Journal of Cleaner Production 245 (2020) 118779

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Zero-waste approach in municipal solid waste incineration: Reuse of

bottom ash to stabilize fly ash
Ahmad Assi a, Fabjola Bilo a, Alessandra Zanoletti a, Jessica Ponti b, Andrea Valsesia b,
Rita La Spina b, Annalisa Zacco a, Elza Bontempi a, *
a
INSTM and Chemistry for Technologies Laboratory, Department of Mechanical and Industrial Engineering, University of Brescia, Via Branze, 38, 25123,
Brescia, Italy
b
European Commission Joint Research Center (JRC), Via Enrico Fermi 2749, I - 21027, Ispra, VA, Italy

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

Article history: In this paper a simple method for all waste recovery through municipal solid waste incineration (MSWI)
Received 9 April 2019 is presented. For the first time, MSWI fly ash (FA) is treated using MSWI bottom ash (BA), which is
Received in revised form considered as a new urban mining source due to its pozzolanic characteristics. The proposed technology
25 September 2019
involves mixing these ashes with two other components: flue gas desulphurization residue and coal fly
Accepted 6 October 2019
Available online 7 October 2019
ash. Thermal annealing at a low temperature (120
C for 4 h) can also be performed, to accelerate some
reactions, but it is not necessary for stabilization. The efficacy of the process is demonstrated by the
Handling editor: Yutao Wang comparison of elemental concentrations in leaching solutions that are detected in the untreated ashes
and the obtained stabilized materials, which show the reduced solubility of leachable Zn and Pb (with
Keywords: respect to the starting MSWI FA). The chemical, morphological, and structural characterization of the
Municipal solid waste incineration obtained materials makes it possible to propose and discuss a stabilization mechanism, which was
Bottom ash attributed to carbonation and formation of calcium silicate hydrate (CeSeH). In particular, for the sta-
Fly ash bilized sample, X-ray Diffraction analysis confirmed the formation of calcite, whereas the sample
Pb
morphology shows some fibrils that may be due to amorphous CeSeH with a Ca/Si ratio that is slightly
Zn
smaller than 1.5.
Stabilization
Circular economy Because the proposed method employs wastes produced at the same location, it is reasonable to
conclude that the method may be directly applied to incinerator plants due to the simplification of the
MSWI FA waste management strategy, which generally involves its transport and stabilization treatment
before landfilling. Finally the saved carbon dioxide emissions and the economic benefits that are a result
of the new urban mining proposed approach have been evaluated for Europe. In particular the avoid of
MSWI FA landfilling was evaluated to save approximately 1.6 MV/day, and the saved carbon dioxide
emissions introduced into the atmosphere is approximately 960 kt/year.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Municipal solid waste (MSW) incineration is recognized to be a
fundamental step for sustainable waste management (Brunner and
Rechberger, 2015) when recycling is not possible. The two main
advantages of thermal treatment technologies are the reduction of
land utilization and pollution from landfills and the prevention of
* Corresponding author.
E-mail addresses: a.assi@unibs.it (A. Assi), fabjola.bilo@unibs.it (F. Bilo), a.
zanoletti002@unibs.it (A. Zanoletti), Jessica.PONTI@ec.europa.eu (J. Ponti), Andrea.
VALSESIA@ec.europa.eu (A. Valsesia), Rita.LA-SPINA@ec.europa.eu (R. La Spina),
annalisa.zacco@unibs.it (A. Zacco), elza.bontempi@unibs.it (E. Bontempi).
the environmental impact that is associated with fossil fuel use.
However, incineration has some byproducts including approxi-
mately 25e30% bottom ash (BA, or MSWI BA) and 1e3% fly ash (FA,
or MSWI FA), which are generated in municipal solid waste incin-
eration plants (Quina et al., 2018). These byproducts can contain
leachable heavy metals. Metal concentrations in MSWI BA and FA
depend on metal volatilization. MSWI BA mainly contains heavy
metals with low volatilization, which are present as carbonates. In
contrast, more volatile metals (such as Zn, Ni, Cu, As, Hg, Cr and Cd)
can be found in MSWI FA in a generally leachable form (Quina et al.,
2018).
As a consequence, BA residues from incineration are generally
considered a byproduct (Huber and Fellner, 2018) that is already

https://doi.org/10.1016/j.jclepro.2019.118779
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779
used, for example, during the substitution of quartz sand in cement
production (Li et al., 2018). In contrast, MSWI FA is managed as a
toxic waste and destined for landfilling. It is evident that MSWI FA
disposal turns out to be an irreversible material loss, which is in
contrast with circular economy principles.
Moreover, several other disadvantages make the avoidance of
landfilling among the main environmental priorities in Europe.
Currently, legislative development revealed an increase in landfill
costs and a decrease of available landfill sites (Husgafvel et al.,
2016). Additionally, long-term consequences on the environment
may be caused by MSWI FA landfilling, due to the presence of
leachable contaminants. Finally, it has an impact on climate change
due to generated greenhouse gas emissions.
Therefore, the adequate treatment of ashes and their reutiliza-
tion is preferred rather than landfilling.
To promote MSWI FA reuse, it is fundamental to decrease the
leaching toxicity of potentially heavy metals present in water sol-
uble phases. The stabilization of MSWI fly ash is proposed by
employing several methods, such as using chelating reagents,
washing, cement solidification, calcination, melting, and chemical
agent extraction (Zacco et al., 2014) and promoting its reuse.
However, several of the proposed stabilization technologies have
shortcomings (Zhu et al., 2018). For example, melting requires high
costs. Reagents consumption and the higher mass of treated resi-
dues are underlined as the main drawbacks of chemical reagent
stabilization. Even though some MSWI FA treatment technologies
were defined as zero-waste treatments (Diliberto et al., 2018), they
often require FA pretreatments, which are not suitable for treat-
ment at the incineration plants due to the use of some additional
processes and raw materials.
The present work proposes the use of all waste materials, to
stabilize MSWI FA. In particular, MSWI BA is used according to the
principles of “urban mining”.
It is known that MSWI BA has a complex inorganic composition.
BA is composed mainly of fine materials, synthetic ceramics and
stones, melt components, as well as small quantities of metallic
components.
The literature reports that silicate mineral phases with different
compositions can be found in MSWI BA. However, the glass phases
represent the main incineration products of MSWI BA, accounting
for 50% of its composition (Wei et al., 2011). Characterization of the
melt glass phase composition collected in various incineration fa-
cilities suggests the main representative components as the
following elements: silicon, calcium, aluminium, and some alkaline
and alkaline-earth metals (Youcai, 2016). Moreover, the identifi-
cation of complex silicates and oxides, which are present as pri-
mary melt components in bottom ash products, remain
undetermined (Wei et al., 2011). It is also reported (Loginova et al.,
2019; Wei et al., 2011) that the high amounts of melt glass phases
and different compounds (silicate-mineral and nonsilicate-mineral
phases, such as spinels and metallic inclusions) and calcium-rich
mineral phases (calcite and ettringite in the present work) ac-
count for a considerable proportion of the bottom ash.
Since the main constituents of BA are glass phases, the complex
silicates and oxides cannot be determined, though they are present
in BA as primary melt components (Youcai, 2016).
In the present work, MSWI BA is proposed to be used as heavy
metal stabilizer for MSWI FA. In particular, the presence of amor-
phous unstable phases and the consequent reactivity of BA, were
used as the characteristics to determine the choice of this waste.
Metals recovery from MSWI BA has already been recognized.
Therefore, this ash is classified as an urban mining target to regain
the metals (Tang et al., 2018, 2017). To the authors’ best knowledge,
this is the first time that MSWI BA residues are proposed for MSWI
FA stabilization due to their amorphous components.
In the present case, it is expected that dissolved amorphous
silica and alumina (derived from MSWI BA) in presence of calcium
ions (and in a highly alkaline environment) promote a pozzolanic
reaction with MSWI FA, leading to the formation of cementitious
compounds such as CeSeH and calcium aluminate hydrates (C-A-
H) (Ouhadi et al., 2014). Pozzolanic reaction can reduce the leaching
of heavy metals (Mostafa et al., 2001). In similar processes,
involving the MSWI FA stabilization, it was demonstrated that also
carbonation process can occur due to the calcium hydroxide pre-
sents in the used wastes (Bosio et al., 2014a; Assi et al., 2019),
producing pH reduction, with consequent heavy metals
mobilization.
After metal recovery, MSWI BA is already reused in building
applications, and the proposed technology may be considered a BA
recovery option competitive with existing methods. However, a
very recent paper about MSWI BA characterization (Loginova et al.,
2019) showed that the finest fraction of this byproduct (generally
less than 200 mm) contains a large amount of leachable heavy
metals. Therefore, the authors suggest separating this fraction, from
the rest of the MSWI BA to promote its safer reuse, for reasons other
than in the building industry. Additionally, crystalline silica oxides
(mainly quartz), which are non-reactive, are generally contained in
coarse particles (Loginova et al., 2019) appropriate for building
applications. For this reason, the proposed use of MSWI BA in this
work is devoted to the reuse the finest BA portion.
Fig. 1a reports the schema for the actual BA and FA management
strategy. FA is destined for landfilling. In contrast, BA is generally
reused for building applications after metal recovery. The residual
unused BA fraction is then landfilled. Fig. 1b shows an outline of the
new proposed treatment. It is fundamental to highlight that the
proposed process (described in detail in the experimental section)
uses all waste and byproducts and that the treatment does not need
thermal annealing. The only additional necessary pretreatment is
BA grinding. The proposed technology involves the use of the finest
BA fraction, and does not compete with building reuse. Then, the
new proposed technology is in agreement with the EU policy
approved and implemented for a circular economy that recom-
mends closing the material use loop by utilizing ‘waste’ for suitable
and sustainable applications (European Commission, 2017).
The idea to combine different waste typologies to take advan-
tage of their valuable components to stabilize pollutants is not new
(Bontempi, 2017a). In particular, regarding MSWI FA stabilization
and management, some very recent examples can be found in the
literature, for example, this waste can be mixed with silica fume
(Rodella et al., 2017), red mud (Li et al., 2019), electrolytic manga-
nese residues (Zhan et al., 2018), fishbone waste (Mu et al., 2018),
and biochemical effluents (Xu et al., 2018). The approach of using
sustainable materials (such as wastes) to minimize energy, mate-
rials and emissions for remediation was recently defined as Azure
Chemistry (Zanoletti et al., 2018).
2. Experimental section
2.1. Materials
Four ash typologies including Coal Fly Ash (CFA), Flue Gas
Desuphfurization (FGD), MSWI FA, and MSWI BA were used in this
work. Pulverized coal combustion produces CFA as a byproduct in
thermal power plants. Fly ashes, as fine particulate residues, are
removed by a dust-collection system from the combustion gases
before they are emitted into the atmosphere (Ramezanianpour,
2014). FGD residues are produced as a byproduct during the
removal of sulphur oxides from coal-burning power plants. In this
process, insoluble calcium sulphite and calcium sulphate solids are
formed because absorbed SO2 reacts with lime in scrubbing liquor
 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779
Fig. 1. Flow chart of the actual FA and BA management treatment (a) and the new proposed treatment strategy (b). The last (b) consists in the recycle of the finest BA fraction
(possibly after grinding), used as metals stabilizer.
(Pandey et al., 2005).
In the present work, CFA and FGD residues were collected from
Brescia pulverized coal thermal power plant. MSWI BA and FA were
provided by the Brescia municipal solid waste incinerator plant,
where three combustion lines work daily, and each reaches a ca-
pacity of 880 tons MSW ashes. The flue gas cleaning system consists
of dry scrubbers, fabric filters, an activated carbon injection system,
and a combination of selective non-catalytic and catalytic re-
ductions. Continuous flue gas emissions were monitored using a
device installed in the plant. Emission of dioxin and furan from the
plant ranges between 0.002 and 0.005 ng/Nm3 (Kalogirou, 2017),
which is defined according to European standards (Fontaine and
Vedrine, 2000). Moreover, MSWI FA was also used. MSWI BA
were screened before use to separate larger particles. The finest
MSWI BA portion was milled to reduce the particle dimensions to
less than 700 mm.
2.2. Sample preparation
Approximately 20 g of MSWI BA was added to a mixture of 200 g
of three powders including FA, FGD residues and CFA. The samples
3
have the following relative weight percentage: 65% FA, 20% FGD
and 15% CFA. Then, approximately 200 mL of ultrapure de-ionized
water, obtained from a Milli-Q purifier system (Millipore DirectQ-
5 TM, Millipore S.A. S., 67120, Molsheim, France), was added and
the mixture mixed for 20 min.
Then, each prepared sample was divided, one half was placed in
the oven for 4 h at 120
C (sample A), while the other half was dried
at room temperature (sample B). For analysis, the samples were
treated as follows.
2.2.1. Sample digestion
Aproximately, 0.25 g of each powder was placed in a Teflon
vessel and a mixture of 6 mL of HNO3 (65%), 2 mL of HCl (37%) and
2 mL of HF (48%) was added. The vessels were capped, and a CEM
SP-D microwave system was employed to perform the minerali-
zation process. The complete digestion was obtained using an
automatic procedure through the following five steps: 3 min at
160
C, 5 min at 180
C, 3 min at 200
C, 5 min at 205
C, and
10 min at 210
C. Finally, the digested mixtures were transferred to
50 mL flasks and MQ water was added to adjust the volumes.
4 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779
2.2.2. Leaching tests
Leaching tests on powders and stabilized samples were con-
ducted according to the CEN normative (CEN EN 12457-2) using the
procedure optimized and reported in (Bontempi et al., 2010; Bosio
et al., 2014a; Rodella et al., 2017). Approximately 20 g of each
specimen was mixed with 200 mL MQ water, with a ratio of 1:10 for
the leaching test and then mixed for 2 h using an agitator at room
temperature (Bosio et al., 2014b). Afterwards, 0.45 mm pore mem-
branes were employed to filter the samples. The pH of the filtrates
was measured using an 827 pH Lab Metrohm. The pH of the initial
powders was almost 12.
To verify the efficacy of the process, leaching solutions were
analysed one (1 M) and two months (2 M) after the stabilization
process. During ageing, samples were stored at room temperature
in the laboratory.
2.3. Characterization
The samples were characterized using the following techniques.
2.3.1. XRD
X-ray diffraction (XRD) is employed to structurally characterize
the as received powders and stabilized samples. A PANalytical
X’Pert PRO diffractometer equipped with a Cu Ka anode operating
at 40 kV and 40 mA current was used to perform the XRD mea-
surements on the powder samples. The instrument software was
used to analyse the obtained diffraction patterns.
2.3.2. SEM analysis
SEM analysis was performed using an FEI NOVA 600 Dual Beam
instrument (FEI, currently Thermofisher, Eindhoven, The
Netherlands). Measurements were performed at an acceleration
voltage ranging from 5 KeV to 25 KeV. Elemental analysis and the
surface images were acquired at a 0
tilting angle. An EDAX ana-
lyser (AMETEK BV, The Netherlands) with carbon sensitivity and
element spectral resolution was employed to perform the Energy-
Dispersive X-ray analysis (EDX-SEM). X-ray spectra and the
elemental analysis maps were acquired at 10 KeV. Afterwards, the
elemental maps were produced by scanning the intensity of the X-
rays in the scanned area focusing on the energies of the interested
elements.
2.3.3. TEM
The presence of nanoparticles was determined using a TEM (JEM
2100, JEOL-Italy) instrument running at an accelerating voltage of
120 kV. The powders were suspended in MQ water and diluted 1:2
(v/v). Then, 3 mL of prepared suspensions were deposited on ul-
trathin copper-Formvar carbon coated (200 mesh) grids (Tedpella
Inc.) and dried overnight in a desicator. The identification of ele-
ments present in the samples was performed under vacuum con-
ditions using Energy dispersive X-ray (EDX-TEM) analysis with an
X-Flash Detector 5030 (Brüker, Italy) coupled to a microscope.
2.3.4. TXRF
A S2 Picofox system from Bruker (Bruker AXS Microanalysis
GmbH, Berlin, Germany) equipped with Mo tube operating at 50 kV
and 750 mA and a Silicon Drift Detector (SDD) was employed for the
elemental chemical analysis of the digested and leachate solutions.
To obtain a hydrophobic surface, in the quartz reflectors was
deposited 10 mL of silicon solution in isopropanol (Serva Electro-
phoresis, Heidelberg, Germany). A stock solution of 1 g/L Ga in ni-
tric acid (Ga-ICP Standard Solution, Fluka, Sigma Aldrich) was used
as an internal standard to calculate the concentration of interested
analytes present in the sample. Samples were prepared by weight.
Approximately 0.010 g of 100 mg/L of Ga solution was added to the
prepared solutions to obtain a final concentration of 1 mg/L Ga.
Solutions were homogenized using a vortex shaker for 1 min at
2500 rpm. A 10 mL drop of sample was deposited in the centre of a
siliconized quartz sample carrier or plexiglass reflector for the
leachate or digested solution, respectively. Afterwards, the re-
flectors were dried on a hot plate at 50
C under a laminar hood and
the residues were measured. Three reflectors were prepared for
each sample specimen and irradiated for 600 s of live time. TXRF
spectra were analysed with the instrumental software using
routine deconvolution based on mono-element profiles to evaluate
the peak areas. The TXRF lower detection limits (LOD) evaluated
with similar experimental conditions are reported (Pasquali et al.,
2018). Chemical analysis of elements with atomic numbers less
than 19, such as C, O, and Na, is not possible by TXRF due to their
low fluorescence yield (Colombi et al., 2008). Additionally, Si
cannot be quantified, because the sample holder is made of quartz.
It is also known that lighter elements such as P, S and Cl may be
underestimated under these experimental conditions.
3. Results and discussion
3.1. Samples characterization
To understand the technological advantages of the proposed
process, all starting ashes and the obtained stabilized materials
were analysed. The amount of metals found in the ashes and
leaching solutions used in this work were assessed through
elemental chemical analysis using TXRF. Before analysis, the sam-
ples were prepared as reported in the experimental section.
Table 1 shows the TXRF analysis results from the digested
samples and their leaching solutions. These data highlight the
composition of the starting ashes and their soluble elements.
Table 1 shows that the MSWI BA and FA compositions are in
agreement with data in literature (Chou et al., 2009; Seniunaite and
Vasarevicius, 2017; Youcai, 2016). The essential constituents of
MSWI BA are Ca, Al, and Fe. The literature reports that amorphous
silica, which in more than 50% wt, is the main phase present in
MSWI BA (Li et al., 2018). Other elements, such as Zn, K, and S, are
found in relevant quantities. Generally, the presence of glass in the
waste is responsibile for the higher ratio of silicon in BA than in FA
(Youcai, 2016). Indeed, Al and Fe silicates, which have higher boiling
points, can generally be found in BA (Youcai, 2016). In contrast, the
calcium content is comparable in FA and BA, but in FA, its presence
is due to the addition of Ca(OH)2, which is used to adsorb acid gases
(such as SO2 and HCl), derived from the waste incineration process.
MSWI FA also contains high quantities of S, which is ascribed to the
lower boiling points and higher volatility of the sulphate phases
(Youcai, 2016). With respect to metals, non-volatile elements such
as Fe, Al, Cu, and Cr are present in the BA. Zn and Pb, which are
classified as moderately volatile metals, show significant differ-
ences between FA and BA according to data reported in the litera-
ture (Benassi et al., 2016; Youcai, 2016).
The data reported in Table 1 show that Al, S, K, Ca, and Fe are the
major elements in CFA (Si was not quantified, but it is reported that
CFA is extremely rich in Si) according to the literature
(Ramezanianpour, 2014), while FGD residues are characterized by
the presence of high amounts of S and Ca (due to their origin),
which is in good agreement with previous results (Bontempi et al.,
2010; Rodella et al., 2017). Leaching tests enhanced the lack of large
amounts of soluble heavy metals: quantitative analysis of the
leaching solutions of both CFA and FGD residues revealed that Cr,
Mn, Fe and Cu, if present, are in trace concentrations. Low Zn
amounts are found in the leaching solutions of these ashes, while
Pb was not detected.
In contrast, a leaching test performed on MSWI FA (Table 1)
 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779 5

showed different results.

0.04
0.28
0.04

0.34
200
1.8

0.2
Fig. 2 shows the TXRF spectra of digested (black) and leaching

50
50
2
solution (grey) from MSWI FA. Qualitative analysis identified the
following elements in both spectra: Al, P, K, Ca, Cl, Ba, Fe, Cr, Cu, Mn,

±
±
±
±
±

±
±
±
±

±
Leaching

(mg/L) Zn, Pb, Br, Sr, and Rb, while Ti and Ni were detected only in the

<LOD
<LOD

<LOD

<LOD
<LOD
12.68

1700
digested samples. By comparing the peak intensities, Fig. 2 high-

0.12
0.83
0.10

2.84
320
400
9.4

1.7
10
lights the high concentrations of Fe, Mn, Cu and Zn in the digested
Results from the TXRF analysis and pH values of digested and leachate solutions of MSWI FA, BA, CFA and FGD. Values are expressed as the average ± standard deviation of three TXRF measurements.

9900
samples, while Cl, Pb and Br amounts are significantly higher in the

3380

0.14
leaching solutions (see also the data reported in Table 1). The most
400

270

120
250

200
10

10
30

4
important data for the FA toxicity regard heavy metals leachability.
Table 1 shows that Pb and Zn concentrations, which are generally
±
±
±
±
±

±
±
±
±
±

±
±
the metals of major concern in waste leaching solutions, are
Digested

(mg/kg)

approximately 80 and 5 mg/L, respectively.

54400

38300
<LOD

<LOD

<LOD
1000

2000

2050
2920

2000
2.33

7.50
FGD

160
The high Cl contents in FA may be due to the incineration of
80

20

24
plastics such as PVC (Forestier and Libourel, 1998). Paint materials,
electronic devices, batteries and crystal glass are identified as the
2.47

1.06

0.03

0.01

0.14
0.03

0.18
0.40
2.3
10

30

main sources of Pb and its associated compounds in waste (Wei

et al., 2011). Furthermore, it is reported that high Cl in MSWI FA
±
±
±
±
±
±

±
±

±
±
affects the leachability of Pb, due to water-soluble salt (PbCl2)
Leaching

(mg/L)

formation.
<LOD

<LOD

<LOD

<LOD
12.01

5.71

1.74
30.6

0.21

0.27

0.21
0.20

3.43
0.76
170

450

In contrast, the MSWI BA sample leaching test showed that Cl,

Zn, and Pb concentrations are lower in comparison with MSWI FA.
For this waste, even though the amount of heavy metals is relatively
1160

1118
230

187

916

700

130

280
40
20

30

13

high (see the data about digested samples reported in Table 1), the
6

concentrations of all leachable metals are generally much less than

±
±
±
±
±
±
±
±
±
±
±

±
±

those in MSWI FA. It is reported that metals in MSWI BA usually

Digested

exist as different chemical combinations, even with additional non-

(mg/kg)

21500

<LOD

<LOD
5180

6360
4180

2440

2830

metal elements, principally concentrated in non-silicate minerals

2.30
CFA

690

900

280

710
60

11

58

(like spinels and metallic inclusions) (Wei et al., 2011). This was
observed for Zn2þ, Mn2þ, and Cr3þ. Because Pb has a large ionic
0.12
0.07
0.06
0.06
0.02
0.20

0.13
0.38
0.16

radius, it cannot be easily incorporated into mineral species

80

11
1
7

(Krauskopf, 1979). However, PbO was found to be incorporated in

spinel crystals (Wei et al., 2011).
±
±
±
±
±
±
±
±
±
±
±

±
±
±
Leaching

Stabilized samples revealed a significant decrease in heavy

(mg/L)

<LOD
12.15

metals leaching, independent of the treatment performed at high

0.42
0.16
0.68
1.65
0.11
3.19

2.24
1.57
1.10
670
110
270
40
5

temperatures, while Pb concentration is lower than LOD by TXRF

spectrometery (see Table 2), which is 0.002 mg/L (Pasquali et al.,
7400

9320
460
200
660
310

120

200

2018). The data reported in Table 2 show that Zn concentration is

20
80

80

20

almost one order of magnitude lower than in FA powder. In

contrast, the S concentration in stabilized samples is higher
±
±
±
±
±
±
±
±
±
±

compared with MSWI-FA because of the addition of FGD residues.

Digested

(mg/kg)

The results obtained after the first and second month of the sta-
79100

28820

<LOD
<LOD

<LOD
3960
1590
3700
8520

2420
4280

3740
1.10

320
700

200

bilization process did not show any significant difference in the

BA

elemental concentrations, suggesting that the stabilized materials

are stable over time. The results of the heavy metals leachability
0.07
0.06
0.16
0.16
0.11
830
150
280

0.4
0.3
10

10

allow us to conclude that Pb and Zn are reduced by at least 2 order

5

The amount of these elements is significantly underestimated.

of magnitude, in stabilized samples (see data collected on samples

±
±
±
±
±
±
±
±
±
±
±
±
±

2 M e Table 2) with respect to the starting MSWI fly ash. The lower

Leaching

solubility of these metals must be attributed to a stabilization effect

(mg/L)

10330

<LOD
12.38

1620
6850

by only considering the MSWI FA dilution (that represents more

0.22
0.38
0.26
1.41
4.98

14.3
210
5.0
30
60

80

than 50% of mass of all used ashes), the expected concentration of

these two metals in solution should be approximately one half with
1700
3100
100
900
400

170

200

respect to the original value.

10
10

20

50
3
4

It is fundamental to consider the pH of all starting powders and

final stabilized mixtures to determine the mechanism of heavy
±
±
±
±
±
±
±
±
±
±

±
±

metal stabilization. Indeed, pH is a key factor that affects heavy

MSWI-FA

Digested

(mg/kg)

metals leaching behaviours. It is extremely interesting to note that

13100

24610
69200

<LOD

<LOD
2000

1500

3750

8800

1030
1.53

210
270

710

200

all ashes have a starting pH higher than 12 (see Table 1). In contrast,
44

stabilized samples have a pH lower than 11 (see Table 2). Two

months after stabilization, sample A has a pH lower than 10.
pH

To investigate carbonate phase formation (eventually due to

carbonation process), XRD analysis was performed. XRD patterns of
Elements

initial powders are shown in Fig. 3a. The XRD pattern of the CFA
Table 1

sample was predominately composed of two main crystalline

Mn
Cla

Rb
Zn
Cu

Pb
Ba
Ca

Br
Fe
Cr
Pa

Sr
Sa

phases: quartz (SiO2) and mullite (Al4.75Si1.26O9.63), which is in

6 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779

Pulses

106

105 Br
Rb Mo
Sr Pb
104 Al P Cl K Ba Cr Fe
Si S Ar Ca Ti Mn Ni Cu Zn Ga Pb Br Rb Sr

103

102
2 4 6 8 10 12 14
- keV -
Fig. 2. Raw TXRF spectra of digested MSWI fly ash (black) and leaching solution (grey).

Table 2
Results of the TXRF analysis and pH values of stabilized samples at 120
C (A) and room temperature (B) after the first and second month. Values are expressed as the
average ± standard deviation of three TXRF measurements.

Elements Stabilized Sample-A (mg/L) Stabilized Sample-B (mg/L)

1st month 2nd month 1st month 2nd month

pH 10.66 9.73 10.77 10.14

Pa 20 ± 10 9 ± 5 10 ± 6 6 ± 1
Sa 120 ± 20 210 ± 80 40 ± 16 110 ± 10
Cla 8600 ± 2600 7200 ± 1200 8900 ± 2000 7400 ± 1400
K 760 ± 360 660 ± 250 740 ± 360 620 ± 260
Ca 3120 ± 1130 2600 ± 300 2750 ± 960 2500 ± 500
Cr 0.25 ± 0.07 0.56 ± 0.06 0.19 ± 0.11 0.31 ± 0.17
Mn 0.12 ± 0.08 0.10 ± 0.01 0.18 ± 0.07 0.06 ± 0.01
Fe 1.79 ± 1.56 0.073 ± 0.057 0.39 ± 0.09 0.10 ± 0.05
Zn 0.28 ± 0.08 0.032 ± 0.010 0.12 ± 0.07 0.08 ± 0.02
Br 113 ± 33 110 ± 40 90 ± 4 80 ± 4
Rb 3.3 ± 0.3 2.9 ± 0.2 2.92 ± 0.16 2.47 ± 0.32
Sr 11 ± 1 12 ± 2 12 ± 1 10.6 ± 0.3
Ba 1.70 ± 0.53 0.61 ± 0.44 1.44 ± 0.95 0.56 ± 0.32
Pb <LOD <LOD <LOD <LOD
a
The amount of these elements is significantly underestimated.

agreement with results obtained for CFA from the same origin re-
ported by (Bosio et al., 2014b). The FGD diffraction spectrum
identifies portlandite (Ca(OH)2) as the main mineral phase present
in this material, followed by calcium sulphite hemihydrate
(CaSO3*0.5H2O) and gypsum (CaSO4*2H2O).
MSWI FA mineralogy mostly consists of crystalline phases such
as calcium chloride hydroxide (CaClOH), sodium chloride (NaCl),
sylvine (KCl), calcite (CaCO3), anhydrite (CaSO4), and Ca(OH)2. The
XRD results revealed that MSWI FA are dominated by calcium
minerals, which is in close agreement with previously reported
data (Bayuseno and Schmahl, 2011; Bosio et al., 2014b; Dahl et al.,
2009).
The XRD pattern of MSWI BA is also reported in Fig. 3a. It reveals
that the predominant crystalline phases in BA are quartz (SiO2),
calcite (CaCO3), and ettringite [Ca6Al2(SO4)3(OH)12*26H2O]. Some
peaks that can be ascribed to potassium iron silicate
[(K,Fe)0.97Si1.03O4], and an aluminium calcium (magnesium) silicate
[Al2(Ca,Mg)3O12Si3] are also found.
Stabilized samples A and B (1 M and 2 M) showed similar XRD
patterns (see Fig. 3b). For all samples, the main calcite peak results
in the most intense peak in all the patterns. This is in agreement
with CaCO3 formation that is due to the carbonation reaction. The
XRD patterns of all the stabilized samples also show the presence of
NaCl, quartz (SiO2), calcium sulphite hemihydrate (CaSO3*0.5H2O),
and calcium sulphate (CaSO4).
The XRD patterns of the stabilized materials (see Fig. 3b) also
appear to show a large peak at approximately 28
(in 2Theta) that
can be attributed to calcium silicate hydrate (CeSeH) and is due to
a pozzolanic reaction; this can also be obtained by mixing amor-
phous silica and calcium hydroxide. These compounds can not be
completely crystallized, which makes it difficult to detect pozzo-
lanic reactions. However, calcium hydroxide and calcium chloride
hydroxide phases (present in the initial powders) were not found in
the stabilized samples, suggesting that the phases have reacted
such as with the silica and/or alumina contained in the MSWI BA.
The main differences in the XRD patterns reported in Fig. 3b can
be found at the beginning. In particular, two peaks at approximately
9.7 and 10.3
are observed. These peaks have different intensity
ratios compared to the two spectra reported in Fig. 3b. Thus, it is
reasonable to assume that they derived from two phases. The peak
 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779
Fig. 3. XRD patterns of initial powders (a) and a comparison between stabilized samples at 120
C (A) and room temperature (B) after the first (1 M) and second (2 M) month (b).
at approximately 9.7
(in 2Theta) can be attribute to stilbite
(Al9.34Na5.968Si26.14O72) an aluminosilicate that is already found in
fly and bottom ashes (Goodarzi, 2006; Tzanakos et al., 2014). The
peak at approximately 10.3
can be attributed to kozulite
(Na3[Mn4(Fe)]Si8O22(OH)2) a NaeMneFe silicate. From the XRD
data, it is possible to conclude that sample A contains a NaeMneFe
silicate, that does not appear to have changed over time (comparing
XRD patterns A 1 M and A 2 M collected 2 months after stabiliza-
tion). In contrast, sample B contains stilbite, with a contribution of
kozulite, that appears to be lower compared to sample A. However,
the main kozulite peak increased in the pattern collected two
months after stabilization (B 2 M), probably due to the lower re-
action kinetics with respect to sample A (that was thermally
treated). These silicates may be formed as a consequence of re-
actions occurring in the amorphous matrix. Changes that occurred
in the amorphous phases due to the stabilizing reactions, but did
not involve crystalline phases, cannot be excluded (Benassi et al.,
2017). Another difference in the XRD patterns of the stabilized
samples is the presence of gypsum (CaSO4*2H2O) in sample B (1 M
and 2 M). This phase was not detected in sample A (1 M and 2 M),
probably due to the thermal annealing.
Because it was already reported that pozzolanic reactions can
stabilize metals cations and reduce the leaching of heavy metals
(Mostafa et al., 2001), it is reasonable to suppose that the addition
of BA can benefit in FA stabilization. Additionally, sample A 2 M has
a lower pH compared to sample B 2 M, supporting the hypothesis of
sample carbonation and, in particular, suggesting an accelerated
carbonation reaction for this sample. Carbonation is probably also
responsible (with the pozzolanic reactions) for the absence of cal-
cium hydroxide and calcium chloride hydroxide phases in the
stabilized samples (Bontempi et al., 2010; Assi et al., 2019).
SEM images collected in backscattering mode on stabilized
7
sample B (imagine 8000x) and the map of elements identified by
EDX-SEM analysis are reported in Fig. 4. The presence of spherical
particles, containing Si (possibly silicates, or quartz) with diameters
ranging from 5 to 13 mm was observed. Qualitative EDX-SEM anal-
ysis identified the following elements: C, O, Na, Mg, Al, Si, P, S, Cl, K,
Ca, Ti, Fe and Zn. Pb identification by EDX-SEM was not possible in
either the starting MSWI FA (data not reported) or the stabilized
sample due to the low amount of this metal compared with the
total sample mass. It is worth noting that EDX-SEM maps show the
co-localization of Al with Si, while Fe and Zn appear to have an
independent distribution.
It is already known that CeSeH does not have a uniform dis-
tribution and appears in different morphologies, such as fibres,
flakes, honeycombs and tightly assembled grains (Li, 2011). In
particular, the calcium/silicon ratio was found to be a significant
factor affecting CeSeH morphologies at the nanoscale, showing
that with increasing calcium/silicon ratios, CeSeH changes from a
loose fibril-like morphology when this ratio is lower than approx-
imately 1, to dense granular-like particles when this ratio is higher
than approximately 1.5 (Hou et al., 2015).
TEM observations, coupled with chemical analysis of the ob-
tained images (see Fig. 5) performed at high magnification with
respect to SEM analysis, made it possible to analyse low samples
amounts. Fig. 5 reveals that stabilized sample B contained solid
spherical particles (Fig. 5a, b and c) ranging from approximately 0.1
to 0.5 mm in diameter. Some of these particles are similar to ag-
glomerates in an amorphous matrix (Fig. 5a). In the present case,
the sample morphology appears to include some fibrils (more
evident in Fig. 5b and c), which may be due to a CeSeH with a Ca/Si
ratio lower than 1.5 (Hou et al., 2015).
TEM-EDX maps, which are reported in Fig. 6(aee), are collected
from a single particle found in a small portion of B stabilized
8 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779

Fig. 4. SEM images collected in backscattering mode on stabilized sample B (imagine 8000x) and the map of Al, Si, Zn and Fe identified by EDX-SEM analysis.

Fig. 5. TEM images of stabilized sample B showing the presence of solid spherical particles resembled to agglomerates in an amorphous matrix (a) and in some fibrils (b and c).

sample. This area was chosen because an EDX Pb signal was
detected (Pb was not detectable by EDX-SEM). Table 3 reports the
results as the normalized mass (%) of the chemical analysis per-
formed in the area highlighted in Fig. 6a. The elements present at
higher concentrations are Si, Ca and Zn. This localized analysis
revealed the presence of Pb and highlighted its spatial distribution
(Fig. 6e). The chemical map shows that Pb is mostly co-localized in
proximity to silicon (Fig. 6b) and Zn (Fig. 6c), while Ca appears to be
highly co-localized on the bottom part of the particle (Fig. 6d). The
composition of the identified particles (Fig. 6a) is in good agree-
ment with the CeSeH phase formation. This result strongly sug-
gests the idea that Pb and Zn stabilization, which can be due to
carbonation effects (with pH reduction), is supported by pozzolanic
reactions during CeSeH formation.
Based on the data presented in Table 3 it is also possible to
evaluate probable atoms associations in the compounds detected in
the XRD patterns, in the selected area. For example, Cl, K and Na can
be justified considering that they can form KCl and NaCl (origi-
nating from MSWI FA). However, Na may also be incorporated in
the silicates.
Because Ca is also present, it is possible to evaluate the Ca/Si
atomic ratio, resulting in approximately 1.47. This value
corresponds to changes in the structural morphology of CeSeH
from fibril-like to granular-like particles (Hou et al., 2015). Due to
its composition, it obviously is not possible to exclude that these
particles may be a silicate phase (composition similar to kozulite,
found in the XRD pattern); however the presence of Ca (and the
corresponding Ca/Si atomic ratio according to the particle
morphology) supports the hypothesis that it may correspond to
CeSeH.
In summary, the idea to take advantage of the reactivity of
amorphous phases present in BA originate from its pozzolanic
properties. Owing to the high amounts of silica (and probably
alumina), BA can have pozzolanic or cementitious properties, but,
similar to cement, it must be finely ground to increase the specific
surface area and consequently the reactivity (Caprai et al., 2018).
The addition of FGD residues to stabilize the samples allows to add
calcium hydroxide to promote the pozzolanic reactions. Then, in
addition to the newly formed calcium carbonate, we can suppose
that the glass-derived products also influence the immobilization
of heavy metals.
In conclusion, the calcium hydroxide in the FGD residues has a
double function: carbonation (to form calcite) and pozzolanic re-
actions (to form hydration products).
 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779 9

Fig. 6. EDX maps of Si (b), Zn (c), Ca (d) and Pb (e) distribution in suspended stabilized sample at room temperature (sample B).

Table 3
Normalized atom mass percent (%) evaluated from the EDX-TEM map reported in Fig. 6.

Spectrum Elemental Concentration (%)

O Na Mg Si P S Cl K Ca Fe Zn Br Pb

Sample B 1.27 0.67 0.32 16.48 0.43 1.39 6.29 6.24 34.59 1.64 30.35 0.03 0.31

3.2. Reduced carbon footprint (CF) of the proposed urban mining
technology
Urban mining denotes the systematic reuse of materials with
anthropogenic origins from urban areas (Brunner, 2011). In the
present case, the proposed technology addresses the fact that
valuable materials are incorporated into waste, generated in
municipal solid waste incinerator plants. To promote urban mining
principles and to avoid high costs and low utility, it is fundamental
to define clear goals and strategies for suitable recycling. In this
frame, it is fundamental to evaluate avoided CO2 emissions ob-
tained by proposed urban mining processes. For example, it is re-
ported that metal recovery from BA results in a net saving of 166 kg
CO2-eq/t of BA (Boesch et al., 2014), which may be further increased
by metals recovery maximization. Indeed, the recovery efficiency of
ferrous metals is nearly 80% of the metal fed into the furnace, while
aluminium recovery reaches aproximately 30% and can be
improved. Indeed, urban mining is not only focused on materials
but has the aim to represent a more profound and extensive
approach that comprises energy (and emissions) involved in min-
ing. For example, proposed technologies do not often consider the
place where recycling processes occur (Brunner, 2011). Locating
urban mining processes close to the sources of recovered materials
leads to significant benefits. Indeed, waste transportation (and
eventually raw materials needed for mining) requires energy and
produces carbon dioxide emissions. In the present case, the pro-
posed approach involves waste treatment at the same location
where waste is produced, with advantages in terms of reduced
carbon emissions. Considering the current MSWI FA management
option (see Fig. 1a), avoided CO2 emissions due to MSWI FA land-
filling can be estimated. Indeed, MSWI FA is generally transported
to disposal sites by articulated trucks, producing additional CO2
emissions. Finally, a solidification treatment, using cement (or an
alternative binder) is commonly performed before MSWI FA land-
filling. The solidification also requires the use of enough water to
ensure that hydration reactions will take place for cement binding.
Table 4 shows the avoided CO2 emissions from energy save and
material recovery for 1 t of MSWI FA, when landfilling is neglected,
Table 4
Avoided CO2 emissions from energy savings and material recovery for MSWI FA
based on the method proposed in Fig. 1b. The MSWI BA grinding CO2 emissions are
negative because CO2 is produced and not avoided in this case.
Parameters [kg CO2-eq/t FA]
MSWI FA transport (for 600 km) 36.24
MSWI FA solidification 285.6
Carbonation reactions (new technology) 55
MSWI BA landfilling 0.8
MSWI BA grinding 1.32
Total avoided emissions 376.32
10 A. Assi et al. / Journal of Cleaner Production 245 (2020) 118779
according to the new proposed strategy (shown in Fig. 1b). These
data have been calculated considering very conservative condi-
tions. Considering a mean distance of approxiamtely 600 km, for
example the distance from north Italian incinerator plants to
German landfilling sites, it is possible to estimate that MSWI FA
transport produces at least 36.24 kg CO2-eq/t FA (Granta, 2016). The
solidification treatment before landfilling can be performed using
different amounts of cement. The addition of cement (and addi-
tives) typically increases the mass of waste approxiamtely 50% of
the residue dry weight (European Commission, 2006). To account
for the lower CO2 emitting conditions, a treatment involving the
use of only 30% cement, with respect to the MSWI FA mass, is
considered. In this case, the amount of saved CO2 emissions is 285.6
CO2-eq/t FA (Granta, 2016).
Because the proposed stabilization mechanism involves
carbonation, atmospheric CO2 is also trapped by reactions occur-
ring during carbonation. For similar treatments, involving the use
of amorphous silica to entrap heavy metals, it was shown that
approxiamtely 100 kg of CO2 can be captured from 1 t of FA (Bosio
et al., 2014a). However, to be conservative, the CO2 sequestration
quantity for MSWI FA (not accounting for the addition of other
ashes containing calcium oxide phases) of approxiamtely 55 kg/t FA
is considered (Cue
llar-Franca and Azapagic, 2015). This is a mean
value reported in recent literature for fly ash carbon dioxide
capture.
The saved CO2 emissions must also account for MSWI BA re-
covery and pretreatment. Indeed, although a large amount of this
waste is already used, residues derived from BA are still destined for
landfilling (Boesch et al., 2014), such as after metals recovery
(Fig. 1a).
MSWI BA recovery allows the saving of 6 kg of CO2-eq/t BA,
while MSWI BA grinding produces approxiamtely 9.94 kg of CO2-
eq/t BA (Granta, 2016). To calculate the carbon dioxide emissions
for grinding under conservative conditions were selected. An in-
dustrial apparatus reducing the material (as for example calcite)
dimensions from 1 mm to 100 mm was considered. However, it is
reasonable to suppose that the hardness of the finest part of MSWI
BA is lower than that of pure calcite and that the starting BA fine
particle dimensions are less than 1 mm. Therefore, the CO2-eq
emissions due to grinding are expected to be lower, than the
calculated value. Because the amount of BA necessary for stabili-
zation is approxiamtely 13% with respect to the MSWI FA amount,
the corresponding CO2 emissions are calculated with respect to kg
CO2-eq/t FA and these results are reported in Table 4.
Considering very conservative conditions, we can conclude, that
the proposed process allows one to globally save at least 376.32 kg
CO2-eq/t FA. It is reported that roughly more than 7000 tons of
MSWI FA are produced in Europe every day (European Union,
2016). As a consequence the CO2 emissions that may be avoided
by MSWI FA stabilization using the new proposed technology are
expected to be approximately 960 kt CO2 eq/year in Europe.
After stabilization, the resulting inert material can be reused as a
secondary material (for example, as a substitute for calcite and talc).
This has been shown for similar technologies involving the use of
other waste sources for stabilization (Benassi et al., 2015; Bosio
et al., 2014c; Ponsot et al., 2015; Rodella et al., 2016; Zacco et al.,
2012). These materials can be transformed through suitable and
sustainable ways to stimulate industrial symbiosis, by converting
one industry’s byproduct into another industry’s raw material, and
preserve natural resources. For example, carbon dioxide emissions
from calcite and talc primary production correspond to 16 kg/t and
611 kg/t, respectively (Granta, 2016). The use of stabilized material
instead of natural resources can allow a saving of additional CO2
emissions, in terms of raw materials substitution (Bontempi,
2017b).
It is also possible to evaluate the economic advantages that may
be obtained by applying the new proposed stabilization technique.
In particular, from an economic point of view, the new technology
offers the possibility to save on average approximately 230 V/t FA in
Europe alone, which is required for MSWI FA landfilling (Diliberto
et al., 2018). This cost accounts not only for disposal but also the
transport and stabilization of FA before landfilling. Considering
European MSWI FA production, the total amount corresponds to
approxiamately 1.6 MV/day!
Finally, considering the legislative framework, the possibility to
make the proposed treatment at incineration plants makes it
possible to avoid waste at source: the new proposed technology
improves the efficiency of MSWI, avoids wastes (BA and FA) pro-
duced at incinerator plants, and offers the basis to promote new
business models for the stabilized material, that may be sold as a
filler (to save calcite and talc natural resources).
4. Conclusions
In the present study a new urban mining strategy is proposed
for MSWI FA stabilization, based on the reuse of MSWI BA due to its
content of amorphous phases. CFA and FGD residues were also
used. The stabilization mechanism can be explained based on the
ashes and final products characterization results. The pH evalua-
tion, XRD and TEM analysis concluded that carbonation and
pozzolanic reactions occurred, promoting stabilization of heavy
metals (Pb and Zn).
The simplicity of the proposed technology, which requires only
the mixing of ashes from the same origin, makes it truely suitable to
be applied directly to thermal treatment plants. Consequently, the
new proposed strategy for MSWI waste management can be
actually considered a zero-waste approach due to production of
inert materials.Energy and materials recovery from waste-to-
energy plants provides environmental advantages as it saves vir-
gin materials, returns waste materials to the economic cycle and
avoids the landfilling of incineration residues. It allows a saving of
approximately 2630 t CO2-eq/day.
The versatility of the process, which occurs at room temperature
and requires the use of wastes produced at the same location, has
the following benefits: (1) avoids landfilling of MSWI FA (and some
BA residues); (2) avoids the transport of waste to another area for
stabilization; (3) saves non renewable resources and, consequently,
safeguards them; (4) saves CO2 emission and sequestrates carbon
dioxide due to carbonation reactions with good actions on climate
change; (5) produces materials that may be reused as a filler and (6)
opens new perspectives markets and business models.
Acknowledgements
This work was performed under the framework of the following
project: Energy recovery of waste sludge and their re-use as an
alternative to some natural resources, for the production of "Green"
composites, RENDERING, financed by Ministero dell’Ambiente e
della Tutela del Territorio e del Mare, and supported by the Uni-
versity of Brescia, CSMT, INSTM and Regione Lombardia. The
research leading to these findings resulted from access to the
Nanobiotechnology Laboratory under the Framework for open ac-
cess to the Joint Research Centre Research Infrastructures of the
European Commission. The authors thank Douglas Gilliland, Pascal
Colpo, Giulio Cotogno, Giacomo Ceccone, and Robin Bruno Capo-
maccio for their useful comments on the data analysis.
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