Journal of Hazardous Materials 283 (2015) 672–679

Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

Incineration of tannery sludge under oxic and anoxic conditions:

Study of chromium speciation
P. Kavouras a,∗ , E. Pantazopoulou b , S. Varitis a , G. Vourlias c , K. Chrissafis a ,
G.P. Dimitrakopulos a , M. Mitrakas d , A.I. Zouboulis b , Th. Karakostas a , A. Xenidis e
a
School of Physics, Section of Solid State Physics, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece
b
Division of Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki GR-54124, Greece
c
School of Physics, Section of Applied Physics, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece
d
Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece
e
School of Mining Engineering and Metallurgy, National Technical University of Athens, Zografou Campus, Athens 15780, Greece

h i g h l i g h t s

• A tannery sludge was incinerated at oxic and anoxic conditions without any pretreatment.
• Chromium speciation was investigated by monitoring Cr-bearing crystal phases.
• Complete oxidation of Cr(III) to Cr(VI) ensues at 500 ◦ C, at oxic conditions.
• At higher temperatures, partial reduction of Cr(VI) to Cr(III) ensues.
• Main Cr-bearing crystal phases were CaCrO4 and MgCr2 O4 .

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

Article history: A tannery sludge, produced from physico-chemical treatment of tannery wastewaters, was incinerated
Received 13 May 2014 without any pre-treatment process under oxic and anoxic conditions, by controlling the abundance of
Received in revised form oxygen. Incineration in oxic conditions was performed at the temperature range from 300 ◦ C to 1200 ◦ C
19 September 2014
for duration of 2 h, while in anoxic conditions at the temperature range from 400 ◦ C to 600 ◦ C and varying
Accepted 27 September 2014
durations. Incineration under oxic conditions at 500 ◦ C resulted in almost total oxidation of Cr(III) to Cr(VI),
Available online 19 October 2014
with CaCrO4 to be the crystalline phase containing Cr(VI). At higher temperatures a part of Cr(VI) was
reduced, mainly due to the formation of MgCr2 O4 . At 1200 ◦ C approximately 30% of Cr(VI) was reduced
Keywords:
Tannery sludge
to Cr(III). Incineration under anoxic conditions substantially reduced the extent of oxidation of Cr(III) to
Incineration Cr(VI). Increase of temperature and duration of incineration lead to increase of Cr(VI) content, while no
Chromium ash chromium containing crystalline phase was detected.
Chromium speciation © 2014 Elsevier B.V. All rights reserved.

1. Introduction wastewater, are mainly removed by chemical precipitation before

The predominant leather tanning method is based on chromium
salts; specifically trivalent chromium salts, such as chromium(III)
sulfate, which is the most widely used chemical in tanneries
[1,2]. About 60% of the total amount of chromium, applied dur-
ing leather tanning, is consumed during the tanning process, i.e.
reacts with animal skin. The rest of chromium remains in the
tanning bath and is subsequently discharged into the wastewa-
ter. Dissolved chromium and other spent chemicals present in the
∗ Corresponding author. Tel.: +30 2310 998011; fax: +30 2310 998589.
E-mail address: pkavo@physics.auth.gr (P. Kavouras).
the wastewater is allowed to enter the biological treatment pro-
cess. Precipitation is achieved through pH adjustment usually by
lime and the addition of inorganic coagulants. The precipitated
chromium along with other co-precipitated organic compounds is
discharged as sludge [3]. Direct landfilling of tannery sludge is not
permitted, because it is considered hazardous due to high organic
and trivalent chromium content.
Scientific interest has been drawn upon the environmentally
safe treatment of chromium sludge. One route is through the appli-
cation of incineration of the sludge as a first step for its detoxifica-
tion. Incineration concentrates a number of advantages, since: (a)
it reduces the organic content of the sludge, as well as the potential
health risks posed by the containing pathogenic microorganisms,

http://dx.doi.org/10.1016/j.jhazmat.2014.09.066
0304-3894/© 2014 Elsevier B.V. All rights reserved.
 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679 673

(b) decreases significantly the final volume of the waste and as were studied systematically. At oxic conditions a wide temper-
a result the area demanded for landfilling, (c) it achieves energy ature range was studied, i.e. from 300 ◦ C up to 1200 ◦ C, with a
recovery due to the organic content and (d) chromium recovery relatively narrow step interval, namely 100 ◦ C. At anoxic conditions
and/or stabilization/solidification through the vitrification method the varying parameters were both incineration temperature and
and/or using various additives can be implemented. incineration duration.
One focal point of ongoing research of incineration of tannery Endmost goal of the authors’ ongoing research is the appli-
sludge is its effect on chromium speciation. It is known that incin- cation of the reported results on: (a) chromium recovery using
eration in the presence of oxygen favors the oxidation of Cr(III) hydrometallurgy and (b) stabilization/solidification by the vitrifi-
to Cr(VI), an issue of great concern since Cr(VI) is highly mobile, cation method using synthetic glass formers and/or using various
carcinogenic and toxic [4]. It has been reported that Cr(III) oxi- wastes as additives.
dation can be avoided through starved air combustion at 800 ◦ C
and subsequently stabilized inside a cement gel matrix [5,6]. In 2. Experimental
these works differential thermo-gravimetric analysis until 800 ◦ C
was used to confirm the efficiency of starved-air combustion, while An amount of 10 kg of air dried tannery sludge was recovered
the behavior of the sludge above 800 ◦ C was not investigated. Also, on-site from the main wastewater treatment of the tanneries clus-
Wu et al. [7] studied the thermal reduction of synthetic chromium ter in the industrial area of Thessaloniki in Northern Greece. This
slag in nitrogen atmosphere using sewage sludge as reductant at the chromium-loaded solid waste was composed of weakly adhered
temperature from 200 ◦ C up to 900 ◦ C. In this work no chromium particles and was mechanically homogenized in a crusher, pro-
containing crystalline phase was detected. ducing a chromium-loaded solid waste reference sample. This
Incineration of tannery sludge under the presence of oxygen has mechanically homogenized product was used as the starting point
been applied after a pretreatment step. More specifically, Abreu for further characterization and further processing and will be
et al. [8] applied incineration in air at 700 ◦ C and 1150 ◦ C for the referred to as chromium-loaded initial solid waste (Cr-ISW). The
elimination of organic matter, with a washing step before firing, applied physical and chemical processes that transformed the
for soluble salts extraction, so that the chromium-rich resultant wastewater from tannery facilities into chromium-containing ash
material could be suitably used as a ceramic pigment. The authors are presented in Fig. 1 in the form of a flow chart diagram.
observed the growth of MgCr2 O4 crystalline phase. Tang et al. In order to determine the Cr-ISW chemical composition, a 0.4 g
[9] used tannery sludge pre-treated with 85% phosphoric acid dry sample was placed in a 100 mL PTFE beaker with 20 mL of
before incineration or mixed with hydroxyapatite [10] in order concentrated HNO3 and heated gently until it was completely
to investigate thermal behavior, heavy metal vaporization and dissolved. Characterization of Cr-ISW leachates was assessed by
chromium stabilization through its incorporation inside pyromor- the standard leaching procedure EN 12457-2 with L/S 10. Metal
phite minerals. Also, Jiang et al. [11] focused on kinetic analysis concentrations were determined by atomic absorption spectropho-
and volatilization of different heavy metals during combustion of tometer, Perkin Elmer Analyst 800, either a flame or a graphite
tannery sludge under flow of air at the temperature range of 50 ◦ C
up to 950 ◦ C. The authors found that chromium is the least volatile
heavy metal and they propose incineration temperature at 800 ◦ C.
The authors were not concerned on the structural characterization
of the incinerated sludge.
Verbinnen et al. [12] investigated synthetic mixtures of Cr2 O3
with Na, K or Ca salts incinerated up to 1100 ◦ C. They draw interest-
ing results on the extent of Cr(III) oxidation to Cr(VI) as a function
of temperature and added salt. Finally, information on the pos-
sible chromium-containing amorphous or crystalline phases can
be obtained from recently published works by El-Sheikh et al.
More specifically, filtered tannery waste solution with addition of
ammonia resulted to precipitation of magnesium and chromium
or calcium and chromium hydroxides gel. By heating in the tem-
perature range of 300 ◦ C up to 600 ◦ C, the main crystalline phases
observed were MgCrO4 , MgCr2 O4 [13] or CaCrO4 [14] with traces
of Cr2 O3 and MgO.
Scope of the present work was the investigation of the extent
of: (a) Cr(III) oxidation to Cr(VI) and (b) organic content removal
during the incineration of a tannery sludge under oxic and anoxic
conditions. Incineration was applied directly to the chromium-
containing tannery sludge. No pretreatment step was applied
before incineration, e.g. washing or mixing with other raw materi-
als, at variance with previously published works.
The lack of any pretreatment provides new information on the
following issues: (a) oxidation routes of chromium, i.e. possible
physicochemical processes and growth of chromium-containing
crystalline phases. Despite the fact that Cr(III) oxidation to Cr(VI)
is a well known phenomenon, the exact process of Cr(III) to Cr(VI)
transformation has not been given yet a definitive or unanimous
interpretation. This is plausibly because the extent of Cr(III) oxida-
tion is based on the incineration environment, i.e. pH range, oxygen
Fig. 1. A flow chart diagram of the transformation of chromium-containing waste
partial pressure, type of Cr-containing chemical compounds and forms from the tannery facilities to the final (mechanically and thermally treated)
presence of other compounds [15]. (b) Incineration parameters solid residues.
674 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679

furnace. Carbon and nitrogen of Cr-ISW were determined with Table 2

Characterization of Cr-ISW leachates by the standard leaching procedure EN 12457-
an elemental analyzer Perkin-Elmer 2400-II and dissolved organic
2 with L/S 10. All compositions are expressed in mg/kg.
carbon (DOC) of leachates with a TOC-VCSH E 200 V Schimadzu ana-
lyzer. Parameter Cr-RTW Inert waste Non-hazardous Hazardous
Total humidity content was determined by heating at 110 ◦ C waste waste

for 3 h. Incineration of Cr-ISW was applied under oxic and anoxic As 0.42 0.5 2 25
conditions. Oxic conditions, up to 800 ◦ C were realized at ambient Ba n.d. 20 100 300
Cd n.d. 0.04 1 5
atmosphere in a wide porcelain crucible, where the Cr-ISW was
Cr total 13.5 0.5 10 70
placed so as to form a thin powder layer. For 800 ◦ C up to 1200 ◦ C Cu 1.1 2 50 100
incineration was made inside a Pt crucible with the same provi- Ni 2.2 0.4 10 40
sion for the Cr-ISW amount. Anoxic conditions were realized at the Pb 0.075 0.5 10 50
Sb 0.015 0.06 0.7 5
temperature range of 400 ◦ C–600 ◦ C for 2 h. In this case, a ceramic
Se 0.045 0.1 0.5 7
crucible was used, capped with a ceramic lid, wrapped in aluminum Zn 0.80 4 50 200
foil. Both cap and foil were perforated, in order to allow the out- Chloride 3310 800 15,000 25,000
flow of the combustion gasses. This outflow suspended the entrance Fluoride n.d. 10 150 500
of ambient air inside the capped crucible, creating conditions for Sulphate 6640 1000 20,000 50,000
DOC 2400 500 800 1000
pyrolisis. These conditions have been already mentioned as anoxic,
TDS 32,000 4000 60,000 100,000
not referring to a total absence of oxygen but mainly due to the
pH 8.5 – – –
precautions taken in order not to allow access of additional oxygen
Redox +146 mV – – –
during incineration. EC 3.2 mS/cm – – –
Incineration was made in an LHT 02/18 Nabertherm elec-
n.d., not detected.
tric furnace. Mass losses and thermal stability of Cr-ISW were
studied by Thermo Gravimetric Analysis (TGA) and Differential
Thermal Analysis (DTA) at ambient atmosphere, with a Setaram
TG-DTA SetSys 1750 ◦ C instrument. X-Ray diffraction (XRD) anal- yields trivalent chromium hydroxy species such as Cr(OH)3 [17].
ysis was used for structural characterization. XRD diagrams were Besides, other chromium oxidation states cannot be found, since
recorded at Bragg–Brentano geometry, using a two-cycles Rigaku Cr(II) is readily oxidized to Cr(III), while Cr(IV) and Cr(V) form only
Ultima + powder X-ray diffractometer with a Cu Ka radiation oper- unstable intermediates in chemical reactions between trivalent
ating at 40 kV/30 mA. and hexavalent chromium [18]. Specifically at around neutral pH
After the decomposition of organic content, total chromium and under reducing conditions chromium has a composition corre-
amount of the ash was determined by the same procedure used sponding to chromium(III) hydroxide hydrates, which obtained by
to assess the chemical composition of Cr-ISW, described above. precipitation with alkali of chromium(III) sulphate and are usually
Cr(VI) recovery tests were conducted with 1 M HCl in conical formulated as Cr(H2 O)3 (OH)3 with a bright bluish green color [19].
flasks in a shaking water bath JULABO SW 21 for 1 h at 150 rpm Heating at 110 ◦ C up to 3 h resulted to a total mass reduction of
and 50 ◦ C. In view to optimize Cr(VI) recovery procedure prelim- 10–12 wt%, while for longer heating no additional mass reduction
inary tests were conducted with a sample incinerated at 500 ◦ C was observed, concluding that the total humidity of the Cr-ISW was
implementing various L/S ratios (10–5000) and pH values (2–4). about 10 wt%. Mass loss percentages as a function of temperature
The samples were filtered with a 0.45 ␮m membrane filter and were calculated from the TGA diagram of Fig. 2.
Cr(VI) concentration was determined by the diphenylcarbazide col- The main crystalline phase present in the Cr-ISW was CaCO3 ,
orimetric method [16]. According to this method, Cr(VI) reacts as indicated by the XRD diagram of Fig. 3. Numbered diffraction
with 1,5-diphenylcarbohydrazide in an acidic medium (H2 SO4 ) to peaks correspond to two different CaCO3 polymorphs, where (1)
produce a reddish-purple color, which is measured spectrophoto- designates orthorhombic Calcite and (2) hexagonal Aragonite. Cal-
metrically at a wavelength of 540 nm (Spectrophotometer Hitachi cium comes from the Ca(OH)2 added for pH correction during the
U-2000). wastewater physico-chemical treatment. No indication was found
for a chromium-containing crystalline phase concluding amor-
3. Results and discussion phous state of chromium. Besides, it has been reported that in
freshly precipitated chromium(III) hydroxide a crystalline phase
3.1. Chromium-loaded initial solid waste is observed, whereas after drying in air, aged compounds are X-ray
amorphous [19]. Besides, the curvilinear background of the XRD
The chemical analysis characteristics of Cr-ISW are presented diagram (Fig. 3) is indicative of the presence of an amorphous phase.
in Table 1. The major elements of Cr-ISW were organic carbon The leachate of the Cr-ISW showed a pH value 8.5, elec-
(22.6 wt%), calcium (9.0 wt%) and chromium (8.6 wt%). According to tric conductivity (EC) 3.2 mS/cm and redox potential +146 mV
the redox potential Eh–pH diagram, at pH > 3.5 hydrolysis of Cr(III) (Table 2). In addition, leachates were characterized by the low
values of the most physicochemical parameters in comparison
with the maximum permissible level for landfill disposal of non-
Table 1
Chemical analysis of Cr-ISW. hazardous wastes with the exception of chromium and dissolved
organic carbon (DOC). Total chromium content of leachate was
Element wt% Element mg/kg
found 13.5 mg/kg, higher than the maximum permissible level of
C 22.6 Zn 373 10 mg/kg for disposal in non-hazardous waste landfills. Accord-
Ca 9.0 Mn 120 ing to the diphenylcarbazide colorimetric method no Cr(VI) was
Cr 8.6 Ni 110
N 1.7 Ba 100
detected (<1.4 ␮g/kg), which means that all contained chromium
Mg 1.3 As 62 was in the trivalent form. Considering DOC, a concentration of
Na 0.7 Cu 61 2400 mg/kg was determined in leachate which significantly sur-
Al 0.3 Pb 11 passes the limit value for hazardous wastes landfill disposal
K 0.04 Cd n.d.
(1000 mg/kg) [20]. In addition, it is difficult to categorize organic
n.d., not detected. matter due to its complexity [21].
 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679 675

Fig. 2. TGA diagram of the Cr-ISW, under ambient atmosphere. The remaining mass percentages have been placed at characteristic heating temperatures.

3.2. Incineration at oxic conditions
Fig. 4 depicts the XRD diagrams and the respective main
crystalline phases present in the Cr-ISW, incinerated under oxic
conditions, as a function of temperature, from 300 ◦ C up to 1200 ◦ C.
Diffraction peaks of CaCO3 increase in intensity, from 300 ◦ C up to
500 ◦ C, due to mass reduction that resulted from the decomposi-
tion of organic content. For higher temperatures, CaCO3 diffraction
peak intensity remains roughly the same. Between 700 ◦ C and
800 ◦ C CaCO3 peaks disappear, due to its thermal decomposition.
CaCO3 decomposition does not take place abruptly, but initiates at
about 500 ◦ C. As a result, mass loss between 500 ◦ C and 700 ◦ C is
attributed to CO2 , which is released. Application of the Bernard
method gave the difference in CaCO3 content between 500 ◦ C
and 700 ◦ C to 10% of the total weight, which results to a CO2
weight loss of 4.4%, close to the 3% mass loss observed through
TGA.
Diffraction peaks of CaCrO4 first appeared at 300 ◦ C and their
intensity was increased up to 500 ◦ C, illustrating the oxidation of
Cr(III) to Cr(VI). This phase has been reported as the dominant one
present after heat treatment of chromium in sludges [22,23], as well
as in the presence of CaCO3 [24]. This result is analogous with the
formation of nano-crystalline CaCrO4 observed by El-Sheikh et al.
[14], which however were interested to study this reaction in the
low temperature regime, i.e. up to 600 ◦ C.
CaCrO4 peaks increase in intensity up to 800 ◦ C, after which they
progressively decrease up to 1200 ◦ C due to its decomposition. At
900 ◦ C a new set of peaks, attributed to MgCr2 O4 crystalline phase,
appears. In this phase chromium appears in the trivalent form.
These peaks increase in intensity up to 1200 ◦ C, where they have
the same intensity as those of CaCrO4 , which does not decompose
below 1200 ◦ C to CaCr2 O4 [24].
Fig. 5 depicts the DTA diagram of Cr-ISW, under ambient air con-
ditions. The wide endothermic peak centered at 120 ◦ C is due to the
evaporation of moisture. The following intense exothermic peak
from 250 ◦ C that falls abruptly at 500 ◦ C is related to the decom-
position of Cr-ISW organic content. Thermal decomposition takes
place together with the increase of the XRD peaks corresponding
to the calcium chromate (CaCrO4 ) crystalline phase. Based on XRD
results it can be assumed that up to 500 ◦ C chromium participates
in the formation either of organic complexes [21] or CaCrO4 crys-
talline phase, based on XRD results. The break point at 700 ◦ C is due
to a change in the mass loss gradient. The relatively small endother-
mic peak located at 960 ◦ C, is a mark of melting and is connected
to the sintering of Cr-ISW ash particles that was observed above
1000 ◦ C.

Fig. 3. XRD diagram indicating that the main crystalline phase present in Cr-ISW is CaCO3 that is found in the form of Calcite (PDF code number, 83-0577) and Aragonite
(PDF code number, 76-0606). Their peaks are indicated with 1 and 2, respectively.
676 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679

Fig. 4. XRD diagrams of Cr-ISW as a function of incineration temperature. CaCO3 peaks correspond to Calcite (PDF code number, 83-0577), CaCrO4 (PDF code number,
87-1647) and MgCr2 O4 (PDF code number, 82-1529).

In order to quantify Cr(VI) formation the parameters which
influence chromate dissolution were investigated. Experimental
tests presented in Table 3 showed that chromate solubility favored
by high L/S ratios and low pH values. Optimal chromate recovery
conditions were L/S 5000 and pH 2, since the recovered Cr(VI) was
99% of the total chromium.
Fig. 6 depicts chromate formation results as a function of incin-
eration temperature. Each measurement was made in triplicate.
At 500 ◦ C Cr(VI) concentration was equal to the total chromium
(Crtotal ) content of the Cr-ISW, i.e. all chromium has been trans-
formed into Cr(VI), as already described. At this temperature the
only crystalline phase containing Cr(VI) was CaCrO4 . With Ca/Cr

Fig. 5. DTA diagram of Cr-ISW, under ambient air conditions.

 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679 677

Table 3
Optimization of Cr(VI) recovery procedure from Cr-ISW, which was thermally
treated at 500 ◦ C under oxic conditions.

L/S pH Cr(VI) recovered (wt%)

10 2.0 10.6
200 2.0 24.5
500 2.0 40.2
1000 2.0 61.5
1600 2.0 64.8
2000 2.0 71.0
2500 2.0 90.0
4000 2.0 95.5
5000 2.0 99.7
5000 2.5 82.7
5000 3.0 42.2
5000 3.5 32.7
5000 4.0 15.4

atomic ratio in Cr-ISW being 1.36, there is enough Ca for all con-
tained chromium to participate in the formation of CaCrO4 and,
at the same time, to leave some of the Ca to form CaCO3 , whose
XRD peaks can be clearly observed at 500 ◦ C, as well. As a result,
the “carrier” of all contained chromium in this case, is calcium
chromate.
A part of Cr(VI) was reduced to Cr(III) for incineration tem-
peratures above 500 ◦ C, which was progressively increased up
to 1200 ◦ C. At 800 ◦ C CaCrO4 remained the dominant crystalline
phase, which co-existed with some precursor signs (faint XRD
peaks) of magnesium chromite (MgCr2 O4 ), where chromium is
found as Cr(III). The part of chromium participating in the growth
of MgCr2 O4 represents the amount of chromium that cannot be
leached, i.e. 11% of Crtotal . Besides, MgCr2 O4 is almost insoluble in
water and weak acids, while CaCrO4 is slightly water soluble and
soluble in acids [25].
It has been reported that nano-crystalline MgCrO4 and MgCr2 O4
phases, were grown after heating magnesium and chromium
hydroxides gel at 400 ◦ C, but in this case growth of CaCrO4 was
not observed [13]. In our case, MgCr2 O4 begins to form at 800 ◦ C,
i.e. at the high temperature regime, and not from 300 ◦ C, as has
been reported elsewhere [14]. These differences can be attributed
to the fact that in the cited works chromium containing waste was
not found in sludge form, but in ammonium precipitated hydroxide
gels. In our case, solid state reactions gave rise to the formation of
both calcium chromate and magnesium chromite phases.
In order to evaluate possible Cr(VI) sublimation, the total
chromium content as a function of incineration temperature was
Fig. 6. Cr(VI) formation results. Numbers into white bars give the % Cr(VI)/Crtotal
ratio and error bars indicate the standard deviation between three measurements.
Fig. 7. Results of the total chromium content of the thermally treated Cr-ISW
residues. Error bars indicate the standard deviation between measurements.
evaluated. The results shown in Fig. 7 represent the mean value of
two measurements. The differences in this diagram from 500 ◦ C to
1000 ◦ C are within the repeatability error, i.e. ±1 wt%, while total
chromium loss above 1000 ◦ C was roughly 6 wt%. Consequently,
reduction of Cr(VI) concentration at temperatures up to 1000 ◦ C
(Fig. 6) was due to the growth of MgCr2 O4 , i.e. due to the trans-
formation of Cr(VI) to Cr(III). Reduction of Cr(VI) percentage at
temperatures above 1000 ◦ C was due to Cr(VI) sublimation, which
has been previously observed [26,27]. This assumption conforms to
XRD results; between 1000 ◦ C and 1200 ◦ C diffraction peaks corre-
sponding to MgCr2 O4 have roughly the same intensity, while these
corresponding to CaCrO4 decrease in intensity.
3.3. Incineration at anoxic conditions
Incineration at anoxic conditions was applied to suppress the
extent of Cr(III) oxidation to Cr(VI). Structural analysis of the ashes
obtained by incineration at anoxic conditions is presented in Fig. 8.
The dominant crystal phase for all incineration temperatures and
heating durations was CaCO3 . The increase in the CaCO3 peaks,
with increasing temperature, is due to mass reduction that resulted
from the partial decomposition of organic content. More specifi-
cally, mass losses at 500 ◦ C and 600 ◦ C were of the order of 42% and
45%, respectively, lower compared to the corresponding 55% and
56% observed at oxic conditions.
Upon careful heating, dehydration of Cr(H2 O)3 (OH)3 occurs in
steps, which is converted to a green product, such as Cr2 O3 , with
low solubility; oxygen bridges are formed through the elimina-
tion of water and polynuclear complexes are produced [19]. This
is in accordance to the fact that no Cr-containing crystalline phases
were detected by XRD, a result reported also by Wu et al. [7] for
incineration in nitrogen atmosphere.
At anoxic conditions oxidation of Cr(III) to Cr(VI) is avoided or is
rather limited. Table 4 shows that the oxidation of Cr(III) to Cr(VI)
is avoided at 400 ◦ C for incineration time of 20, 60 and 90 min, since
Cr(VI) content was below the detection limit of the method. How-
ever, after 120 min incineration time a Cr(VI) concentration 0.9 wt%
was determined. At 500 ◦ C after 30 and 60 min, the oxidation of
Cr(III) to Cr(VI) was less extensive than the oxidation at 400 ◦ C
for 120 min, where only 0.1% and 0.3 wt% Cr(VI) was determined
(Table 4).
In contrast, incinerating at 600 ◦ C for 20 min leads to a greater
oxidation of Cr(III) than the previous treatments, since 1.2 wt%
Cr(VI) was detected. Conclusively, increase of incineration time
and temperature caused an increase in the extent of Cr(III) trans-
formation to Cr(VI) at anoxic conditions, which was by far lower
678 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679

Fig. 8. XRD diagrams of Cr-ISW as a function of thermal treatment temperature and duration at anoxic conditions. The RT indicated diagram is the untreated Cr-SW. (1)
Corresponds to Calcite and (2) to Aragonite. PDF code numbers are given in Fig. 2.

Table 4 4. Conclusions
Percentage of Cr(VI) formed from Cr-ISW, which was thermally treated under anoxic
conditions.
A tannery sludge was incinerated under oxic conditions with
Temperature, ◦ C Duration, min Cr(VI), wt% temperature as varying parameter and under anoxic conditions
400 20 n.d.a with temperature and time as varying parameters. A general
400 60 n.d. description of chromium fate during heating at oxic conditions
400 90 n.d. can be summarized as follows: amorphous Cr(H2 O)3 (OH)3 present
400 120 0.9
in the Cr-ISW, is being decomposed and CaCrO4 crystalline phase
500 30 0.1
500 60 0.3 begun to be formed at 300 ◦ C. Heating at 500 ◦ C lead to the par-
600 20 1.2 ticipation of the whole chromium content in the formation of
a
Not detected, i.e. Cr(VI) < 1.4 ␮g/kg. CaCrO4 , i.e. complete oxidation of chromium content has been
ensued. At higher incineration temperatures a gradual decrease
of Cr(VI) was observed, connected to the partial decomposition
of CaCrO4 and growth of MgCr2 O4 . However, even at 1200 ◦ C,
compared to the corresponding extent achieved under incineration approximately 70% of total chromium was in the form of Cr(VI),
at oxic conditions. i.e. partial reduction, corresponding to approximately one third of
Conclusively, incineration of Cr-ISW at anoxic conditions is oxidized chromium, has been ensued above 500 ◦ C. Incineration
preferred as a pretreatment method for chromium stabiliza- under anoxic conditions suppressed Cr(III) oxidation, while no Cr-
tion/solidification either by vitrification or using various additives. bearing crystalline phases were detected. Mass loss in this case
Despite the fact that a part of around 20 wt% of organic matter was 80% of that detected at incineration under oxic conditions,
remains into the ash, its handling is easier since Cr(III) oxida- implying a partial organic content removal. The obtained results
tion to toxic Cr(VI) was almost completely averted. For chromium provide specific directions for the treatment of the tannery sludge,
recovery, incineration at oxic and anoxic conditions bears specific in order to: (a) achieve minimization of chromium oxidation and
advantages and disadvantages. More specifically, after incineration chromium release in the environment along with the possibility to
at anoxic conditions chromium recovery is expected to be more yield usable products and (b) gain insight on the ongoing research
difficult due to both lower solubility and greater stability of Cr(III) for chromium recovery. More specifically, incineration at anoxic
oxides. However, the recovered Cr(III) could be possibly re-used in conditions proved to be more appropriate as a pretreatment step
the tanning process. After incineration at oxic conditions forma- before the application of stabilization/solidification, because the
tion of Cr(VI), despite its health hazards, could be considered as an suppression of Cr(III) oxidation to Cr(VI), rendered the resulting
advantage, as it is soluble and can be easily separated when looking ash safe for handling. Moreover, Cr(III) stabilization/solidification
for a comprehensive and integrated management. becomes more feasible due to lower solubility and greater stability
 P. Kavouras et al. / Journal of Hazardous Materials 283 (2015) 672–679
of Cr(III) oxides. Apart from the obvious benefit for the environment
and the people involved in the solidification/stabilization process,
incineration at anoxic conditions reduces treatment costs, since: (a)
it involves relatively lower incineration temperatures compared to
oxic conditions and (b) it minimizes precautionary measures. These
issues render incineration at anoxic conditions an attractive treat-
ment method for conditioning tannery ash for further management
through vitrification. Chromium recovery can be achieved from the
ash, which was produced at 500 ◦ C either under oxic conditions as
Cr(VI) or anoxic conditions as Cr(III). Cr(VI) was easily leached at
mild acidic conditions (pH 2), while the recovered Cr(VI) should be
reduced in order to be re-used in tanning process. In contrast, Cr(III)
recovery is expected to be more difficult, but the recovered Cr(III)
could be directly re-used. However, both procedures of recovery
will be further investigated, in order to conclude to the optimal
process in terms of economic, technical and environmental aspects.
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: MIS380038 THALES: reinforcement of the inter-
disciplinary and/or inter-institutional research and innovation. G.P.
Dimitrakopulos acknowledges support by the Research Committee
of the Aristotle University of Thessaloniki (proj. 89318).
References
[1] E. Kilic, J. Font, R. Puig, S. Colak, D. Celik, Chromium recovery from tannery
sludge with saponin and oxidative remediation, J. Hazard. Mater. 185 (2011)
456–462.
[2] A. Zouboulis, P. Samaras, A. Krestou, N. Tzoupanos, Leather production mod-
ification methods towards minimization of tanning pollution: green tanning,
Fresenius Environ. Bull. 21 (2012) 2406–2412.
[3] B. Dhal, H.N. Thatoi, N.N. Das, B.D. Pandey, Chemical and microbial remediation
of hexavalent chromium from contaminated soil and mining/metallurgical soil
waste: a review, J. Hazard. Mater. 250–151 (2013) 272–291.
[4] J. Chen, F. Jiao, L. Zhang, H. Yao, Y. Ninomiya, Use of synchrotron XANES and
Cr-doped coal to further confirm the vaporization of organically bound Cr and
the formation of Chromium(VI) during coal oxy-fuel combustion, Environ. Sci.
Technol. 46 (2012) 3567–3573.
[5] S. Swarnalatha, M. Arasakumari, A. Gnanamani, G. Sekaran, Solidifica-
tion/stabilization of thermally treated toxic tannery waste, J. Chem. Technol.
Biotechnol. 81 (2006) 1307–1315.
[6] S. Swarnalatha, K. Ramani, A. Geetha Karthi, G. Sekaran, Starved air combustion-
solidification/stabilization of primary chemical sludge from a tannery, J.
Hazard. Mater. B137 (2006) 304–313.
[7] C. Wu, H. Zhang, P. He, L. Shao, Thermal stabilization of chromium slag by
sewage sludge: effects of sludge quantity and temperature, J. Environ. Sci. 22
(2010) 1110–1115.
679
[8] M. Abreu, S. Toffoli, Characterization of a chromium-rich tannery waste and its
potential use in ceramics, Ceram. Int. 35 (2009) 2225–2234.
[9] P. Tang, Y. Zhao, F. Xia, Thermal behaviors and heavy metal vaporization of
phosphatized tannery sludge in incineration process, J. Environ. Sci. 20 (2008)
1146–1152.
[10] P. Tang, Y. Zhou, Z. Xie, Effects of hydroxyapatite addition on heavy metal
volatility during tannery sludge incineration, Environ. Sci. Pollut. Res. 20 (2013)
4405–4413.
[11] X.-G. Jiang, C.-Y. Li, Z.-W. Fei, Y. Chi, J.-H. Yan, Combustion characteristics of
tannery sludge and volatilization of heavy metals in combustion, J. Zhejiang
Univ. Sci. A (Appl. Phys. Eng.) 11 (2010) 530–537.
[12] B. Verbinnen, P. Billen, M. Van Coninckxloo, C. Vandecasteele, Heating tem-
perature dependence of Cr(III) oxidation in the presence of alkali and alkaline
earth salts and subsequent Cr(VI) leaching behaviour, Environ. Sci. Technol. 47
(2013) 5858–5863.
[13] S.M. El-Sheikh, M. Rabbah, Novel low temperature synthesis of spinel nano-
magnesium chromites from secondary resources, Thermochim. Acta 568
(2013) 13–19.
[14] S.M. El-Sheikh, M. Rabbah, Optical properties of calcium chromate 1D-nanorods
synthesized at low temperature from secondary resources, Opt. Mater. (2014),
http://dx.doi.org/10.1016/j.optmat.2014.05.034.
[15] A.D. Apte, V. Tare, P. Bose, Extent of oxidation of Cr(III) to Cr(VI) under various
conditions pertaining to natural environment, J. Hazard. Mater. B128 (2006)
164–174.
[16] L. Clesceri, A. Greenberg, R. Trussell, Standard Methods for the Examination of
Water and Wastewater, 17th edition, APHA-AWWA-WEF, Washington, 1989.
[17] D. Mohan, C. Pittman, Activated carbons and low cost adsorbents for remedia-
tion of tri- and hexavalent chromium from water, J. Hazard. Mater. B137 (2006)
762–811.
[18] J. Kotaś, Z. Stasicka, Chromium occurrence in the environment and methods of
its speciation, Environ. Pollut. 107 (2000) 263–283.
[19] G. Anger, J. Halstenberg, K. Hochgeschwender, G. Uecker, U. Korallus, H.
Knopf, P. Schmidt, M. Ohlinger, Chromium compounds, in: W. Gerhartz, Y.S.
Yamamoto, F.T. Campbell, R. Pfefferkorn, J.F. Rounsaville (Eds.), Ullmann’s Ency-
clopedia of Industrial Chemistry, A7, 5th edition, Wiley-VCH, Weinheim, 1986,
pp. 67–96.
[20] Council of the European Union, 2003/33/EC: Council decision of 19 December
2002 establishing criteria and procedures for the acceptance of waste at land-
fills pursuant to Article 16 of and Annex II to Directive 1999/31/EC, Official
Journal of the European Communities, Brussels, 2003.
[21] D. Zou, Y. Chi, J. Dong, C. Fu, F. Wang, M. Ni, Supercritical water oxidation of
tannery sludge: stabilization of chromium and destruction of organics, Chemo-
sphere 93 (2013) 1413–1418.
[22] S. Tahiri, A. Albizane, A. Messaoudi, M. Azzi, J. Bennazha, S. Alami Younssi, M.
Bouhria, Thermal behaviour of chrome shavings and of sludges recovered after
digestion of tanned solid wastes with calcium hydroxide, Waste Manag. 27
(2007) 89–95.
[23] D.W. Kirk, C.C.Y. Chan, H. Marsh, Chromium behavior during thermal treatment
of MSW fly ash, J. Hazard. Mater. B90 (2002) 39–49.
[24] C. Vogel, C. Adam, P. Kappen, T. Schiller, E. Lipiec, D. McNaughton, Chemical
state of chromium in sewage sludge ash based phosphorus-fertilisers, Chemo-
sphere 103 (2014) 250–255.
[25] U.S. Department of Health and Human Services, Toxicological Profile for
Chromium, Public Health Service Agency for Toxic Substances and Disease
Registry, Atlanta, 2012, http://www.atsdr.cdc.gov/toxprofiles/tp7.pdf
[26] C.A. Stearns, R.A. Miller, F.J. Kohl, G.C. Fryburg, Investigation of the formation
of gaseous sodium sulfate in a doped Methane–Oxygen flame, J. Electrochem.
Soc. 124 (1977) 1145–1146.
[27] K.-S. Wang, C.-J. Sun, C.-Y. Liu, Effects of the type of sintering atmosphere on the
chromium leachability of thermal-treated municipal solid waste incinerator fly
ash, Waste Manag. 21 (2001) 85–91.