Journal of Hazardous Materials 320 (2016) 417–426 ! ! ! ! ! !

Contents lists available at ScienceDirect

Journal of Hazardous Materials ! ! !

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

Influence of pyrolysis temperature on properties and environmental ! ! ! ! ! ! !

safety of heavy metals in biochars derived from municipal sewage ! ! !

! ! ! ! ! !

sludge
Junwei Jin a , Yanan Li a,1 , Jianyun Zhang a , Shengchun Wu a , Yucheng Cao a , Peng Liang a , ! ! ! ! ! ! ! ! ! ! !

Jin Zhang a,b,∗ , Ming Hung Wong b , Minyan Wang c,∗∗ , Shengdao Shan d , Peter Christie a
! ! !
! ! ! ! ! ! !

a
Key Laboratory of Soil Contamination Bioremediation of Zhejiang Province, School of Environmental and Resource Sciences, Zhejiang A & F University, 88
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Huancheng North Road, Lin’an, Hangzhou 311300, China ! ! ! ! ! !

b
Consortium on Health, Environment, Education and Research (CHEER), Department of Science and Environmental Studies, The Education University of ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Hong Kong, 10 Lo Ping Road, Tai Po, Hong Kong, China

! ! ! ! ! ! ! ! ! !

c
Jiyang College, Zhejiang A & F University, 77 Puyang Road, Zhuji 311800, China
! ! ! ! ! ! ! ! ! ! ! !

d
Institute of Ecological Environment, Zhejiang University of Science & Technology, 318 Liuhe Road, Hangzhou 310023, China
! ! ! ! ! ! ! ! ! ! ! ! ! ! !

h i g h l i g h t s
! !
! ! ! ! ! ! !

• Disposal of municipal sewage sludge containing HMs poses a high environmental risk. ! ! ! ! ! ! ! ! ! ! !

• Disposal of biochar derived from sludge pyrolysis poses a low environmental risk. ! ! ! ! ! ! ! ! ! ! !

• The effect of pyrolysis temperature on immobilization of HMs in biochar was studied.

! ! ! ! ! ! ! ! ! ! ! !

• Fractionation and bioavailability of heavy metals in sludge and biochar was analyzed. ! ! ! ! ! ! ! ! ! ! !

• The influence of pyrolysis temperature on properties of biochar was studied.

! ! ! ! ! ! ! ! ! !

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

Article history: !

Dried raw sludge was pyrolyzed at temperatures ranging from 400 to 600 ◦ C at the increase of 50 ◦ C
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Received 23 June 2016 ! ! !

intervals to investigate the influence of pyrolysis temperature on properties and environmental safety ! ! ! ! ! ! ! ! ! ! ! !

Received in revised form 14 August 2016 ! ! !

! ! !

of heavy metals in biochar derived from municipal sewage sludge. The sludge biochar yield decreased
Accepted 21 August 2016
! ! ! ! ! ! ! ! ! ! ! ! ! !

significantly with increasing pyrolysis temperature but the pH, ash content and specific surface area
! ! !

Available online 22 August 2016

! ! ! ! ! ! ! ! ! ! ! ! !

increased. Conversion of sludge to biochar markedly decreased the H/C and N/C ratios. FT-IR analysis
! ! ! !

! ! ! ! ! ! ! ! ! ! ! ! ! !

confirmed a dramatic depletion of H and N and a higher degree of aromatic condensation in process of
Keywords:
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

biochar formation at higher temperatures. The total concentrations of Cu, Zn, Pb, Cr, Mn, and Ni increased
Sewage sludge biochar
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

with conversion of sludge to biochar and increasing pyrolysis temperature. However, using BCR sequen-
! !

Heavy metals
! ! ! ! ! ! ! ! ! ! ! ! !

tial extraction and analysis, it was found that most of the heavy metals existed in the oxizable and residual
!

Thermal pyrolysis !
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

BCR sequential extraction

! !
forms after pyrolysis, especially at 600 ◦ C, resulting in a significant reduction in their bioavailability, lead-
! ! ! ! ! ! ! ! ! ! ! ! ! !

Environmental risk assessment ! !

ing to a very low environmental risk of the biochar. The present study indicates pyrolysis is a promising
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

sludge treatment method for heavy metals immobilization in biochar, and highlights the potential to
! ! ! ! ! ! ! ! ! ! ! ! !

minimize the harmful effects of biochar by controlling pyrolysis temperature. ! ! ! ! ! ! ! ! !

© 2016 Elsevier B.V. All rights reserved. ! ! ! ! ! !

1. Introduction !

It is estimated that 60 million tonnes of municipal sewage sludge ! ! ! ! ! ! ! ! ! !

(80% water content) were produced in China in 2015 [1]. As urban-

∗ Corresponding author at: Key Laboratory of Soil Contamination Bioremediation
! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! !

ization continues, the number of municipal wastewater treatment

of Zhejiang Province, School of Environmental and Resource Sciences, Zhejiang A &
! ! ! ! ! ! !

plants is increasing and the sewage sludge produced, an inevitable

! ! ! ! ! ! ! ! ! ! !

F University, 88 Huancheng North Road, Lin’an, Hangzhou 311300, China.

! ! ! ! ! ! ! ! !

byproduct of wastewater treatment processes presents a number

! ! ! ! ! ! ! ! !

∗∗ Corresponding author at: Jiyang College, Zhejiang A & F University, 77 Puyang ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! !

Road, Zhuji 311800, China. ! ! !

of environmental concerns [2]. Sewage sludge contains various

! ! ! ! ! ! !

E-mail addresses: jzhang@zafu.edu.cn (J. Zhang), minyanwang@aliyun.com ! ! ! ! !

pollutants including heavy metals, organic micro-pollutants and

(M. Wang).
! ! ! ! ! !

pathogens [3,4]. Direct disposal of sludge to the environment

!

1
Co-first author.
! ! ! ! ! ! ! !

http://dx.doi.org/10.1016/j.jhazmat.2016.08.050
0304-3894/© 2016 Elsevier B.V. All rights reserved. ! ! ! ! ! !
418 ! J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! !

releases contaminants into soils and waters which could move ! ! ! ! ! ! ! ! mental analyzer (Vario EL III, Hanau, Germany). An internal catalyst, ! ! ! ! ! ! ! ! !

through the food chain, posing a risk to human health [5]. The ! ! ! ! ! ! ! ! ! ! ! tungsten (VI) oxide, was added to each sample in order to enhance ! ! ! ! ! ! ! ! ! ! !

proper management and treatment of sewage sludge is therefore ! ! ! ! ! ! ! ! its full combustion. External calibration standards, CaCO3 and sul-
! ! ! ! ! ! !

an issue of increasing concern.

! ! ! ! fanilic acid were analyzed at intervals of every ten samples for data ! ! ! ! ! ! ! ! ! ! !

There are a number of treatment processes that can kill most of ! ! ! ! ! ! ! ! ! ! ! quality control [16]. ! !

the pathogens and parasites in sewage sludge such as lime stabi-

! ! ! ! ! ! ! ! ! ! The pH values of the sludge and biochar samples (sample: ! ! ! ! ! ! ! ! !

lization, incineration and composting. However, in some countries ! ! ! ! ! ! !

water = 1: 20, w/v) were measured with a pH meter (SevenCompact,
! ! ! ! ! ! ! ! ! ! !

the application of properly treated sludge is restricted to non-food

! ! ! ! ! ! ! ! ! Mettler Toledo, Greifensee, Switzerland) [17]. The ash contents of ! ! ! ! ! ! ! !

crops such as fiber crops and forestry but not food crops [4]. Some ! ! ! ! ! ! ! ! ! ! ! ! the samples were determined according to the method listed in
! ! ! ! ! ! ! ! !

treatment methods involve combustion but this generates diox- ! ! ! ! ! ! ! Industrial Analysis Method of Coal (GB/T 212-2001). The specific ! ! ! ! ! ! ! !

ins which are emitted to the air, and the treated sludge may still
! ! ! ! ! ! ! ! ! ! ! ! surface areas of the samples were determined using N2 sorption ! ! ! ! ! ! ! !

contain pollutants, especially inorganic pollutants [2,4]. Thermal ! ! ! ! ! ! isotherms run on an automated surface area and pore size analyzer ! ! ! ! ! ! ! ! ! !

pyrolysis of sewage sludge, however, may be a promising strategy ! ! ! ! ! ! ! ! ! (SI-MP-10, Quantachrome Corp., Boynton Beach, FL). The specific ! ! ! ! ! ! !

in terms of significantly reducing the volume of sludge, killing thor-

! ! ! ! ! ! ! ! ! !
surface areas were taken from adsorption isotherms using the ! ! ! ! ! ! ! !

oughly pathogens and parasites, and fully decomposing organic ! ! ! ! ! ! ! Brunauer, Emmett and Teller (BET) equation [18]. The surface struc- ! ! ! ! ! ! ! ! !

residues [6]. Potentially useful bio-oils and pyrolytic gas may be ! ! ! ! ! ! ! ! ! ture of the samples was analyzed by scanning electron microscopy
! ! ! ! ! ! ! ! !

produced [7]. The biochar produced may immobilize heavy metals ! ! ! ! ! ! ! ! (S-5500 SEM, Hitachi, Tokyo, Japan). The detailed pH, elemental and ! ! ! ! ! ! ! ! !

[8,9] and its application to soils may enhance soil quality and allow
! ! ! ! ! ! ! ! ! ! ! the BET values of the sludge and biochar are listed in Table 1.
! ! ! ! ! ! ! ! ! ! ! !

the recycling of plant nutrients [10,11].

! ! ! ! !

Sewage sludge biochar (SSB) is the solid carbonaceous residue ! ! ! ! ! ! ! !

2.2.2. Fourier transform—infrared spectroscopy (FT-IR) analysis
! ! ! ! !

resulting from the pyrolysis of the sludge [12]. It can be used ! ! ! ! ! ! ! ! ! ! !

The functional groups of sludge and biochar samples were ! ! ! ! ! ! ! !

as a landfill cover material, a building material or a horticul-

! ! ! ! ! ! ! ! ! !
analyzed using Fourier transform infrared spectroscopy (FT-IR, IR ! ! ! ! ! ! !

tural or forestry substrate [7,13]. However, research is required ! ! ! ! ! ! ! !

Prestige 21, Shimadzu, Kyoto, Japan). The observable FT-IR spectra ! ! ! ! ! ! ! !

on the behavior of heavy metals in these materials to minimize

! ! ! ! ! ! ! ! ! !
were obtained by grinding the biochar samples and mixing with
! ! ! ! ! ! ! ! !

the risk of metal release into the environment. The physical and
! ! ! ! ! ! ! ! ! !
KBr to 0.1 wt% and then pressing into pellets [18]. The spectra were
! ! ! ! ! ! ! ! ! ! ! !

chemical properties of the biochars depend on both the feedstock ! ! ! ! ! ! ! ! !

investigated in the range of 400–4000 cm−1 under 4 cm−1 reso- ! ! ! ! ! ! ! !

and pyrolysis conditions [6,12] and the pyrolysis temperature is a

! ! ! ! ! ! ! ! !
lution using the FT-IR. Thirty-two scans were collected for each ! ! ! ! ! ! ! ! !

key factor determining the immobilization of heavy metals in the

! ! ! ! ! ! ! ! !
spectrum. The spectra were corrected for H2 O and CO2 and ambient ! ! ! ! ! ! ! ! !

biochars [14,15]. The main objectives of the present study were ! ! ! ! ! ! ! ! !

air. The spectrum of the background was measured before analysis
! ! ! ! ! ! ! ! !

therefore to (1) investigate the influence of pyrolysis temperature ! ! ! ! ! ! ! !

of each sample to reduce interference [19].
! ! ! ! ! !

on physicochemical, structural and morphological properties of

! ! ! ! ! !

sewage sludge biochar, (2) explore the effects of pyrolysis tem- ! ! ! ! ! ! ! ! !

2.3. Fractionation and determination of heavy metals
! ! ! ! ! !

perature on the immobilization of heavy metals in biochars, and ! ! ! ! ! ! ! ! !

(3) assess the potential risk of heavy metals leaching from sewage
! ! ! ! ! ! ! ! ! !
The heavy metals in the sludge and biochar samples were ! ! ! ! ! ! ! ! !

sludge biochars into the environment. ! ! ! !

sequentially extracted according to the modified three-step ! ! ! ! ! !

sequential extraction procedure proposed by the Commission of ! ! ! ! ! ! !

the European Communities Bureau of Reference (BCR) [20–22].

2. Materials and methods
! ! ! ! ! ! !

The detailed extraction scheme is shown in Table 2. Through BCR

! ! !

! ! ! ! ! ! ! ! ! !

sequential extraction the fractions of heavy metals can be divided

2.1. Preparation of biochar
! ! ! ! ! ! ! ! !

into four categories: exchangeable and acid-soluble (F1), reducible

! ! !

! ! ! ! ! ! !

(F2), oxidizable (F3), and residual (F4) fractions (Table 2).

The sewage sludge (SS) feedstock for biochar production was
! ! ! ! ! ! ! !

The concentrations of heavy metals in the exchangeable and

! ! ! ! ! ! ! !

collected from the dewatering room of the First Municipal Wastew-

! ! ! ! ! ! ! !

acid-soluble, reducible and oxidizable fractions of sludge and

! ! ! ! ! ! ! ! !

ater Treatment Plant in Lin’an City, Zhejiang province, east China,

! ! ! ! ! ! !

biochar samples were determined directly by inductively coupled

! ! ! ! ! ! ! ! !

in which the triple oxidation ditch process for wastewater treat-

! ! ! ! ! ! !

plasma optical emission spectrometry (ICP-OES, Prodigy 7, Tele-

! ! ! ! ! ! ! ! !

ment was used. The sludge was dried at room temperature (∼20 ◦ C),
! ! ! ! ! ! !

dyne Leeman Labs, Hudson, NH). The residual fraction and total
! ! ! ! ! ! ! ! ! !

crushed and filtered through a 100-mesh sieve, and finally packed

! ! ! ! ! ! ! ! !

concentrations in the sludge and biochar samples were digested

! ! ! ! ! ! ! ! !

in a sealed plastic bag in a dryer for further use.

! ! ! ! ! ! ! !

according to US EPA method 3050B [23] before detection on the

! ! ! ! ! ! ! ! ! !

Pyrolysis of the sewage sludge was carried out in a homemade

! ! ! ! ! ! ! ! ! !

ICP-OES.
! ! ! ! ! ! ! ! ! !

pyrolysis and carbonization furnace (Fig. 1), at the temperature ! ! ! ! ! ! ! !

ranging from 400 to 600 ◦ C at the increase of 50 ◦ C intervals. In

2.4. Statistical analyses
! ! ! ! ! ! ! ! ! ! !

brief, the furnace was firstly heated to the target temperature and
! !

! ! ! ! ! ! ! ! ! !

then 500 g of sludge was loaded slowly into the internal reaction
Statistical analyses were performed using the SPSS statistical
! ! ! ! ! ! ! ! ! ! !

zone of the furnace through the feedstock inlet tube (Fig. 1). After
! ! ! ! ! ! !

package (v. 20.0). The data were subjected to analysis of variance

! ! ! ! ! ! ! ! ! ! !

pyrolysis for 1 h the resultant biochar was cooled to room temper-

! ! ! ! ! ! ! ! ! !

procedures and means were separated using the protected least

! ! ! ! ! ! ! ! ! ! !

ature (∼20 ◦ C) and transferred into a sealed plastic bag for further
! ! ! ! ! ! ! !

significant difference (LSD) test at the 0.05 probability level.

! ! ! ! ! ! ! ! ! !

analysis. A constant flow of N2 at 1 L min−1 was fed throughout

! ! ! ! ! ! ! !

! ! ! ! ! ! ! ! ! !

the pyrolysis process to ensure the absence of O2 in the internal

3. Results and discussion
! ! ! ! ! ! ! ! ! !

reaction zone of the furnace.

! ! !

! ! ! !

3.1. General properties of the sewage sludge biochar

! ! ! ! ! ! !

2.2. Characterization of biochar ! ! !

The properties of the biochars produced at different tem- ! ! ! ! ! ! ! !

2.2.1. Elemental, structural and morphological properties ! ! ! ! ! peratures, specifically yield rate, elemental composition, pH, ash ! ! ! ! ! ! !

The total carbon (C), hydrogen (H), nitrogen (N) and sulfur (S) ! ! ! ! ! ! ! ! ! ! content and specific surface area are summarized in Table 1. The ! ! ! ! ! ! ! ! ! !

contents of sewage sludge and sewage sludge biochar samples were ! ! ! ! ! ! ! ! ! percentage of biochar yield declined steadily from 60.6 to 53.1% ! ! ! ! ! ! ! ! !

determined by dry combustion at 950 ◦ C using an automatic ele- ! ! ! ! ! ! ! ! ! with increasing pyrolysis temperature from 400 to 600 ◦ C due to
! ! ! ! ! ! ! ! !
 J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! ! ! 419

Fig. 1. Schematic diagram of the pyrolysis apparatus used in the present study.
! ! ! ! ! ! ! ! ! ! ! !

Table 1 !

Physical and chemical properties of the raw sewage sludge and its biochars obtained under different pyrolysis temperatures.
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Sample ! Yield (%) ! ! C (%) ! ! H (%) ! ! N (%) ! ! S (%) ! ! H/C ! C/N ! pH ! Ash (%) ! ! SAN2 m2 g−1
ɑ
SS ! / ! 26.52 ± 0.02e ! ! 6.24 ± 1.50b ! ! ! 4.08 ± 0.03e ! ! ! 0.90 ± 0.19a ! ! ! 2.83 ! 7.59 ! 7.19 ± 0.06a ! ! ! 41.3 ± 0.1a ! ! ! 0.68
SSB400 60.57 ! 21.90 ± 0.12d ! ! 1.85 ± 0.02a ! ! ! 3.10 ± 0.03d ! ! ! 0.85 ± ±0.01a ! ! ! 1.01 ! 8.23 ! 8.46 ± 0.16b ! ! ! 64 ± 0.7b ! ! ! 5.49
SSB450 59.55 ! 21.53 ± 0.31c ! ! ! 1.56 ± 0.02a ! ! ! 2.92 ± 0.01c ! ! ! 0.89 ± 0.02a ! ! ! 0.87 ! 8.60 ! 9.74 ± 0.10c ! ! ! 68 ± 0.1c ! ! ! 7.21
SSB500 59.01 ! 21.24 ± 0.24bc ! ! ! 1.20 ± 0.00a ! ! ! 2.83 ± 0.15bc ! ! ! 0.84 ± 0.03a ! ! ! 0.68 ! 8.76 ! 9.75 ± 0.08c ! ! ! 69 ± 0.2d ! ! ! 7.73
SSB550 58.76 ! 20.66 ± 0.22b ! ! ! 1.01 ± 0.02a ! ! ! 2.54 ± 0.11b ! ! ! 0.86 ± 0.01a ! ! ! 0.58 ! 9.48 ! 10.47 ± 0.02d ! ! ! 71 ± 0.2e ! ! ! 8.45
SSB600 53.09 ! 19.88 ± 0.16a ! ! ! 0.71 ± 0.00a ! ! ! 2.04 ± 0.15a ! ! ! 0.87 ± 0.02a ! ! ! 0.43 ! 11.37 ! 11.7 ± 0.05e ! ! ! 74 ± 0.1f ! ! ! 5.99

SS, raw sewage sludge; SSBx, biochar derived from sewage sludge pyrolysis at X ( C) temperature.
! ! ! ! ! ! ! ! ! ! ! ! !
◦
!

SAN2 , the specific surface area determined using N2 sorption isotherms.

! ! ! ! ! ! ! !

ɑ
Lowercase letters after the numerical values show significant differences within each column of data(p < 0.05, n = 5). ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Table 2 !

Modified BCR three-step sequential extraction procedure. ! ! ! ! !

Fraction ! Extraction reagents ! ! Extraction conditions !

F1: ! soluble and exchangeable ! ! 20 mL, 0.01 M HAc ! ! ! ! ! Oscillating, 22 ± 5 ◦ C, 16 h ! ! ! ! !

metals
F2: ! carbonates,oxides and !
20 mL, 0.50 M NH2 OH·HCl
! ! ! ! ! Oscillating, 22 ± 5 C, 16 h ! ! !
◦
! !

reducible metals !

F3: ! metals bound to organic ! ! ! First, 5 mL, 30% (v/v) H2 O2 , ! ! ! ! ! First, water bath, 85 ± 5 ◦ C, 1 h, ! ! ! ! ! ! !

matter, Next, 5 mL, 30% (v/v) H2 O2 , ! ! ! ! !

Next, water bath, 85 ± 5 ◦ C, 1 h, ! ! ! ! ! ! !

oxidisable and sulphidic metals ! ! !

Last, 25 mL, 1.0 M CH2 COONH4
! ! ! ! !
Last, Oscillating, 22 ± 5 ◦ C, 16 h
! ! ! ! ! !

F4: ! residual metals such as silicates ! ! ! ! ! 5 mL, HNO3

! ! Microwave digestion system ! !

gradual decomposition of the organic substances in the sludge. ! ! ! ! ! ! ! ! ilar trend [14,15,25]. There was a highly positive correlation
! ! ! ! ! ! ! !

This was in agreement with other research results [15,18,24]. The

! ! ! ! ! ! ! ! ! between pyrolysis temperature and the pH value of the biochar ! ! ! ! ! ! ! ! !

percentage of ash content increased significantly by 15.6% with ! ! ! ! ! ! ! !

(r = 0.983, p < 0.01). Moreover, there was a significant posi-

! ! ! ! ! ! ! ! ! ! !

increasing pyrolysis temperature from 400 to 600 ◦ C. A similar ! ! ! ! ! ! ! ! tive correlation between the ash content and the pH value of
! ! ! ! ! ! ! ! ! !

observation was obtained by Song et al. [25] and by Chen et al. [15]. ! ! ! ! ! ! ! ! ! ! ! ! ! the biochars pyrolyzed in the temperature range 400–600 ◦ C
! ! ! ! ! ! !

Compared to the ash content in the raw sewage sludge (41.3%), a ! ! ! ! ! ! ! ! ! ! !

(r = 0.991, p < 0.01), indicating that the ash component in the

! ! ! ! ! ! ! ! ! ! ! !

rise in ash content of >50% percent was observed in the sewage

! ! ! ! ! ! ! ! ! ! ! biochar may be a major factor involved in the alkaline nature of ! ! ! ! ! ! ! ! ! ! !

sludge biochar and there was a significant positive correlation

! ! ! ! ! ! ! ! the biochar surface [26,27]. However, it has also been reported that
! ! ! ! ! ! ! ! ! !

between pyrolysis temperature and the ash content of the biochar . ! ! ! ! ! ! ! ! ! ! the highly aromatic structure of the biochar also has a considerable
! ! ! ! ! ! ! ! ! !

This may indicate that the majority of inorganic constituents were

! ! ! ! ! ! ! ! ! impact on the pH value of the biochar [28]. ! ! ! ! ! ! ! !

concentrated and retained in the biochar during the pyrolysis pro- ! ! ! ! ! ! ! ! ! The specific surface area of the biochars compared to the raw ! ! ! ! ! ! ! ! ! !

cess [6,12]. ! sewage sludge increased by roughly an order of magnitude follow- ! ! ! ! ! ! ! ! !

The pH value of the raw sewage sludge was near neutral. ! ! ! ! ! ! ! ! ! ! ing pyrolysis at temperatures of 400–600 ◦ C (Table 1). However,
! ! ! ! ! ! ! !

Pyrolysis of the sewage sludge led to clearly alkaline biochar ! ! ! ! ! ! ! ! !

compared with other adsorbents such as activated carbon, the spe- ! ! ! ! ! ! ! ! !

and the higher the pyrolysis temperature, the more alkaline

! ! ! ! ! ! ! ! cific surface area of the sewage sludge biochars was found to be
! ! ! ! ! ! ! ! ! ! !

the biochar (Table 1). Some other researchers reported the sim-
! ! ! ! ! ! ! ! ! lower and no more than 10 m2 g−1 , possibly due to the fact that the ! ! ! ! ! ! ! ! ! ! ! ! !
420 ! J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! !

tar produced in the sewage sludge pyrolysis process adhered to the

! ! ! ! ! ! ! ! ! ! increased is consistent with a change in trend of the N data which ! ! ! ! ! ! ! ! ! ! ! !

surface of the biochars, resulting in blockage of the porous gaps on ! ! ! ! ! ! ! ! ! ! ! declined significantly with increasing temperature (Table 1). How- ! ! ! ! ! ! !

the biochars [29]. ! ! ever, it has been reported that a band of approximately 1620 cm−1
! ! ! ! ! ! ! ! ! ! !

Pyrolysis reduced the C, H, N and S contents of the sewage sludge ! ! ! ! ! ! ! ! ! ! ! ! represents the conjugated aromatic ring stretching of C C groups ! ! ! ! ! ! ! ! !

and the higher the pyrolysis temperature, the lower the C, H and N
! ! ! ! ! ! ! ! ! ! ! ! in biochar [37]. The bands for aliphatic chains, including CH3 and
! ! ! ! ! ! ! ! !

(but not S) contents in the biochars (Table 1). The biochar S content ! ! ! ! ! ! ! ! ! ! ! ! CH2 groups (∼1430 cm−1 ), did not disappear until 600 ◦ C because ! ! ! ! ! ! ! !

was relatively constant irrespective of changing pyrolysis temper-

! ! ! ! ! ! !
the C H bonds are very strong [19].
! ! ! ! ! ! !

ature. In particular, the C and H contents in the biochars declined ! ! ! ! ! ! ! ! ! ! ! There was a slight change in the intensity of the band for the aro- ! ! ! ! ! ! ! ! ! ! ! ! !

substantially by 17.5–25.0% and 70.4–88.6%, respectively, with the ! ! ! ! ! ! ! matic ring C O stretching vibration at approximately 1035 cm−1 ! ! ! ! ! ! ! ! !

pyrolysis temperature increasing from 400 to 600 ◦ C compared to ! ! ! ! ! ! ! ! irrespective of the temperature increase. This finding is in direct ! ! ! ! ! ! ! ! !

the C and H contents in the sludge, indicating that the majority

! ! ! ! ! ! ! ! ! ! ! contrast to the findings on Manchurian walnut biochar by Zhao ! ! ! ! ! ! ! ! !

of those elements, in the forms of CO, CO2 , H2 Oand hydrocarbon

! ! ! ! ! ! ! ! ! ! et al. [19] who found a large decrease in the band with increas-
! ! ! ! ! ! ! ! ! ! ! !

compounds, were transformed into volatile materials during the ! ! ! ! ! ! ! ing temperature because of the weakness of the aromatic C O
! ! ! ! ! ! ! ! ! !

pyrolysis process [30]. ! !

linkages and considered these bonds likely to be the main ones ! ! ! ! ! ! ! ! ! !

The ratio of molar H/C is a carbonization degree parameter ! ! ! ! ! ! ! ! ! broken when the larger aromatic ring systems are formed. This pro- ! ! ! ! ! ! ! ! ! !

that can be used to characterize the degree aromaticity of the ! ! ! ! ! ! ! ! ! ! cess involves volatilization of the oxygen in different compounds
! ! ! ! ! ! ! !

biochar [31,32]. The molar H/C ratio of biochar declined signifi- ! ! ! ! ! ! ! ! ! during pyrolysis and combination of the reactive aromatic carbon ! ! ! ! ! ! ! !

cantly after pyrolysis of sludge, indicative of a higher degree of ! ! ! ! ! ! ! ! ! ! atom with another active carbon atom for poly-condensation of the ! ! ! ! ! ! ! ! !

aromatic condensation in the biochar [31]. The molar H/C ratio ! ! ! ! ! ! ! ! !

aromatic structure [19]. The result is large aromatic ring systems ! ! ! ! ! ! ! ! !

of biochar declined clearly with increasing pyrolysis temperature,

! ! ! ! ! ! ! with six or more fused benzene rings. Comparing the two differ-
! ! ! ! ! ! ! ! ! !

indicating that the stability of the biochars was enhanced as the ! ! ! ! ! ! ! ! ! !

ent feedstocks, here we may conclude that the raw sewage sludge
! ! ! ! ! ! ! ! ! !

degree of aromatic condensation increased. The ratio of molar C/N ! ! ! ! ! ! ! ! ! contains large amounts of oxygen-containing macromolecular aro- ! ! ! ! ! !

in the biochars increased markedly as the pyrolysis temperature

! ! ! ! ! ! ! ! matic compounds which make the aromatic C O groups fairly ! ! ! ! ! ! ! ! !

rose from 400 to 600 ◦ C, suggesting a greater loss of N-related func- ! ! ! ! ! ! ! ! ! ! !

stable during the sludge pyrolysis process. The intensity between ! ! ! ! ! ! ! !

tional groups on the surfaces of the biochars [15]. Yuan et al. [26] ! ! ! ! ! ! ! ! ! ! ! ! 600 and 800 cm−1 assigned to the presence of aromatic and hetero-
! ! ! ! ! ! ! ! ! !

also reported C/N ratio increment during pyrolysis as a result of N

! ! ! ! ! ! ! ! ! ! ! aromatic compounds [29,35], which also basically changed little, ! ! ! ! ! ! !

depletion. Our results show that the rate of N decline was greater ! ! ! ! ! ! ! ! ! ! ! indicates that the aryl C groups are relatively stable during the ! ! ! ! ! ! ! ! ! !

than that of C, resulting in a higher C/N ratio (Table 1). This was con- ! ! ! ! ! ! ! ! ! ! ! ! ! ! conversion of sludge to biochars by pyrolysis. It has been reported ! ! ! ! ! ! ! ! ! !

sistent with the observation reported by Khanmohammadi et al. ! ! ! ! ! ! ! !

that the aromatic structure can provide !-electrons which have
! ! ! ! ! ! ! !

[14] and Song et al. [25]. The molar C/N ratio has been commonly ! ! ! ! ! ! ! ! ! ! ! ! the potential to strongly bond heavy metal cations [38]. The bands
! ! ! ! ! ! ! ! ! !

used as an indicator of the capacity of organic matter to release ! ! ! ! ! ! ! ! ! ! ! below 600 cm−1 were due to M-X (M-metal, X-halogen) stretch- ! ! ! ! ! ! ! !

inorganic N when biochar is incorporated into soils [33,34]. It can ! ! ! ! ! ! ! ! ! ! ing vibrations in both organic and inorganic halogens compounds
! ! ! ! ! ! ! !

be concluded that, compared to the sewage sludge, there should be

! ! ! ! ! ! ! ! ! ! [35]. The main difference between the FT-IR spectra of the sewage
! ! ! ! ! ! ! ! ! !

less N leached to the soil when biochar is applied.

! ! ! ! ! ! ! ! ! sludge biochars and biochars derived from plant materials was in ! ! ! ! ! ! ! ! !

the presence of metallic compounds in the sludge biochars [39].

! ! ! ! ! ! ! ! !

3.2. Fourier transform—infrared spectroscopic (FT-IR) analysis

! ! ! ! !

Changes in the functional groups in the sludge and biochars ! ! ! ! ! ! ! ! !

obtained at different pyrolysis temperatures are shown in the ! ! ! ! ! ! ! !

3.3. Scanning election microscopic (SEM) analysis
! !
! ! !

FT-IR spectra (Fig. 2). The intensity of the peak at a broad band ! ! ! ! ! ! ! ! ! ! ! !

from approximately 3000–3300 cm−1 decreased rapidly from raw ! ! ! ! ! !

Scanning electron microscopy (SEM) is a potential technique for !
! ! ! ! ! ! !

sewage sludge to biochar samples, suggesting that large amounts of ! ! ! ! ! ! ! ! !

the study of the morphology of solid particles. The SEM images were
! ! ! ! ! ! ! ! ! ! !

free and associated hydroxyl groups and structural hydroxyl groups

! ! ! ! ! ! ! !
taken at 500, 1000, and 2000× magnification to further determine ! ! ! ! ! ! ! ! !

(−COOH and −COH) were decomposed during sludge pyrolysis as ! ! ! ! ! ! ! !

how the surface morphology and porous structure were changed
! ! ! ! ! ! ! !

temperatures were elevated. The observation was in accordance ! ! ! ! ! ! !

by conversion of sludge to biochar as the pyrolysis temperature
! ! ! ! ! ! ! ! !

with which obtained by Lu et al. [29,35]. The peak above 3600 cm−1 ! ! ! ! ! ! ! ! ! ! ! !
increased (Fig. 3). The morphological surface texture of sludge ! ! ! ! ! ! ! !

was corresponded to vibration of OH groups in the mineral mat-

! ! ! ! ! ! ! ! ! !
was flat compared to that of the biochars. The surface morphol-
! ! ! ! ! ! ! ! ! !

ter [35]. Unlike OH vibrations which come from organic matter

! ! ! ! ! ! ! ! !
ogy and porous structure of the biochars developed gradually as
! ! ! ! ! ! ! ! !

(peak at approximately 3000–3300 cm−1 ) the inorganic OH groups ! ! ! ! ! ! ! !

the pyrolysis temperature promoted. The biochar derived from
! ! ! ! ! ! !

could still be detected in the biochar obtained at 600 ◦ C (Fig. 2). The ! ! ! ! ! ! ! ! ! ! ! !
sludge pyrolyzed at 400 ◦ C (SSB400 , Fig. 3) exhibited structures ! ! ! ! ! ! ! !

intense bands for aliphatic CHx (2920 and 2826 cm−1 ) disappeared ! ! ! ! ! ! ! !
resembling fish scale bundles with different particle dispersal of ! ! ! ! ! ! ! !

abruptly upon heating to higher temperatures >450 ◦ C, indicating ! ! ! ! ! ! !

inorganic components [25]. As the pyrolysis temperature increased ! ! ! ! ! ! !

that organic fatty hydrocarbons were decomposed to methane, car- ! ! ! ! ! ! ! !

the changes in texture continued as revealed by the rougher and
! ! ! ! ! ! ! ! ! !

bon dioxide and other gases or to aromatic structures [29]. The FT-IR
! ! ! ! ! ! ! ! ! ! !
more porous surfaces (Fig. 3) on which some highly conjugated ! ! ! ! ! ! ! ! !

spectral change of the C OH and C CHx groups was coincided well ! ! ! ! ! ! ! ! ! ! !

aromatic compounds were found [29]. The inorganic components ! ! ! ! ! ! !

with the variation in elemental H which showed a cliff-fall by con- ! ! ! ! ! ! ! ! ! ! !

adhered irregularly to both the outer surface and the internal pores ! ! ! ! ! ! ! ! ! !

version of sludge to biochar (Table 1). This clearly indicates that the ! ! ! ! ! ! ! ! ! ! !
of the biochars. As displayed in Fig. 4, the biochar produced at 550 ◦ C
! ! ! ! ! ! ! ! ! ! ! !

C OH and C CHx linkages were not stable during the pyrolysis of

! ! ! ! ! ! ! ! ! ! !
remained more porous on its surface and when the temperature ! ! ! ! ! ! ! ! !

sewage sludge [19]. ! !

increased to 600 ◦ C there appeared to be more micropores but the ! ! ! ! ! ! ! ! ! !

The band at 2360 cm−1 might be P-H phosphine [36]. The assign- ! ! ! ! ! ! ! ! ! !
biochar surface was less rough (SSB600 , Fig. 3). This was corrobo- ! ! ! ! ! ! ! ! ! !

ment of 1650 cm−1 refers to amide bond stretching ( CO NH ) ! ! ! ! ! ! ! ! ! ! !

rated by the BET data of the surface areas of sludge and biochars ! ! ! ! ! ! ! ! ! ! ! !

and when the temperature increased the characteristic peak was

! ! ! ! ! ! ! !
listed in Table 1 showing that the BET surface area of biochar pro- ! ! ! ! ! ! ! ! ! ! ! !

offset from 1650 cm−1 to 1610 cm−1 (400 and 450 ◦ C), 1605 cm−1 ! ! ! ! ! ! ! ! !
duced at 550 ◦ C was the highest. Pituello et al. [40] observed the ! ! ! ! ! ! ! ! ! ! !

(500 ◦ C), 1585 cm−1 (550 ◦ C) and 1545 cm−1 (600 ◦ C), and this may ! ! ! ! ! ! ! !
similar changes and thought the interactions among components ! ! ! ! ! ! !

suggest that amide functional groups complexed with heavy met- ! ! ! ! ! ! ! !

of the sludge might affect pyrolysis behavior of the various con-
! ! ! ! ! ! ! ! ! !

als during pyrolysis [29]. The peak also weakening as temperatures

! ! ! ! ! ! ! ! !
stituents and increase the heterogeneity of biochars. ! ! ! ! ! !
 J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! ! ! 421

SSB600 3635
1545
SSB550 3620
781689
553
!5
158
1415 463
1025
SSB500 781 688
3610 463
1025 690
788 521
1605 1435
SSB450 466
3695 688
3615 2360 790
2920 1610 1445 1030 525
SSB400 465
!0
377 690
3620 2360 790
1030 530
SS 3060 2920 466
1610 1445
!0
236
785689
1035 530
467
!6
282 1430
1550
3305 1650
!0
104
4000! 3500! 3000! 2500! ! 0!
200 1500! 1000! 500
Wavenu ! (cm!-1 )
! mbers
Fig. 2. FT-IR spectra of the sewage sludge and its biochars obtained under different pyrolysis temperatures. SS, raw sewage sludge; SSBx, biochar derived from the sewage
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

sludge pyrolysis at X (◦ C) temperature. ! ! ! ! !

3.4. Analysis of heavy metals

! ! ! ! in sludge by converting a large part of the unstable fractions (F1
! ! ! ! ! ! ! ! ! ! !

and F2) into relatively stable (F3) and stable (F4) fractions [9].
! ! !
! ! ! ! ! ! !

3.4.1. Concentrations of total and BCR-extractable fractions

! ! ! ! ! !
Specifically, the main form of Cu in sludge was the reducible ! ! ! ! ! ! ! ! ! !

The concentrations of the total and BCR-extractable fractions ! ! ! ! ! ! ! fraction (87.3%) but after the transformation to biochar the main ! ! ! ! ! ! ! ! !

of the heavy metals in the sludge and biochars are shown in

! ! ! ! ! ! ! ! ! ! ! form changed to the oxidizable fraction (Fig. 4). During the pyrolysis
! ! ! ! ! ! ! ! ! !

Table 3. The concentration of Zn was much higher than those of! ! ! ! ! ! ! ! ! ! ! process the percentage of Cu in sludge in the bioavailable cate- ! ! ! ! ! ! ! ! ! !

other heavy metals in sludge, with a maximum concentration of ! ! ! ! ! ! ! ! ! gory (98.6%, F1 + F2) decreased significantly to 28.6% in biochar at
! ! ! ! ! ! ! ! ! ! !

2579.8 mg kg−1 , perhaps related to the large-scale use of galvanized ! ! ! ! ! ! ! ! ! ! 400 ◦ C and declined to <20% with increasing temperature to 600 ◦ C. ! ! ! ! ! ! ! ! !

pipes in domestic areas of the cities [41,42]. The total concentra-

! ! ! ! ! ! ! ! ! ! In addition, Cu in the oxidizable (F3) and the residual (F4) fractions
! ! ! ! ! ! ! ! ! ! !

tions of Cu, Zn, Pb, Cr, Mn and Ni in the biochars were basically
! ! ! ! ! ! ! ! ! ! ! ! ! increased significantly. Similar changes in Ni occurred (Fig. 4). Dur- ! ! ! ! ! ! ! ! !

higher than those in the raw sewage sludge, possibly due to the ! ! ! ! ! ! ! ! ! ! !
ing pyrolysis, almost all of the bioavailable category (F1 + F2) was
! ! ! ! ! ! ! ! ! ! !

lower loss in weight of the heavy metals compared to the loss ! ! ! ! ! ! ! ! ! ! ! immobilized, and with increasing temperature the percentage of ! ! ! ! ! ! !

in weight of organic compounds during pyrolysis, resulting in the

! ! ! ! ! ! ! ! ! stable (F3 + F4) fractions was >95%. A similar result was obtained ! ! ! ! ! ! ! ! ! ! !

enrichment of heavy metals in the biochar matrix [43]. Overall, the ! ! ! ! ! ! ! ! ! ! on pyrolysis of paper mill sludge by Devi et al. [44].The percentage
! ! ! ! ! ! ! ! ! ! !

concentrations of heavy metals in the sludge and biochars followed ! ! ! ! ! ! ! ! ! of the bioavailable category of Cr declined sharply after pyrolysis
! ! ! ! ! ! ! ! !

the sequence of Zn > Cu > Mn > Cr > Ni > Pb.

! ! ! ! ! ! ! ! ! ! ! ! ! of sludge to biochar, and as the temperature increased the per-
! ! ! ! ! ! ! ! ! !

Heavy metals can usually be divided into three categories on the ! ! ! ! ! ! ! ! ! ! centage of the F1, F2 and F3 fractions declined significantly but F4 ! ! ! ! ! ! ! ! ! ! !

basis of their bioavailability: bioavailable, potentially bioavailable,

! ! ! ! ! ! increased substantially, indicating that Cr in biochar was gradu- ! ! ! ! ! ! ! !

and non-bioavailable heavy metals [44]. The exchangeable and acid

! ! ! ! ! ! ! ! ally become more stable as the pyrolysis temperature increased.
! ! ! ! ! ! ! !

soluble fraction (F1) and the reducible (F2) fraction of heavy met- ! ! ! ! ! ! ! ! ! ! Chen et al. observed the similar result by pyrolysis of another type ! ! ! ! ! ! ! ! ! ! !

als from BCR extraction are included in the bioavailable category,

! ! ! ! ! ! ! ! ! of sewage sludge [8]. Mn showed a similar changing trend to Cr,
! ! ! ! ! ! ! ! ! ! !

which is very prone to leaching. The oxidizable (F3) fraction is ! ! ! ! ! ! ! ! ! ! with the percentage of stable (F3 + F4) fractions increasing steadily
! ! ! ! ! ! ! ! ! !

allocated to the potentially bioavailable category which undergoes ! ! ! ! ! ! ! and significantly while the F1 + F2 fractions declined gradually with
! ! ! ! ! ! ! ! ! !

degradation and leaching under very rigorous conditions (highly ! ! ! ! ! ! ! increasing pyrolysis temperature. However, approximately 40% of ! ! ! ! ! !

acidic conditions and an oxidizing atmosphere). The residual (F4) ! ! ! ! ! ! ! ! Mn remained in the bioavailable category (F1 + F2), indicating that
! ! ! ! ! ! ! ! ! !

fraction fall within the non-bioavailable category which is not ! ! ! ! ! ! ! ! Mn continued to pose a higher potential ecological risk after con-
! ! ! ! ! ! ! ! ! !

prone to leaching or degradation [44]. ! ! ! ! ! version to biochar by pyrolysis at higher temperatures (600 ◦ C). Zn ! ! ! ! ! ! ! ! !

Fig. 4 shows that the percentage of the reducible (F2) frac- ! ! ! ! ! ! ! ! ! ! was likely more unstable than Mn. The concentration of Zn in the
! ! ! ! ! ! ! ! ! ! !

tion was the highest of all six heavy metals determined in sludge.
! ! ! ! ! ! ! ! ! ! !
reducible fraction (F2) declined significantly step by step while the ! ! ! ! ! ! ! ! !

Although the reducible fraction percentage of Ni was only 57.3%, ! ! ! ! ! ! ! ! ! concentration in the oxidizable fraction (F3) increased steadily with ! ! ! ! ! ! ! !

less than other heavy metals, the percentage in the bioavailable

! ! ! ! ! ! ! ! ! increasing pyrolysis temperature (Table 3), but an increased per- ! ! ! ! ! ! ! !

category (F1 + F2) still reached 85.4%, higher than Cr (82.5%) which ! ! ! ! ! ! ! ! ! ! ! centage almost fell within the potentially bioavailable category, not ! ! ! ! ! ! ! !

had the lowest percentage in the F1 + F2 fractions, compared to

! ! ! ! ! ! ! ! ! ! ! to mention approximately 40% in the bioavailable category. Chen
! ! ! ! ! ! ! !

other heavy metals in sludge. Thus, only less than one fifth of ! ! ! ! ! ! ! ! ! ! ! et al. also found that Zn was prone to form the F3 fraction with a
! ! ! ! ! ! ! ! ! ! ! ! ! !

the concentration of all heavy metals determined remained in

! ! ! ! ! ! ! ! rise of pyrolysis temperature from 400 to 500 ◦ C [8]. Surprisingly,
! ! ! ! ! ! ! ! !

the potentially available and non-bioavailable category (F3 + F4),

! ! ! ! ! ! ! ! no Pb was found in the exchangeable and acid soluble fraction (F1)
! ! ! ! ! ! ! ! ! ! !

indicative of higher potential ecological risk of the raw sewage ! ! ! ! ! ! ! ! ! in sludge and almost 90% of Pb was in the reducible form (F2). After
! ! ! ! ! ! ! ! ! ! ! ! !

sludge if directly released into the environment [3]. However, a ! ! ! ! ! ! ! ! ! pyrolytic conversion to biochar, the percentage of the reducible ! ! ! ! ! ! ! !

cliff-fall occurred in the percentage of the F1 and F2 fractions of ! ! ! ! ! ! ! ! ! ! !

fraction of Pb decreased sharply and with increasing temperature, ! ! ! ! ! ! ! !

the heavy metals by conversion of sludge to biochar by pyrolysis,

! ! ! ! ! ! ! ! ! ! the percentage of F3 and F4 fractions of Pb increased steadily.
! ! ! ! ! ! ! ! ! !

implying that pyrolysis can significantly immobilize heavy metals ! ! ! ! ! ! !

422 ! J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! !

Fig. 3. Scanning election micrographs of the sewage sludge and its biochars at 500, 1000, and 2000× magnification (Left to Right). SS, raw sewage sludge; SSBx, biochar
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

derived from sewage sludge pyrolysis at X (◦ C) temperature.

! ! ! ! ! ! ! !

The distribution pattern among the four fractions (F1–F4) was

! ! ! ! ! ! ! ! 3.4.2. Ecological risk assessment of heavy metals in biochar
! ! ! ! ! ! ! !

clearly differed for each heavy metal. Generally, the present exper-
! ! ! ! ! ! ! ! ! The eco-toxicity and bioavailability of heavy metals in sludge
! ! ! ! ! ! ! !

iment indicated that the rise of pyrolysis temperature contributed

! ! ! ! ! ! ! !
and its biochars depend not only on the total concentration but also
! ! ! ! ! ! ! ! ! ! !

to the formation of more immobile speciations. The bioavailable

! ! ! ! ! ! ! ! on their chemical forms [45]. Based on BCR extraction, (F1 + F2) frac-
! ! ! ! ! ! ! ! ! ! ! !

category (F1 + F2) declined significantly on pyrolysis of sludge to

! ! ! ! ! ! ! ! ! ! tions of heavy metals represent direct toxicity and bioavailability,
! ! ! ! ! ! ! !

biochar whereas the oxidizable (F3) and residual (F4) fractions

! ! ! ! ! ! ! !
F3 fraction relates to potential toxicity and bioavailability, while
! ! ! ! ! ! ! !

increased significantly during pyrolysis of sludge to biochar, corre- ! ! ! ! ! ! ! ! heavy metals in F4 fraction possess no toxicity and bioavailabil-
! ! ! ! ! ! ! ! !

sponding well with the change in pH of the biochars with increasing ! ! ! ! ! ! ! ! ! ! !

ity [44]. According to this consideration, the contamination and
! ! ! ! ! ! ! !

pyrolysis temperature. Metal oxides and mineral residues as ash

! ! ! ! ! ! ! ! ecological risks of heavy metals can be carried out by using the ! ! ! ! ! ! ! ! ! ! !

content fixed in the biochars rendered the pH more alkaline [15].

! ! ! ! ! ! ! ! ! !
potential ecological risk factor (ER) based on the proportion of the ! ! ! ! ! ! ! ! ! !

This also reveals that the pyrolysis temperature is a controlling

! ! ! ! ! ! ! ! !
sum concentrations of the first three fractions to concentration of
! ! ! ! ! ! ! ! !

factor for immobilization of heavy metals in the biochar [44].

! ! ! ! ! ! ! ! ! each heavy metal in the residual fraction. The each heavy metal
! ! ! ! ! ! ! ! ! !
 J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! ! ! 423

100 Cu 100

Concentration percentage(%)

Concentration percentage(%)
Zn
f
e f d e e
75 c b 75
d
c f
50 50 b e
d
a c
e d f
25 c b 25 b
a
f
e f e a c b d
a b c d e a a b c d a a b b c c d
0 0
F1 F2 F3 F4 F1 F2 F3 F4

100 Pb 100
Concentration percentage(%)

Concentration percentage(%)
f Cr
f
75 75 f
f e
d f e d
50 b c 50 e
e d c
d
c e c
b
25 a d c d 25 e b
b b
a d c a
e d b c aba b a
a a
0 0
F1 F2 F3 F4 F1 F2 F3 F4

100 Mn 100
Concentration percentage(%)

Concentration percentage(%)
Ni

75 f 75 f e
c d
e b
d f
c f
50 e 50
b
a d f
f c e d c e
25 e 25
d f e b a
e b
c a b c b d a bc c b a d
d c
a b
a a
0 0
F1 F2 F3 F4 F1 F2 F3 F4

SS! !SSB400 !SSB450 SS

! B500 SSB550 SSB600

Fig. 4. Fraction distribution of the heavy metals in the sewage sludge and its biochars. Lowercase letters on a column denote a significant difference within the same fraction
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

(p < 0.05, n = 5). SS, raw sewage sludge; SSBx, biochar derived from sewage sludge pyrolysis at X (◦ C) temperature. F1, the exchangeable and acid-soluble fraction; F2, the
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

reducible fraction; F3, the oxidizable fraction; F4, the residual fraction. ! ! ! ! ! ! ! ! !

in sludge and its biochars can be classified by using ER as low

! ! ! ! ! ! ! ! ! ! ! ! tamination (compared to the Cf index in Table 4). The values of Cf ! ! ! !
! ! ! ! ! ! !

risk, moderate risk, considerate risk, high risk and very high risk
! ! ! ! ! ! ! ! ! ! for Cu and Zn in the biochar decreased greatly by 38.0–86.7% and
! ! ! ! ! ! ! ! ! ! !

when which value ranges ≤40, 40–80, 80–160, 160–320, and >320, ! ! ! ! ! ! ! ! !
56.7–82.9%, respectively, by increasing pyrolysis temperature from ! ! ! ! ! !

respectively [46]. The potential ecological risk index (RI) of the ! ! ! ! ! ! ! ! !

400 to 600 ◦ C. This led to a moderate potential ecological risk for

! ! ! ! ! ! ! ! ! ! !

sludge and its biochars is calculated from the total concentrations ! ! ! ! ! ! ! ! !

Cu and a low risk for Zn in the biochar obtained at 600 ◦ C. Similarly
! ! ! ! ! ! ! ! ! ! ! ! !

of heavy metals and is used to assess the ecological risks associated

! ! ! ! ! ! ! ! ! ! !

changes also occurred in Pb, Cr, Mn and Ni (Table 5). All four heavy ! ! ! ! ! ! ! ! ! ! ! ! !

with multiple metals [47] based on the following formulas [46].

! ! ! ! ! ! ! ! !
metals were at low levels of potential ecological risk in the biochar ! ! ! ! ! ! ! ! ! ! !

produced at 600 ◦ C. Consequently, the value of RI of sludge in total

Cf = Ci /Cn (1),
! ! ! ! ! ! ! ! ! ! !

was 663.6, indicating a high degree of potential ecological risk if

!

! ! ! ! ! ! ! ! ! !

Er = Tr · Cf ! ! (2), exposed directly to the environment (heavy metal contamination ! ! ! ! ! ! !

! of soil or water). However, the RI value of the biochar was greatly

! ! ! ! ! ! ! ! ! ! ! !

RI = ! Er (3), decreased by pyrolysis of sludge, and the potential ecological risk ! ! ! ! ! ! ! ! !

to the environment also declined greatly with increasing pyrolysis

! ! ! ! ! ! ! !

where, Cf is the contamination factor of individual heavy metal and ! ! ! ! ! ! ! ! !

temperature, reaching 110.4 at 600 ◦ C, indicating a low potential ! ! ! ! ! ! ! !

Ci andCn are the sum of concentrations of the available and potential ! ! ! ! ! ! ! ! !

ecological risk for the utilization of biochar. A similar observation ! ! ! ! ! ! ! ! !

available (F1 + F2 + F3) and the concentration of the stable fraction ! ! ! ! ! ! ! ! ! ! ! !

was obtained on pyrolysis of paper mill sludge from 200 to 700 ◦ C

! ! ! ! ! ! ! ! ! ! !

(F4) of the heavy metal, respectively [44,47]. Tr is the toxic response

! ! ! ! ! ! ! ! ! !

by Devi et al. [44]. ! ! ! !

factor of the heavy metals, herein the Tr values of the heavy metals ! ! ! ! ! ! ! ! ! ! !

determined in sludge and biochar are Cu (5), Zn (1), Pb (5), Cr (2), Mn ! ! ! ! ! ! ! ! ! ! ! ! ! !

(1), and Ni (6), respectively [44,46]. Er is obtained by multiplying

! ! ! ! ! ! ! ! !
4. Conclusions !

the contamination factor of the individual heavy metal with its toxic
! ! ! ! ! ! ! ! ! !

factor. RI of the solid (sludge or biochar) is obtained by adding the ! ! ! ! ! ! ! ! ! ! ! !

Biochar yield of sewage sludge decreased significantly with ! ! ! ! ! ! !

potential ecological index of each heavy metal present in the solid. ! ! ! ! ! ! ! ! ! !

increasing pyrolysis temperature but the pH, ash content and ! ! ! ! ! ! ! !

The significance of Cf , Er , and RI together with their risk potential

! ! ! ! ! ! ! ! ! ! !

specific surface area increased with increasing temperature. Con- ! ! ! ! ! ! !

is shown in Table 4.
! ! ! !
version of sewage sludge to biochar greatly decreased the H/C ! ! ! ! ! ! ! ! !

The values of Cf , Er , and RI were determined to find out the risk ! ! ! ! ! ! ! ! ! ! ! ! !

ratio, indicative of a higher degree of aromatic condensation in ! ! ! ! ! ! ! ! !

level of the heavy metals in the sludge and its biochars (Table 5).
! ! ! ! ! ! ! ! ! ! ! !

the biochar and a very large loss of hydroxyl functional groups

! ! ! ! ! ! ! ! ! !

It can be observed that the values of Cf for Cu and Zn in the sludge

! ! ! ! ! ! ! ! ! ! ! ! ! !

on the biochar surface as revealed in the changes in FT-IR spec-

! ! ! ! ! ! ! ! ! ! !

were 88.9 and 135.8, respectively, indicating a very high metal con- ! ! ! ! ! ! ! ! ! !

tra with increasing pyrolysis temperature. The C/N ratio increased

! ! ! ! ! ! ! !
424 ! J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! !

Table 3 !

Concentrations of total and BCR-extractable fractions of heavy metals in the raw sewage sludge and its biochars. ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Sample ! SS ! SSB400 SSB450 SSB500 SSB550 SSB600

Total (mg kg−1 ) ! !

Cu ! 1217.71 ± 29.31aɑ ! ! 1551.12 ± 41.43b ! ! ! 1590.91 ± 31.32c ! ! ! 1673.92 ± 74.13e ! ! ! 1639.82 ± 44.32d ! ! ! 1697.12 ± 79.92f ! !

Zn ! 2579.81 ± 106.61a ! ! ! 2572.42 ± 43.23a ! ! ! 2727.12 ± 51.43b ! ! ! 2822.22 ± 87.01c ! ! ! 3042.62 ± 127.61d ! ! ! 3368.12 ± 90.71e ! !

Pb ! 95.11 ± 2.51c ! ! ! 84.71 ± 3.07a ! ! ! 92.01 ± 5.22b ! ! ! 98.82 ± 4.72d ! ! ! 108.72 ± 5.71e ! ! ! 110.72 ± 13.52f ! !

Cr ! 449.21 ± 25.71a ! ! ! 664.99 ± 18.34b ! ! ! 947.82 ± 59.33c ! ! ! 1064.82 ± 16.43d ! ! ! 1318.12 ± 88.32e ! ! ! 1374.31 ± 115.72f ! !

Mn ! 748.31 ± 53.72b ! ! ! 731.19 ± 11.04a ! ! ! 1010.0 ± 45.21c ! ! ! 1076.22 ± 36.33d ! ! ! 1542.91 ± 59.32f ! ! ! 1382.72 ± 108.42e ! !

Ni ! 112.1 ± 6.23a ! ! ! 147.42 ± 5.02b ! ! ! 176.51 ± 5.41c ! ! ! 187.42 ± 3.03d ! ! ! 231.12 ± 4.01f ! ! ! 218.61 ± 16.12e ! !

BCR-extractable (mg kg−1 ) ! !

Cu F1 137.64 ± 1.08f ! ! ! ! ! 7.19 ± 0.13a ! ! ! 12.7 ± 0.34b ! ! ! 17.69 ± 0.41c ! ! ! 20.73 ± 0.44d ! ! ! 33.34 ± 1.52e ! !

F2 1063.59 ± 27.06f ! ! ! ! 436.14 ± 6.04e ! ! ! 343.67 ± 1.80c ! ! ! 336.13 ± 26.94b ! ! ! 407.27 ± 20.54d ! ! ! 302.03 ± 21.69a ! !

F3 2.96 ± 0.23a ! ! ! ! 1080.15 ± 34.95b ! ! ! 1184.14 ± 26.52c ! ! ! 1257.73 ± 45.61d ! ! ! 1110.79 ± 21.75b ! ! ! 1229.6 ± 55.6d ! !

F4 13.54 ± 0.93a ! ! ! ! 27.63 ± 0.24b ! ! ! 50.42 ± 2.62c ! ! ! 62.32 ± 1.13d ! ! ! 101.04 ± 1.60e ! ! ! 132.12 ± 1.10f ! !

Zn F1 693.72 ± 44.00e ! ! ! ! ! 179.93 ± 9.30c ! ! ! 121.86 ± 5.61a ! ! ! 156.19 ± 5.57b ! ! ! 155.18 ± 5.54b ! ! ! 216.99 ± 7.94d ! !

F2 1867.22 ± 60.80e ! ! ! 1852.77 ± 16.12e ! ! 1692.48 ± 20.45d ! ! 1525.84 ± 35.86c ! ! 1424.67 ± 12.69b ! ! 1109.56 ± 5.74a ! !

F3 ND ! ! 496.66 ± 15.41a ! ! ! 866.59 ± 22.63b ! ! ! 1086.72 ± 42.19c ! ! ! 1403.9 ± 107.05d ! ! ! 1902.5 ± 65.3e ! !

F4 18.85 ± 1.74a ! ! ! ! 42.99 ± 2.31b ! ! ! 46.17 ± 2.72bc ! ! ! 53.43 ± 3.35 cd ! ! ! ! 58.85 ± 2.30d ! ! ! 139.04 ± 11.67e ! !

Pb F1 ND ! ! ! ND ! ND ! ND !
ND ! ND
F2 83.98 ± 1.80e ! ! ! ! 34.02 ± 0.82d ! ! ! 32.09 ± 1.01 cd ! ! ! ! 29.9 ± 1.74bc ! ! ! 28.61 ± 1.66b ! ! ! 21.64 ± 5.17a ! !

F3 ND ! ! 35.99 ± 0.85a ! ! ! 39.56 ± 2.99b ! ! ! 49.08 ± 0.94c ! ! ! 56.07 ± 1.95d ! ! ! 55.29 ± 3.36d ! !

F4 11.09 ± 0.66a ! ! ! ! 14.71 ± 1.40b ! ! ! 20.33 ± 1.18c ! ! ! 19.85 ± 2.06c ! ! ! 24.03 ± 2.05d ! ! ! 33.79 ± 4.91e ! !

Cr F1 22.42 ± 0.63d ! ! ! ! ! 19.42 ± 0.34c ! ! ! 14.83 ± 0.78a ! ! ! 18.39 ± 0.16b ! ! ! 18.57 ± 0.21b ! ! ! 19.17 ± 0.19c ! !

F2 347.97 ± 6.48e ! ! ! ! 135.92 ± 3.35d ! ! ! 122.09 ± 2.85c ! ! ! 105.25 ± 2.51b ! ! ! 99.57 ± 3.13ab ! ! ! 91.71 ± 9.35a ! !

F3 0.58 ± 0.48a ! ! ! ! 431.81 ± 12.25d ! ! ! 434.36 ± 9.20de ! ! ! 443.33 ± 5.17e ! ! ! 385.48 ± 10.06c ! ! ! 285.56 ± 17.35b ! !

F4 78.21 ± 18.10a ! ! ! 77.84 ± 2.40a ! ! 376.52 ± 46.51b ! ! ! 497.87 ± 8.58c ! ! ! 814.48 ± 74.89d ! ! ! 977.92 ± 88.77e ! !

Mn F1 203.31 ± 11.70e ! ! ! ! ! 144.82 ± 5.51d ! ! ! 116.69 ± 2.93c ! ! ! 75.15 ± 2.17b ! ! ! 52.26 ± 0.81a ! ! ! 51.4 ± 2.08a ! !

F2 477 ± 22.69a ! ! ! ! 515.08 ± 3.24b ! ! ! 573.93 ± 2.73e ! ! ! 554.36 ± 15.16d ! ! ! 531.85 ± 18.66c ! ! ! 554.28 ± 40.92d ! !

F3 ND ! ! 33.46 ± 1.85a ! ! ! 44.06 ± 1.45b ! ! ! 81.56 ± 0.98c ! ! ! 138.19 ± 14.15d ! ! ! 179.69 ± 16.87e ! !

F4 67.95 ± 19.32b ! ! ! ! 37.83 ± 0.44a ! ! ! 275.29 ± 38.07c ! ! ! 365.09 ± 17.94d ! ! ! 820.63 ± 25.64f ! ! ! 597.34 ± 48.56e ! !

Ni F1 31.48 ± 1.13d ! ! ! ! ! 2.20 ± 0.10a ! ! ! 2.71 ± 0.19b ! ! ! 2.47 ± 0.12ab ! ! ! 2.19 ± 0.10a ! ! ! 3.99 ± 0.12c ! !

F2 64.22 ± 3.42e ! ! ! ! 16.8516 ± 0.45d ! ! ! 11.67 ± 0.32c ! ! ! 7.76 ± 0.40b ! ! ! 5.59 ± 0.76a ! ! ! 5.63 ± 0.93a ! !

F3 0.31 ± 0.21a ! ! ! ! 109.23 ± 3.97b ! ! ! 115.79 ± 3.33c ! ! ! 134.71 ± 2.02d ! ! ! 147.24 ± 2.47e ! ! ! 148.62 ± 12.79e ! !

F4 16.05 ± 1.42a ! ! ! ! 19.14 ± 0.50b ! ! ! 46.34 ± 1.54d ! ! ! 42.4 ± 0.48c ! ! ! 76.08 ± 0.69f ! ! ! 60.34 ± 2.22e ! !

ND, not detected. ! !

SS, raw sewage sludge; SSBx, biochar derived from sewage sludge pyrolysis at X (◦ C) temperature.
! ! ! ! ! ! ! ! ! ! ! ! ! !

F1, exchangeable and acid soluble fraction; F2, reducible fraction; F3, oxidizable fraction; F4, residual fraction.
! ! ! ! ! ! ! ! ! ! ! ! ! !

ɑ
Lowercase letters after the numerical values show significant difference among data (p < 0.05, n = 5). ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Table 4 !

Indices for the ecological risk assessment. !

! ! ! !

Cf Metal contamination ! ! Er Potential RI ! Sludge/biochar

ecological risk !
contamination

Cf ≤ 1 ! ! Clean ! Er ≤ 40 ! ! Low ! RI ≤ 150! ! ! Low

1 < Cf ≤ 3 ! ! ! ! Low ! 40 < Er ≤ 80 ! ! ! ! Moderate ! 150 < RI ≤ 300 ! ! ! ! ! Moderate
3 < Cf ≤ 6 ! ! ! ! Moderate ! 80 < Er ≤ 160 ! ! ! ! Considerate ! 300 < RI ≤ 600 ! ! ! ! ! Considerate
6 < Cf ≤ 9 ! ! ! ! Considerate ! 160 < Er ≤ 320 ! ! ! ! High ! RI > 600! ! ! High
Cf > 9 ! ! High ! Er > 320 ! ! Very high !

Cf , contamination factor of the individual heavy metal.

! ! ! ! ! ! !

Er , potential ecological risk factor for the individual heavy metal.

! ! ! ! ! ! ! ! !

RI, sum of the potential ecological risk index (Er ) of each heavy metal.
! ! ! ! ! ! ! ! ! ! ! !

Table 5 !

Ecological risk assessment of the heavy metals in the raw sewage sludge and its biochars. ! ! ! ! ! ! ! ! ! ! ! ! ! !

Heavy metal ! ! Tr Cf Er

SS ! SSB400 SSB450 SSB500 SSB550 SSB600 SS ! SSB400 SSB450 SSB500 SSB550 SSB600

Cu ! 5 ! 88.90 ! 55.14 ! 30.55 ! 25.86 ! 15.23 ! 11.85 ! 444.52 ! 275.71 ! 152.76 ! 129.31 ! 76.15 ! 59.23
Zn ! 1 ! 135.85 ! 58.83 ! 58.07 ! 51.82 ! 50.70 ! 23.22 ! 135.85 ! 58.83 ! 58.07 ! 51.82 ! 50.70 ! 23.22
Pb ! 5 ! 7.57 ! 4.76 ! 3.52 ! 3.98 ! 3.52 ! 2.28 ! 37.86 ! 23.79 ! 17.62 ! 19.90 ! 17.62 ! 11.38
Cr ! 2 ! 4.74 ! 7.54 ! 1.52 ! 1.14 ! 0.62 ! 0.41 ! 9.49 ! 15.09 ! 3.03 ! 2.28 ! 1.24 ! 0.81
Mn ! 1 ! 10.01 ! 18.33 ! 2.67 ! 1.95 ! 0.88 ! 1.31 ! 10.01 ! 18.33 ! 2.67 ! 1.95 ! 0.88 ! 1.31
Ni ! 6 ! 5.98 ! 6.70 ! 2.81 ! 3.42 ! 2.04 ! 2.62 ! 35.90 ! 40.22 ! 16.86 ! 20.51 ! 12.23 ! 15.73
RI ! 673.63 ! 431.97 ! 251.01 ! 225.77 ! 158.82 ! 111.68

Cf , contamination factor of the individual heavy metal; Tr , toxic response factor of the individual heavy metal; Er , potential ecological risk factor for the individual heavy
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

metal obtained by multiplying the contamination factor (Cf ) of the heavy metal with the toxic factor (Tr ) of the heavy metal; RI, the sum of the potential ecological risk index
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

(Er ) of each heavy metal. ! ! ! !

SS, raw sewage sludge; SSBx, biochar derived from sewage sludge pyrolysis at X (◦ C) temperature.
! ! ! ! ! ! ! ! ! ! ! ! ! !

significantly in the biochar suggesting a greater depletion of N with ! ! ! ! ! ! ! ! ! ! FT-IR analyses show that the C OH and C CHx groups dis- ! ! ! ! ! ! ! ! ! !

increasing pyrolysis temperature. ! ! appeared abruptly and the peak of the amide groups weakened ! ! ! ! ! ! ! ! !
 J. Jin et al. / Journal of Hazardous Materials 320 (2016) 417–426
! ! ! ! ! ! ! ! ! ! ! ! 425

gradually with increasing temperature which corresponds well ! ! ! ! ! ! [14] Z. Khanmohammadi, M. Afyuni, M.R. Mosaddeghi, Effect of pyrolysis
! ! ! ! ! ! ! ! !

with the changes in H and N during the pyrolysis process. The FT-IR temperature on chemical and physical properties of sewage sludge biochar, ! ! ! ! ! ! ! ! !

Waste Manag. Res. 33 (2015) 275–283.

! ! ! ! ! ! ! ! ! ! ! !

spectra also show that the raw sewage sludge contains large quan-
! ! ! ! !

! ! ! ! ! ! ! ! ! !

[15] T. Chen, Y. Zhang, H. Wang, W. Lu, Z. Zhou, Y. Zhang, L. Ren, Influence of

tities of aromatic and hetero-aromatic compounds which make the
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! !

pyrolysis temperature on characteristics and heavy metal adsorptive ! ! ! ! ! ! !

aromatic C O groups fairly stable during the sludge pyrolysis pro- performance of biochar derived from municipal sewage sludge, Bioresour. ! ! ! ! ! ! ! !

Technol. 164 (2014) 47–54.

! ! ! ! ! ! ! ! ! !

cess, and C O and C C linkages are further produced with thermal

! ! !

[16] J. Zhang, M. Wang, S. Wu, K. Müller, Y. Cao, P. Liang, Z. Cao, A. Leung, P.

! ! ! ! ! ! ! ! ! ! ! !

poly-condensation by increasing temperature forming stable aro-

! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! !

Christie, H. Wang, Land use affects soil organic carbon of paddy soils: ! ! ! ! ! ! ! ! ! ! !

matic ring stretching C C groups. ! ! ! ! !

empirical evidence from 6280 years BP to present, J. Soils Sediments 16 ! ! ! ! ! ! ! ! ! ! !

(2016) 767–776.
Total concentrations of Cu, Zn, Pb, Cr, Mn, and Ni increased with !

[17] M.R. Carter, E.G. Gregorich, Soil Sampling and Methods of Analysis, CRC Press,
! ! ! ! ! ! ! ! ! ! !

conversion of sewage sludge to biochar and increasing pyrolysis

! ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! !

1993.
temperature, due to the loss in weight of the heavy metals being ! ! ! ! ! ! ! ! ! ! !
[18] H. Yuan, T. Lu, H. Huang, D. Zhao, N. Kobayashi, Y. Chen, Influence of pyrolysis
! !
! ! ! ! ! ! ! ! ! ! ! ! !

temperature on physical and chemical properties of biochar made from

lower than the loss in weight of organic compounds during pyrol- ! ! ! ! ! ! ! ! !

sewage sludge, J. Anal. Appl. Pyrolysis 112 (2015) 284–289.

! ! ! ! ! ! ! ! ! !

ysis, resulting in the enrichment of heavy metals in the biochar

! ! ! ! ! !
! !

! ! ! ! ! ! ! ! ! !

[19] Y. Zhao, D. Feng, Y. Zhang, Y. Huang, S. Sun, Effect of pyrolysis temperature on

! ! ! ! ! ! ! ! ! ! ! ! ! ! !

matrix. However, using BCR sequential extraction and analysis, it ! ! ! ! ! ! ! !

char structure and chemical speciation of alkali and alkaline earth metallic ! ! ! ! ! ! ! ! ! !

was found that most of the heavy metals exist in the oxizable and species in biochar, Fuel Process. Technol. 141 (2016) 54–60. ! ! ! ! ! ! ! !

[20] A. Sungur, M. Soylak, H. Ozcan, Investigation of heavy metal mobility and

! ! ! ! ! ! ! ! ! ! ! !

residual forms after pyrolysis, especially at 600 ◦ C. This would result

! ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! ! !

availability by the BCR sequential extraction procedure: relationship between ! ! ! ! ! ! ! !

in a significant decline in bioavailability, leading to a very low eco-

! ! ! ! ! ! ! ! ! ! !
soil properties and heavy metals availability, Chem. Speciat. Bioavailab. 26
! ! ! ! ! ! ! ! !

logical risk of biochar exposed to the environment. However, it is (2014) 219–230. !

[21] Y.-Y. Long, L.-F. Hu, C.-R. Fang, Y.-Y. Wu, D.-S. Shen, An evaluation of the
! ! ! ! ! ! ! ! ! !

still recommended to monitor the impacts of biochar on soil, water,

! ! ! ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! ! ! !

modified BCR sequential extraction procedure to assess the potential mobility

and plants under field conditions.
! ! ! ! ! ! ! ! !

! ! ! !

of copper and zinc in MSW, Microchem. J. 91 (2009) 1–5.

! ! ! ! ! ! ! ! ! !

To summarize, our results on one hand demonstrate that pyrol- [22] A.M. Ure, P. Quevauviller, H. Muntau, B. Griepink, Speciation of heavy metals
! ! ! ! ! ! ! ! ! ! ! !

in soils and sediments. An account of the improvement and harmonization of

! ! ! ! ! ! ! ! !

ysis is a promising sludge treatment method for heavy metal

! ! ! ! ! ! ! ! ! ! !

extraction techniques undertaken under the auspices of the BCR of the

! ! ! ! ! ! ! ! !

immobilization in biochars. On the other hand, the data further

! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! ! !

commission of the european communities, Int. J. Environ. Anal. Chem. 51 ! ! ! ! ! ! ! ! ! !

highlight the potential to increase the quality and minimize the ! ! ! ! ! ! ! ! !

(1993) 135–151. !

[23] E.M. Lorentzen, H.S. Kingston, Comparison of microwave-assisted and

potential harmful effects of biochar by controlling the temperature ! ! ! ! ! ! ! !

conventional leaching using EPA method 3050B, Anal. Chem. 68 (1996)

! ! ! ! ! ! ! !

of pyrolysis.
! ! ! ! ! ! ! ! !

4316–4320.
[24] A. Méndez, M. Terradillos, G. Gascó, Physicochemical and agronomic
! ! ! ! ! ! ! ! !

properties of biochar from sewage sludge pyrolysed at different

Acknowledgements
! ! ! ! ! ! ! !

temperatures, J. Anal. Appl. Pyrolysis 102 (2013) 124–130. ! ! ! ! ! ! !

[25] X.D. Song, X.Y. Xue, D.Z. Chen, P.J. He, X.H. Dai, Application of biochar from
! ! ! ! ! ! ! ! ! ! ! ! ! !

We thank the Key Scientific and Technological Innovation ! ! ! ! ! ! !

sewage sludge to plant cultivation: influence of pyrolysis temperature and ! ! ! ! ! ! ! ! !

biochar-to-soil ratio on yield and heavy metal accumulation, Chemosphere

Research Team of Zhejiang Province (2013TD12/12) and the
! ! ! ! ! ! ! !

109 (2014) 213–220.

! ! ! ! ! ! !

National Natural Science Foundation of China (41201229) for fund-

! !

! ! ! ! ! ! ! !

[26] J.-H. Yuan, R.-K. Xu, H. Zhang, The forms of alkalis in the biochar produced
! ! ! ! ! ! ! ! ! ! ! ! ! !

ing support. J. Zhang is also grateful for the financial support

! ! ! ! ! ! ! ! ! !
from crop residues at different temperatures, Bioresour. Technol. 102 (2011) ! ! ! ! ! ! ! ! !

3488–3497.
provided by the Innovative Technology Commission of Hong Kong,
[27] H. Zheng, Z. Wang, X. Deng, J. Zhao, Y. Luo, J. Novak, S. Herbert, B. Xing,
! ! ! ! ! ! ! !

(ITS/174/14FX) during his sabbatical leave at The Education Uni-

! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

! ! ! ! ! ! ! !

Characteristics and nutrient values of biochars produced from giant reed at ! ! ! ! ! ! ! ! ! !

versity of Hong Kong. ! ! !

different temperatures, Bioresour. Technol. 130 (2013) 463–471. ! ! ! ! ! !

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! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

biochars derived from corn straw, J. Agro-Environ. Sci. China 31 (2012)

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