Fuel 89 (2010) 913933

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

Review article

An overview of the chemical composition of biomass

Stanislav V. Vassilev a,b,*, David Baxter b, Lars K. Andersen b, Christina G. Vassileva a
a
Central Laboratory of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Soa 1113, Bulgaria
b
Institute for Energy, Joint Research Centre, European Commission, P.O. Box 2, NL-1755 ZG Petten, The Netherlands

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 chemical composition of biomass was conducted. The general consider-
Received 13 July 2009 ations and some problems related to biomass and particularly the composition of this fuel are discussed.
Received in revised form 20 October 2009 Reference peer-reviewed data for chemical composition of 86 varieties of biomass, including traditional
Accepted 21 October 2009
and complete proximate, ultimate and ash analyses (21 characteristics), were used to describe the bio-
Available online 10 November 2009
mass system. It was shown that the chemical composition of biomass and especially ash components
are highly variable due to the extremely high variations of moisture, ash yield, and different genetic types
Keywords:
of inorganic matter in biomass. However, when the proximate and ultimate data are recalculated respec-
Biomass
Biomass ash
tively on dry and dry ash-free basis, the characteristics show quite narrow ranges. In decreasing order of
Chemical composition abundance, the elements in biomass are commonly C, O, H, N, Ca, K, Si, Mg, Al, S, Fe, P, Cl, Na, Mn, and Ti. It
Chemical associations was identied that the chemical distinctions among the specied natural and anthropogenic biomass
groups and sub-groups are signicant and they are related to different biomass sources and origin,
namely from plant and animal products or from mixtures of plant, animal, and manufacture materials.
Respective chemical data for 38 solid fossil fuels were also applied as subsidiary information for clarifying
the biomass composition and for comparisons. It was found that the chemical composition of natural bio-
mass system is simpler than that of solid fossil fuels. However, the semi-biomass system is quite compli-
cated as a result of incorporation of various non-biomass materials during biomass processing. It was
identied that the biomass composition is signicantly different from that of coal and the variations
among biomass composition were also found to be greater than for coal. Natural biomass is: (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 in comparison with coal. The correlations and associations
among 20 chemical characteristics are also studied to nd some basic trends and important relationships
occurring in the natural biomass system. As a result of that ve strong and important associations,
namely: (1) CH; (2) NSCl; (3) SiAlFeNaTi; (4) CaMgMn; and (5) KPSCl; were identied
and discussed. The potential applications of these associations for initial and preliminary classication,
prediction and indicator purposes related to biomass were also introduced or suggested. However, future
detailed data on the phasemineral composition of biomass are required to explain actually such chem-
ical trends and associations.
2009 Elsevier Ltd. All rights reserved.

Contents

1. Introduction and scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914

1.1. General considerations about biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
1.2. Some problems related to biomass investigations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
1.3. Common issues concerning biomass composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
1.4. Common issues concerning chemical composition of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
2. Data and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
2.1. Chemical composition of biomass and comparisons with solid fossil fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
2.1.1. General observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
2.1.2. Proximate composition of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924

* Corresponding author. Address: Central Laboratory of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Soa 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 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.10.022
914 S.V. Vassilev et al. / Fuel 89 (2010) 913933

2.1.3. Ultimate composition of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925

2.1.4. High-temperature ash (HTA) composition of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
2.2. Correlations and associations among chemical composition of biomass and their potential applications . . . . . . . . . . . . . . . . . . . . . . . . . 928
2.2.1. Correlations and associations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
2.2.2. Potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
3. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 931
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 932
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 932

1. Introduction and scope
1.1. General considerations about biomass
Biomass is contemporaneous (non-fossil) and complex biogenic
organicinorganic solid product generated by natural and anthro-
pogenic (technogenic) processes, and comprises: (1) natural con-
stituents originated from growing land- and water-based
vegetation via photosynthesis or generated via animal and human
food digestion; and (2) technogenic products derived via process-
ing of the above natural constituents. The general classication of
biomass varieties as fuel resources can be divided preliminary and
roughly into several groups and sub-groups according to their dis-
tinct biological diversity and similar source and origin (Table 1).
Biomass fuels or biofuels are technogenic solid, liquid or gaseous
fuels generated from natural biomass resources via some process-
ing. Respectively, the bioenergy is the energy produced from
biomass fuels. The major advantages and disadvantages offered
by biomass or biomass fuels are summarized and listed in Table
2 as most of them have been described earlier [14].
Natural biomass is a renewable energy source, while biomass
fuel is still an incomplete renewable energy resource. Since it is
considered that the biomass system and respective biofuels as
sub-systems do not contribute to the greenhouse effect due to
the CO2 neutral conversion, extensive investigations have been car-
ried out worldwide to enhance the biomass use by substituting fos-
sil fuels for energy conversion [4]. The focus on bioenergy as an
alternative has increased tremendously during the last years be-
cause of global warming problems originated mostly from fossil
fuels combustion. However, the scientic community has been
stressed recently that under current policies, the environmental
effects from biofuel production might be worse than those from
fossil fuels [5].
Reasonably, two fundamental aspects related to biomass use as
fuel are: (1) to extend and improve the basic knowledge on compo-
sition and properties; and (2) to apply this knowledge for the most
advanced and environmentally safe utilization. Numerous studies
have been conducted worldwide and extensive data for biomass
and its conversion products have been generated, particularly dur-
ing the last two decades. These results provide a sound foundation
for an initial database that can be used for characterization and
subsequent classication and sustainable exploitation of biomass.
Therefore, a detailed review of the scientic literature including
more than 280 mostly peer-reviewed references and data compila-
tions have been conducted to systematise the results collected for
biomass.
1.2. Some problems related to biomass investigations
It is well-known that the methodology and logic from coal
experiments can be applied to biomass [6]. Surprisingly, it was
found that the long term experience and knowledge achieved for
the most studied solid fuels (coal, peat, petroleum coke, municipal
solid waste, and refuse-derived fuel or char) and their products
have not been implemented very successfully in the eld of bio-
mass. Furthermore, additional problems also occur in many bio-
mass investigations due to use of unsuitable scientic
approaches, incomplete data or unusual and sometimes inappro-
priate terms that lead to inaccurate interpretations and misunder-
standings about the biomass and biomass fuels. The occurrence of
such problems cannot be ignored and an attempt to summarize
them initially is undertaken below:
(1) There is a general agreement that biomass fuel is renewable
energy resource. However, it is still not fully correct to claim
this at present due to the occurrence of some unsolved envi-
ronmental problems during planting, growing, harvesting,
transport and use of biomass fuels, as well as utilization of
biomass waste products, when considering the complete life
cycle assessment [4].
(2) The lack of generally accepted terminology, classication
systems and standards worldwide about biomass and biofu-
els lead to some serious misunderstanding during the inves-
tigations. Analytical and representative sampling problems

Table 1
General classication of biomass varieties as solid fuel resources according to their biological diversity, source and origin.

Biomass groups Biomass sub-groups, varieties and species

1. Wood and woody biomass Coniferous or deciduous; angiospermous or gymnospermous; soft or hard; stems, branches, foliage, bark, chips,
lumps, pellets, briquettes, sawdust, sawmill and others from various wood species
2. Herbaceous and agricultural biomass Annual or perennial and eld-based or processed-based such as:
2.1. Grasses and owers (alfalfa, arundo, bamboo, bana, brassica, cane, cynara, miscanthus, switchgrass, timothy,
others)
2.2. Straws (barley, bean, ax, corn, mint, oat, rape, rice, rye, sesame, sunower, wheat, others)
2.3. Other residues (fruits, shells, husks, hulls, pits, pips, grains, seeds, coir, stalks, cobs, kernels, bagasse, food,
fodder, pulps, cakes, others)
3. Aquatic biomass Marine or freshwater algae; macroalgae (blue, green, blue-green, brown, red) or microalgae; seaweed, kelp, lake
weed, water hyacinth, others
4. Animal and human biomass wastes Bones, meat-bone meal, chicken litter, various manures, others
5. Contaminated biomass and industrial biomass Municipal solid waste, demolition wood, refuse-derived fuel, sewage sludge, hospital waste, paper-pulp sludge,
wastes (semi-biomass) waste papers, paperboard waste, chipboard, breboard, plywood, wood pallets and boxes, railway sleepers,
tannery waste, others
6. Biomass mixtures Blends from the above varieties
 S.V. Vassilev et al. / Fuel 89 (2010) 913933
Nomenclature
A ash yield
AB animal biomass
am as measured
CB contaminated biomass
daf dry, ash-free basis
db dry basis
EDF enrichment/depletion factor
FC xed carbon
HAB herbaceous and agricultural biomass
HAG herbaceous and agricultural grass
associated with biomass also occur and some of them have
been discussed [4].
(3) There is a huge amount of data about the biomass in numer-
ous project reports, scientic proceedings or Internet; how-
ever, the use of such information is insecure because the
data are not peer-reviewed.
(4) The common practice is to avoid the complete description of
biomass used (as samples or feedstock), their place and
manner of collection, as well as storage and processing con-
ditions. For instance, the use of biomass specication such as
wood, fuelwood, rewood, forest or agricultural residue,
bark, straw, grass, manure, coppicing or dedicated energy
crop and short rotation coppice or crop, do not bring suf-
cient information for the real identication and character-
ization of a particular type of biomass. Additionally, the
exact fuel status of the samples studied, namely as collected
(harvested), as received, air-dried (at ambient temperature)
or oven-dried (at specic temperature up to 105 C) basis is
also very often not reported which is a serious omission.
(5) Some studies include peat as biomass resource, but peat is
fossil fuel. Additionally, it should be always considered that
signicant part (occasionally dominant) of contaminated
biomass contains other non-biomass products [7,8]. Hence,
contaminated biomass (semi-biomass) should be considered
separately.
(6) The systematic and complete data from simultaneous prox-
imate, ultimate and ash analyses, as well as from phase,
mineral and trace elements analyses for the biomass varie-
ties and their products are missing or they are very scarce.
Table 2
Major advantages and disadvantages of biomass or biomass fuels.
Advantages
Renewable energy source for natural biomass
CO2 neutral conversion and climate change benets
Commonly low contents of ash, C, S, N, and trace elements
Normally high concentrations of volatile matter, Ca, H, Mg, O, and P
Great reactivity during conversion
Mitigation of hazardous emissions (CH4, CO2, NOX, SOX, trace elements) and wastes separated
Capture of some hazardous components by ash during combustion
Huge availability and relatively cheap resource
Diversication of fuel supply and energy security
Rural revitalization with creation of new jobs
Potential use of oceans and low-quality soils, and restoration of degraded lands
Reduction of biomass-containing wastes
Cheap resource for production of sorbents, fertilizers, liming and neutralizing agents, building
materials, and for some synthesis or recovery of certain elements and compounds
915
HAS herbaceous and agricultural straw
HAR herbaceous and agricultural residue
HTA high-temperature ash (>500 C)
LTA low-temperature ash (100250 C)
M moisture
R2 correlation coefcient
SFF solid fossil fuel
VM volatile matter
WWB wood and woody biomass
% weight%
(7) It is commonly accepted that the concentration and behav-
iour of elements such as Ca, Cl, K, Na, P, S, Si and heavy metals
(more precisely trace elements) are mostly responsible for
many technological and environmental problems during bio-
mass processing. However, the experience from the studies
of other solid fuels [915] shows that the actual reasons for
such problems are most likely connected with the abundance
and behaviour of modes of element occurrence (specic
phases or minerals) in biomass and biomass products.
(8) Most studies used the data from ash yield (shortly ash) or the
bulk chemical composition of ash to explain mineral matter,
mineral composition, minerals, inorganic matter or inorgan-
ics, which is not fully correct and can lead to confusion. Fur-
thermore, the inorganic matter in biomass has generally
been divided into two classes, namely inherent (or intrinsic)
and entrained (or extraneous, adventitious, extrinsic, added,
dirt) materials. However, the actual inorganic matter in
biomass could be divided into detrital (terrigenous) and
authigenic genetic classes which are more informative,
well-known and accepted for the solid fossil fuels (SFFs) [16].
(9) Many ndings 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 (poly-
component) system under non-equilibrium conditions. Such
calculations can be used only as a subsidiary prediction pro-
cedure of the real and direct (input, output) phase studies of
the systems.
Disadvantages
Incomplete renewable energy resource for biomass fuel with
respect to the complete life cycle assessment
Miss of accepted terminology, classication systems and
standards worldwide
Insufcient knowledge and variability of composition, properties
and quality
Commonly high contents of moisture, Cl, K, Na, Mn, and some
trace elements
Low energy density
Potential competition with food and feed production
Possible soil damage and loss of biodiversity
Odour, potential emission and leaching of hazardous
components during disposal
Possible hazardous emissions during heat treatment
Potential technological problems during heat treatment
Regional availability
Great collection, transportation, storage and pre-treatment costs
Unclear utilization of waste products
916 S.V. Vassilev et al. / Fuel 89 (2010) 913933

(10) Sequential chemical fractionation is mostly used to distin-
guish the speciation of elements in biomass fuels and their
ashes. However, this indirect procedure cannot be applied
to identify the actual modes of element occurrence. Leaching
alone has many limitations and can be used only as preli-
minary information for some possible associations of ele-
ments. Other direct methods applied for coal [17] and coal
ash [18] should be used for such a purpose.
(11) The problems related to biomass ash utilization are only at
an initial stage of investigation and they need further clari-
cation. For instance, there is no doubt that biomass ashes
contain plant nutrients, namely some compounds of Ca,
Mg, Na, K and P, that have to be recycled back to the soil.
However, the problem is if these compounds occur in acces-
sible (bioavailable) forms in the ash. There are indications
that signicant proportions of the above nutrients are pres-
ent as water insoluble phases (glass, silicates, phosphates),
while other dangerous trace elements are highly mobile
impurities in surface enriched salts on ash particles. In this
case the fundamental question is what amount of: (1) acces-
sible (water-soluble) or non-accessible (bound into glass)
nutrients; and (2) bioavailable or non-bioavailable trace-ele-
ment contaminants; will be returned to the biomass cycle
with these ashes? Furthermore, washing of alkali-rich bio-
mass fuels prior to their use may reduce some technological
and environmental problems. However, such future large-
scale washing may create new environmental concerns
related to the fate of alkali metals, Cl, S, P, and some hazard-
ous trace elements leached from biomass.
(12) There is a strange acceptance that biomass ash does not con-
tain toxic metals like in the case of coal ash. However, cer-
tain results for biomass ashes are very disturbing. For
example, maximum concentrations of elements such as As
(243 ppm), Ba (0.37%), Cd (657 ppm), Cr (0.17%), Cu
(0.24%), Hg (7.3 ppm), Mn (4.7%), Mo (114 ppm), Pb (5.0%),
Sb (264 ppm), and Zn (16.4%) were detected in some bio-
mass ashes, particularly lter y ashes [1925]. These con-
centrations are much greater than in coal ash and they
even have a unique resource recovery potential. Addition-
ally, the trace elements in biomass ash tend to occur in much
more mobile and hazardous compounds than in coal ash
[4,8,9,14,2629]. Systematic studies about the trace ele-
ments in biomass and biomass products are also only at an
initial stage of investigation.
(13) Regulations exist in some countries which specify the limit-
ing and guiding values for the contents of Ca, Cl, K, N, S, and
some trace elements (Cd, Co, Cr, Cu, Ni, Pb, V, Zn) in biomass
fuel or ash in respect of their unrestricted use. However, the
bulk concentrations of these elements are less informative
than the abundance of their modes of element occurrence.
(14) There are quite limited data about the exploration of the
impact of biomass varieties during their blending with other
solid fuels.
The above listed problems show that additional, systematic and
detailed studies based on proved or new approaches and methods
are required to reduce uncertainties. Therefore, from a critical
review of publications and some own investigations an attempt
will be undertaken: (1) to compile a reliable database; (2) to dene
the basic achievements; (3) to supply additional results; (4) to clar-
ify some of the problems related to composition, properties and
perspectives of biomass; and nally (5) to understand how the fun-
damental knowledge on the composition and properties may be
implemented for the most advanced and environmentally safe uti-
lization of biomass. Peer-reviewed data and own key investigations
on biomass, other solid fuels and their products will be used for
that purpose in the present and future publications.
1.3. Common issues concerning biomass composition
The identication and characterization of chemical and phase
composition of a given solid fuel is the initial and most important
step during the investigation and application of such fuel. This
composition is a unique fundamental code that characterizes and
determines the properties, quality, potential applications and
environmental problems related to any fuel. For that purpose,
well-known physical, chemical, petrographic, mineralogical and
geochemical studies have been used for characterization of solid
fuels. For example, data from: (1) proximate analysis, namely xed
carbon (FC), volatile matter (VM), ash yield (A), and moisture (M);
(2) ultimate analysis (C, O, H, S, N); (3) ash analysis (Si, Al, Fe, Ca, S,
Mg, K, Ti, Na, P, plus occasionally Mn, Cl and trace elements); (4)
petrographic analysis (organic and inorganic ingredients); (5) min-
eralogical analysis (minerals and inorganic phases); (6) separation
procedures (different fractions); and (7) other analyses of fuel,
low-temperature ash (LTA) or high-temperature ash (HTA) have
been traditionally used to characterize specic solid fuels
[17,18,30]. Identical or similar analyses are also applicable for bio-
mass characterization despite of some peculiarities and limitations
[4].
Biomass, similar to SFF, is a complex heterogeneous mixture of
organic matter and, to a lesser extent, inorganic matter, containing
various solid and uid intimately associated phases or minerals
with different origins (Tables 3 and 4 and [16]). The genesis of
the phases in biomass is a result of natural (authigenic and detrital)
and anthropogenic processes during pre-syngenesis, syngenesis,
epigenesis and post-epigenesis of biomass according to the leading
formation process and place, time and mechanism of phase forma-
tion (Table 4). These observations indicate that the natural biomass
system is simpler than that of SFF. This is due to the absence of an-
cient (less-known) plant species and lithiphication (diagenetic)
processes accompanied by highly variable physico-chemical condi-
tions (changes in temperature, pressure, pH and oxidationreduc-
tion potential), which are typical of peat and coal systems.
However, the semi-biomass sub-system (Table 1) is more complex
and quite complicated as a result of incorporation of various non-
biomass materials during biomass processing.

Table 3
Phase composition of biomass.

Matter State and type of Phases and components

constituents
1. Organic matter 1.1. Solid, non-crystalline
1.2. Solid, crystalline
2. Inorganic matter 2.1. Solid, crystalline
2.2. Solid, semi-crystalline
2.3. Solid, amorphous
3. Fluid matter Fluid, liquid, gas
Structural ingredients, namely cellulose, hemicellulose, lignin, extractives, others
Organic minerals such as CaMgKNa oxalates, others
Mineral species from phosphates, carbonates, silicates, chlorides, sulphates, oxyhydroxides, nitrates, and other
mineral classes
Poorly crystallized mineraloids of some silicates, phosphates, hydroxides, others
Amorphous phases such as various glasses, silicates, others
Moisture, gas and gasliquid inclusions associated with both organic and inorganic matter
 S.V. Vassilev et al. / Fuel 89 (2010) 913933 917

Table 4
Origin of phases in biomass.

Formation process Place of formation Time of formation Formation mechanism

1. Natural 1.1. Authigenic (formed in
biomass)
1.2. Detrital (formed outside
biomass, but xed in/on
biomass)
2. Anthropogenic Technogenic (formed outside or
inside biomass and xed in/on
biomass)
1.1.1. Syngenetic (during plant
growing)
1.1.2. Epigenetic (after plant
died)
1.2.1. Pre-syngenetic (before
plant growing)
1.2.2. Pre-syngenetic, syngenetic
or epigenetic
Post-epigenetic (during and after
plant collecting)
Generated by biogenic processes of growing plants
(photosynthesis, diffusion, adsorption, pinocytose, endocytose,
exocytose, hydrolysis, precipitation, others)
Originated by natural processes after plants died (evaporation,
precipitation)
Pre-existing and nely dispersed mineral grains
(commonly < 1 lm) introduced into the plant by water
suspensions during syngenesis (endocytose)
Pre-existing and ne-grained particles (normally < 10100 lm)
introduced by water and wind on plant surfaces and xed in
pores, voids, and cracks
Natural and/or industrial components (dust, materials, additives,
contaminants, others) introduced in biomass during collecting,
handling, transport and subsequent processing

Little information is available on the combined chemical and
phase composition of biomass and biomass ashes [3133]. It was
found repeatedly that biomass shows a wide diversity and its com-
position is signicantly or highly variable [4,23,3339], especially
with respect to inorganic constituents [34,35,37]. On the other
hand, it was noted that the biomass composition is signicantly
[23,38,4042] to fundamentally [35] different from that of coal.
Furthermore, the variations among biomass composition were
found to be greater than for coals [23,43]. The composition of nat-
ural biomass depends on various factors, namely:
 type of biomass, plant species or part of plants [20,3339,41,44
48];
 growth processes, including the ability of plant species to uptake
(extract) selectively specic compounds from water, soil and air,
and to transport and deposit them within the plant tissues
[32,33,48];
 growing conditions [2,3436] such as sunlight [2], geographic
location [2,35,38,41], climate [20,37,46,49], seasons [33,48], soil
types [2,20,34,41,4447], water [2], pH [4,37,39], nutrients [2],
edge of forest [48], and near sea [38] or polluted area [35,48,50];
 age of the plants [4,34,35,39,45,48];
 fertilizer and pesticide doses used [4,8,37,41,47,49,5158],
which are highly important for some elements (Cl, K, N, P, S,
and certain trace elements);
 plant distance from source of pollution such as highways, cities,
factories, and ore mines [35,48,50];
 harvesting time [20,33,37,48,52] and collection technique, as
well as transport and storage conditions [4,20,37,46,51];
 pick-up of extraneous material (dust, dirt, soil) and entrained as
inclusions during biomass harvesting, transport and handling
[4,6,51,52,59];
 variation in ash fraction and type [35];
 blending of different biomass types [4,23,46].
It has been emphasised that the plant species is more important
than soil type [41], growing region [38,41] and treatment by fertil-
izers [41]. For example, wood species grown in different regions
showed small differences of elemental composition [41]. On the
other hand, the occurrence of inorganic and organic non-biomass
contaminants is common in semi-biomass (Tables 1 and 4). This
contaminated biomass contains post-epigenic natural or industrial
components, which are introduced during processing of natural
biomass. For instance, such components in semi-biomass can be
dust particles and various remains from construction materials,
plastics, rubbers, metals, chemicals, glass, porcelain, coloured pa-
per, paints, detergents, char, others [4,7,8,11,34,51,52,56].
1.4. Common issues concerning chemical composition of biomass
Data on bulk chemical composition, as well as some similarities
or differences in common chemical characteristics for biomass
varieties have been reported in almost all investigations. As a
result a huge amount of chemical data exists and some of them
have been summarized earlier [1,4,20,23,33,34,3639,44,4749,
51,56,60,61]. They reveal similar contents of C, H, O and signicant
differences in the contents of N and ash-forming elements in
biomass varieties [37]. Larger variations for Al, Mn, Na, and Si than
for Ca, Cl, Fe, K, Mg, and P were identied in woody biomass [48].
The bark has higher contents of ash, Al and Si than wood
[20,23,36,62]. The wood and woody fuels commonly show lower
values of ash, Cl, K, N, S, and Si and higher concentrations of
C and Ca in comparison with other biomass varieties
[37,39,49,51,60]. Agricultural biomass contains higher ash yields
and thus much more ash-forming elements than most of forestry
biomass [38]. Straws and grasses have relatively high Cl, K, N, Na,
S and Si concentrations [23,34,37,60]. It was also found that annual
and fast-growing crops (small branches and foliage of trees, short-
rotation woods, straws, grasses, fruits) have the greatest contents
of ash, moisture and highly mobile Cl, K, Mg, N, P, and S (occasion-
ally Na) in comparison with stems, trunks, barks and large
branches of trees [1,33,34,44,47,48,56,6062]. On the other hand,
elements like Al, Ca, Mn, and Si are considered to be immobile
and they are accumulated in the tissues by other means than mo-
bile elements [48].
Despite the above listed observations, it was found that the tra-
ditional, complete and peer-reviewed chemical data from simulta-
neous proximate, ultimate and ash analyses for many varieties of
biomass are quite limited. Therefore, such data only for 86 varieties
of biomass (148 samples) were collected for the present study. The
chemical data compiled and used are from 33 references including
an advanced scientic report [63], subsequently published
[34,44,51,60], and other peer-reviewed articles and monographs
[19,25,31,35,40,43,5254,6482]. It should also be noted that some
of these data are mean values from numerous determinations for a
given biomass variety.
The purpose of the present work is to elucidate the chemical
composition of 86 varieties of biomass and their ashes based on
the traditional and complete proximate, ultimate and ash analyses
(19 parameters) plus additional data for other important elements
such as Cl and Mn. The correlations and associations among the
chemical characteristics are also studied to nd some basic trends
and important relationships occurring in the biomass system and
specied biomass groups and sub-groups. Respective traditional
and complete chemical data for 38 SFFs, namely peat [74,75],
Table 5

918
Chemical composition of 86 varieties of biomass plus algae and four solid fossil fuel types based on proximate and ultimate analyses. The Cl contents are additionally given, wt.%.

Biomass group, sub-group and variety Proximate analysis (am)a Proximate analysis (db) b
Ultimate analysis (daf) c
Cl (db) b
nd Reference used
VM FC M A Sum VM FC A Sum C O H N S Sum
1. Wood and woody biomass (WWB)
1. Alder-r sawdust 36.3 9.1 52.6 2.0 100.0 76.6 19.2 4.2 100.0 53.2 40.2 6.1 0.5 0.04 100.04 0.02 1 [63]
2. Balsam bark 70.9 18.3 8.4 2.4 100.0 77.4 20.0 2.6 100.0 54.0 39.5 6.2 0.2 0.10 100.00 1 [51]
3. Beech bark 67.5 17.0 8.4 7.1 100.0 73.7 18.5 7.8 100.0 51.4 41.8 6.0 0.7 0.11 100.01 1 [51]
4. Birch bark 71.9 17.8 8.4 1.9 100.0 78.5 19.4 2.1 100.0 57.0 35.7 6.7 0.5 0.10 100.00 2 [51]
5. Christmas trees 46.1 12.9 37.8 3.2 100.0 74.2 20.7 5.1 100.0 54.5 38.7 5.9 0.5 0.42 100.02 1 [63]
6. Elm bark 67.0 17.2 8.4 7.4 100.0 73.1 18.8 8.1 100.0 50.9 42.5 5.8 0.7 0.11 100.01 1 [51]
7. Eucalyptus bark 68.7 15.1 12.0 4.2 100.0 78.0 17.2 4.8 100.0 48.7 45.3 5.7 0.3 0.05 100.05 0.26 1 [74,75]
8. Fir mill residue 30.4 6.5 62.9 0.2 100.0 82.0 17.5 0.5 100.0 51.4 42.5 6.0 0.1 0.03 100.03 0.19 1 [63]
9. Forest residue 34.5 7.3 56.8 1.4 100.0 79.9 16.9 3.2 100.0 52.7 41.1 5.4 0.7 0.10 100.00 0.03 2 [63,67,68]
10. Hemlock bark 65.9 23.4 8.4 2.3 100.0 72.0 25.5 2.5 100.0 55.0 38.8 5.9 0.2 0.10 100.00 1 [51]
11. Land clearing wood 35.4 7.0 49.2 8.4 100.0 69.7 13.8 16.5 100.0 50.7 42.8 6.0 0.4 0.07 99.97 0.02 1 [63]
12. Maple bark 70.1 17.8 8.4 3.7 100.0 76.6 19.4 4.0 100.0 52.0 41.3 6.2 0.4 0.11 100.01 2 [51]
13. Oak sawdust 76.3 11.9 11.5 0.3 100.0 86.3 13.4 0.3 100.0 50.1 43.9 5.9 0.1 0.01 100.01 0.01 1 [63]
14. Oak wood 73.0 20.0 6.5 0.5 100.0 78.1 21.4 0.5 100.0 50.6 42.9 6.1 0.3 0.10 100.00 1 [43]
15. Olive wood 74.3 16.1 6.6 3.0 100.0 79.6 17.2 3.2 100.0 49.0 44.9 5.4 0.7 0.03 100.03 1 [54,81]
16. Pine bark 70.2 23.3 4.7 1.8 100.0 73.7 24.4 1.9 100.0 53.8 39.9 5.9 0.3 0.07 99.97 0.01 2 [51,73]
17. Pine chips 66.9 20.0 7.6 5.5 100.0 72.4 21.6 6.0 100.0 52.8 40.5 6.1 0.5 0.09 99.99 0.06 1 [77]

S.V. Vassilev et al. / Fuel 89 (2010) 913933

18. Pine pruning 43.3 7.9 47.4 1.4 100.0 82.2 15.1 2.7 100.0 51.9 41.3 6.3 0.5 0.01 100.01 1 [79]
19. Pine sawdust 70.4 14.2 15.3 0.1 100.0 83.1 16.8 0.1 100.0 51.0 42.9 6.0 0.1 0.01 100.01 0.01 1 [73]
20. Poplar 79.7 11.5 6.8 2.0 100.0 85.6 12.3 2.1 100.0 51.6 41.7 6.1 0.6 0.02 100.02 0.03 2 [63]
21. Poplar bark 73.6 16.0 8.4 2.0 100.0 80.3 17.5 2.2 100.0 53.6 39.3 6.7 0.3 0.10 100.00 1 [51]
22. Sawdust 55.1 9.3 34.9 0.7 100.0 84.6 14.3 1.1 100.0 49.8 43.7 6.0 0.5 0.02 100.02 1 [52]
23. Spruce bark 67.3 21.4 8.4 2.9 100.0 73.4 23.4 3.2 100.0 53.6 40.0 6.2 0.1 0.10 100.00 0.03 4 [51,73]
24. Spruce wood 75.7 17.1 6.7 0.5 100.0 81.2 18.3 0.5 100.0 52.3 41.2 6.1 0.3 0.10 100.00 0.01 1 [35,43]
25. Tamarack bark 63.7 24.1 8.4 3.8 100.0 69.5 26.3 4.2 100.0 57.0 32.0 10.2 0.7 0.11 100.01 1 [51]
26. Willow 74.2 14.3 10.1 1.4 100.0 82.5 15.9 1.6 100.0 49.8 43.4 6.1 0.6 0.06 99.96 0.01 11 [63,67,73]
27. Wood 77.5 14.5 7.8 0.2 100.0 84.1 15.7 0.2 100.0 49.6 44.1 6.1 0.1 0.06 99.96 0.01 1 [72]
28. Wood residue 57.4 12.2 26.4 4.0 100.0 78.0 16.6 5.4 100.0 51.4 41.9 6.1 0.5 0.08 99.98 0.05 2 [63]
Mean 62.9 15.1 19.3 2.7 100.0 78.0 18.5 3.5 100.0 52.1 41.2 6.2 0.4 0.08 99.98 0.02 28
Minimum 30.4 6.5 4.7 0.1 69.5 12.3 0.1 48.7 32.0 5.4 0.1 0.01 0.01 28
Maximum 79.7 24.1 62.9 8.4 86.3 26.3 16.5 57.0 45.3 10.2 0.7 0.42 0.05 28
2. Herbaceous and agricultural biomass (HAB)
Mean 66.0 16.9 12.0 5.1 100.0 75.2 19.1 5.7 100.0 49.9 42.6 6.2 1.2 0.15 100.05 0.20 44
Minimum 41.5 9.1 4.4 0.8 59.3 12.4 0.9 42.2 34.2 3.2 0.1 0.01 0.01 44
Maximum 76.6 35.3 47.9 18.6 85.5 37.9 20.1 58.4 49.0 9.2 3.4 0.60 0.83 44
2.1. Grasses (HAG)
29. Arundo grass 46.5 9.5 42.0 2.0 100.0 80.2 16.4 3.4 100.0 48.7 44.5 6.1 0.6 0.13 100.03 0.20 1 [63]
30. Bamboo whole 71.0 15.2 13.0 0.8 100.0 81.6 17.5 0.9 100.0 52.0 42.5 5.1 0.4 0.04 100.04 0.08 3 [64]
31. Bana grass 70.2 15.9 4.5 9.4 100.0 73.6 16.6 9.8 100.0 50.1 42.9 6.0 0.9 0.13 100.03 0.83 1 [63]
32. Buffalo gourd grass 73.5 12.3 10.0 4.2 100.0 81.6 13.7 4.7 100.0 46.1 44.5 6.5 2.6 0.27 99.97 1 [63]
33. Kenaf grass 73.5 15.7 7.5 3.3 100.0 79.4 17.0 3.6 100.0 48.4 44.5 6.0 1.0 0.15 100.05 0.17 1 [73]
34. Miscanthus grass 71.9 14.0 11.4 2.7 100.0 81.2 15.8 3.0 100.0 49.2 44.2 6.0 0.4 0.15 99.95 0.13 3 [63,73]
35. Reed canary grass 67.8 16.3 7.7 8.2 100.0 73.4 17.7 8.9 100.0 49.4 42.7 6.3 1.5 0.15 100.05 0.06 1 [73]
36. Sorghastrum grass 72.4 12.6 11.3 3.7 100.0 81.6 14.2 4.2 100.0 49.4 44.0 6.3 0.3 0.05 100.05 0.04 1 [63]
37. Sweet sorghum grass 71.8 16.8 7.0 4.4 100.0 77.2 18.1 4.7 100.0 49.7 43.7 6.1 0.4 0.09 99.99 0.30 1 [73]
38. Switchgrass 70.8 12.8 11.9 4.5 100.0 80.4 14.5 5.1 100.0 49.7 43.4 6.1 0.7 0.11 100.01 0.08 3 [63]
Mean 69.0 14.1 12.6 4.3 100.0 79.0 16.2 4.8 100.0 49.2 43.7 6.1 0.9 0.13 100.03 0.21 10
Minimum 46.5 9.5 4.5 0.8 73.4 13.7 0.9 46.1 42.5 5.1 0.3 0.04 0.04 10
Maximum 73.5 16.8 42.0 9.4 81.6 18.1 9.8 52.0 44.5 6.5 2.6 0.27 0.83 10
2.2. Straws (HAS)
39. Alfalfa straw 71.6 14.3 9.3 4.8 100.0 78.9 15.8 5.3 100.0 49.9 40.8 6.3 2.8 0.21 100.01 0.50 1 [63]
40. Barley straw 67.4 16.4 11.5 4.7 100.0 76.2 18.5 5.3 100.0 49.4 43.6 6.2 0.7 0.13 100.03 0.27 2 [69,73]
41. Corn straw 67.7 17.8 7.4 7.1 100.0 73.1 19.2 7.7 100.0 48.7 44.1 6.4 0.7 0.08 99.98 0.64 1 [77]
42. Mint straw 58.0 16.2 16.8 9.0 100.0 69.7 19.5 10.8 100.0 50.6 40.1 6.2 2.8 0.28 99.98 0.43 1 [63]
43. Oat straw 73.9 12.5 8.2 5.4 100.0 80.5 13.6 5.9 100.0 48.8 44.6 6.0 0.5 0.08 99.98 0.09 1 [74,75]
44. Rape straw 70.7 16.3 8.7 4.3 100.0 77.4 17.9 4.7 100.0 48.5 44.5 6.4 0.5 0.10 100.00 0.03 1 [77]
45. Rice straw 59.4 14.4 7.6 18.6 100.0 64.3 15.6 20.1 100.0 50.1 43.0 5.7 1.0 0.16 99.96 0.58 3 [63,65,76]
46. Straw 64.3 13.8 12.4 9.5 100.0 73.4 15.8 10.8 100.0 48.8 44.5 5.6 1.0 0.13 100.03 0.54 2 [66,72]
47. Wheat straw 67.2 16.3 10.1 6.4 100.0 74.8 18.1 7.1 100.0 49.4 43.6 6.1 0.7 0.17 99.97 0.61 12 [43,63,69,73,76,78]
Mean 66.7 15.3 10.2 7.8 100.0 74.3 17.1 8.6 100.0 49.4 43.2 6.1 1.2 0.15 100.05 0.41 9
Minimum 58.0 12.5 7.4 4.3 64.3 13.6 4.7 48.5 40.1 5.6 0.5 0.08 0.03 9
Maximum 73.9 17.8 16.8 18.6 80.5 19.5 20.1 50.6 44.6 6.4 2.8 0.28 0.64 9
2.3. Other residues (HAR)
48. Almond hulls 69.0 18.8 6.5 5.7 100.0 73.8 20.1 6.1 100.0 50.6 41.7 6.4 1.2 0.07 99.97 0.02 1 [63]
49. Almond shells 69.5 20.2 7.2 3.1 100.0 74.9 21.8 3.3 100.0 50.3 42.5 6.2 1.0 0.05 100.05 0.06 2 [35,43,63]
50. Coconut shells 70.5 22.0 4.4 3.1 100.0 73.8 23.0 3.2 100.0 51.1 43.1 5.6 0.1 0.10 100.00 1 [53]
51. Coffee husks 68.2 18.5 10.8 2.5 100.0 76.5 20.7 2.8 100.0 45.4 48.3 4.9 1.1 0.35 100.05 2 [53]
52. Cotton husks 73.0 16.9 6.9 3.2 100.0 78.4 18.2 3.4 100.0 50.4 39.8 8.4 1.4 0.01 100.01 1 [53]
53. Grape marc 59.2 23.8 10.0 7.0 100.0 65.8 26.4 7.8 100.0 54.0 37.4 6.1 2.4 0.15 100.05 1 [79]
54. Groundnut shells 68.1 20.9 7.9 3.1 100.0 73.9 22.7 3.4 100.0 50.9 40.4 7.5 1.2 0.02 100.02 0.01 2 [53,71]
55. Hazelnut shells 71.5 19.9 7.2 1.4 100.0 77.1 21.4 1.5 100.0 51.5 41.6 5.5 1.4 0.04 100.04 0.20 1 [35,43]
56. Mustard husks 68.5 22.0 5.6 3.9 100.0 72.6 23.3 4.1 100.0 45.8 44.4 9.2 0.4 0.20 100.00 1 [53]
57. Olive husks 73.7 17.4 6.8 2.1 100.0 79.0 18.7 2.3 100.0 50.0 42.1 6.2 1.6 0.05 99.95 0.20 1 [35,43]
58. Olive pits 72.3 18.7 6.1 2.9 100.0 77.0 19.9 3.1 100.0 52.8 39.4 6.6 1.1 0.07 99.97 0.04 2 [54,63,81]
59. Olive residue 60.2 22.8 10.6 6.4 100.0 67.3 25.5 7.2 100.0 58.4 34.2 5.8 1.4 0.23 100.03 0.20 1 [77]
60. Palm bres-husks 46.3 12.0 36.4 5.3 100.0 72.8 18.9 8.3 100.0 51.5 40.1 6.6 1.5 0.30 100.00 1 [53]

S.V. Vassilev et al. / Fuel 89 (2010) 913933

61. Palm kernels 68.8 15.6 11.0 4.6 100.0 77.3 17.5 5.2 100.0 51.0 39.5 6.5 2.7 0.27 99.97 0.21 1 [77]
62. Pepper plant 60.5 19.5 6.5 13.5 100.0 64.7 20.9 14.4 100.0 42.2 49.0 5.0 3.2 0.57 99.97 0.13 1 [77]
63. Pepper residue 58.5 24.4 9.7 7.4 100.0 64.8 27.0 8.2 100.0 45.7 47.1 3.2 3.4 0.60 100.00 1 [53]
64. Pistachio shells 75.5 15.7 7.5 1.3 100.0 81.6 17.0 1.4 100.0 50.9 41.8 6.4 0.7 0.22 100.02 0.01 1 [63]
65. Plum pits 53.7 11.8 33.6 0.9 100.0 80.8 17.8 1.4 100.0 49.9 42.4 6.7 0.9 0.08 99.98 0.01 1 [63]
66. Rice husks 56.1 17.2 10.6 16.1 100.0 62.8 19.2 18.0 100.0 49.3 43.7 6.1 0.8 0.08 99.98 0.12 2 [63,82]
67. Soya husks 69.6 19.0 6.3 5.1 100.0 74.3 20.3 5.4 100.0 45.4 46.9 6.7 0.9 0.10 100.00 1 [53]
68. Sugar cane bagasse 76.6 11.1 10.4 1.9 100.0 85.5 12.4 2.1 100.0 49.8 43.9 6.0 0.2 0.06 99.96 0.03 2 [63]
69. Sunower husks 69.1 19.0 9.1 2.8 100.0 76.0 20.9 3.1 100.0 50.4 43.0 5.5 1.1 0.03 100.03 0.10 2 [43,53]
70. Walnut blows 61.8 12.9 23.5 1.8 100.0 80.7 16.9 2.4 100.0 54.9 36.9 6.7 1.4 0.11 100.01 0.02 1 [63]
71. Walnut hulls and blows 41.5 9.1 47.9 1.5 100.0 79.6 17.5 2.9 100.0 55.1 36.5 6.7 1.6 0.12 100.02 0.02 1 [63]
72. Walnut shells 55.3 35.3 6.8 2.6 100.0 59.3 37.9 2.8 100.0 49.9 42.4 6.2 1.4 0.09 99.99 0.15 1 [43]
Mean 64.6 18.6 12.4 4.4 100.0 74.0 21.0 5.0 100.0 50.2 41.9 6.3 1.4 0.16 99.96 0.09 25
Minimum 41.5 9.1 4.4 0.9 59.3 12.4 1.4 42.2 34.2 3.2 0.1 0.01 0.01 25
Maximum 76.6 35.3 47.9 16.1 85.5 37.9 18.0 58.4 49.0 9.2 3.4 0.60 0.21 25
3. Animal biomass (AB)
73. Chicken litter 43.3 13.1 9.3 34.3 100.0 47.8 14.4 37.8 100.0 60.5 25.3 6.8 6.2 1.20 100.00 0.50 1 [77]
74. Meat-bone meal 61.7 12.4 2.5 23.4 100.0 63.3 12.7 24.0 100.0 57.3 20.8 8.0 12.2 1.69 99.99 0.87 1 [77]
Mean 52.5 12.8 5.9 28.8 100.0 55.5 13.6 30.9 100.0 58.9 23.1 7.4 9.2 1.45 100.05 0.69 2
4. Mixture of biomass
75. Biomass mixture 63.3 16.5 8.8 11.4 100.0 69.4 18.1 12.5 100.0 56.7 33.1 6.6 2.7 0.85 99.95 0.09 1 [77]
76. Wood-agricultural residue 54.7 12.7 30.3 2.3 100.0 78.5 18.2 3.3 100.0 52.4 41.2 6.0 0.4 0.04 100.04 0.03 2 [63]
77. Wood-almond residue 59.7 12.3 22.7 5.3 100.0 77.2 15.9 6.9 100.0 50.9 42.5 5.9 0.6 0.08 99.98 0.03 1 [63]
78. Wood-straw residue 69.6 15.5 7.3 7.6 100.0 75.1 16.7 8.2 100.0 51.7 41.5 6.3 0.4 0.13 100.03 0.13 1 [63]
Mean 61.8 14.2 17.3 6.7 100.0 75.1 17.2 7.7 100.0 52.9 39.6 6.2 1.0 0.28 99.98 0.07 4
Minimum 54.7 12.3 7.3 2.3 69.4 15.9 3.3 50.9 33.1 5.9 0.4 0.04 0.03 4
Maximum 69.6 16.5 30.3 11.4 78.5 18.2 12.5 56.7 42.5 6.6 2.7 0.85 0.13 4
5. Contaminated biomass (CB)
79. Currency shredded 79.0 11.1 4.7 5.2 100.0 82.9 11.6 5.5 100.0 45.4 46.1 6.3 1.9 0.32 100.02 1 [63]
80. Demolition wood 63.4 14.5 16.3 5.8 100.0 75.8 17.3 6.9 100.0 51.7 40.7 6.4 1.1 0.09 99.99 0.06 4 [52,63,65,77]
81. Furniture waste 72.9 11.8 12.1 3.2 100.0 83.0 13.4 3.6 100.0 51.8 41.8 6.1 0.3 0.04 100.04 0.01 1 [63]
82. Mixed waste paper 76.8 6.8 8.8 7.6 100.0 84.2 7.5 8.3 100.0 52.3 40.2 7.2 0.2 0.08 99.98 1 [63]
83. Greenhouse-plastic waste 61.0 5.5 2.5 31.0 100.0 62.6 5.6 31.8 100.0 70.9 16.4 11.2 1.5 0.01 100.01 0.05 1 [77]
84. Refuse-derived fuel 70.3 0.5 4.2 25.0 100.0 73.4 0.5 26.1 100.0 53.8 36.8 7.8 1.1 0.47 99.97 0.83 2 [25,63]

919
(continued on next page)
 920
Table 5 (continued)

Biomass group, sub-group and variety Proximate analysis (am)a Proximate analysis (db) b
Ultimate analysis (daf) c
Cl (db) b
nd Reference used
VM FC M A Sum VM FC A Sum C O H N S Sum
85. Sewage sludge 45.0 5.3 6.4 43.3 100.0 48.0 5.7 46.3 100.0 50.9 33.4 7.3 6.1 2.33 100.03 0.04 2 [53,72]
86. Wood yard waste 40.9 8.4 38.1 12.6 100.0 66.0 13.6 20.4 100.0 52.2 40.4 6.0 1.1 0.30 100.00 0.30 1 [63]
Mean 63.7 8.0 11.6 16.7 100.0 72.0 9.4 18.6 100.0 53.6 37.0 7.3 1.7 0.46 100.06 0.31 8
Minimum 40.9 0.5 2.5 3.2 48.0 0.5 3.6 45.4 16.4 6.0 0.2 0.01 0.04 8
Maximum 79.0 14.5 38.1 43.3 84.2 17.3 46.3 70.9 46.1 11.2 6.1 2.33 0.83 8
All varieties of biomass
Mean 64.3 15.3 14.4 6.0 100.0 75.4 17.8 6.8 100.0 51.3 41.0 6.3 1.2 0.19 99.99 0.17 86
Minimum 30.4 0.5 2.5 0.1 47.8 0.5 0.1 42.2 16.4 3.2 0.1 0.01 0.01 86
Maximum 79.7 35.3 62.9 43.3 86.3 37.9 46.3 70.9 49.0 11.2 12.2 2.33 0.87 86
Natural biomass
Mean 64.4 16.0 14.7 4.9 100.0 75.8 18.6 5.6 100.0 51.1 41.4 6.2 1.1 0.20 100.00 0.17 78
Minimum 30.4 6.5 2.5 0.1 47.8 12.3 0.1 42.2 20.8 3.2 0.1 0.01 0.01 78
Maximum 79.7 35.3 62.9 34.3 86.3 37.9 37.8 60.5 49.0 10.2 12.2 1.69 0.87 78
Aquatic biomass
Marine macroalgae 45.1 23.1 10.7 21.1 100.0 50.5 25.9 23.6 100.0 43.2 45.8 6.2 2.2 2.60 100.00 3.34 11 [94,95]
Solid fossil fuels
Peat 57.8 24.3 14.6 3.3 100.0 67.6 28.5 3.9 100.0 56.3 36.2 5.8 1.5 0.2 100.0 0.04 1 [74,75]

S.V. Vassilev et al. / Fuel 89 (2010) 913933

Coal 30.8 43.9 5.5 19.8 100.0 32.8 46.3 20.9 100.0 78.2 13.6 5.2 1.3 1.7 100.0 0.03 37 [16,83]
Coal (minimum) 12.2 17.9 0.4 5.0 12.4 20.0 5.7 62.9 4.4 3.5 0.5 0.2 0.005 37 [16,83]
Coal (maximum) 44.5 70.4 20.2 48.9 51.8 71.8 52.0 86.9 29.9 6.3 2.9 9.8 0.11 37 [16,83]
Lignite 32.8 25.7 10.5 31.0 100.0 36.7 28.7 34.6 100.0 64.0 23.7 5.5 1.0 5.8 100.0 0.01 5 [16,83]
Sub-bituminous coal 33.4 34.1 8.2 24.3 100.0 36.4 37.2 26.4 100.0 74.4 17.7 5.6 1.4 0.9 100.0 0.03 10 [16,83]
Bituminous coal 29.1 52.6 3.1 15.2 100.0 30.0 54.3 15.7 100.0 83.1 9.5 5.0 1.3 1.1 100.0 0.04 22 [16,83]
a
As measured at different basis. For some samples without moisture data the mean contents measured for similar biomass varieties were used.
b
Dry basis.
c
Dry, ash-free basis.
d
Number of samples.
 S.V. Vassilev et al. / Fuel 89 (2010) 913933 921

Table 6
Chemical ash composition of 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, ppm.

Biomass group, sub-group SiO2 CaO K2O P2O5 Al2O3 MgO Fe2O3 SO3 Na2O TiO2 Sum Mn na Reference used
and variety (ppm)
1. Wood and woody biomass (WWB)
1. Alder-r sawdust 37.49 26.41 6.10 2.02 12.23 4.04 8.09 0.83 1.81 0.98 100.00 1 [63]
2. Balsam bark 26.06 45.76 10.70 4.87 1.91 2.33 2.65 2.86 2.65 0.21 100.00 20160 1 [51]
3. Beech bark 12.40 68.20 2.60 2.30 0.12 11.50 1.10 0.80 0.90 0.10 100.00 3100 1 [51]
4. Birch bark 4.38 69.06 8.99 4.13 0.55 5.92 2.24 2.75 1.85 0.13 100.00 22870 2 [51]
5. Christmas trees 39.91 9.75 8.06 2.46 15.12 2.59 9.54 11.66 0.54 0.37 100.00 1 [63]
6. Elm bark 4.48 83.46 5.47 1.62 0.12 2.49 0.37 1.00 0.87 0.12 100.00 775 1 [51]
7. Eucalyptus bark 10.04 57.74 9.29 2.35 3.10 10.91 1.12 3.47 1.86 0.12 100.00 10850 1 [74]
8. Fir mill residue 19.26 15.10 8.89 3.65 5.02 5.83 8.36 3.72 29.82 0.35 100.00 13640 2 [63,76]
9. Forest residue 20.65 47.55 10.23 5.05 2.99 7.20 1.42 2.91 1.60 0.40 100.00 13180 3 [44,63,67]
10. Hemlock bark 11.12 59.62 5.12 2.34 2.34 14.57 1.45 2.11 1.22 0.11 100.00 9300 1 [51]
11. Land clearing wood 65.82 5.79 2.19 0.66 14.85 1.81 5.27 0.36 2.70 0.55 100.00 1 [63]
12. Maple bark 8.95 67.36 7.03 0.79 3.98 6.59 1.43 1.99 1.76 0.12 100.00 5430 2 [51]
13. Oak sawdust 29.93 15.56 31.99 1.90 4.27 5.92 4.20 3.84 2.00 0.39 100.00 1 [63]
14. Oak wood 48.95 17.48 9.49 1.80 9.49 1.10 8.49 2.60 0.50 0.10 100.00 14900 2 [31,43]
15. Olive wood 10.24 41.47 25.16 10.75 2.02 3.03 0.88 2.65 3.67 0.13 100.00 1 [54]
16. Pine bark 9.20 56.83 7.78 5.02 7.20 6.19 2.79 2.83 1.97 0.19 100.00 12400 2 [51,73]
17. Pine chips 68.18 7.89 4.51 1.56 7.04 2.43 5.45 1.19 1.20 0.55 100.00 2090 1 [77]
18. Pine pruning 7.76 44.10 22.32 5.73 2.75 11.33 1.25 4.18 0.42 0.17 100.00 1 [79]
19. Pine sawdust 9.71 48.88 14.38 6.08 2.34 13.80 2.10 2.22 0.35 0.14 100.00 10550 2 [19,73]
20. Poplar 3.87 57.33 18.73 0.85 0.68 13.11 1.16 3.77 0.22 0.28 100.00 4500 3 [31,63]
21. Poplar bark 1.86 77.31 8.93 2.48 0.62 2.36 0.74 0.74 4.84 0.12 100.00 2330 1 [51]
22. Sawdust 26.17 44.11 10.83 2.27 4.53 5.34 1.82 2.05 2.48 0.40 100.00 27910 2 [40,52]
23. Spruce bark 6.13 72.39 7.22 2.69 0.68 4.97 1.90 1.88 2.02 0.12 100.00 13950 3 [51]
24. Spruce wood 49.30 17.20 9.60 1.90 9.40 1.10 8.30 2.60 0.50 0.10 100.00 1 [35]
25. Tamarack bark 7.77 53.50 5.64 5.00 8.94 9.04 3.83 2.77 3.40 0.11 100.00 26360 1 [51]
26. Willow 6.10 46.09 23.40 13.01 1.96 4.03 0.74 3.00 1.61 0.06 100.00 11 [63,67,73]
27. Wood 23.15 37.35 11.59 2.90 5.75 7.26 3.27 4.95 2.57 1.20 100.00 35740 1 [72]
28. Wood residue 53.15 11.66 4.85 1.37 12.64 3.06 6.24 1.99 4.47 0.57 100.00 2 [63]
Mean 22.22 43.03 10.75 3.48 5.09 6.07 3.44 2.78 2.85 0.29 100.00 13160 28
Minimum 1.86 5.79 2.19 0.66 0.12 1.10 0.37 0.36 0.22 0.06 775 28
Maximum 68.18 83.46 31.99 13.01 15.12 14.57 9.54 11.66 29.82 1.20 35740 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 1330 44
Minimum 2.01 0.97 2.29 0.54 0.10 0.19 0.22 0.01 0.09 0.01 155 44
Maximum 94.48 44.32 63.90 31.06 14.60 16.21 36.27 14.74 26.20 2.02 4570 44
2.1. Grasses (HAG)
29. Arundo grass 47.38 2.98 32.16 6.60 0.86 3.29 0.92 5.17 0.53 0.11 100.00 1 [63]
30. Bamboo whole 9.92 4.46 53.38 20.33 0.67 6.57 0.67 3.68 0.31 0.01 100.00 3 [64]
31. Bana grass 38.59 4.09 49.08 3.14 0.92 1.96 0.73 0.97 0.44 0.08 100.00 1 [63]
32. Buffalo gourd grass 8.73 14.74 41.40 10.96 1.88 5.24 0.90 9.89 6.20 0.06 100.00 1 [63]
33. Kenaf grass 9.50 44.32 19.14 3.89 2.59 8.64 1.73 8.20 1.87 0.12 100.00 1 [73]
34. Miscanthus grass 56.42 10.77 19.75 5.54 0.79 3.01 0.94 2.28 0.47 0.03 100.00 3100 4 [40,63,73]
35. Reed canary grass 84.92 3.31 2.93 3.88 1.32 1.42 1.04 1.04 0.09 0.05 100.00 1 [73]
36. Sorghastrum grass 73.21 7.02 8.97 4.43 1.83 2.21 0.95 1.11 0.25 0.02 100.00 1 [63]
37. Sweet sorghum grass 66.85 10.41 9.49 3.47 0.81 3.12 0.58 3.47 1.74 0.06 100.00 1 [73]
38. Switchgrass 66.25 10.21 9.64 3.92 2.22 4.71 1.36 0.83 0.58 0.28 100.00 3 [63]
Mean 46.18 11.23 24.59 6.62 1.39 4.02 0.98 3.66 1.25 0.08 100.00 3100 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)
39. Alfalfa straw 7.87 24.87 38.14 10.38 0.10 14.10 0.41 2.62 1.49 0.02 100.00 1 [63]
40. Barley straw 50.78 9.89 28.18 2.97 0.67 2.87 0.95 2.22 1.39 0.08 100.00 2 [69,73]
41. Corn straw 49.95 14.73 18.53 2.42 5.06 4.49 2.53 1.84 0.16 0.29 100.00 620 1 [77]
42. Mint straw 23.49 17.63 32.01 5.77 5.57 6.90 2.82 3.50 1.98 0.33 100.00 1 [63]
43. Oat straw 37.79 12.03 26.84 6.14 4.69 4.45 2.17 4.93 0.72 0.24 100.00 775 1 [74]
44. Rape straw 40.80 30.68 13.45 2.22 5.45 2.00 2.00 2.67 0.44 0.29 100.00 310 1 [77]
45. Rice straw 77.20 2.46 12.59 0.98 0.55 2.71 0.50 1.18 1.79 0.04 100.00 2790 3 [63,65,76]
46. Straw 57.14 6.70 25.82 2.74 0.76 1.67 0.53 3.89 0.70 0.05 100.00 155 2 [66,72]
47. Wheat straw 50.35 8.21 24.89 3.54 1.54 2.74 0.88 4.24 3.52 0.09 100.00 540 14 [43,44,51,63,69,73,76,78]
Mean 43.94 14.13 24.49 4.13 2.71 4.66 1.42 3.01 1.35 0.16 100.00 865 9
Minimum 7.87 2.46 12.59 0.98 0.10 1.67 0.41 1.18 0.16 0.02 155 9
Maximum 77.20 30.68 38.14 10.38 5.57 14.10 2.82 4.93 3.52 0.33 2790 9
2.3. Other residues (HAR)
48. Almond hulls 11.21 9.75 63.90 6.17 2.52 4.00 0.92 0.41 1.06 0.06 100.00 1 [63]
49. Almond shells 16.96 11.55 53.48 4.93 2.99 4.51 2.78 0.93 1.76 0.11 100.00 2 [43,63]
50. Coconut shells 66.75 2.41 8.48 1.54 8.48 1.54 6.16 0.01 4.62 0.01 100.00 1 [53]
51. Coffee husks 14.65 13.05 52.45 4.94 7.07 4.32 2.06 0.53 0.66 0.27 100.00 3 [53]
52. Cotton husks 10.93 20.95 50.20 4.05 1.32 7.59 1.92 1.72 1.31 0.01 100.00 1 [53]
53. Grape marc 9.53 28.52 36.84 8.80 2.63 4.77 1.77 6.29 0.67 0.18 100.00 1 [79]
54. Groundnut shells 27.70 24.80 8.50 3.70 8.30 5.40 10.30 10.40 0.80 0.10 100.00 1 [53]

(continued on next page)

922 S.V. Vassilev et al. / Fuel 89 (2010) 913933

Table 6 (continued)

Biomass group, sub-group SiO2 CaO K2O P2O5 Al2O3 MgO Fe2O3 SO3 Na2O TiO2 Sum Mn na Reference used
and variety (ppm)
55. Hazelnut shells 33.70 15.40 30.40 3.20 3.10 7.90 3.80 1.10 1.30 0.10 100.00 1 [43]
56. Mustard husks 17.43 44.13 7.63 2.06 1.55 9.48 0.82 14.74 2.06 0.10 100.00 1 [53]
57. Olive husks 32.70 14.50 4.30 2.50 8.40 4.20 6.30 0.60 26.20 0.30 100.00 1 [43]
58. Olive pits 21.48 19.97 16.44 9.71 5.95 3.84 4.25 2.30 15.77 0.29 100.00 2 [54,63]
59. Olive residue 22.26 12.93 42.79 6.09 4.10 5.84 1.99 3.73 0.12 0.15 100.00 310 1 [77]
60. Palm bres-husks 63.20 9.00 9.00 2.80 4.50 3.80 3.90 2.80 0.80 0.20 100.00 1 [53]
61. Palm kernels 18.26 9.33 16.54 31.06 6.19 6.59 9.23 2.54 0.14 0.12 100.00 4570 1 [77]
62. Pepper plant 12.60 32.20 24.60 5.20 4.90 7.40 2.00 9.70 0.90 0.50 100.00 1320 1 [77]
63. Pepper residue 15.39 10.02 35.32 11.19 8.39 4.55 3.38 10.61 1.05 0.10 100.00 1 [53]
64. Pistachio shells 8.43 10.26 18.66 12.10 2.23 3.34 36.27 3.89 4.61 0.21 100.00 1 [63]
65. Plum pits 3.64 14.86 45.51 20.40 0.11 11.79 0.69 2.51 0.47 0.02 100.00 1 [63]
66. Rice husks 94.48 0.97 2.29 0.54 0.21 0.19 0.22 0.92 0.16 0.02 100.00 155 5 [51,63,70,80,82]
67. Soya husks 2.01 25.26 36.00 5.79 8.74 8.38 2.95 4.37 6.26 0.24 100.00 1 [53]
68. Sugar cane bagasse 46.79 4.91 6.95 3.87 14.60 4.56 11.12 3.57 1.61 2.02 100.00 2 [63]
69. Sunower husks 23.66 15.31 28.53 7.13 8.75 7.33 4.27 4.07 0.80 0.15 100.00 2 [43,53]
70. Walnut blows 6.41 27.64 34.67 10.28 2.25 14.34 1.05 2.33 0.92 0.11 100.00 1 [63]
71. Walnut hulls and blows 8.29 20.03 39.65 7.52 2.92 16.21 1.37 2.71 1.19 0.11 100.00 1 [63]
72. Walnut shells 23.32 16.72 33.03 6.21 2.40 13.51 1.50 2.20 1.00 0.10 100.00 1 [43]
Mean 24.47 16.58 28.25 7.27 4.90 6.62 4.84 3.80 3.05 0.22 100.00 1590 25
Minimum 2.01 0.97 2.29 0.54 0.11 0.19 0.22 0.01 0.12 0.01 155 25
Maximum 94.48 44.13 63.90 31.06 14.60 16.21 36.27 14.74 26.20 2.02 4570 25
3. Animal biomass (AB)
73. Chicken litter 5.77 56.85 12.19 15.40 1.01 4.11 0.45 3.59 0.60 0.03 100.00 853 1 [77]
74. Meat-bone meal 0.02 41.22 3.16 40.94 2.37 1.38 0.25 4.24 6.41 0.01 100.00 78 1 [77]
Mean 2.90 49.04 7.67 28.17 1.69 2.75 0.35 3.91 3.50 0.02 100.00 466 2
4. Mixture of biomass
75. Biomass mixture 34.75 13.15 3.11 18.07 11.35 2.31 10.44 4.62 1.25 0.95 100.00 1550 1 [77]
76. Wood-agricultural 37.18 25.70 7.76 2.22 11.07 4.77 5.77 2.03 2.57 0.93 100.00 2 [63]
residue
77. Wood-almond residue 47.00 19.55 6.45 1.52 11.08 4.35 4.19 2.12 3.18 0.56 100.00 1 [63]
78. Wood-straw residue 57.83 11.51 6.67 1.08 9.77 2.66 4.97 1.88 3.11 0.52 100.00 1 [63]
Mean 44.19 17.48 6.00 5.72 10.82 3.52 6.34 2.66 2.53 0.74 100.00 1550 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)
79. Currency shredded 3.39 14.05 2.20 0.89 13.53 1.57 22.18 10.55 4.06 27.58 100.00 1 [63]
80. Demolition wood 36.27 21.36 6.98 5.09 9.67 4.77 7.31 4.12 2.83 1.60 100.00 1940 3 [63,65,77]
81. Furniture waste 57.17 13.78 3.74 0.50 12.14 3.25 5.59 0.99 2.34 0.50 100.00 1 [63]
82. Mixed waste paper 28.62 7.63 0.16 0.20 53.53 2.40 0.82 1.73 0.54 4.37 100.00 1 [63]
83. Greenhouse-plastic 28.40 25.80 9.70 3.84 3.90 5.70 18.40 2.65 0.80 0.81 100.00 2330 1 [77]
waste
84. Refuse-derived fuel 38.67 26.81 0.23 0.77 14.54 6.45 6.26 3.01 1.36 1.90 100.00 1 [63]
85. Sewage sludge 33.28 13.04 1.60 15.88 12.91 2.49 15.70 2.05 2.25 0.80 100.00 155 2 [53,72]
86. Wood yard waste 60.10 23.92 2.98 1.98 3.08 2.17 1.98 2.46 1.01 0.32 100.00 1 [63]
Mean 35.73 18.30 3.45 3.64 15.41 3.60 9.78 3.45 1.90 4.74 100.00 1475 8
Minimum 3.39 7.63 0.16 0.20 3.08 1.57 0.82 0.99 0.54 0.32 155 8
Maximum 60.10 26.81 9.70 15.88 53.53 6.45 22.18 10.55 4.06 27.58 2330 8
All varieties of biomass
Mean 29.76 25.27 17.91 5.71 5.51 5.42 4.00 3.28 2.48 0.66 100.00 7540 86
Minimum 0.02 0.97 0.16 0.20 0.10 0.19 0.22 0.01 0.09 0.01 78 86
Maximum 94.48 83.46 63.90 40.94 53.53 16.21 36.27 14.74 29.82 27.58 35740 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 8096 78
Minimum 0.02 0.97 2.19 0.54 0.10 0.19 0.22 0.01 0.09 0.01 78 78
Maximum 94.48 83.46 63.90 40.94 15.12 16.21 36.27 14.74 29.82 2.02 35740 78
Aquatic biomass
Marine macroalgae 1.65 12.39 15.35 9.76 0.85 12.50 1.87 25.74 19.88 99.99 326 11 [94,95]
Solid fossil fuels
Peat 37.53 9.97 1.12 2.75 20.14 2.14 13.83 12.11 0.10 0.31 100.00 775 1 [74]
Coal 54.06 6.57 1.60 0.50 23.18 1.83 6.85 3.54 0.82 1.05 100.00 543 37 [14,16]
Coal (minimum) 32.04 0.43 0.29 0.10 11.32 0.31 0.79 0.27 0.09 0.62 233 37 [14,16]
Coal (maximum) 68.35 27.78 4.15 1.70 35.23 3.98 16.44 14.42 2.90 1.61 1780 37 [14,16]
Lignite 44.87 13.11 1.48 0.20 17.11 2.50 10.80 8.64 0.48 0.81 100.00 736 5 [14,16]
Sub-bituminous coal 54.74 7.05 1.67 0.08 22.86 2.14 5.30 4.07 1.09 1.00 100.00 509 10 [14,16]
Bituminous coal 56.14 4.90 1.61 0.22 24.82 1.55 6.68 2.16 0.77 1.15 100.00 511 22 [14,16]
a
Number of samples.

lignites, sub-bituminous coals, and bituminous coals [14,16,83] are position, as well as for some comparisons and preliminary classi-
also used as subsidiary information for clarifying the biomass com- cation purposes.
 S.V. Vassilev et al. / Fuel 89 (2010) 913933 923

2. Data and discussion Table 8

Decreasing order of mean values for the chemical characteristics of the biomass
groups and sub-groups specied.
2.1. Chemical composition of biomass and comparisons with solid
fossil fuels Symbol Order for groups and sub-groups
M (am) WWB > HAG > HAR > HAB > CB > HAS > AB
2.1.1. General observations VM (db) HAG > WWB > HAB > HAS > HAR > CB > AB
FC (db) HAR > HAB > WWB > HAS > HAG > AB > CB
The bulk chemical composition of biomass is the rst step and
A (db) AB > CB > HAS > HAB > HAR > HAG > WWB
common approach for initial characterization and simplied C (daf) AB > CB > WWB > HAR > HAB > HAS > HAG
expression of this complex system, in contrast to phasemineral O (daf) HAG > HAS > HAB > HAR > WWB > CB > AB
composition. The individual, mean and range values for the tradi- H (daf) AB > CB > HAR > (WWB, HAB) > (HAG, HAS)
tional chemical characteristics plus Cl and Mn of the biomass vari- N (daf) AB > CB > HAR > (HAB, HAS) > HAG > WWB
S (daf) AB > CB > HAR > (HAB, HAS) > HAG > WWB
eties and their groups and sub-groups specied, as well as of other
Cl (db) AB > HAS > CB > HAG > HAB > HAR > WWB
SFFs are given in Tables 5 and 6. The biomass groups studied in- SiO2 HAG > HAS > CB > HAB > HAR > WWB > AB
clude terrestrial wood and woody biomass (WWB), herbaceous CaO AB > WWB > CB > HAR > HAB > HAS > HAG
and agricultural biomass (HAB), animal biomass (AB), contami- K2O HAR > HAB > HAG > HAS > WWB > AB > CB
P2O5 AB > HAR > HAG > HAB > HAS > CB > WWB
nated biomass (CB), and mixture of biomass. The biomass
Al2O3 CB > WWB > HAR > HAB > HAS > AB > HAG
sub-groups investigated are these of grass (HAG), straw (HAS) MgO HAR > WWB > HAB > HAS > HAG > CB > AB
and other residues (HAR) specied from the broadest HAB group Fe2O3 CB > HAR > WWB > HAB > HAS > HAG > AB
(Tables 1, 5 and 6). Hence, the varieties studied herein belong to SO3 AB > HAR > HAG > HAB > CB > HAS > WWB
all of the biomass groups and sub-groups listed in Table 1, exclud- Na2O AB > HAR > WWB > HAB > CB > HAS > HAG
TiO2 CB > WWB > HAR > HAB > HAS > HAG > AB
ing only the aquatic biomass group. However, some incomplete
Mn WWB > HAG > HAR > CB > HAB > HAS > AB
data for algae are provided and discussed additionally for compar-
ison (see Section 2.2.2). Abbreviations: AB, animal biomass; CB, contaminated biomass; HAB, herbaceous
and agricultural biomass; HAG, herbaceous and agricultural grass; HAR, herbaceous
The elements in biomass can be classied into major (>1.0%),
and agricultural residue; HAS, herbaceous and agricultural straw; WWB, wood and
minor (0.11.0%) and trace (<0.1%) elements according to their ele- woody biomass.
mental concentrations recalculated from Tables 5 and 6 as dry ba-
sis (db). In decreasing order of abundance, the major elements are
commonly C, O, H, N, Ca and K, while the minor elements normally and sub-groups are listed in Table 8. The identical or similar orders
include Si, Mg, Al, S, Fe, P, Cl, and Na. The trace elements are Mn of moisture volatile matterMgO; xed carbonK2O; NS; ash
and Ti plus other elements which are not discussed herein. Never- NSCl; P2O5SO3; and Al2O3Fe2O3TiO2 for biomass groups and
theless, there are many cases among biomass varieties where the sub-groups indicate some association between these parameters
above order for certain elements is changeable. The organic-form- in the biomass system.
ing elements in biomass are normally C, O, H, N, and S, whereas the The present chemical data show that there are some signicant
inorganic-forming elements are commonly the other 11 elements. differences and interesting comparative trends between natural
However, some proportions from the organic-forming elements biomass and coal. For instance, biomass or biomass ash are nor-
also occur in inorganic matter, while parts of the inorganic-forming mally enriched in moisture, volatile matter, CaO, Cl, H, K2O, MgO,
elements are also present in organic matter (similar to coal). For Mn, Na2O, O, and P2O5, and depleted in ash, xed carbon, Al2O3,
example, the ash-forming elements in biomass can be all 16 ele- C, Fe2O3, N, S, SiO2, SO3, and TiO2 in comparison with coal or coal
ments listed above. ash (Tables 5 and 6). This comparison is evaluated by the enrich-
In contrast to the above chemical investigations (see Section ment/depletion factor (EDF) dened as a ratio of the content in bio-
1.4), the present compilation of chemical data (Tables 5 and 6) is mass (or biomass ash) to the content in coal (or coal ash),
based on many more biomass varieties and set of samples. The lat- respectively. For that purpose, the mean values for 78 varieties of
ter data conrm that there are signicant differences in the chem- natural biomass and for 37 coals were used. The calculation reveals
ical composition of biomass varieties. The characteristic that the decreasing order of EDF is: Mn (14.9) > K2O (12.1) > P2O5
enrichment or depletion chemical trends among biomass groups (11.8) > Cl (5.7) > CaO (4.0) > MgO, Na2O (3.1) > O (3.0) > moisture
and sub-groups specied are given in Table 7. These trends are in (2.7) > volatile matter (2.1) > H (1.2) > SO3 (0.9) > N (0.8) > C
accordance with most of the literature ndings. However, both (0.7) > Fe2O3, SiO2 (0.5) > xed carbon (0.4) > ash, Al2O3, TiO2
AB and CB groups show the most signicant differences in the bio- (0.2) > S (0.1).
mass system with their high enrichment in ash, C, Cl, H, N, Na, S, The different position of S and SO3 in this order is related to the
and occasionally Al, Ca, Fe, P, and Ti. The above distinctions are re- higher capture behaviour of S in biomass ash than in coal ash due
lated to different biomass sources and origin, namely from plant to self-cleaning properties of some fuels [15]. The highest enrich-
(WWB, HAB) and animal (AB) products or from mixtures of plant, ment (EDF > 2.0) in biomass or biomass ash shows moisture, vola-
animal and manufacture materials (CB). The decreasing order of tile matter, Ca, Cl, K, Mg, Mn, Na, O, and P. On the other hand, the
mean values for the chemical characteristics of the biomass groups highest depletion (EDF 6 0.7) in biomass or biomass ash reveals

Table 7
Characteristic enrichment and depletion trends for the chemical characteristics (mean values) among the biomass groups and sub-groups specied.

Biomass group and sub-group Enriched in Depleted in

1. Wood and woody biomass (WWB) CaO, M, MgO, Mn, VM A, Cl, N, P2O5, S, SiO2, SO3
2. Herbaceous and agricultural biomass (HAB) FC, K2O, O, VM C, H, CaO
2.1. Grasses (HAG) K2O, O, SiO2, VM Al2O3, C, CaO, H, Na2O
2.2. Straws (HAS) Cl, K2O, O, SiO2 C, H, Na2O
2.3. Other residues (HAR) FC, K2O, MgO, P2O5 Cl
3. Animal biomass (AB) A, C, CaO, Cl, H, N, Na2O, P2O5, S, SO3 Al2O3, Fe2O3, M, MgO, Mn, O, SiO2, TiO2, VM
4. Contaminated biomass (CB) A, Al2O3, C, Cl, Fe2O3, H, N, S, TiO2 FC, K2O, P2O5
924 S.V. Vassilev et al. / Fuel 89 (2010) 913933
ash yield, xed carbon, Al, C, Fe, S, Si, and Ti. Relatively comparable
contents (EDF = 0.81.2) show H, N and sulphate S. Similar EDF
trends are also observed between natural biomass and the differ-
ent SFF types (Tables 5 and 6). The literature data show that bio-
mass or biomass ash generally has greater moisture, volatile
matter, Ca, Cl, H, K, Mg, Mn, O and Si contents, and lower Al, C,
Fe, N, S and Ti concentrations in comparison with coal or coal
ash [2,20,35,38,43,46,49]. The relatively comparable N content in
biomass and coal has been also reported earlier [49,53]. Hence,
there is agreement between the present data and reference obser-
vations, excluding only Si and the additional results supplied for
ash, xed carbon, Na, and P in the present study. The disagreement
for Si could be related to the much lesser set of coal and biomass
samples used in the reference investigations than herein.
The present data also indicate some leading tendencies for the
chemical composition of biomass and SFFs. For example, the above
listed EDF trend is indicative for the potential of biomass and bio-
mass products to contain preferably phases with:
(1) more oxygen-containing functional groups (hydroxyl, car-
boxyl, ether and ketone groups) with highly reactive func-
tionalities (COOH, OCH3 and OH), chelates, light
hydrocarbons, carbohydrates, oxyhydroxides, carbonates,
chlorides, and phosphates; and
(2) less aromaticity, functionalities, silicates, and sulphates-
sulphides; in comparison with SFFs [6,16,30,34,52].
The plant materials (dominantly ancient species) are a precur-
sor for coal formation. Therefore, the above EDF trend also indi-
cates the subsequent transformation of plant materials and
formation of SFFs. For instance, coal is enriched in ash, xed car-
bon, Al, C, Fe, N, S, Si and Ti, and depleted in moisture, volatile mat-
ter, Ca, Cl, H, K, Mg, Mn, Na, O, and P in comparison with the
biomass. This observation is in a good agreement with the ndings
about the mobilization, redistribution and formation of stable (en-
riched in coal) and unstable (depleted in coal) discrete phases or
minerals which are bearing constituents of the above elements,
during coal formation and coal rank advance [83,84].
2.1.2. Proximate composition of biomass
There are large variations for the characteristics determined by
the proximate and ultimate analyses of biomass samples (Table 5).
However, these variations are mostly due to the moisture contents
and ash yields, which vary in the greatest intervals. When the mea-
sured parameters are recalculated on dry and dry ash-free basis
their variations are in more narrow ranges for biomass groups
and sub-groups (Table 5). For example, the range values of volatile
matter and xed carbon as measured in grasses are respectively
46.573.5% and 9.516.8%, while these values on dry basis are only
73.481.6% and 13.718.1%, respectively. Therefore, it is better to
use dry, dry ash-free or ash basis for comparative chemical charac-
terization of biomass varieties. The moisture content and ash yield
are important parameters of the biomass system and require a
more detail discussion.
2.1.2.1. Moisture. The moisture content in biomass as measured (at
different basis, but normally as received, air-dried and oven-dried
basis) varies in the interval of 363% (Table 5) and it can reach even
80% for raw wood species [48]. The moisture value seems to de-
crease in the order: WWB > HAG > HAR > HAB > CB > HAS > AB (Ta-
ble 8). In contrast, the moisture occurrence in peat and coal as
measured (mostly air-dried basis) is commonly in the more narrow
range of 120% (Table 5). This characteristic seems to have much
higher contents in biomass than in SFFs at least on raw basis,
respectively as collected (harvested) and run of mine status. Simi-
lar observations have been also mentioned earlier [2,35,38,43].
The moisture in biomass is mineralized aqueous solution con-
taining cations (Al, Ca, Fe, K, Mg, Mn, Na, Ti), anions (Br, Cl, CO3,
F, HCO3, H2PO4, I, NO3, OH, PO4, SO4) or non-charged species
(H4SiO4) [4,48,51,85]. This uid plays a key role for the composi-
tion of biomass because of: (1) high water content in the living
cells; (2) variable total mineralization of water (dissolved solid
matter); and (3) different chemical specication (predominant an-
ions, cations and their ratios) of these water solutions. Therefore,
there is intensive mineral precipitation from a saturated solution
due to moisture evaporation after biomass harvesting and during
biomass drying. This process results mostly in consecutive forma-
tion of water-soluble: (1) phosphates; (2) carbonates; (3) sul-
phates; (4) chlorides; and (5) nitrates, which are a general
sequence of precipitation from less soluble to highly soluble min-
erals in the water system [83,85]. Such mineral formations are
the reason for enhanced leaching of Ca, Cl, K, Mg, Na, P, and S from
biomass harvested and left in the eld for a prolonged period of
time [25,44,49,54,61,86]. Additional conrmation of the above
statement is also the observation that young foliage of wood (bio-
logically active tissues) shows the highest contents of water and
elements such as Cl, K, Mg, P, and S [48]. These are typical mobile
elements not only in the plant physiology [48], but also in the nat-
ural water system [85]. The above observations show the impor-
tance of specifying the exact status used for biomass
characterization.
2.1.2.2. Ash yield. The ash yield (db) determined at 550600 C for
biomass varies in the interval of 0.146% (Table 5) and normally
decreases in the order: AB > CB > HAS > HAB > HAR > HAG > WWB
(Table 8). In contrast, the ash content (815 C) in peat and coal
(db) is in the relatively more narrow range of 452% (commonly
430%) (Table 5). The ash normally shows much lower value in bio-
mass than in SFFs, excluding AB and some CB and HAB samples
(Table 5). The extremely high ash content is characteristic of sew-
age sludge, chicken litter, greenhouse-plastic waste, refuse-derived
fuel, meat-bone meal, and rice straw. The reference data show that
WWB has much lower ash content comparing with HAB because
straws, grasses, cereals, and fruits take up nutrients during their
growing periods [23,38,39]. The ash in WWB decreases in the or-
der: foliage > bark > wood [48]. The high ash yields of some wood
fuels such as chemically treated wood and waste wood are an indi-
cation for increased amounts of mineral and metallic impurities
and other contaminants due to the manufacturing process
[23,56]. Hence, there is agreement between the present and refer-
ence data, but some additional elucidation of this important
parameter is required.
The ash is one of the most studied characteristics of biomass,
but unfortunately with the poorest understanding. The complex
character of this parameter is the reason for such a problem be-
cause ash originates simultaneously from natural and technogenic
inorganic, organic and uid matter during biomass combustion. It
should be stated that the terms ash, inorganic matter and mineral
matter of biomass (Tables 3 and 4) are not synonymous because
they comprise constituents with different nature and quantity,
similar to coal [1618,87]. The inorganic matter comprises solid
crystalline, semi-crystalline and amorphous phases in biomass.
The actual mineral matter, as a part of inorganic matter, excludes
inorganic amorphous matter and includes only minerals and min-
eraloids in biomass that belong to mineral classes, groups and spe-
cies strictly divided and dened in the mineralogical sense. In
contrast, the ash yield is the inorganic residue that results from
the complete combustion (or oxidation) of biomass and is com-
posed of original and newly formed inorganic phases generated
from the inorganic, organic and uid components in biomass.
LTA and HTA are laboratory-produced biomass ashes at regulated
temperatures, respectively: (1) in oxygen plasma at 100250 C;
 S.V. Vassilev et al. / Fuel 89 (2010) 913933
and (2) in air above 500 C. The combustion temperature signi-
cantly affects the total yield of ash from biomass. For example,
the ash yields determined at 10001300 C are 2070% lower than
those produced by LTA or HTA at 500550 C [31,51,56,88]. Such
weight losses for biomass are much higher than for coal and these
differences are a result of more intensive phase transformations
and subsequent volatilization of elements from biomass phases
in the high temperature intervals [89,90]. It should be stated that
the ash yield itself brings relatively limited information when the
composition, abundance and origin of the biomass constituents
are not considered. Hence, the ash should always be interpreted to-
gether with the genesis of constituents in biomass. Such interpre-
tations have a great importance for both organic and inorganic
elements in biomass because their modes of occurrence are related
to mixed natural (authigenic and detrital) and technogenic origin.
Despite the above limitations, the ash yields of biomass can be
measured routinely, while the actual determination of inorganic
constituents is a complex procedure and cannot be quickly and
routinely achieved. Therefore, ash is still an important parameter
for approximating: (1) the bulk inorganic matter; (2) predominant
afnity of elements and compounds to inorganic or organic matter;
and (3) possible contamination of biomass.
2.1.2.3. Volatile matter. The volatile matter content (db) in biomass
varies in the interval of 4886% (Table 5) and normally decreases in
the order: HAG > WWB > HAB > HAS > HAR > CB > AB (Table 8). In
contrast, the volatile matter value in peat and coal (db) is com-
monly in the larger range of 1268% (Table 5). This parameter typ-
ically shows much higher content in biomass than in SFFs (Table
5). The extremely high volatile matter value is characteristic of
some WWB, sugar cane bagasse, and paper waste (Table 5). The
volatile matter yield of biomass commonly includes light hydro-
carbons, CO, CO2, H2, moisture, and tars [43].
2.1.2.4. Fixed carbon. The xed carbon content (db) in biomass var-
ies in the interval of 138% (Table 5) and normally decreases in the
order: HAR > HAB > WWB > HAS > HAG > AB > CB (Table 8). In con-
trast, the xed carbon value in peat and coal (db) is commonly in
the larger range of 2072% (Table 5). This parameter typically re-
veals lower content in biomass than in SFFs (Table 5). The extre-
mely high xed carbon content is characteristic of some wood
Fig. 1. Mean proximate composition of solid fuel types, wt.%.
925
barks and HAB residues (Table 5). Furthermore, biomass commonly
has a volatile matter/xed carbon ratio >3.5, while this ratio for
peat and coal is normally in the interval 0.62.4 (Table 5).
The plotted mean proximate composition (db) of solid fuel
types in Fig. 1 illustrates: (1) the differentiations between the bio-
mass and coals; (2) the relatively closer position of peat to biomass
than coals; and (3) the similarities among various biomass groups
and sub-groups, excluding only AB and CB biomass groups. The
distinctions for the last groups are evidenced by their plots in
Fig. 1 and maximum or minimum values in the above-listed orders
for the proximate characteristics. Both AB and CB groups com-
monly have intermediate positions between SFFs and other bio-
mass groups and sub-groups.
2.1.3. Ultimate composition of biomass
Due to the strong inuence of moisture and ash yield on the
contents of other chemical characteristics in the biomass system,
the dry ash-free (daf) basis of biomass varieties and SFF types are
used for comparative characterizations of the ultimate analysis
(ve elements) plus additional data for Cl contents (db) (Table 5).
2.1.3.1. Carbon (C). The C content in biomass varies in the interval
of 4271% (Table 5) and normally decreases in the order:
AB > CB > WWB > HAR > HAB > HAS > HAG (Table 8). In contrast,
the C value in peat and coal is commonly in the range of 5687%
(Table 5). This element typically shows lower content in biomass
than in SFFs (Table 5). The extremely high C content is characteris-
tic of some wood barks and high-ash greenhouse-plastic waste,
chicken litter, meat-bone meal, and refuse-derived fuel (Table 5).
The higher C content in woody biomass than in herbaceous bio-
mass has been also mentioned earlier [56].
2.1.3.2. Oxygen (O). The O content in biomass is mostly calculated
by difference and varies in the interval of 1649% (Table 5). It nor-
mally decreases in the order: HAG > HAS > HAB > HAR > WWB > C-
B > AB (Table 8). In contrast, the O value in peat and coal is
commonly in the range of 436% (Table 5). This element typically
shows much higher content in biomass than in SFFs (Table 5). The
extremely high O content is characteristic of pepper residues, cof-
fee and soya husks (Table 5).
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
926 S.V. Vassilev et al. / Fuel 89 (2010) 913933
2.1.3.3. Hydrogen (H). The H content in biomass varies in the inter-
val of 311% (Table 5). In contrast, the H concentration in peat and
coal is in the narrow range of 46% (Table 5). This element com-
monly shows higher content in biomass than in SFFs (Table 5).
The extremely high H content is characteristic of greenhouse-plas-
tic waste, tamarack bark, mustard and cotton husks, meat-bone
meal, refuse-derived fuel, and groundnut shells (Table 5). The H va-
lue normally decreases in the order: AB > CB > HAR > (WWB, HAB)
> (HAG, HAS) (Table 8). The similar order of H and C indicates their
association (occurrence and behaviour) in biomass probably as
hydrocarbons and carbohydrates. It is well-known that photosyn-
thesis results in the production of structural and non-structural
carbohydrates comprising the plant tissues [34].
2.1.3.4. Nitrogen (N). The N content in biomass varies in the interval
of 0.112% (Table 5) and normally decreases in the order:
AB > CB > HAR > (HAB, HAS) > HAG > WWB (Table 8). In contrast,
the N value in peat and coal is in the narrow range of 13% (Table
5). This mobile element normally has slightly lower content in bio-
mass than in SFFs, excluding AB and some varieties from CB and
HAB groups. The extremely high N content is characteristic of
meat-bone meal, chicken litter, sewage sludge, pepper residues, al-
falfa and mint straws, palm kernels, and buffalo gourd grass (Table
5). The samples from WWB group typically show the lowest N con-
centration (Table 5) and this nding has been reported earlier [39].
It was also noted that grasses usually show the highest N values
[39]; however, the present data do not support this observation.
2.1.3.5. Sulphur (S). The S content in biomass varies in the interval
of 0.012.3% (Table 5) and normally decreases in the order:
AB > CB > HAR > (HAB, HAS) > HAG > WWB (Table 8). This order is
identical to N and indicates the close association of both N and S.
In contrast, the S concentration in peat and coal is in the range of
0.29.8% (Table 5). This mobile element has typically much lower
content in biomass than in SFFs, excluding AB and some varieties
from CB and HAB groups (Table 5). The extremely high S content
is characteristic of sewage sludge, meat-bone meal, chicken litter,
biomass mixture, pepper residues, refuse-derived fuel, and Christ-
mas trees (Table 5). It was also noted that bark and straw have a
higher S content than wood, but some wood products (pellets
and briquettes) can also contain S-bearing additives [56].
Fig. 2. Mean ultimate composition of solid fuel types, wt.%.
2.1.3.6. Chlorine (Cl). The Cl content in biomass (db) varies in the
interval of 0.010.9% (Table 5) and normally decreases in the order:
AB > HAS > CB > HAG > HAB > HAR > WWB (Table 8). This order is
similar to those of N and S, which indicates their association in bio-
mass probably as salts. In contrast, the Cl value (db) in peat and
coal is in the large range of 0.0050.1% (Table 5). This mobile ele-
ment has commonly much higher content in biomass than in SFFs,
in particular AB and many varieties from CB and HAB groups. The
extremely high Cl content is characteristic of meat-bone meal, re-
fuse-derived fuel, most straws (alfalfa, barley, corn, mint, rice,
wheat), some grasses (bana, sweet sorghum), and chicken litter
(Table 5). On the other hand, most of the WWB and HAR samples
show the lowest Cl contents (Table 5). It was noted that wood con-
tains generally very low Cl concentrations, but certain wood prod-
ucts can contain Cl-bearing additives [39,56]. The reference data
also show high Cl contents in some: wood barks and straws [56];
herbaceous biomass, grains and fruit residues [39]; crops inten-
sively cultivated with fertilizers [4]; wood foliage, trees growing
at the edge of forests, near to motor highways (due to de-icing
salts), and in the cities (from Cl aerosols) [48]; and even close to
the sea [38].
The plotted mean ultimate composition (daf) of solid fuel types
in Fig. 2 (see the reason for its creation in Section 2.2.2) illustrates:
(1) the differentiations between the biomass and coals; (2) the clo-
ser position of peat to biomass than coals; and (3) the similarities
among various biomass groups and sub-groups, excluding again
(like the proximate composition) only the AB and CB biomass
groups. The distinctions for the last groups are evidenced by their
plots in Fig. 2 and maximum or minimum values in the above-
listed orders for the ultimate characteristics. Both AB and CB
groups also have intermediate positions between SFFs and other
biomass groups and sub-groups.
2.1.4. High-temperature ash (HTA) composition of biomass
The traditional chemical data for 10 oxides (normalized to
100%) plus Mn contents in HTAs of biomass varieties, groups and
sub-groups (550600 C), as well as SFF types (815 C) are given
in Table 6 and used for comparative characterizations. It should
be noted that the most abundant oxides could have slightly over-
estimated values after the normalization. It can be seen that the
chemical composition of biomass HTAs shows extremely large
variations. This is due to the highly variable contents of bulk
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
 S.V. Vassilev et al. / Fuel 89 (2010) 913933
inorganic matter and different genetic classes of inorganic matter
in biomass varieties. The characteristic enrichment and depletion
trends for the HTA characteristics in the biomass groups and
sub-groups specied are listed in Table 7. The decreasing order
of these characteristics (mean values) for the biomass groups and
sub-groups are also given in Table 8. The above orders reveal that
there is differentiation between the components as some similari-
ties were observed only for PS and AlFeTi oxides. On the other
hand, according to the mean contents (Table 6) of the most abun-
dant six oxides, their order in decreasing values for the specied
groups and sub-groups are:
 CaO > SiO2 > K2O > MgO > Al2O3 > P2O5 for WWB;
 SiO2 > K2O > CaO > P2O5 > MgO > Al2O3 for HAB and HAG;
 SiO2 > K2O > CaO > MgO > P2O5 > Al2O3 for HAS;
 K2O > SiO2 > CaO > P2O5 > MgO > Al2O3 for HAR;
 CaO > P2O5 > K2O > SiO2 > MgO > Al2O3 for AB;
 SiO2 > CaO > Al2O3 > P2O5 > MgO > K2O for CB.
Hence, there is a characteristic differentiation between the
groups and signicant similarity between the sub-groups (particu-
larly HAG and HAS) among the orders of these six oxides. Three
types of biomass ash system have been described elsewhere in
terms of their chemical composition, namely (1)>Si/>K/<Ca ashes
(grasses); (2)<Si/>K/>Ca ashes (woody materials, pits and shells);
and (3)>Ca/>P ashes (manures, poultry litters and animal wastes)
[51]. So, there is some agreement between the present data and
reference observations, but the present study supplies more data
and indicates that an additional clarication of chemical ash con-
stituents is required.
2.1.4.1. SiO2. The SiO2 content in biomass HTAs varies in the large
interval of 0.0294% (Table 6) and the value of this oxide normally
decreases in the order: HAG > HAS > CB > HAB > HAR > WWB > AB
(Table 8). In contrast, the SiO2 concentration in peat and coal HTAs
is commonly in the more narrow range of 3268% (Table 6). This
oxide represents less mobile Si components in biomass and nor-
mally shows lower content in biomass ash than in SFF ash, exclud-
ing some HAB, WWB and CB samples. The extremely high SiO2
content is characteristic of reed canary grass, sorghastrum grass,
rice straw, and rice husks (Table 6). The reference data also show
that the wood stems contain very little Si, while in some grasses,
straws (especially rice straws), rice husks [34,44,60] and spruce
needles [48] substantial to high amounts of silica were found. It
is interesting to note that some tall grasses and straws contain a
high amount of Si that contributes to the plants sturdiness or rig-
idness [68,73]. This Si is introduced in plant as silicic acid and pre-
cipitates in the form of amorphous and occasionally crystalline
silica as Al is likely to co-precipitate with Si [48,51,71]. On the
other hand, Si (plus Al, Ti, Fe, and Na) may also be introduced in
biomass fuels as sand, clays and other soil components during har-
vest and transport or through processing operations and manufac-
tured products [34,36,51,60].
2.1.4.2. CaO. The CaO content in biomass HTAs varies in the large
interval of 183% (Table 6) and the value of this oxide normally de-
creases in the order: AB > WWB > CB > HAR > HAB > HAS > HAG
(Table 8). In contrast, the CaO concentration in peat and coal HTAs
is commonly in the more narrow range of 0.428% (Table 6). This
oxide represents less mobile Ca components in biomass and nor-
mally shows much higher content in biomass ash than in SFF
ash, excluding some biomass samples mostly from HAB group.
The extremely high CaO content is characteristic of wood barks
and chicken litter (Table 6). The reference data also reveal that
the wood stems, trunks and large branches contain high Ca con-
centrations [44]. Calcium and Mn show similar concentration
927
trends in biomass and they are accumulated in the foliage and bark
through the precipitation of Ca oxalate as Mn co-precipitates in the
oxalate as solid solution with Ca [48].
2.1.4.3. K2O. The K2O content in biomass HTAs varies in the large
interval of 0.264% (Table 6) and the value of this oxide normally
decreases in the order: HAR > HAB > HAG > HAS > WWB > AB > CB
(Table 8). In contrast, the K2O concentration in peat and coal HTAs
is commonly in the narrow range of 0.34% (Table 6). This oxide
represents mobile K components in biomass and mostly shows
much higher content in biomass ash than in SFF ash, excluding
some CB varieties and individual WWB, HAG and AB samples.
The extremely high K2O content is characteristic of HAB group
and particularly HAR sub-group (Table 6). These observations are
in accordance with the literature data. For example, it was found
that the biomass with high annual growth is abundant in alkaline
elements because they are readily taken up from the soil [44].
2.1.4.4. P2O5. The P2O5 content in biomass HTAs varies in the large
interval of 0.241% (Table 6) and the value of this oxide normally
decreases in the order: AB > HAR > HAG > HAB > HAS > CB > WWB
(Table 8). In contrast, the P2O5 concentration in peat and coal HTAs
is commonly in the more narrow range of 0.13% (Table 6). This
oxide represents mobile P components in biomass and mostly
shows much higher content in biomass ash than in SFF ash, exclud-
ing some CB varieties. The extremely high P2O5 content is charac-
teristic of AB group, sewage sludge and some HAB samples (Table
6). The enrichment of this oxide in cereals has been also noted [4].
2.1.4.5. Al2O3. The Al2O3 content in biomass HTAs varies in the large
interval of 0.154% (Table 6) and the value of this oxide normally
decreases in the order: CB > WWB > HAR > HAB > HAS > AB > HAG
(Table 8). In contrast, the Al2O3 concentration in peat and coal
HTAs is commonly in the more narrow range of 1135% (Table
6). This oxide represents less mobile Al components in biomass
and mostly shows much lower content in biomass ash than in
SFF ash, excluding some CB varieties and individual samples from
WWB group and HAR sub-group. The extremely high Al2O3 content
is characteristic of mixed waste paper probably due to the tradi-
tional kaolinite additive used in paper production (Table 6). The
high Al concentration is also usually considered as a marker for
contamination of biomass by soil inclusions (predominantly clays
and oxides), dust or dirt [44,51,71].
2.1.4.6. MgO. The MgO content in biomass HTAs varies in the large
interval of 0.216% (Table 6) and the value of this oxide normally
decreases in the order: HAR > WWB > HAB > HAS > HAG > CB > AB
(Table 8). In contrast, the MgO concentration in peat and coal HTAs
is commonly in the more narrow range of 0.34% (Table 6). This
oxide represents mobile Mg components in biomass and normally
shows much higher content in biomass ash than in SFF ash, exclud-
ing individual samples from all of the groups and sub-groups spec-
ied. The extremely high MgO content is characteristic of alfalfa
straw and some WWB and HAR varieties (Table 6).
2.1.4.7. Fe2O3. The Fe2O3 content in biomass HTAs varies in the
large interval of 0.236% (Table 6) and the value of this oxide nor-
mally decreases in the order: CB > HAR > WWB > HAB > HAS > HA-
G > AB (Table 8). In contrast, the Fe2O3 concentration in peat and
coal HTAs is commonly in the more narrow range of 0.816% (Ta-
ble 6). This oxide represents less mobile Fe components in biomass
and normally shows lower content in biomass ash than in SFF ash,
excluding some WWB, HAR and CB varieties. The extremely high
Fe2O3 content is characteristic of pistachio shells (probably con-
taminated by Fe oxyhydroxides), some industrial wastes, sewage
sludge, sugar cane baggase, and groundnut shells (Table 6).
928 S.V. Vassilev et al. / Fuel 89 (2010) 913933
2.1.4.8. SO3. The SO3 content in biomass HTAs varies in the large
interval of 0.0115% (Table 6) and the value of this oxide normally
decreases in the order: AB > HAR > HAG > HAB > CB > HAS > WWB
(Table 8). In contrast, the SO3 concentration in peat and coal HTAs
is in relatively more narrow range of 0.314% (Table 6). This oxide
represents the mobile S components in biomass that are captured
in biomass ash as sulphates. SO3 normally shows lower content in
biomass ash than in SFF ash, excluding AB and some WWB, HAB
and CB varieties. The extremely high SO3 content is characteristic
of groundnut shells, mustard husks, and pepper residues. The great
SO3 concentration in Christmas trees, and currency shredded (Ta-
ble 6) is probably due to S-bearing contaminants and additives,
respectively.
2.1.4.9. Na2O. The Na2O content in biomass HTAs varies in the large
interval of 0.130% (Table 6) and the value of this oxide normally
decreases in the order: AB > HAR > WWB > HAB > CB > HAS > HAG
(Table 8). In contrast, the Na2O concentration in peat and coal HTAs
is commonly in the more narrow range of 0.13% (Table 6). This
oxide represents relatively less mobile Na components in biomass
and normally shows much higher content in biomass ash than in
SFF ash, excluding some WWB, HAB, AB and CB varieties. The ex-
tremely high Na2O content is characteristic of olive husks and pits,
and r mill residue probably contaminated by solution with halite
composition (see Tables 5 and 6). For example, it was noted that
the high Na concentrations are frequently an indication of intru-
sion of salt water or a process additive [51].
2.1.4.10. TiO2. The TiO2 content in biomass HTAs varies in the large
interval of 0.0128% (Table 6) and the value of this oxide normally
decreases in the order: CB > WWB > HAR > HAB > HAS > HAG > AB
(Table 8). In contrast, the TiO2 concentration in peat and coal HTAs
is commonly in the narrow range of 0.31.6% (Table 6). This oxide
represents less mobile Ti components in biomass and normally
shows much lower content in biomass ash than in SFF ash, exclud-
ing some CB varieties, sugar cane bagasse and individual wood
samples. The extremely high TiO2 content is characteristic of cur-
rency shredded and mixed waste paper probably due to the tradi-
tional Ti-bearing additives (Table 6).
2.1.4.11. Mn. The Mn content in biomass HTAs varies in the large
interval of 0.013.6% (Table 6) and the value of this element nor-
mally decreases in the order: WWB > HAG > HAR > CB > HAB > HA-
S > AB (Table 8). In contrast, the Mn concentration in peat and coal
HTAs is commonly in the narrow range of 0.020.18% (Table 6).
This less mobile element in biomass mostly shows much higher
content in biomass ash than in SFF ash, excluding some HAB, AB
and CB varieties. The extremely high Mn content (together with
Ca) is characteristic of some WWB samples (Table 6).
The contents of CO2 and water are occasionally determined and
included in the bulk chemical composition of biomass HTAs
[23,34,36,44,51,60,6365,67,68,76,91]. These are useful subsidiary
characteristics during the phase identication and characterization
of ashes. However, they are less informative for the bulk balance
and actual chemical ash composition because signicant parts of
them are xed in HTAs from the air CO2 and moisture. Both com-
pounds intensively react with the active and highly abundant alka-
line and alkaline-earth oxides to form hydrates, hydroxides, and
carbonates in ash during the sample oxidation and storage [14].
On the other hand, the loss on ignition content is occasionally also
determined (4501000 C) and included in the bulk chemical com-
position of biomass HTAs to represent the unburned matter
[54,65,76,77,80,92]. However, this parameter is also less informa-
tive because it could not represent the actual organic matter con-
tent in biomass ashes due to their specic phase composition
and ash transformations during heating [14,89,90].
2.2. Correlations and associations among chemical composition of
biomass and their potential applications
2.2.1. Correlations and associations
In contrast to biomass from similar plant species or growth re-
gions, the signicant chemical correlations between numerous bio-
mass varieties worldwide are not common, and dening these
similarities requires special attention. The results from such study
can provide valuable information for the understanding of some
fundamental relationships and trends in biomass. For that purpose,
the complete chemical data obtained from the proximate (db), ulti-
mate (daf) and ash analyses plus results for Cl and Mn (Tables 5
and 6) were used. Data for 78 varieties of natural biomass were
subjected to the Pearsons correlation test [93] to calculate correla-
tion coefcient values among 20 characteristics. The CB biomass
group (8 varieties) was excluded from this database due to the
obvious occurrence of technogenic products. The moisture was
also excluded because of different and insecure biomass basis used
for moisture measurement. The calculated correlation coefcient
values (R2) include the statistically signicant relationships,
namely positive and negative R2 at 99% and 95% condence levels,
as well as statistically insignicant R2 (Table 9). The correlation
data should be used with caution because they could not be exclu-
sive and future use of a larger number of biomass samples (in par-
ticular from aquatic biomass) would likely lead to some changes.
The signicant correlations among elements can be a result of both
direct and indirect genetic associations in biomass. The direct ge-
netic associations in biomass comprise: (1) phase parageneses,
namely simultaneous authigenic phase formations or detrital in-
ux; and (2) phase generations such as subsequent authigenic for-
mations and detrital inux of phases at different stages. On the
other hand, the indirect genetic associations include only the coex-
istence of phase assemblages in this complex system. Hence, addi-
tional subsidiary studies and literature data about the modes of
occurrence of elements, phases or minerals in biomass should al-
ways be applied together with such correlation tests for an expla-
nation of the signicant relationships. Finally, some statistically
insignicant correlations could be important, while other signi-
cant correlations could not be explained by the present knowledge
of biomass.
The present data (Table 9 and Fig. 3) show that there are some
strong:
(1) positive correlations and associations among characteristics
such as ashSNClP, CHCaS, CaMgCMn, Siash
AlTi, AlTiFe, KMgP, NaFe; and
(2) negative correlations between couples, namely ashMn,
ashO, ashMg, CO, ON, OS, OP, OH, ClMn, ClAl,
SiCa, SiMg, SiP, SiK, SiMn, CaK, CaAl, KAl, KTi,
FeCl, and FeCa, that also conrm the above associations.
It should be stated that similar: (1) strong positive correlations
and associations for ashSNCl [34], ashSi [33,47], SP, SiAl
[48], ClP, KP [33,48], KMg, ashP, ashS, NP, SCl, ClK [33];
and (2) strong negative correlations for ashO, SiCa, and SiMg
[34]; have been also detected for biomass varieties in the
literature.
2.2.2. Potential applications
As a result of the present correlations and associations two g-
ures (Figs. 2 and 4) were created using the intersections of three
end members in triangular graphs. Fig. 2 includes: (1) C + H, (2)
O, and (3) N + S + Cl for biomass; whereas Fig. 4 comprises: (1)
SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2, (2) CaO + MgO + MnO, and (3)
K2O + P2O5 + SO3 + Cl2O for biomass ash as end members.
 S.V. Vassilev et al. / Fuel 89 (2010) 913933 929

Table 9
Signicant positive (+) and negative ( ) correlation coefcient values (R2) at 99% (bold font)a and 95% (italic font)b condence levels, and insignicant (normal font) R2 values for
the chemical composition of 78 varieties of natural biomass (excluding eight contaminated biomass varieties).

Symbolc Correlation coefcient value with:

VM (78) (+) Mn(0.43) O(0.41) TiO2(0.20) MgO(0.17) Fe2O3(0.16) Na2O(0.13) K2O(0.08) Al2O3(0.01) CaO(0.01)
( ) A( 0.80) S( 0.58) N( 0.52) Cl( 0.46) FC( 0.44) C( 0.24) P2O5( 0.15) SiO2( 0.10) SO3( 0.09) H( 0.06)
FC (78) (+) MgO(0.19) Mn(0.16) K2O(0.13) SO3(0.13) Al2O3(0.08) C(0.07) CaO(0.06) H(0.02) Fe2O3(0.01)
( ) VM( 0.44) TiO2( 0.21) A( 0.19) SiO2( 0.16) Cl( 0.13) P2O5( 0.12) S( 0.09) N( 0.08) Na2O( 0.04) O( 0.02)
A (78) (+) S(0.70) N(0.63) Cl(0.55) P2O5(0.24) C(0.22) SiO2 (0.21) H(0.05) SO3(0.01)
( ) VM( 0.80) Mn( 0.49) O( 0.44) MgO( 0.31) FC( 0.19) Fe2O3( 0.18) K2O( 0.17) Na2O( 0.12) TiO2( 0.08) Al2O3( 0.07) CaO( 0.05)
C (78) (+) H(0.31) CaO(0.30) S(0.29) N(0.24) P2O5(0.23) A(0.22) Mn(0.12) Fe2O3(0.08) FC(0.07) Cl(0.06) Al2O3(0.05) MgO(0.04) TiO2(0.01) Na2O(0.00)
( ) O( 0.88) K2O( 0.25) SO3( 0.24) VM( 0.24) SiO2( 0.18)
O (78) (+) VM(0.41) SiO2(0.26) K2O(0.19) SO3(0.07) TiO2(0.07) Mn(0.03) Al2O3(0.01)
( ) C( 0.88) N( 0.63) S( 0.62) P2O5( 0.50) H( 0.49) A( 0.44) Cl( 0.30) CaO( 0.26) MgO( 0.03) Na2O( 0.03) FC( 0.02) Fe2O3( 0.02)
H (78) (+) C(0.31) Mn(0.24) CaO(0.20) Cl(0.16) N(0.16) MgO(0.14) P2O5(0.14) S(0.10) SO3(0.09) Na2O(0.07) A(0.05) FC(0.02) Fe2O3(0.02)
( ) O( 0.49) SiO2( 0.16) K2O( 0.15) TiO2( 0.11) Al2O3( 0.06) VM( 0.06)
N (78) (+) S(0.90) P2O5(0.72) A(0.63) Cl(0.53) C(0.24) SO3(0.18) H(0.16) K2O(0.06) Na2O(0.04) CaO(0.02)
( ) O( 0.63) VM( 0.52) Mn( 0.31) SiO2( 0.24) TiO2( 0.15) Al2O3( 0.10) Fe2O3( 0.10) FC( 0.08) MgO( 0.05)
S (78) (+) N(0.90) A(0.70) P2O5(0.63) Cl(0.49) C(0.29) SO3(0.26) H(0.10) CaO(0.04) Al2O3(0.01) Fe2O3(0.00)
( ) O( 0.62) VM( 0.58) Mn( 0.32) MgO( 0.18) SiO2( 0.15) FC( 0.09) K2O( 0.09) TiO2( 0.04) Na2O( 0.03)
Cl (56) (+) A(0.55) N(0.53) S(0.49) P2O5(0.24) H(0.16) K2O(0.10) SiO2(0.08) C(0.06) Na2O(0.03) SO3(0.00)
( ) VM( 0.46) Mn( 0.42) Al2O3( 0.34) O( 0.30) TiO2( 0.29) Fe2O3( 0.27) MgO( 0.19) FC( 0.13) CaO( 0.10)
SiO2 (78) (+) O(0.26) A(0.21) Al2O3(0.21) TiO2(0.15) Cl(0.08) Fe2O3(0.03)
( ) CaO( 0.63) MgO( 0.58) P2O5( 0.39) K2O( 0.36) Mn( 0.28) SO3( 0.24) N( 0.24) C( 0.18) FC( 0.16) H( 0.16) S( 0.15) Na2O( 0.10) VM( 0.10)
CaO (78) (+) MgO(0.35) C(0.30) Mn(0.30) H(0.20) FC(0.06) S(0.04) N(0.02) SO3(0.01) VM(0.01)
( ) SiO2( 0.63) K2O( 0.31) Al2O3( 0.27) O( 0.26) Fe2O3( 0.24) TiO2( 0.11) Cl( 0.10) A( 0.05) Na2O( 0.05) P2O5( 0.05)
K2O (78) (+) MgO(0.26) P2O5(0.22) O(0.19) FC(0.13) Cl(0.10) VM(0.08) N(0.06) SO3(0.06)
( ) SiO2( 0.36) CaO( 0.31) Al2O3( 0.30) TiO2( 0.29) Mn( 0.27) C( 0.25) Fe2O3( 0.20) A( 0.17) Na2O( 0.16) H( 0.15) S( 0.09)
P2O5 (78) (+) N(0.72) S(0.63) A(0.24) Cl(0.24) C(0.23) K2O(0.22) H(0.14) SO3(0.13) MgO(0.07) Fe2O3(0.06) Na2O(0.01)
( ) O( 0.50) SiO2( 0.39) Mn( 0.20) TiO2( 0.16) VM( 0.15) Al2O3( 0.14) FC( 0.12) CaO( 0.05)
Al2O3 (78) (+) TiO2(0.63) Fe2O3(0.44) Mn(0.24) SiO2(0.21) Na2O(0.14) SO3(0.09) FC(0.08) C(0.05) O(0.01) S (0.01) VM(0.01)
( ) Cl( 0.34) K2O( 0.30) CaO( 0.27) MgO( 0.23) P2O5( 0.14) N( 0.10) A( 0.07) H( 0.06)
MgO (78) (+) CaO(0.35) Mn(0.27) K2O(0.26) FC(0.19) VM(0.17) H(0.14) SO3(0.12) P2O5(0.07) C(0.04)
( ) SiO2( 0.58) A( 0.31) Al2O3( 0.23) Cl( 0.19) Fe2O3( 0.19) S( 0.18) TiO2( 0.10) Na2O( 0.08) N( 0.05) O( 0.03)
Fe2O3 (78) (+) Al2O3(0.44) TiO2(0.32) Na2O(0.19) Mn(0.18) VM(0.16) SO3(0.09) C(0.08) P2O5(0.06) SiO2(0.03) H(0.02) FC(0.01) S(0.00)
( ) Cl( 0.27) CaO( 0.24) K2O( 0.20) MgO( 0.19) A( 0.18) N( 0.10) O( 0.02)
SO3 (78) (+) S(0.26) N(0.18) FC(0.13) P2O5(0.13) MgO(0.12) Al2O3(0.09) Fe2O3(0.09) H(0.09) O(0.07) K2O(0.06) A(0.01) CaO(0.01) Mn(0.01) TiO2(0.01) Cl(0.00)
( ) C( 0.24) SiO2( 0.24) VM( 0.09) Na2O( 0.05)
Na2O (78) (+) Fe2O3(0.19) Mn(0.17) Al2O3(0.14) VM(0.13) H(0.07) TiO2(0.07) N(0.04) Cl(0.03) P2O5(0.01) C(0.00)
( ) K2O( 0.16) A( 0.12) SiO2( 0.10) MgO( 0.08) CaO( 0.05) SO3( 0.05) FC( 0.04) O( 0.03) S( 0.03)
TiO2 (78) (+) Al2O3(0.63) Mn(0.36) Fe2O3(0.32) VM(0.20) SiO2(0.15) Na2O(0.07) O(0.07) C(0.01) SO3(0.01)
( ) Cl( 0.29) K2O( 0.29) FC( 0.21) P2O5( 0.16) N( 0.15) CaO( 0.11) H( 0.11) MgO( 0.10) A ( 0.08) S( 0.04)
Mn (33) (+) VM(0.43) TiO2(0.36) CaO(0.30) MgO(0.27) Al2O3(0.24) H(0.24) Fe2O3(0.18) Na2O(0.17) FC(0.16) C(0.12) O(0.03) SO3(0.01)
( ) A( 0.49) Cl( 0.42) S( 0.32) N( 0.31) SiO2( 0.28) K2O( 0.27) P2O5( 0.20)
a
The signicant R2 values at 99% condence level are: P0.28 and 6 0.28, P0.32 and 6 0.32, and P0.42 and 6 0.42 for 78, 56 and 33 variables, respectively.
b
The signicant R2 values at 95% condence level are: P0.22 and 6 0.22, P0.25 and 6 0.25, and P0.33 and 6 0.33 for 78, 56 and 33 variables, respectively.
c
In the parentheses are the number of variables.

The specication of elements from ultimate analysis (Fig. 2) into
three groups is based on: (1) the strong and signicant positive
correlations for CH; and NSCl (P also belongs to this associa-
tion); and (2) the strong and signicant negative correlations be-
tween O and other elements (Table 9). The differentiations and
similarities among solid fuel types according to their mean ulti-
mate composition (daf) plotted in Fig. 2 were listed above (see Sec-
tion 2.1.3.6).
On the other hand, the most abundant six oxides in biomass
HTAs are these of Si, Al, Ca, Mg, K, and P (Table 6) and they were
grouped into three couples (SiAl, CaMg, and KP oxides) accord-
ing to their positive and negative R2 values. The specication of
these couples is based on the strong positive correlations between
the oxides in the couples and their negative correlations with other
oxides. Respectively, the remaining subordinate six oxides or ele-
ments are redistributed to the above couples on the basis of their
strong positive correlations with the oxides in the couples specied
(Table 9 and Fig. 4). It was found that K2O has also signicant po-
sitive correlation with MgO; however, the latter oxide has stronger
positive value with CaO than with K2O (Table 9). Similar twofold
behaviour could be also expected for Na2O depending on its dom-
inant mobile or immobile occurrence. For example, highly mobile
Na can occur in algae (seaweeds), which are greatly abundant in
this element [94,95].
The plotted mean HTA composition of solid fuel types in Fig. 4
illustrates: (1) the distinctions between the biomass and SFFs;
(2) the closer position of peat to coals than biomass (in contrast
to Figs. 1 and 2); (3) the differentiations among the biomass groups
and the similarities for HAB sub-groups; (4) the distinctions for the
CB and AB with other biomass groups evidenced by their plots and
maximum or minimum values in the above-listed orders for the
ash characteristics; and (5) the intermediate position of CB be-
tween SFFs and other biomass groups and sub-groups. These
observations show signicant differences in comparison with
those detected from proximate (Fig. 1) and ultimate (Fig. 2) analy-
ses as a result of the highly variable composition of inorganic com-
ponents in biomass. Therefore, the plotted mean HTA composition
of these solid fuel types in Fig. 4 can be used as initial and prelimin-
ary chemical classication system for the inorganic matter of bio-
mass. This is due to the distinctive and highly informative plot
distributions of:
(1) all varieties of biomass (close to the centre of the triangular
graph);
(2) WWB (Ca + Mg + Mn oxides above 30%);
(3) HAB, HAG, HAS and HAR (K + P + S + Cl oxides above 30%);
(4) AB (both sums of Ca + Mg + Mn oxides and K + P + S + Cl oxi-
des above 30% and Si + Al + Fe + Na + Ti oxides below 40%);
930 S.V. Vassilev et al. / Fuel 89 (2010) 913933
Fig. 3. Some signicant correlations among the chemical composition of biomass, wt.%.
(5) SFFs (Si + Al + Fe + Na + Ti oxides above 70%);
(6) CB (Si + Al + Fe + Na + Ti oxides between 40 and 70%).
This approach resulted in four chemical biomass ash types (S, C,
K and CK types) further specied into seven sub-types (with high,
medium and low acid tendencies). The positions of all samples
from the present study were also plotted in Fig. 4 for illustration.
The above approach, composition-based criteria and explanation
of the three end members in Fig. 4 are also comparable to those
identied and applied earlier for the chemical classication of coal
y ashes [14] and HTAs [16] of coals despite the different constit-
uents included as end members and borders used. The chemical
biomass ash types and sub-types specied would have different
behaviour during biomass processing as it was found for coal
[1416]. Such approach could also be useful for the development
of new combined biomass and coal classication systems to permit
fuel prediction and selection for co-combustion applications.
Furthermore, Figs. 2 and 4 demonstrate the closest chemical
composition between HAG and HAS sub-groups. Hence, they may
be combined in one biomass sub-group and their future separate
characterization can be avoided. On the other hand, HAR sub-group
may be split in several sub-sub-groups due to the more variable
composition. Additionally, the unusual position of some samples
in Fig. 4 may indicate their possible contamination by detrital
and/or technogenic materials. For instance, certain biomass varie-
ties from the WWB group (samples 1, 5, 8, 11, 13, 14, 17, 24, and
28) and HAR sub-group (samples 57 and 68) are most likely
inuenced by such contamination and some of these samples were
mentioned above.
It is interesting to note that the mean composition of 11 algae
(seaweed) samples [94,95] from the aquatic biomass group was also
plotted in Figs. 1, 2 and 4 for comparison, despite incomplete chem-
ical analyses. These marine macroalgae show higher contents of ash,
xed carbon, Cl, MgO, N, Na2O, O, P2O5, S, and SO3 (particularly ash,
Cl, S, Na, and Mg) than the mean values for the terrestrial biomass
(Tables 5 and 6). The seaweeds reveal relatively similar ultimate
(Fig. 2) and different proximate (Fig. 1) and ash (Fig. 4) composition
in comparison with other terrestrial biomass groups and sub-
groups. It can be seen that the algae belong to K ash type with low
acid tendency and its position is closer to ash samples mostly from
HAR sub-group and, to a lesser extent, HAG sub-group (Fig. 4).
Finally, the specied oxide associations in biomass HTAs (Fig. 4)
are also indicative for the preferable occurrence and possible gen-
esis of inorganic elements in biomass. For example, the upper cor-
ner (SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2) in Fig. 4 may represent
commonly the occurrence of FeNaTi-bearing silicates, alumino-
silicates and hydroxides with detrital, authigenic and technogenic
origin. The left corner (CaO + MgO + MnO) could include normally
CaMgMn-containing carbonates, oxyhydroxides and oxalates
with preferable authigenic origin. The right corner (K2O + P2O5 +
SO3 + Cl2O, as N also belongs to this association) may represent
commonly the mobile K-bearing phosphates, sulphates, chlorides
and nitrates with authigenic origin. The last association also ts
to the typical fertilizers. Certainly, some of the phases or minerals
could have mixed contribution to the different corners because of
their complex composition and genesis.
It should be stated that the actual explanation of the above-
described chemical differentiations, similarities, trends, and
 S.V. Vassilev et al. / Fuel 89 (2010) 913933
WWB - wood and woody biomass (samples 1-28)
HAB - herbaceous and agricultural biomass (samples 29-72)
HAG - herbaceous and agricultural grass (samples 29-38)
HAS - herbaceous and agricultural straw (samples 39-47)
HAR - herbaceous and agricultural residue (samples 48-72)
AB - animal biomass (samples 73-74)
MB - mixture of biomass (samples 75-78)
CB - contaminated biomass (samples 79-86)
AVB - all varieties of biomass (samples 1-86)
P - peat
L - lignite
S - sub-bituminous coal
B - bituminous coal
A - algae
Fig. 4. Chemical classication system of the inorganic matter in high-temperature biomass ashes based on 78 varieties of biomass, wt.%.
associations is only possible after signicant knowledge of the
phasemineral composition of biomass varieties. The presence,
abundance and distribution of modes of element occurrence have
a leading role for the characterization of biomass composition.
These are actual phases or minerals with well-known forms of
element combination and properties and are of vital importance
for understanding the biomass system. For example, most of the
elements in biomass occur in both organic and inorganic matter,
and each element is combined in different phases or minerals with
variable genesis and proportions, and has dominant associations
and afnities with the constituents. Unfortunately, the bulk chem-
ical composition of biomass does not provide any direct informa-
tion about the actual modes of element occurrence in this fuel.
3. Conclusions
Some conclusions for the chemical composition of biomass
based on the available and peer-reviewed reference data from tra-
ditional and complete proximate, ultimate and ash analyses for 86
varieties of biomass can be made:
(1) The chemical composition of biomass is highly variable as
determined by proximate, ultimate and particularly ash
analyses. When the proximate and ultimate data are recal-
culated respectively on dry and dry ash-free basis, the char-
acteristics show quite narrow ranges. This is due to the
extremely high variations of moisture, bulk ash yield and
different genetic types of inorganic matter in biomass.
(2) In decreasing order of abundance, the elements in biomass
are commonly C, O, H, N, Ca, K, Si, Mg, Al, S, Fe, P, Cl, Na,
Mn, and Ti. The determination of Cl and Mn contents in
931
biomass is required and such data should be always included
in the complete ultimate and ash analyses because these ele-
ments also have an important role for the biomass system.
(3) The typical enrichment trends for chemical characteristics
among biomass groups and sub-groups are: moisture, vola-
tile matter, Ca, Mg, and Mn for WWB; xed carbon, volatile
matter, K, and O for HAB; volatile matter, K, O, and Si for
HAG; Cl, K, O, and Si for HAS; xed carbon, K, Mg, and P
for HAR; ash, C, Ca, Cl, H, N, Na, P, and S for AB; ash, Al, C,
Cl, Fe, H, N, S, and Ti for CB. Both AB and CB groups show
the most signicant differences in the biomass system. The
above distinctions are related to different biomass sources
and origin, namely from plant (WWB, HAB) and animal
(AB) products or from mixtures of plant, animal and manu-
facture materials (CB). On the other hand, the aquatic bio-
mass group is highly enriched in ash, Cl, Mg, Na, and S.
(4) The chemical composition of natural biomass system is sim-
pler than that of solid fossil fuels; however, the semi-bio-
mass system is quite complicated as a result of
incorporation of various non-biomass materials during bio-
mass processing. The biomass composition is signicantly
different from that of coal. The variations among biomass
composition were also found to be greater than for coal.
(5) Natural biomass is normally enriched in moisture, volatile
matter, Ca, Cl, H, K, Mg, Mn, Na, O, and P and depleted in
ash, xed carbon, Al, C, Fe, N, S, Si, S, and Ti in comparison
with the respective characteristics in coal. The highest
enrichment in biomass commonly shows
Mn > K > P > Cl > Ca > (Mg, Na) > O > moisture > volatile mat-
ter, whereas the highest depletion normally reveals S > (ash,
Al, Ti) > xed carbon > (Fe, Si) > C.
932 S.V. Vassilev et al. / Fuel 89 (2010) 913933
(6) The correlation analysis among the chemical characteristics
found ve strong and important associations in the natural
biomass system, namely CH, NSCl, SiAlFeNaTi, Ca
MgMn, and KPSCl. As a result of that two gures were
created using the intersections of three end members in tri-
angular graphs. The rst gure includes (1) C + H, (2) O, and
(3) N + S + Cl for biomass; whereas the second gure com-
prises (1) SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2, (2) CaO +
MgO + MnO, and (3) K2O + P2O5 + SO3 + Cl2O for biomass
ash as end members. Both gures can be used for classica-
tion, prediction and indicator purposes:
 The plotted chemical characteristics of biomass varieties
in both gures show: the similar chemical composition
between HAG and HAS sub-groups and their possible
combination in one biomass sub-group for future
descriptions; the variable composition of HAR sub-group
and its possible split in several sub-sub-groups; and the
possibility for identication of some contamination in
biomass fuels by detrital and/or technogenic materials.
 The plotted associations Si + Al + Fe + Na + Ti oxides,
Ca + Mg + Mn oxides, and K + P + S + Cl oxides were
applied for an initial specication of the inorganic matter
in biomass system. This approach resulted in four chem-
ical biomass ash types (S, C, K and CK types) further spec-
ied into seven sub-types (with high, medium and low
acid tendencies). The above approach, composition-based
criteria and explanation of the three end members are
also comparable to those identied and applied earlier
for the chemical classication of coal ashes despite the
different constituents and borders used. Such approach
could be useful for the development of new combined
biomass and coal classication systems to permit fuel
prediction and selection for co-combustion applications.
 The specied associations in biomass HTAs are also indic-
ative for the preferable occurrence and possible genesis
of inorganic elements in biomass. For example, the sum
SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2 may represent com-
monly the occurrence of FeNaTi-bearing silicates, alu-
mino-silicates and hydroxides with detrital, authigenic
and technogenic origin. The association CaO +
MgO + MnO could include normally CaMgMn-contain-
ing carbonates, oxyhydroxides and oxalates with
preferable authigenic origin. The sum K2O + P2O5 +
SO3 + Cl2O (as N also belongs to this association) may
represent commonly the mobile K-bearing phosphates,
sulphates, chlorides and nitrates with authigenic origin.
Finally, it should be stated that the actual explanation of the
above-described chemical differentiations, similarities, trends,
and associations is only possible after signicant knowledge of
the phasemineral composition of biomass varieties. The presence,
abundance and distribution of modes of element occurrence have a
leading role for the characterization of biomass composition.
Unfortunately, the bulk chemical composition of biomass does
not provide any direct information about the actual modes of ele-
ment occurrence in this fuel. The crucial importance of the phase
mineral composition and modes of element occurrence, as well as
trace element contents, thermal behaviour of phases, and some
properties and applications of biomass and biomass ash will be de-
scribed in future publications.
Acknowledgements
The present work was carried out in part within the European
Commissions research programme and in part within the research
programme of the Bulgarian Academy of Sciences. Stanislav
Vassilev would like to express his gratitude to the Joint Research
Centre (European Commission) for the possibility to perform
studies at the Institute for Energy (Petten, The Netherlands) as a
Detached National Expert.
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