Bioresource Technology 162 (2014) 308–315

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Risk analysis of pyrolyzed biochar made from paper mill effluent

treatment plant sludge for bioavailability and eco-toxicity of heavy
metals
Parmila Devi, Anil K. Saroha ⇑
Department of Chemical Engineering, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110016, India

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

 Disposal of toxic sludge containing

heavy metals poses an environmental
risk.
 Pyrolysis of sludge was performed to
explore the potential of biochar for
reuse.
 The effect of pyrolysis temperature on
partitioning of heavy metals was
studied.
 Fractionation and bioavailability of
heavy metals in sludge and biochar
was analyzed.
 The leachability and ecotoxicity of
heavy metals in biochar were
determined.

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

Article history: The risk analysis was performed to study the bioavailability and eco-toxicity of heavy metals in biochar
Received 6 February 2014 obtained from pyrolysis of sludge of pulp and paper mill effluent treatment plant. The sludge was pyro-
Received in revised form 13 March 2014 lyzed at different temperatures (200–700 °C) and the resultant biochar were analyzed for fractionation of
Accepted 18 March 2014
heavy metals by sequential extraction procedure. It was observed that all the heavy metals get enriched
Available online 27 March 2014
in biochar matrix after pyrolysis, but the bioavailability and eco-toxicity of the heavy metals in biochar
were significantly reduced as the mobile and bioavailable heavy metal fractions were transformed into
Keywords:
the relatively stable fractions. Moreover, it was observed that the leaching potential of heavy metals
Sludge
Biochar
decreased after pyrolysis and the best results were obtained for biochar pyrolyzed at 700 °C.
Pyrolysis Ó 2014 Elsevier Ltd. All rights reserved.
Heavy metal
Leaching

1. Introduction
Sludge handling and disposal is a universal problem as it con-
tains significant amount of heavy metals, organic toxins and path-
ogenic microorganisms (Fang et al., 2012; Ren et al., 2012; Azeez
et al., 2011). The contaminated sludge can have direct toxic effects
on aquatic ecosystem, and through the bioaccumulation of toxic
⇑ Corresponding author. Tel.: +91 1126591032; fax: +91 1126581020.
E-mail address: aksaroha@chemical.iitd.ac.in (A.K. Saroha).
contaminants in the food chain, which can cause an indirect risk
to the humans (Nzihou and Stanmore, 2013). Accumulation and
bioavailability of heavy metals is the limiting factor for disposal
and utilization of sludge. The recycling of sludge is only possible
if the toxic dioxins and heavy metals are removed or stabilized,
thus allowing the treated sludge to recycle into the materials cycle.
In order to reduce the toxicity of heavy metals in the sludge,
two main approaches can be applied, i.e. removal of heavy metals
from the sludge or heavy metal immobilization inside the sludge
(Shi et al., 2013). Various methods like chemical extraction (Silva

http://dx.doi.org/10.1016/j.biortech.2014.03.093
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315
et al., 2005), bioleaching (Pathak et al., 2008), and bioremediation
(Gaur et al., 2014) are used for heavy metal removal from the
sludge. But these methods are time consuming and it is very diffi-
cult to control the heavy metal removal efficiency. Heavy metal
immobilization is widely used in sludge remediation due to its
simplicity and cost effective management. Pyrolysis is an effective
technique to immobilize the heavy metals in the pyrolysis residue
(biochar). Immobilization of heavy metals decreases the direct tox-
icity or leachable fraction of heavy metals, resulting in significant
reduction in the environmental risks. Various studies have been
reported in the literature on the mobility of heavy metals in the
biochar produced from sewage sludge. Kistler and Widmer
(1987) studied the behavior of heavy metals Cr, Ni, Cu, Zn, Cd,
Pb, and Hg during the pyrolysis of sewage sludge and found that
the heavy metals were highly immobile in the char due to its alka-
line properties. Debela et al. (2012) tested the optimum combina-
tion of high heating temperature (HHT) and heating time to
effectively immobilize heavy metals in the biochar. Similar reduc-
tions in metal leaching from dredged sediments after pyrolysis
have been reported by Zhang et al. (2009b).
The content and mobility of heavy metals in the biochar matrix
should be determined to assess the risk to the environment by the
recycling of biochar. The total heavy metal concentration is a useful
pollution indicator, but it provides no information on the mobility of
heavy metals, which depends on their chemical form (Su and Wong,
2003). Chemical speciation or sequential extraction of heavy metals
from the sludge is a useful technique for determining the chemical
forms in which the heavy metals are present in the sludge and the
biochar. Such information is valuable for determining the mobility,
bioavailability and leaching potential of heavy metals in the sludge
and the biochar (Flyhammar, 1998). Therefore, the evaluation of
sludge toxicity by chemical fractionation is important in deciding
the suitability as well as the optimum use rate of sludge in recycling.
Pulp and paper industry is capital-intensive with high consump-
tion of raw materials, chemicals and utilities. Huge amount of efflu-
ent (20–250 cubic meters per metric ton (m3/t) of air dried pulp) is
generated and the disposal of waste (liquid, solid and suspended
matter) generated (10–400 kg/ton of paper produced) during the
paper manufacturing process contributes to a very high impact on
the environment (Pokhrel and Viraraghavan, 2004). To the best of
our knowledge, there is no study reported in the literature investi-
gating the bioavailability and eco-toxicity of the sludge generated
from the effluent treatment plant in the pulp and paper mill. The lack
of the information limits the use of the sludge in various applica-
tions. Therefore, efforts have been made in the present study to
immobilize the heavy metals present in the sludge using pyrolysis
to explore the potential of reutilization of the biochar in agricultural
and other purposes like brick formation, use as low-cost adsorbents
etc. The pyrolysis of the sludge leads to the production of biogas, bio-
oil and biochar and the heavy metals present in the sludge can par-
tition in any of the products depending on the pyrolysis tempera-
ture. The effect of pyrolysis temperature on partitioning and
mobility of the six heavy metals (Cr, Cu, Ni, Zn, Pb, and Cd) was stud-
ied. The speciation and fractionation of the heavy metals in the
sludge and biochar was analyzed. The toxicity and bioavailability
of the heavy metals in the sludge and biochar was examined. The
leachability of the heavy metals and the effect of solution pH on
the leachability of the heavy metals were investigated.
2. Methods
2.1. Pyrolysis of paper mill sludge
Paper mill sludge (PMS), collected from the effluent treatment
plant of a pulp and paper mill, and was used as a raw material
309
for biochar production. The PMS was characterized and results
are given in Table S1 (Supplementary materials). Pyrolysis of
PMS was carried out according to the procedure reported else-
where (Devi and Saroha, 2013). The pyrolysis was performed in
the temperature range 200–700 °C and the resultant biochar sam-
ples were assigned codes BC200, BC300, BC 400, BC500, BC600 and
BC700 depending on their pyrolysis temperature. The produced
biochars were stored in air-tight containers for further use.
2.2. Acid digestion
Heavy metal concentration in PMS, biochar and bio-oil were
determined by acid digestion method (Ramteke and Moghe,
1988; Rodriguez et al., 2009). Initially, 1 g of the solid sample (bio-
char or PMS; 1 mL in case of bio-oil) was added in 25 mL of HNO3–
HClO4 (3:1) and was heated gently for 4 h. A colorless solution was
obtained which was evaporated to near dryness. After completion
of the digestion and adequate cooling of residues, solutions were
made up to 25 mL by adding 0.04 N HNO3.
2.3. Sequential extraction
The PMS and biochar samples were sequentially extracted as
per the procedure shown in Fig. 1. The procedure categorizes the
heavy metals in five fractions (F1, F2, F3, F4 and F5), according to
their nature and mode of occurrence. Similar procedure for
sequential extraction has been reported by Poykio et al. (2006).
After each extraction, the supernatant was collected by centri-
fugation at 5000 rpm for 10 min in a centrifuge and filtered
through a 0.45-lm nylon filter. The resultant filtrate was diluted
to the desired volume (25 mL) by adding 2% HNO3. All the extract-
ants were analyzed using atomic absorption spectrophotometer
(AAS) for the six heavy metals.
The heavy metal concentration was determined using the fol-
lowing Eq. (1):
 
mg
HM concentration
kg
 
HM concentration mg
L
 total volume makeup ðmLÞ
¼ ð1Þ
weight of solid sample ðgÞ
2.4. Leaching tests
Leaching behavior of the heavy metals was analyzed using the
toxicity characteristic leaching procedures (TCLP). The US EPA TCLP
procedure involves adding 10 g powder sample in 100 mL of 0.1 M
acetic acid with a liquid/solid ratio of 10:1 and shaking for 18 h in a
rotary incubator shaker at 32 rpm. The resultant mixture was fil-
tered through a 0.45 lm nylon filter and the concentration of the
heavy metals in the leachate was determined using AAS. The leach-
ing potential of a heavy metal was determined by dividing its con-
centration in the leachate with its initial concentration in the solid.
2.5. Effect of pH on heavy metal leaching
Experiments were conducted to study the effect of pH of the
solution (pH 3–13) on heavy metals leaching from PMS and bio-
char samples. The solid sample (5 g) was mixed with 50 mL of dis-
tilled water and the pH of the solution was adjusted to the desired
value by addition of 0.1 N HCl/NaOH solutions. The solution was
kept for 24 h and was filtered using 0.45 lm nylon filter. The resul-
tant filtrate was analyzed for heavy metals using AAS.
The reproducibility of the experimental results was checked
and the error in the experimental results was found to be ±2%.
310 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315

Fig. 1. Sequential extraction procedure of the heavy metals in PMS and biochar.

3. Results and discussion

In the present study, pyrolysis of the sludge collected from the

effluent treatment plant of a pulp and paper mill was carried out to
explore the potential of reutilization of the biochar. The effect of
pyrolysis temperature on the partitioning and mobility of the
heavy metals was investigated.

3.1. Effect of pyrolysis temperature on heavy metal partitioning

The partitioning of heavy metals in the pyrolysis products was

studied by performing the pyrolysis of PMS in the temperature
range 200–700 °C and the results are shown in Fig. 2. It can be
observed that Zn and Cu were present in significant quantities in
the PMS compared to other heavy metals and their concentration
was found to be 193.48 and 83.98 mg/kg respectively. The heavy
metals partitioned into the solid (biochar), liquid (bio-oil) and gas-
eous products (biogas) on pyrolysis, depending upon the pyrolysis
Fig. 2. Partitioning of the heavy metals in biochar pyrolyzed at different
temperature and speciation of the heavy metals. It can be noticed
temperatures.
from Fig. 2 that the major amount of the heavy metals were parti-
tioned in the biochar, and the heavy metals concentration (mass
basis, mg of heavy metal/kg of the sample) was not significant in
the bio-oil and biogas samples (Table S2; Supplementary materi- Table 1
Enrichment of heavy metals in biochar pyrolyzed at different temperatures.
als). The concentrations of the heavy metals in the PMS and the
biochar was found in the order Zn > Cu > Pb > Ni > Cr > Cd. Temperature Enrichment factor (Ef)
The concentration of the heavy metals in the biochar was found (°C)
Chromium Copper Nickel Zinc Lead Cadmium
to be higher compared to their concentration in the PMS except for (Cr) (Cu) (Ni) (Zn) (Pb) (Cd)
Cd. This is due to the fact that decomposition of the organic matter 200 1.18 1.09 1.55 1.04 1.28 0.77
present in the sludge causes the release of heavy metals bound to 300 1.23 1.14 1.481 1.14 1.53 1.07
the organic matter. The heavy metals precipitated in the biochar 400 1.24 1.17 1.32 1.19 1.90 0.73
matrix and resulted in the partitioning of large fraction of heavy 500 1.26 1.44 1.14 1.26 2.01 0.71
600 1.28 1.55 1.01 1.49 2.09 0.59
metals into the biochar (Bo et al., 2009). Further, there was a loss 700 1.29 1.75 0.87 1.72 2.22 0.53
in the weight of the sludge due to the decomposition of the organic
 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315 311

Fig. 3. Fractionation and bioavailability of the heavy metals in PMS and biochar (a) Cr; (b) Cu; (c) Ni; (d) Zn; (e) Pb; (f) Cd. F1 = water soluble fraction; F2 = exchangeable
fraction; F3 = reducible fraction; F4 = oxidizable fraction; and F5 = residual fraction.

matter during pyrolysis. But the loss in the weight of the heavy
metals was lower compared to the loss in weight of the organic
matter during pyrolysis, resulting in the enrichment of heavy met-
als in the biochar matrix (Yeiwei et al., 2008). The concentration of
Cd in biochar was found to be lower as it may have volatilized into
the biogas during pyrolysis (Shi et al., 2013). The partitioning of the
heavy metals in biochar was quantified in terms of enrichment fac-
tor (Ef) which is defined as the ratio of heavy metal concentration
in the biochar to its concentration in the PMS (Yeiwei et al., 2008).
The value of the enrichment factor of the heavy metals in biochar
for different pyrolysis temperatures is shown in Table 1. It can be
noticed from Table 1 that the enrichment factor was found to
increase with an increase in the pyrolysis temperature for Cu, Zn
and Pb. No significant effect of pyrolysis temperature on the
enrichment factor for Cr was observed. The enrichment factor for
Ni and Cd were found to decrease with an increase in the pyrolysis
temperature since Ni and Cd may have volatilized to the gas
stream at higher temperatures (Shi et al., 2013).
312 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315

3.2. Fractionation and bioavailability of heavy metals
Heavy metals can be divided into three categories on the basis
of their bioavailability: (a) bioavailable (Cbio), (b) potentially bio-
available (Cpbio), and (c) non-bioavailable heavy metals (Cnon-bio).
Bio-available category includes the water soluble (F1) and
exchangeable (F2) fraction of the heavy metals, which are easily
prone to leaching. Potentially bioavailable category includes reduc-
ible (F3) and oxidizable (F4) fractions which undergo degradation
and leaching under very rigorous conditions (highly acidic condi-
tions and oxidizing atmosphere). Non-bioavailable category
includes residual (F5) fraction, which is not prone to leaching
and degradation. The fractionation of the heavy metals in the
PMS and biochar was analyzed using sequential extraction proce-
dure and the results are shown in Fig. 3a–f. It was observed that
pyrolysis could immobilize heavy metals by converting a part of
unstable fractions (F1, F2, F3 and F4) into stable fraction (F5).
The total heavy metals concentration obtained by sequential
extraction procedure (i.e. sum of all the five fractions) must be
equal to the heavy metals concentration determined by acid diges-
tion method. The comparison between the two heavy metal con-
centrations obtained by sequential extraction procedure and acid
digestion method highlights the complete sequential extraction
of the heavy metal from the solid and the agreement is reported
in terms of Recovery. The result for the evaluation of the proce-
dures is shown in Table 2 and a good agreement (±4%) between
the two heavy metals concentrations can be noticed. A deviation
of ±1–8% has been reported in the literature (Filgueiras et al.,
2002).
The fractionations of Cr in PMS and biochar are shown in Fig. 3a.
It can be noticed that the concentration of Cr in the water soluble
and exchangeable fractions was reduced from 20% in PMS to
13.57% in biochar after pyrolysis at 700 °C (BC700). In contrast,
the concentration of Cr in the residual fraction was found to
increase from 30.81% in PMS to 47.51% in biochar BC700. This
could be due to the formation of free CaO during pyrolysis which
can immobilize Cr by forming a stable complex (Hu et al., 2013).
The XRD analysis of the PMS showed the presence of CaCO3 in sig-
nificant quantity (Devi and Saroha, 2013). The chemical speciation
of Cu changed significantly when PMS was pyrolyzed at different
temperatures (Fig. 3b). The major amount of the Cu existed in
the potentially bioavailable form (Cpbio ’ 60%), in the PMS and bio-
char. The bioavailable fraction (F1 + F2) of the Cu decreased signif-
icantly from 22.02% (PMS) to 1.70% (BC700) after the pyrolysis. The
large fraction of the Ni (70%) existed in non-bioavailable category
in the PMS and biochar and the fraction of Ni in bioavailable cate-
gory was not significant (Fig. 3c). The Ni content in the residual
phase was found to increase with an increase in the pyrolysis
temperature.
The Zn content in the bioavailable category in PMS was found to
be 22.02% which was reduced to 0.89% in BC700 after pyrolysis
(Fig. 3d). The Zn content in the non-bioavailable category, 18.36%
in the PMS was found to increase to 45.32% in biochar BC700 after
the pyrolysis. This may be due to the fact that CaCO3, which is pres-
ent in significant amount in PMS, may act as a strong adsorbent for
Zn and could lead to the formation of complex salts like CaCO3-
ZnCO3 during precipitation of Zn (Banerjee, 2003).
The major content of Pb was found in the reducible (F3) and
oxidizable (F4) fractions in PMS. The Pb content in water soluble
(F1) and exchangeable (F2) fractions were not significant and were
found to decrease in the biochar after pyrolysis (Fig. 3e). The Pb
content in residual fraction (F5) in PMS was found to increase sig-
nificantly in the biochar after pyrolysis. This may be due to the fact
that at higher temperature biochar formed is alkaline in nature
(Hossain et al., 2011), which leads to the formation of lead hydrox-
ide. The lead hydroxide eventually results in the formation of insol-
uble PbO during precipitation, which eventually gets fixed as
residual fraction in the biochar matrix (Song et al., 2013).
The speciation behavior of Cd is slightly different compared to
other five heavy metals (Fig. 3f). It can be noticed from Fig. 3f that
about 30% of the Cd in PMS is present in bioavailable form (Cbio),
which is easily prone to leaching. This may be due to the presence
of Cd as their chlorides or as free metal (Abanades et al., 2002).It
can be further noticed from Fig. 3f that Cd is mainly associated
with the oxidizable fraction in the biochar. Similar results have
reported in the literature for other types of sludge (Jamali et al.,
2007; He et al., 2010).
It can be concluded from the Fig. 3a–f that the distribution pat-
tern in the five fractions (F1–F5) differs with each heavy metal. The
bioavailable fractions (F1 and F2) of the heavy metals were found
to decrease on pyrolysis of PMS to biochar whereas the non-bio-
available fractions (F5) for the heavy metals were found to increase
significantly on pyrolysis. Since the residual fraction is the most
stable form of the heavy metals, the pyrolysis temperature is a
decisive factor for immobilization of heavy metals in the biochar.
3.3. Leaching studies
The heavy metals present in the sludge are major restrictive fac-
tor for reutilization of PMS and PMS derived biochar. The environ-
mental behavior of heavy metals depends strongly on their specific
chemical fractions or binding characteristics in PMS and biochar.
The leaching characteristics of PMS and biochar were studied by
performing the experiments as per toxicity characteristic leaching
procedure (TCLP) recommended by USEPA. The effect of the pH of
the solution on the leaching behavior of the heavy metals was also
studied.

Table 2
Percentage recovery of heavy metals calculated by comparison of analytical
procedures.

Samples % Recovery
Cr Cu Ni Zn Pb Cd
Sludge 97.82 97.86 99.55 98.50 92.64 101.16
BC 200 98.83 100.0 98.73 99.19 98.72 101.01
BC 300 98.78 100.0 99.42 98.02 97.92 101.01
BC 400 99.82 100.0 98.33 99.63 98.53 99.76
BC 500 98.37 99.65 101.01 99.46 102.36 99.55
BC 600 98.41 97.15 97.02 101.41 104.51 98.23
BC 700 99.60 99.95 99.49 98.83 102.71 100.82
Fig. 4. Leaching potential of the heavy metals.
 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315 313

The results of the TCLP test for the six heavy metals in the PMS
and biochar are shown in the Fig. 4. In case of PMS, the leaching
potential of the six heavy metals followed the following sequence:
Zn > Cu > Cd > Cr > Ni > Pb. The leaching potential of the heavy
metals in the biochar was found to be lower compared with that
in the PMS and decreased with an increase in the pyrolysis temper-
ature from 200 °C to 700 °C. The result is in agreement with the
fractionation pattern of the heavy metals where the bioavailable
fraction (F1 + F2) was found to be lower in biochar and decreased
with an increase in the pyrolysis temperature. The leaching poten-
tial of the heavy metals in BC700 was found to follow the sequence
Zn > Cr > Cd > Ni > Cu > Pb.
It was observed that the leaching of the heavy metals in the bio-
char was within the limits as their concentrations in the leachate of
TCLP test were lower than the statuary limits prescribed by Indian
Standards for Industrial and Sewage Effluents Discharge (inland
surface water) (Ramteke and Moghe, 1988) Table 3.
except for Cr, the leaching potential of the heavy metals in the bio-
char was lower compared to that in the PMS. This may be due to
the fact that the biochar obtained after pyrolysis at elevated tem-
peratures is relatively alkaline in nature compared to the PMS.
The decomposition of carbonate form of alkaline earth metals at
the higher temperature leads to the formation of metal oxides
which are not prone to leaching (Zhang et al., 2009a,b). In case of
Cr, the availability of CaO after the decomposition of carbonates
leads to the formation of leachable CaCrO4 (Zheng et al., 2010).
3.5. Ecological risk assessment
Potential ecological risk index (RI) was used to assess the degree
of potential risk of heavy metal pollution in PMS and biochar using
the Eqs. (2)–(4) proposed by Hakanson (1980).
C f ¼ C i =C n ð2Þ

Er ¼ T r C f ð3Þ
3.4. Effect of solution pH on heavy metals leaching
X
The solution pH is an important parameter affecting the leach- RI ¼ Er ð4Þ
ability of the heavy metals. Experiments were carried out at differ-
where, C f is the contamination factor; Ci and Cn are the mobile and
ent solution pH (3–13) to study the effect of solution pH on the
stable fractions of the heavy metals respectively, Er is the potential
leaching potential of the heavy metals from the PMS and biochar
ecological index for individual heavy metal; T r is toxic factor of the
(BC700) and the results are shown in Fig. 5. It can be noticed that
individual heavy metal; and RI is the potential ecological risk index.
all the heavy metals present in the PMS and biochar showed max-
The T r values used for calculation of potential ecological index for
imum leaching potential at pH 3 as low pH conditions generally
individual metal are Cr (2), Cu (5), Ni (6), Zn (1), Pb (5) and Cd
enhance the metal dissolution. The leaching of the heavy metals
(30) (Hakanson, 1980; Chabukdhara and Nema, 2012).
was found to decrease with an increase in solution pH from 3 to
Contamination factor (Cf) of a heavy metal is the ratio of the
7. Further increase in the solution pH from 7 to 13 resulted in an
sum of the concentrations of the heavy metal extracted in the first
increase in the leaching of the heavy metals. The leaching potential
four fractions of the sequential extraction (F1 + F2 + F3 + F4) to the
was significant in case of Cr and Cd. It can be further noticed that
concentration of the heavy metal in the residual fraction (F5)
(Jamali et al., 2007). The value of the contamination factor of a
Table 3 heavy metal is inversely proportional to the leaching potential of
Concentration of different heavy metals (mg/L) in leachate (TCLP). the heavy metal. The potential ecological index of a heavy metal
Samples Sludge BC200 BC300 BC400 BC500 BC600 BC700 Permissible (Er) is obtained by multiplying the contamination factor of the
limits heavy metal with the toxic factor (Tr) of the heavy metal. The
Cr 1.71 2.75 2.72 2.59 2.39 2.11 1.80 2.0 potential ecological risk index (RI) of the solid (PMS/biochar) is
Cu 23.03 16.67 3.72 2.71 4.00 3.41 1.97 3.0 obtained by adding the potential ecological index of each heavy
Ni 1.77 1.21 1.81 1.20 0.88 0.69 0.54 3.0 metal present in the solid. The significance of the Cf, Er and RI along
Zn 28.05 16.20 7.98 4.18 3.05 2.71 1.42 5.0 with their risk potential is shown in Table 4.
Pb 0.84 0.76 0.72 0.80 0.74 0.57 0.20 0.1
The values of Cf, Er and RI were determined to find out the risk
Cd 0.32 0.22 0.25 0.13 0.11 0.11 0.14 2.0
level of the heavy metals in the PMS and biochar (BC700) and are

Fig. 5. Effect of pH on leachability of heavy metals from PMS and biochar (S = PMS; BC = Biochar pyrolyzed at 700 °C).
314 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315

Table 4
Indices for the ecological risk assessment.

Cf Metal contamination Er Potential ecological risk RI Sludge/biochar contamination

Cf < 1 Clean Er < 40 Low RI 6 50 Low
1 < Cf < 3 Low 40 6 Er < 80 Moderate 50 < RI 6 100 Moderate
3 < Cf < 6 Moderate 80 6 Er < 160 Considerable 100 < RI 6 200 Considerable
6 < Cf < 9 Considerable 160 6 Er < 320 High RI > 200 High
Cf > 9 High Er P 320 Very high

Table 5
Ecological risk assessment of the heavy metals in sludge and biochar.

Heavy metal Tr Contamination factor (Cf) Potential ecological risk index (Er)
Sludge BC200 BC300 BC400 BC500 BC600 BC700 Sludge BC200 BC300 BC400 BC500 BC600 BC700
Cr 2 1.11 1.11 1.06 1.02 0.99 0.99 0.99 2.22 2.22 2.12 2.04 1.98 1.98 1.98
Cu 5 2.02 2.03 1.91 1.73 1.58 1.58 1.58 10.14 10.15 9.55 8.65 7.9 7.9 7.91
Ni 6 0.66 0.61 0.56 0.42 0.39 0.31 0.27 3.96 3.66 3.36 2.52 2.34 1.86 1.67
Zn 1 3.31 13.19 13.24 13.17 1.29 1.27 1.17 3.31 13.19 13.24 13.17 1.29 1.27 1.17
Pb 5 13.19 3.39 3.28 1.13 1.05 1.03 0.77 65.95 16.95 16.4 5.65 5.25 5.15 3.85
Cd 30 18.22 15.17 15.15 12.38 3.59 2.48 1.62 546.67 455.1 454.5 371.4 107.7 74.4 48.59
Potential ecological risk index (RI) 632.25 501.27 499.17 403.43 126.46 92.56 65.17

tabulated in Table 5. It can be noticed that the values of Cf for Pb
and Cd in the PMS are13.19 and 18.22 respectively indicating a
high metal contamination. The values of Cf for Pb and Cd in the bio-
char (BC700) are 0.77 and 1.62 respectively, indicating a significant
reduction in the metal contamination after pyrolysis. Similarly, the
value of RI of PMS was found to be 632.26 indicating a high degree
of contamination by the heavy metals. The value of RI for the bio-
char (BC700) was 65.19 indicating a significant reduction in the
degree of potential risk of heavy metal pollution.
4. Conclusions
The risk analysis of pyrolyzed biochar made from pulp and
paper mill effluent treatment plant sludge was carried out for bio-
availability and eco-toxicity of heavy metals. Most of the heavy
metals were found to exist in the residual form in the biochar pyro-
lyzed at 700 °C. It was found that the pyrolysis is a promising
sludge treatment method for heavy metals immobilization result-
ing in significant reduction in the bioavailability and leaching
potential of the heavy metals in the biochar. The eco-toxicity of
the heavy metals reduced significantly after the pyrolysis, resulting
in a decrease in the environmental risk of biochar utilization.
Acknowledgement
The authors wish to acknowledge the funding received for the
project from CSIR, New Delhi (India).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2014.
03.093.
References
Abanades, S., Flamant, G., Gagnepain, B., Gauthier, D., 2002. Fate of heavy metals
during municipal solid waste incineration. Waste Manage. Res. 20, 55–68.
Azeez, A.M., Meier, D., Odermatt, J., 2011. Temperature dependence of fast pyrolysis
volatile products from European and African biomasses. J. Anal. Appl. Pyrolysis
90, 81–92.
Banerjee, A.D.K., 2003. Heavy metal levels and solid phase speciation in street dusts
of Delhi, India. Environ. Pollut. 123, 95–105.
Bo, D., Zhang, F.S., Zhao, L., 2009. Influence of supercritical water treatment on
heavy metals in medical waste incinerator fly ash. J. Hazard. Mater. 170, 66–71.
Chabukdhara, M., Nema, A.K., 2012. Heavy metals in water, sediments, and
aquatic macrophytes: river Hindon, India. J. Hazard. Toxic Radioact. Waste 16,
273–281.
Debela, F., Thring, R.W., Arocena, J.M., 2012. Immobilization of heavy metals by co-
pyrolysis of contaminated soil with woody biomass. Water Air Soil Pollut. 223,
1161–1170.
Devi, P., Saroha, A.K., 2013. Effect of temperature on biochar properties during paper
mill sludge pyrolysis. Int. J. ChemTech Res. 5, 682–687.
Fang, L., Yuan, N., Wu, Y., Zhao, X., Sun, H., 2012. Evolution of heavy metals
leachability and speciation in residues of sewage sludge treated by microwave
assisted pyrolysis. Appl. Mech. Mater. 178–181, 833–837.
Filgueiras, A.V., Lavilla, I., Bendicho, C., 2002. Chemical sequential extraction for
heavy metal partitioning in environmental solid samples. J. Environ. Monit. 4,
823–857.
Flyhammar, P., 1998. Use of sequential extraction on anaerobically degraded
municipal solid waste. Sci. Total Environ. 212, 203–215.
Gaur, N., Flora, G., Yadav, M., Tiwari, A., 2014. A review with recent advancements
on bioremediation-based abolition of heavy metals. Environ. Sci.: Process.
Impacts 16, 180–193.
Hakanson, L., 1980. An ecological risk index for aquatic pollution control: a
sedimentological approach. Water Res. 14, 975–1001.
He, Y.D., Zhai, Y.B., Li, C.T., Yang, F., Chen, L., Fan, X.P., Peng, W.F., Fu, Z.M., 2010. The
fate of Cu, Zn, Pb and Cd during the pyrolysis of sewage sludge at different
temperatures. Environ. Technol. 31, 567–574.
Hossain, M.K., Strezov, V., Chan, K.Y., Ziolkowski, A., Nelson, P.F., 2011. Influence of
pyrolysis temperature on production and nutrient properties of wastewater
sludge biochar. J. Environ. Manage. 92, 223–228.
Hu, H.Y., Liu, H., Shen, W.Q., Luo, G.Q., Li, A.J., Lu, Z.L., Yao, H., 2013. Comparison of
CaO’s effect on the fate of heavy metals during thermal treatment of two typical
types of MSWI fly ashes in China. Chemosphere 93, 590–596.
Jamali, M.K., Kazi, T.G., Afridi, H.I., Arain, M.B., Jalbani, N., Memon, A.R., 2007.
Speciation of heavy metals in untreated domestic wastewater sludge by time
saving BCR sequential extraction method. J. Environ. Sci. Health A 42, 649–659.
Kistler, R.C., Widmer, F., 1987. Behaviour of chromium, nickel, copper, zinc,
cadmium, mercury, and lead during the pyrolysis of sewage sludge. Environ.
Sci. Technol. 21, 704–708.
Nzihou, A., Stanmore, B., 2013. The fate of heavy metals during combustion and
gasification of contaminated biomass—A brief review. J. Hazard. Mater. 256–
257, 56–66.
Pathak, A., Dastidar, M.G., Sreekrishnan, T.R., 2008. Bioleaching of heavy metals
from anaerobically digested sewage sludge. J. Environ. Sci. Health A: Tox.
Hazard Subst. Environ. Eng. 43, 402–411.
Pokhrel, D., Viraraghavan, T., 2004. Treatment of pulp and paper mill wastewater – a
review. Sci. Total Environ. 333, 37–58.
Poykio, R., Nurmesniemi, H., Kuokkanen, T., Peramaki, P., 2006. The use of
sequential leaching procedure for assessing the heavy metal leachability in
lime waste from the lime kiln at a caustizicing process of a pulp mill.
Chemosphere 65, 2122–2129.
Ramteke, D.S., Moghe, C.A., 1988. Manual on Water and Wastewater Analysis.
National Environmental Engineering Research Institute (NEERI), Nagpur, India.
Ren, X., Liang, B., Liu, M., Xu, X., Cui, M., 2012. Effects of pyrolysis temperature, time
and leaf litter and powder coal ash addition on sludge-derived adsorbents for
nitrogen oxide. Bioresour. Technol. 125, 300–304.
Rodriguez, L., Ruiz, E., Azcarate, J.A., Rincon, J., 2009. Heavy metal distribution and
chemical speciation in tailings and soils around a Pb–Zn mine in Spain. J.
Environ. Manage. 90, 1106–1116.
 P. Devi, A.K. Saroha / Bioresource Technology 162 (2014) 308–315
Shi, W., Liy, C., Ding, D., Lei, Z., Yang, Y., Feng, C., Zhang, Z., 2013. Immobilization of
heavy metals in sewage sludge by using subcritical water technology.
Bioresour. Technol. 137, 18–24.
Silva, J.E., Paiva, A.P., Soares, D., Labrincha, A., Castro, F., 2005. Solvent extraction
applied to the recovery of heavy metals from galvanic sludge. J. Hazard. Mater.
B120, 113–118.
Song, F., Gu, L., Zhu, N., Yuan, H., 2013. Leaching behavior of heavy metals from
sewage sludge solidified by cement-based binders. Chemosphere 92, 344–350.
Su, D.C., Wong, J.W.C., 2003. Chemical speciation and phytoavailability of Zn, Cu, Ni
and Cd in soil amended with fly ash-stabilized sewage sludge. Environ. Int. 29,
895–900.
315
Yeiwei, C., Guijian, L., Lei, W., Yu, K., Jianli, Y., 2008. Occurrence and fate of some
trace elements during pyrolysis of yima coal, China. Energ. Fuel. 22, 3877–3882.
Zhang, D., He, S., Dai, L., Xie, Y., Wu, D., Bu, G., Peng, K., Kong, H., 2009a. Impact of
pyrolysis process on the chromium behavior of COPR. J. Hazard. Mater. 172,
1597–1601.
Zhang, D., Kong, H., Wu, D., He, S., Hu, Z., Dai, L., 2009b. Impact of pyrolysis
treatment on heavy metals in sediment. Soil Sediment Contam. 18, 754–765.
Zheng, L., Wang, W., Shi, Y.C., 2010. The effects of alkaline dosage and Si/Al ratio on
the immobilization of heavy metals in municipal solid waste incineration fly
ash-based geopolymer. Chemosphere 79, 665–671.