3.1. Effects of Metal Combinations on EC of AD Effluent
The anaerobic digestate was treated by EC using different combinations of Al and Fe electrodes. At the fixed current of 2 A, the change of electric potential for all combinations of electrodes (Fe–Fe, Al–Al, Al–Fe, and Fe–Al) followed the same pattern that started at 10 V and ended at 20 V during 10 minutes of the EC reaction. Correspondingly, they consumed the same amount of energy (6.5 Wh) to treat 500 mL AD effluent. The anode metal served as the coagulant metal, which dissolved in water via oxidation and formed mono/polyatomic hydroxide complexes [
16]. The cathode reduced water to form H
2 (g) and
OH− accompanied by dissolution and/or deposition of anodic metal [
30]. Correspondingly, these reactions led to occurrence of coagulation, flocculation, and settling during the EC, which formed three distinct layers (liquid phase sandwiched between the foam layer at the top and solid layer at the bottom) in the reactor (
Figure 1b). As the EC reaction continued, formation of flocs became visible, and the turbidity of liquid phase was significantly reduced (
Figure 3). All electrode combinations after the two-step process (10 minutes EC followed by 10 minutes settling) demonstrated very good turbidity removal of more than 90% (
Figure 3), though different electrode combinations also showed a significantly (
P < 0.05) different EC performance from each other. Al–Fe combination had coagulation, flocculation, and settling simultaneously occur during the EC reaction. The following settling step had no significant (
P > 0.05) improvement in turbidity removal of the reclaimed water (
Figure 3). Meanwhile, the EC performance of three other electrode combinations (Fe–Fe, Fe–Al, and Al–Al) indicated that the settling step after EC is necessary to further remove turbidity (
Figure 3).
Considering the effects of different metals used as anode and cathode on turbidity removal during treatment (both EC and settling), it was observed that there were no significant (
P > 0.05) differences between Fe and Al once they served as the anode (
Figure 4c). However, Fe as the cathode outperformed the Al cathode (
Figure 4f). The reclaimed water after EC treatment with Fe–Fe and Al–Fe electrode combinations had a turbidity of 32.6 and 30.9 NTU, respectively, which were significantly (
P < 0.05) lower than those from the treatment with Al–Al and Fe–Al electrode combinations (
Table 2 and
Figure 3). Meanwhile, the pH of the reclaimed water was greatly influenced by anode metal (i.e., Al) that released more hydroxyl ions in the water, which led to much higher pH (8.62 and 8.17) than those (7.46 and 7.82) using Fe as the anode (
Table 2).
Different electrode combinations also influenced removal of other contaminants, especially those associated with the solid particles (e.g., tCOD and TP). All four combinations greatly reduced tCOD and TP in the reclaimed water during EC (
Table 2). Among the combinations, Al–Fe showed a better performance on tCOD removal. The reclaimed water from the treatment of Al–Fe combination had a tCOD of 156.7 mg/L, which was much (
P < 0.05) lower than that in the other three combinations (206.7, 313.3, and 256.7 mg/L for Fe–Fe, Al–Al, and Fe–Al, respectively). As for TP removal, Fe–Fe, Fe–Al, and Al–Fe combinations can reduce TP in the reclaimed water down to less than 1 mg PO
4/L level, which were significantly (
P < 0.05) lower than the treatment with the Al–Al combination (5.6 mg PO
4/L) (
Table 2). The analysis on the effects of individual metals as anode and cathode on tCOD and TP removal further concluded that Fe as cathode had a positive (
P < 0.05) effect on tCOD removal, and Fe and Al used as either anode or cathode had no significant (
P > 0.05) influence on TP removal (
Figure 4a,b,d,e).
In addition, the amount of electrode metal consumed during EC treatment was also recorded (
Table 2). The Al–Fe combination used the smallest amount of metals (0.25 g/L) to carry out the reaction, compared to 0.77, 0.34, and 0.70 g/L for the Fe–Fe, Al–Al, and Fe–Al combinations, respectively. The amount of metal consumed during EC reaction was confirmed using Faraday’s electrolysis equation as follows:
where
m is the mass of electrode consumed (g),
I is the current applied (A),
t is time (second),
M is the molecular weight of the metal (g/mol),
F is Faraday’s constant (96485.33 C/mol), and
z is the number of electrons transferred.
The calculations confirmed the consumption of 0.696 g Fe /L and 0.220 g Al/L during 10 min EC carried out powered by 2 A constant current, which are not significantly different from the weight loss measurements of the electrodes during the EC process.
According to the experimental results, it is apparent that Al–Fe is the best combination in terms of overall EC treatment performance and metal consumption. However, the use of aluminum has the disadvantage of increasing the residual concentration of Al
3+ ions in water. It has been reported that Al
3+ accumulation in drinking water is related with Alzheimer’s disease [
31]. The maximum concentration of Al
3+ in drinking water has been limited to less than 0.2 mg/L (Secondary Drinking Water Standards, USEPA). Therefore, aluminum use needs to be avoided. The Fe–Fe combination was the second best after the Al–Fe combination. There was no significant (
P > 0.05) difference on removal of turbidity and TP between Fe–Fe and Al–Fe, but tCOD removal of Fe–Fe was lower (
P < 0.05) than that of Al–Fe. Considering both environmental health and overall treatment performance, Fe–Fe was selected as the electrode combination for the rest of the study.
3.2. EC Treatment of Water Reclamation and Microorganism Removal
Electrocoagulation using the Fe–Fe electrode combination was studied to elucidate its effects on water quality of the reclaimed water during the treatment process. The results showed that turbidity was quickly removed by 90% in the first 2 minutes and then leveled off for the rest of the EC (
Figure 5a). This phenomenon could be attributed to the characteristics of the AD effluent. The effluent contains big solid particles, cell flocs, and small suspended solids. Surface charge of the big solid particles and cell flocs with a small surface area is relatively less stable and much easier to be neutralized by a small amount of metal coagulants from the EC reaction [
18]. This would be the reason the turbidity of the solution was quickly removed at the beginning of the EC. With the progress of removing big solid particles and cell flocs, small particles (with a much bigger surface area) in the solution demand more coagulants to form flocs and settle down, which took a longer time to be removed. Small suspended particles in the effluent also contributed to the dark color of the solution. As a result, with removing the small particles, the treated effluent started becoming clear. In addition, the settling step clearly demonstrated the benefit on removing the particles and significantly (
P < 0.05) improved the quality of the reclaimed water. At the end of the EC treatment (with both EC and settling), 99.4% of the original turbidity had been removed. A reclaimed water was obtained with a turbidity of 32 NTU (
Figure 5a).
Changes of tCOD, TN, and TP during the treatment process (after the settling) were measured as well (
Figure 5b–d). Similar to the trend of turbidity changes, the tCOD and TP of the treated solution exponentially decreased. The tCOD and TP of the reclaimed water were 336.7 mg/L and 0.5 mg PO
4/L, respectively. The corresponding removal of tCOD and TP was 99.2% and 99.8%. However, TN removal was insignificant during treatment (
Figure 5d), which is similar to a previous study [
9]. Nitrogen-based compounds in the effluent include ammonia, nitrate, and nitrite. Due to the strong electronegativity of nitrogen in these compounds, they are very hydrophilic. EC technology is not able to remove them. An electrooxidation process using boron doped diamond (BDD) electrodes was designed and applied to oxidize the nitrogen compounds and remove the TN in the reclaimed water (the results are presented in the
Supplementary Materials).
The microbial parameters also indicated that the EC treatment significantly (
P < 0.05) removed total coliforms, E. coli, Enterococci, and somatic coliphage in the reclaimed water by 1.52 log, 1.71 log, 1.02 log, and 1.96 log, respectively (
Figure 5e). It is apparent that reduction of the biological indicators is directly correlated with removal of solids and flocs. During EC, microbes were attached and embedded by solid particles and flocs and correspondingly removed by solids settling and floc flotation. This result demonstrated that EC could potentially facilitate removing pathogens during wastewater treatment. Evaluation of human virus and protozoan removal is warranted to examine final reclaimed water quality, which would dictate the type of reuse and the “fit for purpose” applications.
The experimental data also demonstrated that the treatment (10 minutes EC plus 10 minutes settling) had a relatively higher water recovery of 84% compared to another study by Liu et al., which reported 54.9% water recovery using two-stage EC [
9]. There was 420 mL of the reclaimed water and 80 mL of the sludge yielded from 500 mL of the original AD effluent. Water recovery was used to carry out the mass balance in the following technoeconomic analysis.