How ß-Cyclodextrin-Functionalized Biochar Enhanced Biodenitrification in Low C/N Conditions via Regulating Substrate Metabolism and Electron Utilization.

Biodenitrification plays a vital role in the remediation of nitrogen-contaminated water. However, influent with a low C/N ratio limits the efficiency of denitrification and causes the accumulation/emission of noxious intermediates. In this study, ß-cyclodextrin-functionalized biochar (BC@ß-CD) was synthesized and applied to promote the denitrification performance of Paracoccus denitrificans when the C/N was only 4, accompanied by increased nitrate reduction efficiency and lower nitrite accumulation and nitrous oxide emission. Transcriptomic and enzymatic activity analyses showed BC@ß-CD enhanced glucose degradation by promoting the activities of glycolysis (EMP), the pentose phosphate pathway (PPP), and the tricarboxylic acid (TCA) cycle. Notably, BC@ß-CD drove a great generation of electron donors by stimulating the TCA cycle, causing a greater supply of substrate metabolism to denitrification. Meanwhile, the promotional effect of BC@ß-CD on oxidative phosphorylation accelerates electron transfer and ATP synthesis. Moreover, the presence of BC@ß-CD increased the intracellular iron level, causing further improved electron utilization in denitrification. BC@ß-CD helped to remove metabolites and induced positive feedback on the metabolism of P. denitrificans. Collectively, these effects elevated the glucose utilization for supporting denitrification from 36.37% to 51.19%. This study reveals the great potential of BC@ß-CD for enhancing denitrification under low C/N conditions and illustrates a potential application approach for ß-CD in wastewater bioremediation.

Ligand-Enhanced Electron Utilization for Trichloroethylene Degradation by ·OH during Sediment Oxygenation.

The potential of oxygenating Fe(II)-bearing sediments for hydroxyl radical (·OH) production and contaminant degradation has been proposed recently. Here, we further show that specific ligands can largely enhance contaminant degradation during sediment oxygenation due to increased utilization efficiency of sediment electrons. With the addition of 0-2 mM sodium ethylene diamine tetraacetate (EDTA) or sodium tripolyphosphate (TPP) in sediment suspension (50 g/L, pH 7.0), trichloroethylene (TCE, 15 µM) degradation increased from 13% without ligand to a maximum of 80% with 2 mM TPP and was much higher with TPP than EDTA because EDTA competes for ·OH. Electron utilization efficiency for ·OH production increased with increased ligand concentration and was enhanced by up to 6-7 times with 2 mM EDTA or TPP. Electron transfer from sediment to dissolved Fe(III)-ligand is mainly accountable for the enhanced electron utilization efficiency by the ligands with low adsorption affinity (i.e., EDTA), and additional variation of sediment surface Fe(II) coordination is mainly responsible for the enhancement by the ligands with high adsorption affinity (i.e., TPP). Output of this study provides guidance and optional strategies for enhancing contaminant degradation during sediment oxygenation.

Effects of environmental factors on the removal of heavy metals by sulfide-modified nanoscale zerovalent iron.

Sulfide-modified nanoscale zerovalent iron (S-nZVI) has excellent reducing performance for heavy metals in water. The influence of environmental factors on the reactivity can be used to explore the practical feasibility of S-nZVI and analyze the reaction mechanism in depth. This study compared the removal effect and mechanism of Cu2+ and Ni2+ by nanoscale zerovalent iron (nZVI), S-nZVI, and carboxymethyl cellulose-modified nanoscale zerovalent iron (CMC-nZVI). The results show that the pseudo-first-order kinetic constant of Cu2+ removal by nZVI, S-nZVI, and CMC-nZVI was 1.384, 1.919, and 2.890 min-1, respectively, and the rate of Ni2+ removal was 0.304, 0.931, and 0.360 min-1, respectively. The removal mechanism of S-nZVI was similar to that of nZVI and CMC-nZVI. Specifically, Cu2+ was predominantly removed by reduction, while Ni2+ removal included adsorption and reduction. Environmental factors had a specific inhibitory effect on the removal of Cu2+ but had a negligible impact on Ni2+. The condition of low pH, the presence of Cl- and humic acid (HA) promoted the corrosion consumption of Fe0, in which H+ directly corroded Fe0 at low pH. At the same time, Cl- and HA inhibited the adsorption or binding of heavy metal ions on the particle surface, thereby reducing the electron transfer and utilization efficiency. The passivation of NO3- reduced the anaerobic corrosion of the material in water but suppressed the release of electrons, thereby reducing the reduction efficiency of the three types of materials. The anaerobic corrosion of S-nZVI was less affected by environmental factors, and it can still maintain more than 80% of the electronic utilization efficiency under different environmental factors, which illustrates that S-nZVI has broad prospects for practical applications in heavy metal polluted water.

Calcined pyrite accelerates sulfur metabolic and electron transfer in driving targeted microbial fuel cell denitrification.

The sulfur powder as electron donor in driving dual-chamber microbial fuel cell denitrification (S) process has the advantages in economy and pollution-free to treat nitrate-contained groundwater. However, the low efficiency of electron utilization in sulfur oxidation (ACE) is the bottleneck to this method. In this study, the addition of calcined pyrite to the S system (SCP) accelerated electron generation and intra/extracellular transfer efficiency, thereby improving ACE and denitrification performance. The highest nitrate removal rate reached to 3.55 ± 0.01 mg N/L/h in SCP system, and the ACE was 103 % higher than that in S system. More importantly, calcined pyrite enhanced the enrichment of functional bacteria (Burkholderiales, Thiomonas and Sulfurovum) and functional genes which related to sulfur metabolism and electron transfer. This study was more effective in removing nitrate from groundwater without compromising the water quality.

Dramatically enhanced phenol degradation upon FeS oxygenation by low-molecular-weight organic acids.

Oxidizing potential of FeS for organic contaminants degradation due to hydroxyl radicals (•OH) production has been recently documented, but the oxidizing efficiency was limited. Here, we revealed that low-molecular-weight organic acids (LMWOAs) can immensely enhance phenol degradation during FeS oxygenation due to increased utilization efficiency of FeS electron for •OH production. Upon oxygenation of 0.5 g/L FeS, phenol degradation boosted from 7.1% without LMWOAs to 91.5%, 84.6% and 95.0% with the addition of 1 mM oxalate, citrate and EDTA, respectively. Electron utilization efficiency of Fe(II) for •OH production dramatically rose from 0.3% with FeS alone to respective 2.0%, 2.5% and 2.7% in the LMWOAs systems. An increase in oxalate concentrations benefited •OH formation and phenol degradation. Coexisting oxalate led to an additional •OH production pathway from Fe(II)-oxalate oxidation, which expanded the O2 reduction to H2O2 from a two- to one-electron transfer process. Meanwhile, electron transfer from FeS to dissolved Fe(III)-oxalate promoted the redox cycling of Fe(III)/Fe(II), thus supplying the Fe(II) oxidation for •OH production. Moreover, the presence of oxalate decreased the crystallinity and particles size of lepidocrocite generated from FeS oxidation. Consequently, this study shed lights on the LMWOAs-enhanced contaminant degradation in either natural or engineered FeS oxidation systems.

Supporting nanoscale zero-valent iron onto shrimp shell-derived N-doped biochar to boost its reactivity and electron utilization for selenite sequestration.

Nanoscale zero-valent iron (nZVI) has been widely used in the reductive removal of contaminants from water, yet it still fights against the inherent passive cover and the raise of medium pH. In this study, nZVI was supported onto a nitrogen-doped biochar (NBC) that was prepared by pyrolyzing shrimp shell for efficiently sequestrating aqueous selenite (Se(IV)). The resultant composite (NBC-nZVI) revealed a higher reactivity and electron utilization efficiency (EUE) than the bare nZVI in Se(IV) sequestration because of the positive charge, the buffering effect and the good conductivity of NBC. The kinetic rate and EUE of NBC-nZVI were increased by 143.4% and 15.3% compared to the bare nZVI, respectively, at initial pH of 3.0. The high removal capacity of 605.4 mg g-1 for NBC-nZVI was obtained at Se(IV) concentration of 1000 mg L-1, initial pH of 3.0, NBC-nZVI dosage of 1.0 g L-1 and contact time of 12 h. Moreover, NBC-nZVI exhibited a strong tolerance to solution pHs and coexisting compounds (e.g., humic acid) and could reduce the Se(IV) concentration from 5.0 mg L-1 to below the limit of drinking water (50 µg L-1) in real-world samples. This work exemplified a utilization of shrimp shell-derived NBC to simultaneously enhance the reactivity and EUE of nZVI for reductively removing contaminants.

Alkalinity regulation in a sulfur autotrophic denitrifying filter substantially reduced total dissolved solids and sulfate in effluent.

Sulfur autotrophic denitrification (SAD) filters are considered a promising technology due to their stable and excellent performance in nitrogen removal, affordable costs, and operational advantages. In this work, a novel operational strategy that employed sodium bicarbonate as an alkalinity source in the autotrophic denitrification filter (S-SAD) was established. With the sufficient supply of alkalinity, the S-SAD reached an excellent denitrification performance (98.01%±0.43%) with a nitrate concentration of 10 mg/L in influent and hydraulic retention time of 3 hrs. The total dissolved solids increment and sulfate concentration in effluent were significantly reduced by one-third, compared with that of the traditional SAD process under the same conditions. The analysis of microbial community indicated that Thiobacilhus, typical species with the functions of simultaneous sulfur oxidation and denitrification, was evidently enriched in the S-SAD. Thus, this present work demonstrated a feasible, relatively cost-effective and environmentally friendly approach to operate SAD towards further application.

Strong influence of degree of substitution on carboxymethyl cellulose stabilized sulfidated nanoscale zero-valent iron.

Carboxymethyl cellulose (CMC) has been widely adopted as stabilizer to enhance the subsurface mobility of nanoscale zerovalent iron (nZVI). However, CMC surface modification also cause severe decrease of the longevity and electron utilization efficiency (εe) of nZVI, which is still not well understood. In this study, we demonstrate the negative influence of CMC on the properties of sulfidated nZVI (S-nZVI) could be reversed by increasing the degree of substitution (D.S.) of CMC. Consistent with previous study, the sample CMC-S-nZVI prepared with commercial CMC with degree of substitution (D.S.) of 0.75 exhibited a considerable low longevity of 33 days with εe of 4.5%, much lower than that of sulfidated nZVI (S-nZVI, 113 days and 13%). In sharp contrast, the sample HCMC-S-nZVI synthesized with CMC with super high D.S. of 1.76 demonstrated significantly enhanced longevity of 139 days and εe of 20%. The enhancement was attributed to compatible molecular structure of CMC with super high D.S. Moreover, the HCMC-S-nZVI also exhibited higher mobility in porous media than CMC-S-nZVI. Our work provides a feasible way to prepare S-nZVI with desired properties including high subsurface transportability, high longevity and high εe.

Citrate ligand-enhanced microscale zero-valent aluminum corrosion for carbon tetrachloride degradation with high electron utilization efficiency.

Carbon tetrachloride (CT) is highly toxic and recalcitrant in groundwater. In recent years, zero-valent aluminum (ZVAl) is highly reductive but limited by its surface passivation film. One of the effective ways to overcome this bottleneck is to add ligands. In this paper, compared with several other ligands, sodium citrate (SC), a natural organic ligand, was introduced to enhance microscale ZVAl (mZVAl) reactivity for the reductive degradation of CT. The results showed that the SC system could effectively reduce but not completely dechlorinate CT and electron utilization efficiency was as high as 94%. However, without ligands, mZVAl is chemically inert for CT degradation. Through SEM-EDS, BET, XRD, and XPS characterizations and H2 evolution experiments, enhanced mZVAl surface corrosion at the solid-liquid interface of mZVAl/SC system was verified. SC participated in the complexation corrosion reaction with surface inert film to form Al[Cit] complex, which made internal Al0 active sites exposed and then promoted mZVAl corrosion. In the five consecutive reuse experiments of mZVAl, CT can be completely degraded, which indicates that mZVAl, with the help of SC, has excellent sustainable utilization efficiency.