In spite of more effective removal of algae with the higher current density, increasing the current density could also lead to the
increase of applied potential, which resulted in the sharp increase
of the energy consumption of the ECF system (Eq. (12)). According
to Fig. 5, it could be observed that as current densities varied from
0.5 to 5.0 mA/cm2, the energy consumption increased dramatically
from 0.20 to 2.28 kWh/m3 , correspondingly.
Therefore, it might be important to optimize the current input
for the ECF process, to avoid the post pH adjustment and extrahigher energy consumption. In this investigation, the current
density of 1 mA/cm2 was found to be the optimum value when
considering the energy consumption, the removal efficiency, and
the effluent pH simultaneously.
3.3. Effect of initial pH
It has been long recognized that the solution pH is one of the
key parameters influencing the performance of ECF process [12,16].
Initial pH exhibited different effects on the ECF for different target
pollutants, such as turbidity and Eriochrome Black T [8,17]. However, the influence of pH for algae removal has not been made clear
yet. Thus, in this study, the effect of initial pH on the algae removal
was also examined, with the pH varied in the range of 4–10.
Fig. 5. Electrical energy consumption as a function of current density for complete
removal of algae. Conditions: room temperature; initial pH, 7.0; volume, 1.0 dm3 ;
initial cell density 1.2 × 109–1.4 × 109 cells/L.
Fig. 6. Removal efficiency of algae as a function of electrolysis time with different initial pH. Conditions: room temperature; current density, 1 mA/cm2 ; volume,
1.0 dm3 ; initial cell density, 1.2 × 109–1.4 × 109 cells/L.
From Fig. 6, it could be found that low initial pH was beneficial to
algae removal. For the first 15 min, the ECF exhibited low efficiency
for the algae removal when initial pH was in the alkaline range.
The treatment efficiency decreased with the increase of initial pH.
When tECF = 55 min, the ECF removed the algae in the raw water
completely with the pH of 4–7; while the removal efficiencies were
99%, 90% and 87.2% when initial pH was 8, 9 and 10, respectively.
It was observed from Fig. 6 that the algae removal could
be improved by decreasing the initial pH and/or increasing the
electrolysis time. This might be explained by the aluminumspecies in the solution, which relies significantly on the pH
and aluminum concentration according to the concentrationpH aluminum-species diagram [35]. In acidic and neutral pH
range (4–7), aluminum hydroxide precipitates and monomerichydroxoaluminum cations, as well as polymeric species such as
Al13 O4(OH)247+ are the primary species in the solution according
to [40]. As a result, positively charged precipitates could be formed
(i.e. aluminum hydroxide together with the adsorbed hydroxoaluminum cations). Therefore, the negatively charged algae would
be easily adsorbed onto the positively charged precipitates, which
facilitated the removal of algae through subsequent flotation.
In alkaline conditions, monomeric-hydroxoaluminum anions
dominated in solution, which led to negative charges of the aluminum hydroxide precipitates [8], and consequently reduced the
adsorption capacity of negatively charged algae. Thus, the ECF
exhibited worse algae removal under alkaline condition as compared with that under acid and neutral conditions. Nevertheless,
as the electrolysis time increased, the efficiency of algae removal
improved significantly as a result of the sweeping and enmeshment
effect through the continuous generation of aluminum coagulants.
The results obtained in this investigation were similar to that
obtained by Zhu et al. for the virus removal [36].
To better understand the removal mechanisms of algae in the
above experiments, two samples of algal flocs with the similar
removal efficiency (about 70%) were collected for AFM analysis.
As shown in Fig. 7a, the fresh algae cells before ECF treatment
appeared to have smooth surface; while after ECF treatment under
initial pH of 6, a number of small floccules were adsorbed on the
algae (Fig. 7b), which was due to the charge neutralization between
the positively charged floccules and the negatively charged algae.
Fig. 7c shows that the treated algae were covered almost completely
with a large amount of flocs under the initial pH of 9; thus the algae
cells were considered to be removed through the mechanism of
sweeping flocculation and enmeshment.
340 S. Gao et al. / Journal of Hazardous Materials 177 (2010) 336–343
Fig. 7. AFM topographic images of algal flocs, scan rate: 0.5003 Hz. (a) Algae in
fresh culture before treatment, (b) after ECF treatment, conditions: initial pH, 6; current density, 1 mA/cm2 ; electrolysis time, 5 min; effluent pH, 7.4; the algae removal
efficiency, 70.2% (c) after ECF treatment, conditions: initial pH, 9; current density,
1 mA/cm2 ; electrolysis time, 35 min; effluent pH, 8.9; the algae removal efficiency,
71.4%.
Besides, variation of the solution pH during the ECF process was
investigated. It could be observed in Fig. 8 that when the initial pH
was 4–8, the solution pH increased gradually with the electrolysis
time. The increase of pH was mainly due to the continuous formation of OH− ions at the cathode as a consequence of the H2 evolution
process (Eq. (4)). In addition, Eq. (3) would shift towards the left,
which could also lead to the increase of pH [41]. On the other hand,
when the initial pH was increased to 9 and 10, a slight decrease of
the pH was observed at the beginning, which might be explained
by the consumption of OH− as a consequence of the formation of
Al(OH)4− ; and then almost a constant pH level was maintained,
probably due to the buffer effect of Al(OH)3 /Al(OH)4− (Eq. (13)).
Al(OH)3 + OH− ↔ Al(OH)4− (13)
As shown in Fig. 6, when the initial pH varied in the range of
4–7, the electrolysis time for complete algae removal was 45 min
under the experimental conditions. Thus, the energy consumption
was almost constant at the level of about 0.3 kWh/m3 (Fig. 9). However, as the initial pH further increased from 7 to 9, the electrolysis
time for complete algae removal increased from 45 to 75 min correspondingly, which led to the increase of energy consumption
Fig. 8. Variation of pH as a function of electrolysis time at different initial pH. Conditions: room temperature; current density, 1 mA/cm2 ; volume, 1.0 dm3 ; initial cell
density 1.2 × 109–1.4 × 109 cells/L.
from 0.29 to 0.53 kWh/m3 . On the other hand, the similar energy
consumption was observed for the initial pH values of 9 and 10
(0.53 kWh/m3 vs. 0.60 kWh/m3 ), mainly due to the same electrolysis time of 75 min required for complete algae removal.
In conclusion, higher efficiency of algae removal could be
obtained in acidic and neutral conditions. With lower pH, low
aluminum dosage would be required for algae removal through
the charge neutralization mechanism; while at higher pH, higher
aluminum dosage was needed to achieve the similar removal
efficiency, through the mechanism of enmeshment and sweeping flocculation. And both coagulation mechanisms were equally
important for algae removal in ECF process.
3.4. Effect of initial algae cell density
In natural waters, different algae cell densities might occur in
different regions and different seasons. Thus, the effectiveness of
ECF for algae removal with different initial algae cell densities was
evaluated. Fig. 10 shows the influence of initial cell density on
algae removal, which decreased notably with the increase of cell
density. This behavior could be attributed to the fact that no sufficient aluminum was available for the removal of excessive algae
cells with short electrolysis time. Furthermore, the reaction rate
Fig. 9. Electrical energy consumption as a function of initial pH for complete
removal of algae. Conditions: room temperature; current density, 1 mA/cm2 ; volume, 1.0 dm3 ; initial cell density 1.2 × 109–1.4 × 109 cells/L.
S. Gao et al. / Journal of Hazardous Materials 177 (2010) 336–343 341
Fig. 10. Removal efficiency of algae as a function of electrolysis time with different
initial cell densities. Conditions: initial pH, 7.0; current density, 1 mA/cm2 ; volume,
1.0 dm3 .
decreased when the initial cell density was increased according
to Emamjomeh and Sivakumar [42]. The similar results were also
obtained by Ghosh et al. [43].
In the experiments, when the cell densities were 0.55 × 109,
1.10 × 109, 1.55 × 109 and 2.10 × 109 cells/L, the energy consumption of the ECF process for complete algae removal were 0.20, 0.21,
0.30 and 0.26 kWh/m3 , respectively. The initial cell density did not
seem to greatly influence the energy consumption.
Fig. 11. Removal efficiency of algae as a function of electrolysis time under different
temperature. Condition: initial pH, 7.0; current density, 1 mA/cm2 ; volume, 1.0 dm3 ;
initial cell density 1.2 × 109–1.4 × 109 cells/L.
3.5. Effect of temperature
Water temperature is one of the most important environmental factors that might influence algae removal in the ECF. However,
previous studies showed that water temperature exerted different
effects on electrocoagulation for the removal of different pollutants [44,45]. Thus, it is necessary to examine the effect of water
temperature on algae removal. As shown in Fig. 11 , it was found
Fig. 12. SEM-EDX analysis of the algal flocs produced by ECF. (a and b) SEM micrograph at different magnifications; EDX analysis of elemental compositions (c) on the algae
cells and (d) on the agglutinant.
342 S. Gao et al. / Journal of Hazardous Materials 177 (2010) 336–343
Table 1
Elemental composition and relative contents of atoms on the flocs by SEM-EDX analysis.
Element CK NK OK AlK PK SK NaK FeK MgK Total
Spectrum 1 65.40% 9.49% 16.17% 3.78% 2.99% 1.21% 0.36% 0.49% 0.11% 100%
Spectrum 2 42.57% 9.85% 22.15% 14.27% 6.89% 2.05% 0.55% 1.39% 0.28% 100%
that the algae removal was dramatically improv
แม้ว่าการเพิ่มประสิทธิภาพการกำจัดสาหร่ายที่มีความหนาแน่นของกระแสสูง เพิ่มความหนาแน่นปัจจุบันอาจยังทำการเพิ่มศักยภาพใช้ ซึ่งมีผลในการเพิ่มความคมชัดปริมาณการใช้พลังงานของระบบ ECF (Eq. (12)) ตามการ Fig. 5 มันสามารถถูกสังเกตที่เป็นปัจจุบันความหนาแน่นที่แตกต่างกันจาก0.5-5.0 mA/cm2 ปริมาณการใช้พลังงานที่เพิ่มขึ้นอย่างมากจาก 0.20 จะไม่ 2.28/m3 ตามลำดับดังนั้น มันอาจจะต้องเพิ่มประสิทธิภาพการป้อนข้อมูลปัจจุบันใน ECF กระบวนการ การหลีกเลี่ยงการลงค่า pH extrahigher และปรับปรุงการใช้พลังงาน ในการสอบสวนนี้ ปัจจุบันพบความหนาแน่นของ 1 mA cm2 จะ มีประสิทธิภาพสูงสุดมูลค่าเมื่อพิจารณาการใช้พลังงาน ประสิทธิภาพกำจัด และค่า pH น้ำทิ้งพร้อมกัน3.3. ผลของ pH เริ่มต้นมันได้รับนานรู้ว่า pH โซลูชันเป็นหนึ่งในพารามิเตอร์หลักที่มีอิทธิพลต่อประสิทธิภาพของกระบวนการ ECF [12,16]ค่า pH เริ่มต้นจัดแสดงลักษณะพิเศษต่าง ๆ ใน ECF สำหรับเป้าหมายที่แตกต่างกันสารมลพิษ ความขุ่นและ Eriochrome ดำ T [8,17] อย่างไรก็ตาม อิทธิพลของค่า pH สำหรับกำจัดสาหร่ายไม่ได้ชัดเจนยัง ดังนั้น ในการศึกษานี้ ผลของ pH เริ่มต้นกำจัดสาหร่ายยังตรวจสอบ มีค่า pH ที่แตกต่างกันในช่วง 4 – 10Fig. 5 การใช้พลังงานไฟฟ้าเป็นฟังก์ชันของความหนาแน่นของกระแสการดำเนินกำจัดสาหร่าย เงื่อนไข: อุณหภูมิห้อง ค่า pH เริ่มต้น 7.0 ปริมาตร 1.0 dm3initial cell density 1.2 × 109–1.4 × 109 cells/L.Fig. 6. Removal efficiency of algae as a function of electrolysis time with different initial pH. Conditions: room temperature; current density, 1 mA/cm2 ; volume,1.0 dm3 ; initial cell density, 1.2 × 109–1.4 × 109 cells/L.From Fig. 6, it could be found that low initial pH was beneficial toalgae removal. For the first 15 min, the ECF exhibited low efficiencyfor the algae removal when initial pH was in the alkaline range.The treatment efficiency decreased with the increase of initial pH.When tECF = 55 min, the ECF removed the algae in the raw watercompletely with the pH of 4–7; while the removal efficiencies were99%, 90% and 87.2% when initial pH was 8, 9 and 10, respectively.It was observed from Fig. 6 that the algae removal couldbe improved by decreasing the initial pH and/or increasing theelectrolysis time. This might be explained by the aluminumspecies in the solution, which relies significantly on the pHand aluminum concentration according to the concentrationpH aluminum-species diagram [35]. In acidic and neutral pHrange (4–7), aluminum hydroxide precipitates and monomerichydroxoaluminum cations, as well as polymeric species such asAl13 O4(OH)247+ are the primary species in the solution accordingto [40]. As a result, positively charged precipitates could be formed(i.e. aluminum hydroxide together with the adsorbed hydroxoaluminum cations). Therefore, the negatively charged algae wouldbe easily adsorbed onto the positively charged precipitates, whichfacilitated the removal of algae through subsequent flotation.In alkaline conditions, monomeric-hydroxoaluminum anionsdominated in solution, which led to negative charges of the aluminum hydroxide precipitates [8], and consequently reduced theadsorption capacity of negatively charged algae. Thus, the ECFexhibited worse algae removal under alkaline condition as compared with that under acid and neutral conditions. Nevertheless,as the electrolysis time increased, the efficiency of algae removalimproved significantly as a result of the sweeping and enmeshmenteffect through the continuous generation of aluminum coagulants.The results obtained in this investigation were similar to thatobtained by Zhu et al. for the virus removal [36].To better understand the removal mechanisms of algae in theabove experiments, two samples of algal flocs with the similarremoval efficiency (about 70%) were collected for AFM analysis.As shown in Fig. 7a, the fresh algae cells before ECF treatmentappeared to have smooth surface; while after ECF treatment underinitial pH of 6, a number of small floccules were adsorbed on thealgae (Fig. 7b), which was due to the charge neutralization betweenthe positively charged floccules and the negatively charged algae.Fig. 7c shows that the treated algae were covered almost completelywith a large amount of flocs under the initial pH of 9; thus the algaecells were considered to be removed through the mechanism ofsweeping flocculation and enmeshment.340 S. Gao et al. / Journal of Hazardous Materials 177 (2010) 336–343Fig. 7. AFM topographic images of algal flocs, scan rate: 0.5003 Hz. (a) Algae infresh culture before treatment, (b) after ECF treatment, conditions: initial pH, 6; current density, 1 mA/cm2 ; electrolysis time, 5 min; effluent pH, 7.4; the algae removalefficiency, 70.2% (c) after ECF treatment, conditions: initial pH, 9; current density,1 mA/cm2 ; electrolysis time, 35 min; effluent pH, 8.9; the algae removal efficiency,71.4%.Besides, variation of the solution pH during the ECF process wasinvestigated. It could be observed in Fig. 8 that when the initial pHwas 4–8, the solution pH increased gradually with the electrolysistime. The increase of pH was mainly due to the continuous formation of OH− ions at the cathode as a consequence of the H2 evolutionprocess (Eq. (4)). In addition, Eq. (3) would shift towards the left,which could also lead to the increase of pH [41]. On the other hand,when the initial pH was increased to 9 and 10, a slight decrease ofthe pH was observed at the beginning, which might be explainedby the consumption of OH− as a consequence of the formation ofAl(OH)4− ; and then almost a constant pH level was maintained,probably due to the buffer effect of Al(OH)3 /Al(OH)4− (Eq. (13)).Al(OH)3 + OH− ↔ Al(OH)4− (13)As shown in Fig. 6, when the initial pH varied in the range of4–7, the electrolysis time for complete algae removal was 45 minunder the experimental conditions. Thus, the energy consumptionwas almost constant at the level of about 0.3 kWh/m3 (Fig. 9). However, as the initial pH further increased from 7 to 9, the electrolysistime for complete algae removal increased from 45 to 75 min correspondingly, which led to the increase of energy consumptionFig. 8. Variation of pH as a function of electrolysis time at different initial pH. Conditions: room temperature; current density, 1 mA/cm2 ; volume, 1.0 dm3 ; initial celldensity 1.2 × 109–1.4 × 109 cells/L.from 0.29 to 0.53 kWh/m3 . On the other hand, the similar energyconsumption was observed for the initial pH values of 9 and 10(0.53 kWh/m3 vs. 0.60 kWh/m3 ), mainly due to the same electrolysis time of 75 min required for complete algae removal.In conclusion, higher efficiency of algae removal could beobtained in acidic and neutral conditions. With lower pH, lowaluminum dosage would be required for algae removal throughthe charge neutralization mechanism; while at higher pH, higheraluminum dosage was needed to achieve the similar removalefficiency, through the mechanism of enmeshment and sweeping flocculation. And both coagulation mechanisms were equallyimportant for algae removal in ECF process.3.4. Effect of initial algae cell densityIn natural waters, different algae cell densities might occur indifferent regions and different seasons. Thus, the effectiveness ofECF for algae removal with different initial algae cell densities wasevaluated. Fig. 10 shows the influence of initial cell density onalgae removal, which decreased notably with the increase of celldensity. This behavior could be attributed to the fact that no sufficient aluminum was available for the removal of excessive algaecells with short electrolysis time. Furthermore, the reaction rateFig. 9. Electrical energy consumption as a function of initial pH for completeremoval of algae. Conditions: room temperature; current density, 1 mA/cm2 ; volume, 1.0 dm3 ; initial cell density 1.2 × 109–1.4 × 109 cells/L.S. Gao et al. / Journal of Hazardous Materials 177 (2010) 336–343 341Fig. 10. Removal efficiency of algae as a function of electrolysis time with differentinitial cell densities. Conditions: initial pH, 7.0; current density, 1 mA/cm2 ; volume,1.0 dm3 .decreased when the initial cell density was increased accordingto Emamjomeh and Sivakumar [42]. The similar results were alsoobtained by Ghosh et al. [43].In the experiments, when the cell densities were 0.55 × 109,1.10 × 109, 1.55 × 109 and 2.10 × 109 cells/L, the energy consumption of the ECF process for complete algae removal were 0.20, 0.21,0.30 and 0.26 kWh/m3 , respectively. The initial cell density did notseem to greatly influence the energy consumption.
Fig. 11. Removal efficiency of algae as a function of electrolysis time under different
temperature. Condition: initial pH, 7.0; current density, 1 mA/cm2 ; volume, 1.0 dm3 ;
initial cell density 1.2 × 109–1.4 × 109 cells/L.
3.5. Effect of temperature
Water temperature is one of the most important environmental factors that might influence algae removal in the ECF. However,
previous studies showed that water temperature exerted different
effects on electrocoagulation for the removal of different pollutants [44,45]. Thus, it is necessary to examine the effect of water
temperature on algae removal. As shown in Fig. 11 , it was found
Fig. 12. SEM-EDX analysis of the algal flocs produced by ECF. (a and b) SEM micrograph at different magnifications; EDX analysis of elemental compositions (c) on the algae
cells and (d) on the agglutinant.
342 S. Gao et al. / Journal of Hazardous Materials 177 (2010) 336–343
Table 1
Elemental composition and relative contents of atoms on the flocs by SEM-EDX analysis.
Element CK NK OK AlK PK SK NaK FeK MgK Total
Spectrum 1 65.40% 9.49% 16.17% 3.78% 2.99% 1.21% 0.36% 0.49% 0.11% 100%
Spectrum 2 42.57% 9.85% 22.15% 14.27% 6.89% 2.05% 0.55% 1.39% 0.28% 100%
that the algae removal was dramatically improv
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