G Model

JIEC 2396 15

Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

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

2 Heavy metal chemical extraction from industrial and municipal mixed

3 sludge by ultrasound-assisted citric acid
4 Q1 Xuejiang Wang *, Jie Chen, Xiangbo Yan, Xin Wang, Jing Zhang, Jiayu Huang, Jianfu Zhao
5 State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China

A R T I C L E I N F O A B S T R A C T

Article history: Citric acid chemical extraction technology in combination with ultrasonication was used to remove
Received 23 June 2014 heavy metals from industrial and municipal mixed sludge. The removal efciencies of Zn, Ni, Cr and Cu
Received in revised form 4 January 2015 reached 53.5%, 40.2%, 35.4% and 13.1%, respectively, at citric acid concentration of 0.2 M assisted by
Accepted 20 January 2015
ultrasound for 20 min. The extracted Zn, Ni and Cr mainly came from acid-soluble, reducible and
Available online xxx
oxidizable fractions, and Cu mainly came from oxidizable and reducible fractions. The presence of Fe3+,
Al3+ and Ca2+ improved the extraction efciency of Cu from the sludge signicantly. The extracted sludge
Keywords:
could be used for soil amendment.
Heavy metal
Sludge
2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Extraction Chemistry.
Ultrasound
Citric acid

6
7 Introduction Chemical extraction is a process of separating contaminants 28
from soil, sludge, and sediment by using extracting chemicals to 29
8 Q2 Wastewater treatment plants usually generate millions of tons reduce the volume of hazardous wastes for treatment. The 30
9 of residual sludge worldwide every year [1]. As sewage sludge extractants can be inorganic acids (HNO3, HCl and H2SO4), organic 31
10 contains high levels of the major plant nutrients, such as nitrogen acids (oxalic and citric acid), chelating agents (NTA and EDTA), and 32
11 and phosphorus, and is rich in organic substances, its land- some inorganic chemicals [911]. As compared with inorganic 33
12 application has been regarded as an effective way of recycling this acids and chelating agents, organic acids can be more promising 34
13 kind of organic solid waste [2]. However, in China, the increasing because the extraction can be performed at mildly acidic 35
14 trend toward combining industrial and municipal wastewater for conditions (pH 34). Moreover, organic acids are biodegradable 36
15 treatment in sewage plants increases the possibility of high level of which implies that the decontaminated sludge does not have to be 37
16 heavy metals in the sewage sludge [3]. The retained heavy metals conditioned, resulting in a substantial reduction of wastewater 38
17 in sewage sludge can pose a serious environmental risk to the required for washing the sludge. It is also important to note that 39
18 agricultural ecosystem, and consequently threaten human health one of the main limitations of chemical extraction procedures is its 40
19 through the food chain since heavy metals are nonbiodegradable extremely time consuming [12]. Previous studies showed that 41
20 and accumulate in the environment, which restricts signicantly ultrasound, as an assisted extraction method, could efciently 42
21 the reuse of sewage sludge [4]. A signicant way for overcoming release heavy metals from sludge and spent catalysts and shorten 43
22 the problem is to remove the heavy metals from sludge. Hence, extraction time [13,14]. Ultrasound is a pressure wave that 44
23 several methods such as chemical extraction, bioleaching, super propagates through a medium with a vast amount of energy 45
24 critical uid extraction and electrokinetic remediation have been dissipation generating numerous gas and vapor bubbles which 46
25 used by many researchers [58]. Among them, chemical extraction may grow, and then collapse violently at high speeds to cause 47
26 of heavy metals has received extensive attention due to its simple acoustic cavitation. Sonication of sewage sludge is capable of 48
27 operation, short extraction time and high removal efciency. destroying the ocs, which can enhance the ability of the 49
extractant to leach metals. Although many literature reports have 50
documented releases of heavy metals from sewage sludge under 51
sonication, few have focused on the investigation of concurrent 52
* Corresponding author. Tel.: +86 21 65980440; fax: +86 21 65980440. releases of organic constituents, nitrogen and phosphorus species. 53
E-mail address: wangxj@tongji.edu.cn (X. Wang). Given the land use of treated sewage sludge, the losses of organic 54

http://dx.doi.org/10.1016/j.jiec.2015.01.016
1226-086X/ 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.

Please cite this article in press as: X. Wang, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.01.016
 G Model
JIEC 2396 15

2 X. Wang et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

55 substances and especially the nitrogen and phosphorus in sewage molar ratio of citric acid to the sum of the total heavy metals in the 101
56 sludge after ultrasound-assisted chemical extraction should be sewage sludge was kept in the range from 1:1 to 10:1. The 102
57 concerned. inuence of the solution pH on the extraction efciency was 103
58 Most of the previous studies have been limited only to the examined at pH from 1 to 10, which was adjusted with HNO3 or 104
59 determination of the total concentration of metals. However, the NaOH. 105
60 total heavy metal content does not provide a complete information For each batch test, 1.0 g of solid sewage sludge was suspended 106
61 in respect to the available soil pollution and toxic effects caused on in 10 mL of the solution (1:10). Ultrasound was used to assist citric 107
62 the corresponding cultivated plants [15]. Metal fractionation in acid in extracting heavy metals from sludge by varying sonication 108
63 different chemical forms associated to the matrix sample requires time from 0 to 60 min. The ultrasonic apparatus manufactured by 109
64 the application of the sequential extraction methods [16]. Sonxi Ultrasonic Corp., China (FS-300) was equipped with an MS73 110
65 Recently, sequential extraction procedures have been developed titanium cylindrical probe with a diameter of 20 mm and a length 111
66 and applied to extract elements from sediment under different of 135 mm. It operated at a frequency of 20 kHz and supplied an 112
67 conditions. This procedure is proposed by BCR, which is the adjustable power of 1001000 W. During treatment, the probe was 113
68 European Community Bureau of Reference [15]. The original BCR immersed into the sludge at a depth of 10 mm, the power output 114
69 three-stage sequential extraction procedure has been applied to was 250 W. After the extraction, all suspensions were centrifuged 115
70 soil [17] and, later, to a variety of matrices including sewage sludge at 4000 r/min for 20 min and passed through 0.45 mm paper lter 116
71 [18] and dust [19]. However, during certication of BCR CRM 601, before analysis of the metal content. 117
72 signicant inter-laboratory variability was apparent, which led to
73 the development of a modied BCR sequential extraction Analytical methods 118
74 procedure [20,21]. The procedure gives a summary of the method
75 of extracting metals in four fractions representing: exchangeable, To determine the total content of heavy metals in tested sewage 119
76 carbonate bound, FeMn oxides bound, organic matter bound and sludge, sludge samples were digested with HFHClHNO3 with 120
77 residual fractions [15]. ETHOS E Microwave Extraction/Digestion System (Mile Stone S.r.l., 121
78 In this work, the effectiveness of ultrasound-assisted citric acid Italy). For determining the fractional distribution of heavy metals 122
79 extraction for metal from municipal and industrial sludge was in sewage sludge, samples of 0.5 g sewage sludge were analyzed by 123
80 investigated, parameters inuencing the extraction such as modied BCR sequential extraction method [15,22] before and 124
81 extraction time, citric acid concentration, pH and so on were after the extraction with citric acid. 125
82 performed. Fractionation of heavy metals and other plant nutrients The concentration of dissolved heavy metals and TK in the 126
83 in samples after extraction was also analyzed. digestion solutions and extraction solutions were measured with 127
Optima 2100 DV Inductively Coupled Plasma Optical Emission 128
84 Experimental Spectrometry (PerkinElmer, USA). The extraction solution pH was 129
measured with PP-15 Professional pH meter (Sartorius, Germany). 130
85 Materials The TOC of the sewage sludge was determined by SSM-5000A Total 131
Organic Carbon Analyzer (SHIMADZU, Japan). Analyses of TN, TP 132
86 Samples of sewage sludge were collected from Jiaxing Munici- were performed according to the Standard Methods [23]. 133
87 pal Wastewater Treatment Plant in Zhejiang, China. It should be Triplicate extractions and analyses were performed for all 134
88 noted that the treatment plant treats both industrial and domestic samples to evaluate the reproducibility of the results, and then the 135
89 wastewaters with industrial wastewater accounts for 45% of the data from the three parallel experiments were averaged. 136
90 total sewage. The sewage sludge samples were air dried naturally,
91 ground, and sieved to a size less than 2 mm. Heavy metal contents Results and discussion 137
92 of the sludge samples were presented in Table 1. The contents of Cr,
93 Cu, Zn and Ni all exceed the third level limited value of Effect of citric acid concentration 138
94 Environmental Quality Standard for Soils in China and the limited
95 level of Sludge Agricultural Utilization Standard for Soil in China. The effect of citric acid concentration on heavy metal removal 139
96 Thus, only these four heavy metals were investigated. efciency was shown in Fig. 1. From Fig. 1, it could be seen that the 140
extraction efciencies increased signicantly with the increase of 141
97 Extraction experiments citric acid concentration from 0 to 0.2 M. Further increases in citric 142
acid concentration led to only a slight increase in the extraction of 143
98 The extraction was performed in batch experiments using heavy metals. Even if the further increases in citric acid 144
99 aqueous suspensions in centrifuge tubes. Different concentrations concentration might extract more heavy metals from sludge, 145
100 of citric acid (A.R., SigmaAldrich, USA) were applied, and the however, the increases in processing costs and the difculty of pH 146
readjustment for sludge composting had to be considered. Thus, 147
the optimal concentration of citric acid to extract heavy metals was 148
Table 1
Heavy metal content of sewage sludge compared to Chinese legal standards for 0.2 M. At the concentration, Zn had the highest removal efciency, 149
heavy metals in sludge for agricultural use. while Cu was the most difcult metal to remove from the sludge. 150
Similar high removal efciency for Zn and low removal efciency 151
Heavy Content The sludge Environment
metal (mg kg1) agriculture quality standard for Cu was reported by other authors who worked with the same 152
utilization for soils (the organic acids [11,24]. 153
standarda third level)b

A B Effect of extraction time 154

Cr 1688 500 1000 400
Cu 1416 500 1500 400 In order to assess the effect of extraction time on the heavy 155
Ni 287 100 200 200 metal removal efciency by citric acid with or without the 156
Zn 4946 1500 3000 500 assistance of ultrasound, batch experiments were conducted at 157
a
National Standard CJ/T309-2009, China. citric acid concentration of 0.2 M. The results presented in Fig. 2 158
b
National Standard GB 15618-1995, China. showed that heavy metal removal efciencies increased with the 159

Please cite this article in press as: X. Wang, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.01.016
 G Model
JIEC 2396 15

X. Wang et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx 3

Fig. 2. Heavy metal extraction efciency of citric acid at different extraction times:
Fig. 1. Effect of citric acid concentration on heavy metal extraction assisted by
solid graphics, heavy metal extraction using citric acid; hollow graphics, heavy
ultrasound. Ultrasonic time = 20 min; solid/liquid ratio = 1:10; temperature = 25 8C;
metal extraction using ultrasound-assisted citric acid. Acid concentration = 0.2 M;
pH = 2.7.
solid/liquid ratio = 1:10; temperature = 25 8C; pH = 2.7.

160 increase of extraction time whether or not the sludge was during the extraction and that these were important factors 193
161 extracted with the application of ultrasound. As for the extraction affecting heavy metal extraction. Many studies demonstrated that 194
162 of heavy metals with citric acid alone, the extraction percentages of between the two processes, acidication was predominant and 195
163 all the tested heavy metals increased slowly and eventually acoustic cavitation was an important and necessary assisting 196
164 attained equilibrium within 24 h. When ultrasound was used to method in improving the ability to dissolve heavy metals [2628]. 197
165 assist citric acid in extracting heavy metals, the extraction rates
166 were improved signicantly and the extraction could be accom- Effect of pH 198
167 plished within 20 min. However, it was clear that ultrasound-
168 assisted treatment did not enhance the heavy metal extraction Fig. 3 showed the extraction of Cu, Cr, Zn and Ni with 0.2 M 199
169 efciency, since that ultrasound alone was not an effective method citric acid assisted by ultrasound for 20 min at different pH values. 200
170 for extracting heavy metals from sludge [13]. The removal Generally, desorption of the heavy metals will decrease when pH 201
171 efciencies of Zn, Ni, Cr and Cu reached 53.5%, 40.2%, 35.4% and value of the extractor goes up, as many metal compound has lower 202
172 13.1%, respectively, at citric acid concentration of 0.2 M assisted by solubility at higher pH [25]. From Fig. 2, it could be seen that the 203
173 ultrasound for 20 min. The low removal efciency of Cu was four metals extracted from the municipal and industrial municipal 204
174 attributable to its insoluble forms existing in sludge and the sludge decreased when pH of citric acid solution increased from 2 205
175 stronger binding of Cu to sludge biomass [11]. to 7. However, the extraction efciency of Cu varied slightly when 206
176 The kinetic dependence of extraction of the four metals was pH of citric acid solution exchanged from 3 to 7, even though Cu 207
177 tted with Elovich formula (Table 2). Elovich formula is an solubility increased with decreasing pH. It could be argued that the 208
178 empirical equation, useful in describing reactions composed of a extraction treatment was merely removal of pollutants based on 209
179 series of complex processes, especially reactions occurring on the their solubility as a function of pH. A more important parameter 210
180 solid/liquor interface of soil/water and sediment/water. From than pH was the stability of metalorganic complexes in aqueous 211
181 Table 2, it could be seen that desorption of the heavy metals from solution [29]. 212
182 the sludge could t the Elovich formula well. As for the ultrasound-
183 assisted citric acid extraction, the constant B of the four metals was Effect of Fe3+, Al3+ and Ca2+ on the extraction 213
184 much higher than those of citric acid extraction alone, which
185 implied higher desorption rate appeared due to the assistance of As we know, in wastewater treatment plants (WWTPs), Fe3+, 214
186 ultrasound [25]. Because heavy metals were predominantly Al3+ and Ca2+ are widely used as coagulating agents for their 215
187 adsorbed or precipitated inside the biosolid matrix, in the rst remarkable effects in promoting activated sludge occulation and 216
188 step of the extraction process they had to be either desorbed or settle ability [30]. Therefore, it is necessary to study the effect of 217
189 dissolved. Thereafter, the solubilized metals had to diffuse from them on the extraction of heavy metals from the sludge by citric 218
190 the biosolid matrix into the solution, a process that took time. As acid (Fig. 4). From Fig. 4, it could be seen that the extraction 219
191 for the method of citric acid extraction assisted by ultrasound, it efciency of Zn dropped obviously with the increase of Fe3+, Al3+ 220
192 was clear that both acidication and acoustic cavitation occurred and Ca2+ concentrations, and on the contrary, the extraction 221

Table 2
Kinetic dependence of desorption of the metals described by Elovich formula. Acid concentration = 0.2 M; solid/liquid ratio = 1:10; pH = 2.7; temperature = 25 8C.

S = A + Blnt Zn Ni Cr Cu

B R2 B R2 B R2 B R2

Citric acid 223.5  25 0.978* 85.4  17 0.960* 36.1  2.7 0.955* 12.1  2.2 0.913*
Citric acid + ultrasound 347.4  31 0.944* 191.2  23 0.951* 130.5  15 0.966* 47.4  22 0.942*

S: amount of the metals desorbed at time t (mg kg1); t: time (min).

*
p < 0.001.

Please cite this article in press as: X. Wang, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.01.016
 G Model
JIEC 2396 15

4 X. Wang et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

Fig. 3. Heavy metal extraction efciency of citric acid at different pH values.

Acid concentration = 0.2 M; ultrasonic time = 20 min; solid/liquid ratio = 1:10;
temperature = 25 8C.

222 efciency of Cu increased signicantly except for Ca2+. This result

223 could help us to understand the citric acid extraction mechanism
224 as following: Citric acid could act as polidentate organic ligands
225 (chelators) due to its carboxylic functional groups. Heavy metal
226 extraction by organic chelators was based on the afnity of the
227 organic ligand for heavy metals. The extent of complexation
228 between polidentate organic ligands and heavy metals depended
229 on the competition between the metal-binding functional groups
230 from the biosolid structure and the organic chelator for the metal.
231 Metals that formed more stable complexes with the organic
232 chelator than with the biosolid functional groups were likely to be
233 easily extracted from biosolid according to Eq. (1).

BiosoidMen RCOOHm Biosolid RMen COOHm (1)

236
235
234 From Eq. (1), it could be deduced that the high removal
237 efciency of Zn might be attributed to its strong complexing
238 tendency with citric acid, while Cu seemed to form more stable
239 complexes with the sludge functional groups than with citric acid.
240 The presence of Fe3+, Al3+ and Ca2+ could form tridentate Fe(III)
241 citrate, Al(III)citrate and bidentate Cacitrate complexes, which
242 could compete with Zn, subsequently, when citrate level was
243 insufcient to chelate Zn, its extraction efciency decrease seemed
244 to be inevitable [31]. On the other hand, Fe3+ and Al3+ also
245 possessed a higher binding afnity for activated sludge than that of
246 Ca2+ [32], so that Fe3+ and Al3+ could displace Cu from recalcitrant
247 Cusludge complex, thus improving the extraction efciency of Cu
248 from the sludge.

249 Speciation of heavy metal after the extraction

250 The factors which affected the extraction efciency of metals Fig. 4. Effect of Fe3+, Al3+, and Ca2+ on heavy metal extraction of ultrasound-assisted
251 from sludge included not only the system pH and citric acid citric acid. Acid concentration = 0.2 M; ultrasonic time = 20 min; temperature
= 25 8C; solid/liquid ratio = 1:10; pH = 2.7.
252 concentrations, but also the content and fractional distribution of
253 the heavy metals in the solid sludge. The distribution of heavy
254 metal fractions in tested sewage sludge before and after the
255 extraction with ultrasound-assisted citric acid was shown in Fig. 5. and metal oxide could also react with chelating agents resulting in 261
256 From Fig. 5, it could be found that extraction with citric acid the release of the associated metals [33,34]. As we know, Cu is a 262
257 resulted in the signicant reduction of acid-soluble, reducible and chalcoplic element, it is mainly bound to suldes in nature [15]. 263
258 oxidizable fractions of Zn, Ni and Cr. Previous researches also Therefore, before extraction, Cu existed mainly in oxidizable and 264
259 showed that acid-soluble fraction and reducible fraction were the reducible fractions in the tested sludge. After the extraction with 265
260 main fractions that affected by chelating agents during extraction, citric acid, the fractional distribution of Cu changed slightly, and it 266

Please cite this article in press as: X. Wang, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.01.016
 G Model
JIEC 2396 15

X. Wang et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx 5

of citric acid extraction solution. The optimal citric acid 296

concentration was 0.2 M and sonication time was 20 min for 297
heavy metals extraction, and at which the removal efciencies of 298
Zn, Ni, Cr and Cu reached 53.5%, 40.2%, 35.4% and 13.1%, 299
respectively. During heavy metal extraction, desorption of the 300
heavy metals from the sludge could t the Elovich formula well, it 301
was clear that both acidication and acoustic cavitation occurred 302
during the extraction, and higher desorption rates appeared due to 303
the assistance of ultrasound. The extracted Zn, Ni and Cr mainly 304
came from acid-soluble, reducible and oxidizable fractions, and Cu 305
mainly came from oxidizable and reducible fractions. The presence 306
of Fe3+, Al3+ and Ca2+ improved the extraction efciency of Cu from 307
the sludge signicantly. The low percentage of trace metals in the 308
exchangeable fraction suggested weak bioavailability of metal in 309
the treated sludge. The extracted sludge had higher contents of 310
organic carbon, total N and P, and it could be used for soil 311
Fig. 5. Distribution of heavy metal fractions in sludge before (a) and after (b)
extraction with ultrasound-assisted citric acid.
amendment. 312

Acknowledgements 313

Table 3
This work was supported by the National Hi-Tech Research and Q3314
Physicochemical properties of sludge before and after the extraction by citric acid.
Acid concentration = 0.2 M; ultrasonic time = 20 min; solid/liquid ratio = 1:10;
Development Program (863) of China (No. 2012AA063608-03), 315
temperature = 25 8C; pH = 2.7. International S&T Cooperation Program of China (2014DFA91650), 316
and the Fundamental Research Funds for the Central Universities 317
Organic TN (g/kg) TP (g/kg) TK (g/kg)
carbon (g/kg)
(No. 0400219270). 318

Before extraction 256.2 14.97 34.94 3.17 References 319

After extraction 376.7 14.84 18.28 2.96
[1] Y.X. Zhao, J. Yin, H.L. Yu, N. Han, F.J. Tian, Water Sci. Technol. 56 (2007) 167. 320
[2] S.L. Rochebrochard, E. Naffrechoux, P. Drogui, G. Mercier, J.F. Blais, Ultrason. 321
Sonochem. 20 (2013) 109. 322
267 was worth noting that acid-soluble Cu increased inversely. The [3] M. Chen, X.M. Li, Q. Yang, G.M. Zeng, Y. Zhang, D.X. Liao, J.J. Liu, J.M. Hu, L. Guo, J. 323
268 results of the low extraction efciency and the change of Hazard. Mater. 160 (2008) 324. 324
[4] O. Hanay, H. Hasara, N.N. Kocer, J. Hazard. Mater. 169 (2009) 703. 325
269 distribution of Cu before and after the extraction with citric acid [5] L.H. Zhang, Z.L. Zhu, R.H. Zhang, C.S. Zheng, H. Zhang, Y.L. Qiu, J.F. Zhao, J. Environ. 326
270 were in consistent. Sci. 20 (2008) 970. 327
[6] Y.X. Chen, Y.M. Hua, S.H. Zhang, G.M. Tian, J. Hazard. Mater. 123 (2005) 196. 328
[7] K. Park, J. Lee, J. Sung, Chemosphere 91 (2013) 616. 329
271 Fertilizing properties preservation [8] J. Gao, Q.S. Luo, J. Zhu, C.B. Zhang, B.Z. Li, Chemosphere 93 (2013) 2869. 330
[9] Y.C. Kuan, I.H. Lee, J.M. Chern, J. Hazard. Mater. 177 (2010) 881. 331
272 The effect of extraction by citric acid assisted with ultrasound [10] L.H. Zhang, Z.L. Zhu, Pedosphere 22 (2012) 131. 332
[11] M. Gheju, R. Pode, F. Manea, Hydrometallurgy 108 (2011) 115. 333
273 process on fertilizing properties of the sludge was presented in [12] T.G. Kazi, M.K. Jamali, A. Siddiqui, G.H. Kazi, M.B. Arain, H.I. Afridi, Chemosphere 334
274 Table 3. The data contained in Table 3 showed that after the 63 (2006) 411. 335
275 chemical extraction, organic matter in the sludge increased from [13] J.C. Deng, X. Feng, X.H. Qiu, Chem. Eng. J. 152 (2009) 177. 336
276 256.2 to 376.7 g/kg due to the residual of citric acid, which could [14] M. Mara, A. Stanislaus, Ind. Eng. Chem. Res. 50 (2011) 9495. 337
[15] M. Tuzen, Microchem. J. 74 (2003) 105. 338
277 act as a nutrient source for fertilizers. There was not signicantly [16] H. Altundag, M. Imamoglu, S. Doganci, E. Baysal, S. Albayrak, M. Tuzen, J. AOAC Int. 339
278 different in total N and total K of the sludge before and after the 96 (2013) 864. 340
279 extraction. However, as for the total P, it decreased from 34.94 g/kg [17] C.M. Davidson, A.L. Duncan, D. Littlejohn, A.M. Ure, L.M. Garden, Anal. Chim. Acta 341
363 (1998) 45. 342
280 to 18.28 g/kg after the extraction. In China, the mean contents of [18] M.K. Jamali, T.G. Kazi, H.I. Afridi, M.B. Arain, N. Jalbani, A.R. Memon, J. Environ. Sci. 343
281 soil were 1040 g/kg for organic matter, 1.02.0 g/kg for total N, Health A: Toxic Hazard. Subst. Environ. Eng. 42 (2007) 649. 344
282 0.440.85 g/kg for total P and about 16 g/kg for total K, respectively [19] H. Altundag, M.S. Dundar, S. Doganc, M. Celik, M. Tuzen, J. AOAC Int. 96 (2013) 345
166. 346
283 [35]. Comparing the contents of sludge with those of soils, the [20] K.F. Mossop, C.M. Davidson, Anal. Chim. Acta 478 (2003) 111. 347
284 extracted sludge had higher contents of organic carbon, total N and [21] S. Saracoglu, M. Soylak, L. Elci, J. AOAC Int. 92 (2009) 1196. 348
285 total P, but lower content of the total K. Nonetheless, this sludge [22] K.F. Mossop, C.M. Davidson, Anal. Chim. Acta 478 (2003) 111118. 349
[23] L. Clesceri, A. Greenberg, A. Eaton (Eds.), Standard Methods for the Examination of 350
286 had a good manure value and could be used for soil amendment. Water and Wastewater, twentieth ed., APHA, Washington, DC, 2001. 351
[24] A.H.M. Veeken, H.V.M. Hamelers, Water Sci. Technol. 40 (1999) 129. 352
[25] Z.H. Ding, Q.Y. Wang, X. Hu, Procedia Environ. Sci. 18 (2013) 679. 353
287 Conclusion [26] X. Feng, H.Y. Lei, J.C. Deng, Q. Yu, H.L. Li, Chem. Eng. Process. 48 (2009) 187. 354
[27] C.P. Chu, B.V. Chang, G.S. Liao, D.S. Jean, D.J. Lee, Water Res. 35 (2001) 1038. 355
[28] B. Lesa, E. Aneggi, G. Rossi, C. Comuzzi, D. Goi, J. Hazard. Mater. 171 (2009) 647. 356
288 Citric acid chemical extraction technology in combination with [29] T. Van Gerven, H. Cooreman, K. Imbrechts, K. Hindrix, C. Vandecasteele, J. Hazard. 357
289 ultrasonication was used to remove heavy metals from industrial Mater. 140 (2007) 376. 358
290 and municipal mixed sludge. The inuences of extraction time, [30] S.B. Subramanian, S. Yan, R.D. Tyagi, R.Y. Surampalli, Water Res. 44 (2010) 2253. 359
[31] J.W. Qian, Y. Tao, W.J. Zhang, X.H. He, P. Gao, D.P. Li, J. Hazard. Mater. 263 (2013) 367. 360
291 citric acid concentration, pH, and the presence of Fe3+, Al3+ and Ca2+ [32] H.S. Li, Y. Wen, A.S. Cao, J.S. Huang, Q. Zhou, P. Somasundaran, Bioresour. Technol. 361
292 on the extraction efciency for Zn, Cr, Ni and Cu were discussed. 114 (2012) 188. 362
293 The results indicated that the extraction efciencies of heavy [33] S. Tandy, R. Schulin, B. Nowack, Environ. Sci. Technol. 39 (2005) 6819. 363
[34] B. Nowack, Environ. Sci. Technol. 36 (2002) 4009. 364
294 metals increased with the increase of extraction time and citric [35] S. Bao, R. Wang, C. Yang, Soil and Agricultural Chemistry Analysis, third ed., 365
295 acid concentration, and with the decrease of the original pH value Chinese Agricultural Press, Beijing, 2000. 366

Please cite this article in press as: X. Wang, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.01.016