Preparation of ceramsite using solid residue from anaerobic digestion of waste activated sludge and its enhancing effect on catalytic ozonation.

Anaerobic digestion is an environmentally friendly method for reclaiming waste activated sludge. However, it cannot be overlooked that the solid residue generated from this process can still pose environmental risks and impose economic pressure on society. To mitigate and recycle the solid residue, this study utilized it as a primary raw material for manufacturing ceramsite with potential applications in wastewater treatment. The optimal ratio of solid residue to fly ash was demonstrated to be 6:4 with an additional 15% of clay supplementing the raw ceramsite materials. Furthermore, the optimal sintering process was established as preheating at 300 °C for 25 min followed by sintering at 1085 °C for 10 min, as determined through an L16 (44) Orthogonal test. The prepared ceramsite demonstrated advantageous performance parameters that exceeded the standards outlined in the Chinese industry standard CJ/T 299-2008 for water treatment artificial ceramsite. When utilized in an ozonation system, the ceramsite exhibited remarkable catalytic activity for phenol degradation by promoting the decomposition of molecular O3 into hydroxyl radicals. Additionally, it displayed minimal leaching of heavy metals and lower application costs. These findings emphasize its attractiveness in water and wastewater treatment processes and present a practical strategy for reclaiming this solid residue.

Remediation of arsenic- and nitrate-contaminated groundwater through iron-dependent autotrophic denitrifying culture.

Groundwater contamination with arsenic and nitrate poses a pressing concern for the safety of local communities. Bioremediation, utilizing Fe(II)-oxidizing nitrate reducing bacteria, shows promise as a solution to this problem. However, the relatively weak environmental adaptability of a single bacterium hampers practical application. Therefore, this study explored the feasibility and characteristics of a mixed iron-dependent autotrophic denitrifying (IDAD) culture for effectively removing arsenic and nitrate from synthetic groundwater. The IDAD biosystem exhibited stable performace and arsenic resistance, even at a high As(III) concentration of 800 µg/L. Although the nitrogen removal efficiency of the IDAD biosystem decreased from 71.4% to 64.7% in this case, the arsenic concentration in the effluent remained below the standard (10 µg/L) set by WHO. The crystallinity of the lepidocrocite produced by the IDAD culture decreased with increasing arsenic concentration, but the relative abundance of the key iron-oxidizing bacteria norank_f_Gallionellaceae in the culture showed an opposite trend. Metagenomic analysis revealed that the IDAD culture possess arsenic detoxification pathways, including redox, methylation, and efflux of arsenic, which enable it to mitigate the adverse impact of arsenic stress. This study provides theoretical understanding and technical support for the remediation of arsenic and nitrate-contaminated groundwater using the IDAD culture.

Energy Taxis toward Redox-Active Surfaces Decreases the Transport of Electroactive Bacteria in Saturated Porous Media.

The fate and transport of bacteria in porous media are essential for bioremediation and water quality control. However, the influence of biological activities like extracellular electron transfer (EET) and swimming motility toward granular media on cell transport remains unknown. Here, electroactive bacteria with higher Fe(III) reduction abilities were found to demonstrate greater retention in ferrihydrite-coated sand. Increasing the concentrations of the electron donor (1-10 mM lactate), shuttle (0-50 µM anthraquinone-2,6-disulfonate), and acceptor (ferrihydrite, MnO2, or biochar) under flow conditions significantly reduced Shewanella oneidensis MR-1's mobility through redox-active porous media. The deficiency of EET ability or flagellar motion and inhibition of intracellular proton motive force, all of which are essential for energy taxis, enhanced MR-1's transport. It was proposed that EET could facilitate MR-1 to sense, tactically move toward, and attach on redox-active media surface, eventually improving its retention. Positive linear correlations were established among parameters describing MR-1's energy taxis ability (relative taxis index), cell transport behavior (dispersion coefficient and relative change of effluent percentage), and redox activity of media surface (reduction potential or electron-accepting rate), providing novel insights into the critical impacts of bacterial microscale motility on macroscale cell transport through porous media.

Novel Anaerobic Electrochemical Membrane Bioreactor with a CNTs Hollow Fiber Membrane Cathode to Mitigate Membrane Fouling and Enhance Energy Recovery.

A novel anaerobic treatment system that combines the impact of applied voltage with membrane filtration over carbon nanotubes hollow fiber membranes (CNTs-HFMs) was developed at low temperature (15-20 °C) to mitigate membrane fouling, treat wastewater, and recover energy (CH4). Herein, electro-assisted CNTs-HFMs served a dual function as the cathode and membrane filtration. In contrast with other two anaerobic membrane bioreactors (AnMBRs; polyvinylidene fluoride hollow fiber membranes and CNTs-HFMs without electro-assistance), the CNTs-HFMs with electro-assistance (-1.2 V applied voltage) had slower transmembrane pressure (TMP) increasing rates and better TMP recovery with a more than 95% effluent chemical oxygen demand (COD) removal rate during an almost 100-day operation period. This result can be attributed to the presence of an electrostatic repulsion force pushing pollutants (mainly extracellular polymeric substances, EPS) away from the membrane surface, thereby hindering the formation of a gel layer and mitigating membrane pore blocking in the anaerobic electro-assisted membrane bioreactor (AnEMBR). Due to the almost two-times higher Methanomicrobia content and more H2-utilizing methanogens than the other two AnMBRs, approximately more than 111.12 mL/gVSS d of CH4 was obtained in the AnEMBR with electro-assistance. This work provides an efficient strategy for mitigating membrane fouling, improving water quality, and enhancing CH4 yield.

Accelerating effects of humin on sulfide-mediated azo dye reduction.

As an important fraction of humic substances, humin has been found capable of stimulating bioreduction reactions. However, whether humin could promote abiotic reduction and the effects of coexisting soluble humic substance and insoluble mineral remained unsolved. In this study, a humin sample was isolated from a paddy soil. Cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses of the humin indicated the existence of redox-active quinone moieties and other oxygen-containing groups. The humin could be reduced by sulfide and its presence stimulated the abiotic reduction of acid red 27 (AR27) and four other azo dyes by sulfide. In the presence of 100-1000 mg/L intact humin, the sulfide-mediated AR27 reduction efficiency in 7 d was enhanced from 56.3% to 92.5%. The stimulating behavior of intact humin was observed for 100-300 mg/L AR27 and increased with the increase of sulfide concentration (1.2-3.0 mM). Much higher stimulating effects were found with the presence of humin pre-reduced by sulfide. Moreover, for sulfide-mediated AR27 reduction, the coexistence of humin (500 mg/L) and humic acid (10-30 mg/L) or Wyoming sodium-montmorillonite (SWy-2, 1-4 g/L) led to better promotion activities than the presence of single component. And synergistic promotion of sulfide-mediated AR27 reduction was observed with coexisting humin and SWy-2 due to enhanced Fe(II) production. These findings extended our understanding of the influence of humin on reductive transformation of pollutants in the environment.

Biogenic Fenton-like Reaction Involvement in Cometabolic Degradation of Tetrabromobisphenol A by Pseudomonas sp. fz.

Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant (BFR) that has frequently been detected in various environmental compartments. Although TBBPA biotransformation has been observed under both aerobic and anaerobic conditions, knowledge of the detailed mechanism of direct aerobic TBBPA biodegradation still remains limited. In this study, the underlying mechanism of cometabolic degradation of TBBPA by Pseudomonas sp. fz under aerobic conditions was investigated. Two key degradation pathways (beta scission and debromination) were proposed based on triple quadrupole liquid chromatography-mass spectrometry (LC-MS) analysis. TBBPA degradation by strain fz was demonstrated to be an extracellular process associated with the low-molecular-mass component (LMMC). Moreover, LMMC was preliminarily identified as oligopeptides, mainly consisting of glycine, proline, and alanine in a 2:1:1 molar ratio. Quenching studies suggested the involvement of hydroxyl radicals ((•)OH) in extracellular TBBPA degradation. To the best of our knowledge, we provide the first evidence that TBBPA was degraded by a biogenic Fenton-like reaction mediated via extracellular H2O2 and Fe(II)-oligopeptide complexes by the genus Pseudomonas. This study provides a new insight into the fate and biodegradation of TBBPA and other organic pollutants in natural and artificial bioremediation environments.

CO2 Fixation, Lipid Production, and Power Generation by a Novel Air-Lift-Type Microbial Carbon Capture Cell System.

An air-lift-type microbial carbon capture cell (ALMCC) was constructed for the first time by using an air-lift-type photobioreactor as the cathode chamber. The performance of ALMCC in fixing high concentration of CO2, producing energy (power and biodiesel), and removing COD together with nutrients was investigated and compared with the traditional microbial carbon capture cell (MCC) and air-lift-type photobioreactor (ALP). The ALMCC system produced a maximum power density of 972.5 mW·m(-3) and removed 86.69% of COD, 70.52% of ammonium nitrogen, and 69.24% of phosphorus, which indicate that ALMCC performed better than MCC in terms of power generation and wastewater treatment efficiency. Besides, ALMCC demonstrated 9.98- and 1.88-fold increases over ALP and MCC in the CO2 fixation rate, respectively. Similarly, the ALMCC significantly presented a higher lipid productivity compared to those control reactors. More importantly, the preliminary analysis of energy balance suggested that the net energy of the ALMCC system was significantly superior to other systems and could theoretically produce enough energy to cover its consumption. In this work, the established ALMCC system simultaneously achieved the high level of CO2 fixation, energy recycle, and municipal wastewater treatment effectively and efficiently.

Catalytic performance of functionalized polyurethane foam on the reductive decolorization of Reactive Red K-2G in up-flow anaerobic reactor under saline conditions.

Soluble anthraquinone compounds including anthraquinone-2-sulfonate (AQS) and anthraquinone-2,6-disulfonate can accelerate anaerobic decolorization of azo dyes. To realize the application of these compounds, the catalytic performance and stability of AQS-modified polyurethane foam (AQS-PUF) for Reactive Red K-2G decolorization were investigated in an up-flow anaerobic bioreactor under saline conditions. The results showed that the optimal influent pH value and hydraulic retention time were 7 and 10 h, respectively, in a continuous-flow bioreactor amended with AQS-PUF (R1). Under the above conditions, R1 (93.8 % color removal) displayed better decolorization performance than the bioreactor amended with PUF (R2, 64 % color removal) in 10 days, when influent K-2G concentration was 50 mg/L. Moreover, compared with R2, R1 could more effectively cope with 50-400 mg/L K-2G and exhibited better stability with over 85 % color removal efficiency within 75 days. Further bacterial community analysis using polymerase chain reaction-denaturing gradient gel electrophoresis showed that AQS-reducing bacteria played an important role in accelerating K-2G decolorization in R1. Extracellular polymeric substances analysis found that biofilm formed on AQS-PUF had very limited negative effects on K-2G decolorization. The catalytic performance of used AQS-PUF only decreased less than 9 % in batch experiments. These findings indicate that AQS-PUF has potential application for the treatment of azo dye-containing wastewater.

Reductive transformation of p-nitrotoluene by a new iron-fly ash packing.

A new iron-fly ash packing was studied for reductive transformation of p-nitrotoluene. The packing was made of iron, fly ash and kaolin with the mass ratio of 36:7:2. A reactor was designed to investigate the long-term performance of the packing. The results showed that the reduction of p-nitrotoluene increased with decreasing pH, because the reduction potential of reaction increased with the concentration of H(+). The pH was one of the key factors impacting the reductive transformation of p-nitrotoluene. Comparing iron-activated carbon packing with the new iron-fly ash packing, the reduction efficiencies were respectively 76.61% and 75.36% after 20days. The reduction efficiency for both was around 50% at 40days. It was evident that these two kinds of packing had no significant difference in their capability for p-nitrotoluene reductive transformation. Compared with iron-activated carbon, the new iron-fly ash packing had obvious advantages in terms of manufacturing costs and environmental pollution degradation. This study showed that the new iron-fly ash packing had good performance in reductive transformation of nitrotoluene compounds.

Treating reverse osmosis brine of petrochemical wastewater using preparative vertical-flow electrophoresis (PVFE) with multi-objective optimization by response surface method.

Electrochemical desalination is an effective method for recovering salts from reverse osmosis (RO) brine. However, traditional technologies like bipolar membrane technology often face challenges related to membrane blockage. To overcome this issue, a preparative vertical-flow electrophoresis (PVFE) system was used for the first time to treat RO brine of petrochemical wastewater. In order to optimize the PVFE operation and maximize acids and bases production while minimizing energy consumption, the response surface method was employed. The independent variables selected were the electric field intensity (E) and flow rate (v), while the dependent variables were the acid-base concentration and energy consumption (EC) for acid-base production. Using the central composite design methodology, the operation parameters were optimized to be E = 154.311 V/m and v = 0.83 mL/min. Under these conditions, the base concentrations of the produced bases and acids reached 3183.06 and 2231.63 mg/L, respectively. The corresponding base EC and acid EC were calculated to be 12.57 and 11.62 kW·h/kg. In terms of the acid-base concentration and energy consumption during the PVFE process, the electric field intensity was found to have a greater influence than the flow rate. These findings provide a practical and targeted solution for recycling waste salt resources from RO brine.

Decolorization of azo dyes by Geobacter metallireducens.

Geobacter metallireducens was found to be capable of decolorizing several azo dyes with different structures to various extents. Pyruvate, ethanol, acetate, propionate, and benzoate could support 66.3 ± 2.6-93.7 ± 2.1 % decolorization of 0.1 mM acid red 27 (AR27) in 40 h. The dependence of the specific decolorization rate on AR27 concentration (25 to 800 µM) followed Michaelis-Menten kinetics (K m = 186.9 ± 1.4 µΜ, V max = 0.65 ± 0.02 µmol mg protein(-1) h(-1)). Enhanced AR27 decolorization was observed with the increase of cell concentrations ranging from 7.5 to 45 mgL(-1). AR27 decolorization by G. metallireducens was retarded by the presence of goethite, which competed electrons with AR27 and was reduced to Fe(II). The addition of low concentrations of humic acid (1-100 mgL(-1)) or 2-hydroxy-1,4-naphthoquinone (0.5-50 µM) could improve the decolorization performance of G. metallireducens. High-performance liquid chromatography analysis suggested reductive pathway to be responsible for decolorization. This was the first study on azo dye decolorization by Geobacter strain and might improve our understanding of natural attenuation and bioremediation of environments polluted by azo dyes.

Decolorization of azo dyes by marine Shewanella strains under saline conditions.

Azo dye decolorization was studied with Shewanella strains under saline conditions. Growing cells of Shewanella algae and Shewanella marisflavi isolated from marine environments demonstrated better azo dye decolorization capacities than the other three strains from non-saline sources. Cell suspensions of S. algae and S. marisflavi could decolorize single or mixed azo dyes with different structures. Decolorization kinetics were described with Michaelis-Menton equation, which indicated better decolorization performance of S. algae over S. marisflavi. Lactate and formate were identified as efficient electron donors for amaranth decolorization by the two strains. S. algae and S. marisflavi could decolorize amaranth at up to 100 g L(-1) NaCl or Na2SO4. However, extremely low concentration of NaNO3 exerted strong inhibition on decolorization. Both strains could remove the color and COD of textile effluent during sequential anaerobic-aerobic incubation. Lower concentrations of NaCl (20-30 g L(-1)) stimulated the activities of azoreductase, laccase, and NADH-DCIP reductase. The decolorization intermediates were identified by high-performance liquid chromatography and Fourier transform infrared spectroscopy. Decolorization metabolites of amaranth were less toxic than original dye. These findings improved our knowledge of azo-dye-decolorizing Shewanella species and provided efficient candidates for the treatment of dye-polluted saline wastewaters.

Accelerated removal of Sudan dye by Shewanella oneidensis MR-1 in the presence of quinones and humic acids.

Although there have been many studies on bacterial removal of soluble azo dyes, much less information is available for biological treatment of water-insoluble azo dyes. The few bacterial species capable of removing Sudan dye generally require a long time to remove low concentrations of insoluble dye particles. The present work examined the efficient removal of Sudan I by Shewanella oneidensis MR-1 in the presence of redox mediator. It was found that the microbially reduced anthraquinone-2,6-disulfonate (AQDS) could abiotically reduce Sudan I, indicating the feasibility of microbially-mediated reduction. The addition of 100 µM AQDS and other different quinone compounds led to 4.3-54.7 % increase in removal efficiencies in 22 h. However, adding 5-hydroxy-1,4-naphthoquinone into the system inhibited Sudan I removal. The presence of 10, 50 and 100 µM AQDS stimulated the removal efficiency in 10 h from 26.4 to 42.8, 54.9 and 64.0 %, respectively. The presence of 300 µM AQDS resulted in an eightfold increase in initial removal rate from 0.19 to 1.52 mg h⁻¹ g⁻¹ cell biomass. A linear relationship was observed between the initial removal rates and AQDS concentrations (0-100 µM). Comparison of Michaelis-Menten kinetic constants revealed the advantage of AQDS-mediated removal over direct reduction. Different species of humic acid could also stimulate the removal of Sudan I. Scanning electronic microscopy analysis confirmed the accelerated removal performance in the presence of AQDS. These results provide a potential method for the efficient removal of insoluble Sudan dye.

Removal of nitric oxide from simulated flue gas via denitrification in a hollow-fiber membrane bioreactor.

A hollow-fiber membrane bioreactor (HMBR) was studied for its ability to treat nitric oxide (NO) from simulated flue gas. The HMBR was operated for 9 months and showed a maximum elimination capacity of 702 mg NO/(m2.day) with a removal efficiency of 86% (gas residence time of 30 sec, inlet NO concentration of 2680 mg/m3, pH 8). Varying operation parameters were tested to determine the stability and response of the HMBR. Both the inlet NO concentration and gas residence time influenced the removal of NO in the HMBR. NO elimination capacity increased with an increase in inlet NO concentration or a shortening of gas residence time. Higher removal efficiency of NO was obtained at a longer gas residence time or a lower inlet NO concentration. Microbial communities of the HMBR were sensitive to the variation in pH value and alkalescence corresponding to an optimum pH value of 8. In addition, NO elimination capacity and removal efficiency were inversely proportional to the inlet oxygen concentration. Sulfur dioxide had no great influence on elimination capacity and removal efficiency of NO. Product analysis was performed to study N20 and N2 production and confirmed that the majority of the microorganisms were denitrifying bacteria in the HMBR. Compared to other bioreactors treating NO, this study showed that the denitrifying HMBR was a good option for the removal of NO.

Alkaline-thermal hydrolysate of waste activated sludge as a co-metabolic substrate enhances biodegradation of refractory dye reactive black 5.

Aromatic azo dyes possess inherent resistance and are known to be carcinogenic, posing a significant threat to human and ecosystems. Enhancing the biodegradation of azo dyes usually requires the presence of co-metabolic substrates to optimize the process. In addressing the issue of excessive waste activated sludge (WAS) generation, this study explored the potential of utilizing alkaline-thermal hydrolysate of WAS as a co-metabolic substrate to boost the degradation of reactive black 5 (RB5) dyes. The acclimated microbial consortium, when supplemented with the WAS hydrolysate obtained at a hydrolysis temperature of 30 °C, achieved an impressive RB5 decolorization efficiency of 90.3% (pH = 7, 35 °C) with a corresponding COD removal efficiency of 45.0%. The addition of WAS hydrolysate as a co-substrate conferred the consortium with a remarkable tolerance to high dye concentration (1500 mg/L RB5) and salinity levels (4-5%), surpassing the performance of conventional co-metabolic sugars in RB5 degradation. 3D-EEM analysis revealed that protein-like substances rich in tyrosine and tryptophan, present in the WAS hydrolysate, played a crucial role in promoting RB5 biodegradation. Furthermore, the microbial consortium community exhibited an enrichment of dye-degrading species, including Acidovorax, Bordetella, Kerstersia, and Brevundimonas, which dominated the community. Notably, functional genes associated with dye degradation and intermediates were also enriched during the RB5 decolorization and biodegradation process. These findings present a practical strategy for the simultaneous treatment of dye-containing wastewater and recycling of WAS.

Facile preparation of coprecipitates between iron oxides and dissolved organic matter for efficient Fenton-like degradation of norfloxacin.

As two important components of dissolved organic matter (DOM), dissolved black carbon (DBC) and humic acid (HA) possess different chemical and structural properties, which might influence their activities like metal complexation and mediating electron transfer. In this study, a series of coprecipitates of iron oxides (FeOx) and DOM (HA or DBC) having different C/Fe molar ratios (0.2-3.0) was prepared under ambient conditions, which exhibited excellent catalytic efficiencies upon Fenton-like degradation of norfloxacin (NOR). Pseudo-first-order rate constant of NOR oxidation catalyzed by DBC-FeOx (C/Fe=3.0, 1.13 h-1) was 30.5, 4.3-14.2, and 1.3-15.7 folds higher than those mediated by FeOx alone, HA-FeOx and DBC-FeOx coprecipitates having C/Fe molar ratios of 0.2 and 1.6, respectively. Due to the higher concentrations of surface-bound Fe(III)/Fe(II) in the DBC-FeOx mediated systems, improved Fe(III)/Fe(II) cycling rates, •OH accumulation and NOR degradation were observed as compared with those of counterpart systems mediated by HA-FeOx. Besides functioning in Fe-C complexation to accelerate FeOOH cleavage, carbonyl/carboxyl groups of the coprecipitates also serve as electron shuttles, both of which improved Fe(III)/Fe(II) cycling and •OH production. Our findings emphasized the influence of DOM source and compositions on Fe(III)/Fe(II) cycling and provided a facile approach of preparing Fe-C catalyst for contaminants elimination.

Amino acid preparation and recovery from refractory sludge by the oxidative acid hydrolysis process.

After the anaerobic digestion of excess sludge, dissolved organic matter is absorbed and used, but the treatment of refractory sludge is a headache. The oxidative acid (performic acid and hydrochloric acid) hydrolysis process can effectively prepare amino acids from refractory sludge. During the preparation process, insoluble proteins in sludge were turned into soluble proteins and peptides. All of them eventually hydrolyse into amino acids. The optimum conditions in the single-factor experiment were as follows: a temperature of 110°C, a reaction time of 24 h, and a hydrochloric acid (HCl) concentration of 6 M. The results showed that the maximum total yield of amino acids from refractory sludge was 94.76%. In the orthogonal experiment, the maximum total yield of amino acids was 97.20% under the optimum conditions of a temperature of 113.45°C, a reaction time of 26.79 h, and 5.92 M HCl. The recovery rate of purity amino acids was 17.16 g per 100 g of dry sludge. The recovery rate of the hydrochloric acid was approximately 70%. There were 17 kinds of amino acids in the hydrolysate, which could be used as deodorants, food additives, preservatives, and corrosion inhibitors. This new technology is expected to be very effective in the treatment of refractory sludge.

Role of extracellular polymeric substances in the immobilization of hexavalent chromium by Shewanella putrefaciens CN32 unsaturated biofilms.

Microbial remediation provides a promising avenue for the management and restoration of heavy metal-contaminated soils. Microorganisms in soils usually exist within unsaturated biofilms, however, their response to heavy metals is still limited compared to saturated biofilms. This work investigated the Cr(VI) immobilization by Shewanella putrefaciens CN32 unsaturated biofilms, and explored the underlying mechanisms of Cr(VI) complexation. Results reveal a dose-dependent toxicity of Cr(VI) to the growth of the unsaturated biofilms. During the early growth stage, the Cr(VI) addition stimulated more extracellular polymeric substances (EPS) production. In the meantime, the EPS were demonstrated to be the primary components for Cr(VI) immobilization, which accounted for more than 60% of the total adsorbed Cr(VI). The Fourier transform infrared spectra and X-ray photoelectron spectra corroborated that the binding sites for immobilizing Cr(VI) were hydroxyl, carboxyl, phosphoryl and amino functional groups of the proteins and polysaccharides in EPS. However, for the starved unsaturated biofilms, EPS were depleted and the EPS-bound Cr(VI) were released, which caused approximately 60% of the adsorbed Cr(VI) onto cell components and further aggravated the Cr(VI) stress to cells. This work extends our understanding about the Cr(VI) immobilization by unsaturated biofilms, and provides useful information for remediation of heavy metal-contaminated soils.

Decolorization of azo dyes by Shewanella oneidensis MR-1 in the presence of humic acids.

The effects of humic acid (HA) on azo dye decolorization by Shewanella oneidensis MR-1 were studied. It was found that HA species isolated from different sources could all accelerate the decolorization of Acid Red 27 (AR27). Anoxic and anaerobic conditions were required for the enhancement of azo dye decolorization by HA. In the presence of 50 mg DOC L⁻¹ Aldrich HA, 15-29% increases in decolorization efficiencies of azo dyes with different structures were achieved in 11 h. The enhancing effects increased with the increase of HA concentrations ranging from 25 to 150 mg DOC L⁻¹, and the decolorization rates were directly proportional to the HA concentrations when they were below 100 mg DOC L⁻¹. Lactate and formate were good electron donors for AR27 decolorization in the presence of HA. Both nitrate (0.1-3.0 mM) and nitrite (0.3-1.2 mM) inhibited AR27 decolorization in the presence of HA, and negligible decolorization was observed before their removal. Soluble FeCl3 could accelerate the decolorization process in the presence of HA, whereas insoluble hematite could not. These findings may affect the understanding of bioremediation of azo dye-polluted environments and help improve the treatment of azo dye wastewaters.

Goethite-humic acid coprecipitate mediated Fenton-like degradation of sulfanilamide: The role of coprecipitated humic acid in accelerating Fe(III)/Fe(II) cycle and degradation efficiency.

While extensive studies found that dissociative and iron mineral-adsorbed humic acid (HA) could either stimulate or inhibit Fenton-like processes, little was known about the influence of iron mineral-coprecipitated HA on Fenton-like reactions. Here, goethite and HA (Gt-HA) coprecipitates having different C:Fe molar ratios (C:Fe = 0.16-0.99) were biologically prepared, and for the first time, investigated for their abilities of H2O2 activation and catalytic degradation of sulfanilamide. For system containing Gt-HA with the optimal C:Fe ratio of 0.30, over 91.1% of sulfanilamide (10 mg/L) was removed in 2 h, which was 46.2% higher than that of the control Gt system. Additionally, H2O2 decomposition, •OH production, and organic carbon removal in Gt-HA systems were all more efficient than those in Gt system. Higher carbon moieties stability and lower micropore surface area of Gt-HA decreased the competition for •OH and H2O2, thus helped to improve degradation efficiency. Electrochemical analysis, quenching experiments, and Fe species detection showed that the coprecipitated HA could serve as electron shuttle and complex with Fe(III) mainly via carboxyl groups at octahedral sites to improve Fe(III)/Fe(II) transformation. This study improved our understanding of Fe(III)/Fe(II) cycling in Fe‒C coprecipitates and demonstrated the potential of developing Fe‒C coprecipitates as efficient catalysts in Fenton-like processes.