Journal of Analytical and Applied Pyrolysis 102 (2013) 137–143

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Journal of Analytical and Applied Pyrolysis

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

Characterization of sewage sludge-derived biochars from different

feedstocks and pyrolysis temperatures
Huanliang Lu a,b , Weihua Zhang b,c , Shizhong Wang b,c,∗ , Luwen Zhuang b , Yuxi Yang b ,
Rongliang Qiu b,c
a
Guangdong Provincial Academy of Environmental Science, Guangzhou 510045, China
b
School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China
c
Guangdong Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275, China

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

Article history: The surface characteristics of sludge-derived biochar (SDBC) made from three feedstocks of wastewater
Received 18 October 2012 sludge under different pyrolysis temperatures were investigated. Results showed that the sludge from
Accepted 12 March 2013 Waste Water Treatment Plant (WWTP) with pure domestic wastewater influent and less mixed indus-
Available online 26 March 2013
trial wastewater produced the highest biochar yield, and these SDBC samples have the highest isoelectric
point (IEP) and the most uniform charge distribution, compared with other sources. For different pyrol-
Key words:
ysis temperatures, 400 ◦ C tend to achieve more uniform surface charge distribution of SDBC, due to the
Feedstock
oxidation process more occurred on the external surface than internal matrix at this temperature. In
Pyrolysis temperature
Sludge-derived biochar (SDBC)
addition, a pyrolysis temperature of 300 ◦ C resulted in the most reduction in DTPA-extractable metals of
Surface characterization SDBCs, owing to the organo-metallic complex formed with the abundant presence of functional groups
Point of zero charge (PZC) and available phosphorus content, which were easily decomposed or degraded at higher temperatures.
Isoelectric point (IEP) © 2013 Elsevier B.V. All rights reserved.

1. Introduction
Biochar refers to the carbon-rich material of pyrolysis of biomass
from a wide variety of biomass residues (e.g. wood chips, compost
and animal manure) in an oxygen-free or low oxygen environment
[1,2]. It is widely used as a soil amendment for agricultural applica-
tion to improve physical properties of soils such as air permeability,
water and nutrient retention capacity and surface drainage.
Recently attention has been given to biochar derived from
sewage sludge because of its potential for soil amelioration and
the potential additional benefits for sewage sludge treatment
[3,4]. Sewage sludge is an organic waste which usually contains
high levels of nitrogen and phosphorous as well as significant
concentrations of micronutrients. Currently, with the substantive
construction of Waste Water Treatment Plants (WWTPs) in China,
more than 25 million tons of sewage sludge (with a moisture
content of approximately 80%) from WWTPs has been annually pro-
duced. Management of the increasing volume of sewage sludge has
been one of the prime environmental issues in China in recent years.
The application of wastewater sludge-derived biochar (SDBC) to
∗ Corresponding author at: School of Environmental Science and Engineering, Sun
Yat-sen University, Guangzhou 510275, China. Tel.: +86 20 84113454;
fax: +86 20 84113616.
E-mail address: wshizh2@mail.sysu.edu.cn (S. Wang).
land has been reported to significantly increase the soil electrical
conductivity, phosphorus and nitrogen content [5]. It has also been
recently reported that biochar can effectively remove heavy metals
and organic pollutants from contaminated soil and waters [6–8].
Biochar properties can be significantly influenced by feedstock
source along with pyrolysis conditions such as temperature, resi-
dence time and activation treatment [2,8–11]. It is these differences
in physicochemical properties that govern the specific interactions
between biochar and a wide range of organic and inorganic com-
pounds in the environment. For example, biochars produced from
crop residues (e.g. rye, maize), manures and seaweed are gen-
erally finer and less robust (i.e. lower mechanical strength). The
latter are also nutrient-rich, and therefore, more readily degrad-
able by microbial communities in the environment [12]. The ability
of high temperature biochars are limited for nutrient cation reten-
tion capacity of soil due to their decrease in surface acidity and
Cation Exchange Capacity (CEC), compared with low-temperature
biochars [13]. The manure-based biochars may mineralize and
release nutrients more rapidly in soil than the plant-based biochars
rich in condensed aromatic structures [9,13]. Additionally, the
concentration of extractable phosphorus was found increased in
tropical soils amended with a variety of charred materials [14,15].
The chemical properties of the biochar produced from wastewa-
ter sludge has been recently reported to be significantly influenced
by pyrolytic temperature [16]. However, literature is limited on the
relationship between the characteristics of SDBC with its different

0165-2370/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.03.004
138 H. Lu et al. / Journal of Analytical and Applied Pyrolysis 102 (2013) 137–143
sources of sludge. Little work has been conducted to determine
the effects of sludge which has received no anaerobic digestion on
biochar production. For sewage sludge to be considered as feed-
stocks for biochar production, a rigorous study should be carried out
to assess the biochar characteristics and the potential risks of bioac-
cumulation that may be associated with its subsequent applications
(e.g. to land).
The present work has been undertaken to evaluate the influence
of sources of feedstock and pyrolysis temperatures on the surface
characteristics of SDBC and to determine whether heavy metal lim-
its are exceeded for specific application rates. Our objectives were
to prepare biochars with the optimal surface characteristics while
minimize their environmental risk.
2. Experimental methods
2.1. SDBC sample preparation
The sewage feedstocks for the preparation of the SDBC used in
this study were sourced from three different WWTPs, Xilang WWTP
(XL), Liede WWTP (LD), and Datansha WWTP (DTS), all located in
Guangzhou, China. In common, the sewage sludge was belt filtered
or centrifuged for dewatering without any anaerobic digestion
pretreatment in China and therefore contained large amounts of
organic matter.
Each time about 100 g sludge from different feedstock was
introduced to prepare SDBC by pyrolysis in a fixed bed reactor at
temperatures between 300 and 600 ◦ C in a nitrogen atmosphere.
The pyrolysis heating rate was employed at 10 ◦ C min−1 and Nitro-
gen gas was injected at a rate of 80–100 ml min−1 to ensure an
oxygen-free environment. When the temperature was increased
to between 100 and 127 ◦ C, the water vapor could be driven out
until totally dried. After that, the temperature was increased to
the setpoint (i.e. 300, 400 ◦ C) and was held for 2 h, as our pre-
liminary study showed that 2 h was the most appropriate time
for carbonization. The weight of the moisture, biogas and biochar
during pyrolysis was investigated by thermo-gravimetric analysis
(TGA). The biochar samples were ground and sieved to 0.5–1.0 mm
sized particles. After several rinses with deionized (DI) water to
remove impurities such as ash, all the samples were dried at 80 ◦ C
for chemical analysis and batch sorption experiments.
2.2. Characterization of SDBC
2.2.1. Chemical analysis
Elemental C, N, S and H abundances were determined using a
Vario EL CNS analyser. Corg (organic carbon) content was exam-
ined according to HJ615-2011 [17]. Total P concentrations were
determined by the modified ascorbic acid method [18]. Concen-
trations of the other major and trace elements were determined
by digesting biochar samples in a mixture of nitric acid and per-
chloric acid and the heavy metal concentrations in the filtrates
were determined using ICP–OES (Optima 5300DV, Perkin-Elmer
Instruments, USA). Metals (Pb, Zn, Cu, Cd, Fe and Mn) were DTPA-
extracted using the method of Lindsay and Norvell [19]. The metals
were extracted from 1.0 g of sludge-derived biochar using 15 ml
of a solution containing 5 mM DTPA and 10 mM CaCl2 in a 50 ml
polypropylene centrifuge tube. The tube was then shaken on a
reciprocating shaker for 2 h, centrifuged for 20 min at 3857 × g, and
the supernatant filtered through a 0.45 ␮m filter paper. The con-
centrations of DTPA-extractable metals were then analyzed using
ICP-OES (Optima 5300DV, Perkin-Elmer Instruments, USA).
2.2.2. FT-IR and SEM analysis
Fourier transform infrared (FT-IR) analysis of the biochars was
performed to identify the chemical functional groups present in
the original SDBCs. To obtain the observable FT-IR spectra, the
different SDBCs were ground and mixed with KBr to 0.1 wt% and
then pressed into pellets. The spectra of the samples were mea-
sured using a Thermo Nicolet IS10 Spectrometer, Thermo Nicole
Corporation, Madison, USA. IR absorbance data were obtained for
wavenumbers in the range of 400–4000 cm−1 .
The surface structure of the sludge-derived biochars was ana-
lyzed by scanning electron microscopy (SEMS-520, Hitachi, Japan).
2.2.3. Measurement of isoelectric point and zeta potential
The zeta potential of the SDBCs was measured using a Zeta-
master potentiometer (Nano-zs90, Malvern Instruments, UK). One
gram of each SDBC sample was added to 100 mL of deionized water
and the solution was shaken at 250 rpm for 30 min using a mechan-
ical mixer. The shaken solution was then placed in a sonic bath
to break the particles into colloids and the solution filtered using
a 0.45 ␮m filter paper. Measurement of the isoelectric point (IEP)
and assessment of the adsorption of potential-determining ions by
the biochars were made following the procedures detailed by Spos-
ito [20]. The point of zero charge (PZC) was determined using the
methods described by Qiu and Ling [21].
3. Results and discussion
3.1. Biochar yield rates
For the raw sludge containing high moisture of water, the pro-
cess of pyrolysis may be divided into two phases, evaporation
and carbonization. The energy for the two processes was cal-
culated to be 2.47 MJ kg−1 and 0.62 MJ kg−1 on the wet basis of
raw sludge, respectively. After the water vapor has been emitted
in the temperature between 100 and 127 ◦ C, the dried biosolids
may continue to be decomposed from 127 to 219 ◦ C and followed
by a slow pyrolysis process when the temperature increased to
550 ◦ C. Our previous study has proved the viability of pyrolysis
to prepare biochar materials [7]. Therefore, the process of pyrol-
ysis transformed sewage sludge into three different components,
as vapor, biogas and biochar in different proportions depending
upon both the feedstock and the conditions. In our study, increasing
the pyrolytic temperature from 300 ◦ C to 600 ◦ C caused a substan-
tial decrease in the biochar content for the three different WWTPs
(Table 1). At 300 ◦ C the sequence of biochar production rates was
LD (15%) > XL (12%) > DTS (10%), which decreased to LD (13%) > XL
(9%) > DTS (7%) at 600 ◦ C. The difference in the biochar content
between the WWTPs may be related to existence of various metals
that may catalyze the pyrolysis reactions. However, the biochar
yield rate of sewage sludge from the WWTPs was lower than that
derived from other biomass such as sugarcane bagasse or corn-
cob [16], probably due to water content accounting for more than
80% of the sludge. Pyrolysis of sewage sludge between 300 and
600 ◦ C resulted in considerable mass loss and generates a product
with a rigid amorphous C matrix. Additionally, the yield of biochar
decreased while the proportion of biogas rose as the pyrolytic tem-
perature increased for three different sources of feedstocks. This
may be due to the conversion of the solid organic matter in the
sewage sludge during pyrolysis into volatile gases. It has been pre-
viously reported that the yield of biochar was positively correlated
with temperature and higher temperature promoted the conver-
sion of organic matter into biogas [13].
3.2. Characteristics of SDBC
Total C, H, N and S was observed to decrease with the temper-
ature in the three biochars during the pyrolysis process (Table 2).
Total carbon content in biochar was found to range between 15.24
and 33.18%, and the sequence of total C content of the biochars
 H. Lu et al. / Journal of Analytical and Applied Pyrolysis 102 (2013) 137–143 139

Table 1
The relative proportions of end products (including water vapor, biochar and biogas) after pyrolysis of different feedstocks at a range of temperatures.

WWTP Conditions Water vapor (%) Biochar (%) Biogas (%)

XL 300 ◦ C, 2 h 83 12 6
400 ◦ C, 2 h 10 7
500 ◦ C, 2 h 10 7
600 ◦ C, 2 h 9 8
LD 300 ◦ C, 2 h 79 15 6
400 ◦ C, 2 h 14 8
500 ◦ C, 2 h 13 8
600 ◦ C, 2 h 13 9
DTS 300 ◦ C, 2 h 85 10 5
400 ◦ C, 2 h 8 7
500 ◦ C, 2 h 8 7
600 ◦ C, 2 h 7 8

Table 2
The elemental composition of sewage sludge and biochars from different feedstocks.

Samplea C Corg H N S P Ca Mg K Na Al H/Corg BET

(%) (%) (%) (%) (%) (g kg−1 ) m2 g−1

DTS25 33.2 8.4 4.9 5.6 1.1 28.4 4.8 4.1 1.2 1.4 31 0.58 /
DTS300 31.5 11.2 3.3 5.4 0.67 42.6 8.1 8.2 2.1 2.2 52.2 0.29 4
DTS400 27.5 9.8 2 4.4 0.62 58.8 8.4 8.4 2.4 2.3 47.8 0.20 8.7
DTS500 26.7 9.0 1.9 3.7 0.42 59.5 8.8 8.2 2.4 2.3 32.4 0.21 10.2
DTS600 26 6.6 1.3 3.4 0.43 57.6 10.4 9.3 2.8 2.7 55.2 0.20 6.3
LD25 23.8 6.0 4.4 4 0.72 20.1 6.7 6.3 0.8 1 26.2 0.73 /
LD300 21.7 7.7 2.8 3.4 0.49 29.5 11.6 11 1.6 1.7 38.1 0.36 5.3
LD400 16.4 5.5 1.7 2.8 0.54 29.2 11.9 13.4 2 1.9 53.7 0.31 12.2
LD500 15.4 5.8 1.6 2.3 0.47 34.1 12.2 12.5 2.2 2.1 42.2 0.28 21.4
LD600 15.2 3.9 1 2 0.57 35.5 14.6 14.5 2.6 2.5 50.8 0.26 10.6
XL25 28.1 7.1 4.5 5.1 1 21.4 1.5 4.1 1.3 1.5 43.2 0.63 /
XL300 27.1 9.6 3 4.4 0.7 32.7 1.8 5.4 1.8 1.7 59.7 0.31 6.7
XL400 22.6 7.6 1.9 3.7 0.66 38.1 2 5.5 2.1 1.9 48.5 0.25 17.7
XL500 22.1 8.3 1.7 3.3 0.61 40 2.1 5.9 2.2 2 75.7 0.21 26.5
XL600 21.9 5.6 1.1 2.7 0.66 41 2.3 3 2.3 2.1 38.5 0.20 18.2
a
The samples’ name consists of the feedstock (WWTP) and the pyrolysis temperature, wherein “25” refers to raw sludge dried at 25 ◦ C without pyrolysis treatment.

was DTS > XL > LD. The degree of carbon stability can be indicated due to the addition of CaO during the conditioning process before
by the H/Corg molar ratio. The low H/Corg molar ratios for the dewatering.
biochars (Table 2) suggested their greater carbon stability, which
may be due to the secondary charring reactions occurring at a very 3.3. Surface charge of SDBC samples
slow rate, resulting in the formation of recalcitrant residual solid
forms of biochar [22]. In addition, The H/Corg ratio of the SDBC sam- The PZC is regarded as the net total (external and internal) sur-
ples at different pyrolysis temperatures were all below 0.7, which face charge of the particles, whereas the IEP is only representative
showed that they were thermochemically converted materials that of the external surface charges of carbon particles in solution. Gen-
had a greater proportion of fused aromatic ring structures [23]. The erally, the PZC is the point on the pH scale where the sum of anion
decreased nitrogen content of biochars may not be necessarily ben- and cation exchange are in equilibrium and that as the degree of
eficial to crops, since N is mostly present in an unavailable form [24]. oxidation increases, the PZC occurs at lower pH values, while the
C/N ratio has been commonly used as an indicator of the capacity IEP is the pH value at the point of zero potential. Hence the dif-
of organic substrates to release inorganic N when incorporated into ference (i.e. PZC-IEP) can be interpreted as a measure of surface
soils. The increase of C/N with the increase of pyrolytic tempera- charge distribution of porous carbons [26]. The PZC values for the
tures from 300 ◦ C to 600 ◦ C was seen for the biochars from the three three biochars studied ranged from 7.14 to 8.54 (Table 3), consis-
WWTPs, indicating the greater loss of nitrogen at higher tempera- tent with the findings that biochar pH values from a wide variety of
tures. Therefore the biochar produced at lower temperatures may feedstocks had an average pH of 8.1 and a pH range of 6.2 to 9.6 [24].
be favored as soil amendments.
Phosphorus in the biochars increased with pyrolytic tempera- Table 3
ture, potentially due to the loss of C and O and P evaporation in Electrochemical properties of the SDBCs investigated.
this study [1]. Additionally, the high P content was found in the
Type of SDBCs PZC IEP PZC-IEP
biochar sourced from LD and DTS WWTP, which applying modi-
DTS300 7.50 3.80 3.70
fied A/A/O technology and proving effective biological phosporous
DTS 400 7.30 4.60 2.70
removal. However, the P remaining in the biochars from the dif- DTS 500 7.66 4.32 3.34
ferent feedstocks may provide a source of P for plant growth as DTS 600 8.54 4.70 3.84
previous studies have suggested that P in sludge biochar is plant LD300 7.21 4.94 2.27
available and can provide nutrient recovery [25]. LD400 7.14 5.40 1.74
LD500 7.58 5.30 2.28
The alkaline and alkaline-earth cations of the feedstock is largely
LD600 8.10 5.30 2.80
retained in the resulting biochar, where it concentrates due to the XL300 7.27 3.90 3.37
gradual loss of C, H and O during processing [22]. High pyrolytic XL 400 7.45 4.60 2.85
temperature favored the relative accumulation of Ca, Mg, K and XL 500 7.70 4.50 3.20
XL 600 8.50 4.82 3.68
Na. The relative high proportion of Ca for LD-sludge biochar may
140 H. Lu et al. / Journal of Analytical and Applied Pyrolysis 102 (2013) 137–143

Hossain et al. [16] reported that wastewater sludge biochar pro-

duced at low temperatures is acidic whereas at high temperature
the biochar alkaline. This suggests that biochars may be suitable
for amelioration of acidic and alkaline soils with their suitability
for application to acidic or alkaline soils controlled by the temper-
ature of their formation. In this study, consistent with the findings
of Hossain et al. [16], as the temperature of pyrolysis increases, the
PZC generally increases, which is due to the fact that most of the
active sites are stabilized during the thermal treatment and, con-
sequently, the number of acidic oxygen-containing surface groups
is much lower than the number of oxygen-free Lewis base sites on
the biochar surface. Table 3 illustrated the relatively low IEP values
for the biochars studied form the different feedstocks. The slight
increase in IEP with increasing temperature of pyrolysis, such as
the increase from 4.94 to 5.30 for the LD biochar (Table 3), sug-
gested that more acidic oxygen-containing surface groups were
removed from the external carbon surfaces. When sewage sludge is
heated in a N2 atmosphere, it is known that most of the functional
groups are removed from the surface [26]. However, in this study
the high value of PZC showed that the internal surface preserves its
basic character. The values for PZC-IEP showed no consistent trend
with increasing temperature of pyrolysis for the different biochars
indicating that the pyrolysis treatment affects the surface of the
biochars to a different extent. It is interesting to note that the PZC-
IEP reached its minimum at the pyrolysis temperature of 400 ◦ C for
all three feedstocks, due to the fact that most of the acidic oxygen-
containing functional groups were removed from the surface of
biochar at this temperature under an inert atmosphere, which may
indicate that the oxidation process occurred on the external surface
at this point, and the surface charge distribution was more uniform.
The results from Table 3 confirmed that by carefully selecting the
pyrolysis conditions related to different feedstocks, it was possible
to prepare SDBCs with different pH levels and oxygen surface group
distributions. This could be very useful for the tailoring of biochar
production to the adsorption of specific soil/water contaminants
(e.g. heavy metals).

3.4. Microstructure of SDBC samples

FT-IR spectra of biochars from different feedstocks were similar

and therefore the spectroscopic assignment of LD biochar sam-
ples were shown in Fig. 1. The intensity of the peak at 3367 cm−1
decreased rapidly from raw sludge to biochar samples, suggesting
that large amounts of hydroxyl groups were decomposed during
biomass pyrolysis at elevated temperatures [16,27]. The intense
bands for aliphatic CH2 (2957, 2922, and 2852 cm−1 ) disappeared
abruptly when heating to higher temperatures, indicating organic
fatty hydrocarbons was decomposed into methane, carbon dioxide
and other gases or aromatic structures [22,28].
The assignment of 1657 cm−1 refers to amide bond stretching,
when the temperature increased, its characteristic peak was off-
set from 1657 cm−1 to 1613 cm−1 (300 ◦ C), 1607 cm−1 (400 ◦ C),
1607 cm−1 (500 ◦ C) and 1606 cm−1 (600 ◦ C), which may suggest
that amide functional groups complexed with heavy metals dur-
ing pyrolysis. However, while the temperature was higher than
300 ◦ C, the amides were unstable and decomposed, therefore, its
characteristic peaks remained unchanged.
Breaking and rearrangement of the chemical bonds in the
biomass during processing results in the formation of numer-
ous functional groups occurring predominantly on the outer and
inner surface of the biochars. The intensity between 600 and
800 cm−1 assigned to the presence of aromatic and heteroaromatic
compounds increased for samples treated at 300 ◦ C and higher tem-
peratures (Fig. 1). As the pyrolytic temperature increases, so does
the proportion of aromatic carbon in the biochar, due to the con-
version of alkyl and O-alkyl C to aryl C [22,28].
Fig. 1. FTIR spectra of the SDBCs from LD WWTP sludge
The results of the FT-IR analysis confirmed that the SDBCs
present different functional groups and characteristic bands of
hydroxylic and carboxylic acid groups which are able to react with
cations in aqueous solutions, whereas the aromatic and aliphatic
compounds in the biochars make them more recalcitrant. The
mechanical stability and recalcitrance of biochar once incorporated
in the soil, would determine long term effects on water retention
and soil structure. This is likely to be determined by feedstock
type and pyrolysis temperature as well as the prevalent physical-
chemical conditions in the soil which will determine the biochar
weathering and the compaction and compression of the biochar
material over time.
To further determine how the minerals phases have changed,
the SEM photograph were taken at 600× magnifications to observe
the surface morphology of a typical SDBC sample LD500 (Fig. 2).
The SEM micrograph in Fig. 2a showed that most of the particles
were largely amorphous and granular with the dimension varied
from 5 to 20 ␮m, which were formed during the pyrolysis process.
Under high magnification (Fig. 2b), the structure of SDBC contained
a wide range of mineral and organic matter, some highly conjugated
aromatic compounds could be found on the biochar surface, which
may contribute to variation of surface charge and functional groups
of SDBC samples.
 H. Lu et al. / Journal of Analytical and Applied Pyrolysis 102 (2013) 137–143 141

Fig. 2. SEM micrographs of the LD500 sample ((a) 600X magnification and (b) 2000X magnification).

Table 4
Total and DTPA-extractable contents of Pb, Zn, Cu, Cd, Fe and Mn in different feedstocks and their sludge-derived biochars.

Samples Pb Zn Cu Cd Fe Mn
−1
Total (mg kg )
DTS25 136.5 ± 3.7 900.4 ± 30.8 611.3 ± 6.5 3.39 ± 0.05 14,254.3 ± 372.8 253.3 ± 2.2
DTS300 241.8 ± 5.6 1493.0 ± 23.3 1034.3 ± 9.2 5.68 ± 0.06 24,347.3 ± 633.8 425.2 ± 6.1
DTS400 274.8 ± 6.1 1661.7 ± 32.2 1197.7 ± 19.8 5.97 ± 0.07 29,032.7 ± 586.8 521.9 ± 5.6
DTS500 299.2 ± 9.2 1798.1 ± 48.6 1267.3 ± 27.8 6.44 ± 0.09 30,853.4 ± 551.7 545.1 ± 6.3
LD25 138.5 ± 3.8 629.1 ± 13.1 401.0 ± 0.7 2.28 ± 0.05 20,278.1 ± 341.5 476.6 ± 5.0
LD300 189.5 ± 4.2 849.3 ± 31.1 479.9 ± 8.5 3.30 ± 0.05 28,005.7 ± 615.1 654.7 ± 5.7
LD400 194.2 ± 4.4 911.6 ± 32.3 548.6 ± 5.9 3.76 ± 0.06 30,345.8 ± 419.8 667.3 ± 7.2
LD500 211.8 ± 5.0 1014.5 ± 38.5 564.9 ± 9.7 4.25 ± 0.07 33,656.7 ± 314.3 783.6 ± 6.8
XL25 224.5 ± 4.9 1237.9 ± 43.8 451.3 ± 0.7 5.26 ± 0.07 23,247.5 ± 482.9 256.1 ± 4.9
XL300 350.0 ± 5.8 1909.4 ± 50.0 686.9 ± 10.1 7.45 ± 0.10 37,230.2 ± 688.0 403.0 ± 6.1
XL400 438.3 ± 6.3 2103.6 ± 61.1 690.8 ± 4.3 9.82 ± 0.03 43,192.8 ± 407.6 419.4 ± 4.2
XL500 506.4 ± 9.1 2304.8 ± 65.5 692.1 ± 14.1 8.85 ± 0.11 44,171.5 ± 395.5 479.8 ± 3.5
86/278/EEC 750–1200 2500–4000 1000–1750 20–40 – –
Annex 1Ba
GB4284-84b 300–1000 500–1000 250–500 5–20 – –

DTPA extractable (mg kg−1 )

DTS25 21.46 ± 2.5 739.6 ± 84.1 265.1 ± 63.1 1.84 ± 0.16 842.7 ± 48.5 86.87 ± 18.1
DTS300 ND 1.30 ± 0.39 1.28 ± 0.14 ND 18.6 ± 4.7 ND
DTS400 1.83 ± 0.29 15.0 ± 1.2 17.6 ± 0.89 ND 84.8 ± 2.1 2.86 ± 0.28
DTS500 2.46 ± 0.26 18.0 ± 1.3 23.0 ± 1.5 ND 64.2 ± 2.4 2.52 ± 0.37
LD25 32.54 ± 5.74 324.3 ± 23.2 63.7 ± 1.55 0.28 ± 0.16 1715.5 ± 143.9 311.6 ± 24.4
LD300 ND 8.57 ± 1.05 2.07 ± 0.18 ND 116.7 ± 18.6 8.45 ± 2.16
LD400 10.04 ± 1.11 76.5 ± 4.5 9.2 ± 0.67 ND 562.3 ± 26.3 72.1 ± 3.1
LD500 7.45 ± 2.53 92.6 ± 22.77 15.9 ± 4.1 ND 281.7 ± 88.8 34.9 ± 9.2
XL25 50.55 ± 3.08 695.8 ± 2.2 89.2 ± 6.9 3.20 ± 1.02 984.7 ± 18.7 86.6 ± 0.8
XL300 ND 3.66 ± 0.72 1.69 ± 0.52 ND 37.6 ± 2.7 ND
XL400 10.38 ± 0.35 47.5 ± 4.2 11.3 ± 0.4 ND 196.6 ± 1.5 10.49 ± 0.80
XL500 9.50 ± 0.64 41.9 ± 3.5 14.7 ± 1.2 ND 96.3 ± 6.3 7.30 ± 0.83

DTPA/total
DTS25 0.16 0.82 0.43 0.54 0.06 0.34
DTS300 0 0 0 0 0 0
DTS400 0.01 0.01 0.01 0 0 0.01
DTS500 0.01 0.01 0.02 0 0 0
LD25 0.23 0.52 0.16 0.12 0.08 0.65
LD300 0 0.01 0 0 0 0.01
LD400 0.05 0.08 0.02 0 0.02 0.11
LD500 0.04 0.09 0.03 0 0.01 0.04
XL25 0.23 0.56 0.2 0.61 0.04 0.34
XL300 0 0 0 0 0 0
XL400 0.02 0.02 0.02 0 0 0.03
XL500 0.02 0.02 0.02 0 0 0.02

ND means not detected

a
Council Directive 86/278/EEC of 12 June 1986, on the protection of the environment, and in particular of the soil, when sewage sludge is used in agriculture
b
GB4284-84 is Chinese control standards for pollutants in sludges from agricultural use executed on 18 May, 1984.
142 H. Lu et al. / Journal of Analytical and Applied Pyrolysis 102 (2013) 137–143
3.5. Total and DTPA-extractable heavy metals from sewage
sludge and SDBCs
The composition of sewage sludge is commonly heterogeneous,
however, analysis of the total heavy metals concentrations in
sludge from the different WWTP feedstocks was determined to
be surprisingly consistent (Table 4). For example, the total Zn
was 629.1–1237.9 mg kg−1 in the raw sludge of the three WWTPs,
and 136.5–224.5 mg kg−1 , 401.0–611.3 mg kg−1 , 2.3–5.3 mg kg−1 ,
14254.3–23247.5 mg kg−1 , 253.3–476.6 mg kg−1 for Pb, Cu, Cd, Fe
and Mn respectively. The data in Table 4 illustrated that the con-
centrations of Pb, Zn, Cu and Cd were less than the regulatory limits
stipulated in the European Union Council Directive 86/278/EEC
(The Sewage Sludge Directive), however, Zn (1238 mg kg−1 ) and Cu
(611 mg kg−1 ) in the XL and DTS sludges respectively, exceeded the
Chinese GB4284-84 standard, which is more stringent compared
with those set in the Council Directive 86/278/EEC. The widespread
use of galvanized pipeline for transporting wastewater may be
responsible for the high concentration of Zn in the sewage sludge.
The high concentration of Cu in the sludge may be due to the high
proportion of trade effluent contaminated with a range of chemicals
including heavy metal rinses.
Organic wastes (e.g. sewage sludge or biosolids) are known to
generally contain high concentrations of metals, which remain in
the final biochar product following pyrolysis [24,29]. As expected,
heavy metals accumulated in the biochar with the increase of
pyrolytic temperature (Table 4). Bridle and Pritchard [25] who also
reported high concentrations of Cu, Zn, Cr and Ni in biochar pro-
duced from sewage sludge.
The DTPA extractable fraction has been widely used to estimate
bioavailability of metals in soils and sludge [30], due to its capacity
to chelate a wide range of metallic elements. The ability of DTPA to
form stable chelates with a variety of metallic elements in soils has
been reported by Hong et al. [31].
The DTPA-extractable metal content of the sludge feedstock
accounts for a certain percent of the total for three feedstocks. For
example, for the feedstock from DTS, the DTPA-extractable Zn was
82% of the total, and 16%, 43%, 54%, 6%, 34% of that of Pb, Cu, Cd,
Fe and Mn, respectively. However, the soluble and extractable frac-
tions of heavy metals in the biochars were significantly decreased
when compared to the original sludge feedstocks (Table 4). Gener-
ally, the DTPA-extractable metal content in the biochars was in the
range of 0–4%, 0–9%, 0–3%, 0–2%, 0–4% of the total concentrations of
Pb, Zn, Cu, Fe and Mn, respectively. For the three feedstocks studied,
a pyrolysis temperature of 300 ◦ C was the most effective in reducing
DTPA extractability, with decreases in DTPA-extractable metals of
nearly 100%. Similar results were found for Cu in wastewater sludge
biochar [16].
There are several reasons for the reduction of DTPA extractable
metals: (1) small molecular compounds in the sludge tend to dis-
solute and volatilize rather than decompose or degrade at the low
temperature of 300 ◦ C; (2) the nitrogen-containing groups (i.e.,
amine and amides) preserved at temperature 300 ◦ C may serve as
ligands for binding metals in the sludge and combining into the
residue of the carbon structure network; (3) the abundant func-
tional groups (such as carboxyl, hydroxyl) in the sludge surface
at 300 ◦ C contribute to the formation of organo-metallic complex
in the in the biochar particles; (4) available phosphorus content
was the highest at the temperature of 300 ◦ C, and thus lead to the
formation of phosphate precipitation.
4. Conclusions
The conversion of sewage sludge to biochar offers a solution
for minimizing waste volume and producing potentially valuable
biochar adsorbents. Environmental risk of SDBCs can be minimized
and managed by controlling the source of feedstock and pyroly-
sis temperature. For those WWTPs with pure sewage influent, the
wastewater sludge may be more suitable for preparing biochars
with more uniform charge distribution. Compared with higher tem-
peratures, controlling the pyrolysis temperature to 300 ◦ C may
dramatically reduce the potential environmental risk associated
with metal bioavailability and cut down the energy consumption
for biochar preparation. Further studies are underway to test the
impact of best selected biochar on metal adsorption and soil ame-
lioration.
Acknowledgments
This study was financially supported by the Natural Sci-
ence Foundation of China (Nos. 41171374 and 41225004) and
the National Environmental Protection Department Public Bene-
fit Research Foundation (No. 201109020) and the Fundamental
Research Funds for the Central Universities.
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