Chemosphere 182 (2017) 76e84

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Chemosphere
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Reductive solidification/stabilization of chromate in municipal solid

waste incineration fly ash by ascorbic acid and blast furnace slag
Xian Zhou a, Min Zhou a, Xian Wu b, Yi Han a, Junjun Geng a, Teng Wang a, Sha Wan a,
Haobo Hou a, *
a
School of Resource and Environmental Science, Wuhan University, Wuhan, Hubei, 430072, PR China
b
School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Ascorbic acid was used as S/S reagent

for Cr reduction in MWSI fly ash.

The leaching concentration of Cr is
strongly dependent on the pH of the
solution.

The lowest leaching concentrations
of Cr was in the pH range of 6e8.

C-S-H and ettringite formed by
GGBFS can hold Zn and Cr in its
crystal structure.

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

Article history: Fly ash is a hazardous byproduct of municipal solid waste incineration (MSWI). Cementitious material
Received 2 January 2017 that is based on ground-granulated blast furnace slag (GGBFS) has been tested and proposed as a binder
Received in revised form to stabilize Pb, Cd, and Zn in MSWI fly ash (FA). Cr, however, still easily leaches from MSWI FA.
8 April 2017
Different reagents, such as ascorbic acid (VC), NaAlO2, and trisodium salt nonahydrate, were investi-
Accepted 16 April 2017
Available online 21 April 2017
gated as potential Cr stabilizers. The results of the toxicity characteristic leaching procedure (TCLP)
showed that VC significantly improved the stabilization of Cr via the reduction of Cr(VI) to Cr(III). VC,
Handling Editor: X. Cao however, could interfere with the hydration process. Most available Cr was transformed into stable Cr
forms at the optimum VC content of 2 wt%. Cr leaching was strongly pH dependent and could be rep-
Keywords: resented by a quintic polynomial model. The results of X-ray diffraction and scanning electron
Municipal solid waste incineration fly ash microscopy-energy dispersive analysis revealed that hollow spheres in raw FA were partially filled with
Chromium hydration products, resulting in the dense and homogeneous microstructure of the solidified samples.
Stabilization The crystal structures of CeSeH and ettringite retained Zn and Cr ions. In summary, GGBFS-based
Specification distribution
cementitious material with the low addition of 2 wt% VC effectively immobilizes Cr-bearing MSWI FA.
pH-dependence test
© 2017 Published by Elsevier Ltd.

1. Introduction

Incineration, a significant component of the municipal solid

* Corresponding author.
waste management program, can regain energy from waste and
E-mail address: houhb@whu.edu.cn (H. Hou).

http://dx.doi.org/10.1016/j.chemosphere.2017.04.072
0045-6535/© 2017 Published by Elsevier Ltd.
 X. Zhou et al. / Chemosphere 182 (2017) 76e84
simultaneously reduce the amount of waste by up to 90% in volume
and 70% in weight (Abanades et al., 2005; Zhang et al., 2008).
Municipal solid waste incineration (MSWI) produces fly ash (FA),
which accounts for approximately 3e5 wt.% of the original waste
amount. FA contains various hazardous materials, such as high
levels of Pb, Cr, Cd, Ni, Hg, and As metals; soluble salts, particularly
leachable alkali chlorides; and persistent organic pollutants,
including polychlorinated dibenzo-p-dioxins and dibenzofurans
(Colangelo et al., 2012; Diaz-Loya et al., 2012). Therefore, FA is
designated as hazardous waste in many countries and must be
treated to solidify or stabilize heavy metals prior to disposal in
hazardous-waste landfills (Tang et al., 2013).
Methods to treat MSWI FA are grouped into the three following
classes (Wang et al., 2015; Ye et al., 2016): (i) separation, which
includes washing (Wang et al., 2016), leaching (Komonweeraket
et al., 2015), bioextraction (Ishigaki et al., 2005; Nam et al., 2005),
and electrochemical processes (Pedersen et al., 2003; Lima et al.,
2010); (ii) thermal methods, which include sintering (Chou et al.,
2009b), melting (Nowak et al., 2010; Okada and Tomikawa, 2013),
vitrification (Wang et al., 2008), and evaporation (Jakob et al.,
1995); and (iii) solidification/stabilization (S/S), which include
chemical stabilization, chemical fixation and solidification, and
geopolymer technology (Zacco et al., 2014). Chemical stabilization
processes utilize chemical agents, such as sulfides, phosphate (Rani
et al., 2008), and carbonates, to transform residual heavy metals
into insoluble mineral species. Chemical fixation and solidification
processes involve mixing MSWI FA with binders (Li et al., 2014),
such as cement-based materials, colloidal silica (Bontempi et al.,
2010), and bitumen, to produce a monolithic solid with structural
integrity and long-term stability. Geopolymers are inorganic
binders that are obtained by activating aluminosilicate solids with
highly concentrated alkaline solution (Lancellotti et al., 2010).
Geopolymer binders are similar to cement binders, which also
reduce heavy metal mobility. S/S procedures are inexpensive, easy,
and ensures the easy handling and geotechnical stability of mate-
rial mixtures in a landfill (Benassi et al., 2016). Therefore, MSWI FA
is commonly treated via S/S procedures.
Research has mainly focused on the leaching of the cationic
heavy metals Pb, Cd, and Zn and stabilization methods for MSWI FA
with respect to the leaching of these metals. Nevertheless, prob-
lems that are related to the leaching of heavy metal oxyanions, such
as Cr, remain unresolved. Cr is probably one of the most critical
elements in MSWI FA leachate (Astrup et al., 2005).
Cr is a redox-sensitive element during leaching (Leisinger et al.,
2014). Therefore, the leaching behavior of Cr is highly dependent on
its redox state in MSWI FA (He and Traina, 2005; Cornelis et al.,
2008). Many researchers have reported that Cr(VI) is more solu-
ble and more toxic than Cr(III). Fe(II) is an important reductant of
Cr(VI) in natural environments (Patterson et al., 1997) but exhibits
low reduction capacity (<20%) under alkaline conditions (He and
Traina, 2005). Xu et al. have found that the reduction of Cr(VI) by
ascorbic acid (VC) can occur in alkaline solution (Xu et al., 2004).
However, there are few reports on the availability of VC for the
stabilization/solidification of heavy metals in MSWI FA that con-
tains both cations and oxyanions.
Chemical inclusion is an alternative method to stabilize Cr(VI).
MSWI FA belongs to the system of CaOeCaCl2eCaSO4eSiO2eAl2O3,
which is rich in sulfur and chlorine. Cr(VI) leaching concentrations
can decrease via hydration with a binder and via isomorphic sub-
stitution (Pollmann and Auer, 2012), in which CrO2 4replaces
SO2 4or/and Cl and is incorporated into newly formed pozzo-
lanic products, such as Ca6Al2(OH)12(SO4)3$26H2O (ettringite or
AFt) (Leisinger et al., 2010; Shao et al., 2016); Ca4A-
l2(OH)12SO4$6H2O (monosulfoaluminate or SO4-AFm) (Leisinger
et al., 2012); and Ca4Al2(OH)12 Cl2$4H2O (Friedel’s salt or
77
CleAFm) (Dai et al., 2009; Shao et al., 2013). The formation of solid
solutions can decrease the solubility of solids. Ettringite and
monosulfoaluminate are less effective in MSWI FA given the very
narrow pH stability domain for chromate ettringite (Perkins and
Palmer, 2000; Geelhoed et al., 2002; Chrysochoou and Dermatas,
2006) and the metastability of monosulfoaluminate under 25  C
and 1 bar pressure (Matschei et al., 2007). Friedel’s salt exhibits a
strong fixing capacity for Zn and Pb (Qian et al., 2006). Qian found
that the optimal proportions for the Friedel matrix in MSWI FA are
80% MSWI FA and 20% aluminous cement (Qian et al., 2009), which
increases the volume of the final mass. Nevertheless, current
published reports on the large-scale application of Friedel’s salt to
stabilize Cr in MSWI FA are unavailable.
The present study aims to 1) investigate the feasibility and
effectiveness of the Friedel matrix in stabilizing/solidifying MSWI
FA with ground-granulated blast furnace slag (GGBFS) as the main
raw material and a low addition of cement and VC; and 2) discuss
the phase transformation and stable mechanism of Cr in the so-
lidified product. The results of this study provide a useful basis for
the highly efficient and safe utilization of VC and blast furnace slag
(BFS) from MSWI.
2. Material and methods
2.1. Materials
MSWI FA was obtained from a bag filter of Likeng Waste Incin-
eration Power Plant in Guangzhou, China. GGBFS (S95) was pro-
vided by Wuxin Materials Company in Wuhan, China. Class P II 42.5
ordinary Portland cement (OPC) was procured from Jianfeng
Cement Corporation (Jinhua, China). The major elements of the raw
materials were identified via X-ray fluorescence spectrometry
(Bruker AXS, GmbH, Germany). To measure the trace element
content of the raw materials, samples were digested with a com-
bination of hydrochloric, nitric, and hydrofluoric acids. The digested
samples were then analyzed via inductively coupled plasma-atomic
emission spectrometry (ICP-AES) in accordance with ASTM Stan-
dard Method D6357-00a (Shao et al., 2016). As shown in Table 1,
oxides, including CaO, SiO2, and Al2O3, account for more than 40% of
the total mass of the MSWI FA. Although this product composition
indicates the pozzolanic activity of MSWI FA, the large amount of
chloride and sulfate salts could negatively affect the solidified
product (Chen et al., 2012). BFS had a similar CaO content as MSWI
FA and a considerably higher Al2O3 and SiO2 content than MSWI FA.
Therefore, BFS will release a high content of alumina to form AFm
phases, which will lead to relatively high early strength. OPC as a
source of silicon will further promote strength development.
2.2. Solidification/stabilization process
MSWI FA samples were homogenized with a cement paste
mixer. Then, subsamples were obtained by quartering. As shown in
Table 2, MSWI FA subsamples were then mixed with various
combinations of binders and chemical stabilizers, including BFS,
OPC, VC, NaAlO2, and trisodium salt nonahydrate (TMT). The liq-
uidesolid ratio was fixed at 0.18. VC, NaAlO2, and TMT were dis-
solved prior to addition to the mixtures. The mixtures were fully
mixed in cement paste mixers and molded in cylinder metallic
molds (50 mm diameter  50 mm length). The mixtures in the
molds were stirred for 15 min and compacted at 38 kN. Subse-
quently, the mixtures were demolded, covered with plastic films,
and cured at 25  C (95% relative humidity) for 28 days. The solids
were subjected to compressive strength and leaching tests after 3,
14, and 28 days of curing. Given the very low mixing amounts of
BFS and OPC and low contents of trace metals, the exogenous
78 X. Zhou et al. / Chemosphere 182 (2017) 76e84

Table 1 leaching.
Chemical compositions of the raw materials.

Major Mass percentage Trace Concentration (mg/kg) 2.5. pH-dependence test

components (wt%) elements

MSWI FA GGBFS OPC MSWI FA GGBFS OPC This test aimed to characterize the behavior of MSWI FA with
and without treatment. In the test, pH was considered as a relevant
Na2O 10.03 0.35 0.34 Cd 231.21 21.67 106.34
MgO 1.72 8.10 1.62 Cr 2793.12 79.34 93.76 factor that controls leachability. Raw MSWI FA and solidified
Al2O3 2.36 16.69 5.37 Cu 689.65 135.46 83.94 sample BOVC2 were ground in an agate mortar until the samples
SiO2 7.13 32.18 21.54 Pb 1397.29 80.34 65.13 could pass through a 45-mm sieve. The sieved samples were then
P2O5 1.10 0.06 0.01 Zn 6917.43 17.36 124.65
divided into 14 equal 1-g portions. To obtain target Hþ ions,
SO3 10.37 2.77 0.90
Cl 19.88 0.08 0.02 deionized water was added to each solid in combination with HNO3
K2O 6.12 0.56 0.27 or NaOH with the addition of 16.5, 15, 13.5, 12, 10.5, 9, 7.5, 6, 4.5, 3,
CaO 31.93 37.91 61.54 1.5, 0, 1.5, and 3 mmol/g FA. A negative value refers to OH ion
Fe2O3 1.39 0.29 3.91 addition (NaOH solutions). All subsamples were sealed in suitable
polypropylene vessels at a constant liquidesolid mass ratio of 10.
The system was stirred for 48 h at room temperature. At the end
Table 2 of the tests, stirring was suspended for at least 30 min and leachate
Mixture proportions of different samples (by weight).
pH was measured. The supernatant was collected and filtered
Sample MSWI FA GGBFS OPC NaAlO2 TMT VC water through a 0.45-mm membrane filter and then acidified with a drop
OPC 90 10 18 of concentrated HNO3 (ultrapure) to pH < 2.
GGBFS 90 10 18
BFSOPC 90 8.5 1.5 18 2.6. Structural and morphological characterization
BOSM 88.5 8.5 1.5 1.5 18
BOTMT 89.5 8.5 1.5 0.5 18
BOVC1 88 8.5 1.5 1 18
The mineralogical characteristics of the raw materials and the S/
BOVC2 88 8.5 1.5 2 18 S solids were analyzed via X-ray diffraction (XRD). The morpho-
BOVC3 88 8.5 1.5 3 18 logical analyses of the solids were conducted by scanning electron
BOVC4 88 8.5 1.5 4 18 microscopy (SEM, JSM-5610LV, Electron Optics Laboratory, Japan)
after coating with Au for 10 min.
fraction of heavy metals that were produced by BFS and OPC were
3. Results and discussion
negligible compared with the raw MSWI FA.

3.1. Leachability of heavy metals in raw MSWI FA

2.3. Leaching test
Toxicity characteristic leaching procedure (TCLP) tests (Chou
et al., 2009a) were conducted by mixing solid samples with TCLP
leachate in capped polypropylene bottles. As all samples were
highly alkaline materials, 1 L of 0.1 M acetic solution (pH 2.88) was
selected at a liquidesolid mass ratio of 20. The extraction vessels
were rotated at 30 rpm for 18 h. After mixing, the leachate was
filtered through a 0.45-mm membrane filter and analyzed for total
dissolved Cr and Cr(VI).
To investigate the effects of pH on the leaching mechanisms of
trace metals, leaching tests for MSWI FA were performed in natural
(original pH of the leachate) and basic solutions (NaOH solutions,
pH ¼ 12).
The concentrations of total dissolved Cr in the filtrates were
measured by ICP-AES (Perkin-Elmer Optima 4300 DV). Cr(VI) con-
centrations were analyzed using an ultraviolet spectrophotometer
(Lambda35 UV/VIS Spectrometer, Perkin-Elmer, USA) in accordance
with the diphenylcarbohydrazide spectrophotometric method
(Zhao et al., 2015).
2.4. Sequential extraction of heavy metals
The chemical speciation of heavy metals in MSWI FA samples
and solidification/stabilization products were analyzed via
sequential extraction in accordance with a modified Tessier’s
method (Huang et al., 2007) for six metal categories: (I) water
soluble ions, (II) exchangeable fraction, (III) carbonate-bound
fraction, (IV) reducible phase, (V) organic matter- or sulfide-
bound fraction, and (VI) residual fraction. Each sample had five
replicates. The first three frictions (I þ II þ III) are available under
neutral conditions. Frictions IV and V are potentially available un-
der reducing conditions. The residual fraction (VI) is inactivated for
Table 3 shows the TCLP test data for the raw MSWI FA. As can be
seen from Table 3, 6% Pb, 37% Cr, 78% Cd, and 47% Zn could be
leached from FA. Moreover, hexavalent Cr was present in leachate
solutions. These results implied that Cd, Cr, and Zn are the three
dominant heavy metal contaminants in the MSWI FA and will be
released into the environment if they come in contact with acidic
liquids, such as landfill leachate (Chen et al., 2009). The distribu-
tions of heavy metal species in the raw MSWI FA are shown in Fig. 1.
The chief Pb fractions were FeeMn oxides and sulfides. In raw
MSWI FA, the predominant Cd and Zn fractions were the carbonate
fraction. The experimental results revealed that heavy metals in the
first three fractions (water soluble þ exchangeable þ carbonates)
were easily leached out in the TCLP test. The comparison of
sequential extraction and the TCLP test of raw MSWI FA indicated
that Cr(VI) is the most available Cr species.
As can be seen in Table 1, OPC has a relatively high Cd concen-
tration. Thus, the TCLP test was also performed on cement clinker.
The leaching concentration of Cd in cement clinker was 0.23 mg/L,
which was nearly 40 times lower than that in MSWI FA. Therefore,
the TCLP test from OPC has a negligible effect on the mixed samples.
Leaching tests under natural and alkali conditions were also
performed. As shown in Table 3, Zn and Cd leaching under natural
and alkali conditions are considerably lower than those in the TCLP
test. Zhang found that Zn and Cd leaching from FA alone mildly
decreased from a high concentration under acidic condition
(pH < 4) and then rapidly decreased with increasing pH (Zhang
et al., 2016). The leaching behavior of Pb followed an amphoteric
pattern with low solubility at natural pH. According to Benassi, Pb
concentration has a V-shaped dependency on pH and changes by
more than three orders of magnitude with minimal solubility in the
pH range of 8e10 (Benassi et al., 2016). In our test, total Cr and
Cr(VI) mildly changed with pH because the predominant oxidation
 X. Zhou et al. / Chemosphere 182 (2017) 76e84 79

Table 3
Concentrations of heavy metals in the leaching tests from the raw MSWI FA.

Leaching tests pH1a pH1b Leaching concentrations (mg/L)

Pb Total Cr Cr(VI) Cd Zn As

TCLP leaching 2.88 5.72 ± 0.04 4.40 ± 0.80 51.44 ± 7.18 47.50 ± 4.73 9.07 ± 0.76 161.20 ± 18.66 0.014 ± 0.001
water leaching 7 10.35 ± 0.10 2.83 ± 0.17 45.75 ± 2.29 37.54 ± 1.87 3.51 ± 0.10 2.38 ± 0.15 0.014 ± 0.011
alkali leaching 12 12.67 ± 0.07 3.22 ± 0.07 52.58 ± 3.33 50.11 ± 6.77 5.44 ± 0.17 0.74 ± 0.04 0.002 ± 0.002
TCLP limits 5 5 2.5 1 NLc 5
a
pH before leaching.
b
pH after leaching.
c
No limit.

Fig. 1. Chemical fractionation patterns of Cd, Cr, Pb and Zn in MSWI FA.

state of Cr in MSWI FA samples was Cr(VI), which is present as a
soluble anion. According to Hyks (Hyks et al., 2009), (Cr,S)
O4eettringite and Ba(S,Cr)O4 solid solution controls Cr(VI) leaching
from FA. The reduction of Cr(VI) to Cr(III) is another approach to
increase Cr precipitation at low pH (Quina et al., 2009). The leachate
pH in all tests increased after leaching. Thus, the MSWI FA used in
this study is an alkaline waste with very low reductive capacity.
3.2. Effect of solidification/stabilization treatment
3.2.1. TCLP leaching behavior of GGBFS- and OPC-stabilized heavy
metals
The TCLP leaching test results for MSWI FA, BSCOPC, GGBSC, and
OPC S/S solids are shown in Fig. 2. The leaching concentrations of
Cd and Zn greatly decreased in all S/S solids. Based on the leaching
concentrations of heavy metals, the effects of S/S on heavy metals
in BFSOPC, GGBFS, and OPC stabilized samples exhibited the
following order: Zn > Cd > Pb > Cr. The leaching concentrations of
Cd, Zn, and Pb in all solidified samples were below TCLP limits,
whereas those of Cr and Cr(VI) exceeded TCLP limits. All S/S solids
had the lowest efficiency for Cr solidification given the low degree
of precipitation of hexavalent Cr. As shown in Fig. 3, the TCLP
leaching concentrations of total Cr and Cr(VI) in the GGBFS solidi-
fied sample (37.24 and 25.52 mg/L) were lower than those in raw
MSWI FA (51.44 and 47.50 mg/L). However, the leaching concen-
trations of Cr(III) in the GGBFS solidified sample increased from
3.94 mg/L to 11.72 mg/L because GGBFS reduced Cr(VI) to Cr(III)
(Laforest and Duchesne, 2005; Zhang et al., 2017). Meanwhile, in
the BFSOPC solidified sample, the TCLP leaching concentrations of
Cr(III) decreased to 2.96 mg/L; this decrease was likely caused by
the precipitation of Cr(III) to the OPC hydration products CeSeH.
The immobilization efficiency of Zn, Pb, and Cr in BFSOPC was
better than those obtained in OPC. In addition, replacing OPC with
GGBFS is environmentally and economically advantageous. Based
on the above results, BFSOPC (8.5% GGBFS and 1.5% OPC) was
selected as the binder. The other chemical additives were assessed
using Cr and Cr(VI) as the target heavy metal ions.
3.2.2. TCLP leaching behavior of BFSeOPC-stabilized Cr with other
chemical additives
To increase the immobilization efficiency of Cr in the solidified
products, NaAlO2, TMT, and VC (1/2/3/4 g) were added during the
80 X. Zhou et al. / Chemosphere 182 (2017) 76e84

Fig. 2. Heavy metal concentrations in the TCLP leachates from the MSWI FA, BSC-OPC, BSC, and OPC at 28 days.

Fig. 3. TCLP results of Total Cr and Cr(VI) from solidified samples at the curing age for 28 days.

28-day curing period. As shown in Fig. 3, Cr(VI) and total Cr


decreased slightly in BOSM and BOTMT. Cr(VI) concentration 2CrO2 3þ
4 þ 3C6 H8 O6 þ2H2 O/2Cr þ 3C6 H6 O6 þ 10OH ; (1)
decreased sharply in solidified samples with the addition of VC,
indicating that in the BFSeOPCeMSWI FA curing system, VC re-
Cr3þ þ 3OH ¼ CrðOHÞ3 Y: (2)
duces Cr(VI) to Cr(III) and that Cr(III) is deposited on the matrix as
the stable and insoluble Cr(OH)3. The reaction can be formulated as Note that total Cr concentration in leachate decreased previ-
follows: ously and then increased with the addition of VC. This result likely
 X. Zhou et al. / Chemosphere 182 (2017) 76e84 81

Fig. 4. (a) The XRD patterns of the MSWI FA, OPC, GGBFS, BFSOPC, BOSM and BOTMT at the curing age for 28 days. (b) The XRD patterns of the MSWI FA, BFSOPC, BOVC1, BOVC2,
BOVC3 and BOVC4 at the curing age for 28 days.

occurred because VC interfered with the hydration of OPC and
GGBFS. Although VC converts Cr(VI) to Cr(III), Cr(III) may be also
mobile when hydration products are absent.
Fig. 3 shows that total Cr and Cr(VI) in MSWI FA were success-
fully stabilized when using the VC-containing binder, and that the
optimum VC content is 2 wt%. Given that VC is a nontoxic material,
VC-stabilized FA meets standards with a reduced risk of secondary
pollution.
3.3. Material characterization of solid products
3.3.1. X-ray diffraction analysis
The raw MSWI FA and the solid FA were analyzed using XRD. As
shown in Fig. 4a, SiO2 (quartz, PDF 46-1045), CaSO4 (anhydrite, PDF
37-1496), KCl (sylvite, PDF 41-1476), CaCO3 (calcite, PDF 05-0586),
and NaCl (halite, PDF 05-0628) existed in crystalline form in the
raw FA. Meanwhile, Ca4Al2 (OH)12 Cl2$4H2O (Friedel’s salt, PDF 54-
0851) were identified in OPC, BFSOPC, and BOTMT solidified
82 X. Zhou et al. / Chemosphere 182 (2017) 76e84

samples. Ettringite (Ca6Al2(OH)12(SO4)3$26H2O, PDF 41-1451) was

identified in GGBFS, BFSOPC, and BOCM solidified samples. The
intensity of the main characteristic peak of CeSeH (calcium silicate
hydrate, PDF 33-0306) increased significantly in the hydrated
pastes that were cured for 28 days. Some new crystalline CeSeH
were formed because of the hydration of GGBFS and OPC in the
highly alkaline environment. The intensity of the main character-
istic peak of anhydrite in the solid that was cured for 28 days
decreased significantly, indicating phase transformation. Anhydrite
was the original phase in the raw MSWI FA, wherein the hydration
products were gypsum in OPC paste and ettringite in GGBFS-added
pastes. The reaction can be formulated as shown below. Mean-
while, ettringite stabilizes solids and increases Cr(VI) uptake into
the matrix, thus playing an important role in Cr(VI) binding
(Leisinger et al., 2010). The different hydration products of anhy-
drite are likely a key reason for the lower Cr(VI) immobilization
efficiency of OPC that of GGBFS. In BOSM, the appearance of the
ettringite peak and the increase in the calcite peak showed that
carbonation, and hydration to lesser extent, occurred. The carbon-
ation of MSWI residues possibly decreases the leaching behavior of
Cr (Wang et al., 2010). These results demonstrated that the
BFSeOPC-based cementitious material can effectively solidify/sta-
bilize MSWI FA via the formation of CeSeH phase, Friedel’s salt,
and ettringite. However, total Cr and Cr(VI) may still exceed TCLP
limits.

CaSO4 þ 2H2 O ¼ CaSO4 $2H2 O; (3)

3CaðOHÞ2 þ 3CaSO4 $2H2 O

þ Al2 O3 þ 23H2 O ¼ Ca3 Al2 O6 $3CaSO4 $32H2 O: (4)

Fig. 4b presents the XRD patterns of solid samples with different

VC contents and that were cured for 28 days. All solidified samples
contained ettringite and CeSeH phases. By contrast, the intensities
of the Friedel’s salt peaks decreased as VC addition increased,
indicating that adding VC inhibited the formation of Friedel’s salt.

3.3.2. SEM analysis

Fig. 5 shows the SEM and energy dispersive spectroscopy (EDX)
images of the raw FA and solidified samples. An agglomerated
structure is present in the SEM image of the raw MSWI FA (Fig. 5a).
EDX analysis revealed that Ca, Si, Mg, Na, and Cl-containing com-
pounds were enriched on the surface. The sample was highly
agglomerated. Small particles (<3 mm) adhered to the large parti-
cles, forming agglomerates. The EDX results for OPC-solidified
samples (Fig. 5b) suggested that these products are mainly
CaSO4$XH2O. This finding is consistent with the XRD results shown
in Fig. 4a, which shows that gypsum formed after hydration. Some
rough, hollow spheres in raw FA were filled with hydration prod-
ucts, thus forming a dense and homogeneous microstructure in all
solidified samples (Fig. 5bee). This finding indicated that strong
chemical bonds formed between the surfaces of heavy metal ele-
ments and the hydration products, thus hindering leaching. EDX
analysis further validated this observation because trace Zn and Cr
were detected in the CeSeH (Fig. 5d) and ettringite phase (Fig. 5e),
respectively. Although SEM micrographs did not reveal the exis-
tence of significant quantities of Friedel’s salt in the solidified
samples, this may be the result of the low SEM magnification.
3.4. Chemical specification distribution of Cr
The distributions of Cr species in the raw MSWI FA and solidified
samples are shown in Fig. 6a. Compared with raw FA, the total
content of water soluble, exchangeable, and carbonate Cr in all
Fig. 5. SEM/EDX analysis of raw MSWI fly ash and solidified samples: (a) raw MSWI fly
ash; (b) OPC solidified samples; (c) GGBFS solidified samples; (d) BFSOPC solidified
samples; (e) BOVC2 solidified samples.
solidified samples decreased by different degrees. The available Cr
(I þ II þ III) was closely related to TCLP results (Fig. 3), with some
variations. The results showed that 30.6% Cr in raw MSWI FA,
16.64% Cr in OPC-solidified sample, and 5.58% Cr in GGBFS-
solidified sample are in available forms. Thus, GGBFS exerted a
better solidification effect on Cr than OPC. In all samples, BOVC2
had the lowest content of available Cr (2.83%). The remaining Cr
was found in the FeeMn oxide and residual fractions, which
accounted for 40.05% and 43.31% Cr, respectively. This result
signified that almost all Cr ions that were present in the water
soluble, exchangeable, and carbonate forms were converted to
stable forms. Therefore, the stabilization of Cr in FA with VC is
considerably better than that with NaAlO2 and TMT.
 X. Zhou et al. / Chemosphere 182 (2017) 76e84
Fig. 6. (a) Chemical fractionation patterns of Cr in MSWI FA before and after solidifi-
cation treatments. (b) Effect of addition amount of VC on the phase transformation of
Cr.
The first three steps of Cr extracting from the solidified samples
with different VC additions are shown in Fig. 6b. As can be seen in
this figure, water-soluble and carbonate Cr decreased as VC dosage
increased. At the same time, exchangeable Cr decreased to zero at
2% VC dosage and then increased. The results showed that
exchangeable Cr exhibits similar characteristics as available Cr
(fraction I þ II þ III). This finding implied that reduced Cr(III) is
mainly distributed in the exchangeable fraction that cannot be
transformed into FeeMn oxides and sulfide fractions when excess
VC inhibits the formation of some hydration products.
3.5. pH-dependence test of Cr
Fig. 7a shows Cr leachate concentrations versus the pH values of
the raw MSWI FA and its S/S solids stabilized by BFSeOPC and VC
systems (BOVC2).
As show in Fig. 7a, the leaching concentration of Cr is strongly
dependent on solution pH. The leaching behaviors of MSWI FA and
bottom ash have been previously described with polynomial curves
(Quina et al., 2009; Benassi et al., 2016). In this case, fifth-order
equations were established to fit the total Cr leaching from both
raw MSWI FA and BOVC2 solid. The lowest leaching concentration
83
Fig. 7. (a) Total Cr leachability of raw MSWI fly ash and BOVC2 versus pH. (b) Eh-pH
diagram for the chromium-water-oxygen system (Diagram modified from Hem, J.D
(Jacobs and Testa, 2005).
of Cr were observed between pH 6 and 8. Insoluble and amorphous
Cr(OH)3 forms in the chromiumewatereoxygen system (Fig. 7b
(Jacobs and Testa, 2005),) at a pH of approximately 8.0 and under
reducing (eEh) conditions. The Cr solubility increases at low pH
values, specifically at pH values below 6, because amorphous
Cr(OH)3 dissolves to form the soluble chromium hydroxide cations
CrOH2þ and Cr(OH)þ 2 . At high pH (pH > 8), Cr solubility increases
again because soluble chromate CrO2 4 is reformed during leaching.
At pH values greater than 11, Cr leachate concentrations in BOVC2
solid decreased slightly. This likely occurred because some Cr(VI)
was incorporated into minerals with low solubility, such as
ettringite and Friedel’s salt, which are stable at alkaline conditions
(pH from 10 to 12.5) (Quina et al., 2009). The Cr leachability of
BOVC2 is lower than that of the corresponding raw FA at different
pH values. Therefore, BFSeOPC þ VC effectively stabilizes Cr.
4. Conclusions
In the present work, OPC and GGBFS were employed as curing
agents in the solidification/stabilization treatment of MSWI FA. Zn,
Cd, and Pb were effectively immobilized in the BFSOPC solid paste
after 28 days of curing. The leachability of these heavy metals
decreased below the TCLP limit. The addition of 2 wt% VC showed a
high potential to convert Cr(VI) into Cr(III). The leaching concen-
trations of Cr were pH-dependent, with the lowest leaching con-
centrations in the pH range of 6e8.
84 X. Zhou et al. / Chemosphere 182 (2017) 76e84
Structural and morphological characterization showed that the
solidified samples had dense microstructures with the formation of
CeSeH and the ettringite phase. Strong chemical bonds between
the heavy metal elements and the hydration products on the sur-
face decreased the leaching concentration of Cr. The adsorption of
trace Zn and Cr on the surface of CeSeH and ettringite further
proved that CeSeH and ettringite retain Zn and Cr in their crystal
structures via anion exchange.
Acknowledgment
This work was financially supported by the Major Scientific and
Technological Innovation Project of HuBei Province, China (No.
2016ACA162).
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