Waste Management 116 (2020) 147–156

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Bottom ash derived from municipal solid waste and sewage sludge
co-incineration: First results about characterization and reuse
Ahmad Assi, Fabjola Bilo, Stefania Federici, Annalisa Zacco, Laura E. Depero, Elza Bontempi ⇑
INSTM and Chemistry for Technologies Laboratory, Department of Mechanical and Industrial Engineering, University of Brescia, Via Branze, 38, 25123 Brescia, Italy

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

Article history: This paper reports a complete characterization of the lowest fractions of bottom ash derived from co-
Received 23 March 2020 combustion of municipal solid waste with sewage sludge (COBA), with the aim to suggest suitable reuse
Revised 6 July 2020 strategies of this by-product. X-Ray Microanalysis is coupled with mineralogical characterization, based
Accepted 20 July 2020
on X-Ray Diffraction and Rietveld refinement, to extract information about COBA crystalline and amor-
Available online 12 August 2020
phous phases. The composition of different particle size fractions shows that amount of amorphous
increases with the increase of fractions sizes. In particular, the finest COBA size fraction (<300 lm) shows
Keywords:
more leachable heavy metals (i.e. Pb, and Zn) compared to the investigated fraction with the highest sizes
Municipal solid waste
Sewage sludge
(1400 mm). On the basis of their composition, lowest particle size fractions show a better hydraulic
Bottom ash behavior compared to bottom ash obtained from incineration of only municipal solid waste, suggesting
Heavy metals possible attractive COBA applications, as for example, Portland cement substitution. In addition, COBA
Stabilization with size fractions in the range of 1000–1400 lm are proposed to be used to produce glass and ceramic.
Finally, due to its high amount of reactive amorphous phase (about 73% for fraction size of 1400 lm)
COBA is used, in combination with other by-products (coal fly ash and flue gas desulphurization resi-
dues), to stabilize municipal solid waste incinerator fly ash produced at the same incinerator plant, fol-
lowing the azure chemistry principle of use a waste to stabilize another waste.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction
In the incineration of municipal solid waste, municipal inciner-
ated bottom ash (MIBA) is the most significant by-product,
accounting about 80% of the residual wastes remaining after com-
bustion (Allegrini et al., 2014). The other waste produced as conse-
quence of incineration is fly ash (MIFA), that is generally
considered as a toxic residue because of the presence of leachable
heavy metals (Zacco et al., 2014). MIBA recycle is a common prac-
tice in several EU (Spain, Italy, Germany, Denmark, Netherlands,
Belgium, etc.) and non-EU countries (such as China, USA, and Tai-
wan) (Mininni and Santori, 1987). This is possible thanks to MIBA
chemical composition; this by-product is mainly composed by
oxide aggregates like stones, silicate and metals (Jurič et al., 2006),
Abbreviations: MSW, municipal solid waste; MSWI, municipal solid waste
incineration; BA, bottom ash; FA, fly ash; MIBA, municipal solid waste incineration
bottom ash; MIFA, municipal solid waste incineration fly ash; COBA, Bottom ash
derived from co-combustion of municipal solid waste and sewage sludge; SS,
sewage sludge.
⇑ Corresponding author.
E-mail address: elza.bontempi@unibs.it (E. Bontempi).
with the latter ones present as large pieces of scrap metals. Then,
the main MIBA recycle applications concern to the building indus-
try (Ashraf et al., 2019). Indeed, even if limited, some full scale
applications of this by-product reused as cement kiln feed are
available, mainly in Asian countries (Sarmiento et al., 2019).
Nevertheless, MIBA have been already used to synthesize adsor-
bents (Chiang et al., 2012), mesoporous silica (Alam et al., 2019a),
zeolites (Penilla et al., 2003), ceramics (Bourtsalas et al., 2014), and
other building materials (Caprai et al., 2018), (Dhir OBE et al.,
2017).
According to European regulation, MIBA can be reused (for
example in construction field, or other materials) if the quantities
of salts and toxic elements, which can leach into ground water, are
below a certain threshold (Hjelmar et al., 2007). However, there is
no harmonized test methods and EU countries have developed
their own rules to regulate MIBA reuse in the construction sector
(Blasenbauer et al., 2020). For example, recent works have shown
that MIBA chemical characteristic may, sometimes, not comply
with some local existing limit values for its unlimited reuse as,
for instance, in clinker production and in road construction
(Huber et al., 2019). For this reason, MIBA treatment becomes nec-
essary before its recycle. In particular, a standard pre-treatment of

https://doi.org/10.1016/j.wasman.2020.07.031
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
148 A. Assi et al. / Waste Management 116 (2020) 147–156
MIBA, which involves a screening stage to remove the oversized
metals fractions (fractions larger than 1 cm) (Stabile et al., 2019),
is generally performed. Separating the various size fractions of
MIBA is also proposed (Funari et al., 2015), which leads to an
increase recovery of the valuable materials. Finally, MIBA grinding
is a suggested procedure to reduce the average particle size and
make it more suitable for uses as building materials in construction
field.
Depending on its final destination, the MIBA particle size can be
subjected to adjustment such as sieving for use as fine building
aggregate or grinding for further uses as a cement component
(Al-Rawas et al., 2005; Tang et al., 2015).
The above-mentioned procedures are considered simple and
cost-effective pre-treatment strategies, which can also be imple-
mented at a plant scale. In this context, it is evident that the differ-
ent MIBA size fractions must be studied in detail, to better address
their recycle strategy. For recovery purposes, MIBA fraction below
4 mm is usually separated because it contains leachable heavy
metals, such as Mo, Pb, Zn, Sb, Cu, and Cr (Chimenos et al., 1999)
and inorganic salts (such as chlorides and sulfates) (Chen and
Chiou, 2007).
Several works about MIBA characterization are available in lit-
erature (see for a global literature view the reference (Dhir OBE
et al., 2017)). Some recently publishes studies (Alam et al.,
2019b; Caviglia et al., 2019; Huber et al., 2019; Loginova et al.,
2019) demonstrate the high scientific interest to investigate differ-
ent possibilities to recover this waste, by particles size selection.
However, despite that several works discuss the MIBA composi-
tion and detailed phases amount, often the amorphous content is
not considered. Amorphous is formed due to a rapid waste com-
bustion, cooling, and quenching, in conditions that are far from
equilibrium. As a consequence, MIBA can contain large amount of
amorphous phase that make it generally metastable under envi-
ronmental conditions (Dhir OBE et al., 2017). This can severely
affect a reliable MIBA characterization, because it is highly suscep-
tible to chemical and mineralogical alteration over time.
In recent years, with the strategy to suitably manage different
waste typologies, the practice of different wastes co-incineration
was also investigated. In particular, sewage sludge (SS) has been
considered for co-combustion with municipal solid waste. Indeed,
the diffuse practice of SS agricultural land spreading has generated
several problems (for example juridical contentions in Italy), since
SS contains numerous pathogenic agents, toxic inorganic sub-
stances, and microorganism (Mininni and Santori, 1987). As a con-
sequence, SS incineration and co-combustion with MSW have been
rapidly proposed as a possible solution to manage this waste typol-
ogy. Despite the promising results of SS pyrolysis (Chanaka et al.,
2019; Chanaka Udayanga et al., 2019, 2018), industrial interest in
the MSW and SS co-combustion is growing, as demonstrated by
the recent activities established at real scale, i.e Brescia plant in
Italy (Biganzoli et al., 2012) and Shandong Province in China
(Chen et al., 2019). The co-combustion strategy allows to use the
already existing incineration plants (such as municipal solid waste
incineration plants) avoiding the need to construct new incinerator
devoted to mono-combustion.
In the frame of a growing problem concerning SS management,
the incineration with urban solid wastes is becoming an interest-
ing solution that produces co-combustion wastes, with character-
istics that must be investigated, because they can differ from
that of MIBA.
In the present study, bottom ash derived from co-combustion
processes involving municipal solid waste and sewage sludge
(COBA) is characterized in detail. To the best of authors’ knowl-
edge, this is the first study dealing with this topic, offering a basis
work, also with the aim to propose COBA recycle.
In this manuscript, we have performed a deep characterization
of COBA based on various size fractions. The COBA reactivity is
investigated on the basis of a recent proposed technology used to
stabilize MIFA (Assi et al., 2020c). It is based on the use of Flue
Gas Desulphurization (FGD) residues, Coal Fly Ash (CFA), silica
fume, and bottom ash (Assi et al., 2020c). The stabilization mecha-
nism is attributed to pozzolanic and carbonation reactions pro-
moted by the use of specific by-product materials (Assi et al.,
2020c). This process is selected because it offers the advantage to
treat at the incinerator plant location different wastes (MIFA and
COBA) originated by the same industrial process. In addition, liter-
ature suggests the possible reuse of different combustion ashes,
such as MIFA and MIBA, as raw materials for building applications
(Phua et al., 2019; Yin et al., 2018).
This low cost technology is a virtuous example of the circular
economy strategy in the frame of the recent proposed azure chem-
istry approach (Zanoletti et al., 2018). In particular, the use of a
waste to stabilize another waste can be considered a suitable strat-
egy in the development of sustainable remediation technologies.
2. Experimental
2.1. Materials
Bottom ash derived from co-combustion of municipal solid
waste and sewage sludge (COBA) was provided by the thermal-
valorization plant A2A S.p.A. located in Brescia (Italy). The plant
is working since 1998 and burns about 710 Mt of waste per year,
with three separate lines of combustion. Since 2017 the sewage
sludge is co-incinerated with solid urban waste at concentration
around 7%. The combustion temperature in the three different lines
varies from 953 °C to 1004 °C, depending on the amount of co-
combusted SS. After sampling, COBA with dimensions higher than
2 cm was manually separated, since fractions with higher dimen-
sions are generally associated to ferrous and non-ferrous metals
and unburned waste (such as piece of ceramic and glass materials).
Due to high sample moisture, COBA was dried at 100 °C for about
2 h. Then, a series of six sieves with diameter from 1400 mm to less
than 300 mm were employed to obtain various fractions of COBA. In
particular, metals that were separated from COBA could be subse-
quently used as a secondary raw material in metal industry. The
particle size distribution of COBA was evaluated by the weight of
each individual fraction retained within each sieve. Thus, the per-
centage of the total initial weight per every single grain size class
to which it belongs was evaluated. A sample (named COBA Mix)
containing all the investigated size fractions was also considered.
For XRD, leaching tests, and EDXS characterization (see in the fol-
lowing), each fraction and COBA Mix was grounded till to reach a
particles dimension of about 100 mm to obtain homogenous and
fine particles. This also allowed avoiding preferred orientation
effects in XRD data collection.
To verify the COBA reactivity in metals immobilization, a
method already tested (Assi et al., 2020c) was carried out involving
also MSW co-incinerated FA (MIFA) provided by the same plant.
The stabilization technology consisted in the use of CFA, FGD resi-
dues, and silica fume as reported by previous works (Rodella et al.,
2017). In particular, FGD residues were selected because they con-
tain calcium hydroxide. Silica fume is made by amorphous silica
and CFA contains aluminosilicate glass (Liu et al., 2019). Detailed
characterization of these materials was very recently published
(Assi et al., 2020c). As better described in the available literature
about the proposed method (see for example (Benassi et al.,
2016)), the materials selection for MIFA stabilization was made
with the intention to use wastes and/or by-products as stabilizing
agents.
 A. Assi et al. / Waste Management 116 (2020) 147–156
Table 1
Samples description. MIFA: Municipal solid waste Incineration Fly Ash; CFA: Coal Fly
Ash; FGD: Flue Gas Desulphurization, COBA CO-combustion Bottom Ash at difference
sieved fractions.
Samples Powder mass (g)
MIFA CFA FGD SiO2 COBA
1 130 30 40 20 — Microanalysis GmbH, Berlin, Germany) equipped with Mo tube
1400 mm
2 130 30 40 — 20
COBA Mix
3 130 30 40 — 20
<300 mm
4 130 30 40 — 20
In the present study, four samples were prepared (see Table 1)
by mixing 20 g of silica fume with 200 g of [MIFA + CFA + FGD]
(Rodella et al., 2017) or 20 g of three COBA fractions (1400 mm;
<300 mm; and COBA Mix) with 200 g of [MIFA + CFA + FGD]. The
samples exhibited a relative weight percentage as follow: 65%
MIFA, 20% FGD and 15% CFA. Then, approximately 200 mL of milliQ
water (Millipore DirectQ-5 TM, Millipore S.A. S., 67120, Molsheim,
France), was added and the mixture mixed for 20 min. Samples
were aged for 2 months at room temperature.
2.2. Characterization techniques
2.2.1. XRD
X-ray diffraction (XRD) was employed for phase identification
of different COBA fractions. XRD patterns were acquired using a
PANalytical X’Pert PRO Bragg Brentano diffractometer equipped
with a Cu Ka anode and operating at 40 kV and current of
40 mA. Scans (2h) were performed from 5° to 90°, with a step inter-
val of 0.0167°. Philips X’Pert software (associated with the COD
open database) was utilized to identify the phase composition.
To quantify the amount of the individual components of the crys-
talline and amorphous phases, quantitative XRD analyses were
performed, by using Rietveld’s method as it was already reported
by Assi et al. (2019). This is a full-pattern analysis that is based
on the principle of minimization the difference between experi-
mental and calculated XRD spectra by a least-squares procedure
(Rietveld, 1969). The approach is based on the use of the diffraction
pattern of each mineral to evaluate the quantity of detected
phases, rather than relying upon several peaks for the phases
determination. The phases scaling factors, optimized during the
refinement procedure, were used to evaluate the proportion of
detected crystalline phases. The method was combined with the
internal standard procedure (De La Torre et al., 2001) to account
the amorphous contribution. For this aim, high purity of Al2O3
corundum was used as an internal standard for Rietveld analysis
since it was not present in the interested samples. All powder sam-
ples were mixed with Al2O3 corundum (50% in weight). For this
study, data refinement was made by PROFEX software packages
(Doebelin and Kleeberg, 2015).
2.2.2. Leaching test e TXRF
Leachates were prepared from the selected size fractions of
COBA without prior washing. The CEN EN 12457-2 normative
(EN 13055-1:2002 – CEN/TC 154 – CEN – CEN, 2002) was carried
out to conduct the leaching tests of powders and stabilized sam-
ples (see Table 1), according to optimized procedure (Assi et al.,
2020c; Bontempi et al., 2010). Approx. 20 g of each sample was
mixed with 200 mL of milliQ water (1:10) and then mixed at room
temperature for 2 h by means of a stirrer. Samples were filtered by
a 0.45 mm pore membranes and the filtrates pH recorded by a pH-
meter (Metrohm, model 827 Lab, Origgio, Italy). Finally, leaching
149
solutions were analyzed one (1 M) and two months (2 M) after
the stabilization in order to investigate the efficacy of the process.
During this time samples were naturally aged in laboratory at
room temperature.
The elemental chemical analysis of the leachate solutions was
investigated by a S2 Picofox system from Bruker (Bruker AXS
operating at 50 kV and 750 mA and a Silicon Drift Detector (SDD)
following the protocol previously described in (Assi et al., 2020c).
Briefly, approx. 0.010 g of 100 mg/L of a Ga solution adopted as
internal standard (Ga-ICP Standard Solution, Fluka, Sigma Aldrich,
Saint Louis, MO, USA) was added to the prepared solutions to reach
a final concentration of 1 mg/L Ga (homogenization by a vortex
shaker at 2500 rpm for 1 min). A droplet of 10 mL of sample was
deposited in the center of a plexiglas reflector and three replicates
were prepared. Spectra were recorded for 600 s of live time and the
deconvolution to evaluate the peak areas were performed with the
instrumental software based on mono-element profiles. Under the
present experimental conditions, low Z elements such as P, S, and
Cl were underestimated (Klockenkämper and von Bohlen, 2014).
For this reason, the quantification of these elements was corrected
using the calculated relative sensitivities for P and S obtained by
the calibration curves (Borgese et al., 2018). Total reflection X-ray
Fluorescence (TXRF) spectrometry is a non-destructive technique
for simultaneous multi-elemental chemical analysis of various
sample matrices: water (Borgese et al., 2014) soil and sediments
(Bilo et al., 2014) bio-indicators (Bilo et al., 2017) food (Bilo
et al., 2016; Borgese et al., 2015).
2.2.3. SEM – EDXS
The morphology of the raw powders was characterized by a
scanning electron microscope (SEM) Zeiss LEO EVO 40XVP (Carl
Zeiss Microscopy GmbH, Oberkochen, Germany) equipped with a
Link Analytical probe for energy dispersive X-ray spectroscopy
(EDXS, Oxford Instruments NanoAnalysis, Buckingamshire, UK). A
very thin layer of gold was deposited on the specimen surface in
order to ensure the electrical charge. To characterize the compos-
ites, the morphology of samples was scanned under backscatter
mode.
Although XRF has been widely employed for elements analysis,
recently studies have demonstrated that EDXS large area mapping
can be successfully applied to characterize amorphous and crys-
talline MIBA phases (Alam et al., 2019b). Generally, datasets
obtained from two techniques are in good agreement (Alam
et al., 2019b). Nevertheless, EDXS is preferred since light elements
(such as phosphorus) are usually underestimated by XRF (Carmona
et al., 2010; Dreibrodt et al., 2017). P is an interesting element that
may derive from SS. For this reason, EDXS large area mapping was
employed to evaluate the elemental concentrations.
3. Results
After separation of the larger particles size (>2 mm), the result-
ing COBA were fractionated as reported in the experimental sec-
tion. Cumulative particle size distribution of COBA is shown in
Fig. 1. Generally, the retained amount of COBA decreases with
the reduction of the sieve opening. On the contrary, the amount
of material size fractions below 300 mm is about 24%. This result
may be related to the combustion chamber of MSWI injecting urea
to decompose NOX, and many of these fine particles stick to the
surface of the bigger particles as reported in literature (Chang
and Wey, 2006; Yu et al., 2013).
Results of XRD analysis and quantification of crystalline phases
performed by Rietveld’s method of various COBA fractions are
reported in Table 2. The assumed error in this procedure is
150 A. Assi et al. / Waste Management 116 (2020) 147–156

stabilized materials (collected one or two months after the applied

procedure) are very similar.

4. Discussion

Data reported in Table 2 reveal that the most abundant crys-

Fig. 1. Cumulative particle size distribution of COBA.
reported to be lower than the uncertainty introduced by the
heterogeneity of the samples or the analytical methodology
(del Valle-Zermeño et al., 2017).
The detected crystalline phases are the following: calcite,
quartz, anhydrite, cristobalite, hydrocalumite, hydroxylapatite,
hematite, magnesite, sodium chloride, portlandite, and albite.
Results of leaching tests performed for seven various COBA frac-
tions are reported in Table 3.
SEM – EDXS analyses were also performed in all COBA fractions.
The obtained morphological images are very similar, then only
images collected on one fraction are reported in Fig. S1 (see
supporting information). For all samples an area of about
2.5 mm2 was selected for the EDXS analysis.
Table 4 presents the mean of three measurements of EDXS anal-
ysis performed on the selected area for all analyzed size fractions.
For all samples, this analysis was performed on three different
areas, with the same dimensions. The data show that O, Si, and
Ca are in higher concentrations than other elements. Other ele-
ments found in COBA fractions were Na, Mg, S, Cl, K, Ti, which is
in accordance with literature data about MIBA (Loginova et al.,
2019; Zevenbergen et al., 1994), except for P, that generally is
not reported/found.
Table 5 shows the results of leaching tests made on all stabi-
lized samples (see Table 1 for samples composition), relative to
one (1 M) and two months (2 M) after the aging at laboratory
conditions.
The XRD pattern of the sample 3 (see Table 1) collected one
month after the stabilization is reported on supporting information
(see Fig. S2 in supporting information). All the XRD patterns of the
talline phase in all samples, independently by the granularity, is
calcite, that can have both natural and industrial origin (Alam
et al., 2019b). One of the most interesting result of the Rietveld
refinement concerns the amorphous: its content in these samples
is almost more than one order of magnitude higher (>60%) com-
pared to each single crystalline phase. The high amount of the
amorphous indicates that COBA was mainly produced by an off-
equilibrium thermal process (Caviglia et al., 2019), suggesting its
potentially high reactivity (Benassi et al., 2019). As a consequence,
the amounts of evaluated crystalline silica phases are lower (rang-
ing from about 4% to about 8%), compared to data found for MIBA,
where quartz is reported to be the prevalent phase in all the ash
fractions (Loginova et al., 2019; Wei et al., 2011). Crystalline silicon
oxides (quartz and cristobalite) can derive from natural (known as
common mineral on the earth’s surface) or anthropogenic sources
(providing from uses in building materials) (Alam et al., 2019b).
Due to their crystalline structure, quartz and cristobalite are inert
in comparison with amorphous silica. In addition, they are charac-
terized by high mechanical resistance. As expected, they were
found to be more abundant in bigger COBA fractions in accordance
with other studies where the crystalline silicon oxides were gener-
ally found in relatively large particles (Alam et al., 2019b).
Several papers have already shown that the composition of dif-
ferent size fractions of MIBA can differ significantly (Caviglia et al.,
2019). In the present case, apart the difference in the amount of
amorphous, COBA fractions with the smallest particle size
(<300 mm) are particularly rich in calcite and portlandite. In addi-
tion, gypsum and ettringite cannot be detected in COBA fractions
(see Table 2) because they are generally weathering products
(Alam et al., 2019b) (Huber et al., 2019). Hydrocalumite is another
crystalline phase identified in all COBA fractions. This phase com-
monly derives from the reaction of calcium hydroxide and alumi-
nates in pH range of 10–11 in fresh bottom ash (Saffarzadeh
et al., 2011). Hydrocalumite is unstable and is converted to more
stable phases by natural weathering (Saffarzadeh et al., 2011).
Albite, a plagioclase feldspar phase, is also identified in COBA sam-
ples. Data show that it is present in low quantities (few percent),
confirming results already reported for MIBA (Caviglia et al., 2019).
Results of leaching tests performed for seven various COBA (see
Table 3) show that despite the heavy metals concentration is lower
than that reported in other works (Clavier et al., 2019) an increase

Table 2
Results of Rietveld analysis for various COBA fractions.

Phases COBA fractions size (mm)

1400 1000 710 500 300 <300
(%) (%) (%) (%) (%) (%)
Amorphous 73 70 69 67 64 60
Calcite (CaCO3) 6 6 8 8 9 13
Anhydrite (CaSO4) <1 <1 <1 <1 1 <1
Cristobalite (SiO2) 2 1 <1 <1 <1 <1
Quartz (SiO2) 5 5 3 5 3 4
Hydrocalumite (Ca4Al2O6Cl2
10H2O) 2 7 8 6 7 8
Hydroxylapatite (Ca5(PO4)3(OH)) 5 5 6 7 8 7
Hematite (Fe2O3) 1 1 1 1 1 1
Magnesite (MgCO3) 1 2 2 2 2 2
Sodium Chloride (NaCl) 1 1 <1 <1 1 1
Portlandite (Ca(OH)2) <1 1 1 1 1 2
Albite (NaAlSi3O8) 2 2 2 2 2 1
 A. Assi et al. / Waste Management 116 (2020) 147–156 151

Table 3
TXRF results of leachate solutions of different COBA granularities. Data are reported as the average ± standard deviation of three TXRF measurements. *calculated values based on
a calibration curve.

Elements Elemental concentration of COBA (mg/L)

1400 mm 1000 mm 710 mm 500 mm 300 mm <300 mm COBA Mix
P* 12.8 ± 4.4 21.7 ± 9.0 18.7 ± 0.5 28.4 ± 11.9 24.2 ± 9.8 15.6 ± 1.5 17.3 ± 0.9
S* 127 ± 39 199 ± 38 136 ± 51 190 ± 23 158 ± 46 107.9 ± 3.3 91.1 ± 3.7
Cl 572 ± 115 1203 ± 53 1173 ± 403 1252 ± 76 1557 ± 335 932 ± 78 969 ± 28
K 121 ± 3 231 ± 15 232 ± 86 225 ± 7 270 ± 41 151 ± 13 176 ± 7
Ca 358 ± 91 556 ± 94 535 ± 168 671 ± 281 710 ± 198 817 ± 29 869 ± 19
Mn <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Fe 0.15 ± 0.10 0.21 ± 0.11 0.15 ± 0.11 0.92 ± 0.71 0.63 ± 0.37 0.15 ± 0.12 0.3 ± 0.03
Ni 0.09 ± 0.03 0.19 ± 0.07 0.19 ± 0.11 0.27 ± 0.16 0.25 ± 0.04 0.14 ± 0.04 0.18 ± 0.03
Cu 7±2 11 ± 3 11 ± 4 12 ± 2 13 ± 4 7±1 8.6 ± 0.3
Zn 0.07 ± 0.01 0.19 ± 0.1 0.09 ± 0.06 0.13 ± 0.07 0.14 ± 0.07 0.38 ± 0.06 0.37 ± 0.11
Br 2.6 ± 0.3 4.9 ± 0.3 5.7 ± 1.6 5.2 ± 0.4 6.9 ± 0.9 4.1 ± 0.5 4.7 ± 0.2
Sr 2.7 ± 0.5 4.7 ± 1.1 5.1 ± 2.7 4.7 ± 0.3 6.1 ± 1.4 4.7 ± 0.4 5.7 ± 0.2
Ba 0.91 ± 0.53 0.99 ± 0.05 0.93 ± 0.30 0.90 ± 0.30 1.1 ± 0.03 1.01 ± 0.78 2.07 ± 0.33
Pb 0.42 ± 0.03 0.08 ± 0.04 0.26 ± 0.19 0.21 ± 0.06 0.21 ± 0.13 0.94 ± 0.07 0.72 ± 0.02

Table 4
Results of energy dispersive X-ray spectroscopy (EDXS) performed on different COBA fractions. Three different selected area with the same dimension were considered and the
mean value (with corresponding standard deviation) for each element is reported.

Elements Elemental Concentration (%) in COBA samples

1400 mm 1000 mm 710 mm 500 mm 300 mm <300 mm COBA Mix
O 52 ± 1 57 ± 1 54 ± 1 58 ± 1 56.7 ± 0.1 58 ± 1 56 ± 1
Na 1.92 ± 0.13 1.79 ± 0.26 1.56 ± 0.08 1.80 ± 0.31 1.81 ± 0.08 1.89 ± 0.29 1.94 ± 0.27
Mg 2.19 ± 0.12 1.66 ± 0.28 1.33 ± 0.24 1.43 ± 0.16 1.65 ± 0.09 1.62 ± 0.18 1.74 ± 0.22
Al 4.12 ± 0.10 3.60 ± 0.32 3.24 ± 0.20 3.56 ± 0.14 3.25 ± 0.15 2.84 ± 0.26 3.39 ± 0.33
Si 12.7 ± 0.4 7.51 ± 0.39 5.54 ± 0.44 6.37 ± 0.19 5.70 ± 0.27 4.91 ± 0.10 7.07 ± 0.22
P 1.35 ± 0.26 2.08 ± 0.10 1.55 ± 0.18 1.79 ± 0.05 1.45 ± 0.25 1.09 ± 0.18 1.39 ± 0.26
S 1.18 ± 0.87 1.16 ± 0.05 1.29 ± 0.10 1.34 ± 0.22 1.44 ± 0.13 1.38 ± 0.27 1.58 ± 0.15
Cl 1.85 ± 0.21 2.20 ± 0.12 2.32 ± 0.24 2.48 ± 0.13 2.89 ± 0.25 3.07 ± 0.12 2.41 ± 0.22
K 1.27 ± 0.03 0.94 ± 0.14 0.67 ± 0.12 0.76 ± 0.07 0.67 ± 0.07 0.73 ± 0.12 0.76 ± 0.12
Ca 18.5 ± 0.6 18.1 ± 0.4 17.7 ± 0.3 19.8 ± 1.1 21.1 ± 0.2 21.5 ± 0.5 20.4 ± 0.8
Ti 0.78 ± 0.12 0.66 ± 0.11 0.60 ± 0.16 0.85 ± 0.09 0.94 ± 0.07 0.73 ± 0.08 0.77 ± 0.26
Fe 3.66 ± 0.75 3.04 ± 0.51 2.24 ± 0.24 2.32 ± 0.18 2.07 ± 0.02 1.85 ± 0.24 2.65 ± 0.23

of Cl, Zn, Cu, Ba, and Pb concentration by decreasing the COBA par-
ticle size fractions is found in the leachate solutions, in accord with
some already reported results for MIBA (Loginova et al., 2019). The
higher amount of leachable heavy metals in finest BA fraction
(<300 lm), compared to the other fractions, is explained by the
highest quantity of amorphous, which is generally found, in the
MIBA with the lowest particle size (Huber et al., 2019). In recent
literature (Guo et al., 2018), it is suggested that amorphous silica
is responsible of heavy metals adsorption, in SS co-combustion
with plants used to remove heavy metals from soil. In the present
case, the situation is slightly different: the highest amount of
amorphous is detected on largest fraction size (1400 lm), but with
a not linear behavior of leaching for some metals, such as Pb and
Cu (in Table 3, for example, it is shown that Pb concentration of
sample 1400 lm is higher than that of samples with lower grain
sizes, except sample <300 lm). As a consequence, this considera-
tion may suggest that amorphous is not rich in silica.
Chemical analysis of COBA (not reported here) shows that the
concentration of most abundant elements (as for example Ca, Fe,
K, Ti) is in accord with data reported in literature for MIBA (Dhir
OBE et al., 2017). Also heavy metals concentration (Pb, Zn, Cr)
results in the literature ranges reported for MIBA (Dhir OBE et al.,
2017). Data about COBA chemical composition of different frac-
tions (reported in Table 4) show that the total contents of Si and
Fe decrease with reducing the particle sizes. This behavior is in
agreement with the results already reported in literature (Huber
et al., 2019; Loginova et al., 2019). The decrease of Fe amount
may be attributed to the residue of stainless-steel wastes, which
is generally present as large fractions. Indeed, it is easily removed
during BA pre-treatment, involving separation of large dimension
wastes. While, the contents of other elements in various COBA size
fractions do not show significant differences.
Data series obtained by XRD and Rietveld refinement (Table 2)
and EDXS (Table 4) can be coupled to extract valuable information
about the composition of amorphous, which is commonly not eval-
uated in literature. The amount of each element is determined by
EDXS, while Rietveld analysis only accounts for elements that are
in crystalline phases. Obviously, because EDXS is not sensitive to
the crystalline phases, the elements amount must be always higher
(or comparable), compared to the corresponding values quantified
by XRD. Then, the difference among the reported data can be
attributed to the amount of the elements that may be in the amor-
phous. Fig. 2 shows the comparison of elements concentrations
evaluated by EDXS and XRD reporting the data concerning ele-
ments with a resulting difference higher than 2% considering EDXS
and XRD (except for P). The results about oxygen are not reported.
It is interesting to notice that P content evaluated by EDXS corre-
sponds to the expected amount of this element in the hydroxylap-
atite, i.e. in the crystalline state for COBA size fractions lower than
500 mm. Largest particle size fractions (till to 1400 mm) have higher
amount of P, compared to that found in the crystalline part (also if
this difference is not high), showing that P is probably contained
152 A. Assi et al. / Waste Management 116 (2020) 147–156

Results of the TXRF analysis and pH values of stabilized samples with various COBA fractions after the first (1) and second (2) month. Values are expressed as the average ± standard deviation of three TXRF measurements. Relative
also in the amorphous phase. The presence of P in the COBA may

3.8 ± 1.2

4.2 ± 0.6
4.0 ± 0.2
derive from co-combustion of sewage sludge in the incineration

65 ± 4
<LOD
<LOD

<LOD

<LOD

<LOD
plant (Adam et al., 2009).

Pb
Fig. 2 allows to conclude that, compared to the crystalline part,
amorphous phase appears to have relatively high content of Si, Al,

2.1 ± 0.7

1.6 ± 0.4

1.4 ± 0.2

1.5 ± 0.7
and Ca. Fe seems to be in the amorphous part, but mainly in high

<LOD
<LOD

<LOD

<LOD

<LOD
Ba size fractions. In particular, Ca shows the major difference among
its total amount (determined by EDXS) and the quantity found in
crystalline phases. In addition, it is extremely interesting to high-
1
4
3
1
1
1
1
1
1
±
±
±
±
±
±
±
±
±
light that an inverse correlation is established among the total
14
19
12
13
15
16
13
14
14
Sr

amount of crystalline phases containing Ca and the amount of

amorphous, both evaluated by XRD (see Fig. 2), using data reported
0.4
0.7
0.7
0.2
0.5
0.3
0.4
0.2
0.2
in Table 2. This strongly suggest that amorphous phase is extre-
±
±
±
±
±
±
±
±
±
mely rich in Ca, allowing to justify the reduced capability of heavy
6.3
4.6
4.1
2.8
4.4
3.2
3.7
3.1
3.9
Rb

metals adsorption of the amorphous (see the leaching data).

A published book (Dhir OBE et al., 2006), which summarizes the
197 ± 16
101 ± 11
96 ± 17

84 ± 11

data about SS ash, shows that this ash is mainly composed of cal-
81 ± 3
92 ± 6
89 ± 9
75 ± 9
88 ± 3

cium, aluminum, and silicon oxide. It shows that variability in SS

Br

ash composition over worldwide is high, with the highest coeffi-

cient of variation for CaO. This could justify the high amount of
0.080 ± 0.002

Ca in the amorphous phase found in COBA.

0.91 ± 0.27

1.06 ± 0.19
0.50 ± 0.37

1.07 ± 0.10
0.05 ± 0.01

0.05 ± 0.01

Based on these considerations it is possible to expect a poz-

13 ± 1

<LOD

zolanic behavior for COBA (Benassi et al., 2019). Moreover, Fig. 2

Zn

highlights that large grain sizes (1000–1400 mm) show a composi-

tion with increased SiO2 + Al2O3 species. This is extremely interest-
0.02
0.03
0.03
0.02
0.04

0.03

ing because Si and Al are the promoters of networking in glasses

0.1

(Bernasconi et al., 2018), with the possibility to develop silicate

0.44 ±

0.13 ±
0.05 ±
0.07 ±
0.08 ±
0.07 ±

0.07 ±
sensitivities for elements with * were calculated based on a calibration curve (see the experimental section). LOD – lower detection limit.

<LOD
<LOD

crystals or ceramic glass structures (by using thermal energy). Lit-

Cu

erature suggests the possibility to reuse also MIBA in the ceramics

production (due to significant quantities of SiO2 and Al2O3) (Dhir
0.39

0.18
0.14
0.11
0.17
0.21
0.10

0.09
0.10

OBE et al., 2017). However, the CaO amount found in COBA, which
±
±

±
±
±
±
±
±
±

is higher than that of several ceramic materials, may contribute to

0.67
0.28

0.41
0.23
0.39
0.28
0.27
0.32
0.20
Fe

lower the melting temperature of the mix, and possibly lead to

energy savings in the ceramics manufacturing process. These find-
ings suggest attractive reuses of COBA largest fractions (1000–14
240
780

230
220

360
150
300
60

90

00 mm), investigated in this work, that seems more suitable com-

±
±
±
±
±
±
±
±
±
2580
1970
1280
2850
1140
2590
1480
2940
1410

pared to MIBA for glass and ceramic manufacturing. However, to

Ca

propose a targeted recycle of this waste, the ternary phase diagram

of CaO-Al2O3-SiO2 for all the investigated COBA fractions is also
160

110
100

presented (Fig. 3). It allows to evaluate the total amount of calcium,

17

90
60

60
60
40
±
±
±
±
±

±
±
±
±

silicon, and aluminum oxides, on the basis of EDXS data reported in

267
571
244
480
450

520
340
530
350

Table 4, for all size fractions.

K

Each circle in ternary phase diagram in Fig. 3 represents a single

COBA particle size fraction. The sum of these three oxides in COBA
370
380

320
480

240
430
400

500
50

fractions ranges from 43 to 61% of the total oxide content. Results

±
±

±
±
±
±
±
±
±
3280
2610

3760
1860
3460
2310
3880
2180
2070
Elemental Concentration (mg/L)

obtained by this study are compared with data reported in litera-

Cl

ture considering 187 samples of MIBA from all over the world
(Dhir OBE et al., 2017). They show that for MIBA the sum of mean
110

190

110

values of these three oxides (CaO, SiO2, and Al2O3) counts for about
40

30
80

90

30
70
±
±
±
±
±
±
±
±
±

70% of the total oxide content. The calculated percentages of others

130
650
330
350
280
340
380
320
500

oxides are 2.3% for P2O5, 2.8% for Na2O, and 2.0% for MgO (Dhir OBE
S*

et al., 2017). Instead, the COBA samples revealed the highest con-
centrations of MgO (ranging from 2.2 to 3.6%) and P2O5 (ranging
18

11
17

12
1

9
2

5
8
±
±
±
±
±
±
±
±
±

from 2.5 to 4.8%). This result is reasonable due to the presence of

15
39
23
54
23
37
29
47
27
P*

high amounts of these elements in sewage sludge (Sommers

et al., 1976).
11.12

12.17

12.16

12.14
10.26
10.05
12.2

9.26

9.38

Due to the main MIBA reuse in the building sector, data about
pH

bottom ash composition are generally compared with cementi-

tious materials. For this reason, in Fig. 3 the area corresponding
(Month)

to pozzolanic and hydraulic materials behavior are highlighted.

Time

Single literature data points about MIBA (not reported here for
—
1
2
1
2
1
2
1
2

clarity) scatter between the highlighted regions of latent hydraulic

and the pozzolanic behaviors, due to the waste variability inciner-
Samples

ated by the different facilities. Moreover, MIBA has a generally

MIFA
Table 5

higher CaO content than pozzolanic materials, but below that of

1

the hydraulic Portland Cement (PC) (Dhir OBE et al., 2017). On

 A. Assi et al. / Waste Management 116 (2020) 147–156 153

P Fe
3 5
4
Amount (%)

Amount (%)
2
3
SEM SEM
1 2
XRD XRD
1
0 0
< 300 300 500 710 1000 1400 < 300 300 500 710 1000 1400
Parcles size [µm] Parcles size [μm]

Si Al
15 5
13 4

Amount (%)
10
Amount (%)

3
8 SEM SEM
2
5
XRD 1
XRD
3
0 0
< 300 300 500 710 1000 1400 < 300 300 500 710 1000 1400
Parcles size [μm] Parcles size [μm]

Total amount of crystalline

Ca 35
25
phases with Ca (%)
30
20 25
Amount (%)

15 20
SEM 15
10 10
5 XRD 5
0
0
55 60 65 70 75 80
< 300 300 500 710 1000 1400
Parcles size [μm] Amorphous amount (%)

Fig. 2. Amount of P, Fe, Si, Al, Ca (%) and the total amount of crystalline phases containing Ca (%) compared to the amorphous amount (%).

the contrary, COBA obtained from sewage sludge and municipal this appears to be more suitable for the lowest size fractions.
solid waste co-incineration process shows a better hydraulic Indeed, Fig. 3 shows that fraction with the largest size (1400 mm)
behavior compared to MIBA, due to the high amount of amorphous is more similar to MIBA mean data, and a decreasing of size frac-
reactive phases. These findings open the possibility to propose new tion corresponds to a better proximity to the region of hydraulic
attractive COBA applications, i.e Portland cement substitution, and behavior.
Other high added values applications could be investigated, on
the basis of the high amount of amorphous contained in this waste.
MIBA sample For this purpose, the reactivity of COBA was investigated by mixing
COBA mix SiO2 with fly ash derived from the same thermal valorization process
COBA 1400 µm (MIFA), with the aim to test their heavy metals immobilization
COBA 1000 µm capacity. The capability of BA to stabilize leachable Pb and Zn
was recently proved (Assi et al., 2020c). Because it is based on
COBA 500 µm
the use of wastes produced in the same location (BA and FA), it
COBA 710 µm
is suitable to be applied with low impact on incinerator plants,
COBA 300 µm
allowing to simplify the actual waste strategy management of
COBA <300 µm MIFA, which generally involves its transport and stabilization
treatment before its landfilling.
Table 5 shows that stabilized samples revealed a significant
decrease in heavy metals leaching, especially Pb and Zn (almost
one orders of magnitude), compared to MIFA, due to the stabiliza-
tion effect. Two months after the stabilization, Ba and Pb concen-
trations result to be lower than the instrument detection limit,
(PC)
and Cu concentration (that was higher than 7 ± 2 mg/L in the COBA
leaching solutions) always results lower than 0.10 ± 0.07 mg/L.
Thanks to the use of BA, the stabilization mechanism is attributed
CaO Al2O3 to a pozzolanic reaction, able to reduce heavy metals solubility. In
particular, as a result of the COBA characterization that shows the
Fig. 3. Ternary phase diagram of Municipal Incineration Bottom Ash (MIBA) – data high amount of glassy phase in this by-product (containing Si, Al,
about MIBA sample, pozzolanic, latent hydraulic, and hydraulic region adapted
and Ca), it is possible to suppose that the reaction of silica and/or
from (Dhir OBE et al., 2017), and COBA different fractions of this study. PC = Portland
Cement. alumina with calcium hydroxide, mainly derived from FGD resi-
154 A. Assi et al. / Waste Management 116 (2020) 147–156
dues, promotes the formation of an hydration product (C-S-H cal-
cium silicate hydrate and/or C-A-H calcium aluminate hydrate),
which is reported to be able to stabilize hazardous elements pre-
sent in MIFA. The proposed stabilization mechanism was recently
discussed using the same raw materials (the only difference is that
MIBA was used instead of COBA) (Assi et al., 2020c). A similar reac-
tion was already proposed in literature (Silva et al., 2019), but con-
sidering MIBA addition to cement, that contains Ca(OH)2.
Data reported in Table 5 reveals that when silica fume is used,
samples are better-stabilized (considering results obtained one
month after the process). This is probably due to the fact that silica
fume is completely amorphous. Although, COBA contains consider-
ably amounts of reactive amorphous phase, it is lower of almost
30–40% (depending on the considered size fraction), compared to
silica fume. Table 5 also shows that better stabilization results
(Pb and Zn leachability is reduced) are obtained if samples are aged
for two months. This is due to carbonation reactions. Indeed, as
already shown in several papers (Assi et al., 2019; Benassi et al.,
2017; Bosio et al., 2014), the use of by-products with high amount
of Ca(OH)2 allows to form calcium carbonate, able to reduce pH to
a more neutral level, promoting Pb and Zn stabilization (Assi et al.,
2019).
XRD patterns collected on stabilized samples (see Fig. S2 in sup-
porting information) reveal that detected phases correspond to
those already reported for samples obtained by using the proposed
stabilization technology (see for example (Rodella et al., 2017)
(Assi et al., 2020a,b,c)). In particular, as described and discussed
in the literature (Bosio et al., 2014) (Assi et al., 2019) the presence
of intense calcite peaks, coupled with the absence of calcium
hydroxide, strongly supports that carbonation reactions occurred.
Moreover, as already found (Assi et al., 2020a,b,c), C-S-H and C-
A-H phases cannot be completely crystallized, making difficult to
highlight pozzolanic reactions by XRD. The obtained stabilized
material shows characteristics very similar to compounds obtained
following the same treatments, but using MIBA and other by-
products (such as silica fume) for stabilization, allowing to suppose
that these materials may have promising applications as substitute
of some natural resources (Assi et al., 2020b, 2020a; Rodella et al.,
2016). In particular it was also shown that these materials result to
be biologically safe (Bilo et al., 2015; Guarienti et al., 2016, 2014),
suggesting that also the investigation of other characteristics, such
as the aquatic toxicity of the resulted inert, should be realized in
the next future.
In summary, data shown in Table 5 allows to conclude that,
despite of the difference on the amorphous content in the tested
fractions is not determinant, for this application, the reactive
phases present in COBA make it suitable for the heavy metals
stabilization.
5. Conclusions
Co-incineration of sewage sludge and municipal solid waste is a
well-established technology. However, few data are available in lit-
erature about the complete characterization of the obtained bot-
tom ash. In this work, a detailed analysis of the finest fractions
(<1500 mm) of BA produced from municipal solid waste co-
incineration with sewage sludge (COBA) is reported. From the min-
eralogical point of view, results show that the amount of amor-
phous phases varies with particle size fractions. In addition, the
coarsest fraction (>500 mm) is just slightly contaminated with
leachable heavy metals, while fraction with grain sizes >1000 mm
contains the highest amount of amorphous. COBA large grain sizes
(1000–1400 mm) fractions shows a composition with increased
SiO2 + Al2O3 species, more similar to that of MIBA. On the contrary,
COBA finest fractions, that present high CaO content, are expected
to have a better hydraulic behavior. Based on these results, COBA
recovery is proposed. In particular, the use for glass and ceramics
production is suggested for the largest investigates COBA fractions,
rich in Si, Ca, and Al oxides. Moreover, the high amount of amor-
phous reactive phase of this by-product suggests the possibility
to propose it for Portland cement substitution, with a decrease of
size fraction corresponding to an increased hydraulic behavior.
Finally, COBA reactivity opens the possibility to propose its use
for MIFA stabilization, to directly treat at the same location wastes
originated from the same incinerator plant.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This research was funded by Ministero dell’Ambiente e della Tutela
del Territorio e del Mare and supported by Regione Lombardia,
INSTM, CSMT and University of Brescia, project: Energy recovery
of waste sludge and their re-use as an alternative to some natural
resources, for the production of ‘‘Green” composites, RENDERING,
CUP: D71I18000170008. The activity was also partially financed
by FANGHI project, financed by Regione Lombardia, in the frame
of the call HUB Ricerca e Innovazione.
The authors acknowledge Prof. Marcello Gelfi for assistance
with the SEM technique and insightful discussion.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.wasman.2020.07.031.
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