AI summary

78% confidence

This review synthesizes nitrogen removal in bioelectrochemical systems (BESs), emphasizing cathodic biofilm-driven processes including denitrification, nitrification, simultaneous nitrification–denitrification (SND), shortcut SND, and anammox. BESs enable treatment of low C/N ratio wastewaters by supplying electrons from the cathode rather than organic carbon, achieving removal rates up to 0.66 kg N m⁻³ d⁻¹ and nitrogen removal efficiencies >94%. The paper reviews reactor configurations, operating factors (HRT, DO, pH, aeration), biofilm stratification, and microbial community structure, highlighting trade-offs between aeration energy cost and complete nitrogen conversion.

Key insights

  • Mechanism Autotrophic denitrifiers in the biofilm outcompete heterotrophs for electrons at the cathode, enabling >97% NO₃⁻ removal at C/N ratio as low as 0.75 with no NO₂⁻ accumulation, whereas conventional processes fail at such low C/N.

    So what. Design BES cathodes for low C/N wastewaters (groundwater, coke oven effluent) without supplemental organic carbon; prioritize biofilm enrichment of autotrophic denitrifiers.

  • Trade-off Dissolved oxygen concentration creates a trade-off: increasing DO from 0.2 to 1.2 mg/L at HRT 20–90 h increased anammox removal efficiency to 94.8% but decreased denitrifier activity and shifted electron acceptance from nitrate to oxygen, reducing overall nitrogen removal.

    So what. Operate at intermediate HRT (60 h reported) and control DO to 0.2–1.2 mg/L range; excessive aeration shifts electron acceptor preference away from nitrogen species.

  • Threshold Limited dissolved oxygen (1–3.5 mg/L) favors ammonia-oxidizing bacteria (AOB) over nitrite-oxidizing bacteria (NOB), accumulating NO₂⁻ at NO₂⁻/NO₃⁻ ratio of 3:1 for shortcut SND, achieving 99.9% total nitrogen removal at 3.5 mg/L DO.

    So what. Maintain DO at 1–3.5 mg/L in nitrification chambers to suppress NOB and accumulate NO₂⁻; separate nitrification and denitrification into independent cathode chambers to stabilize operation.

  • Trade-off Addition of NaN₃ to inhibit NOB increased total nitrogen removal by 50% to 0.075 kg m⁻³ d⁻¹ but increased N₂O yield 5.6-fold, indicating inhibitor-driven NOB suppression also suppresses nitrite reduction, diverting electrons to N₂O formation.

    So what. Avoid chemical NOB inhibitors; use DO control instead to prevent unintended N₂O accumulation in shortcut SND systems.

  • Mechanism Biofilm stratification by oxygen gradient (aerobic outer layer with nitrifiers, anaerobic inner layer with denitrifiers) is essential for complete nitrogen conversion; thin biofilms penetrated by DO fail to achieve anoxic zones needed for denitrification.

    So what. Design cathode substrates (carbon felt, membrane-aerated) to support thick biofilms (>100 µm inferred); control aeration to maintain DO gradient; monitor biofilm thickness during operation.

Contradictions1

Tensions the paper itself points to. Each side quotes the passage it comes from.

  • Within the paper NaN₃ inhibitor increased nitrogen removal rate but simultaneously increased N₂O yield, suggesting NOB inhibition suppresses both nitrite oxidation and reduction pathways.

    One side

    Addition of NaN₃ increased total nitrogen removal by 50% to 0.075 ± 0.008 kg m⁻³ d⁻¹

    “With the addition of NaN3, for example, the total nitrogen removal was increased by 50% to the highest removal rate of 0.075 ± 0.008 kg m⁻³ net cathode chamber d−1”
    Other side

    Addition of NaN₃ increased N₂O yield by 5.6, indicating inhibitor-driven NOB suppression also limited nitrite reduction

    “However, a recent research revealed that the addition of NaN3 decreased the nitrate production, while it increased the N2O yield by 5.6, demonstrating the addition of an inhibitor limited the NOB activity and also, to a certain extent, the ”

    Authors’ reading. Authors acknowledge that NOB inhibition is a double-edged sword: it prevents NO₃⁻ formation but also impairs NO₂⁻ reduction, diverting electrons to N₂O. This suggests NOB and denitrifiers share overlapping enzymatic pathways or that NOB inhibition destabilizes the biofilm redox balance.

Opportunity areas6

Specific gaps in this paper, with an experiment that would close each.

  • High No systematic study of cathode potential (vs. SHE or Ag/AgCl) operating windows for nitrogen species reduction. Table 1 lists theoretical potentials (NO₃⁻/NO₂⁻ = +0.233 V, NO₂⁻/NO = +0.150 V, N₂O/N₂ = +1.155 V vs. Ag/AgCl) but paper does not report actual applied potentials or show how potential affects N₂O vs. N₂ selectivity.

    Section 2.1 and Table 1 present thermodynamic potentials but no experimental data on applied cathode potential; Section 3 mentions N₂O production in inner biofilm but does not link it to potential control. This is critical for preventing N₂O accumulation.

    Try. Vary applied cathode potential from −0.3 to −0.8 V vs. Ag/AgCl in a controlled MEC; measure N₂O, N₂, NO₂⁻, and NO₃⁻ in effluent and gas phase; correlate with biofilm norB gene expression.

  • High Catholyte pH is mentioned as a factor affecting biofilm stability (Section 2.3: 'minimized impact of pH') but no data on optimal pH range or pH drift during operation. Nitrification and denitrification have different pH optima; no study reported here explores pH control strategy.

    Section 2.3 states three-chamber design minimizes pH impact but provides no pH values, drift rates, or buffering strategy. Equations (1)–(5) show H⁺ production/consumption but no pH management protocol is described.

    Try. Operate SND reactor at pH 6.5, 7.0, 7.5, 8.0 with and without buffer; measure NH₄⁺ removal rate, NO₂⁻/NO₃⁻ ratio, N₂O yield, and biofilm composition over 30 days.

  • High N₂O accumulation is mentioned (Section 3: 'norB genes were more abundant within the inner layer' and 'N₂O was mainly produced within the inner portion') but no quantitative data on N₂O concentration, yield (mol N₂O per mol NO₃⁻ reduced), or operating conditions that minimize it.

    Section 3 identifies N₂O production in inner biofilm but provides no N₂O measurements, yields, or mitigation strategies. This is critical for environmental compliance (N₂O is a potent greenhouse gas).

    Try. Measure N₂O in gas and liquid phases using GC-MS; vary biofilm thickness, DO, and cathode potential; report N₂O yield (%) and identify threshold conditions for <5% N₂O.

  • Medium Current density range for optimal nitrogen removal is not systematically explored. Table 2 and 3 report current densities of 4.10 A m⁻² (ref. 46) and applied voltages (0.70–0.80 V) but no study varies current density across a wide range (0.1–10 A m⁻²) to identify performance plateau or mass transfer limitation.

    Section 2.2 reports current density 4.10 A m⁻² for one system but no paper in the review systematically scans current density. This is essential for scale-up and energy optimization.

    Try. In a dual-chamber MEC, vary current density from 0.5 to 10 A m⁻² at fixed HRT = 24 h; measure NH₄⁺ removal rate, NO₂⁻/NO₃⁻ ratio, power consumption, and biofilm thickness.

  • Medium Biofilm thickness is stated as critical (Section 3: 'thickness of the biofilm should be high enough to form an oxygen gradient') but no quantitative target thickness is provided, and no study reports actual biofilm thickness measurements or growth kinetics.

    Section 3 qualitatively describes need for thick biofilm but provides no thickness data, growth rates, or substrate design rules. This limits reproducibility and scale-up.

    Try. Measure biofilm thickness weekly using OCT or cross-section microscopy in carbon felt, membrane, and electrode materials; correlate thickness with DO penetration depth and nitrogen removal rate.

  • Medium Anode biofilm composition and its role in electron supply is not characterized. Paper focuses on cathode biofilm but does not report anode microbial community, electron transfer rate, or how anode design affects cathode nitrogen removal performance.

    Section 2.4 mentions anammox sludge as anode catalyst (14.9% improvement) but no systematic study of anode biofilm optimization. Anode performance directly limits cathode electron availability.

    Try. Compare anode biofilms (acetate-fed, anammox sludge, mixed inoculum) in identical dual-chamber MEC; measure anode potential, current output, and cathode nitrogen removal rate; profile anode microbial community.

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What they did

System
REVIEW
Substrate
synthetic mixture

What worked

Power density945mW/m²best of 4
Current density4.10A/m²best of 2
Coulombic efficiency21.6%
Voltage0.04Vbest of 2

Abstract

Nitrogenous compounds attract great attention because of their environmental impact and harmfulness to the health of human beings. Various biological technologies have been developed to reduce the environmental risks of nitrogenous pollutants. Bioelectrochemical systems (BESs) are considered to be a novel biological technology for removing nitrogenous contaminants by virtue of their advantages, such as low energy requirement and capacity for treating wastewaters with a low C/N ratio. Therefore, increasing attention has been given to carry out biological processes related to nitrogen removal with the aid of cathodic biofilms in BESs. Prior studies have evaluated the feasibility of conventional biological processes including nitrification, denitrification, and anaerobic ammonia oxidation (anammox), separately or combined together, to remove nitrogenous compounds with the help of BESs. The present review summarizes the progress of developments in BESs in terms of the biological process, cathodic biofilm, and affecting factors for efficient nitrogen removal.

Keywords

AnammoxBiochemical engineeringPollutantNitrificationSimultaneous nitrification-denitrificationDenitrification

Identifiers

Journal
Processes
Year
2020
Extraction

Reported parameters

169 extracted values

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