and sub-types could have primary
importance when predicting the behaviour of a particular
fuel during processing and potential applications of biomass
conversion (combustion, pyrolysis and gasification)
products.
(12) There is a big advantage when the biomass and BA classifica-
tion systems are based on the identification and implemen-
tation of significant relationships between elemental
concentrations, combined chemical and phase–mineral
associations and especially on an application of genetic
approaches for specification of the phases. In this case the
reasons for different problems or benefits during biomass
processing can be systematically identified.
(13) Certain major associations related to the occurrence, content
and origin of elements and phases were identified in the BA
system and they include: (1) Si–Al–Fe–Na–Ti (mostly glass,
silicates and oxyhydroxides); (2) Ca–Mg–Mn (commonly
carbonates, oxyhydroxides, glass, silicates and some phos-
phates and sulphates); and (3) K–P–S–Cl (normally phos-
phates, sulphates, chlorides, glass and some silicates and
carbonates). These associations were applied for classifica-
tion of BAs to four types and six sub-types. Such systematic
relationships have a key importance in both fundamental
and applied aspects, namely their potential applications for
classifications and indicator purposes connected with inno-
vative and sustainable processing of BA.
The potential utilization, technological and ecological advanta-
ges and challenges related to BA using the above classification ap-
proach are described in Part 2 of the present work.
Acknowledgements
The present work was carried out in part within the European
Commission’s research programme and in part within the research
programme of the Bulgarian Academy of Sciences. Stanislav Vassi-
lev would like to express his gratitude to the Joint Research Centre
(European Commission) for the possibility to perform studies at
the Institute for Energy and Transport (Petten, The Netherlands)
as a Detached National Expert.
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