Journal of Sustainable Cement-Based Materials

ISSN: 2165-0373 (Print) 2165-0381 (Online) Journal homepage: https://www.tandfonline.com/loi/tscm20

Use of biomass ash from different sources and

processes in cement

Christoph Maschowski, Peter Kruspan, Ali Talib Arif, Patxi Garra, Gwenaëlle
Trouvé & Reto Gieré

To cite this article: Christoph Maschowski, Peter Kruspan, Ali Talib Arif, Patxi Garra, Gwenaëlle
Trouvé & Reto Gieré (2020): Use of biomass ash from different sources and processes in cement,
Journal of Sustainable Cement-Based Materials, DOI: 10.1080/21650373.2020.1764877

To link to this article: https://doi.org/10.1080/21650373.2020.1764877

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Journal of Sustainable Cement-Based Materials, 2020
http://dx.doi.org/10.1080/21650373.2020.1764877

Use of biomass ash from different sources and processes in cement

Christoph Maschowskia
, Peter Kruspanb, Ali Talib Arifc,d , Patxi Garrae ,
Gwena€elle Trouvee and Reto Gieref,g
a
Institute of Earth and Environmental Sciences-Geochemistry, University of Freiburg, Freiburg,
Germany; bTEC Lab, Holcim (Schweiz) AG, Wuerenlingen, Switzerland; cInstitute for Infection
Prevention and Hospital Epidemiology, University Medical Center Freiburg, University of
Freiburg, Faculty of Medicine, University of Freiburg, Freiburg, Germany; dKurdistan
Institution for Strategic Studies and Scientific Research (KISSR), Qirga - Sulaimani, Iraq;
e
Laboratoire Gestion des Risques et Environnement (LGRE), Universite de Haute-Alsace,
Mulhouse Cedex, France; fDepartment of Earth and Environmental Science, University of
Pennsylvania, Philadelphia, PA, USA; gCenter of Excellence in Environmental Toxicology,
University of Pennsylvania, Philadelphia, PA, USA

Substitution of cement clinker with suitable excess materials from other processes is an
effective way to reduce CO2 emissions of cement production. Moreover, specific
properties of the resulting mortar or concrete can be designed with different clinker
replacement materials and their mixing ratios. In this study, bottom and fly ashes from
six biomass power plants with different power scales and various flue-gas treatment
strategies were admixed to mortars, whose properties (influence of water requirement
and final compressive strength) were then assessed in the laboratory by following
industrial standard procedures. Results reveal that fly ash from a cyclone of a medium-
scale combustor burning Miscanthus straw amended with 2 wt % Ca(OH)2 (to prevent
slagging during combustion) turned out to be well suited as a clinker replacement
material, even boosting final compressive strength of the mortar. Wood-chip bottom
ashes and fly ash from a cyclone exhibited acceptable results, whereas fly ash from
electrostatic precipitators (ESPs) and baghouse filters lowered final compressive
strength of the mortar when admixed. The scale of the power plant is positively
correlated with final compressive strength in the case of ESPs. Cenospheres, typical fly
ash particles present in cyclone ash, seem to have a positive effect on water-to-binder
ratio and final compressive strength. In contrast, potassium salts, which are most
abundant in ash from ESPs and baghouse filters, appear to have a negative influence on
these properties. Grinding of the biomass ashes to a typical Portland cement fineness
had a positive effect on mortar quality. All fly ashes had high contents of Cd, and
baghouse filter ash contained As in amounts about four times the Swiss limit value for
cement of 30 ppm; only bottom ash and cyclone ash from Miscanthus exhibited
concentrations below respective limit values for all critical trace elements. To assess
the immobilization potential of contaminating elements during the cement hardening
process, blended mortars were crushed and subjected to multistep leaching, followed
by subsequent analysis of the leachates by atomic absorption spectroscopy.
Immobilization of Cd by the mortar was particularly effective. Our results indicate that
fly ash from wood-chip combustion is most suitable as an amendment to cement when
it was trapped by a cyclone rather than by the ESPs or baghouse filters.
Keywords: cement; biomass; ash; crm; leaching; recycling

Supplemental data for this article is available online athttps://doi.org/10.1080/21650373.

2020.1764877.

Corresponding author. Email: christoph@maschowski.de
ß 2020 Informa UK Limited, trading as Taylor & Francis Group
2 C. Maschowski et al.
1. Introduction
Conventional production of Portland
cement is a major contributor to the large
amounts of CO2 released into the atmos-
phere by concrete production, and in total
accounts for about 5% of the global
anthropogenic greenhouse gas emissions
[1, 2]. It may even account for up to 8%
when considering emissions from fossil
fuel combustion needed for this high-tem-
perature process and the generation of elec-
trical power needed [3]. In detail, typically
about 90 percent by weight (90 wt %) of
these emissions are derived from the
decomposition of the raw materials, com-
monly limestone, to form clinker (60 wt %)
and from the burning of fossil fuels needed
for this high-temperature process (30 wt
%). Ten percent is related to emissions
from energy consumption of the cement
plant [4]. To meet European Union (EU)
targets for reducing greenhouse gas emis-
sions (The 2015 Paris Climate Change
Conference: COP21 [5]), the cement indus-
try must reduce CO2 emissions [6] without
sacrificing the high-quality standards of its
products. This cannot be achieved by the
usage of renewable energy for electrical
power demand and the substitution of the
fossil fuel used for clinker production only,
but it requires substituting a significant
amount of the cement clinker itself by other
materials, which are, at best, by-products
elsewhere [7]. Substitution of common
cement clinker by limestone, coal fly ash,
natural volcanic materials, burnt oil shale
(BOS of LafargeHolcim), blast-furnace
slag [8], or zeolites [9] are state-of-the-art
measures, which are also reflected in the
EN 197-1 European standard for cement
[10]). These cement types are often called
blended cements or Portland composite
cements. The influences of cement clinker
replacement materials (CRM) on cement
quality are manifold, but with proper prod-
uct design, blending will improve specific
cement properties according to the charac-
teristics of the constituents added [11, 12].
Coal fly ash as one of the most prominent
materials for the substitution of cement
clinker is continuously declining as coal-
fired power plants are being substituted by
facilities that use alternative energy sour-
ces, such as wind energy, solar power and
energy from biomass combustion [13, 14].
Recent studies have been assessing alterna-
tive waste products as CRM candidates,
such as municipal waste sewage sludge
[15], technogenic pozzolans [16] and ash
from various wood species [17–31]. By
now, biomass ashes are considered import-
ant and auspicious alternative raw-material
carriers for CaO, SiO2, Al2O3 and Fe2O2 in
cement systems [32]. In addition to the
reduction of CO2 emissions, the utilization
of many CRM types can enhance the
cement performance. On the other hand,
the degree of substitution is often limited to
proportions of less than 50 wt % of the
cement part [11].
Heavy metals in wood ashes can be
present in considerable concentrations and
are mobile to variable degrees [33, 34].
Their possible fixation rates in the cement
matrix are important factors for environ-
mental concerns [35, 36].
The aim of this work was to assess the
influences of regionally available biomass
fuel type, fuel amendment, combustor scale,
and flue-gas treatment strategy on the final
mortar quality (water requirement and com-
pressive strength) when biomass ash is used
as CRM at specific mixing ratios.
Furthermore, the leaching behavior of the
tested mortars was investigated in order to
assess the immobilization potential of con-
taminating elements present in the ashes.
2. Materials and methods
2.1. Biomass ash samples
Mortar tests were conducted with the fly
ash (FA) and bottom ash (BA) samples
from combustion facilities listed in Table
1. Depending on the flue-gas treatment
devices used, the following types of FA
 Journal of Sustainable Cement-Based Materials 3

Table 1. Sources of fly ash samples with corresponding information on installation site, fuel
and boiler type, total thermal power, and flue-gas treatment device; CYC: cyclone; ESP: elec-
trostatic precipitator; BAG: baghouse filter.
Total Flue-gas
Installation site Fuel type Boiler type thermal power treatment device
Ammertzwiller Wood chips Fixed bed 400 kW CYC
(France)
Ammertzwiller Miscanthus straw þ Fixed bed 400 kW CYC
(France) 2 wt % Ca(OH)2
St. Peter Wood chips Fixed bed 1.7 MW ESP
(Germany)
Freiburg i.Br. Wood chips Fixed bed 2.3 MW ESP þ CYC
(Germany)
Rixheim Wood chips Fixed bed 2.8 MW BAG
(France)
Colmar Wood chips Fixed bed 8.0 MW ESP
(France)
Saint- Wood chips þ 2 wt % Fluidized bed 17.3 MW BAG
Louis (France) corn residues

were investigated: electrostatic precipitator Rietveld refinement was used to determine

ash (ESPA), cyclone ash (CA), Miscanthus
cyclone ash (MCA), baghouse filter ash
(BAGA), and ash trapped by a combination
of an electrostatic precipitator and a cyc-
lone (ESPA þ CA). At two of the studied
facilities, amendments were added to the
fuels: in Ammertzwiller, Miscanthus straw
was amended with Ca(OH)2 to prevent
slagging during combustion, whereas in
Saint-Louis, corn residues were co-com-
busted with wood chips, because they are a
locally available biofuel. Most attention,
however, was paid to the ashes from pure
biomass fuels, because the composition of
ashes from fuels that were combusted with
an amendment was predominantly con-
trolled by the amendment rather than by
the biomass itself.
2.2. Characterization of the
biomass ashes
The ash samples have been characterized
in detail by various analytical techniques
(for details, see [37]) at the Institute of
Earth and Environmental Sciences of the
University of Freiburg (Germany). Briefly,
X-ray diffraction (XRD) with subsequent
semi-quantitatively the types of crystalline
species and the content of amorphous
material present in the ash. The bulk chem-
ical composition of the ash samples was
analyzed by X-ray fluorescence (XRF) to
determine the concentrations of the main
components, and by inductively coupled
plasma-mass spectrometry (ICP-MS) and
inductively coupled plasma-atomic emission
spectrometry (ICP-AES) to determine the
concentrations of the minor and trace ele-
ments. The physicochemical characteriza-
tion of individual ash particles was
performed by means of scanning electron
microscopy in combination with energy dis-
persive X-ray spectroscopy (SEM-EDX).
Atomic absorption spectroscopy (AAS) was
applied to quantify and compare the concen-
trations of selected contaminating trace ele-
ments in both the ashes and the leachates
from multistep leaching tests performed
with these ashes and finely crushed hard-
ened mortar prisms used in the mortar tests.
2.3. Mortar properties
All cement-related tests were performed at
LafargeHolcim TEC Lab in W€urenlingen,
4 C. Maschowski et al.
Switzerland. Mortar mixes consisting of EN
196-1 standard sand [38] and various pro-
portions of EN 197-1 [10] Portland cement
(brand name Normo 4), water and biomass
ash as partial cement replacement1 at 2.5, 5
and 30 wt % were prepared (see Table 2).
Those mixes were compared with reference
mortars that contained as binder 100 wt %
Portland cement, 100 wt % Portland com-
posite cement (brand name Optimo 4) or
mixes of 70 wt % Normo 4 with either 30 wt
% limestone or 30 wt % burnt oil shale
(BOS) (see shaded rows in Table 2). Details
on mortar constituents are listed in Table S1
in the Supplementary Materials.
In order to better reflect market-rele-
vant conditions on the concrete level—
while still operating on the mortar level,
requiring much less labor intensity—an
application-related protocol for mortar mix
proportioning was applied. Those mortars
always contained 1350 g of EN 196-1
standard sand, while the added amounts of
binder and water were adjusted to the cal-
culated sand-to-mortar volume ratio of a
corresponding concrete mix, in which the
same type and composition of binder
would have been used (Table 2). The sand-
to-mortar volume ratio only depends on the
specific densities of the respective constitu-
ents when volumetric proportioning is kept
constant. In the present study, a Swiss mass
concrete type with regular workability was
taken as basis for calculating all sand-to-
mortar volume ratios in Table 2. This con-
crete contains 300 kg/m3 of binder, 174 kg/
m3 of total water, and 1927 kg/m3 of dry
alluvial sand and gravel from the M€ulligen
quarry (Switzerland) in a size fraction from
0 to 32 mm. The concrete is devoid of any
admixtures such as water reducers or
plasticizers.
Specific densities were determined with
a Helium pycnometer (Ultrapycnometer
1000 T) of Quantachrome (Boynton Beach,
U.S.A) at a target pressure of 18 p.s.i.
(1.242 bar) and an equilibrium time of 60 s;
the densities were recorded as average of 3
to 10 measurements per sample. Powder
fineness was measured with a CILAS
920 L laser-diffraction device (CILAS,
Orleans, France), by wet dispersion in
99.5% pure isopropanol obtained from
Chemia Brugg (Brugg, Switzerland), 60 s
of ultrasonic treatment, and by using the
Fraunhofer model.
In this study, the primary focus was on
assessing the strength contribution of vari-
ous biomass ash types (see Section 2.3.2)
in relation to their water demand (see
Section 2.3.1). In this way, their general
and basic suitability as CRM is identified.
Hence, at this stage further performance
properties, such as detailed setting behav-
ior, strengths at later ages (56 days or
91 days) or aspects concerning durability
(e.g. dimensional stability over time, corro-
sion risk) are excluded.
2.3.1. Slump-flow determination
To determine the actual water requirement
for each binder type, which is decisive for
the corresponding strength development,
three different mortars with three different
water-to-binder (w/b) ratios were prepared.
Mixing of each mortar was done in an EN
196-1 compliant mortar mixer of Toni
Technik GmbH (Berlin, Germany). Total
mixing time was 9 min, including idle time
of 1 min after 2 min. Low mixing speed
was chosen at all times to ensure complete
homogenization of the mortar mix, also
when containing potentially high water-
absorbing materials such as biomass ash.
After mixing, the fresh mortar was immedi-
ately filled as two individually compacted
equal layers into a cone having a lower
inner diameter of 100 mm and an overall
height of 150 mm (Figure 1A). The cone
was then gently lifted within 2 s so that the
mortar gravitationally collapsed, without
applied shock, into all directions on the
glass plate (Figure 1B). Ten and 45 min
after the start of mortar mixing, the diam-
eter of the collapsed mortar was measured
in two perpendicular directions; the
Table 2. Physical parameters of reference mortar mixtures (shaded rows) and blended cement mortars obtained during two separate sets of experiments; S/
M: sand-to-mortar volume ratio; w/b: water-to-binder ratio (calculated,

measured); bold values represent good rating;
indicates ground ash; compressive
strength is listed as index percent relative to pure Normo 4 Portland cement; n.a.: no data available.
Binder Specific Compressive strength (Index %)
Fineness of density of S/M w/b
Portland cement CRM CRM d50 total binder volume ratio (at 10 min) 1 day 2 days 28 days
Units: [mm] [g  cm3] % – % % %
First set of experiments:
100 wt % 3.15 52.2 0.50 100 100 100
Normo 4
100 wt % 3.07 51.8 0.55 87 97 86
Optimo 4
70 wt % Normo 4 30 wt % limestone 16.3 3.03 51.7 0.52 55 64 63
70 wt % Normo 4 30 wt % BOS 7.6 3.04 51.7 0.61 53 61 80
70 wt % Normo 4 30 wt % BA (St. Peter) 29.7 3.06 51.8 0.83 2 12 17
70 wt % Normo 4 30 wt % ESPA (St. Peter) 87.4 2.97 53.8 1.04 0 12 20
70 wt % Normo 4 30 wt % BA
(St. Peter) 14.8 3.06 51.8 0.73 11 26 36
70 wt % Normo 4 30 wt % ESPA
(St. Peter) 9.9 2.97 53.8 0.92 0 16 27
Second set of experiments:
100 wt % 3.15 52.2 0.49 100 100 100
Normo 4
70 wt % Normo 4 30 wt % ESPA þ CA (Freiburg) 19.3 2.96 51.4 0.73 2 13 17
70 wt % Normo 4 30 wt % CA (Ammertzwiller) n.a. 2.94 51.4 < 0.7

n.a. n.a. n.a.
Additional
experiments:
70 wt % Normo 4 30 wt % MCA (Ammertzwiller) 5.7 3.00 51.5 0.51 81 89 93
Journal of Sustainable Cement-Based Materials

70 wt % Normo 4 30 wt % BAGA (Rixheim) 14.8 2.98 51.5 1.00 0 0 26

95 wt % Normo 4 5 wt % BAGA (Rixheim) 14.8 3.12 51.5 0.50 110 124 99
97.5 wt % 2.5 wt % BAGA (Rixheim) 14.8 3.13 51.5 0.49 125 121 102
Normo 4
70 wt % Normo 4 30 wt % BAGA (St. Louis) 15.3 2.98 51.5 0.70 33 50 45
95 wt % Normo 4 5 wt % BAGA (St. Louis) 15.3 3.12 51.5 0.50 107 111 96
97.5 wt % 2.5 wt % BAGA (St. Louis) 15.3 3.14 51.5 0.48 112 114 103
Normo 4
5
6 C. Maschowski et al.
Figure 1. Slump-flow test of fresh mortar; left photograph shows filling of cone with mortar,
right photograph shows spread of mortar on glass plate and measuring of width in two perpen-
dicular directions.
average of these measurements is the so-
called ‘mortar slump flow’ of the respect-
ive mix.
The very same procedure was then
applied for the two additional mortar
mixes, in which the water and binder con-
tents—and hence the w/b ratios—were var-
ied in such a way that finally three
measured mortar slump-flow values suffi-
ciently covered the range between 150 mm
(sticky mortar) and 250 mm (fluid mortar)
after 10 min. The determination of the
resulting linear curve in such a ‘w/b ratio’
to ‘mortar slump flow’-plot ultimately
allowed for calculation of the needed w/b
ratio of a chosen binder type to obtain
200 mm after 10 min (Table 2). 200 mm
mortar slump flow corresponds to a regular
workable concrete slump flow of F3/F4
(480–500 mm) according to EN 206 [39],
when determined with EN 12350-5 [40].
By applying this procedure, the water
requirement of different binder types is
determined in a statistically robust manner
so that direct comparisons can be realized
also quantitatively (Table 2).
2.3.2. Determination of compres-
sive strength
From each of the three mortars prepared
for a specific binder, one EN 196-1 steel
mold for three mortar prisms of the dimen-
sion 4  4  16 cm was filled right after
the determination of the slump flow after
45 min. These molds allow for hardening at
a relative humidity of 100% and a tempera-
ture 20 ± 2  C, which are both held constant
during the entire hardening period. The
compressive strength of one prism was
determined according to EN 196-1 after
24 h, that of the second after 2 days, and
that of the third after 28 days. The set of
compressive strengths at those ages was
used together with the mortar slump-flow
values at 10 min to calculate the compres-
sive strengths at a mortar slump flow of
200 mm (Table 2). Finally, in order to be
able to directly compare the compressive
strength of mortars made with reference
cement Normo 4 taken from different
batches, index values were calculated by
defining the compressive strength results of
the 100% Normo 4 mix as being 100% at
1 day, 2 days and 28 days, respectively
(Table 2). Yearly averages of EN 196-1
compressive strengths of 100% Normo 4
are at 17 MPa (1 day), 28 MPa (2 days),
and 56 MPa (28 days).
2.4. Leaching tests
Leaching behavior was investigated on
both selected biomass ashes (raw materials)
and hardened mortar prisms after prior
compressive strength tests to provide data
for calculation of the immobiliza-
tion potential.
 Journal of Sustainable Cement-Based Materials
We chose a sequential leaching method
in three steps, adapted from the sequential
extraction procedure of Finkelman et al.
[41]. The principle of this method was pre-
viously applied in several studies on coal
and coal ash [42–44], on biomass ash [45],
and on mortars blended with wood FA [46,
47]. The sample material was suspended in
an aqueous solution for 24 h of agitation at
20  C for each leaching sequence. The first
leaching step was performed with 5 g sam-
ple mass (dry basis) in 50 mL ultrapure
water to extract water-soluble species, the
second step with 25 mL ion-exchangeable
ammonium acetate, and the final step with
25 mL hydrochloric acid (1 mol  L1). The
second and third steps were applied on the
centrifuged residual material from the pre-
vious leaching steps after drying for 24 h at
105  C. All leachates were analyzed by
AAS for the elements Zn, Ni, Pb, Cd,
and As.
2.4.1. Sample preparation for leach-
ing tests
Biomass ash samples were not treated prior
to leaching tests, like they were not treated
prior to mortar tests for the
chosen samples.
Hardened mortar prisms were crushed
with a jaw crusher and ground in an agate
mill to a fineness < 5 mm at the Institute of
Earth and Environmental Sciences,
University of Freiburg (Germany). For
each mortar type, at least two different
prisms were processed for repeated
determinations.
2.4.2. Atomic absorption spectros-
copy (AAS)
All AAS analyses were carried out at the
Institute of Earth and Environmental
Sciences, University of Freiburg
(Germany) using an AAS Vario 6 instru-
ment (Analytik Jena, Jena, Germany). Two
digestions of each biomass ash sample
were prepared using nitric acid (HNO3)
7
and microwave treatment with a MLS
Microprep 1500 device (Leutkirch,
Germany). The initial weight of each sam-
ple was 250 mg and the amount of acid
used was 50 mL. The microwave program
was designed specifically for wood diges-
tion, with duration of 45 min and a max-
imum temperature of 200  C. These
digestions were then analyzed via AAS for
Ni, Cd, Zn, Cu, Pb, and As. High accuracy
was achieved through the use of calibration
curves, prepared from standards and repeat-
ing measurements three times for each
sample. Prior to analysis, 1.0 mL of lan-
thanum tri-nitrite (La(NO2)3) and 1.0 mL
of cesium chloride (CsCl) were added to
the samples to control ionization
interference.
3. Results
3.1. Performance of mortars
Mortars with regular and constant work-
ability were prepared with Normo 4 cement
and different proportions and types of bio-
mass ash. In addition, mortars with two
industrial cements (Normo 4 and Optimo
4) and two mortars blended with limestone
and BOS, respectively, were produced as
reference materials for comparison. All
data, including fineness of Portland (com-
posite) cement and other relevant physical
parameters, are given in Table 2; they rep-
resent data collected during two separate
sets of experiments.
In general, an addition of 30% of bio-
mass ash drastically increases the w/b ratio
from 0.49 or 0.50 (i.e. the level of the two
batches of Normo 4 used in this study) to a
range of 0.70 to 1.04, being much higher
than for limestone (0.52) or BOS (0.61).
Consequently, the compressive strength
indices of the biomass ash mixes sharply
decrease to a range of only 0% to 50%;
most of the biomass ashes, however, show
a slightly increasing strength contribution
(i.e. pozzolanic effect) from 1 day to
28 days. Only with the peculiar sample
8 C. Maschowski et al.

Figure 2. Final compressive strength (after 28 days) of hardened mortar prisms according to
Holcim methodology; arrows indicate improvement of maximum compressive strength due to
grinding (solid arrow) and due to lower cement substitution levels (dashed arrow).

MCA from Ammertzwiller produced with
Miscanthus straw plus Ca(OH)2, both,
water requirement and strengths, are
achieved at similar and thus sufficient lev-
els of 100% Normo 4.
The biomass ash samples from St.
Peter (Table 2) allow for a direct compari-
son between bottom ash (BA) and fly ash
(in this case ESPA), when the same fuel
type (in this case wood chips) is used.
Furthermore, the effect of sample grinding
can be studied (see arrows in Figures 2 and
3;
in Table 2 indicates ground sample).
Water demand of BA is always 20% lower
than that of ESPA, irrespective of whether
or not it was ground. Due to excessively
high w/b ratios of ESPA (0.92 and 1.04),
the corresponding mortars fail the strength
test at 1 day. Grinding of ESPA to cement
fineness (from 87.4 to 9.9 mm d50) lowers
the water demand by 10% and therefore
slightly improves strengths at 2 days (plus
4% pt.) and 28 days (plus 7% pt.).
Grinding of BA to cement fineness (from
29.7 to 14.8 mm d50) also lowers the water
demand by 10%, but increases strengths by
9% pt. (at 1 day), 14% pt. (at 2 days) and
19% pt. (at 28 days).
When the fraction of cement replace-
ment is lowered from 30 wt % to levels of
5 and 2.5 wt %, the corresponding w/b
ratios can be reduced to the levels of the
pure Portland cement (around 0.50). This
results in a significant increase in compres-
sive strength (see dashed arrow in Figure
2); the effect in this case is much more pro-
nounced at early ages (i.e. at one and two
days, see Table 2), pointing to a pore-filling
instead of pozzolanic effect.
3.2. Leaching behavior of selected
wood-chip ash samples
Concentrations of the contaminant ele-
ments Zn, Ni, Pb, Cd, and As in the leach-
ates of BA and their corresponding FA are
presented in Table 3, which also lists the
AAS-determined concentrations (bold val-
ues) for the elements of interest in the two
bulk FA samples used for the leaching
experiments (data from 37].
After leaching with ultrapure water
(Step 1), significant amounts of Zn were
 Journal of Sustainable Cement-Based Materials
Figure 3. Particle size distribution of reference cements (Normo 4) and ESPA (St. Peter) before
and after grinding.
observed in the leachates from the FA sam-
ples only (St. Peter ESPA, 6.21 ppm;
Freiburg ESPA þ CA, 5.76 ppm;
Ammertzwiller CA, 0.85 ppm; Rixheim
BAGA, 7.24 ppm). Zinc concentrations
were at or near the detection limit of
0.04 ppm in the leachates from all BA.
Concentrations of Ni were near or below
the detection limit of 0.05 ppm for all sam-
ples, except for St. Peter ESPA and
Rixheim BAGA (each 0.11 ppm). Lead
concentration was relatively high in the
leachates from Freiburg ESPA þ CA
(1.14 ppm) and Rixheim BAGA (5.8 ppm),
but near or below the detection limit of
0.005 ppm in all other samples. Both Cd
and As were not detectable in the leachates
from any sample (< 0.017 and <
0.01 ppm, respectively).
After leaching with ammonium acetate
(Step 2), Zn concentrations in the leachates
were elevated in all FA samples, ranging
from 4.05 ppm for Ammertzwiller CA to
49.8 ppm for Rixheim BAGA. Nickel con-
centrations in the leachates from ashes
ranged from 0.11 ppm (Ammertzwiller
CA) to 1.25 ppm (Freiburg ESPA þ CA).
Cadmium had variable concentrations in
the leachates, ranging from 0.068 ppm (St.
Peter BA) to 1.2 ppm (Rixheim BAGA).
Both Pb and As were near or below their
respective detection limits in all leachates.
After leaching with hydrochloric acid
(Step 3), Zn concentrations in the leachates
were high in leachate of Ammertzwiller
CA (58.8 ppm) and Freiburg ESPA þ CA
9
(108 ppm). Nickel was low and relatively
constant in the leachates of all samples,
ranging from 0.95 ppm for Ammertzwiller
CA to 2.25 ppm for Rixheim BA. Lead
was relatively low for all leachates, with
concentrations ranging from 0.099 ppm for
St. Peter BA to 3 ppm in Freiburg
ESPA þ CA, except for Rixheim BAGA
(Pb ¼ 31.4 ppm). Cadmium was detectable
in the leachate from FAs (0.31 ppm for
Ammertzwiller CA, 0.46 ppm for Freiburg
ESPA þ CA, 0.65 ppm for St. Peter ESPA,
and 0.84 ppm for Rixheim BAGA), but in
the leachates from BA samples, Cd con-
centrations were below the detection limit
of 0.017 ppm. Arsenic was low and rela-
tively constant in all leachates, with a max-
imum concentration of 11.1 ppm
(Rixheim BAGA).
The elemental concentrations in the
leachates were compared to the respective
bulk compositions in the original FAs of
two samples, St. Peter ESPA and
Ammertzwiller CA (also measured by
AAS after total digestion, Table 3), to cal-
culate the relative amount of each element
released, or mobilized, at each leaching
step, and thus, to estimate the extent of
leaching (Figure 4). The first mobilization
of Zn took place during step 1 from St.
Peter ESPA (which had a greater initial Zn
concentration), but only during step 2 from
Ammertzwiller CA. During the final step
(step 3), more than 50% of the original Zn
content in the ashes became mobile for
both ash types. A qualitatively similar
 10 C. Maschowski et al.

behavior can be observed for Ni, but the

Detection
Table 3. Elemental concentrations (in ppm) in leachates of the 3-step extraction from wood-chip ashes. BA: bottom ash; ESPA: electrostatic precipitator

0.005
0.017
limit
0.04
0.05

0.01
final relative amount released is signifi-
cantly higher for St. Peter ESPA (63%)
than for Ammertzwiller CA (16%). Lead

31.40
0.840
1.70

11.1
268
3
BAGA was retained in Ammertzwiller CA until
the last step, where about 31% had been

0.009
1.200
ash; CA: cyclone ash; BAGA: baghouse filter ash; bulk: concentration in bulk ash n.d.: not detected. All concentrations represent AAS data.

49.8
0.70

0.11
2
released, whereas in the case of St. Peter
ESPA, it was mobilized during steps 1 and
5.800
7.24
0.11

n.d.
n.d.
Rixheim

0.710 3, but with a final loss that was signifi-

0.170
cantly smaller ( 5%). Cadmium started to
44.1
2.25

0.15
3

become mobile during step 2 in both ashes.

0.093

After step 2, more than 50% of the initial

0.15
0.17

0.03
BA

n.d.
2

Cd content was released from St. Peter

0.05
n.d.
n.d.
n.d.
n.d.

ESPA and about 13% from Ammertzwiller

1

CA. The relative overall released Cd

1.300
0.310
58.8
0.95

0.11

amounts after step 3 are extended almost

3
Ammertzwiller

linearly from step one for both ashes, and

0.006
0.180
4.05
0.11

0.02
2

almost all of the Cd was released from St.

CA

Peter ESPA and 29% from Ammertzwiller

0.012
0.85
n.d.

n.d.
n.d.
1

CA. Arsenic remained fixed during step 1,

became slightly mobile at step 2 in both
20.06
9.188
1016
bulk

67.8
42.4

ash samples, and at step 3, 15% from

Ammertzwiller CA and 79% from St. Peter
3.000
0.460
1.79

0.54
108
3

ESPA had been released.

ESPA þ CA

0.007
0.760
24.3
1.25

0.01
2

3.3. Leaching behavior of crushed

1.140
5.76
0.09

mortar samples
n.d.
n.d.
Freiburg

Concentrations of the contaminant ele-

0.114
0.11
1.93

0.12
n.d.

ments Zn, Ni, Pb, Cd, and As in the leach-

3

ates of crushed blended mortar specimens

0.007
0.071
0.22
1.00

n.d.
BA

are presented in Table 4.

2

After leaching with ultrapure water

0.067
0.07
n.d.

n.d.
n.d.
1

(Step 1), Zn and Ni concentrations were at

or near the detection limit of 0.04 and
0.210
0.650
91.0
1.63

0.65
3

0.05 ppm in the leachates from all mortar

samples. Lead concentration was also near
0.007
0.560
11.2
0.38

0.01
2

or below the detection limit of 0.005 ppm

ESPA

in all samples. Both Cd and As were not

0.150
6.21
0.11

n.d.
n.d.
1

detectable in the leachates from any sample

St. Peter

(< 0.017 and < 0.01 ppm, respectively).

36.33

15.32
8.571
2076
bulk

102

After leaching with ammonium acetate

(Step 2), Zn concentrations in the leachates
0.099
1.36

0.09
n.d.

n.d.
3

from crushed blended mortar samples were

low, with 1.08 ppm for ESPA þ CA as
0.006
0.068
BA

0.06
0.83

n.d.
2

highest value (28 d), but were near or

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

below the detection limit of 0.04 ppm in

1

the leachates from mortar with 100%

Step

Cd
Zn

As
Pb
Ni

Normo 4 in the cement part. Nickel

 Journal of Sustainable Cement-Based Materials 11

Figure 4. Leaching behavior of selected elements (Zn, Ni, Pb, Cd, As) in Ammertzwiller CA
and St. Peter ESPA; Cumulative percentage of released elements (circles) and absolute concen-
tration (columns) in ppm (mg  kg1) in leachates shown on the secondary y-axis (on right-hand
side); Initial conc.: initial concentration in leachates.

concentrations were relatively low and uni-
form for the mortar leachates
(0.23–0.3 ppm). Cadmium was detectable
only in the leachate from mortars with
ESPA þ CA (0.025 and 0.031 ppm). Both
Pb and As were near or below their
respective detection limits in all leachates.
After leaching with hydrochloric acid
(Step 3), Zn concentrations in the leachates
from the mortar specimens with amend-
ment of Ammertzwiller CA and Freiburg
ESPA þ CA were 7.86–8.15 ppm and
13.4–13.8 ppm, respectively. Nickel was
low and relatively constant in the leachates
of all samples, ranging from 0.63 ppm for
mortar with CA (2 d) to 0.81 ppm for mor-
tar with ESPA þ CA (28 d). The first time
Pb was detected at considerable concentra-
tions in all leachates was after step 3, with
highest concentration of 1.270 in mortar
with ESPA þ CA (28 d). Cadmium con-
centrations in the leachates from mortar
samples were mostly near or below the
detection limit of 0.017 ppm. Arsenic was
low and relatively constant in all leachates,
with a maximum concentration of
0.22 ppm for mortar with ESPA þ CA
(28 d).
4. Discussion
Density of total binder, relative water
amounts or w/b ratio required to produce
workable mortars, and compressive
12 C. Maschowski et al.

strength of the hardened mortar prisms

Detection
28 days). ESPA: electrostatic precipitator ash; CA: cyclone ash; BAGA: baghouse filter ash; w/b: water-to-binder ratio; n.d.: not detected. All concentrations
Table 4. Elemental concentrations (in ppm) in leachates of the 3-step extraction from crushed mortar samples after different curing times (1, 2 and

0.005
0.017
limit
0.04
0.05

0.01
vary depending on the type and dosage of
cement replacement, as our results and lit-
erature (e.g. [48]) show. Normo 4 is an

1.270
0.059
13.4
0.81

0.22
industrial Portland cement and was taken
30% ESPA 1 CA 1 70% Normo 4 (w/b ¼ 0.7)

3
as a reference and base cement for the bio-
mass ash additions, because it has well-

0.031
1.08
0.30
n.d.

n.d.
28
2
known properties as well as reliable work-
ability and final strength.
0.007 In contrast to the standard EN 196-1
n.d.
n.d.

n.d.
n.d.
1

concept, which is operated at a constant w/

b ratio of 0.50 and mass proportioning, the
1.100
0.068

approach with volumetric proportioning

13.8
0.76

0.20
3

and adapted w/b ratios used in this study

better reflects common concrete practice
0.025
0.74
0.29

0.01
n.d.

and thus allows for a robust application-

2
2

relevant assessment of novel binder types,

such as those with biomass ash.
0.690 0.008
8.15 0.06
0.73 0.07

0.041 n.d.
n.d.
1

Scaling the influences of the parame-

ters that control mortar quality, i.e. fuel
0.13

type, flue-gas treatment strategy, boiler size

3

and design, is challenging. Because of the

30% CA 1 70% Normo 4 (w/b ¼ 0.7)

0.42
0.26
28

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

complexity of possible interdependencies,

2

and also due to fluctuating fuel quality, it is

0.05
0.06
n.d.
n.d.
n.d.
1

not possible to quantitatively evaluate

0.644
0.046

influencing parameters in a statistical man-

7.86
0.63

0.11
3

ner within the scope of this study, but these

parameters can be described qualitatively
0.30
0.23
n.d.
n.d.
n.d.
2
2

and as such be used for showing the

0.05
0.06
n.d.
n.d.
n.d.

way forward.
1

0.662
0.044
7.93
0.65

0.12
3

4.1. Influences of flue-gas treatment

strategy and boiler design on
0.29
0.23
n.d.
n.d.
n.d.
2
2

mortar quality
0.05
0.05
n.d.
n.d.
n.d.
1

Water requirements to produce workable

mortars are inversely correlated with final
0.400
1.64
0.73

0.21
n.d.
3

compressive strength (Figure 5). There is a

100% Normo 4 (w/b ¼ 0.53)

remarkable difference in physical proper-

0.05
0.25
n.d.
n.d.
n.d.
28
2

ties between unblended mortars and mor-

0.05
0.06

tars blended with ashes from wood chips,

n.d.
n.d.
n.d.
1

as also reported in other recent studies, e.g.

0.384
1.65
0.66

0.18
n.d.

[26]. Mortars blended with ESPA and

3
represent AAS data.

BAGA required the highest amounts of

0.27
n.d.

n.d.
n.d.
n.d.
1

water to achieve regular workability and

2

exhibited lowest compressive strength

0.04
0.06
n.d.
n.d.
n.d.
1

when compared to BA. This is mainly

linked to the excessive content of highly
Days
Step

Cd
Zn

As
Pb
Ni

soluble substances, such as potassium salts,

 Journal of Sustainable Cement-Based Materials 13

Figure 5. Correlation between w/b ratio and final compressive strength (28 days) of the reference
mortars and mortars with blended cements; arrows indicate lowering of w/b ratio and improve-
ment of maximum compressive strength due to grinding.

as well as lower total content of strength-
enhancing mineral phases, such as belite,
lime, portlandite and the amorphous frac-
tion initiating the pozzolanic reaction [37].
The light color observed for the mortar
blended with ESPA [49] is also consistent
with this interpretation. In contrast, CA
seems to have a positive effect on water
consumption. The chosen w/b ratio of 0.7
for CA turned out to be too high to produce
a workable mortar paste and therefore, we
conclude that the workability of this ash
type was underestimated in our study, as
was probably its final compressive strength
(not plotted in Figure 5). The dark color of
this blend [49] points to the presence of
small particles in CA and lesser amounts of
potassium salts.
The compressive-strength data further
show a notable positive effect of reduced
grain size of the ashes due to grinding
(Figure 5; see also Figure 2), because of
improved kinetics of water-mineral interac-
tions during the hardening process and bet-
ter particle packing of the whole mortar
system. As shown in Figure 3, the original
ESPA from St. Peter was rich in particles
with physical diameters >100 mm, whereas
the size-distribution pattern after grinding
is quite similar to those of Portland cement,
including only particles <100 mm in diam-
eter. In addition, depending on the flue-gas
treatment strategy, there are significant dif-
ferences in water requirement to obtain
workable mortars and reasonable compres-
sive strength of the hardened mortar prisms
(Figure 5), which is also reflected by their
color: mortar prisms blended with CA have
a markedly darker color than those blended
with ESPA or ESPA þ CA, or the pure
Normo 4 [49].
Boiler size and design were not specif-
ically addressed in the experiments
reported here but the available data point to
a general correlation with mortar quality:
the larger the boiler, the higher the tem-
perature and thermal energy content within
the combustion chamber, the more com-
pletely the processes of calcination, mineral
transformation as well as elimination of
organics can take place, all of which is
favorable for ash reactivity in mortar sys-
tems. Another positive effect of bigger
boiler size is the variety of flue-gas treat-
ment devices installed; final ash mixtures
could be designed for virtually every need
14 C. Maschowski et al.
as cement replacement. In large-scale com-
bustors, the composition of FAs is domi-
nated by the components of fluidized beds,
which in this case are rich in Ca, and there-
fore, the ashes represent a material that,
from a chemical perspective, is usable as
cement additive. Nevertheless, due to lower
combustion temperatures and the resulting
incompletely calcined ashes from fluidized
bed boilers, the positive effect is dimin-
ished [50].
MCA had no negative impact on mor-
tar workability and final compressive
strength. Mineralogical analyses [37]
revealed that MCA consisted primarily of
Ca phases originating from the amendment
of 2 wt % Ca(OH)2) to the fuel, with only
small amounts of other constituents, includ-
ing the potassium sulfate arcanite (2 wt %).
Therefore, although it is the most promis-
ing CRM candidate, MCA was not com-
pared with the wood-chip ashes.
4.2. Leaching behavior
4.2.1. Immobilization potential of
wood-chip ashes
Data from sequential leaching of selected
raw materials (biomass ash samples CA and
ESPA) can document the immobilization
potential of the ash itself when compared to
compositional data from total digestion
(Table 3, Figure 4). For Zn, there is almost
no difference in the relative cumulated
amount between the two ash types, although
the total concentrations are higher for
ESPA. This may be an indicator that the
released Zn is not incorporated well or at
least not in ash-specific components,
because the two ash samples do have differ-
ent compositions. More likely, Zn was
adsorbed to particle surfaces. Nickel is
immobilized at least four times better in CA
than in ESPA at each step. In the end, more
than 80 wt % of the initial Ni remained in
CA and almost 40 wt % in ESPA. It is not
likely that Ni first dissolved and then
resorbed as Ni(II) by fly ash particles in CA,
as described for bagasse fly ash by Rao
et al. [51]. A possible mechanism in add-
ition to adsorption could be dissolution of
calcite and sulfates, followed by precipita-
tion of other metal carbonate- and sulfate-
like minerals at the lower pH of steps 2 and
3 [52]. Lead became mobile only at step 3
from CA in a significant amount (about
30 wt %). Due to high amorphous content in
ESPA [37], Pb adsorption capacity might be
elevated due to formation of hydroxy soda-
lite [53]. Nevertheless, this mechanism may
be limited through low Na content.
Cadmium was released nearly linearly at
steps 2 and 3 from both ash samples, ending
in a total loss of about 30 wt % for CA and
almost 100 wt % for ESPA. This difference
is probably due in part to Cd sorption, which
can take place by the formation of com-
plexes on particle surfaces and by bonding
to Fe oxides [54], which are abundantly pre-
sent in CA and nearly absent in ESPA [37].
4.2.2. Immobilization potential of hard-
ened, crushed mortar prisms
The potential of the blended mortars for
immobilizing contaminating elements can
be assessed by comparing the leaching
results of the biomass ashes with those of
the corresponding mortars. To represent a
worst-case scenario in real life, the largest
possible surface area and most effective
leaching potential was achieved by crushing
and grinding the hardened mortar prisms to
fineness below 5 mm. To calculate the nor-
malized concentrations of contaminating
elements in ash leachate (cash), their meas-
ured concentrations in the ash leachates
(cash0, listed in Table 3) were multiplied by
the ratio of ash amendment in the mortars,
and then added to the contributing part of
the median concentration in leachates of ref-
erence mortars (cref, listed in Table 4)
according to the following equation:
mbinder  mash
mbinder
cash ¼ cash0 
msand þ mbinder þ mwater
þ cref
 Journal of Sustainable Cement-Based Materials 15

Figure 6. Immobilization potential of the blended mortars at each leaching step for the contami-
nating elements Zn, Ni, Pb, Cd, and As; green columns represent normalized concentrations in
leachates from the wood-chip ashes, grey columns indicate normalized concentrations in leach-
ates from the crushed mortar prisms. Dotted lines represent detection limits. Immobilization rate
was rounded to integers.

where: mash ¼ weighed mass of ash, and
msand, mbinder, mwater ¼ mass of mor-
tar components.
The immobilization can be quantified
as immobilization rate (the ratio of the nor-
malized concentrations in ash and in mor-
tar, cash/cmortar), which is shown as rounded
integers in Figure 6 and underlines the
immobilization effect for Zn and Pb of the
mortars blended with ESPA
and ESPA þ CA.
During the first leaching step (leaching
with ultrapure water), significant amounts
of Zn (ESPA and ESPA þ CA) and Pb
(ESPA þ CA) were released from the ashes
(Figure 6, Table S2). The corresponding
mortars seem to have an immobilization
effect on Zn and Pb, as indicated by the
low or undetectable Zn and Pb concentra-
tions in their leachates. Nevertheless,
immobilization rates vary from relatively
high (11, 10, 6) to intermediate (3, 2).
The second leaching step (leaching
with ammonium acetate) washed some
additional Zn as well as Ni from both the
ashes and the blended mortars. Cadmium
16 C. Maschowski et al.
started to be leached from pure ashes only,
albeit only a very small amount of Cd was
leached from CA, and remained fixed in
the mortars.
During the final leaching step (leaching
with hydrochloric acid), additional Zn, Ni,
and Pb, but also As were washed from all
specimens. However, only small amounts
of Cd were released from mortars by
hydrochloric acid.
The immobilization of Zn and Pb dur-
ing the first step (immobilization rates 2)
and of Cd during the second step (immobil-
ization rate ¼ 2) is probably due to fixation
in the structure of cement phases, such as
ettringite [55]. These results suggest that
fixation rates of contaminating elements
are good at neutral pH, representing normal
handling and utilization. Only Cd remains
fixed at lower pH and thus is mostly
unaffected by weathering processes. In
contrast, long-term degeneration of con-
crete debris might release all contaminat-
ing elements.
Because none of the ashes contained
Cr(VI) that could be detected with our ana-
lytical method (Table 5), its immobilization
potential by the blended mortars could not
be investigated. However, in a recent study
by Zhang et al. [56], the immobilization
potential of Cr(VI) was positively corre-
lated with final compressive strength of
alkali-activated slag cement due to struc-
tural encapsulation and the reduction of
chromium from hexavalent to trivalent.
4.3. Overall rating of ash-
blended cements
According to Swiss regulations [57] and
SIA 2049 [58], the contents of some critical
chemical elements in biomass ash deter-
mine whether the ash can be used in
cement systems or must be disposed of in
landfills. The ICP data of this study show
that most of the critical elements in the
wood-chip ashes occurred in concentra-
tions below the respective limit values.
However, the concentrations of some
elements, including As, Cd, and Zn exceed
the limit values in some of the ashes. The
exceedance is most notable in BAGA from
Rixheim and in ESPA from Colmar
(Table 5).
To assess the overall rating of the ashes
and the ash-amended mortars, however, the
full set of physical and chemical data must
be considered. Inspection of the combined
data sets shown in Tables 2–5 suggests that
none of the investigated wood-chip ash
types receives a good rating with respect to
all three quality parameters, i.e. trace elem-
ent concentrations and immobilization,
workability (w/b ratio), and final compres-
sive strength: either one or more limit val-
ues of certain elements are exceeded, or the
rating of physical cement properties are
insufficient, or both. However, of the
wood-chip ashes studied here, CA from
Ammertzwiller has a promising overall rat-
ing: the concentration of only one element
(Cd) exceeds the Swiss limit value as listed
in Table 5, but the Cd is well retained by
the cement during leaching until and
including step three (see Figure 6), and
although final compressive strength tests
could not be completed due to insufficient
sample volume available, water require-
ment was unexpectedly low, which should
have a positive effect on final compressive
strength (Figure 5). MCA has the best
overall rating without any limitations in
terms of trace element concentrations
(lower than all other FAs; leaching data not
available), workability and final compres-
sive strength, but this is primarily due to
the chemistry of the amendment (calcium
hydroxide) rather than a result of the
fuel itself.
5. Conclusions
The mineralogical composition of ash par-
ticles resulting from the thermal conversion
of inorganic species in wood, and, more
specifically, the calcination reaction, which
can produce lime, portlandite and C2S
phases, is a crucial parameter that needs to
Table 5. Concentrations of critical elements (in mg  1 kg1 (ppm)) and total organic carbon (TOC Leco, in wt %) in the studied biomass ashes (data from
[37]) and the respective limit values according to Swiss (CH) regulations. Data for MCA obtained by AAS analysis, data for other ashes by ICP-AES (Cr
and Zn) and ICP-MS (all other elements). n.d.: not detected; bold values represent exceedance of one or more limit values. n.a.: no data available.
Limit SIA Limit VVEA Limit VVEA Type
St. Peter Freiburg Ammertzwiller 2049 Type B_'Inertstoff' D_'KVA
Critical elements Rixheim Colmar (CH) (CH) Schlacke' (CH)
SIA 2049 BA ESPA BA ESPA þ CA BA CA MCA BAGA ESPA Cement Landfill Landfill
As < 30 < 30 < 30 < 30 < 30 < 30 2 125 43 30 30 50
Cd < 0.9 16 < 0.9 16 < 0.9 25 2 30 52 5 10 10
Co 7 5 7 5 6 7 n.a. 6 <3 250
Cr 114 48 96 43 57 98 n.a. 69 50 500 500 1000
Cu 214 231 912 204 88 193 23 259 281 500 500 5000
Ni 31 28 49 32 116 72 19 33 34 500 500 1000
Pb < 30 131 45 130 < 30 142 4 572 341 500 500 2000
Sb < 30 < 30 < 30 < 30 < 30 < 30 n.a. < 30 < 30 30 30 50
Sn < 20 < 20 59 < 20 < 20 < 20 n.a. 28 < 20 10
Zn 135 1790 66 1780 19 1030 383 4570 7090 2000 1000 5000
TOC Leco 0 7 0 7 2 2 n.a. 1 0 2 2
Cr(VI) < 50 < 50 < 50 < 50 < 50 < 50 n.a. < 50 < 50 2 1 5
Journal of Sustainable Cement-Based Materials
17
18 C. Maschowski et al.
be considered when the ashes are to be
used as CRM. The improved kinetics of
water exchange provided by fly ash
spheres, which are most abundant in CA,
appears to be beneficial for workability
(i.e. lower water requirements), thus
enhancing final strength of blended mor-
tars. In contrast, highly water-soluble
potassium salts, which are most abundant
in ESPA, clearly influence negatively the
water consumption as well as the final
compressive strength. In regard of contami-
nating elements, the immobilization poten-
tial of mortars blended with ESPA is not as
high as that of mortars blended with CA, as
documented by leaching tests with crushed
samples of the hardened mortars. Some of
the ashes contained contaminating ele-
ments in considerable amounts, but only
concentrations of Cd and sporadically As,
Cu, Pb, Sn and Zn exceed limit values
given by Swiss national regulations [57,
58] for wood ash allowed for application in
cement products. Good fixation of these
elements in the cement structure, however,
suggests that their limit values for wood
ash should be re-assessed.
Both the use of fluidized beds and the
amendment of calcium hydroxide to the
fuel had a significant influence on the com-
position of fly ashes and thus, on their
reuse potential as cement additives in terms
of clinker substitution: the data presented
here show positive effects on final com-
pressive strength of the hardened mortar
blended with these ashes. Whichever ash
type will be suitable as CRM, the main
challenge would be to provide constant ash
quality and/or sophisticated blend-
ing operations.
Acknowledgements
The authors would like to thank the labora-
tory staff at the Institute of Earth and
Environmental Sciences in Freiburg, espe-
cially Isolde Schmidt and Sigrid Hirth-
Walther for help in chemical analysis and
leaching experiments. Furthermore we
would like to thank operators of the com-
bustion facilities for their kind cooperation.
Holcim (Schweiz) AG is acknowledged for
providing lab, staff and material for
cement tests.
Disclosure statement
No potential conflict of interest was
reported by the author(s).
Funding
This work would not have been possible
without financial support from the EU
Interreg IV 746 Program (Oberrhein, pro-
ject C35 BIOCOMBUST; www.biocom-
bust.eu). This work was further supported
in part by P30-ES13508 awarded by the
National Institute of Environmental Health
Sciences (NIEHS). The findings are not
the official opinions of NIEHS or NIH.
Note
[1] In our experiments, we substituted the
cement rather than the clinker itself
by CRM candidates. Portland cement
consists of ground clinker (about
90 wt %), calcium sulphate and a
small amount of other materials.
ORCID
Christoph Maschowski https://orcid.org/
0000-0003-4211-3700
Ali Talib Arif http://orcid.org/0000-
0001-9229-5683
Patxi Garra http://orcid.org/0000-0003-
3036-3411
Gwena€elle Trouve http://orcid.org/
0000-0003-4212-4661
Reto Giere http://orcid.org/0000-0001-
8507-1956
 Journal of Sustainable Cement-Based Materials
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