Jin 2016
Jin 2016
Jin 2016
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
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
b
Consortium on Health, Environment, Education and Research (CHEER), Department of Science and Environmental Studies, The Education University of ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
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. ! ! ! ! ! ! ! ! ! ! !
• Fractionation and bioavailability of heavy metals in sludge and biochar was analyzed. ! ! ! ! ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
intervals to investigate the influence of pyrolysis temperature on properties and environmental safety ! ! ! ! ! ! ! ! ! ! ! !
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
! ! !
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 !
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
sludge treatment method for heavy metals immobilization in biochar, and highlights the potential to
! ! ! ! ! ! ! ! ! ! ! ! !
1. Introduction !
! ! ! ! ! ! ! !
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-
! ! ! ! ! ! !
There are a number of treatment processes that can kill most of ! ! ! ! ! ! ! ! ! ! ! quality control [16]. ! !
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 ! ! ! ! ! ! !
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 risk of metal release into the environment. The physical and
! ! ! ! ! ! ! ! ! !
KBr to 0.1 wt% and then pressing into pellets [18]. The spectra were
! ! ! ! ! ! ! ! ! ! ! !
(3) assess the potential risk of heavy metals leaching from sewage
! ! ! ! ! ! ! ! ! !
The heavy metals in the sludge and biochar samples were ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! !
ment was used. The sludge was dried at room temperature (∼20 ◦ C),
! ! ! ! ! ! !
dyne Leeman Labs, Hudson, NH). The residual fraction and total
! ! ! ! ! ! ! ! ! !
ICP-OES.
! ! ! ! ! ! ! ! ! !
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
! ! ! ! ! ! !
ature (∼20 ◦ C) and transferred into a sealed plastic bag for further
! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! ! !
! ! ! !
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.
! ! ! ! ! ! ! ! ! ! ! ! !
◦
!
ɑ
Lowercase letters after the numerical values show significant differences within each column of data(p < 0.05, n = 5). ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
Table 2 !
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, ! ! ! ! ! ! !
gradual decomposition of the organic substances in the sludge. ! ! ! ! ! ! ! ! ilar trend [14,15,25]. There was a highly positive correlation
! ! ! ! ! ! ! !
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
! ! ! ! ! ! !
between pyrolysis temperature and the ash content of the biochar . ! ! ! ! ! ! ! ! ! ! the highly aromatic structure of the biochar also has a considerable
! ! ! ! ! ! ! ! ! !
concentrated and retained in the biochar during the pyrolysis pro- ! ! ! ! ! ! ! ! ! The specific surface area of the biochars compared to the raw ! ! ! ! ! ! ! ! ! !
The pH value of the raw sewage sludge was near neutral. ! ! ! ! ! ! ! ! ! ! ing pyrolysis at temperatures of 400–600 ◦ C (Table 1). However,
! ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! ! !
compounds, were transformed into volatile materials during the ! ! ! ! ! ! ! ing temperature because of the weakness of the aromatic C O
! ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! ! !
degree of aromatic condensation increased. The ratio of molar C/N ! ! ! ! ! ! ! ! ! contains large amounts of oxygen-containing macromolecular aro- ! ! ! ! ! !
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-
! ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! ! ! !
[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
! ! ! ! ! ! ! !
FT-IR spectra (Fig. 2). The intensity of the peak at a broad band ! ! ! ! ! ! ! ! ! ! ! !
with which obtained by Lu et al. [29,35]. The peak above 3600 cm−1 ! ! ! ! ! ! ! ! ! ! ! !
increased (Fig. 3). The morphological surface texture of sludge ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! !
bon dioxide and other gases or to aromatic structures [29]. The FT-IR
! ! ! ! ! ! ! ! ! ! !
more porous surfaces (Fig. 3) on which some highly conjugated ! ! ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! ! ! ! !
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- ! ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
and F2) into relatively stable (F3) and stable (F4) fractions [9].
! ! !
! ! ! ! ! ! !
The concentrations of the total and BCR-extractable fractions ! ! ! ! ! ! ! fraction (87.3%) but after the transformation to biochar the main ! ! ! ! ! ! ! ! !
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. ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! !
Heavy metals can usually be divided into three categories on the ! ! ! ! ! ! ! ! ! ! centage of the F1, F2 and F3 fractions declined significantly but F4 ! ! ! ! ! ! ! ! ! ! !
soluble fraction (F1) and the reducible (F2) fraction of heavy met- ! ! ! ! ! ! ! ! ! ! Chen et al. observed the similar result by pyrolysis of another type ! ! ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! !
category (F1 + F2) still reached 85.4%, higher than Cr (82.5%) which ! ! ! ! ! ! ! ! ! ! ! centage almost fell within the potentially bioavailable category, not ! ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! ! ! !
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
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
clearly differed for each heavy metal. Generally, the present exper-
! ! ! ! ! ! ! ! ! The eco-toxicity and bioavailability of heavy metals in sludge
! ! ! ! ! ! ! !
increased significantly during pyrolysis of sludge to biochar, corre- ! ! ! ! ! ! ! ! heavy metals in F4 fraction possess no toxicity and bioavailabil-
! ! ! ! ! ! ! ! !
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
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. ! ! ! ! ! ! ! ! !
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 ! ! ! ! ! !
changes also occurred in Pb, Cr, Mn and Ni (Table 5). All four heavy ! ! ! ! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! ! !
factor of the heavy metals, herein the Tr values of the heavy metals ! ! ! ! ! ! ! ! ! ! !
the contamination factor of the individual heavy metal with its toxic
! ! ! ! ! ! ! ! ! !
is shown in Table 4.
! ! ! !
version of sewage sludge to biochar greatly decreased the H/C ! ! ! ! ! ! ! ! !
level of the heavy metals in the sludge and its biochars (Table 5).
! ! ! ! ! ! ! ! ! ! ! !
were 88.9 and 135.8, respectively, indicating a very high metal con- ! ! ! ! ! ! ! ! ! !
Table 3 !
Concentrations of total and BCR-extractable fractions of heavy metals in the raw sewage sludge and its biochars. ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
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 ! !
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 ! !
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 !
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
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
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, ! ! ! ! ! ! ! ! !
spectra also show that the raw sewage sludge contains large quan-
! ! ! ! !
! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! !
aromatic C O groups fairly stable during the sludge pyrolysis pro- performance of biochar derived from municipal sewage sludge, Bioresour. ! ! ! ! ! ! ! !
! ! ! ! ! !
Christie, H. Wang, Land use affects soil organic carbon of paddy soils: ! ! ! ! ! ! ! ! ! ! !
(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,
! ! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! !
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
! !
! ! ! ! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! ! !
was found that most of the heavy metals exist in the oxizable and species in biochar, Fuel Process. Technol. 141 (2016) 54–60. ! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! !
[21] Y.-Y. Long, L.-F. Hu, C.-R. Fang, Y.-Y. Wu, D.-S. Shen, An evaluation of the
! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! ! !
! ! ! !
To summarize, our results on one hand demonstrate that pyrol- [22] A.M. Ure, P. Quevauviller, H. Muntau, B. Griepink, Speciation of heavy metals
! ! ! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! ! !
of pyrolysis.
! ! ! ! ! ! ! ! !
4316–4320.
[24] A. Méndez, M. Terradillos, G. Gascó, Physicochemical and agronomic
! ! ! ! ! ! ! ! !
[25] X.D. Song, X.Y. Xue, D.Z. Chen, P.J. He, X.H. Dai, Application of biochar from
! ! ! ! ! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! !
[26] J.-H. Yuan, R.-K. Xu, H. Zhang, The forms of alkalis in the biochar produced
! ! ! ! ! ! ! ! ! ! ! ! ! !
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,
! ! ! ! ! ! ! !
! ! ! ! ! ! ! !
[28] L. Li, Y. Lu, Y. Liu, H. Sun, Z. Liang, Adsorption mechanisms of Cadmium (II) on
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
2277–2283.
[29] H. Lu, W. Zhang, S. Wang, L. Zhuang, Y. Yang, R. Qiu, Characterization of
! ! ! ! ! ! ! ! ! ! ! ! ! !
[2] H. Chen, S.H. Yan, Z.L. Ye, H.J. Meng, Y.G. Zhu, Utilization of urban sewage
! ! ! ! ! ! ! ! ! ! ! ! ! !
of sewage sludge: the influence of pyrolysis temperature on biochar, liquid
! ! ! ! ! ! ! ! ! !
[3] R.P. Singh, M. Agrawal, Potential benefits and risks of land application of
! ! ! ! ! ! ! ! ! ! ! !
Switzerland, 2012, pp. 3412–3420. ! ! !
and new methods—a review, Renew. Sustain. Energy Rev. 12 (2008) 116–140. ! ! ! ! ! ! ! ! ! !
202 (2015) 135–138. ! !
[6] D. Chen, L. Yin, H. Wang, P. He, Pyrolysis technologies for municipal solid
! ! ! ! ! ! ! ! ! ! ! ! !
[33] M. Qayyum, D. Steffens, H. Reisenauer, S. Schubert, Biochars influence
! ! ! ! ! ! ! ! ! !
[8] F.F. Chen, Y.Y. Hu, X.M. Dou, D.Z. Chen, X.H. Dai, Chemical forms of heavy
! ! ! ! ! ! ! ! ! ! ! ! ! !
organic nitrogen cycling but stimulates soil nitrification in a temperate arable ! ! ! ! ! ! ! ! ! !
carbonization for biochar applications. the fate of heavy metals, Energy Fuels ! ! ! ! ! ! ! ! ! !
sludge biochar, J. Environ. Manag. 92 (2011) 223–228. ! ! ! ! ! ! !
28 (2014) 5318–5326. ! !
[36] H. Jin, R.O. Arazo, J. Gao, S. Capareda, Z. Chang, Leaching of heavy metals from
! ! ! ! ! ! ! ! ! ! ! ! ! ! !
[10] D. Wang, Y. Wang, Z. Yu, J. Liu, S. Zhou, Synergistic effect on carbon and
! ! ! ! ! ! ! ! ! ! ! ! ! ! !
fast pyrolysis residues produced from different particle sizes of sewage
! ! ! ! ! ! ! ! !
[11] H. Yuan, T. Lu, Y. Wang, Y. Chen, T. Lei, Sewage sludge biochar: nutrient
! ! ! ! ! ! ! ! ! ! ! ! ! !
mineral-enriched biochar by FTIR, Raman and SEM–EDX, Vib. Spectrosc. 62 ! ! ! ! ! ! ! ! !
composition and its effect on the leaching of soil nutrients, Geoderma 267 ! ! ! ! ! ! ! ! ! ! !
(2012) 248–257. !
(2016) 17–23. !
[38] O.R. Harvey, B. Herbert, R.D. Rhue, L.-J. Kuo, Metal interactions at the
! ! ! ! ! ! ! ! ! ! ! !
Characterization of chemical-physical, structural and morphological ! ! ! ! ! effluent treatment plant sludge for bioavailability and eco-toxicity of heavy
! ! ! ! ! ! ! ! !
[41] H. Weng, F. Fu, Z. Liu, J. Zhang, Z. Ji, X. Ma, Mechanisms of heavy metal
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! heavy metals in sewage sludge by using subcritical water technology,
! ! ! ! ! ! ! ! !
stabilization during sludge drying, Acta Sci. Circumstantiae 30 (2010) ! ! ! ! ! ! ! ! Bioresour. Technol. 137 (2013) 18–24. ! ! ! !
1401–1409. [46] L. Hakanson, An ecological risk index for aquatic pollution control.a
! ! ! ! ! ! ! ! ! !
[42] T. Chen, Q. Huang, D. Gao, Y. Zheng, J. Wu, Heavy metal concentrations and
! ! ! ! ! ! ! ! ! ! ! ! ! ! sedimentological approach, Water Res. 14 (1980) 975–1001. ! ! ! ! ! !
23 (2003) 561–569. ! !
metals during the hydrothermal treatment of sewage sludge, Bioresour.
! ! ! ! ! ! ! !
[43] Y. Chen, G. Liu, L. Wang, Y. Kang, J. Yang, Occurrence and fate of some trace
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! Technol. 200 (2016) 991–998. ! ! !
elements during pyrolysis of Yima coal, China, Energy & Fuels 22 (2008)
! ! ! ! ! ! ! ! ! ! !
3877–3882.