Waste Management xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

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

Vitrification of incinerated tannery sludge in silicate matrices for

chromium stabilization
S. Varitis a, P. Kavouras a, E. Pavlidou a, E. Pantazopoulou b, G. Vourlias a, K. Chrissafis a, A.I. Zouboulis b,
Th. Karakostas a, Ph. Komninou a,⇑
a
Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece
b
Department of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece

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

Article history: The vitrification process was applied for the stabilization and solidification of a rich in chromium ash that
Received 21 March 2016 was the by-product of incineration of tannery sludge. Six different batch compositions were produced,
Revised 8 September 2016 based on silica as the glass former and sodium and calcium oxides as flux agents. As-vitrified products
Accepted 10 October 2016
(monoliths) were either composed of silicate matrices with separated from the melt Eskolaite (Cr2O3)
Available online xxxx
crystallites or were homogeneous glasses (in one case). All as-vitrified products were thermally treated
in order to transform them to partially crystallized, i.e. devitrified products. Devitrification is an impor-
Keywords:
tant part of the work since studying the transformation of the initial as-vitrified products into glass-
Vitrification
Devitrification
ceramics with better properties could result to stabilized products with potential added value. The devit-
Incineration rified products were diversified by the effective crystallization mode and separated crystal phase compo-
Glass-ceramics sition. These variations originated from differences in: (a) batch composition of the initial as-vitrified
Thermal treatment products and (b) thermal treatment conditions. In devitrified products crystallization led to the separa-
Stabilization tion of Devitrite (Na2Ca3Si6O16), Combeite (Na4Ca4Si6O18) and Wollastonite (CaSiO3) crystalline phases,
Microstructure while Eskolaite crystallites were not affected by thermal treatment. Leaching test results revealed that
Silicate matrix chromium was successfully stabilized inside the as-vitrified monoliths. Devitrification impairs chromium
Tannery sludge
stabilization, only in the case where the initial as-vitrified product was a homogeneous glass. In all other
Chromium
cases, devitrification did not affect successful chromium stabilization.
SEM-TEM
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Currently, most of the global leather production utilizes chro-
mium salts for leather tanning (Alibardi and Cossu, 2016; Mao
et al., 2016; Celary and Sobik-Szołtysek, 2014). During the tanning
process 60% of total chromium reacts with raw hides and animal
skin, while the remaining 40% is discharged diluted in the wastew-
ater. The processing of one metric ton of raw hide/skins produces
50 m3 of wastewater (Kolomaznik et al., 2003), which contains
500–5500 mg/L trivalent chromium (Pathe et al., 2005). According
to Kanagaraj et al., 2006, in annual basis about 6.5 million tons of
wet salted hides are being processed, producing 300–500 mil-
lion m3 of wastewater annually, on global scale (Jaghava Rao
et al., 2003).
Tannery sludge is the by-product from the processing of this
wastewater through chemical precipitation achieved by the addi-
tion of lime and inorganic coagulants (Dhal et al., 2013). Through
⇑ Corresponding author.
E-mail address: komnhnoy@auth.gr (Ph. Komninou).
this treatment almost all chromium is removed from the wastew-
ater, forming a sludge with varying moisture content. The tannery
sludge cannot be freely deposited due to its high organic carbon
and trivalent chromium content. Additionally, high environmental
risks stem from the potential transformation of trivalent chromium
to hexavalent chromium, which is highly mobile, carcinogenic and
toxic (Chen et al., 2012). Different methods of Cr stabilization/
solidification have been proposed to further treat tannery wastes
such as encapsulation, solidification or vitrification which are able
to transform the sludge in pigments, cementitious, ceramics, and
vitrificates (Chen et al., 2015; Celary and Sobik-Szołtysek, 2014;
Montanes et al., 2014; Abreu and Toffoli, 2009) that could be either
safely landfilled or even used in building applications (Xu et al.,
2013).
Vitrification concentrates a significant number of advantages,
which render it one of the most effective methods of solidifica-
tion/stabilization of municipal and industrial solid wastes
(Pisciella et al., 2001) including chromium containing wastes
(Celary and Sobik-Szołtysek, 2014; Lazău and Vancea, 2014;
Sobiecka and Szymanski, 2014). Its place in the field of solid waste

http://dx.doi.org/10.1016/j.wasman.2016.10.011
0956-053X/Ó 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
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2 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx
management has been crucial since early 1960s, when it started
developing as the method for immobilization of high-level radioac-
tive wastes (Ojovan and Lee, 2014). A short list of vitrification’s
advantages comprises of (a) the high chemical stability of the
end products, (b) their endurance with time, (c) their attractive
physical characteristics (e.g. superior mechanical properties), (d)
its versatility with respect to the broad range of wastes it can
immobilize (Colombo et al., 2003), (e) the ability for complete
decomposition of organic content and (f) the significant volume
reduction of the waste varying from 20% up to 97% (Bernardo
et al., 2012).
These significant advantages stem from the nature of the vitrifi-
cation products and the conditions demanded for their synthesis.
More specifically, numerous toxic elements can be incorporated in
oxide glass matrices (LaGrega et al., 2001), while waste content
can reach 60 wt.% of the batch materials (Kavouras et al., 2003a).
Oxide glass structures have excellent chemical stability and durabil-
ity, i.e. they are highly resistant against attack from water or other
chemical agents. Consequently, vitrification products have low envi-
ronmental impact and can potentially be deposited in landfills with-
out any problems (Conner and Hoeffner, 1998). Additionally, in most
cases the existing overarching framework of glass science can be uti-
lized without the need to produce novel basic knowledge.
The fact that vitrification involves high temperature processing
brings forth the only disadvantage of this process: its relatively high
implementation cost. To this argument, several counter-arguments
can be raised: (a) International, regional and State regulatory sys-
tems progressively become stricter on issues including classification
of waste streams, maximum permissible extraction levels for toxic
elements, and prerequisites for new landfill areas (Tchobanoglous
et al., 1993). (b) Increasing social pressure. (c) There are several cases
where solid wastes or their solid residues cannot be safely deposited
in land filling areas, leaving no alternative apart from vitrification
(Bernardo et al., 2012). (d) The ongoing transition from a linear to
a circular approach of waste management strategies. After the appli-
cation of urban mining concept in municipal and industrial waste
streams (Baccini and Brunner, 2012), the residues should be placed
in geological repositories, closing in such a way the material cycle
(Cossu, 2012). (e) Vitrification products can be easily transformed
into glass-ceramic materials, whose physical properties can be tai-
lored, e.g. chemical resistance, appearance, mechanical properties
(Strnad, 1986). These products result from the thermal treatment
of vitreous materials and due to their enhanced properties could
lead to the fabrication of value-added products for building or dec-
orative applications, (Rawlings et al., 2006) lowering the cost of
the total process. Vitrification technology as a remediation method
for waste treatment has been practiced in many countries, particu-
larly the United States. In the present work the vitrification method
was applied in a laboratory scale, in order to stabilize/solidify a
chromium-loaded ash that was the residue of incineration of
chromium-containing tannery sludge with high organic carbon
and trivalent chromium content. The scope was to investigate the
ability to synthesize vitrified monoliths using chromium-loaded
ash, considering chromium’s low solubility in silicate melts and
the subsequent production of glass-ceramics through controlled
thermal treatment and crystallization of the initial as-vitrified prod-
ucts. The work was dictated from the fact that composition, shape
and spatial distribution of the separated ceramic phases can be rel-
atively easily controlled, by tuning devitrification conditions
(Kavouras et al., 2003b). In connection, it has been proved that they
straightforwardly affect chemical, morphological and mechanical
properties (Pisciella et al., 2001). The novelty of this work lies upon
the utilization of reagent grade raw materials in the vitrification step
and the subsequent production of glass ceramics that would
improve the properties of the vitreous products and potentially
lower the cost of vitrification as they are proposed as added value
Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
ment (2016), http://dx.doi.org/10.1016/j.wasman.2016.10.011
materials. In addition, research on the devitrification routes of all
initial as-vitrified monoliths has depicted the role of the devitrifica-
tion temperature and time on the stability, the microstructure and
the properties of the end glass-ceramics. Special attention was paid
on the fate of chromium after every treatment step, which was mon-
itored through leaching tests.
2. Materials and methods
The initial waste was recovered from the industrial zone of
Thessaloniki in northern Greece in the form of dried sludge. The
sludge was pretreated in order to remove as much organic content
as possible, while avoiding oxidation of chromium from the triva-
lent to the hexavalent form. The pretreatment step was composed
of incineration at starved air conditions for 90 min at 500 °C. These
conditions have been proved to remove 80% of sludge’s organic
content, while preventing chromium oxidation (Kavouras et al.,
2015). The resulting ash was subsequently homogenized by
mechanical action in a Fritsch Pulverizette 6 planetary mill.
Batch mixtures were prepared by mixing silica (SiO2), soda ash
(Na2CO3) and lime (CaCO3) reagent grade powders in various pro-
portions as it is listed in Table 1. SiO2 is the glass forming oxide,
while Na2O and CaO glass modifying oxides (flux agents). Powder
mixtures were co-melted for 120 min in a platinum crucible at
1400 °C and 1500 °C, depending on the batch composition, in order
to achieve a homogenous melt. The melt was casted in air on a
refractory stainless steel plate and cooled rapidly.
As-vitrified products were subsequently thermally treated, in
order to foster crystallization and produce devitrified products.
The vitreous nature of the as-vitrified products and the respective
thermal treatment temperatures were determined by Differential
Thermal Analysis (DTA) applied by a Setaram TG-DTA SetSys
1750 °C instrument in air. Heating and cooling rates were set at
10 °C/min and the samples were placed in Al2O3 crucibles.
All as-vitrified and devitrified products were structurally char-
acterized by X-ray diffraction (XRD) technique with a Rigaku pow-
der diffractometer, using CuKa1 radiation. Morphological
characterization was made by optical microscopy and Scanning
Electron Microscopy (SEM). The respective instruments were a
Zeiss Axiolab-A metallographic microscope and a JEOL JSM-840A
electron microscope. Elemental analysis for all products was made
by Energy Dispersive Spectrometry (EDS) with an OXFORD ISIS-300
EDS analyzer, attached on the SEM instrument. Morphological
observations were conducted on mirror-like polished or chemically
etched surfaces of the products, depending on the type of charac-
terization needed. Polishing was made by wet grinding utilizing
SiC papers. The final finishing was achieved with 5.0 lm and
0.3 lm Al2O3 pastes. Chemical etching was made by attacking
the samples’ surface by HF 10% w/v solution, for duration of 5 min.
To get a first estimation on their environmental impact and the
efficiency of the specific waste treatment processes used, the stabi-
lization of Cr at the as-vitrified and devitrified products was veri-
fied by leaching tests. The standard leaching test EN 12457-4
(liquid per solid ratio – L/S 10 L/kg) was used to characterize the
solidified materials. According to this test, as-vitrified and devitri-
fied products were crashed to form pieces of less than 10 mm in
diameter and were placed in bottles with deionized water (leach-
ing solvent) for 24 h rotational mixing at 10 rpm. Total Cr in the
leachates was determined using a Perkin Elmer Analyst 400 atomic
absorption spectrophotometer and the examined solidified prod-
ucts were characterized based on the EU decision 2003/33/EC,1
1
Council of the European Union, 2003/33/EC: Council decision of 19 December
2002 establishing criteria and procedures for the acceptance of waste at landfills
pursuant to Article 16 of and Annex II to Directive 1999/31/EC, Official Journal of the
European Communities, Brussels, 2003.
 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx 3

Table 1
The wt.% proportions of tannery ash and vitrifying agents in the six different batches.

Product Ash SiO2 Na2O CaO

B1 20 55 15 10
B2 15 55 15 15
B3 13 50 10 27
B4 13 56 7.5 23.5
B5 13 56 5 26
B6 10 55 15 20

Table 2
Atomic percentage of cations (at%) in the ash incinerated at
starved air conditions, obtained by EDS analyses.

Element at%
Ca 47.4 ± 4.1
Cr 36.4 ± 4.9
Mg 8.3 ± 1.1
S 3.4 ± 0.7
Na 1.6 ± 0.5
Si 1.4 ± 0.4 Fig. 1. Position of all six batch compositions in the SiO2-rich, corner of SiO2-Na2O-
Al 0.8 ± 0.4 CaO ternary phase diagram.
Fe 0.7 ± 0.3

regarding the acceptance of wastes in landfills. Two different sam-
ples were measured from each batch composition. Kosson et al.
(2002) have reported a tiered approach in the leaching procedure
in order to study the leaching potential of inorganic species from
secondary treated wastes in different environmental conditions.
Among others, they are discussing the MT001.1 protocol on the mass
transfer rates in monolithic materials. The main effort of the current
work is to study the structural properties of the vitrified and devit-
rified monoliths. Mass transfer test (Kosson et al., 2002) for potential
toxic element (Cr) from the original chromium-loaded ash and the
vitrified monoliths (cylinders) would be considered in a future work.
3. Results
3.1. Rich in chromium ash
Table 2 contains the composition of the mechanically homoge-
nized ash, characterized by ten EDS analyses on 100  100 lm
areas. Although homogenized, three different samples of ash were
analyzed. The composition is expressed in atomic percentage (at%)
of the elements in the waste. It has been shown (Kavouras et al.
(2015)) that calcium is found as crystalline CaCO3 in the forms of
Calcite and Aragonite, while chromium is found in non-
crystalline form, possibly in the form of partially dehydrated Cr
(H2O)3(OH)3, i.e. in trivalent form. Since the ash contains signifi-
cant quantities of Ca and Cr, it can provide significant quantities
of glass modifying cations like Ca2+ and Cr3+ (Mihradi and
Medhikhani, 2011) and potentially glass forming cations like Cr6+
(Casalboni et al. (1996)), in case of chromium oxidation during
batch melting. Small amounts of Si4+ cannot be considered to sub-
stantially aid at the glass-forming ability. Loss On Ignition (LOI)
content was found at 32 wt.%, by prolonged heating at 1100 °C.
3.2. As-vitrified products
Based on the elemental analysis of the ash, where no significant
content of vitrifying agents was detected, the batch compositions
prepared are listed in Table 2. The proportions of Na2O and CaO
listed correspond to the remaining oxides after thermal decompo-
sition of Na2CO3 and CaCO3 respectively in the batch during the
melting process and release of CO2. Initial tests revealed that batch
mixtures with SiO2 content between 40 and 50 wt.% did not lead to
the production of glass-forming melts (not listed in Table 2). Use of
SiO2 powder together with CaO and Na2O as flux agents gave the
ability to tune the batch compositions in order to: keep liquidus
temperature below 1500 °C, avoid regions of phase separation
from the melt of the main constituents and eventually choose
between possible crystalline phases separated after devitrification
process. Additionally, the interchange between CaO and Na2O can
potentially affect long-range diffusion, which controls reconstruc-
tive transformation mechanisms, i.e. susceptibility for devitrifica-
tion. This is based on the mixed cation effect (Rao, 2002) and has
been utilized to alternate crystallization mode from surface to bulk
to similar silica-based systems (Kavouras et al. (2007)).
Fig. 1 depicts the SiO2-rich corner of the SiO2-Na2O-CaO ternary
phase diagram [NIST Database], where the positions of all batch
compositions are indicated with an arrow. These positions were
found by keeping only SiO2, Na2O and CaO oxides in the overall
batch composition and renormalizing the respective proportions.
Only B5 batch composition could not be poured at 1400 °C and
was melted at 1500 °C. This experimental observation complies
with the fact that only this batch composition is found at areas
where the liquidus is above 1400 °C.
All as-vitrified products were homogenous upon optical inspec-
tion and were colored with varying tones of dark green. More
specifically, increase of the ash content shifted the color of the
as-vitrified products from black to dark green. XRD characteriza-
tion for all as-vitrified products is depicted in Fig. 2. All as-
vitrified products, except B6, produced diffractograms that contain
Eskolaite (Cr2O3) peaks superimposed on an amorphous back-
ground. As a result, they are comprised of an X-ray amorphous sil-
icate matrix inside which Eskolaite crystallites have been
separated. B6 was the only as-casted product that did not contain
separated crystallites, and as a result was X-ray amorphous.
Four characteristic SEM micrographs obtained from as-vitrified
products B1, B2, B4 and B6 are shown in Fig. 3. They were obtained
under the same magnification on mechanically polished sections,
from the interior of the as-vitrified products. Micrographs 3a, 3b
and 3c show the following morphology: light-colored inclusions
almost homogeneously dispersed inside a dark grey-colored back-
ground. The composition and morphology of the inclusions was
obtained by SEM after chemical etching. HF (10% w/v) solution
selectively attacked the amorphous matrix, leaving the inclusions
intact. As shown in Fig. 4, these inclusions were randomly oriented

Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
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4 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx

Fig. 2. XRD diffractograms of all as-vitrified products. Peaks indicated with the white triangle correspond to Eskolaite (Cr2O3) crystalline phase.

Fig. 3. SEM micrographs from (a) B1, (b) B2, (c) B4 and (d) B6 products.

hexagonally shaped flake-like crystallites. EDS analyses made on
these crystallites confirmed that they contained chromium. They
were the Eskolaite crystallites detected from XRD observations.
Their size did not significantly depend on batch composition, while
their population density decreased with decreasing ash content.
This result is in agreement with the fact that the ash is the only
chromium-containing component in the batch mixtures, and com-
plies with the decreasing intensity of Eskolaite peaks with decreas-
ing ash content as shown in Fig. 3.
According to EDS results, the dark grey-colored background was
consisted of all the elements from the batch mixtures. It is the vit-
reous matrix within which the Eskolaite crystallites were sepa-
rated and dispersed. B6 product, depicted in Fig. 3d, did not
contain Eskolaite crystallites. This SEM micrograph is featureless,

Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
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 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx 5

Fig. 4. Eskolaite hexagonal flake-like crystallites revealed by chemical etching in (a) B1 and (b) B4 as-vitrified products.

Table 3
Atomic percentage of chromium in the glass matrix and total chromium content
measured by EDS, percentage of total chromium incorporated in Eskolaite crystallites,
Si/O atomic ratio and basicity values of the six different batches.

Product Cr matrix Total Cr Cr2O3/ Si/O (CaO + Na2O)/

(at%) content (at%) Cr(total) (%) (at%) SiO2 (at%)
B1 1.6 ± 0.3 4.5 ± 0.4 64 0.37 0.53
B2 2.2 ± 0.3 3.3 ± 0.3 33 0.37 0.60
B3 2.1 ± 0.4 3.5 ± 1.1 40 0.34 0.84
B4 1.7 ± 0.4 3.7 ± 1.7 54 0.36 0.64
B5 2.1 ± 0.2 3.3 ± 0.9 36 0.36 0.65
B6 2.4 ± 0.6 2.4 ± 0.6 – 0.36 0.67

indicative of a homogeneous X-ray amorphous material. Fifteen

different EDS analyses were conducted in three different samples,
listed in Table 3, from the silicate amorphous matrices of B1-B5
products, revealed the presence of chromium. Consequently, sepa-
rated Eskolaite did not contain the whole of chromium content of
the as-vitrified products. Chromium was obviously present inside
the amorphous silicate matrix of B6 product, with the respective
chromium content value being the highest, compared to all other
as-vitrified products, since no Eskolaite crystallites were present
to ‘‘consume” a part of chromium content from the silicate matrix.
Table 3 also contains Si/O and (CaO + Na2O)/SiO2 atomic ratios
the latter being the basicity value. These two ratios correspond
to parameters describing glass structure (Shelby, 1997) and gen-
eral trend of the redox equilibrium of chromium (Duffy, 1993),
respectively.

3.3. Devitrified products

As-vitrified products were subsequently thermally treated for

crystal phase separation to be induced. The selection of thermal
treatment temperatures was based upon DTA results. Fig. 5 depicts
DTA thermographs from all as-vitrified products and the tempera-
ture of each exothermic peak’s maximum is indicated. Since
exothermic peaks mark crystallization, thermal treatment was
applied at temperatures near the maxima of these peaks. As-
vitrified samples were thermally treated for 30 min in a preheated
oven at temperatures (Tth) listed in Table 4. Moreover, by inspect-
ing the DTA thermographs it is observed that all as-vitrified prod-
ucts exhibit a glass transition between 600 °C and 700 °C. The
respective glass transition temperatures (Tg) are also listed in
Fig. 5. DTA thermographs of as-vitrified products. Temperatures indicate the
maximum of each exothermic peak that marks crystal phase separation.
Table 4. The detection of a glass transition indicates that the X-
ray amorphous phase in all as-vitrified products is of vitreous nat-
ure (Zarzycki, 1991).
A list of the separated crystalline phases present in all devitri-
fied products is given in Table 5; the respective XRD diagrams

Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
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6 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx

Table 4 vitrified product gave rise to Combeite (Na4Ca4Si6O18) and Wollas-

Glass transition (Tg) and thermal treatment temperatures (Tth) for all batch tonite (CaSiO3) in both two temperatures applied. Treatment of B4
compositions.
and B5 as-vitrified products gave rise to Wollastonite and Devitrite,
Product Tg (°C) Tth (°C) while in the case of B6 as-vitrified product only Combeite was sep-
B1 580 850 arated in all three temperatures applied. B1 and B2 devitrified
B2 590 800 products were more extensively crystallized compared to B3-B5
B3 640 720, 800 products, inferring that Wollastonite and Combeite growth ensues
B4 660 880
B5 680 920
with relatively lower rate compared to Devitrite. B6 devitrified
B6 595 760, 800, 880 products were more extensively crystallized compared to all other
devitrified products. Comparative observations on the extent of
crystallization can be obtained from XRD results presented below.
Table 5 Thermal treatment gave rise to separation of crystalline phases
Crystalline phases present in all devitrified products. nucleated from the surface, except in the case of B6 at 880 °C
where bulk crystallization took place. A series of SEM micrographs,
Product Eskolaite Devitrite Wollastonite Combeite
obtained from mechanically polished sections, from devitrified
B1   – –
products are illustrated in Fig. 7. In the case of surface crystallized
B2   – –
B3 (720 °C)  –   products the micrographs were obtained from near surface areas,
B3 (800 °C)  –   in order to inspect the morphology of the separated crystallites.
B4    – These devitrified products were composed of a crystallized surface
B5    – layer and a central region unaffected from thermal treatment.
B6 (all) – – – 
Fig. 7f was obtained from the central region of the devitrified
sample. Bulk crystallization of B6 product at 880 °C was also man-
ifested by the higher intensity of XRD peaks in this product (Fig. 6),
are depicted in Fig. 6. Thermal treatment of B1 and B2 as-vitrified compared to the other surface crystallized products, together with
products gave rise to Devitrite (Na2Ca3Si6O16). Treatment of B3 as- the fact that the amorphous hump in this case could not be

Fig. 6. XRD diagrams obtained from all devitrified products.

Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
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 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx 7

Fig. 7. SEM micrographs obtained from polished sections of all devitrified products. White arrows indicate Eskolaite crystallites.

detected. Despite the fact that bulk crystallization took place dur-
ing thermal treatment of B6 as-vitrified product at 880 °C, a layer
of apparent surface crystallization was detected. This layer was
composed of longer and thicker Combeite crystallites. Their mor-
phology resembled that of Combeite crystallites that grew from
the surface of B6 devitrified products at 760 °C and 800 °C.
The fact that Escolaite was detected in all devitrified products,
except B6, is an indication that this phase was not affected by
the devitrification process. This is more clearly shown in the SEM
micrograph of Fig. 7a. There, the Eskolaite crystallites (shown with
white arrows) coexist with Devitrite needle-like crystallites crys-
tallized from the surface of the as-vitrified sample. Qualitatively,
the dispersion of Eskolaite crystallites resembles that observed in
Fig. 3a, obtained from the respective as-vitrified sample.
The morphology of the separated crystallites in the devitrified
products was revealed by SEM observations on etched surfaces. A
characteristic micrograph is shown in Fig. 8. The micrograph was
obtained from the central region of B6 product thermally treated
at 880 °C, i.e. the only devitrified product that exhibited bulk crys-
tallization. It is observed that the Combeite crystallites have a Fig. 8. SEM micrograph showing Combeite crystallites from the central region of B6
feather-like morphology distributed in successive layers. devitrified product thermally treated at 880 °C.

3.4. Leaching tests vitrified products leached Cr total was below the detection limit
(0.01 mg/kg). Consequently, as-vitrified products can be freely dis-
Leaching test results are presented in Table 6. As-vitrified prod- posed in non-hazardous waste landfills, since leached Cr total was
ucts B2 and B4 showed Cr total leaching, while in all other as- lower than 10 mg/kg (EU decision 2003/33/EC). However, these

Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
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8 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx
Table 6
Leaching test results for as-vitrified products.
Product Leached Cr total⁄ (mg/kg)
As-vitrified Thermal treatment temperature (°C)
720 760
B1 n.d. – –
B2 1.88 ± 0.3 – –
B3 n.d. n.d. – n.d.
B4 0.77 ± 0.07 – –
B5 n.d. – –
B6 n.d. – 13.1 ± 3.6
⁄
Cr total limit value for wastes acceptable at non-hazardous wastes landfills: 10 mg/kg (EU decision 2003/33/EC). Total Cr leaching was obtained from two different samples
of each batch composition (n.d. strands for non-detectable).
glassy products can be also used as non-hazardous constituents for
further by-products fabrication (glass-ceramics composites). After
thermal treatment, Cr total leaching remained below the limit
value of 10 mg/kg in all cases, except B6. In this case thermal treat-
ment caused a detrimental increase in Cr total leaching, which
increased with increasing thermal treatment temperature. It is
noted that increase of thermal treatment temperature from
800 °C to 880 °C led to an increase of the Cr total leaching from
approximately 38 mg/kg to almost 70 mg/kg.
4. Discussion
4.1. As-vitrified products
The fact that all as-vitrified products are considered as non-
hazardous and can be freely disposed in waste landfill sites is, in
general, a reflection of the way that chromium was incorporated
inside those vitreous products, during the melt process. As Table 3
reads, a considerable percentage of chromium was incorporated in
Eskolaite crystallites, except at B6 product. This crystalline phase
secludes chromium from environmental action; this was verified
by leaching tests and it was also evidenced by the fact that etching
left Eskolaite crystallites intact. Accordingly, despite the fact that
B1 as-vitrified product contains the highest ash content, namely
20 wt.%, chromium release was negligible since this product was
the most extensively crystallized. As a result, the silicate matrix
was depleted from approximately 65% of the total chromium con-
tent, i.e. the highest compared to all other as-vitrified products.
Additionally, chromium included into the silicate glass matrix
was also effectively stabilized. This can be ascribed to the silicate
glass matrix degree of polymerization, expressed by the Si/O
atomic ratio that in all cases was higher than 0.33 (Table 3). This
value is considered the lowest limit for an extended silicate glass
network to be formed with a dimensionality of three (Shelby,
1997) and is used as a criterion for the formation of a glass network
with sufficient structural integrity. Consequently, the part of chro-
mium that did not formed Eskolaite, remained in a structurally
stable silicate glass matrix. For example, in the case of B6 as-
vitrified product the leachability of chromium was below the
detection limit despite the fact that no Eskolaite crystallization
ensued.
In principle, alkali and alkaline earth content affect chromium
solubility in silicate melts. The glass basicity index, listed in Table 3,
quantitatively expresses this effect. More specifically, it has been
recognized that increase in glass basicity enhances chromium sol-
ubility inside silicate matrices (Atkarskaya, 2011). This trend,
though, cannot be said to be followed straightforwardly in this
work’s set of batch compositions. Assuming that Eskolaite crystal-
lization is a consequence of excessive, i.e. above the solubility limit,
chromium concentration, the remaining chromium in the silicate
matrix (Table 3) is an index of chromium solubility. Indeed, the
Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
ment (2016), http://dx.doi.org/10.1016/j.wasman.2016.10.011
800 850 880 920
– n.d. – –
0.87 ± 0.17 – – –
– – –
– 0.71 ± 0.01 –
– – – n.d.
38.1 ± 3.96 – 69.8 ± 6.4 –
lowest chromium content (1.6 at%) was found in the glass matrix
of B1 as-vitrified product, which presented the lowest basicity
value. On the other hand, the highest chromium content (2.4 at%)
was found in B6 as-vitrified product, which did not have the high-
est glass basicity value, but the second highest. Consequently, the
general trend of the effect of glass basicity value on chromium sol-
ubility is followed only in rough lines in the present work.
Finally, through the realization of numerous point EDS analyses
and observations of glass surfaces via secondary electrons mode,
there could not be found any signs of elemental inhomogeneities.
This is important, since any segregation of chromium could lead
to the formation of non-chemically durable areas. Additionally,
homogeneity is a prerequisite for waste glasses to ensure consis-
tent and predictable glass properties. The observation of homoge-
neously dispersed chromium was a result of the melting
conditions, i.e. temperature and duration.
4.2. Devitrified products
The resulting crystal phases for all thermally treated products
are listed in Table 5. There is a correlation between the crystal
phases grown after the devitrification process to those expected
from the batch composition of the as-casted products, as it is pre-
dicted from the CaO-Na2O-SiO2 ternary phase diagram. In particu-
lar, Devitrite was grown in both the B1 and B2 devitrified products
although this phase could only be grown in the case of B2. In the
case of B3, B4 and B5 devitrified products Wollastonite was the
main separated crystal phase, which is in accordance to the phase
diagram. In these products, the growth of Wollastonite as the main
crystalline phase resulted to Si and Ca consumption and the
enrichment of the remaining vitreous matrix composition with
Na. As a result secondary crystal phases were also grown. Conse-
quently, in the case of B3 Combeite was grown as a secondary crys-
talline phase while in the case of B4 and B5 Devitrite was grown,
since the remaining composition approached the Combeite and
Devitrite region in the ternary phase diagram (Fig. 1) respectively.
After devitrification either leached chromium remained below
the detection limit (products B1, B3 and B5) or remained well
below the limit for waste acceptance (products B2 and B4), accord-
ing EU decision 2003/33/EC. Leaching tests revealed that devitrifi-
cation did not impair chromium stabilization, except in the case of
B6 product. This strikingly different behaviour plausibly stems
from the fact that chromium had not been separated in the form
of Eskolaite crystallites during glass-making or devitrification pro-
cess. Bulk crystallization is not connected to enhanced chromium
release, since leach deterioration was detected after thermal treat-
ment at 760 °C and 800 °C where only surface crystallization
ensued. Bulk crystallization did enhance chromium release, how-
ever chromium level in the leachate was already well above the
limits of waste acceptance.
 S. Varitis et al. / Waste Management xxx (2016) xxx–xxx
Lack of Eskolaite crystallites alone cannot interpret chromium
release, since as-vitrified completely amorphous B6 product safely
stabilized chromium. Chromium release must be connected to
devitrification process, where Combeite crystallites where sepa-
rated in all thermal treatment temperatures. Combeite is com-
posed of Si, Na and Ca oxides, and these elements are depleted
from the silicate matrix during devitrification. In areas where Com-
beite growth took place, the remaining silicate matrix necessarily
contains an excess of chromium. This assumption explains the fact
that increase of thermal treatment temperature increases chro-
mium release: increase in thermal treatment temperature led to
increase of crystal growth extent of Combeite producing larger
areas of remaining glass matrix with enriched chromium content.
It must be noted that bulk crystallization took place only in B6
product, due to the fact that a higher content of chromium was dis-
persed inside the silicate matrix. Chromium oxide is known to act
as a nucleating agent (Rezvani et al., 2005). On the other hand,
Eskolaite crystallites proved not to foster crystallization. Products
B1-B5 showed surface crystallization that was not affected by
Eskolaite crystallites. For example, Fig. 7a depicts the coexistence
of Eskolaite and Devitrite crystallites in B1 devitrified product,
without any sign of nucleation of the latter on the former.
5. Conclusion
The mechanisms of transformation of Cr-rich ash, originating
from incinerated chromium-rich tannery sludge, with high organic
carbon and trivalent chromium content, into non-toxic monolithic
vitreous products were investigated in relation to their microstruc-
ture. Towards this, six different batch compositions were studied
which were a combination of Cr-rich ash with reagent grade glass
forming oxides (SiO2, Na2O and CaO). The maximum Cr-ash incor-
poration was 20 wt.%. Since temperature and time are the main
parameters of the processing, a series of thermal runs were imple-
mented based on the existing phase diagrams. All the resulting
products were monolithic homogeneous vitreous materials at the
mesoscopic scale. However, analytical SEM and TEM techniques
combined with XRDs revealed that they contain Cr2O3 crystalline
flakes separated from the silicate matrix except one which was a
homogenous glass even at the nanoscale. Leaching tests indicated
that in all these products total Cr leaching was below the E.U. lim-
its for safe disposal in non-hazardous waste landfills.
Towards lowering the vitrification cost, the transformation of
the as-vitrified products into glass-ceramics was investigated.
Devitrification temperatures were systematically determined by
DTA. Post-annealing resulted to different modes and extent of crys-
tallization (surface and bulk) depending on the thermal treatment
temperature and time. Non Cr-containing separated crystalline
phases were detected as those of Devitrite, Combeite and Wollas-
tonite. All devitrified products, expect one, could be safely utilized
in applications, as structural materials, since chromium stabiliza-
tion was not impaired by the thermal treatment as it was proven
by the leaching tests. The idea to implement vitrification technol-
ogy to transform hazardous waste sludge into monolithic stable
solid material using low cost reagents may open a sustainable
way of waste management.
Acknowledgements
This research has been co-financed by the European Union
(European Social Fund - ESF) and Greek national funds through
the Operational Program ‘‘Education and Lifelong Learning” of
the National Strategic Reference Framework (NSRF) - Research
Funding Program: THALES: ‘‘WasteVal”, Reinforcement of the
Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
ment (2016), http://dx.doi.org/10.1016/j.wasman.2016.10.011
9
interdisciplinary and/or inter-institutional research and innova-
tion. Grant number MIS380038.
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Please cite this article in press as: Varitis, S., et al. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manage-
ment (2016), http://dx.doi.org/10.1016/j.wasman.2016.10.011