Congener-welded crystalline carbon nitride membrane for robust and highly selective Li/Mg separation.

Extracting lithium from salt-lake brines critically relies on the separation of Li+ and Mg2+, which could combat the lithium shortage. However, designing robust sieving membrane with high Li+/Mg2+ selectivity in the long-time operation has remained highly challenging. Here, we demonstrate a bioinspired congener-welded crystalline carbon nitride membrane that can accomplish efficient and stable monovalent ion sieving over divalent Mg ion. The crystalline carbon nitrides have uniform and narrow pore size to reject the large hydrated Mg2+ and rich ligating sites to facilitate an almost barrierless Li+ transport as suggested by ab initio simulations. These crystals were then welded by vapor-deposited congeners, i.e., amorphous polymer carbon nitride, which have similar composition and chemistry with the crystals, forming intimate and compatible crystal/polymer interface. As a result, our membrane can sieve out highly dilute Li+ (0.002 M) from concentrated Mg2+ (1.0 M) with a high selectivity of 1708, and can be continuously operated for 10 days.

Sulfur autotrophic denitrification filter and heterotrophic denitrification filter: Comparison on denitrification performance, hydrodynamic characteristics and operating cost.

Sulfur autotrophic denitrification (SAD) process, as an alternative to heterotrophic denitrification (HD) filter, receives growing interest in polishing the effluent from secondary sewage treatment. Although individual studies have indicated several advantages of SAD over HD, rare study has compared these two systems under identical condition and by using real secondary effluent. In this study, two small pilot scale filters (SAD and HD) were designed with identical configuration and operated parallelly by feeding the real secondary effluent from a WWTP. The results showed SAD filter can be started up without the addition of soluble electron donor, although the time (14 days) was about 3 times longer than that of HD filter. The nitrate removal rate of SAD filter at HRT of 1.4 h was measured as 0.268 ± 0.047 kg N/(m3∙d). Similar value was observed in HD filter with supplementing 90 mg/L COD. The COD concentration of effluent always kept lower than that of influent in SAD filter but not in HD filter. In addition, SAD filter could maintain a stable denitrification performance without backwash for 15 days, while decline of nitrate removal rate was observed in HD filter just 2 days after stopping the backwash. This different behavior was further confirmed as the SAD filter had a better hydraulic flow pattern. Analysis according to high-throughput 16S rRNA gene-based Illumina MiSeq sequencing clearly showed the microbial community evolution and differentiation among the samples of seed sludge, SAD and HD filters. Finally, the economic assessment was carried out, showing the operation cost of SAD filter was over 50% lower than that of HD filter.

Efficient and synergistic decolourization and nitrate removal using a single-chamber with a coupled biocathode-photoanode system.

With the continuous development of the chemical industries, synergistic removal of carbon and nitrogen contaminants has drawn much attention. In this work, a novel strategy for the synergistic removal of methyl orange (MO) and nitrate was developed in a single reactor by combining a TiO2/g-C3N4 nanosheet/graphene photoanode and denitrifying biofilm cathode. Under xenon light illumination, the photocatalytic MO decolorization rate exceeded 90% (the initial concentration of MO was as high as 100 mg·L-1) with a biocathode potential bias of -0.5 V vs Ag/AgCl; additionally, the decolourization rate apparently followed first-order kinetics with a constant of 0.11 ± 0.02 h-1. The improved MO decolourization rate was mainly because the biocathode effectively enhanced the charge separation of the photogenerated charge at the TiO2/g-C3N4 nanosheet/graphene photoanode interface. In the meantime, the effluent nitrate was lower than 1 mg·N·L-1 at a biocathode potential of -0.5 V vs Ag/AgCl. The results indicated that the coupled biocathode-photoanode system could serve the purpose of simultaneously degrading MO and accomplishing nitrate reduction. Considering the sustainability of sunlight and the use of a biocathode, the coupled biocathode-photoanode system is a promising alternative for the simultaneous removal of biorefractory organics and nitrate.

Enhanced treatment of coal gasification wastewater in a membraneless sleeve-type bioelectrochemical system.

A bioelectrochemical system (BES) is a technology with potential for accelerating the degradation of recalcitrant compounds, the components and configurations of which are important for treatment performance. In the present work, a membraneless sleeve-type BES (termed BioE) was designed for the treatment of synthetic coal gasification wastewater (CGW, phenol as a model pollutant) and real CGW. Compared with the biological control (termed Bio), the phenol removal rate and COD removal efficiency increased by 2.6 and 2.1 fold in the BioE, respectively. However, the coulombic efficiency of this system was relatively low, ranging from 0.42% to 2.6%. This combination of results indicated that anode respiration was not the main process in the BioE. The increased CH4 production and higher levels of methanogens obtained from the BioE confirmed that the methanogenic process proceeded, possibly facilitated by the diffusion of H2 from the cathode to the anode. This study provides new insight into biocathode function for COD oxidation removal in BESs. Moreover, this study indicates that pursuing a high coulombic efficiency may not be necessary for wastewater treatment, as it consumes less energy at the lower value.

Coupled Sulfur and Iron(II) Carbonate-Driven Autotrophic Denitrification for Significantly Enhanced Nitrate Removal.

Sulfur-based denitrification process has attracted increasing attentions because it does not rely on the external addition of organics and avoids the risk of COD exceeding the limit. Traditionally, limestone is commonly employed to maintain a neutral condition (SLAD process), but it may reduce the efficiency as the occupied zone by limestone cannot directly contribute to the denitrification. In this study, we propose a novel sulfur-based denitrification process by coupling with iron(II) carbonate ore (SICAD system). The ore was demonstrated to play roles as the buffer agent and additional electron donor. Moreover, the acid produced through sulfur driven denitrification was found to promote the Fe(II) leaching from the ore and likely extend the reaction zone from the surface to the liquid. As a result, more biomass was accumulated in the SICAD system compared with the controls (sulfur, iron(II) carbonate ore and SLAD systems). Owing to these synergistic effects of sulfur and iron(II) carbonate on denitrification, SICAD system showed much higher denitrification rate (up to 720.35 g·N/m3·d) and less accumulation of intermediates (NO2- and N2O) than the controls. Additionally, sulfate production in SICAD system was reduced. These findings offer great potential of SICAD system for practical use as a highly efficient postdenitrification process.

A novel bioelectrochemical method for real-time nitrate monitoring.

Nitrate is one of the most common pollutants in the water environment. A key factor for the effective control and removal of nitrate is the ability to accurately determine the nitrate concentration in groundwater and the secondary effluent of wastewater treatment plants. Here, a bioelectrochemical method for real-time detection of the nitrate was developed. In this work, a kinetic model was developed to describe the correlation between the nitrate concentration and the current. Standard addition experiments showed the relative error between indicator predictions and ion chromatographic values ranged from 3.14% to 9.74%. The monitoring results of secondary effluent showed that the system could give a good response at different nitrate concentrations. The average error of not >10.85% between the indicator predictions and ion chromatographic values was demonstrated. This study offers a new method for the development of sustainable bioelectrochemical system (BES)-based technology for the real-time detection of nitrate in groundwater and the secondary effluent.

Kinetic competition between microbial anode respiration and nitrate respiration in a bioelectrochemical system.

The Nernst-Monod model is used to describe bio-anode performance with respect to the effect of the electron donor and anode potential. However, electron competition is not considered in the model, limiting its application in wastewater treatment systems. In this work, nitrate was employed to describe the influence of a competitive electron acceptor on bio-anode performance. A new dynamic model of microbial anode respiration and nitrate respiration was developed for the removal of nitrogen oxides. The competitive relationship between microbial anode respiration and nitrate respiration was investigated based on electron transfer as described by the kinetics of Nernst-Monod electron transfer and nitrate reduction. The experimental results showed that nitrate had a significant influence on microbial anode respiration. The model parameters were estimated with the experimental results obtained in a continuous-flow bioelectrochemical system (BES) fed with acetate. The simulated results revealed that nitrate respiration could indirectly affect the microbial anode respiration by altering the available substrate concentration. In addition, bacterial community analysis indicated that there were two dominant functional microorganisms coexisting in the anode chamber. The first microorganism was represented by Geobacter, which has extracellular electron-transfer abilities. The second was denitrifying bacteria, which can use the carbon sources in the anodic chamber and electrons from the electrode for nitrate reduction. This is the first time that mathematical modelling of nitrate reduction has been applied to BESs.

Microbial Photoelectrotrophic Denitrification as a Sustainable and Efficient Way for Reducing Nitrate to Nitrogen.

Biological removal of nitrate, a highly concerning contaminant, is limited when the aqueous environment lacks bioavailable electron donors. In this study, we demonstrated, for the first time, that bacteria can directly use the electrons originated from the photoelectrochemical process to carry out the denitrification. In such photoelectrotrophic denitrification (PEDeN) systems (denitrification biocathode coupling with TiO2 photoanode), nitrogen removal was verified solely relying on the illumination dosing without consuming additional chemical reductant or electric power. Under the UV illumination (30 mW·cm-2, wavelength at 380 ± 20 nm), nitrate reduction in PEDeN apparently followed the first-order kinetics with a constant of 0.13 ± 0.023 h-1. Nitrate was found to be almost completely converted to nitrogen gas at the end of batch test. Compared to the electrotrophic denitrification systems driven by organics (OEDeN, biocathode/acetate consuming bioanode) or electricity (EEDeN, biocathode/abiotic anode), the denitrification rate in PEDeN equaled that in OEDeN with a COD/N ratio of 9.0 or that in EEDeN with an applied voltage at 2.0 V. This study provides a sustainable technical approach for eliminating nitrate from water. PEDeN as a novel microbial metabolism may shed further light onto the role of sunlight played in the nitrogen cycling in certain semiconductive and conductive minerals-enriched aqueous environment.

Corrugated stainless-steel mesh as a simple engineerable electrode module in bio-electrochemical system: Hydrodynamics and the effects on decolorization performance.

The application of bio-electrochemical system (BESs) is strongly depended on the development of the engineering applicable electrode. Here we described an economical and readily processable electrode module with three-dimensional structure, the corrugated stainless-steel mesh electrode module (c-SMEM). This novel developed electrode module was demonstrated to provide a good hydrodynamic characteristic and significantly enhanced the decolorization performance of the BES when serving for treating azo dye (acid orange 7, AO7) containing wastewater. Compared to the conventional planar electrodes module (p-SMEM), c-SMEM was found to prolong the mean residence time (MRTθ) of AO7 and change the flow pattern closer to the plug flow. As a result, the maximum enhancement of the volumetric decolorization rate (vDR) can reach to 255%, even when the c-SMEM and p-SMEM have the same electrode surface area. In addition, a techno-economic analysis model was established to elucidated the effects of the decolorization performance and the material cost on the initial capital cost, which revealed the BES with c-SMEM could be economically comparable to or even better than the traditional bio-decolorization technologies. These results suggest c-SMEM holds great potential for engineering application, which may help paving the way of applying BES at large-scale.

Efficient treatment of azo dye containing wastewater in a hybrid acidogenic bioreactor stimulated by biocatalyzed electrolysis.

In this study, a novel scaled-up hybrid acidogenic bioreactor (HAB) was designed and adopted to evaluate the performance of azo dye (acid red G, ARG) containing wastewater treatment. Principally, HAB is an acidogenic bioreactor coupled with a biocatalyzed electrolysis module. The effects of hydraulic retention time (HRT) and ARG loading rate on the performance of HAB were investigated. In addition, the influent was switched from synthetic wastewater to domestic wastewater to examine the key parameters for the application of HAB. The results showed that the introduction of the biocatalyzed electrolysis module could enhance anoxic decolorization and COD (chemical oxygen demand) removal. The combined process of HAB-CASS presented superior performance compared to a control system without biocatalyzed electrolysis (AB-CASS). When the influent was switched to domestic wastewater, with an environment having more balanced nutrients and diverse organic matters, the ARG, COD and nitrogen removal efficiencies of HAB-CASS were further improved, reaching 73.3%±2.5%, 86.2%±3.8% and 93.5%±1.6% at HRT of 6 hr, respectively, which were much higher than those of AB-CASS (61.1%±4.7%, 75.4%±5.0% and 82.1%±2.1%, respectively). Moreover, larger TCV/TV (total cathode volume/total volume) for HAB led to higher current and ARG removal. The ARG removal efficiency and current at TCV/TV of 0.15 were 39.2%±3.7% and 28.30±1.48 mA, respectively. They were significantly increased to 62.1%±2.0% and 34.55±0.83 mA at TCV/TV of 0.25. These results show that HAB system could be used to effectively treat real wastewater.