Simultaneous Anaerobic Ammonium Oxidation and Electricity Generation in Microbial Fuel Cell: Performance and Electrochemical Characteristics
Jiqiang Zhang, Zaiwang Zhang, Kun Rong, Haiying Guo +7
AI summary
82% confidenceThis study demonstrates an anode anammox MFC using highly active anammox bacteria to simultaneously remove nitrogen and generate electricity from inorganic nitrogen media. The system achieved 90% removal of NH4+-N and NO2−-N with a maximum volumetric nitrogen removal rate of 3.01 kgN/(m³·d) and power density of 1308 mW/m³, substantially outperforming prior anode nitrification MFCs. However, coulombic efficiency remained very low (4.09–5.99%), limited primarily by anode charge transfer resistance (90% of total anode resistance), revealing that anammox bacteria's compartmentalized cell structure creates an electron transfer barrier that severely constrains energy recovery.
Key insights
Threshold Substrate inhibition occurs sharply at NH4+-N = 300 mg/L and NO2−-N = 396 mg/L, causing removal efficiency to collapse from >90% to near zero, but inhibition is reversible by washout and gradual re-acclimation.
So what. Operators must maintain inlet NH4+-N below 250 mg/L and NO2−-N below 330 mg/L to avoid system collapse; if inhibition occurs, implement washout protocol rather than assuming permanent damage.
Mechanism Anode charge transfer resistance dominates (59.7–68.2% of total anode resistance) and decreases from 407 Ω at 25 mg/L NH4+-N to 209 Ω at 250 mg/L, but remains the primary bottleneck for power output.
So what. Electrode material and mediator selection should prioritize reducing charge transfer resistance; consider carbon nanotubes or artificial electron mediators rather than plain graphite felt.
Mechanism Output voltage and volumetric nitrogen removal rate show strong correlation (R² = 0.9862, p < 0.05), indicating electricity generation is directly coupled to ammonium oxidation rate, not substrate concentration alone.
So what. Maximize nitrogen removal kinetics (via inoculum activity, HRT optimization, or temperature) to improve power output; power is not independent of treatment performance.
Mechanism Anammox reactions require lower anode potentials (NO2− reduction at +0.38 V vs. SHE) than aerobic nitrification (+0.73 V), yet coulombic efficiency (4–6%) remains 10–70× lower than organic MFCs (43–72%), indicating the anammoxosome compartment creates a severe electron transfer barrier.
So what. Anammox MFCs are fundamentally limited by microbial physiology; genetic engineering of electron transport chains or use of external mediators may be necessary to approach organic MFC efficiency levels.
Trade-off Coulombic efficiency declines from 5.99% to 4.09% as substrate concentration increases from 25 to 250 mg/L NH4+-N, indicating fuel utilization efficiency worsens at higher loads despite higher absolute power output.
So what. Higher nitrogen loads increase power but decrease energy recovery per mole of substrate oxidized; optimize for treatment goals (nitrogen removal vs. energy recovery) rather than assuming both improve together.
Opportunity areas6
Specific gaps in this paper, with an experiment that would close each.
High No systematic variation of HRT (only 4 h tested); nitrogen removal rate and power output may be optimizable by testing HRT from 2–12 h to find the window where kinetics and residence time balance.
Section 2.2 states 'The hydraulic retention time (HRT) was set to 4 h' with no justification or sensitivity analysis. Maximum removal rate of 3.01 kgN/(m³·d) may not be the true optimum.
Try. Vary HRT from 2 to 12 h at fixed inlet NH4+-N 200 mg/L; measure nitrogen removal efficiency, volumetric rate, and power density to identify optimal residence time.
High No investigation of cathode potential or cathode reaction kinetics; cathode potential remained stable at ~865 mV vs. SHE but no optimization attempted.
Section 3.2 and Figure 4 show 'the cathode potential remained nearly stable (about 865 mV vs. SHE)' and 'the cathodic polarization was not significant', but no exploration of whether different cathode potentials (e.g., 700–1000 mV) could improve overall voltage or power.
Try. Use potentiostat to set cathode potential at 700, 800, 900, 1000 mV vs. SHE; measure anode potential, output voltage, and power density at fixed inlet NH4+-N 200 mg/L.
High No testing of external electron mediators (e.g., anthraquinone, phenazine) to reduce anode charge transfer resistance, despite authors identifying it as the primary bottleneck.
Section 3.3 concludes 'adding artificial electron mediators in the electrolyte' as a potential solution but provides no experimental data. Charge transfer resistance is 59–68% of anode resistance.
Try. Add 0.1–1 mM anthraquinone-2,6-disulfonate (AQDS) or other mediators to anode chamber; measure anode charge transfer resistance via EIS and power density at inlet NH4+-N 200 mg/L.
Medium No measurement of N2O or other nitrogen oxide intermediates; only NH4+-N, NO2−-N, NO3−-N, and TN reported, leaving incomplete nitrogen balance and potential N2O emissions unquantified.
Section 3.1 reports stoichiometry matches anammox reaction (Equation 1) but does not measure N2O, which is a known byproduct of anammox under certain conditions and a potent greenhouse gas.
Try. Use gas chromatography or membrane inlet mass spectrometry to quantify N2O in anode off-gas at inlet NH4+-N 100, 200, 250 mg/L; correlate with anode potential and current density.
Medium No variation of NH4+-N to NO2−-N ratio; ratio fixed at 1:1.32 (stoichiometric for anammox) but no exploration of sub- or super-stoichiometric ratios and their effect on power or byproduct formation.
Section 2.2 states 'The ratio of NH4+-N to NO2−-N was fixed at 1:1.32' with no justification. Deviations from stoichiometry might reveal kinetic limitations or reveal whether NO2− or NH4+ is rate-limiting.
Try. Test NH4+-N:NO2−-N ratios of 1:1.0, 1:1.32, 1:1.5, 1:2.0 at fixed total inlet N = 200 mg/L; measure removal efficiency, power density, and effluent NO2−-N and NH4+-N to identify limiting substrate.
Medium No investigation of anode potential control or optimization; anode potential allowed to drift passively with current, not actively set to maximize power or minimize charge transfer resistance.
Polarization curves (Figure 6B) show anode potential varies from ~600 mV to ~900 mV vs. SHE across current densities, but no potentiostatic control attempted to find optimal anode potential for anammox bacteria.
Try. Use potentiostat to set anode potential at 400, 500, 600, 700 mV vs. SHE; measure nitrogen removal rate, power output, and anode charge transfer resistance via EIS at each potential.
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What they did
- System
- MFC
What worked
Abstract
In this study, a microbial fuel cell (MFC) that can achieve simultaneous anode anaerobic ammonium oxidation (anammox) and electricity generation (anode anammox MFC) by high-effective anammox bacteria fed with purely inorganic nitrogen media was constructed. As the influent concentrations of ammonium (NH4+-N) and nitrite (NO2−-N) gradually increased from 25 to 250 mg/L and 33–330 mg/L, the removal efficiencies of NH4+-N, NO2−-N and TN were over 90%, 90% and 80%, respectively, and the maximum volumetric nitrogen removal rate reached 3.01 ± 0.27 kgN/(m³·d). The maximum voltage and maximum power density were 225.48 ± 10.71 mV and 1308.23 ± 40.38 mW/m³, respectively. Substrate inhibition took place at high nitrogen concentrations (NH4+-N = 300 mg/L, NO2−-N = 396 mg/L). Electricity production performance significantly depended upon the nitrogen removal rate under different nitrogen concentrations. The reported low coulombic efficiency (CE, 4.09–5.99%) may be due to severe anodic polarization. The anode charge transfer resistance accounted for about 90% of the anode resistance. The anode process was the bottleneck for energy recovery and should be further optimized in anode anammox MFCs. The high nitrogen removal efficiency with certain electricity recovery potential in the MFCs suggested that anode anammox MFCs may be used in energy sustainable nitrogen-containing wastewater treatment.
Keywords
Identifiers
- Journal
- Processes
- Year
- 2022
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