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Artigo 8 - Drinking Water Treatment Sludge As An Efficient Adsorbent For Heavy Metals Removal
Artigo 8 - Drinking Water Treatment Sludge As An Efficient Adsorbent For Heavy Metals Removal
Research paper
Drinking water treatment sludge as an efficient adsorbent for heavy metals MARK
removal
S.A. Abo-El-Eneina, Ahmed Shebla,⁎, S.A. Abo El-Dahabb
a
Chemistry Department, Faculty of Science, Ain Shams University, Abbassia 11566, Cairo, Egypt
b
Holding Company for Water and Wastewater, Egypt
A R T I C L E I N F O A B S T R A C T
Keywords: Green chemists paid much more attention towards the alternative ways to reutilize waste materials instead of its
Drinking water treatment sludge disposal in a non-ecofriendly manner. In this study, drinking-water treatment sludge (DWTS), which is a by-
Lead cadmium nickel removals product resulted from drinking water treatment plants, was successfully applied as an adsorbent for Pb(II), Cd(II)
Adsorption and Ni(II) removal from wastewater. The physicochemical characteristics of DWTS were investigated using X-ray
Quartz
diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM) and N2 adsorption-desorption
Illite
isotherms.
Albite
The XRD analysis revealed that the DWTS under study consists of quartz and illite phases which had been
reported for their adsorption efficiency. Firing of DWTS at 500 °C causes the appearance of albite phase in
addition to previous ones which enhances the adsorption capacity of these materials. The influence of different
parameters such as firing temperature of DWTS, contact time, pH, DWTS dose and initial metal ions con-
centration on the adsorption of heavy metal ions and, consequently, on their removal were investigated. DWTS
exhibit an adsorption efficiency towards Pb(II) > Cd(II) > Ni(II). The extremely high efficiency of DWTS
towards Pb(II) adsorption can nominate it as a specific low-cost adsorbent for Pb ions.
1. Introduction et al., 2012; Yang and Cui, 2013; Keränen et al., 2015). These heavy
metals are considered as hazardous materials where their toxicity to
Drinking-water treatment sludge (DWTS) is a by-product from the living organisms comes from their tendency to accumulate in living
coagulation-flocculation process using aluminum or iron based salts to tissues since they are not biodegradable causing several health hazards
precipitate clay, colloidal particles, algae and humic substances from like kidney problems, anemia, lung cancer and dyspnoea
water resources. Due to its high production rate and its environmentally (Ahmaruzzaman, 2011; Visa et al., 2012). Therefore, a tremendous
unfavored disposal to landfill, several researchers paid a considerable number of researches deals with the removal of such heavy metals
attention for using this waste material in different applications espe- especially via adsorption process (Bailey et al., 1999; Babel and
cially those of low cost. The chemical composition of DWTS varies Kurniawan, 2003; Ngah and Hanafiah, 2008; Tofighy and Mohammadi,
depending on the source of water under treatment as well as the type of 2015; Castaldi et al., 2015; Isaac et al., 2015; Dobrowolski et al., 2017;
coagulant used. These applications include utilization of DWTS for Azimi et al., 2017).
ceramic products (Zamora et al., 2008; Kizinievic et al., 2013; Mymrin The aim of this study is to get a beneficial use of DWTS as a low cost
et al., 2017), cement and concrete production (Rodríguez et al., 2010; adsorbent for the removal of lead, cadmium and nickel metal ions from
Sales et al., 2011; Hwang et al., 2017) as well as wastewater treatment wastewater.
as an adsorbent for the removal of phenolic compounds (Fragoso and
Duarte, 2012), phosphates (Razali et al., 2007; Piaskowski, 2013), dyes 2. Experimental
from textile industry discharge (Chu, 1999) and heavy metals (Ippolito
et al., 2011; Siswoyo et al., 2014). 2.1. Starting materials
Pollution of water resources by heavy metals such as lead, cadmium
and nickel which are continuously discharged in huge amounts from The material used in this investigation is DWTS waste produced
different growing industrial activities has been recognized (Ribeiro during 4 months from El-Fustat drinking water treatment plant (Egypt).
⁎
Corresponding author.
E-mail address: a_ahmed@sci.asu.edu.eg (A. Shebl).
http://dx.doi.org/10.1016/j.clay.2017.06.027
Received 1 May 2017; Received in revised form 13 June 2017; Accepted 23 June 2017
Available online 27 June 2017
0169-1317/ © 2017 Elsevier B.V. All rights reserved.
S.A. Abo-El-Enein et al. Applied Clay Science 146 (2017) 343–349
Table 1 (XRD) analysis using a stabilized X-ray generator fitted with a copper
Chemical oxide composition of DWTS. target X-ray tube, (Geiger Muller tube). The settings used were tube run
at 30 kV, 15 mA divergence, receiving and scatter solids, 1, 1, cm and 1
Oxide Weight, %
respectively and chart speed 100 C.P.S.
SiO2 36.51 Adsorption–desorption isotherm of purified N2 at 77K was carried
Al2O3 22.21 out using Nova 2000, Quanta Chrome (commercial BET unit). The ex-
Fe2O3 5.65
ternal morphology of DWTS was observed using scanning electron
CaO 2.66
Na2O 1.35 microscope (SEM) FEI Quanta 250 FEG. The heavy metals analysis was
MgO 1.34 examined using Inductive Coupled Plasma (ICP) instrument Perkin
K2O 0.49 Elmer Model: ICP – OES Optima 7300 DV; in which an ICP source
Sulphate as SO3 0.08 consists of a flowing stream of argon gas ionized by an applied radio
Loss on ignition (L.O.I) 28.1
frequency field typically oscillating at 40 MHz; this generates about
6000 to 8000 K which called plasma. The high temperature of the
Its chemical composition is given in Table 1. plasma excites atomic emission efficiently. Ionization of a high per-
centage of atoms produces ionic emission spectra.
2.2. Preparation and firing of DWTS
3. Results and discussion
DWTS was dried at 110 °C for 48 h, and then crushed. The crushed
3.1. Physicochemical characteristics of DWTS
DWTS was fired at different temperatures of 100, 400, 500, 600 and
700 °C for a period of 2 h and then quenched in air.
3.1.1. Chemical composition
The results of chemical analysis of DWTS are given in Table 1 in
2.3. Chemicals terms of oxide composition. It is obvious that DWTS composed mainly
of silica and alumina as a result of precipitated clay as well as coagulant
The synthetic solutions used in this study were prepared from Pb used in the treatment.
(NO3)2 99% produced by LOBA Chemie, Cd(NO3)2·4H2O 99% produced
by LOBA Chemie and Ni(NO3)2·6H2O 98% produced by Oxford la-
3.1.2. X-ray diffraction analysis
boratory reagent. Solutions of 0.1 M nitric acid and ammonium hy-
The mineral composition of DWTS, fired at different temperatures,
droxide were used to adjust pH.
was identified by means of XRD analysis as shown in Fig. 1. The results
indicate the presence of quartz and illite phases in all samples while
2.4. Batch adsorption experiments albite phase appears additionally at 500 °C. It had been recorded in
previous researches the potential application of quartz- silicon oxide-
Batch adsorption experiments including the effects of firing tem- (Tikhomolova et al., 2001; Reich et al., 2010; Al-Anber, 2010; Bellucci
perature, contact time, adsorbent dosage, initial metals concentration et al., 2015) and illite (Ozdes et al., 2011; Benedicto et al., 2014a,
and initial solution pH were studied. Batch experiments were carried 2014b; Cui et al., 2015) in heavy metal removal as adsorbents. Illite is a
out at room temperature by addition of known weight of burnt DWTS clay mineral of the layer type 2:1. It has the general formula of
into a number of 100 mL glass stoppered conical flasks on a rotary KyAl4(Si8−y, Aly)O20(OH)4, usually with 1 < y < 1.5, and composed
shaker at 200 rpm containing individual 50 mL of nitrate solutions of of two silica tetrahedral sheets that sandwich an alumina octahedral
Pb(II), Cd(II) or Ni(II) (100 mg/L) in distilled water. sheet (Alvarez-Puebla et al., 2005; Hongxia et al., 2016). The efficiency
The effect of firing temperature was conducted to DWTS by shaking of illite as an adsorbent for heavy metal ions is ascribed to ion exchange
0.5 g of DWTS, after burning at different temperatures (100, 400, 500, reaction with its potassium ions that are trapped in its interlayer spaces;
600 and 700 °C), with 50 mL of the individual nitrate solutions of Pb as well as inner-sphere complexes formation through ^SieO− and
(II), Cd(II) or Ni(II) (100 mg/L) in distilled water for 24 h. The effect of ^AleO− groups are located at the edges (McBride, 1994; Sheng et al.,
contact time was conducted by shaking 0.5 g of burnt DWTS at op- 1999; Celis et al., 2000; Gu and Evans, 2007).
timum firing temperature and individual nitrate solutions of Pb, Cd or
Ni (100 mg/L) in distilled water for different time intervals of 2, 4, 6, 8,
Q+I
12 and 24 h. The effect of initial pH was performed by shaking 0.5 g of
burnt DWTS at optimum conditions of firing temperature and contact I
Q I I I 700 C
o
time and individual nitrate solutions of Pb, Cd or Ni (100 mg/L) at
different initial pH values of 3, 4, 5, 6, 6.5, 7, 7.5, 8 in addition to
original pH value of metal nitrate solution.
The effect of adsorbent dosage was conducted by adding desired o
600 C
amounts of burnt DWTS (0.5, 1, 1.5 and 2 g) at the optimum conditions
Intensity
tions of 100, 200, 300, 450 and 650 mg/L in distilled water. Effect of
competitive adsorption at the optimum conditions was also carried out
by mixing groups of Pb(II)-Cd(II), Pb(II)-Ni(II) and Pb(II)-Cd(II)-Ni(II) o
at different initial concentrations of 200 and 450 ppm. 100 C
10 20 30 40 50 60
2.5. Methods for physicochemical characterization
2 θ (deg.)
DWTS was characterized by X-ray fluorescence (XRF) technique Fig. 1. XRD analysis of the DWTS fired at different temperatures. (Q = quartz, I = illite
using Pnanalytical Axios advanced XRF; as well as X-ray diffraction and A = albite).
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S.A. Abo-El-Enein et al. Applied Clay Science 146 (2017) 343–349
Table 2
Surface area and pore structure characteristics of DWTS after thermal treatment at 100, 500 and 700 °C.
Temperature (°C) SBET C constant Vp (mL/g) Mean pore radius (Å) St (m2/g) Most probable radius (Å)
radius of narrow pores can be calculated (Fig. 2a); meanwhile, the ra-
dius of wider pores can be calculated from the relative vapor pressure of 80
0.70 where capillary condensation takes place where the radii of
narrow entrance and wider body could be calculated by using Kelvin 60
equation (Abo-El-Enein et al., 1974).
However, thermal treatment of the DWTS at 500 °C resulted in a sort
40
of pore opening as indicated by the wider hysteresis loop which is
closed at a relative vapor pressure of 0.35 just after the formation of the
first adsorbed layer (monolayer capacity), (Fig. 2b), with a consequent 20
increase in the specific surface area of the DWTS heated at 500 °C,
(Table 2).Therefore, a large number of pores become accessible for the
0
removal of a larger fraction of pollutants as reported later in this study 0.0 0.2 0.4 0.6 0.8 1.0
(Fig. 4).
Moreover, thermal treatment of the DWTS at 700 °C resulted in a P/Po
sort of sintering with a consequent decrease in the specific surface area 140
where mesopores become more dominant; mesopores possess lower (c)
surface areas and larger pore volumes as compared with micropores 120
(Fig. 2c). This could be clearly distinguished from the results of Table 2.
Therefore, the percentage removal of pollutants by the DWTS after
Volume adsorbed (cc/g)
100
thermal treatment at 700 °C decreases as reported later in this study
(Fig. 4). 80
345
S.A. Abo-El-Enein et al. Applied Clay Science 146 (2017) 343–349
100
90
80
70
Removal (%)
60
50
40
30
20 Pb
Cd
10 Ni
0
100 200 300 400 500 600 700 800
Firing Temperature (oC)
Fig. 4. Effect of firing temperature of DWTS on the removal percent of metal ions (metal
ion conc. = 100 ppm; adsorbent dose = 0.5 g; solution volume = 50 ml; contact
time = 24 h; temperature = 25 ± 2 °C; agitation speed = 200 rpm; pH = 5.5).
100
Fig. 3. SEM images of DWTS heated at a) 100 °C, b) 500 °C and c) 700 °C.
80
such a structure leads to an increase in the surface area available for
adsorption of larger amounts of metal ions from their aqueous solution.
Removal (%)
60
These SEM micrographs are also confirmed by the increase in surface
area available for the removal of metal ions; the contents of pore size
distribution proved that the pore system is composed mainly of meso-
40
pores which are accessible for adsorption of larger amounts of metal
ions.
Thermal treatment of DWTS at 700 °C, however, the results of SEM Pb
20
micrograph displayed the presence of quartz and illite phases in addi- Cd
tion to algae and diatoms with the disappearance of albite phases Ni
within a noticeable decrease in surface area available to the removal of
0
small fraction of metal ions as confirmed by the results of pore structure 0 5 10 15 20 25
which indicated assort of pore narrowing with consequent decrease in
Time (Hours)
the fraction of mesopores which are accessible to the removal of metal
ions, Fig. 3c. Fig. 5. Effect of contact time on the removal percent of metal ions (metal ion
conc. = 100 ppm; adsorbent dose = 0.5 g; adsorbent firing temperature = 500 °C; solu-
tion volume = 50 ml; temperature = 25 ± 2 °C; agitation speed = 200 rpm; pH = 5.5).
346
S.A. Abo-El-Enein et al. Applied Clay Science 146 (2017) 343–349
100 100
90
80 80
70
Removal (%)
60
Removal (%)
60
50
40
40
30
Pb
20
Cd Pb
10 Ni 20
Cd
0 Ni
3 4 5 6 7 8 9
0
pH 0.5 1.0 1.5 2.0
Fig. 6. Effect of initial solution pH on the removal percent of metal ions (metal ion Dose (g)
conc. = 100 ppm; adsorbent dose = 0.5 g; adsorbent firing temperature = 500 °C; so-
lution volume = 50 ml; contact time = 4 h; temperature = 25 ± 2 °C; agitation Fig. 7. Effect of burnt DWTS dose on the removal percent of metal ions (metal ion
speed = 200 rpm). conc. = 100 ppm; adsorbent firing temperature = 500 °C; solution volume = 50 ml;
contact time = 4 h; temperature = 25 ± 2 °C; agitation speed = 200 rpm; pH = 5.5).
60
3.2.3. Effect of pH 50
Fig. 6 shows the effect of solution pH on the removal percent of 40
metal ions using 0.5 g of DWTS fired at the optimum firing temperature
30
of 500 °C and contact time of 4 h. The metal ions removal percent in-
Pb
creases by increasing the pH value of the solution. This could be ex- 20
Cd
plained as follows: at lower pH the protonation takes place on the Ni
10
DWTS surface blocking the active sites available for positive metals ions
adsorption while as pH value increases the protonation will be de- 0
100 200 300 400 500 600 700
creased and the negative charges on DWTS surface will be more ex-
posed resulting in electrostic attraction towards positive metal ions in Concentration (ppm)
solution. Fig. 8. Effect of initial metal ions concentration on the removal percent of metal ions
(adsorbent dose = 2 g; adsorbent firing temperature = 500 °C; solution volume = 50 ml;
3.2.4. Effect of burnt DWTS dose contact time = 4 h; temperature = 25 ± 2 °C; agitation speed = 200 rpm; pH = 5.5).
347
S.A. Abo-El-Enein et al. Applied Clay Science 146 (2017) 343–349
Table 3
Removal percent of Pb(II), Cd(II) and Ni(II) in binary and tertiary mixtures.
At 200 ppm At 450 ppm At 200 ppm At 450 ppm At 200 ppm At 450 ppm
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