2.2. Effect of pH
The behavior of heavy metals in solution (such as hydrolysis, complexation or precipitation) is influenced by its pH value. Additionally, the initial pH of the solutions with metal ion content plays an important role in the adsorption process due to the fact that it influences both the species of the metal present in the solution and the surface of the adsorbent. For this reason, the pH effect upon the adsorption performance of the sewage sludge ash in the removal process of lead and copper ions from aqueous solutions were discussed.
At pH higher than 7, the lead ions are efficiently removed from solution, but in this case were not removed due to an adsorption process but were removed due to precipitation process according to the potential–pH diagram for Pb ions in water systems [
23,
24,
25,
26]. Dissolved ionic species present at pH values higher than 7 are Pb(OH)
+ (aq), Pb
4(OH)
44+ (aq) and Pb(OH)
2. Cu
2+ is a copper predominant species at pH < 5.00, and for pH values higher than 5.00, species such as CuOH
+ (aq), [Cu
2(OH)
2]
2+ (aq) and Cu(OH)
2 (aq) are present [
15,
26]. The variation in pH between 2 and 7 avoided the precipitation of Pb (II) and Cu (II).
The pH has a strong influence on the sorption of Pb (II) and Cu (II) on the SSA because H
+ ions can compete adsorption sites with Pb
2+ and Cu
2+. The effect of the initial pH on the adsorption capacity and removal rate of Pb (II) and Cu (II) in single system is presented in
Figure 2.
The adsorption of Cu (II) at pH = 2 was negligible while for Pb (II) the adsorption capacity was 0.53 mg/g SSA. The adsorption capacity increased for both of Pb (II) and Cu (II) with the increase of the initial pH. For Pb (II) the plateau was reached after pH = 3 when the adsorption capacity was 2.49 mg/g SSA. On the other hand, the adsorption capacity for Cu (II) continued to increase with the increase of the initial pH reaching the maximum of 2.49 mg/g SSA at pH = 7. Therefore, the pH = 6 was considered to deliver the best performance for both metals. Similar results were obtained when the polypyrrole-based activated carbon, sawdust and rice husks were used as adsorbents for the removal of Pb, and the maximum adsorption capacity occurring at pH = 5–6.5 [
27,
28,
29]. Additionally, the removal of copper took place at an initial pH value close to 6 when bottom ash of expired drug incineration, and shells of lentil, wheat and rice were used as adsorbents [
30,
31,
32].
2.4. Kinetic Studies
Kinetic studies were used to determine the optimum necessary time to establish the equilibrium between SSA and Pb (II) and Cu (II) in single and binary systems. The effect of contact time on the adsorption of Pb (II) and Cu (II) in single and binary systems is presented in
Figure 4.
The adsorption process occurred already in the first minutes of contact between SSA and both metals in single and binary systems. After 210 min, the adsorption capacity rate decreased. Comparing the adsorption in single and binary systems, the latter one became slower in the presence of the competitive metal ion. For example, the adsorption capacity for Pb (II) in single system at 210 min was 9.87 mg/g, and the adsorption capacity for Pb (II) in the presence of Cu (II) dropped to 4.80 mg/g. Additionally, the adsorption capacity for Cu (II) in single system at 210 min was 3.49 mg/g and dropped to 1.57 mg/g in the presence of Pb (II).
The adsorption kinetics that describe the removal rate of the studied metal ions is an important feature that defines the efficiency of the adsorption process. In order to determine the mechanism of adsorption of metal ions on the studied material, the experimental data were processed using the pseudo-order kinetic model one, the pseudo-order kinetic model and intraparticle diffusion model. The kinetic models used to stimulate the kinetics of Pb (II) and Cu (II) in single and binary systems on the SSA are presented in
Figure 5.
The kinetic parameters together with the obtained correlation coefficients are presented in
Table 2. The results showed that the values of correlation coefficient for both single and binary systems were higher for the pseudo-second-order kinetic model than those obtained for pseudo-first-order kinetic model. Additionally, the calculated adsorption capacities for the pseudo-second-order kinetic model remained similar to the experimentally reported ones.
Following the analysis of the plots according to the intraparticle diffusion kinetic model (
Figure 5e,f, it can be observed that the straight line does not pass through origin. Therefore, the rate-limiting step for Pb (II) and Cu (II) adsorption is not the intraparticle diffusion model. Additionally, the line presents a discontinuity after a while, suggesting that the adsorption process is more complex. The fast adsorption of Pb (II) and Cu (II) in the first minutes was due to the film diffusion when the sewage sludge ash surface was covered by Pu (II) and Cu (II) ions. The second straight line obtained through the representation of q
t versus t
1/2 suggested that after the surface coverage, the transport of Pb (II) and Cu (II) ions inside the sewage sludge ash occurred [
33].
Therefore, the pseudo-second-order kinetic model can be used to simulate the experimental data regarding Pb (II) and Cu (II) adsorption in single and binary systems using SSA as an adsorbent. Nevertheless, this means that the process is controlled by chemical sorption [
34,
35].
2.5. Equilibrium Studies
Figure 6 displays the dependence of the adsorption capacities as a function of the Pb (II) and Cu (II) concentrations at equilibrium. Increasing the initial concentration of Pb (II) and Cu (II) increased the active sites available, and therefore the adsorption capacity increased. The maximum q
e during Pb (II) and Cu (II) removal was 25 mg/g and 7.5 mg/g, respectively.
In order to achieve the design of this adsorption study, the maximum adsorption capacity of SSA, the equilibrium coefficient and the adsorption mechanism must be considered. Therefore, several isotherms in their linear form were studied: Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (DR). The Langmuir isotherm states that the adsorption process takes place in a single layer on a uniform surface and equivalent sites of the adsorbent. The Freundlich isotherm expresses the affinity of the adsorbent to the metals, while the Temkin isotherm states that the surface of the adsorbent is heterogenous.
In order to design the equilibrium adsorption regarding Pb (II) and Cu (II) removal using sewage sludge ash as an adsorbent, the linear graphs and the equilibrium sorption isotherms were plotted and can be consulted in
Figure 7 and
Table 3 respectively. By comparing the results from
Table 3 it can be concluded that both Pb (II) and Cu (II) removal from aqueous solutions occurred as a monolayer at the uniform surfaces of the SSA because the Langmuir isotherm obtained the highest regression coefficients (0.999 for Pb (II) and 0.998 for Cu (II)). Further, there was no significant difference between the maximum adsorption capacity determined experimentally and those calculated from its plot for both Pb (II) and Cu (II). The lowest regression coefficients were obtained for DR isotherms. Likewise, a difference for the qs parameter can be as well observed when comparing the values of the theoretically determined to the ones experimentally obtained.
2.6. Adsorption Mechanism and Performance
The overlapped XRD spectra of the SSA after Pb (II), Cu (II) and binary adsorption presented in
Figure 8 show the formation of new crystalline phases. After Pb (II) and Cu (II) adsorption, quartz and hematite remained in the SSA. Calcium phosphate was also present in the SSA, yet the peak at 2θ = 28° could not be identified anymore.
Furthermore, after Pb (II) adsorption, new peaks associated with lead phosphate (Pb2P2O7) could be identified. After Cu (II) adsorption, new peaks associated with copper oxide (CuO) could be detected. The binary system adsorption led to the identification of the lead silicate (Pb2SiO4) and copper oxide (CuO) peaks. These new crystalline phases identified by XRD confirmed that chemical reactions between SSA and Peb (II) and Cu (II) took place and also suggested that Ca–P bound in the SSA was partially broken.
Wang et al. [
14] studied the adsorption of lead using incinerated sewage sludge ash as an adsorbent and identified new crystalline phases, suggesting the precipitation of lead as PbSO
4. Nevertheless, the adsorption of copper in single and binary systems (Cu–Zn, Cu–Cd) [
15] did not show any new crystalline phases.
The micrographs displayed in
Figure 9 show a topographical change following the adsorption of Pb (II) and Cu (II) in both single and binary systems. The surface was much denser, and uniformly sized crystalline phases were formed as agglomerates in a much more regular way. Additionally, the EDX spectra presented in
Figure 9 shows the presence of Pb and Cu after adsorption on the surface of the SSA.
The adsorption capacity and concentrations of Ca, K and Mg after sorption experiments for both Pb (II) and Cu (II) for 10, 75 and 150 mg/L are presented in
Table 4. The adsorption capacity of Pb (II) was considerably higher than for Cu (II) due to the electronegativity of Pb
2+ and Cu
2+. Stronger attraction occurred between adsorbent and metal ion with higher electronegativity values (Pb: 2.33 and Cu: 1.95) [
36]. Additionally, the smaller the hydrated ionic radius, the greater the affinity of the metal for the adsorption process (Pb: 4.01 Å and Cu: 4.19 Å) [
37]. Therefore, it can be stated that the adsorption affinity of Pb (II) is higher than that of Cu (II).
Additionally, another important aspect in order to evaluate the adsorption mechanism is to note that higher adsorption capacities and higher concentrations of Pb (II) and Cu (II) led to higher concentrations of Ca, Mg and K in solutions after sorption experiments. This suggests that the adsorption mechanism of Pb (II) and Cu (II) by SSA is associated with cationic exchange. When the Cu (II) concentration was increased from 10 mg/L to 150 mg/L, the concentrations of Ca, K and Mg increased from 4.80 mg/L, 0.470 mg/L and 0.190 mg/L to 4.92 mg/L, 0.580 mg/L and 0.240 mg/L, respectively. For the same initial concentration of Pb (II) and Cu (II), the adsorption capacity and Ca, K and Mg concentration at equilibrium were higher for Pb (II).
Higher concentration of cations (Ca
2+, Mg
2+, K
+) in solution after sorption experiments led to higher values of final pH (
Figure 10). The final pH value at the end of the process led to an increase from 3 to 7.55 for Pb (II) and from 3.1 to 7.2 for Cu (II). The alkali properties of the sewage sludge ash and the neutralization effect on aqueous solutions could be noticed.
Correlating the results from RX diffractograms, SEM images and EDX spectra with the changes in final pH and in cation concentrations in solution after sorption experiments, it can be concluded that the heavy metal ion adsorption process onto SSA is controlled by chemisorption involving cation exchange.
Likewise, the pseudo-second-order kinetic model indicates that the process is controlled by chemisorption involving cation exchange. Wang et al. [
15] also indicated that the primary adsorption mechanism of the studied heavy metal ions (Cu, Zn and Cd) by the incinerated SSA (ISSA) was cation exchange.
In order to determine if the SSA is a reliable adsorbent for Pb (II) and Cu (II) removal and to evaluate the potential environmental risk, due to the presence of metals in the sewage sludge ash [
22], the influence of pH on the metal leaching of the SSA was investigated.
Table 5 presents the results regarding the leaching of metals from SSA under different values of pH. As expected, the lower the pH was, the higher was the concentration of metals leached. For pH = 2, the concentrations of Zn, Mn and Al were 0.98 mg/L, 3.41 mg/L and 13.6 mg/L, respectively. For pH = 3, the concentration of Zn was 0.18 mg/L, and for Mn it was 0.27 mg/L. As the pH increased, the concentrations of leached metals decreased to values lower than 0.15 mg/L. At pH = 6, the amount of metals leached from SSA was negligible. Therefore, the SSA is a reliable adsorbent with low environmental risk.
The adsorption performances of the sewage sludge ash in the removal of process of Pb (II) and Cu (II) from aqueous solutions were compared with the adsorption capacities developed by other wastes reported in the literature. The comparison of the values (
Table 6) show that the sewage sludge ash can be efficiently used as a high performance adsorbent for wastewater treatment.