565210

research-article2014
WMR0010.1177/0734242X14565210Waste Management & ResearchKhanmohammadi et al.

Original Article

Waste Management & Research

Effect of pyrolysis temperature on

2015, Vol. 33(3) 275283
The Author(s) 2015
Reprints and permissions:
chemical and physical properties of sagepub.co.uk/journalsPermissions.nav
DOI: 10.1177/0734242X14565210

sewage sludge biochar wmr.sagepub.com

Zahra Khanmohammadi, Majid Afyuni and Mohammad

Reza Mosaddeghi

Abstract
The objective of this study was to evaluate the effects of pyrolysis temperatures (300, 400, 500, 600 and 700C) on properties of
biochar produced from an urban sewage sludge. Biochar yield significantly decreased from 72.5% at 300C to 52.9% at 700C,
whereas an increase in temperature increased the gas yield. Biochar pH and electrical conductivity increased by 3.8 and 1.4 dS m1,
proportionally to the increment of temperature. Biochar produced at low temperatures had higher total nitrogen and total organic
carbon content but a lower C/N ratio, calcium carbonate equivalent, and total P, K and Na contents. Total and diethylene triamine
penta acetic acid (DTPA)-extractable concentrations of Fe, Zn, Cu, Mn, Ni, Cr and Pb increased with increment of temperature.
Lower DTPA-extractable concentrations of Fe, Zn, Cu, Mn, Ni and Pb were found in biochars compared to the sewage sludge.
Pyrolysis decreased bulk density, whereas particle density and porosity increment was observed upon pyrolysis with increment
of temperature. Sewage sludge saturated water content (s) was 130.4 g 100g1 and significantly greater than biochar, but biochar
s significantly increased with temperature (95.7 versus 105.4 g 100g1 at 300 and 700C, respectively). Pyrolysis decreased the
biochars water repellency, assessed by molarity of ethanol droplet (MED), compared to the sewage sludge. The lowest MED of
0.2 and water repellency rating of 3 were found for the biochar produced at 700C. Based on our results and considering the energy
consumption, pyrolysis temperature in the range of 300400C may be suggested for sewage sludge pyrolysis.

Keywords
Pyrolysis, sewage sludge biochar, heavy metals, bulk density, water repellency, molarity of ethanol droplet

Introduction
Population growth and economic developments have resulted in
increasing sewage sludge production. The role of sewage sludge
utilization on agricultural lands as a fertilizer is known to result
in the recycling of valuable components, including organic mat-
ter, N, P, K and micronutrients (Singh and Agrawal, 2007).
However, high concentrations of heavy metals (HMs), such as
Zn, Cu, Cr, Ni, Cd, and high amounts of pathogens in sewage
sludge led to concerns regarding soil and groundwater pollution
(Gasc etal., 2005; Wang etal., 2008). In addition, high concen-
trations of N and P in sewage sludge have adverse environmental
effects (Sumner, 2000). Sewage sludge effect on soil organic
matter (SOM) and cation exchange capacity (CEC), improving
plant water availability and uptake of micronutrients such as Zn
and Cu in calcareous soils have been reported (Karami etal.,
2008; Yeganeh etal., 2010).
Pyrolysis of organic wastes, such as sewage sludge, crop resi-
dues or wood, involves the thermal transformation of biomass
under partial or no oxygen supply to solid (charcoal or biochar),
liquid (bio-oil) and gas phases (Laird, 2008; Lehmann, 2007).
When biochar is applied to the soils, it remains in an essentially
permanent form and leads to net removal of carbon from the
atmosphere (Glaser etal., 2009; Laird, 2008; Lehmann, 2007). In
fact, the polycyclic aromatic structure of biochar is the reason for
its stability and carbon sequestration in the soil (Verheijen etal.,
2010). In addition, incorporation of biochar can improve soil
physical, chemical and biological properties (Lehmann and
Joseph, 2009). Biochar application to the soil increases the soil
aeration (Laird, 2008), porosity and specific surface area (Laird
etal., 2010; Steiner etal., 2007), water-holding capacity and
drainage condition (Ibrahim etal., 2013; Steiner etal., 2007), soil
fertility and following plant yield responses (Major etal., 2010;
Park etal., 2011).
Pyrolysis conditions and feedstock characteristics largely
control the physical and chemical properties (e.g. composition,
particle and pore size distribution) of the biochar, which in turn
Department of Soil Science, College of Agriculture, Isfahan University
of Technology, Isfahan, Iran
Corresponding author:
Zahra Khanmohammadi, College of Agriculture, Isfahan University of
Technology, Isfahan 84156-83111, Iran.
Emails: zahra_khanmohamadi@yahoo.com
276 Waste Management & Research 33(3)
Figure 1. Schematic diagram of pyrolysis apparatus used in this study.
determine its suitability for a given application (Chan and Xu,
2009). Fu etal. (2011) reported that increasing pyrolysis tem-
perature decreases biochar and liquid yield but raises gas yield.
Yuan etal. (2011) studied the forms of alkalis of the biochars
produced from the straws of canola, corn, soybean and peanut at
different pyrolysis temperatures. They reported that the alkalinity
and pH of biochars increased with raising pyrolysis temperature.
Hossain etal. (2011) found that biochar yield of wastewater
sludge decreased from 72.3% at 300C to 52.4% at 700C.
Besides, pH of the produced biochars increased with increasing
pyrolysis temperature from 300 to 700C but the electrical con-
ductivity (EC) of the biochars had a decreasing trend with tem-
perature. Liu etal. (2014) investigated the nutrients and HMs in
biochar produced at 450C from sewage sludge. They found
that total and available N contents of biochar were lower,
whereas total and available P and K contents were higher when
compared to sewage sludge. Total concentrations of HMs were
greater in the biochar than in sewage sludge, but their diethyl-
ene triamine penta acetic acid (DTPA)-extractable concentra-
tions were lower in the biochar. In a recent study, Claoston etal.
(2014) reported that porosity and surface areas (determined by
the BrunauerEmmettTeller method) of empty fruit bunch and
rice husk biochars increased with pyrolysis temperature
increment.
Therefore, sewage sludge pyrolysis can be an acceptable
method for its management (Hwang etal., 2007). Pyrolysis
removes sewage sludge pathogens, reduces its volume and trans-
port costs (Caballero etal., 1997), and has positive effects on soil
properties and agricultural outputs. Various studies have been
conducted on the pyrolysis of biomass as a potential carbon
sequestrator (Glaser etal., 2009; Laird, 2008; Verheijen etal.,
2010). Although some chemical and physical properties of sew-
age sludge biochar, including nutrient, HMs, specific surface
area, pore volume and its morphology, have been studied, less
attention has been given to the effect of pyrolysis temperatures
on the water repellency and water-holding capacity of sewage
sludge biochar. The objective of this study was to investigate the
effects of pyrolysis temperature on chemical and physical prop-
erties of urban sewage sludges biochar with emphasis on physi-
cal properties, such as water repellency and water-holding
capacity.
Materials and methods
Pyrolysis experimental setup and
procedure
A secondary anaerobically digested sewage sludge was collected
from Isfahan wastewater treatment plant (32 48 21 N 51 35
21 E). The sewage sludge was oven-dried at 40C for 24 h. The
sewage sludge was then grinded and sieved to obtain particle
sizes less than 2 mm, then stored in air-tight plastic bags until it
was pyrolized. The sample was pyrolized under controlled condi-
tions to ensure uniform heating.
A modified electrical furnace was used to produce the limit-
ing-oxygen condition of pyrolysis (Figure 1). A cubic iron
encasement with dimensions of 16 cm in diameter and 45 cm in
length with three shelves was designed and put in the electrical
furnace. The door of the enclosure had an inlet for inert gas and
an outlet to pass the produced liquid phase and gases. Sewage
sludge samples were placed on the encasement shelves, and then
the encasement was put in the chamber of the electrical furnace
(Figure 1).
Sewage sludge pyrolysis was done at 300, 400, 500, 600 and
700C at a rate of 3C min1 and using a continuous inflow of
argon (inert gas) in three replicates. Therefore, 15 samples were
pyrolized (5 temperatures 3 replicates). Approximately 1.4 kg
sewage sludge was used for pyrolysis for each temperature and
replicate. The argon inflow pushed the air out of the encasement
to maintain the limiting-oxygen condition during pyrolysis. The
final temperature was maintained for 2 h. Then the furnace was
Khanmohammadi et al. 277
cooled down to 100C slowly. As shown in Figure 1, the liquid
phase (effluent) flowing through the outlet tube was collected in
a container. The percentage of biochar yield at various tempera-
tures was calculated using Equation (1):
1
mass of mass of original
Biochar yield = 100 (1)
biochar sewage sludge
Liquid phase yield was calculated similar to the biochar
yield. The gas yield percentage was obtained with subtraction of
biochar and liquid yields from 100.
Chemical analysis
The pH and EC of sewage sludge and biochars were measured in
0.01M CaCl2 solution (1:10 ratio) and 1:10 biochar:deionized
water ratio, respectively, based on the method of Blakemore etal.
(1987). The pH and EC in the liquid phase were measured directly
in the effluent by a pH meter (Metrohm) and an EC meter
(Metrohm), respectively. Total organic carbon (TOC) and total
nitrogen (TN) were determined with a TOC analyser (CS22
SKALAR) and the Kjeldahl method, respectively. To determine
total P, K and Na, sewage sludge and biochars were first com-
busted at 550C and the resulting ash was extracted with 2 M
HCl. Then the total P in the solution was determined using ascor-
bic acidNH4molybdate blue colorimetry at 880 nm. Total K
and Na were measured by flame photometry. Calcium carbonate
equivalent (CCE) was determined by the back-titration method
with NaOH (Sims, 1996).
Total concentration of Fe, Zn, Cu, Mn, Ni, Cr, Pb, Co, and Cd
was measured according to the US-EPA Method3050B (US
Environmental Protection Agency, 1996). In order to determine
the plant available form of trace elements, extraction was done
with 0.005 M DTPA and the metal concentrations in the extracts
were measured using atomic absorption (AA, model Perkin
Elmer A200) (Lindsay and Norvell, 1978).
Physical analysis
Particle density (PD) of biochar and sewage sludge samples was
determined using the method of Gupta etal. (2002). In this
method, the volume of oven-dried material was determined using
a conventional pycnometer (density bottle) by volume displace-
ment with kerosene. Bulk density (BD) of sewage sludge and
biochars was determined using the core method (Grossman and
Reinsch, 2002). The organic samples were poured into a stainless
cylinder with a diameter of 5 cm and a height of 7.8 cm, and then
the BD of loose materials (BDloose) was calculated. It is generally
believed that the BD values of different soils under a similar
loading condition are easily comparable (Havaee etal., 2014;
Keller and Hkansson, 2010). We applied this concept to our
experiment with organic materials: organic samples were put in
the stainless cylinder, and loaded with a confined axial stress of
100 kPa using a uni-axial compression apparatus. The BD of
loaded samples (BD100kPa) was also determined, which is better
comparable among the treatments due to the well-defined com-
paction condition. The porosity () of samples was calculated at
loose (loose) and 100 kPa (100kPa) conditions as follows:
f = 1 ( BD / PD ) (2)
Water-holding capacity (i.e. saturated water content) of sew-
age sludge and biochars was measured. Fifteen grams of dried
sewage sludge and biochars were poured into stainless cylinders
with a diameter of 2 cm and a height of 4 cm. Then, the cylinders
were saturated with distilled water from beneath to avoid air
entrapment. After 24 h when the water absorption was completed
(i.e. equilibrated), the samples were weighed and the gravimetric
water content at saturation (s) was calculated.
Persistence of water repellency of sewage sludge and biochars
was determined using the water droplet penetration time (WDPT)
test. Three droplets of distilled water were placed on the flat sur-
face of oven-dried samples by a medical syringe. The average
time for penetration of water droplets into the samples was
recorded as WDPT (Letey etal., 2003). Water repellency of
sewage sludge and biochars was determined according to the
molarity of ethanol droplet (MED) test (King, 1981; Watson and
Letey, 1970). The MED test determines the ethanol concentration
at which a droplet will infiltrate the surface of the sample within
10 s, which provides an index of water repellence for sample.
A series of ethanol concentration with 0.2 M increment was
prepared from a 96% ethanol stock solution. Since water repel-
lency depends on the media wetness, temperature and surface
roughness, all the water repellency tests were done on oven-dried
samples with flat surface at 25C (Roy and McGill, 2002). Water
repellency rating (WRR) and water repellence severity (WRS)
were determined from the MED values according to Table 1,
adapted from King (1981). The MED is an index of water repel-
lency but is not a fundamental physical-chemical property of the
solidliquid interaction. Therefore the MED value was used to
calculate fundamental wetting properties of media solids, includ-
ing 90 surface tension (ND), surface tension of the solution for
which there is transition from penetration to settling on the sur-
face, solidair surface tension (s) and solidwater contact angle
() using the following equations (Letey etal., 2003):
(
ND = 58.49 ( 6.846 MED ) + 0.512 MED 2 )
(3)
( )
0.0139 MED + (13.88 expp(MED))
3
ND
s = (4)
4
ND
cos = ( ) 1 (5)
s
278 Waste Management & Research 33(3)

Table 1. Water repellency ranking (severity and rating) according to molarity of ethanol (MED) values (adapted from King,
1981).

Molarity of ethanol (MED) Water repellency severity Water repellency rating

0a Never apparent 1
0a Very low 2
0.00.3 3
0.30.7 Low 4
0.71.1 5
1.11.5 6
1.51.9 Moderate 7
1.92.3 8
2.32.7 9
2.73.1 Severe 10
3.13.5 11
3.53.9 Very severe 12
>3.9
aThe categories never apparent and very low can be distinguished using the water droplet penetration time (Watson and Letey, 1970).

Figure 2. Yields of produced phases of sewage sludge biochar at different pyrolysis temperatures. The bars on the columns
indicate standard deviations.

Statistical analysis Results and discussion

All the measurements were set up in a completely randomized
design (organic material type or pyrolysis temperature) with
three replicates. Results were analysed using analysis of vari-
ance (ANOVA) procedures and means were separated using the
protected least significant difference (LSD) test at the 0.05 prob-
ability level. Pearson correlation analysis between different
physical properties and parameters (i.e. MED, ND, , WDPT,
and s) was examined (SAS Institute, 2000).
Products yield
Biochar yield significantly decreased with increasing pyrolysis
temperature from 72.5% at 300C to 52.9% at 700C (Figure 2).
The decrease in the biochar yield could be due to greater decom-
position of raw materials at higher temperatures (Fu etal., 2011).
The gas yield significantly increased from 9.7% at 300C to
27.5% at 700C (Figure 2). Liquid yield slightly increased with
increasing pyrolysis temperature, but its change was less than
Khanmohammadi et al. 279

Table 2. The pH and electrical conductivity (EC) in sewage sludge and its biochars produced at different temperatures and
their liquid phase.

Phase Property Sewage Biochar produced at temperature (C)

lsludge
300 400 500 600 700
Solid phase pH 6.8f (0.2) 8.2e (0.1) 9.2d (0.2) 9.7c (0.2) 11.0b (0.3) 12.0a (0.2)
(1:10 solution) EC (dS m1) 2.2a (0.05) 0.5e (0.05) 0.8c (0.04) 0.7d (0.03) 0.6d (0.04) 1.9b (0.05)
Liquid phase pH 7.8e (0.06) 8.5c (0.08) 9.0a (0.07) 8.7b (0.04) 8.3d (0.05)
EC (dS m1) 43.2e (0.5) 48.0d (1.0) 50.5c (0.5) 55.5b (0.3) 63.6a (0.6)

Note: Each value represents the mean of three replicates; figures in the parentheses are standard deviations; in each row, different letters
stand for significant difference at p < 0.05 according to the least significant difference test.

Table 3. Chemical properties of sewage sludge and its biochars produced at different pyrolysis temperatures.

Property Unit Sewage sludge Biochar produced at temperature (C)

300 400 500 600 700

TN g 100g1 3.3a (0.033) 2.7b (0.066) 2.1c (0.038) 2.0d (0.033) 1.7e (0.004) 1.1f (0.013)
TOC g 100g1 40.8a (0.6) 34.0b (0.1) 33.0c (0.7) 32.7c (0.1) 26.9d (0.3) 25.1e (0.3)
C/N ratio 12.4c (0.2) 12.8c (0.3) 15.4b (0.5) 16.0b (0.3) 15.6b (0.2) 23.3a (0.3)
P g 100g1 1.1c (0.05) 1.7b (0.12) 1.8b (0.18) 2.20a (0.01) 2.1a (0.1) 2.3a (0.2)
K g 100g1 0.20d (0.015) 0.26c (0.033) 0.29c (0.035) 0.36b (0.026) 0.41b (0.023) 0.47a (0.014)
Na g 100g1 0.20e (0.007) 0.24d (0.015) 0.27c (0.013) 0.30b (0.002) 0.32b (0.018) 0.35a (0.011)
CCE g 100g1 16.9d (0.3) 23.0c (0.9) 24.5b (0.4) 27.5a (0.5) 24.9b (0.3) 24.4b (0.4)

TN: total nitrogen content; TOC: total organic carbon content; P: total phosphorous content; K: total potassium content; Na: total sodium
content; CCE: calcium carbonate equivalent.
Note: Each value represents the mean of three replicates; figures in the parentheses are standard deviations; in each row, different letters
stand for significant difference at p < 0.05 according to the least significant difference test.

those for solid and gas phases. The minimum liquid yield was
produced at 300C and there was no significant change between
500 and 600C. Wei etal. (2006) found that fast secondary reac-
tions in the gas phase, following by over-cracking of pyrolysis
vapours may result in gas yield increment at high temperatures.
Besides, increase in pyrolysis temperature through secondary
decomposition of char could produce non-condensable gases and
consequently increased the gas yield (Fu etal., 2011).
pH and EC
The sewage sludge pH was 6.8 and increased with pyrolysis
(Table 2). The biochar pH significantly increased with increasing
pyrolysis temperature. Yuan etal. (2011) also reported similar
results. The liquid phase pH increased from 7.8 at 300C to 9.0
at 500C, and then decreased to 8.3 at 700C. EC of sewage
sludge was 2.2 dS m1 and significantly decreased after pyroly-
sis (Table 2). The EC increased with increasing temperature and
biochar produced at 300C had the lowest EC among the pyroly-
sis temperatures.The EC of solid-phase suspension and liquid
phase of the produced biochar increased with increasing pyroly-
sis temperature (Table 2).
The liquid-phase EC was very high, indicating that soluble
ions were mainly separated by the effluent from the solid phase
(biochar). This led to a low concentration of soluble ions in the
biochar solid-phase suspension compared to sewage sludge. The
liquid-phase EC increased with increasing pyrolysis temperature
from 43.2 dS m1 at 300C to 63.6 dS m1 at 700C.
Chemical analysis
Total N in sewage sludge significantly decreased with biochar
production and rising pyrolysis temperature (Table 3).The bio-
char TN decreased by 59.7% with increasing temperature from
300 to 700C. Probably emission of different nitrogen groups,
such as NH4N or NO3N, at low temperatures and pyridine at
high temperatures (>600C) caused TN decline (Bagreev etal.,
2001).
The pyrolysis process decreased the TOC of sewage sludge as
well (Table 3). The TOC of biochars decreased with increasing
pyrolysis temperature; however, there was no significant differ-
ence between the TOC of biochars produced at 400 and 500C. It
seems organic C transferred from solid phase into liquid or gas
phases during pyrolysis. There was no significant difference in
the C/N ratio of sewage sludge and biochar produced at 300C.
As the pyrolysis temperature rose, C/N ratio increased and the
maximum C/N ratio was found at 700C. Yuan etal. (2011)
reported C/N ratio increment during pyrolysis as a result of the N
depletion. Our results showed the rate of TN decline was greater
than TOC decrease rate, which resulted in a higher C/N ratio.
There was no significant difference in C/N ratio of the biochars
produced at 400, 500 and 600C (Table 3). The biochars had
280 Waste Management & Research 33(3)

Table 4. Total and diethylene triamine penta acetic acid (DTPA)-extractable concentrations of heavy metals in sewage sludge
and its biochars produced at different temperatures.

Heavy metal Sewage sludge Biochars produced at temperature (C)

300 400 500 600 700

Total concentration (mg kg1)
Fe 12,210f (225) 16,330e (190) 17,730d (225) 18,890c (265) 19,490b (80) 20,930a (50)
Zn 910d (60) 1150c (30) 1350b (20) 1430a (45) 1470a (25) 1470a (30)
Cu 256c (30) 352b (22) 362ab (15) 396a (28) 386a (24) 414a (20)
Mn 298c (22) 386a (8) 380ab (18) 400a (21) 364b (12) 392a (10)
Ni 60b (7) 72a (3) 62b (3) 68ab (5) 70a (6) 76a (4)
Cr 92b (22) 88b (16) 100b (26) 178a (14) 96b (8) 104b (26)
Pb 107c (11) 107c (9) 116bc (14) 142ab (10) 132b (8) 152a (10)
Co ND ND ND ND ND ND
Cd ND ND ND ND ND ND
DTPA-extractable concentration (mg kg1)
Fe 288.0a (22) 27.6d (13) 54.6c (16) 53.2c (8) 68.0c (12) 248.0b (11)
Zn 130.0a (4.0) 2.5d (0.5) 7.0c (1.0) 6.7c (0.7) 8.0c (1.0) 13.3b (1.2)
Cu 20.5a (1.5) 0.5d (0.3) 0.8d (0.1) 1.6d (0.8) 6.2c (0.1) 15.3b (0.9)
Mn 23.3a (0.6) 2.0d (0.4) 6.7c (0.7) 5.5c (0.8) 5.7c (0.5) 11.5b (0.6)
Ni 3.6a (0.3) ND 0.3c (0.1) 0.3c (0.1) 0.3c (0.2) 1.2b (0.1)
Cr 1.2b (0.2) 1.3b (0.2) 1.3b (0.1) 1.3b (0.1) 1.5ab (0.2) 1.8a (0.2)
Pb 13.2a (1.0) 1.4e (0.0) 6.2d (0.2) 6.2d (0.4) 10.9b (0.8) 8.6c (0.7)
Co ND ND ND ND ND ND
Cd ND ND ND ND ND ND

Note: Each value represents the mean of three replicates; figures in the parentheses are standard deviations; in each row, different letters
stand for significant difference at p < 0.05 according to the least significant difference test.
ND: Non-detectable by atomic absorption spectrophotometer.

higher total P contents compared to sewage sludge (Table 3). Liu
etal. (2014) and Yuan etal. (2011) reported similar results. Total
P in the biochar increased with increasing pyrolysis temperature,
but there were no significant differences between 500, 600 and
700C. Greater P content of biochars produced at high tempera-
tures is attributable to the relation between P and the sewage
sludge inorganic part. In addition, sewage sludge pyrolysis con-
centrated the P components in the biochars (Yuan etal., 2011).
The K and Na increased with increasing pyrolysis tempera-
ture, indicating K and Na in sewage sludge is mainly in the inor-
ganic part (Hossain etal., 2011). Pyrolysis increased the
carbonate content (CCE%) compared to sewage sludge. It seems
that elevating the mineral part ratio may cause the CCE incre-
ment upon pyrolysis. The pyrolysis temperature slightly affected
the CCE of the biochar. The CCE% decreased at temperatures
above 500C, presumably due to destruction of carbonates.
Table 4 shows the total and DTPA-extractable concentra-
tions of HMs in sewage sludge and biochars. The HMs concen-
tration in the sewage sludge was below the upper critical limits
suggested by the USEPA (US Environmental Protection
Agency, 1993). Total concentrations of Fe, Zn, Cu, Mn, Ni, Cr
and Pb in the biochars were higher than those in the original
sewage sludge (Table 4). Probably dissociation of organic com-
pounds and some minerals, such as carbonates, with pyrolysis
temperature participated in the increased HMs concentrations.
For example, HMs chlorides and sulphide-chloride compounds
are easily vapourized forms but their sulphide compounds are
more resistant to vapourization (Yau and Naruse, 2009). The
greatest concentration of Mn and Cr in the biochar was found at
500C. Concentration of Cr significantly decreased with
increasing temperature above 500C. In the case of Ni and Pb,
the highest concentrations were obtained at 700C (Table 4).
The concentrations of Co and Cd in the sewage sludge and all
of the biochars were below the detection limit of atomic absorp-
tion spectroscopy (AAS).
The DTPA-extractable concentration of HMs was regarded
as their available form for plant uptake (Soltanpour and Schwab,
1977). The DTPA-extractable concentrations of Fe, Zn, Cu,
Mn, Ni, and Pb decreased with pyrolysis (Table 4). The higher
pH of the biochars compared to sewage sludge probably pre-
vented the HMs release. Therefore, pyrolysis reduced the solu-
ble forms into more insoluble forms. For example, pyrolysis
could transform exchangeable compounds of Zn and Pb to oxide
and sulphide forms, which are less soluble (Liu etal., 2014).
However, rising pyrolysis temperature increased the DTPA-
extractable concentrations of Fe, Zn, Cu, Mn, Ni and Pb. The
highest availability of Pb in biochars was found at 600C. The
DTPA-extractable concentration of Cr increased with biochar
production and increasing pyrolysis temperature, but the
increase was only significant at 700C (Table 4). There was no
significant difference in the DTPA-extractable concentrations
of Fe, Zn, Mn and Ni between 400, 500 and 600C. The DTPA-
extractable concentration of Cu did not differ significantly
between 300, 400 and 500C (Table 4).
Khanmohammadi et al. 281

Table 5. Particle density, bulk density, porosity, saturated water content and water repellency indices of sewage sludge and its
biochars produced at different pyrolysis temperatures.

Property Unit Sewage sludge Biochars produced at temperature (C)

300 400 500 600 700

PD Mg m3 1.53e (0.033) 1.81d (0.056) 1.96c (0.051) 1.99bc (0.054) 2.07ab (0.039) 2.16a (0.051)
BDloose Mg m3 0.62a (0.04) 0.56ab (0.02) 0.58ab (0.03) 0.56ab (0.02) 0.53b (0.03) 0.52b (0.04)
loose m3 m3 0.59d (0.013) 0.69c (0.018) 0.70c (0.013) 0.72bc (0.016) 0.74ab (0.011) 0.76a (0.019)
BD100kPa Mg m3 0.70a (0.06) 0.62ab (0.03) 0.63ab (0.02) 0.64ab (0.06) 0.62ab (0.04) 0.58b (0.04)
100kPa m3 m3 0.54c (0.02) 0.66b (0.02) 0.68b (0.01) 0.68b (0.01) 0.70ab (0.01) 0.73a (0.03)
s g 100g1 130.4a (1.58) 95.7e (0.44) 97.2d (0.38) 97.1d (0.70) 103.8c (0.62) 105.4b (0.12)
WDPT min 26e (1.00) 201c (07.64) 220ab (4.36) 230a (14.00) 214bc (7.50) 43d (5.70)
MED M 5.4a (0.10) 5.2b (0.05) 2.2c (0.05) 0.5d (0.05) 0.5d (0.05) 0.2e (0.00)
ND dynes cm1 51d (0.31) 51.6dc (0.33) 67.6c (0.93) 157.8b (17.16) 157.8b (17.16) 815a (0.00)
125.5a (0.08) 125.3a (0.09) 121.1b (0.22) 105.1c (2.54) 105.1c (2.54) 47.0d (0.00)
WRR 12 12 8 4 4 3
WRS Very severe Very severe Moderate Low Low Low

PD: particle density; BDloose and loose: bulk density and porosity at loose state, respectively; BD100kPa and 100kPa: bulk density and porosity under
confined axial stress 100 kPa, respectively; s: saturated water content; WDPT: water droplet penetration time; MED: molarity of ethanol drop-
let; ND: 90 surface tension; : solidwater contact angle; WRR: water repellency rating; WRS: water repellency severity.
Note: Each value represents the mean of three replicates; figures in the parentheses are standard deviations; in each row, different letters
stand for significant difference at p<0.05 according to LSD test.

Physical analysis 1.70 Mg m3 (Oberlin, 2002). Scheffer and Schachtschabe

PD of biochars was significantly higher than that of sewage
sludge. The PD of biochar increased significantly with increasing
pyrolysis temperature (Table 5).
Nature of feedstock and pyrolysis process affects the biochar
PD values (Pandolfo etal., 1994). The typical PD value of bio-
chars has been reported to be in the range 1.51.7 Mg m3
(Jankowska etal., 1991; Oberlin, 2002). However, biochars pro-
duced at high temperatures can have PD values near the solid
graphite (i.e. 2.25 Mg m3). Kercher and Nagle (2002) found that
biochar PD increases with increasing pyrolysis temperature
because low-density disordered C converts to high-density tur-
bostratic C. Moreover, increment in the pyrolysis temperature,
dissociates and/or partly volatilizes the organic part of sewage
sludge and elevates the mineral part ratio, which may increase
the PD (Table 5).
BD of sewage sludge decreased upon pyrolysis, but the
biochar BD values at 600 and 700C were significantly lower
than that of original sewage sludge (Table 5). Despite the PD
increase, the BD decreases upon pyrolysis indicating highly
porous structure of the biochar, which overrides the effect of the
greater fraction of the heavier mineral part. The porosity ()
increased with biochar production and also with increasing
pyrolysis temperature in both loose and 100 kPa stress condi-
tions. Ding etal. (2010) found biochar BD reduction (i.e.
increment) during the pyrolysis process, particularly at high
temperatures. The organic materials under confined axial stress
of 100 kPa had greater BD and lower . Besides, significant
difference was only observed between BD100kPa values of
sewage sludge and biochar produced at 700C (Table 5). The
biochar BD content depends on the original matter of biochar
and production condition. It has been reported that biochar BD
varies in the range from 0.08 (Gundale and De Luca, 2006) to
(2002) reported common BD values of mineral soils range from
1.16 to 2.00 Mg m3; therefore, biochar addition to the soil has
a positive effect on soil physical quality due to lowering BD (or
increasing ).
Saturated water content (s) of sewage sludge was signifi-
cantly higher than that of biochar samples (Table 5), presumably
due to greater TOC and organic materials and significant swell-
ing property of sewage sludge upon water absorption. Similar to
porosity (f), the s of biochar significantly increased with
increasing pyrolysis temperature, so that the biochar produced at
700C had the highest s among the biochars (Table 5). It was
observed that the biochar swelling upon wetting was negligible
showing the water-stability of its pores.
Water repellency is a serious limitation of organic-based
amendments including sewage sludge and biochars. The WDPT
test showed that sewage sludge and biochars are water-repellent.
The WDPT indicates the persistence of water repellency (Letey
etal., 2003). The minimum WDPT value was 26 min for sewage
sludge (Table 5) indicating the water repellency of sewage
sludge is slightly persistent. The maximum WDPT values of bio-
chars 400 and 500C were significantly higher than the others.
Among the pyrolysis temperatures, biochar produced at 700C
had the lowest WDPT value. It is known that at low pyrolysis
temperatures, aliphatic hydrocarbons induce water repellency.
However, decomposition of hydrophobic groups at high tem-
peratures would decrease the water repellency (Spokas, 2010).
DeBano (1981) investigated the relationship between water
repellency and soil temperature. He showed that when soils were
heated between 280 and 400C in an aerobic environment,
destruction of water repellency occurs. These findings confirm
our results but it seems that destruction of water repellency
during pyrolysis process (limiting-oxygen condition) occurs at
higher temperatures.
282 Waste Management & Research 33(3)
The MED varied significantly from 5.4 to 0.2 for sewage
sludge and biochar produced at 700C. Water repellency of sew-
age sludge and biochar produced at 300C was very severe with
WRR equal to 12. Increasing pyrolysis temperature decreased the
water repellency of biochars, as WRR of 3 was found for the
biochar produced at 700C. Water repellency severity (WRS) did
not differ between biochars produced at 500 and 600C.
Ninety-degree surface tension (ND) significantly increased
with biochar production and the greatest value was obtained at
700C. Novak etal. (2012) found that biochar ND increased with
pyrolysis temperature increment. They reported the greatest ND
for pecan shell biochar produced at 700C. Therefore, biochars
produced at higher temperatures have lower water repellency and
greater tendency to absorb water, as revealed by the s values
(Table 5) in accordance with the findings of Novak etal. (2012)
with pecan shell biochar. Accordingly, the solidwater contact
angle () significantly decreased with the pyrolysis temperature.
The role of pyrolysis condition and feedstock type on the struc-
tural groups of organic compounds is well-known. Hydrophobicity
degree of biochar is affected by its structural surface groups
(Amonette and Joseph, 2009). High water repellency of sewage
sludge is probably due to the presence of hydrophobic organic
materials/groups, such as lipids and detergents. Biochars formed
at lower temperatures (i.e. 300 and 400C) still contain the char-
acteristics of the original feedstock. It seems that conversion of
aliphatic C to aromatic C and decomposition of hydrophobic
groups at high temperatures would decrease the water repellency
(Spokas, 2010).
Although a significant negative correlation (r = 0.505, p <
0.05) was found between ND and WDPT, no significant correla-
tion was observed between MED or and WDPT, indicating that
water repellency rate (MED or ) might not be interrelated with
water repellency persistence (WDPT). The s did not signifi-
cantly correlate with MED, ND or . However, a significant
negative correlation (r = 0.79, p < 0.01) was obtained between
s and WDPT, showing that water repellency persistence would
mainly control the water-holding capacity of the organic
materials.
Conclusion
1) Biochar yield of sewage sludge significantly decreased with
increasing pyrolysis temperature, whereas gas yield increased
with elevating temperature. Pyrolysis increased pH of sewage
sludge but decreased its EC. The soluble ions were mainly
concentrated in the liquid phase (i.e. effluent of biochar) dur-
ing pyrolysis. Biochar pH and EC increased with tempera-
ture. The EC of biochars liquid phase was higher than the EC
of biochars solid suspension and increased significantly with
rising temperature.
2) The biochars had higher concentrations of P, K and Na and
lower TN content compared to sewage sludge. Therefore, N
fertilizers may be required when sewage sludge biochar is
applied to agricultural soils. Pyrolysis of sewage sludge
lowered the biochar TOC content. The C/N ratio significantly
increased in biochars with the pyrolysis temperature applied.
3) Total concentrations of Fe, Zn, Cu, Mn, Ni, Cr and Pb increased
with biochar production and rising pyrolysis temperature.
Biochars had lower DTPA-extractable concentrations of Fe,
Zn, Cu, Mn, Ni and Pb compared to sewage sludge. There were
some variations in the DTPA-extractable concentrations of
HMs with increasing temperature, indicating the changes in
their chemical forms during the pyrolysis process.
4) PD was greater in biochars produced at high temperatures.
The pyrolysis process decreased the BD, but it did not differ
significantly between temperatures. Saturated water content
of sewage sludge was significantly higher than biochar.
Nevertheless, the biochar s values were still high and signifi-
cantly increased with temperature. Conversions of sewage
sludge to biochar decreased WRS from very severe at 300C
to low at 700C. Water repellency rating of sewage sludge
was 12, which declined to 3 for the biochar produced at
700C. This reduction indicates decomposition of hydropho-
bic groups at high temperatures.
5) Based on the overall assessment of chemical and physical
properties and energy consumption, pyrolysis temperature in
the range of 300400C is suggested for urban sewage sludge
pyrolysis. It is recommended to monitor the impacts of bio-
chars on soil and plant attributes in field conditions.
Acknowledgement
Our sincere appreciation is extended to Prof. AA Mahboubi of the
School of Engineering, University of Guelph, Canada for improving
the English in this paper.
Declaration of conflicting interests
The authors declare that there is no conflict of interest.
Funding
This work was supported by the Isfahan University of Technology,
Isfahan, Iran.
References
Amonette JE and Joseph S (2009) Characteristics of biochar: Microchemical
properties. In: Lehmann JL and Joseph ST (eds) Biochar for Environmental
Management. London: Earthscan Publishers Ltd, pp. 3352.
Bagreev A, Bandosz TJ and Locke DC (2001) Pore structure and surface
chemistry of adsorbents obtained by pyrolysis of sewage derived ferti-
lizer. Carbon 39: 19711979.
Blakemore LC, Searle PL and Daly BK (1987) Methods for chemical analy-
sis for soils. NZ Soil Bureau Scientific Report 80, pp.7879.
Caballero JA, Front R, Marcilla A, etal. (1997) Characterization of sewage
sludges by primary and secondary pyrolysis. Journal of Analytical and
Applied Pyrolysis 4041: 433450.
Chan KY and Xu Z (2009) Biochar: Nutrient properties and their
enhancement. In: Lehmann J and Joseph S (eds) Biochar for
Environmental Management: Science and Technology. London:
Earthscan, pp.6784.
Claoston N, Samsuri AW, Ahmad Husni MH, etal. (2014) Effects of pyroly-
sis temperature on the physicochemical properties of empty fruit bunch
and rice husk biochars. Waste Management & Research 32: 331 339.
DeBano LF (1981) Water repellent soils: a state-of-the-art. USDA Forest
Service General Technical Report PS W-46, 21p.
Khanmohammadi et al. 283
Ding Y, Liu YX, Wu WX, etal. (2010) Evaluation of biochar effects on
nitrogen retention and leaching in multi-layered soil columns. Water, Air
and Soil Pollution 213: 4755.
Fu P, Yi W, Xueyuan B, etal. (2011) Effect of temperature on gas com-
position and char structural features of pyrolized agricultural residues.
Bioresource Technology 102: 82118219.
Gasc G, Lobo MC and Guerrero F (2005) Land application of sewage
sludge: A soil columns study. Water SA 31: 309318.
Glaser B, Parr M, Braun C, etal. (2009) Biochar is carbon negative. Nature
Geoscience 2: 2.
Grossman RB and Reinsch TG (2002) Bulk density and linear extensibil-
ity. In: Dane JH and Topp GC (eds) Methods of Soil Analysis, Part 4.
Physical Methods. Soil Sci. Am. Book Series No. 5. Madison, WI: ASA
and SSSA, pp.202228.
Gundale M and De Luca T (2006) Temperature and source material influence
ecological attributes of ponderosa pine and Douglas-fir charcoal. Forest
Ecology and Management 231: 8693.
Gupta M, Yang J and Roy C (2002) Density of softwood bark and softwood
char: Procedural calibration and measurement by water soaking and kero-
sene immersion method. Fuel 81: 13791384.
Havaee S, Ayoubi S, Mosaddeghi MR, etal. (2014) Impacts of land use on
soil organic matter and degree of compactness in calcareous soils of cen-
tral Iran. Soil Use and Management 30: 29.
Hossain MK, Strezov V, Yin Chan K, etal. (2011) Influence of pyrolysis
temperature on production and nutrient properties of wastewater sludge
biochar. Journal of Environmental Management 92: 223228.
Hwang IH, Ouchi Y and Matsuto T (2007) Characteristics of leachate from
pyrolysis residue of sewage sludge. Chemosphere 68: 19131919.
Ibrahim HM, Al-Wabel MI, Usman ARA, etal. (2013) Effect of Conocarpus
biochar application on the hydraulic properties of a sandy loam soil. Soil
Science 178: 165173.
Jankowska H, Swiatkowski A and Choma J (1991) Active Carbon. New
York: Ellis Horwood.
Karami M, Afyuni M, Rezainejad Y, etal. (2008) Heavy metal uptake by
wheat from a sewage sludge-amended calcareous soil. Nutrient Cycling
in Agroecosystems 83: 5161.
Keller T and Hkansson I (2010) Estimation of reference bulk density from
soil particle size distribution and soil organic matter content. Geoderma
154: 398406.
Kercher AK and Nagle DC (2002) Evaluation of carbonized medium-density
fiberboard for electrical applications. Carbon 40: 13211330.
King PM (1981) Comparison of methods for measuring severity of water
repellence of sandy soils and assessment of some factors that affect its
measurement. Australian Journal of Soil Research 19: 275286.
Laird DA (2008) The charcoal vision: A win-win-win scenario for simul-
taneously producing bioenergy, permanently sequestering carbon, while
improving soil and water quality. Agronomy Journal 100: 178181.
Laird DA, Fleming P, Davis DD, etal. (2010) Impact of biochar amendments
on the quality of a typical Midwestern agricultural soil. Geoderma 158:
443449.
Lehmann J (2007) A handful of carbon. Nature 447: 143144.
Lehmann J and Joseph S (eds) (2009) Biochar for Environmental
Management: Science and Technology. London/Sterling, VA: Earthscan.
Letey J, Carillo MLK and Pang XP (2003) Characterizing the degree of
repellency. In: Ritsema CJ and Dekker LW (eds) Soil Water Repellency:
Occurrence, Consequences and Amelioration. Amsterdam: Elsevier,
pp.5157.
Lindsay WL and Norvell WA (1978) Development of a DTPA soil test for
zinc, iron, manganese and copper. Soil Science Society American Journal
42: 421428.
Liu T, Liu B and Zhung W (2014) Nutrients and heavy metals in biochar
produced by sewage sludge pyrolysis: Its application in soil amendment.
Polish Journal of Environmental Studies 23: 271275.
Major J, Rondon M, Molina D, etal. (2010) Maize yield and nutrition during
4 years after biochar application to a Colombian Savanna Oxisol. Plant
and Soil 333: 117128.
Novak JM, Busscher WJ, Watts DW, etal. (2012) Biochars impact on
soil-moisture storage in an Ultisol and two Aridisols. Soil Science 177:
310320.
Oberlin A (2002) Pyrocarbons. Carbon 40: 724.
Pandolfo AG, Amini-Amoli M and Killingley JS (1994) Activated car-
bons prepared from shells of different coconut varieties. Carbon 32:
10151019.
Park JH, Choppala GK, Bolan NS, etal. (2011) Biochar reduces the bio-
availability and phytotoxicity of heavy metals. Plant and Soil 348:
439451.
Roy JL and McGill WB (2002) Assessing soil water repellency using the
molarity of ethanol droplet (MED) test. Soil Science 167: 8397.
SAS Institute (2000) SAS/STAT Users Guide, Release 8. Cary, NC: SAS
Institute.
Scheffer F and Schachtschabel P (2002) Lehrbuch der Bodenkunde. 15th ed.
Stuttgart: Ferdinand Enke.
Sims JT (1996) Lime requirement. In: Sparks RL (ed.) Methods of Soil
Analysis, Part 3, Chemical Methods, SSSA Book Series No. 5. Madison,
WI: Soil Science Society of America, pp.491515.
Singh RP and Agrawal M (2007). Effects of sewage sludge amendment on
heavy metal accumulation and consequent responses of Beta vulgaris
plants. Chemosphere 67: 22292240.
Soltanpour PN and Schwab AP (1977) A new soil test for simultaneous
extraction of macro and micronutrients in alkaline soils. Communications
in Soil Science and Plant Analysis 8: 195207.
Spokas KA (2010) Review of the stability of biochar in soils: predictability of
O: C molarratios. Carbon Management 1: 289303.
Steiner C, Teixeira WG, Lehmann J, etal. (2007) Long term effects of
manure, charcoal and mineral fertilization on crop production and fertil-
ity on a highly weathered Central Amazonian upland soil. Plant and Soil
291: 275290.
Sumner ME (2000) Beneficial use of effluents, wastes and biosolids.
Communications in Soil Science and Plant Analysis 31: 17011715.
US Environmental Protection Agency (1996) Acid digestion of sediments,
sludges, and soils. Method 3050 B. USEPA, Washington, DC.
Verheijen F, Jeffery S, Bastos AC, etal. (2010) Biochar application to soils.
JRC Scientific and Technical Reports.
Wang X, Chen T, Ge Y, etal. (2008) Studies on land application of sew-
age sludge and its limiting factors. Journal of Hazardous Materials 160:
554558.
Watson CL and Letey J (1970) Indices for characterising soil-water repel-
lency based upon contact-surface tension relationships. Proceedings of
the Soil Science Society of America 34: 841844.
Wei L, Xu S, Zhang L, etal. (2006) Characteristics of fast pyrolysis of bio-
mass in a free fall reactor. Fuel Processing Technology 87: 863871.
Yau H and Naruse I (2009) Using sorbents to control heavy metals and par-
ticulate matter emission during solid fuel combustion. Particuology 7:
477482.
Yeganeh M, Afyuni M, Khoshgoftarmanesh AH, etal. (2010) Transport of
zinc, copper, and lead in a sewage sludge amended calcareous soil. Soil
Use and Management 26: 176182.
Yuan JH, Xu RK and Zhang H (2011) The forms of alkalis in the biochar
produced from crop residues at different temperatures. Bioresource
Technology 102: 34883497.