Unveiling the mechanisms of Fe(III)-loaded chitosan composite (CTS-Fe) in enhancing anaerobic digestion of waste activated sludge.

Anaerobic digestion (AD) of waste activated sludge (WAS) is usually limited by the low generation efficiency of methane. Fe(III)-loaded chitosan composite (CTS-Fe) have been reported to effectively enhanced the digestion of WAS, but its role in promoting anaerobic sludge digestion remains unclear. In present study, the effects of CTS-Fe on the hydrolysis and methanogenesis stages of WAS anaerobic digestion were investigated. The addition of CTS-Fe increased methane production potential by 8%-23% under the tested conditions with the addition of 5-20 g/L CTS-Fe. Besides, the results demonstrate that the addition of CTS-Fe could effectively promote the hydrolysis of WAS, evidenced by lower protein or polysaccharides concentration, higher soluble organic carbon in rector adding CTS-Fe, as well as the increased activity of extracellular hydrolase with higher CTS-Fe concentration. Meanwhile, the enrichment of Clostridia abundance (iron-reducing bacteria (IRBs)) was observed in CTS-Fe adding reactor (8.9%-13.8%), which was higher than that in the control reactor (7.9%). The observation further suggesting the acceleration of hydrolysis through dissimilatory iron reduction (DIR) process, thus providing abundant substrates for methanogenesis. However, the presence of CTS-Fe was inhibited the acetoclastic and hydrogenotrophic methanogenesis process, which could be ascribed to the Fe(III) act as electron acceptor coupled to methane for anaerobic oxidation. Furthermore, coenzyme F420 activity in the CTS-Fe added reactor was 34.9% lower than in the blank, also abundance of microorganisms involved in hydrogenotrophic methanogenesis was decreased. Results from this study could provide theoretical support for the practical applications of CTS-Fe.

Periodate activation by pyrite for the disinfection of antibiotic-resistant bacteria: Performance and mechanisms.

The propagation of antibiotic-resistant bacteria (ARB) greatly endangers the ecological safety and human health. This study employed pyrite (FeS2, naturally abundant mineral) for periodate (PI) activation to disinfect ARB. FeS2/PI system could disinfect 1 × 107 CFU mL-1 of kanamycin-resistant E.coli below the limit of detection in 20 min. Efficient ARB inactivation performance was achieved in pH from 3 to 9, ionic strength from 0 to 300 mM, with HA (0.1-10 mg L-1) in suspension, and in real water samples including tap water, river water and sewage. FeS2/PI system could also efficiently disinfect gentamycin-resistant E.coli and Gram-positive B. subtilis. The generated reactive species including Fe(IV), ·O2- and ·OH would attack cell membrane and overwhelmed intracellular defense system. The intracellular kanamycin resistance genes in cells would be released and then degraded in FeS2/PI system. PI preferred to be adsorbed on Fe site of FeS2 (with lower adsorption energy, more occupancy of bonding state and stronger bonding strength). The subsequent transfer of electron cloud from Fe site to PI would cleave IO bond to generate reactive species. Moreover, FeS2/PI system could also combine with sand filtration system to efficiently capture and disinfect ARB. Therefore, FeS2/PI system is a promising approach to inactivate ARB in different scenarios.

Thiadiazole-Based Covalent Organic Frameworks with a Donor-Acceptor Structure: Modulating Intermolecular Charge Transfer for Efficient Photocatalytic Degradation of Typical Emerging Contaminants.

As novel metal-free photocatalysts, covalent organic frameworks (COFs) have great potential to decontaminate pollutants in water. Fast charge recombination in COFs yet inhibits their photocatalytic performance. We found that the intramolecular charge transfer within COFs could be modulated via constructing a donor-acceptor (D-A) structure, leading to the improved photocatalytic performance of COFs toward pollutant degradation. By integrating electron donor units (1,3,4-thiadiazole or 1,2,4-thiadiazole ring) and electron acceptor units (quinone), two COFs (COF-TD1 and COF-TD2) with robust D-A characteristics were fabricated as visible-light-driven photocatalysts to decontaminate paracetamol. With the readily excited electrons in 1,3,4-thiadiazole rings, COF-TD1 exhibited efficient electron-hole separation through a push-pull electronic effect, resulting in superior paracetamol photodegradation performance (>98% degradation in 60 min) than COF-TD2 (∼60% degradation within 120 min). COF-TD1 could efficiently photodegrade paracetamol in complicated water matrices even in river water, lake water, and sewage wastewater. Diclofenac, bisphenol A, naproxen, and tetracycline hydrochloride were also effectively degraded by COF-TD1. Efficient photodegradation of paracetamol in a scaled-up reactor could be achieved either by COF-TD1 in a powder form or that immobilized onto a glass slide (to further ease recovery and reuse) under natural sunlight irradiation. Overall, this study provided an effective strategy for designing excellent COF-based photocatalysts to degrade emerging contaminants.

Photocatalytic degradation of paracetamol and bisphenol A by chitosan supported covalent organic framework thin film with visible light irradiation.

Covalent Organic Frameworks (COFs) have attracted extensive attention for the photocatalytic degradation of emerging organic contaminants. The difficulty in separation and recovery after use yet would hinder the practical application of COFs in powder form. In present study, COFs in film form were fabricated via using chitosan as the film-substrate to support COFs (CSCF). We found that CSCF could effectively degrade two types of emerging organic contaminants under visible light irradiation. Particularly, CSCF could effectively degrade 99.8% of paracetamol (PCT) and 94.0% of bisphenol A (BPA) within 180 min under visible light irradiation. •O2- and h+ played dominant roles during the photocatalytic degradation process. Hydroxylation and cleavage were the main degradation processes. CSCF exhibited good photocatalytic degradation performance in a broad range of ionic strengths, in the presence of common coexisting ions including Cl-, NO3- and SO42-, in a wide range of pH (5-11), and in real water samples including tap water, river water and lake water. Moreover, CSCF could be easily collected after use and exhibited excellent degradation performance in five successive cycles. CSCF has potential applications to treat water with either PCT or BPA contamination. This study provided a new insight into the practical application of COFs.

Catalyst-Free Periodate Activation by Solar Irradiation for Bacterial Disinfection: Performance and Mechanisms.

Periodate (PI)-based advanced oxidation process has recently attracted great attention in the water treatment processes. In this study, solar irradiation was used for PI activation to disinfect waterborne bacteria. The PI/solar irradiation system could inactivate Escherichia coli below the limit of detection (LOD, 10 CFU mL-1) with initial concentrations of 1 × 106, 1 × 107, and 1 × 108 CFU mL-1 within 20, 40, and 100 min, respectively. •O2- and •OH radicals contributed to the bacterial disinfection. These reactive radicals could attack and penetrate the cell membrane, thereby increasing the amount of intracellular reactive oxygen species and destroying the intracellular defense system. The damage of the cell membrane caused the leakage of intracellular K+ and DNA (that could be eventually degraded). Excellent bacterial disinfection performance in PI/solar irradiation systems was achieved in a wide range of solution pH (3-9), with coexisting humic acid (0.1-10 mg L-1) and broad solution ionic strengths (15-600 mM). The PI/solar irradiation system could also efficiently inactivate Gram-positive Bacillus subtilis. Moreover, PI activated by natural sunlight irradiation could inactivate 1 × 107 CFU mL-1 viable E. coli below the LOD in the river and sea waters with a working volume of 1 L in 40 and 50 min, respectively. Clearly, the PI/solar system could be potentially applied to disinfect bacteria in water.

Improved removal performance of Gram-negative and Gram-positive bacteria in sand filtration system with arginine modified biochar amendment.

Bacterial removal by sand filtration system is commonly inefficient due to the low bacterial adsorption capacity of sand. To improve the bacterial removal performance, biochar fabricated at different temperatures (400 °C, 550 °C and 700 °C) and arginine modified biochar were added into sand filtration columns as filter layers (0.5 and 1 wt%). Addition of biochar into sand columns could improve the removal efficiency for both Escherichia coli and Bacillus subtilis under both slow (4 m/day) and fast (240 m/day) filtration conditions. Bacterial removal efficiency in sand columns with the addition of biochar fabricated at 700 °C were higher than those fabricated at 400 °C and 550 °C due to its best bacterial adsorption capacity. Modification of biochar with arginine could further improve the bacterial removal performance. Specifically, complete bacterial removal (1.35 × 107 ± 10% cells/mL) could be achieved under both slow and fast filtration conditions in sand columns with 1 wt% arginine functionalized biochar amendment. The enhanced bacterial adsorption capacity mainly contributed to the increased bacterial capture performance in columns with addition of arginine-modified biochar. Bacteria more tightly bounded with arginine-modified biochar than bulk biochar. Moreover, complete bacterial removal with the copresence of 5 mg/L humic acid in suspensions was acquired in columns with addition of 1 wt% arginine-modified biochar. Efficient bacterial removal in actual river water, multiple filtration cycles as well as longtime injection duration (100 pore volumes injection) was also obtained. The results of this study demonstrated that arginine-modified biochar had great potential to treat water contaminated by pathogenic bacteria.

Insight into efficient phosphorus removal/recovery from enhanced methane production of waste activated sludge with chitosan-Fe supplementation.

Fe(III)-loaded chitosan (CTS-Fe) composite was used for the first time to remove and recover phosphorus (P) from waste activated sludge (WAS) via anaerobic digestion (AD). The P transformation pathway and the effect of CTS-Fe addition on the AD process were investigated using batch experiments. The P fractionation results indicate that non-apatite inorganic phosphorus (NAIP) reduction in the solid phase of sludge at 20 g/L of CTS-Fe addition (6.72 mg/g-SS) was 2.4 times higher than that in the control (2.77 mg/g-SS, no CTS-Fe addition). This is probably brought about by the added CTS-Fe enhanced the reduction of Fe(III)-P compounds in the sludge with phosphate released into the liquid phase. CTS-Fe can efficiently recover 95% of P from the liquid digestate of WAS. Notably, partial Fe(III) on the CTS-Fe was reduced and effectively combined with P to form vivianite crystals on the CTS-Fe surface during the AD process. Characterization analysis demonstrated that ligand exchange and chemical precipitation were the dominant mechanisms for P removal/recovery. Furthermore, the addition of CTS-Fe increased methane production by 11.9 - 32.2% under the tested conditions, likely attributable to the enhanced hydrolysis of WAS under CTS-Fe supplementation. As the P-loaded CTS-Fe particles can be easily separated and recovered from the AD system and further reutilized in agriculture, this study could provide a new approach for simultaneous P removal/recovery and enhanced methane production from AD of WAS.