Journal Pre-proof

Removal of heavy metals from industrial sludge with new plant–based washing
agents

Xiaoxun Xu, Yan Yang, Guiyin Wang, Shirong Zhang, Zhang Cheng, Ting Li,
Zhanbiao Yang, Junren Xian, Yuanxiang Yang, Wei Zhou

PII: S0045-6535(20)30006-0
DOI: https://doi.org/10.1016/j.chemosphere.2020.125816
Reference: CHEM 125816

To appear in: ECSN

Received Date: 14 September 2019

Revised Date: 7 December 2019
Accepted Date: 1 January 2020

Please cite this article as: Xu, X., Yang, Y., Wang, G., Zhang, S., Cheng, Z., Li, T., Yang, Z., Xian, J.,
Yang, Y., Zhou, W., Removal of heavy metals from industrial sludge with new plant–based washing
agents, Chemosphere (2020), doi: https://doi.org/10.1016/j.chemosphere.2020.125816.

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 1 Removal of heavy metals from industrial sludge with new

2 plant–based washing agents

3 Xiaoxun Xu a,b,1, Yan Yang a,1, Guiyin Wang a,b, Shirong Zhang a,b,*, Zhang

4 Cheng a, Ting Li c, Zhanbiao Yang a, Junren Xian a, Yuanxiang Yang a and Wei

5 Zhou c

7 a. College of Environmental Sciences, Sichuan Agricultural University, Chengdu 611130, China;

8 b. Key Laboratory of Soil Environment Protection of Sichuan Province, Chengdu 611130, China

9 c. College of Resources, Sichuan Agricultural University, Chengdu 611130, China

10 1. These authors contributed equally to this work and should be considered co–first authors

11

12 * Correspondence: srzhang01@aliyun.com; Tel.: +86–28–8629–0995

1
13 Abstract: Washing is one of the techniques for permanent removal of heavy metals

14 from industrial sludge, for which washing agents are a key influence factor. However,

15 high–efficiency, eco–friendly, and inexpensive agents are still lacking. In this study, the

16 solutions derived from the three plant materials including Fatsia japonica, Hovenia

17 acerbaand Pterocarya stenoptera were employed to remove Cd, Cu, Pb, and Ni from

18 industrial sludge. The effects of washing solution concentration, pH, washing time and

19 temperature on metal removal were investigated. The metal removal efficiencies were

20 found to increase with increasing solution concentrations or washing temperatures,

21 decline with increasing pH, and presented various trends with increasing washing time.

22 Among the three agents that derived from H. acerba showed relatively high removal

23 for Cu (75.81%), Pb (63.42%), Ni (27.52%), and Cd (56.99%). After washing,

24 environmental risks of residual metals were markedly diminished in sludge,

25 attributable to decrease in their exchangeable forms. Furthermore, the applications of

26 the plant washing agents increased sludge organic carbon, alkali–hydrolysable

27 nitrogen, available phosphorus, and available potassium. Fourier transform infrared

28 spectroscopy analysis suggested that the hydroxyl, carboxyl, ether, and amide may be

29 the main functional groups in the three plant materials binding the heavy metals.

30 Overall, the agent derived from H. acerba appears to be a feasible washing material

31 for heavy metals removal from sludge.

32 Keywords: Plant washing agent; Industrial sludge; Heavy metals; Hovenia acerba

2
33 1. Introduction

34 A large amount of sludge is inevitably produced in various industries, such as

35 electroplating, tanning, and mechanical manufacturing processing (Kulkarni et al.,

36 2019; Yadav and Garg, 2019). One of the most potential of handling sludge is the

37 application to land for improving soil fertility and structure (Suanon et al., 2016; Xu et

38 al., 2017; Tang et al., 2018; Li et al., 2019a). However, because potentially toxic

39 elements in sludge such as Cd, Pb, Ni, and Cu pose serious threats to plant, animal, and

40 human health (Lee et al., 2017; Li et al., 2019b), it is crucial to develop effective

41 strategies to reduce and remove these metals from sludge (Dai et al., 2019).

42 The techniques of bioleaching, supercritical fluid extraction, electrokinetic

43 separation, and chemical washing have been developed for the removal of heavy

44 metals in sludge ( Park et al., 2013; Xu et al., 2017; Marchenko et al., 2018; Tang et al.,

45 2018). Among these methods, chemical washing has been attracting more attention

46 owing to its unsophisticated operation, high efficiency, and relatively inexpensive cost

47 (Wu et al., 2015). Heavy metals removal with chemical washing is closely associated

48 with washing agents (WSA), pH, washing time, and contact temperature (Piccolo et

49 al., 2019). Recently, acids, chelates, and surfactants have been employed to extract

50 heavy metals from sludge (Gusiatin and Klimiuk, 2012; Suanon et al., 2016). However,

51 they negatively affect sludge fertility and microbial properties (Ren et al., 2015). For

52 example, washing with N, N–bis (carboxymethyl) glutamic acid and citric acid

53 decreased the total nitrogen, total phosphorus, and total potassium of sludge (Ren et

3
54 al., 2015; Wang et al., 2015). Previous study have reported that

55 ethylenediaminetetraacetic acid may pose a high risk to microorganisms and plants due

56 to poor biodegradability and high persistence in soil, and result in secondary pollution

57 via leaching to groundwater (Wu et al., 2015; Suanon et al., 2016). Therefore,

58 biodegradability and minimal damage to sludge fertility are consequential

59 considerations when searching for highly efficient WSA.

60 WSA derived from plant materials may be a promising alternative to these

61 disadvantageous materials as they contain various functional groups that could bind

62 with metal cations (Sfaksi et al., 2014; Ali et al., 2016). Some studies had reported that

63 water–soluble extracts of certain plant species, such as pineapple peel, soybean straw,

64 Clematis brevicaudata and Coriaria nepalensis, can diminish soil nutrient loss and

65 maintain soil organic matter (Cao et al., 2017; Feng et al., 2018). Furthermore, plant

66 materials are biodegradable, widely sourced, and of low–cost. Therefore, it is

67 essential to investigate more plant materials.

68 Fatsia japonica (FJ) and Hovenia acerba (HA) contain various active constituents,

69 such as triterpenoid saponins, flavonoids, and fatty acids (Aoki et al., 1976; Zhang et

70 al., 2012; Ye et al., 2014), and the major ingredients of Pterocarya stenoptera (PS) are

71 tannin, naphthoquinone, terpene, and steroid (Zhang et al., 2014; Xu et al., 2015).

72 They have potential to bind with metal cations. Nevertheless, previous research on

73 plant WSA mainly focused on soil heavy metals treatment (Cao et al., 2017; Feng et

74 al., 2018). It would thus be interesting to test the capacity of removing heavy metals

4
75 from sludge using plant WSAs. Therefore, screening of plant WSAs for sludge

76 washing is significant.

77 The aims of our study are to explore the efficiencies of FJ, HA, and PS for heavy

78 metals removal (Cd, Cu, Pb, and Ni), reveal changes in characteristic functional

79 groups, identify the feasibility of sludge for land application, and provide evidence

80 and reference to achieve land application of sludge.

81 2. Materials and methods

82 2.1. Samples preparation and characterization

83 Metal–contaminated sludge samples were derived from an industrial sewage

84 treatment plant (104.35°E, 31.07°N) in Sichuan, China. The sludge was air–dried,

85 ground, and then sieved (200 mesh) prior to chemical analysis. Heavy metals in the

86 sludge were digested with a 1:1:1 HNO3–HF–HClO4 mixture (Wang et al., 2016) and

87 measured by a flame atomic absorption spectrophotometer (FAAS, Thermo Solaar M6,

88 Thermo Fisher Scientific Ltd., USA). The concentrations of Cd, Pb, Ni, and Cu in the

89 sludge were 6.22, 53.9, 139.95, and 104.30 mg kg–1.

90 HA, FJ, and PS were obtained from the fields in Chengdu, Sichuan. They were

91 air–dried, ground, passed through the 50 mesh, and then added into plastic bottles with

92 1000 mL distilled water. The bottles were continuously shaken on a shaker (150 rpm,

93 24 h) at 25 °C. Subsequently, the suspensions were filtered to collect their extracts. By

94 adding different weights of plant materials, a series of WSA from HA,FJ, and PS with

95 different concentrations was prepared for the washing experiment (Feng et al., 2018).

5
 96 Their concentrations were expressed as the ratio of the initial mass of plant powder and

97 the volume of the distilled water. The WSAs were then stored at 4 °C, and none of the

98 heavy metals (Cd, Cu, Pb, and Ni) were detected in the WSAs by FAAS.

99 2.2. Sludge washing experiments

100 Acid–rinsed plastic bottles (100.00 mL) containing 2.00 g sludge were prepared

101 for washing experiments, followed by the addition of WSA (40.00 mL). Control

102 experiments were conducted by distilled water. The suspensions were filtrated after

103 shaking. The concentrations of Cd, Cu, Pb, and Ni in the filtrate were measured by

104 FAAS. The effects of WSA concentration, washing time, pH level and temperature

105 were investigated as follows:

106 In order to investigate the effect of WSA concentration, the experiment was

107 conducted with the WSA concentration ranging from 20.00 g L–1 to 100.00 g L–1 for

108 180 min at an initial pH of 4.0.

109 The effect of washing time on the heavy metals removal of 50.00 g L–1 WSA was

110 investigated at an initial pH of 4.0. The experiment was conducted at different time

111 intervals (5, 30, 60, 120, 180, and 240 min).

112 Five different pH levels (3.0–7.0) were applied to 50.00 g L–1 WSA for 180 min

113 to determine the effects of initial pH on heavy metals removal. The initial pH of the

114 mixture was adjusted with dilute HNO3 or NaOH. The mixture was agitated at room

115 temperature (25 ± 2 °C).

116 The effect of temperature on heavy metals removal was observed at 15, 25, 35,

6
 –1
117 45, and 55 °C for 50.00 g L with an initial pH of 4.0.

118 2.3. FTIR analysis for plant materials

119 In order to identify the participant functional groups of water–soluble plant

120 extracts obtained from HA, FJ, and PS during the sludge washing process, the original

121 plant powder and residual plant powder extracted by distilled water were analysed

122 using a Fourier transform infrared spectroscopy (FTIR) spectrophotometer (Spectrum

123 Two; PerkinElmer Inc., Waltham, Massachusetts, USA). The materials were ground

124 with KBr sufficiently in an agate mortar at a ratio of 1:100 and pressed into a disk under

125 high pressure (Feng et al., 2018). The spectra were recorded from 450 to 4000 cm–1 at a

126 resolution of 4 cm–1. The samples of residual plant powder were collected after

127 washing (50.00 g L−1 WSA, 180 min of reaction at 1:20 w/v, 25 °C and pH 4.00).

128 2.4. Sludge chemical analysis

129 In this study, the chemical properties of the original and washed sludge (50.00 g

130 L−1 WSA, 180 min of reaction at 1:20 w/v, 25 °C and pH 4.00) were analysed. Sludge

131 organic carbon (OC) concentration was measured via potassium dichromate oxidation

132 (Nelson et al., 1996), and total nitrogen (TN) was determined through the Kjeldahl

133 method (Bremner et al., 1996). Total phosphorus (TP) and total potassium (TK)

134 concentrations were detected using the molybdenum antimony colorimetry method

135 and by flame photometry after calcination and extraction by NaOH, respectively

136 (Sparks et al., 1996). Alkali–hydrolysable nitrogen (AN) available potassium (AK),

137 and available phosphorus (AP) were determined through NaOH hydrolysis (Cornfield.,

7
138 1960), ammonium acetate extraction and subsequent flame photometer analysis (Tan et

139 al., 1995), and sodium bicarbonate extraction and spectrophotometer analysis (Li et al.,

140 2019b), respectively.

141 2.5. Fraction distribution of heavy metals in sludge

142 The fractions of Cd, Cu, Pb, and Ni were performed using sequential extraction

143 based on Tessier et al. (1979). The metal fractions include exchangeable, carbonate

144 bound, iron and manganese oxide bound (Fe–Mn oxide bound), organic matters bound,

145 and residual fractions.

146 2.6. Quality control and statistical analysis

147 All chemical reagents used were analytically pure. A sludge sample (RTC–

148 CRM031) with certified concentrations of Cd, Cu, Pb, and Ni was used as a reference.

149 Each treatment was performed in triplicate and reagent blanks were also used to ensure

150 the accuracy and precision of the analysis. The total metal recovery rates ranged from

151 86.1% to 109.3% (Cd, Cu, Pb, and Ni). All data statistical analyses were performed in

152 SPSS version 20.0 (SPSS Inc., USA). One–way analysis of variance (ANOVA) was

153 tested to compare whether the metal removal under different experimental conditions

154 was significantly different. Statistical significance (p < 0.05) was determined by

155 Fisher’s least significant difference test.

8
156 3. Results and discussion

157 3.1. Removal of heavy metals with WSA

158 3.1.1. Effect of WSA concentration

159 The concentrations of WSA significantly affect heavy metals removal (Zhang et

160 al., 2019). As shown in Fig. 1, heavy metals removal considerably increased with

161 concentrations up to 65.00 or 80.00 g L–1 (p < 0.05). The concentration of plant WSA

162 determines the amount of functional groups in the reaction, and a higher concentration

163 could supply more complexing sites to heavy metals (Zhang et al., 2019). However,

164 removal efficiencies generally reached a plateau at concentrations > 80.00 g L–1,

165 which is attributed to the low concentration of exchangeable and carbonate bound

166 fractions of Cd, Cu, Pb, and Ni in sludge (Ren et al., 2015).

167 Among the three materials, the HA derived WSA exhibited the highest

168 efficiencies of heavy metals removal, reaching 75.81% for Cu, 25.44% for Ni, and

169 63.42% for Pb at the concentration of 100.00 g L–1. Nevertheless, the FJ derived WSA

170 (100 g L–1) provided the highest removal efficiency of Cd (71.36%). In contrast, the

171 metal removal efficiencies in the control experiment were less than 5%. This

172 phenomenon may related to available functional groups in plant WSA such as carboxyl,

173 amino, and amide groups, which can exchange hydrogen ions for metal cations or

174 increase the electronic donating ability, thus promoting heavy metals removal from

175 sludge (Sahmoune, 2018; Chen et al., 2019).

9
176 3.1.2. Effect of pH

177 The pH of WSA could affect the adsorption–desorption behaviour of heavy metals

178 and the ionisation degree of functional groups in the extracts, and result in the change

179 of the removal efficiency of heavy metals in sludge (Pérez–Esteban et al., 2013; Feng et

180 al., 2018). In this study, Cd, Cu, Pb, and Ni removal efficiencies in sludge were highly

181 pH–dependent (Fig. 2). Regardless of the types of plant materials, the maximum

182 metal removal of Cd (72.04%), Pb (47.80%), Cu (56.41%) and Ni (26.46%) were

183 observed at pH 3.00, after which it declined. At a low pH, the WSAs could reduce the

184 negative surface charge of the sludge particles and organic matter, and facilitate the

185 dissolution of Fe–Mn oxides and the formation of soluble metal–organic chelates,

186 resulting in the removal of associated metals (Pérez–Esteban et al., 2013; Feng et al.,

187 2018).

188 3.1.3. Effect of washing time

189 In addition to the pH of the washing solution, washing time also influences the

190 adsorption–desorption behaviour of heavy metals in sludge (Zhang et al., 2019). As

191 shown in Fig. 3, the removal efficiencies of heavy metals generally increased with

192 washing time up to 60 min, which can be attributed to the extraction of more heavy

193 metals from sludge. Moreover, electrostatic repulsion between the metal cations on the

194 adsorbent prevented the adsorption of subsequent metal cations (Zou et al., 2009; Chen

195 et al., 2019). The kinetic models (pseudo–first order, pseudo–second order and

196 Elovich) were fitted at a range of 5–120 min to understand possible adsorption

10
197 mechanism (Bhatnagar et al., 2010; Al–Qahtani, 2016). As shown in Table S1, the

198 pseudo–second order has a higher correlation coefficient (R2), which means that

199 chemisorptive interactions are dominant in the experiments (Jang and Kan, 2019).

200 The high R2 value of the Elovich model indicated that chemisorption was the

201 controlling step, similar to other studies using this model for the adsorption kinetics of

202 metal ions (Ali et al., 2016; Lasheen et al., 2012). However, the removal of some

203 heavy metals decrease with washing time at 120 min, which may be attributed to the

204 stability of soluble metal–organic polymers (Ho et al., 2012). In addition, the metal

205 removal may be affected by re–sorption and re–precipitation and decreased with

206 increasing washing time.

207 3.1.4. Effect of contact temperature

208 As shown in Fig. 4, the metal removal efficiencies increased significantly with the

209 increasing washing temperature, and reached the maximum level at 55 °C (58.19% for

210 Cu, 74.19% for Cd, 45.97% for Pb, and 25.72% for Ni). The enhancement in removal

211 efficiencies with temperature may be attributed to the decrease in the thickness of the

212 boundary layer surrounding the fine particles of sludge with temperature, decreasing

213 the mass transfer resistance of sludge particles in the boundary layer (Kołodyńska,

214 2011). In addition, increasing washing temperature, which could also enhance the

215 dissolution and diffusion rate of heavy metals, is effective for improving removal

216 efficiencies (Shaker and Hassan, 2014). Cd removal did not increase significantly with

217 washing temperature over 45 °C (p > 0.05). As washing temperature was increased, the

11
218 restricting factor of Cd removal changed from washing temperature to washing

219 concentration, and pH (Prakash et al., 2013). However, more energy need to be used to

220 get a high washing temperature, washing sludge at room temperature is more

221 substantial.

222 3.2. FTIR analysis of plant materials

223 FTIR analysis is essential for identifying some characteristic functional groups

224 present in these sorbents (Abdolali et al., 2016). Several peaks in the spectra of the

225 plant powder were observed, with different peaks corresponding to different

226 functional groups. As shown in Fig. 5, the strong broad band observed at 3425 cm–1

227 corresponds to stretching of the O–H bond of the hydroxyl groups from the alcohols,

228 phenols and carboxylic acids (Jiménez–cedillo et al., 2013). The bands at 2922, 2847,

229 1057 and 596 cm–1 are assigned to stretches of C–H, C–H, C–O–C and S–O (Lammers

230 et al., 2009; Farooq et al., 2010; Siengchum et al., 2013). The absorption peaks at 1637,

231 1443 and 1249 cm–1 could all be attributed to C=O stretching vibration of the carboxyl

232 group (Stewart, 1996; Lammers et al., 2009; Barka et al., 2013; Calero et al., 2013).

233 Comparing the peaks of different plant powders, some peaks of plant powder extracted

234 by distilled water changed in intensity, shifted in position, and increased or decreased

235 in number, indicating that some phytochemical components were extracted to WSA.

236 Functional groups of the phytochemical components could combine and exchange

237 heavy metals ions in sludge colloids (Alikhani and Manceron, 2015). Consequently, the

238 hydroxyl, carboxyl, ether, and amide groups may be the main functional groups in the

12
239 three plant materials, and they have been identified as potential sites responsible for

240 binding heavy metals ions to the biomass (Feng et al., 2018).

241 3.3. Changes of heavy metals fractions in sludge

242 The fractional distribution of the heavy metals has significant effects on heavy

243 metals removal from sludge (Wang et al., 2015). It can be noticed in Fig. 6 that metal

244 fraction distribution in the sludge changed depending on the washing process. Before

245 sludge washing, the Fe–Mn oxide bound fraction was the main fraction of Cd, Cu, Pb,

246 and Ni (62.32, 48.34, 38.13 and 46.93%). However, the ratio of heavy metals in

247 exchangeable and carbonate bound fractions is related to solubility and mobility of

248 heavy metals (Ren et al., 2015; Wang et al., 2018b). The ratios of Cd, Cu, and Pb in

249 exchangeable and carbonate bound fractions were higher than that of Ni, which may

250 result in relatively higher removal efficiencies of Cd, Cu and Pb than Ni ( Guo et al.,

251 2018).

252 After washing, the exchangeable, carbonate bound, and Fe–Mn oxides bounds

253 fractions of heavy metals significantly declined (Fig. 6). Nevertheless, the content of

254 Cd in the exchangeable fraction remained high. We speculated that the newly formed

255 metal–ligand complex might have been re–adsorbed by the sludge surface, where the

256 ligand formed a bridge between the sludge surface and the metal cations (Chen et al.,

257 2016). The fraction distribution of heavy metals determines ecological risk. After

258 washing with the three WSAs, the potential ecological risk of sludge from Cd, Cu, Pb,

259 and Ni was appreciably reduced (Suanon et al., 2016; Asgari Lajayer et al., 2019).

13
260 3.4. Changes of chemical properties in sludge

261 Decreasing nutrient loss is essential for achieving the reuse of sludge. In this

262 regard, the washing technology may change the chemical properties (Ren et al., 2015;

263 Wang et al., 2015). Compared with the untreated sludge, significant increases of OC,

264 AN, AP, and AK in sludge were observed after washing (Table 1, p < 0.05). The

265 increase of organic matter was also observed in previous studies using citric acid to

266 treat sludge (Ren et al., 2015; Wang et al., 2015). This enhancement may be related to

267 these washing solution residues with rich organic carbon and nutrients (Feng et al,

268 2018).

269 Comparatively, more efficient improvement was observed for AP and AK after

270 washing with the three WSAs (Table 1). This improvement might be related to the

271 transformation and dissolving of unavailable P and K to the AP andAK under acidic

272 washing conditions (Liu and Lin, 2013; Ren et al., 2015). N, N–bis (carboxymethyl)

273 glutamic acid, and citric acid have been reported to decrease TN, TP, and TK during

274 the washing process (Ren et al., 2015; Wang et al., 2015). These results revealed that

275 three WSAs can effectively moderate the effects of washing on sludge chemical

276 properties. In China, the mean TN, TP, and TK contents of soil are 1.0–2.0, 0.44–0.85

277 and about 16 g kg–1, respectively (Wang et al., 2015). Considering this, the treated

278 sludge has potential for application to soil amendment and manure.

279 4. Conclusions

280 Three WSAs derived from HA, FJ, and PS, effectively removed Cd, Pb, Ni, and

14
281 Cu from sludge. The concentrations, pH, washing time, and washing temperature of

282 the WSAs were closely related to heavy metals removal efficiencies, and the washing

283 process of WSA may be dominated by chemisorptive interactions. The optimal Cd,

284 Cu, Pb, and Ni removal efficiencies were 56.99, 75.81, 63.42, and 27.52%

285 respectively for HA, 74.19, 26.99, 42.02, and 21.53% respectively for FJ, and 23.88,

286 26.09, 48.55, and 26.46% respectively for PS. After washing, the WSAs mainly

287 removed easily extractable fractions of the metals, such as the exchangeable and

288 carbonate–bond fractions. In addition, the potential ecological risk of sludge was

289 reduced and the organic carbon and nutrient in sludge was supplemented. Therefore,

290 the WSAs derived from HA, FJ, and PS proved to be novel washing agents for the

291 removal of heavy metals from sludge, and they can be beneficial to the further

292 application of sludge to land. The impact of agricultural use of sludge washed by

293 WSAs on soil fertility, microorganisms and plant productivity are also worth

294 exploring.

295 5. Acknowledgments

296 The authors are grateful for the support of Key Research and Development

297 Projects of Sichuan Province, China, Grant No. 2019YFN0020, Environmental

298 Protection Science and Technology Projects of Sichuan Province, China, Grant No.

299 2018HB30.

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 Table 1. Sludge chemical properties before and after washing.

OC (g kg-1) TN (g kg-1) TP (g kg
-1
) TK (g kg-1) AN (g kg-1) AP (g kg
-1
) AK (g kg-1)
Original sludge 245.01 ± 4.71d 18.45 ± 1.07a 15.02 ± 0.35ab 7.23 ± 0.26a 2.35 ± 0.18b 4.13 ± 0.34b 1.03 ± 0.13c
HA 258.63 ± 9.16c 17.89 ± 0.48a 14.59 ± 0.66b 6.50 ± 0.58b 2.45 ± 0.24b 4.74 ± 0.67a 1.18 ± 0.19bc
FJ 284.54 ± 11.71b 18.23 ± 0.56a 14.32 ± 0.48b 7.01 ± 0.31a 2.70 ± 0.13a 4.51 ± 0.92ab 1.34 ± 0.11a
PS 307.72 ± 8.53a 18.35 ± 1.03a 15.12 ± 0.33a 6.50 ± 0.14b 2.17 ± 0.16c 4.41 ± 0.41ab 1.23 ± 0.17ab

HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya stenoptera; OC, organic carbon; TN, total nitrogen; TP, total phosphorus; TK, total potassium; AN,

alkali-hydrolyzable nitrogen; AP, available phosphorus; AK, available potassiu

Fig. 1 Effects of the concentrations on the removals of Cd, Cu, Pb, and Ni with plant

water-soluble extracts from sludge.

Fig. 2 Effects of the pH on the removals of Cd, Cu, Pb, and Ni with plant

water-soluble extracts from sludge.

Fig. 3 Effects of the washing time on the removals of Cd, Cu, Pb, and Ni with plant

water-soluble extracts from sludge.

Fig. 4 Effects of the washing temperature on the removals of Cd, Cu, Pb, and Ni with

plant water-soluble extracts from sludge.

Fig. 5 FTIR spectra of HA, FJ and PS before and after washing.

Fig. 6 Comparative distribution of Cd, Cu, Pb and Ni in the sludge before and after

washing with three plant water-soluble extracts.

Fig. 1 Effects of the concentrations on the removals of Cd, Cu, Pb, and Ni with
plant water-soluble extracts from sludge.
Note: HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya stenoptera. Error
bars represent the standard deviations (n = 3).
Fig. 2 Effects of the pH on the removals of Cd, Cu, Pb, and Ni with plant
water-soluble extracts from sludge.
Note: HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya stenoptera. Error
bars represent the standard deviations (n = 3).
Fig. 3 Effects of the washing time on the removals of Cd, Cu, Pb, and Ni with
plant water-soluble extracts from sludge.
Note: HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya stenoptera. Error
bars represent the standard deviations (n = 3).
Fig. 4 Effects of the washing temperature on the removals of Cd, Cu, Pb, and Ni
with plant water-soluble extracts from sludge.
Note: HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya stenoptera. Error
bars represent the standard deviations (n = 3).
Fig. 5 FTIR spectra of HA, FJ and PS before and after washing.
Note: HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya stenoptera. W-FJ, FJ
powder extracted by distilled water. W-HA, HA powder extracted by distilled water.
W-PS, PS powder extracted by distilled water
Fig. 6 Comparative distribution of Cd, Cu, Pb and Ni in the sludge before and
after washing with three plant water-soluble extracts.
Note: Before, original sludge; HA, Hovenia acerba; FJ, Fatsia japonica; PS, Pterocarya
stenoptera. EXC, exchangeable fraction, CAR, carbonates bound fraction, FeMn, Fe-Mn oxides
bound fraction, ORG, organic matter bound fraction, RES, residual fraction
Highlights:

•Heavy-metal removal from sludge using plant washing agents was evaluated.

•The agent from Hovenia acerba effectively removed heavy metals from sludge.

•The washing agents tended to moderate changes in the chemical properties of sludge.

•The sludge is suitable as manure and can be used for soil amendment after washing.
 The author Xiaoxun Xu, Yan Yang and Shirong Zhang did the experimental

work and wrote the manuscript. Guiyin Wang, Zhang Cheng, Ting Li and Zhanbiao

Yang contributed to the data analysis and prepared Figures and Tables. Junren Xian

Yuanxiang Yang, and Wei Zhou contributed to experimental design and the

experiment operation. All authors reviewed the manuscript and contributed to the

scientific discussion.
Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered as
potential competing interests: