Accepted Manuscript

Moringa stenopetala bark: A novel green adsorbent for the removal of metal ions from
industrial effluents

Temesgen Girma Kebede, Simiso Dube, Alemayehu Abebaw Mengistie, Thabo TI.
Nkambule, Mathew Muzi Nindi

PII: S1474-7065(18)30002-0
DOI: 10.1016/j.pce.2018.08.002
Reference: JPCE 2701

To appear in: Physics and Chemistry of the Earth

Received Date: 12 January 2018

Revised Date: 29 June 2018
Accepted Date: 2 August 2018

Please cite this article as: Kebede, T.G., Dube, S., Mengistie, A.A., Nkambule, T.T., Nindi, M.M.,
Moringa stenopetala bark: a novel green adsorbent for the removal of metal ions from industrial
effluents, Physics and Chemistry of the Earth (2018), doi: 10.1016/j.pce.2018.08.002.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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3 Moringa stenopetala bark: a novel green adsorbent for the removal of metal ions from industrial
4 effluents
5 Temesgen Girma Kebede1, Simiso Dube1, Alemayehu Abebaw Mengistie2,

6 Thabo TI Nkambule3, Mathew Muzi Nindi1

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7 Department of Chemistry, University of South Africa, Corner Christian de Wet and Pioneer Avenue,

8 Florida Park, 1709, South Africa

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9 Department of Applied Chemistry, Ambo University, P. O. Box 19, Ambo Town, Western Shoas,

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10 Ethiopia
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11 Nanotechnology and Water Sustainability (NanoWS) Research Unit, College of Science, Engineering

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12 and Technology (CSET), University of South Africa, Corner Christian de Wet and Pioneer Avenue,
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13 Florida Park, 1709, South Africa

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15 Keywords: Moringa stenopetala bark; Adsorption isotherm; Adsorption kinetics; Thermodynamics;

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16 Metal Remediation
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18 *Corresponding author: Department of Chemistry, University of South Africa, Corner Christian de wet
19 and Pioneer Avenue, Florida, 1709, South Africa. E-mail address: [email protected]
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29 Abstract

30 This work demonstrates the potential of Moringa stenopetala bark powder as an adsorbent for the

31 removal of heavy metals from wastewater. The bark powder was characterised using FTIR, XRD, zeta

32 potential, TGA, SEM and BET techniques. Several processing parameters such as; contact time,

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33 adsorbent dose, concentration, pH, agitation speed and temperature were optimised. Using the optimum

34 conditions the maximum removal efficiency of three heavy metals, Cd (II), Pb (II) and Cu (II) were99.08,

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35 99.68 and 99.60% from synthetic wastewater respectively. When applied to industrial real wastewater the

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36 removal efficiency was 94.80, 95.50 and 94.23% for Cd (II), Pb (II) and Cu (II) respectively. The

37 adsorption equilibria observed is in accordance to the Freundlich isotherm than the Langmuir isotherm.

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38 The maximum adsorption capacity of 38.46 ± 0.21, 35.71 ± 0.86 and 34.48 ± 0.93 mg g-1was observed for
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39 Cd (II), Pb (II) and Cu (II).The interaction of the cationic species with the bark powder was

40 predominately via chemisorption rather than physisorption. The adsorption of the three metals ions,Cd
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41 (II), Pb (II) and Cu (II) was well defined by the pseudo-second order model (R2=1).The thermodynamic
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42 parameters such as ∆S, ∆H and ∆G were also determined. The calculated values of ∆H and ∆S were
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43 positive which indicated that the adsorption of metal ions on the adsorbent was an endothermic process.

44 However, ∆G exhibited the negative values confirming that the adsorption process was spontaneous.
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53 1. Introduction

54 Several anthropogenic activities are the main contributors of heavy metal ions and other chemicals in the

55 aquatic environment. The continuous discharges of heavy metals into aquatic environment increase the

56 concentration of these metal ions and consequently, disrupt the aquatic fauna and flora. The presence of

57 heavy metals in the environment, their toxicity and adverse effects on the receiving water remain a great

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58 concern. Since heavy metals are non- biodegradable, they tend to bioaccumulate in living organisms

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59 (Ambasht R and Ambasht P , 2005). Due to the expansion of new cleaning technologies and stern

60 legislation, discharge of heavy metals into the aquatic environment has been reduced in several countries.

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61 However, there is still need to develop economical and environmentally friendly methods for the removal

62 of heavy metals.

63
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Cadmium (Cd), lead (Pd) and copper (Cu) are amongst the most commonly detected heavy metals in the
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64 aquatic environment. Lead is known to have a toxic effect on the renal, nervous system, reproductive and
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65 cardiovascular system in human. Exposure to lead also causes hyperactivity and mental retardation in

66 children (Demayo et al., 2009). In human, Cd interferes with certain enzyme like acetylcholinesterase and
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67 causes behavioural disturbances and cholinergic neurotransmission. Exposure to high levels of copper
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68 may lead to lung cancer (Aydin et al., 2008).

69 Membrane separation, chemical precipitation, solvent extraction, coagulation, ion-exchanges, electrolysis

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70 are some of the methods that have been explored for the removal of heavy metals from water (Esmaeili et

71 al., 2005; Kozlowski C and Walkowiak W, 2002; Rengaraj et al., 2002). These methods have
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72 demonstrated promising results; however they have practical drawbacks which limit their wide
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73 application. For example, ion exchange and membrane technologies are very costly due to their energy

74 requirements, while chemical precipitation is ineffective in removing metals at low concentration.

75 Adsorption has shown to be the fundamental and economically feasible technique for the treatment of

76 heavy metals from wastewater due to the removal efficiency, affordable investment cost, less energy

77 demand and reusability. It can be applied at pilot-scale level due to simplicity of design, easy operation,
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78 and low harmful secondary products. This method normally uses adsorbents such as activated carbons,

79 zeolites, clays, nano-magnetic particles and others. However; these adsorbents suffer from low adsorption

80 capacities and selectivity due to poor porosity, low surface area, lack of functional groups and surface

81 deactivation. Therefore, there is a need to develop adsorbents with large surface area to volume ratio, high

82 porosity and high functionalities.

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83 The search for low-cost and eco-friendly adsorbents from agricultural by-products, biomaterials and

84 industrial by-products has been of great interest as alternative approaches. Heavy metals have been

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85 removed by using low-cost adsorbents such as plants straw, leaves, seeds, and barks such as teff straw

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86 (Tadesse et al., 2014), palm pressed fibers and coconut husk (Tan et al., 1993), brown seaweed ecklonia

87 biomass (Park et al., 2004), peat moss (Park et al., 2004) duckweed Wolffia globosa (Park et al., 2004),

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88 lignocellulosic substrate extracted from wheat bran (Dupont et al., 2003), Rhizopus nigricans (Bai R and
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89 Abraham T, 2001), cork and Yohimbe bark wastes (Villaescusa et al., 2000) and leaves of indigenous

90 biomaterials, Tridax procumbens (Freeland et al., 1974). In addition modified adsorbents such as
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91 chemically treated teff straw (Wassie A and Srivastava V, 2016), phenol formaldehyde cationic matrices
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92 (Singanan M and Vinodhini S, 2006), polyethylenamine-modified wood fibers (Freeland et al., 1974b)
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93 and sulphur-containing modified silica gels (Verwilghen et al., 2004) have also shown capability of

94 removing of heavy metals.

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95 Moringa stenopetala bark powder which is a locally available natural bio-adsorbent exhibits attractive
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96 property which meet the requirements as a suitable adsorbent towards removal of Cd , Pb2+ and Cu2+
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97 ions. To our knowledge no work has been reported previously on the potential of Moringa stenopetala
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98 bark powder to remove more than one heavy metal from water. Thus the aim of this study was (1) to
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99 evaluate the potential of Moringa stenopetala bark powder towards removal of Cd Pb2+ and Cu2+

100 metals from industrial wastewater and (ii) to propose the possibility of using a cheaper and greener

101 (environmentally friendly), yet effective adsorbent to different industries for the removal of heavy metal

102 ions from industrial effluents before they discharge it to different water systems.

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103 2. Material and methods

104 2.1. Chemicals and reagents

105 Analytical grade chemicals of highest purity (≥ 98 %) were used in this study. The heavy metals in the

106 form of cadmium nitrate (Cd (NO3)2.4H2O), lead nitrate (Pb (NO3)2) and copper nitrate (Cu (NO3)2.3H2O)

107 were purchased from Merck, USA.

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108

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109 2.2. Instrumentation

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110 Fourier transform infrared spectra (FTIR) of Moringa bark powder was measured using a vertex series

111 (Bruker optic GmbH, Hamburg, Germany).Metal ions were analysed using atomic absorption

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112 spectrometer, AAnalyst 600 model (Perkin–Elmer, USA), equipped with deuterium-arc background
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113 corrector and Zeeman correction devices, AS-800 autosampler, and hallow cathode lamp. HANNA

114 instruments pH meter (pH 209 models, Portugal) was used to determine the pH of the solution. The X-ray
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115 diffraction (XRD) patterns of Moringa bark powder was measured using a high resolution SmartLab X-

116 ray diffractometer (Rigaku, Japan).The zeta potential of bark powder was measured using a Zetasizer
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117 Nano ZS (Malvern Instruments, UK). The scanning electron microscope (SEM) image of bark powder
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118 was recorded byJSM-6010PLUS/LA JEOL(Rikagu, Japan) which is equipped with Oxford X-ray energy

119 dispersive spectroscope (EDS).Thermogravimetric analysis (TGA) of the Moringa bark powder was
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120 studied using a TA Instruments TGA Q500 (DE, USA). The total pore volume, surface area and average
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121 pore size of Moringa bark powder was studied using Brunau-Emmett-Teller (BET) a micromeritics
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122 TriStar II 3020 instrument.All weightings were measured using electronic balance (Mettler Toledo,

123 Model AG204, and Switzerland) with accuracy of 0.0001 g.

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127 2.3. Sampling and preparation of bark powder

128 Moringa stenopetala bark samples were collected from Kola Share village, in Ethiopia. The bark was

129 washed with distilled water and dried in an oven at 105 °C for 24 hours. The material was ground by

130 mortar and pestle into fine powder and sieved through a sieve mesh size of 0.25 - 0.5 mm.

131

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132 2.4. Preparation of calibration standards and sample solutions

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133 Heavy metals stock solutions were prepared by dissolving accurately weighed masses of each compound

using double-distilled water and making up to 250 mL to make concentration of 1000 mg L-1. Working

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134

135 standard solutions were prepared from stock solutions. The calibration curves were prepared by using six

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136 concentration levels of standard solutions within the concentration range of 0.02 mg mL-1 to 0.12 mg mL-
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137 . All calibration standards were prepared from a stock solution of 1 mg mL-1. The pH of the sample

138 solutions was adjusted using either NaOH or HNO3 (0.125 mol L-1) solution as necessary.
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140 2.5. Sampling

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141 Akaki River (Addis Ababa, Ethiopia) receives effluent from the neighbouring industrial activities.

142 Industrial wastewater samples were collected in duplicate into 2.5 L amber bottles. In preparation for
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143 sampling, the bottles were washed and rinsed with double distilled water and then flushed at least three

144 times with wastewater before collection. Samples were packed in an ice cooler box and transported to the
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145 laboratory. All the sample solutions were mixed and homogenised using a mechanical Gemmy orbit
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146 shaker (Taipei, Taiwan) for 30 minutes. The homogenised sample was vacuum filtered immediately

147 through the Whatman No. 90 filter paper. The samples were then stored at < 4 oC until ready for analysis.

148 The water quality was measured using various methods as shown in Table 1.

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151 2.6. Batch adsorption experimental procedures

152 The batch experiment was carried out by firstly weighing 0.25 – 2.5 mg of dried and sieved powered

153 bark. A desired amount of the stock solution was added and the mixture shaken in a mechanical shaker at

154 100 - 350 rpm for a definite period of time (15 – 360 min) until equilibrium was reached. After

155 equilibration, the mixture was allowed to settle for 30 min and then the supernatant was carefully filtered

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156 through Whatman No. 42 filter paper which was pre-saturated with distilled water (Agarwal et al., 2006).

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157 The metals were further analysed with atomic adsorption spectroscopy. The concentration was measured

158 at wavelength of 283.3 nm, 279.5 nm and 228.2 nm with slit 0.7, 0.2, and 0.7 for lead, copper and

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159 cadmium respectively. The experiments were carried out in three times and mean values were taken for

160 calculation. The adsorption efficiency (%) was calculated according to the expressions:

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162 % Adsorption = ∗ 100 (1)
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164 where Co is the initial concentration (mg L-1) and Cf is the solution concentration at the end of the
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165 sorption process (mg L-1) (Agarwal et al., 2006). The adsorption capacity at equilibrium, qe (mg g-1), of
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166 the metals were calculated using equation 2;

167
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168 =( − )∗ (2)
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170 where, Co and Ce (mg L-1) are the liquid-phase concentrations of Pd 2+, Cu 2+ and Cd 2+ at time zero and

171 equilibrium respectively. V is the volume (L) of the sample solution and W is the weight (g) of the dry

172 sorbent.

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175

176 3. Result and Discussions

177 3.1. Characterization of Moringa stenopetala bark powder

178 3.1.1. FTIR characterisation

179 In order to understand the interaction between the metal ion and the adsorbent it was necessary to

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180 characterise the bark powder using FTIR. Figure 1 shows a broad band at 3313 cm−1 attributed to

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181 stretching of OH and/or NH stretch in the secondary amide group. The band between 2914-2842 cm−1

182 was due to symmetrical and asymmetrical stretching of CH and CH2 methyl groups present in fatty acids.

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183 The band at 1728 cm−1 is assigned to C=O bond stretching of carboxylic and carbonyl group present in

184 the fatty acid and protein structures (Kebede et al., 2018). The peak at 1600 cm−1 and 769 cm−1 could be

185
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attributed to NH2 deformation (Centeno S and Shamir J, 2008). The band at 1504 cm−1, 1413 cm−1, 1365
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186 cm−1 and 1309 cm−1 is associated with NH bending, C = C aromatic ring vibration, CN stretching and C-
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187 CH deformation respectively (Centeno S and Shamir J, 2008; Czarnik-Matusewicz et al., 2006). The

188 absorbance bands at 1222 cm−1, 1020 cm−1 and 881 cm−1 are related to C-O stretching/O-H in plane
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189 deformation in COOH, C – O stretch and C-H out of plane deformation respectively (Centeno S and
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190 Shamir J, 2008).

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192 3.1.2. XRD characterisation of the bark powder

193 The crystallinity of the bark powder was characterised using X-ray and the diffraction pattern are shown
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194 in Figure 2. The results showed characteristic peaks at different diffraction planes. The material
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195 demonstrated a semi crystalline nature due to the fact that the bark powder is composed of heterogeneous

196 and complex matrix with several substances such as lipid, proteins, carbohydrates and ash (Araújo et al.,

197 2010). This was also confirmed by the presence of broad bands at 2Ɵ = 6.76°, 2Ɵ = 13.39 ͦ and 2Ɵ = 21.22
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198 which are due to the constituents of protein and other components that have a more amorphous nature.

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200

201 3.1.3. Surface morphology of bark powder

202 The SEM image demonstrated a flake-like morphology of different sizes as shown in Figure 3. As

203 indicated by Araújo et al such morphology is usually related to the heterogeneous and relatively porous

204 matrix of a material (Araújo et al., 2010). Such a structure favours the adsorption of metals to the bark

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205 powder, due to different sized interstices of the surface.

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207 3.1.4. Thermal properties of bark powder

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208 The thermogram in Figure 4 shows mass loss curve from 50 ͦ C – 238 ͦ C, with 1.81% weight loss due to

209 water desorption. A28 % weight loss at 288 °C – 366 °C, was due to the loss of low molecular weight

210
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gases probably CO2 and NH3. This is probably due to the breakdown of side chain groups of amino acid
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211 residues of protein and fatty acids (Araújo et al., 2010; Mhuka, 2014). Finally, a curve observed in
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212 between 386 – 511°C, that could be due to total the structural decomposition of the bark powder.

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214 3.1.5. Surface charge of bark powder

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215 The surface charge of the bark powder was evaluated between pH 2 and 12, using zeta potential (ζ)
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216 measurement. It is apparent as shown in Figure 5 that changes in pH influence the surface charge of the

217 bark. For example at pH range of 1.5 – 2.2, the bark surface was predominately positive. This could be
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218 explained by the protonation of the amine and amide functional groups at very low pH. Increasing the pH
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219 between 3-12 resulted in bark powder having a negatively charged surface. This change in the surface

220 could be attributed to the deprotonation of amine and amide functional groups. The highly negative

221 charged surface implies that the bark powder will have affinity for the metals ions through electrostatic

222 interactions. Therefore, adsorption of Pb (II), Cd (II) and Cu (II) using bark powder will result in

223 enhanced adsorption capability at pH ranges from 3 – 12.

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224 3.1.6. The Brunauer-Emmett-Teller (BET)

225 A micromeritics TriStar II 3020 instrument was used to measure surface area, total pore volume, and

226 average pore size of bark powder. The results showed that the BET surface area, total pore volume, and

227 average pore diameter of bark powder were 4.6 m2g-1, 0.0015 cm3g-1, and 210.44A°, respectively.

228

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229 3.2. Effect of experimental parameters on adsorption of Pb (II), Cd (II) and Cu (II)

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230 Different parameters that affect the adsorption efficiency of bark powder; adsorbent dose, initial

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231 concentration, agitation speed, contact time and pH were studied and the optimum conditions for each

232 parameter were selected. For every analysis, each analyte was measured five times.

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234 3.2.1. Effect of initial concentration on the adsorption of metal ions

235 All adsorbents have the ability to bind metal ions based on the availability of free active sites. It is
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236 therefore importance to evaluate the effect of the initial concentration of the metal ions. As expected the
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237 adsorption process is concentration dependant (Figure 6). The concentration of the metal ions solution
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238 was varied from 10-100 mg L-1 while other parameters were kept constant (i.e. dose = 1.5 g, volume = 50

239 mL, pH= 4 , contact time 60 min, temperature 23 ͦ C and agitation speed 150 rpm). It was observed that
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240 the percentage adsorption increased with a decrease of the initial concentration. At a low concentration,

241 there are fewer metal ions which can attach to the active sites on the bark powder surface. However, upon
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242 increasing the concentration, the population of the metals ions increases leading to the saturation of the
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243 surface. The maximum percentage removal of 98.05, 99.45 and 97.50% was obtained at a concentration

244 10 ppm for each of the Cd (II), Pb (II) and Cu (II) ions, respectively. R. Sitko et al also reported that at

245 higher concentrations, the available sites for adsorption become fewer, and hence the percentage removal

246 of the metal ions, which depends upon the initial concentration, decreased (Sitko et al., 2013).

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248 3.2.2. Effect of adsorbent dose on the adsorption of metal ions

249 Adsorbent dose is basically the most important parameter that determines the extent of removal and may

250 also be used to predict the cost of the material required for treatment. The study of the effect of adsorbent

251 dose on the removal of Cd (II), Pb (II) and Cu (II) was investigated using 0.25 – 2.5 g of the bark powder

252 while other parameters were maintained constant. Figure 7 shows that an increase in the adsorbent dose

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253 resulted in an improved removal efficiency of Cd (II), Pb (II) and Cu (II). The maximum removal

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254 efficiencies at high adsorbent dose of 1.5 g were found to be 98.50, 99.23, and 97.70% for Cd (II), Pb (II)

255 and Cu (II) respectively. This is to be expected since the increase of the adsorbent dose result in an

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256 increase in the number of active sites (Dubey S and Gopal K, 2007). No further increase was observed

257 above 1.5 g adsorbent dose. Since acceptable removal efficiency was achieved at 0.75 g of the adsorbent

258
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(96.90, 97.90 and 95.50% Cd (II), Pb (II) and Cu (II) respectively) this dosage was taken as optimum.
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260 3.2.3. Effect of contact time on the adsorption of metal ions

261 The effect of contact time of metals ions on the surface of bark powder was investigated between 15 –
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262 360 min. Figure 8 shows that as the contact time increased the adsorption efficiency also increased until it
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263 reached 120 minutes where the adsorption equilibrium was established. Beyond this time there was no

264 further increase in absorption efficiency for all metals. The maximum removal efficiencies observed at
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265 120 minutes were 99.02, 99.43 and 98.50% for Cd (II), Pb (II) and Cu (II) respectively.
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266
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267 3.2.4. Effect of agitation speed on the adsorption of metal ions

268 The agitation speed has an effect on the effectiveness of the adsorbent in removal of metals (Dubey S and

269 Gopal K, 2007). The agitation allows the adsorbate to equilibrate faster, by decreasing the boundary layer

270 resistance and increasing the mobility of the system. Hence, it increases the diffusion rate of the adsorbate

271 from the bulk into the adsorbent particles. The agitation speed varied from 100 to 350 rpm while other

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272 parameters were kept constant. As observed in Figure 9 there was an increase in the percentage removal

273 of Cd (II), Pb (II) and Cu (II) as the agitation speed was increased from 50 to about 200 rpm. Thereafter

274 the removal efficiency remained fairly constant. Therefore, 200 rpm was taken as the optimum agitation

275 speed, which gave the maximum removal of 99.70, 99.80 and 99.1% for Cd (II), Pb (II) and Cu (II)

276 respectively.

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277

278 3.2.5. Effect of temperature on the adsorption of metal ions

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279 Figure 10 shows the effect of temperature on the adsorption of metals on the bark powder at a range of 10

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280 – 50 ͦ C. At high temperatures the kinetic energy of the metal ions in the solution increases resulting in

281 their faster diffusion to the adsorbent. Since diffusion is an endothermic process, the increase in

282
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temperature leads to activate diffusion and causes the micro-pores to widen and deepen and thus create
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283 more surface for adsorption (Mengistie et al., 2008). The maximum removal obtained was 99.65, 99.66

and 99.42% for Cd (II), Pb (II) and Cu (II) metal ions respectively at 40 °C. Conversely at low
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285 temperature, the kinetic energy of the metal ions is low and fewer metal ions reach the adsorbent active
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286 sites and consequently, less removal is expected. However, it was also observed that at 30 ͦ C the
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287 percentage removal was 99.28, 99.33 and 99.15% for Cd (II), Pb (II) and Cu (II) ions respectively; hence,

288 30 ͦ C was chosen as the optimum temperature.

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290 3.2.6. Effect of pH on the adsorption of metal ions

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291 pH influences the surface charge of the adsorbent, the degree of ionization of the material present in the

292 solution, the dissociation of functional groups on the active sites of the adsorbent and the solution

293 chemistry of metal ions. In the current study, the adsorption of metal ions was investigated between 2 and

294 9.5 as shown in Figure 11.The adsorption efficiencies of Cd (II), Pb (II) and Cu (II) slightly increased as

295 pH increased between 1.5 – .3. At this pH range, the predominant species of cadmium, lead and copper

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296 are Cd2+, Pb2+ and Cu2+ (>90%) (Sitko et al., 2013). Moreover, as it was observed from the zeta potential

297 results, the surface charge of the bark powder was predominately positively charged at pH 1.5 – 2.3.

298 Thus, under these conditions both the adsorbent and adsorbate are positively charged and the effect is

299 explained by the lower adsorption efficiencies. This is due the existence of electrostatic repulsion between

300 the cationic metal ions and positively charged surface of Moringa bark powder. The maximum percentage

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301 removal of 98.96, 99.72 and 99.33% for Cd (II), Pb (II) and Cu (II) respectively was observed at pH 5.

302 The increase on removal efficiency was observed at pH between 3 – 5, due to an alteration of the surface

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303 charge of the bark powder followed by the deprotonation of positively charged amine and amide

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304 functional groups. In addition to that, unprotonated carboxylic acid groups rendering the adsorbent

305 negatively charged and thus favouring the electrostatic attraction between the metal ions and the

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306 adsorbent. However, at pH > 6.0, the Cd (II), Pb (II) and Cu (II) were precipitated due to hydroxide
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307 anions forming metal ion hydroxide precipitate and resulting in decreased percentage removal.

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309 3.3. Adsorption isotherms

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310 In order to fully understand the applicability of the adsorption process it is essential to determine
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311 physicochemical information from adsorption equilibrium (Yeddou N and Bensmaili A, 2007). Langmuir

312 and Freundlich equations allows for the investigation of the relationship between the quantities of the
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313 metal ions adsorbed and the concentration at equilibrium (Ce).

314
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315 3.3.1. Langmuir isotherm

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316 In the present study, the interaction between the bark powder and metal ions was evaluated by fitting the

317 obtained adsorption results to the linear Langmuir equation, as it is expressed by the following linear

318 Langmuir equation (3) (Igwe J and Abia A, 2007).

319

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320 =( ) + (3)
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322 where, qe (mg g-1) is the amount of adsorbate adsorbed at the equilibrium concentration, Ce (molL-1) is the

323 equilibrium concentration of adsorbate, qmax (mg g-1) represents the maximum monolayer adsorption

324 capacity and b (L mol-1) is the Langmuir constant related to energy of adsorption and the affinity of the

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325 binding sites. The plot of 1/qe vs. 1/Ce gave a liner relationship as described in Figure 12 (A). The values

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326 of qmax, b and R2are presented in Table 2.The Langmuir dimensionless constant separation factor RL, used

327 to predict favourability of the isotherm was calculated using the following equation (9) (Igwe J and Abia

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328 A, 2007):

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330 "# =
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331
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332 where b is Langmuir constant and Co is initial concentration of analytes. As reported by Jagtap et al., if

333 RL < 1, then adsorption is favourable while RL > 1 represent unfavourable adsorption and RL = 0
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334 irreversible process (Jagtap et al., 2011). The value of r for all analytes is given in Table 2.
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335

336 3.3.2. Freundlich isotherm

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337 The Freundlich isotherm model deals with multilayer physicochemical adsorption on heterogeneous
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338 surfaces (Acar F and Malkoc E, 2004). The linear form of Freundlich adsorption isotherm is expressed by
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339 the following equation (5) (Igwe J and Abia A, 2007):

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341 log (q) ) = log K + + , log(C) ) (5)

342

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343 where, qe is solid phase equilibrium concentration (mg g-1), Ce is liquid-phase equilibrium concentration

344 (mg L-1), Kf is the Freundlich constant which indicates the adsorption capacity and represents the strength

345 of the adsorptive bond while n is the heterogeneity factor representing the bond distribution and

346 adsorption intensity. The values of Kf and 1/n were obtained from the intercept and slope of the plot of

347 log qe vs. log Ce is shown in Table 2 and Figure 12(B). From the result obtained it was observed that both

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348 Langmuir and Freundlich model found to be in close relation for the selected metal ions removal.

349 However, the number of higher correlation coefficient obtained from the Langmuir plot is less than the

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350 Freundlich plot, which confirmed that the adsorption of Cd (II), Pb (II) and Cu (II) ions by Moringa bark

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351 powder is governed through multilayer coverage of the surface suggesting that chemisorption is

352 predominat. Thus, the Freundlich model was found to fit the Cd (II), Pb (II) and Cu (II) adsorption very

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353 well than the Langmuir model.
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354

355 3.4. Adsorption Kinetics

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356 Adsorption kinetics must be taken into account for the study of reaction rate phenomenon, since they
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357 explain how fast the chemical reaction occurs and provides information on the factors affecting the
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358 reaction rate. Adsorption kinetics also describes the important characteristic in evaluating the efficiency

359 of adsorption (Ibrahim et al., 2006). In order to investigate the mechanism of adsorption and potential
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360 rate-controlling steps such as mass transport and chemical reaction processes, kinetic models are

361 commonly used to test experimental data (Ho Y and McKay G, 1998). In order to achieve this goal,
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362 pseudo-first and pseudo-second order models were applied in the current study.
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363

364 3.4.1. Pseudo-first order kinetics

365 The linear form of pseudo first order equation is expressed as follows (Chatterjee S and Woo S, 2009):

366

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01
367 log( − .) = log / − 6 (6)
2.454

368

369 where qe and qt (mg g-1) are the amount of metal ions adsorbed per unit mass of the adsorbent at

370 equilibrium and time t, respectively and K1 is the adsorption rate constant. As it is showed in Figure 13A,

371 the value of qe and K1 were obtained from the slope and intercept of the plot of log (qe – qt) vs. t. The

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372 numerical values of qe and K1 determined in the current study were found to be 0.079 mg g-1 and 0.053

min−1, respectively.

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373

374

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375 3.4.2. Pseudo-second order kinetics

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376 When the rate of adsorption follows the pseudo second order mechanism, the chemisorption kinetic linear
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377 equation can be expressed as given in equation (7) (Chatterjee S and Woo S, 2009; Ho Y and McKay G,

378 1998).
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379
.
380 =8 + t (7)
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9
7 9

381
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2
382 ℎ = <2 (8)
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383

384 where qe and qt (mg g-1) are the amount metal ions adsorbed per unit mass of the adsorbent at equilibrium
C

385 and time t, respectively, h is initial sorption rate (mg g-1 min-1) and K2 is the rate constant for the second
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386 order kinetic model. The plot of t/qt vs. t gave a straight line as it is described in Figure 13 (B). The value

387 of K2, h and correlation coefficient (R2) obtained from the linear plots are presented in Table 3. As shown

388 in Figure 13 (A and B) and Table 3, the pseudo-first order and pseudo-second order reaction models were

389 used to study the adsorption kinetics of Cd (II), Pb (II) and Cu (II) ions on the Moringa bark powder. The

390 pseudo-second order model showed an excellent fit than pseudo-first order, which has described by the

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391 respective value of R2. Furthermore, the calculated value of qe (6.667 mg g-1) obtained from pseudo-

392 second order plot agrees with the experimental value of qe (6.619 – 6.650). Therefore, in the present

393 study, the adsorption of Cd (II), Pb (II) and Cu (II) on the bark powder was found to follow pseudo-

394 second order kinetic model which relies on the assumption that chemisorption or chemical adsorption is

395 the rate-determining step.

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396

397 3.5. Thermodynamics studies

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398 To identify the thermodynamic feasibility and confirm the nature of the adsorption process, the three

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399 basic thermodynamic parameter; standard Gibbs free energy change (∆G), standard enthalpy change (∆H)

400 and standard entropy change (∆S) were calculated. The value ∆H and ∆S were calculated from the slope

401 and intercept using equation (9):

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AN
402
?@ ?B
M

403 ln <> = − (9)

A AC

404
D

405 where ∆S = entropy change for the process, ∆H enthalpy change for the process, R gas constant, T
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406 absolute temperature.

407 The distribution coefficient (Kd) on the surface of Moringa bark powder was calculated using the
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408 equation (10):

C

409
AC

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410 <> = ( )
∗ (10)

411

412 where, Ce is the concentration of metal ions at equilibrium (mg L-1), and Co is the initial ion concentration,

413 mg L-1, V volume of solution (L) and m mass of the adsorbent (g). The changes in free energy (∆G) for

414 the specific adsorption have also been calculated using the equation (11);

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415

416 ∆G = −"HIJ<> (11)

417

418 The values of ∆H and ∆S calculated from the plot of lnKd vs 1/T (Figure 14), and ∆G at various

419 temperatures were calculated using equation (11) and were listed in Table 4. The positive value of ∆H

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420 showed that the adsorption of Cd (II), Pb (II) and Cu (II) ions on the surface of Moringa bark powder is

421 an endothermic process. As it has suggested by G. Crine et al., ∆H for chemisorption is greater than 40

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422 KJ mol-1 (Crini et al., 2008).

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423

424 Moreover, the positive values of ∆H affirmed that the adsorption of metal ions by Moringa bark powder

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425 was through a chemical interaction. The positive value of ∆S reveals the increase in randomness at solid
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426 solution interface during the fixation of metal ions on the active site of the adsorbent. The negative values

427 of ∆G throughout all the temperature ranges confirmed that the adsorption of metal ions on the surface of
M

428 adsorbent was spontaneous and thermodynamically favourable. However, decrease in ∆G value with
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429 increasing temperature reveals that adsorption of the metal ions on the adsorbent becomes favourable at
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430 higher temperature (313 K).

431
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432 3.6. Application on real sample

433 The industrial wastewater was analysed and the results are summarized in Table 5. The adsorption of
C

434 metal ions in industrial wastewater samples was carried out using the method optimized and developed
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435 using a synthetic wastewater prepared in the laboratory. The result showed that the Moringa bark powder

436 was effective in the removal of selected metal ions from industrial effluent (Figure 15). The maximum

437 removal obtained was 94.17, 94.67 and 92. 81% for Cd (II), Pb (II) and Cu (II) ions respectively from real

438 wastewater sample. The percentage removal efficiencies of the metal ions from real wastewater sample

439 were lower than 99.40, 99.70 and 99.80% obtained for mixture of standard solution under the same
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440 experimental conditions. The difference observed could be explained by the presence of different

441 competing ions in the industrial effluent sample. However, the comparison results in Table 6 confirmed

442 that Moringa bark powder is an effective adsorbing material for the removal of selected heavy metals and

443 can be applied for industry application.

444

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445 3.7. Conclusions

446 The Moringa stenopetala bark powder showed characteristic properties as a suitable adsorbent material

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447 due to a proper functional groups, high crystallinity, surface morphology, thermal stability, dynamic

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448 negative surface charge and large surface area of the bark powder was confirmed by FTIR, XRD, SEM,

449 TGA, zeta potential and BET techniques. Thus the bark powder was evaluated for adsorption of

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450 simultaneous removal of Cd (II), Pb (II) and Cu (II) ions. The optimum conditions for the adsorption of
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451 three metal ions were; initial concentration 10 ppm, doss 0.75 g, volume 50 mL, pH 5, contact time 120

452 min, temperature 30 ͦC and agitation speed 200 rpm. The developed method for the removal of selected
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453 metal ions using synthetic wastewater sample was applied on industrial effluent collected at the
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454 discharging point of paint factories, Ethiopia and the results obtained were in good agreement. It is
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455 therefore, possible to conclude that, the method developed for the removal of the three metal ions in the

456 laboratory can be applied for the treatment of industrial effluents before they discharge in to nearby
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457 rivers. In general, the method developed for the removal of metal ions using the bark powder was simple,

458 cost effective, environmental friendly and easily applicable. Since, no other chemicals were involved
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459 which indicates that the method served as green approach and provided environmental protection and
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460 profitability.

461

462

463

464

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465 Acknowledgement

466 The authors gratefully acknowledge the Department of Chemistry, Ambo University for the laboratory

467 facilities and chemicals supplied for this work. The Department of analytical chemistry, University of

468 South Africa (UNISA) and Nanotechnology and Water Sustainability (NanoWS) Research Unit, College

469 of Science, Engineering and Technology (CSET), University of South Africa are greatly acknowledged

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470 for allowing us to use their Instruments. Last but not least, we greatly appreciate the Department of

471 Chemical Engineering for availing their SEM for analysis.

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472

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474

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484
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489

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490 References

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573 Ecklonki biomass. Environ. Sci. Technol. 38, 4860–4864. https://doi.org/10.1021/es035329+

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575 removal of Co(II), Cr(III) and Ni(II) by IRN77 cation-exchange resin. J. Hazard. Mater. 92, 185–
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576 198. https://doi.org/10.1016/S0304-3894(02)00018-3

577 Singanan M, Vinodhini S, A.A., 2006. Phytoremediation of heavy metals from industrial waste waters by
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578 using indigenous biomaterials. Indian J. Environ. Prot. 26, 385–391.

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579 Sitko, R., Turek, E., Zawisza, B., Malicka, E., Talik, E., Heimann, J., Gagor, A., Feist, B., Wrzalik, R.,
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580 2013. Adsorption of divalent metal ions from aqueous solutions using graphene oxide. Dalt. Trans.

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582 Tadesse, B., Teju, E., Megersa, N., 2014. The Teff straw: a novel low-cost adsorbent for quantitative

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584 https://doi.org/10.1080/19443994.2014.968214
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585 Tan, W.T., Ooi, S.T., Lee, C.K., 1993. Removal of chromium(VI) from solution by coconut husk and

586 palm pressed fibres. Environ. Technol. 14, 277–282. https://doi.org/10.1080/09593339309385290

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590 Villaescusa, I., Martínez, M., Miralles, N., 2000. Heavy metal uptake from aqueous solution by cork and

591 yohimbe bark wastes. J. Chem. Technol. Biotechnol. 75, 812–816. https://doi.org/10.1002/1097-

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593 Wassie, A.B., Srivastava, V.C., 2016. Chemical treatment of teff straw by sodium hydroxide, phosphoric

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595 2426. https://doi.org/10.1007/s13762-016-1080-6

596 Yeddou, N., Bensmaili, A., 2007. Equilibrium and kinetic modelling of iron adsorption by eggshells in a

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597 batch system: effect of temperature. Desalination 206, 127–134.

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598 https://doi.org/10.1016/j.desal.2006.04.052

599 Yu, J., Tong, M., Sun, X., Li, B., 2007. Cystine-modified biomass for Cd(II) and Pb(II) biosorption. J.

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600 Hazard. Mater. 143, 277–284. https://doi.org/10.1016/j.jhazmat.2006.09.021
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616 Table caption
617

618 Table1: Characterisation of industrial wastewater around Akaki River was characterized following

619 standard procedures

620 Table 2: Langmuir and Freundlich model parameters for adsorption of metal ions by Moringa bark

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621 powder

622 Table 3: Pseudo first and pseudo second order kinetic model parameters for adsorption of metal ions

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623 Table 4: Adsorption studies of Cd (II), Pb (II) and Cu (II) ions on Moringa bark powder as a

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624 function of temperature

625 Table 5: The result of wastewater characterized

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626
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627 Table 6: Adsorption capacity of different adsorbents for Pb (II), Cd (II) and Cu (II) as reported in
628 the literature
629
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642 Figure caption
643
644 Figure 1: FTIR spectrum of Moringa stenopetala bark powder

645 Figure 2: XRD pattern of bark powder

646 Figure 3: SEM surface morphology of Moringa stenopetala bark powder

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647 Figure 4: TGA curves for the Moringa bark powder

648 Figure 5: Zeta potential trends of Moringa bark powder as a function of pH

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649 Figure 6: Effect of initial concentration on percentage removal of metal ions

650 Figure 7: Effect of adsorbent dose on percentage removal of metal ions on bark powder

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651 Figure 8: Effect of contact time on percentage removal of metal ions on bark powder

652 Figure 9: Effect of agitation speed on percentage removal of metal ions on bark powder

653 Figure 10:

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Effect of temperature on percentage removal of metal ions on bark powder
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654 Figure 11: Effect of pH on percentage removal of metal ions on bark powder
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655 Figure 12: Figure 12: Langmuir (A) and Freundlich (B) model of Cd (II), Pb (II) and Cu (II)

656 adsorption on the bark of Moringa

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657 Figure 13: Pseudo-first order (A) and pseudo-second (B) order kinetics of Cd (II), Pb (II) and Cu (II)
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658 adsorption on the bark of Moringa stenopetala

659 Figure 14: Plot of ln Kd vs 1/T for Cd (II), Pb (II) and Cu (II)
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660 Figure 15: Removal of metal ions from real wastewater sample

661
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664

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667 Table1:

668
Parameters Analysis Method

pH pH meter

Total dissolved solid TDS-meter

COD Titration

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BOD at 270C Titration

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DO DO-meter

Sulphate Titration

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Cadmium, Lead and Copper AAS

Conductivity Conductivity meter

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669
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670
671
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672

673
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674
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675

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681

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685 Table 2:

686

Langmuir Freundlich

Metal ions Qo(mg/g) b(L/mg) RL R2 Kf (L/mg) n R2

Cadmium 38.46 ± 0.21 4 1.04 ± 0.11 0.01 – 0.09 0.965 14.48 ± 1.47 2.23 ± 0.45 0.991

PT
Lead 35.71 ± 0.86 4.00 ± 0.08 0.01 – 0.03 0.940 20.71 ± 0.42 2.72 ± 0.83 0.987

Copper 34.48 ± 0.93 0.91 ± 0.45 0.01 – 0.09 0.953 12.11± 2.10 2.34 ± 0.75 0.991

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687

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688
689

690

691
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692

693
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694
D

695
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696

697
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698

699
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700
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701

702

703

704

705

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706 Table 3:

707

Pseudo-first order Pseudo-second order

Analytes qe(mg/g)exp qe(mg/g)cal K1(min-1) R2 qe(mg/g)cal K2(min-1) h(mg/g min) R2

Cadmium 6.64 ± 0.09 0.21± 1.2 0.02 ± 0.35 0.818 6.67 ± 0.06 0.523 ± 0.26 23.26±0.13 1.000

PT
Lead 6.65 ± 0.51 0.21± 0.12 0.02 ± 0.09 0.858 6.66 ± 0.21 0.833± 0.44 37.03±0.69 1.000

Copper 6.62 ± 0.33 0.39 ± 0.41 0.01± 0.53 0.903 6.67 ± 0.53 0.221± 0.06 9.80± 0.81 1.000

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708

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709

710

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711
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712

713
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714

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716
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723

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726 Table 4:

727

Metal ions Temperature (K) Kd Ln(Kd) ∆G ͦ(KJ/mo ∆H ͦ(KJ/mol) ∆S ͦ(J/(mol K)) R2

l)

Cadmium 283 23.14 3.14 -7391.95 41.55 172.52 0.980

PT
296 43.78 3.78 -9300.22

303 73.41 4.29 -10822.30

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308 82.67 4.41 -11305.10

313 132.67 4.89 -12719.50

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Lead 283 11.45 2.43 -5737.19 64.84 250.50 0.965

296 59.94 4.09 -10073.50

U
303 77.76 4.35 -10967.60

308 101.89 4.62 -11840.60

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313 189.81 5.25 -13651.60

Copper 283 6.35 1.84 -4349.48 63.60 241.11 0.953

M

296 24.03 3.17 -7823.54

303 59.94 4.09 -10311.70

D

308 66.00 4.19 -10728.50

TE

313 73.41 4.29 -11179.50

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728

729
C

730
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731

732

733

734

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737 Table 5:

738

Parameters Results

pH 0.9

Total dissolved solid 1954 mg L-1

3600 mg L-1

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COD

BOD 3230 mg L-1

0.25 mg L-1

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DO

Sulphate 400 mg L-1

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Cadmium 1.2 mg L-1 ± 0.33

Lead 1.39 mg L-1 ± 1.02

12.5 mg L-1 ± 0.81

U
Copper

Conductivity 14.09 mS/cm

AN
739

740
M

741

742
D

743
TE

744

745
EP

746
C

747
AC

748

749

750

751

752

32
 ACCEPTED MANUSCRIPT
753 Table 6:
754

Adsorbents Metal ions Qo (mg/g) Kf (L/mg) pH Reference

Cd(II) 2.4347 0.0126
Limestone Pb(II) 2.0051 0.0128 8–9 (Aziz et al.,
Cu(II 2.9147 0.0155 2008)

PT
Polyporus tenuiculus Cd(II) 11.4 ± 0.42 2.7 ± 0.9 5.2 ± 1.2 (Grassi et al.,
Pb(II) 92 ± 13 1.42 ± 0.43 4.31 ± 0.75 2011)
Cu(II 14.7 ± 0.84 1.8 ± 0.8 4.35 ± 0.55

RI
Mimosa pudica without Cd(II) 26.10 - 6 (Chen et al.,
inoculation Pb(II) 22.70 5 2008)

SC
Cu(II) 25.30 5

Lignin Cd(II) 25.40 - 5 (Guo et al.,

Pb(II) 89.51 2008)
Cu(II) 25.87

Chemically modified Cd(II) 313

U 98.3 6
AN
sugarcane bagasse Pb(II) 313 62.8 6 (Karnitz et al.,
Cu(II 139 14.7 5 2007)

Pristine biomass Pb(II) 19.01 11.56 4.5 (Yu et al.,

M

Cd(II) 3.9 2.42 2007)

Pristine modified biomass Pb(II) 45.87 35.35 4.5 (Yu et al.,

D

Cd(II 11.63 7.65 2007)

Moringa stenopetala seed Cd(II) 23.26 ± 0.21 209.14 ± 1.47 5 (Kebede et al.,
TE

powder Pb(II) 16.13 ± 0.86 280.54 ± 0.42 2018)

Cu(II 10.20 ± 0.93 213.30 ± 2.1

Moringa stenopetala bark Cd(II) 38.46 ± 0.21 14.48 ± 1.47 4–5 Current study
EP

powder Pb(II) 35.71 ± 0.86 20.71 ± 0.42

Cu(II 34.48 ± 0.93 12.11± 2.10
755
756
C
AC

33
 ACCEPTED MANUSCRIPT
Figure 1:

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 10:

102

100

98

PT
% Removal

96
Cd
94

RI
Pb

92 Cu

SC
90

88
0 5 10 15 20 25 30 35 40 45

U
Temperature ( ͦC )
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 11:

120

100

PT
80
% Removal

60 Cd

RI
Pb
40 Cu

SC
20

U
0
0 2 4 6 8 10
AN
pH
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 12:

0.18
0.16
A
0.14

PT
0.12
1/qe (g\mg)

0.1
Cadmium

RI
0.08
Lead
0.06
Copper
0.04

SC
0.02
0
0 5 10 15 20

U
1/Ce(L/mg)
AN
M

2
D

1.8
B
1.6
TE

1.4
log qe (mg/g)

1.2
1 Cadmium
EP

0.8 Lead
0.6 Copper
0.4
C

0.2
0
AC

-0.5 0 0.5 1 1.5 2

log Ce (mg/L)
 ACCEPTED MANUSCRIPT
Figure 13:

0.5

0 A
0 50 100 150 200

PT
-0.5

-1
log(qe-qt)

Cadmium

RI
-1.5
Lead
-2 Copper

SC
-2.5

-3

U
-3.5
Time (min)
AN
M

60
D

50
B
TE
t/qt (min g/mg)

40

30 Cadmium
EP

Lead
20
Copper
10
C

0
AC

0 50 100 150 200 250 300 350 400

Time (min)
 ACCEPTED MANUSCRIPT
Figure 14:

PT
Ln(Kd)

3 Cadmium

RI
Lead
2 Copper

SC
1

U
0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/T
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 15:

95.6
95.4

PT
95.2
% Removal

95

RI
94.8
94.6

SC
94.4
94.2
94

U
Cadmium Lead Copper
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Figure 4:

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 5:

10

5
Zeta potential (mV)

0
0 2 4 6 8 10 12 14 16

PT
-5

-10

RI
-15

-20

SC
-25
pH

U
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Figure 6:

120

100

PT
80
% Removal

RI
60 Cd
Pb
40

SC
Cu

20

U
0
0 20 40 60 80 100 120
AN
Metal ion concentration (mg/L)
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Figure 7:

120

100

PT
80
% Removal

Cd

RI
60
Pb

40

SC
Cu

20

U
0
0 0.5 1 1.5 2 2.5 3
AN
Adsorbent mass (g)
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 8:

120

100

80
% Removal

PT
60
Cd
40

RI
Pb
20 Cu

SC
0
0 50 100 150 200 250 300 350 400
Contact time (min)

U
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 9:

120

100

80

PT
% Removal

60 Cd
Pb

RI
40
Cu

20

SC
0
0 50 100 150 200 250 300 350 400

U
Agitation speed (rpm)
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 2:

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Figure 3:

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Highlights

The bark powder form Moringa stenopetala was characterized

PT
The removal efficiency of the bark powder towards Cd (II), Pb (II) and Cu (II) ions has tested

The effects of concentration, dosage, solution pH, contact time and agitation speed were studied

RI
Models: Isotherm, kinetics and thermodynamics ware studied

U SC
AN
M
D
TE
C EP
AC