Efficient bio-refractory industrial wastewater treatment with mitigated membrane fouling in a membrane bioreactor strengthened by the micro-scale ZVI@GAC galvanic-cells-initiated radical generation and coagulation processes.

Micro-scale ZVI@GAC-based iron-carbon galvanic-cells (ZVI@GACs) were prepared with the Ca-Si-H/Ca-H formation process and first applied to initiate radical generation and coagulation processes in MBR for treating bio-refractory industrial wastewater (IWW). Batch tests revealed the H2O2 production (0.19-0.28 mg/L) and •OH generation (p-CBA decay, k1 = 0.040 min-1) in ZVI@GACs-dosed system (packing volume of 5%) under aeration. Adoption of ZVI@GACs into aerobic activated sludge process (ZVI@GACs/AS) enhanced TOC degradation (k2) and phenolic compounds (PHENs) destruction (k3). ZVI@GACs/AS at ZVI@GACs packing volume of 5%, 10% and 20% improved k2 from 0.11 h-1 (bare AS) to 0.17, 0.21 and 23 h-1 and k3 from 0.24 h-1 to 0.36, 0.49 and 0.57 h-1, respectively. The oxygen uptake rate (OUR) and 15-min acute bio-toxicity demonstrated that the bio-toxicity of IWW was reduced and the activity of biomass was enhanced in the ZVI@GACs/AS system. In MBR, ZVI@GACs at packing volume of 10% enhanced COD and PHENs removal by 14% and 22%, respectively. Membrane fouling cycle was prolonged by 71%. The accumulations of EPS-proteins, EPS-polysaccharides, SMP-proteins and SMP-polysaccharides were reduced by 6%, 67%, 27% and 60%, respectively. Fourier transform infrared spectroscopy (FTIR) confirmed the oxidation of SMP-polysaccharides in ZVI@GACs-MBR. The iron ions released from ZVI@GACs showed inhibition on the secretion of SMP-/EPS-proteins. Floc particle size distribution (PSD) and X-ray diffraction (XRD) spectrum confirmed that the coagulation effects of Fe(OH)3 and FeOOH triggered by Fe3+ increased the sludge floc size and contributed to membrane fouling mitigation. Genus Enterococcus was enriched in MBR with the destruction of PHENs by the ZVI@GACs-initiated radical generation process. The findings of this study confirmed successful development and adoption of ZVI@GACs into MBR for bio-refractory IWW treatment. It also provided an in-depth understanding on the mechanisms of ZVI@GACs-MBR system.

FeOx@GAC catalyzed microbubble ozonation coupled with biological process for industrial phenolic wastewater treatment: Catalytic performance, biological process screening and microbial characteristics.

Phenolic compounds are common ccontaminants in industrial effluents. In this study, a combined catalytic microbubble ozonation and biological process was developed and applied for efficient industrial phenolic wastewater (PWW) treatment. Catalytic activity of an iron-oxides (FeOx) doped granular activated carbon (GAC) catalyst (FeOx@GAC) in microbubble ozonation for PWW treatment was investigated. The results demonstrated that the FeOx@GAC catalyzed microbubble ozonation (O3/FeOx@GAC) obtained significantly higher reaction rate constant (k1 = 0.023 min-1) in TOC removal compared to the bare GAC catalyzed microbubble ozonation (O3/GAC, k1 = 0.013 min-1) and ordinary microbubble ozonation (k1 = 0.008 min-1). Destruction rate constant of phenolic compounds (k2) was improved from 0.014 min-1 (ordinary microbubble ozonation) to 0.025 min-1 (O3/FeOx@GAC). The 60-min pretreatment of PWW by O3/FeOx@GAC process enhanced BOD5/COD ratio from 0.31 to 0.76 and reduced the acute bio-toxicity by 79.2%. Screening and characterization of biological post-treatment processes were conducted among activated sludge process (ASP), up-flow anaerobic sludge blanket (UASB) and membrane bioreactor (MBR). UASB and ASP showed limited phenolic compounds removal of 35.4% and 57.0% with lower bio-toxicity resistance than MBR (94.9% phenolic compounds removal). The combined process O3/FeOx@GAC-MBR was thus developed and achieved high COD removal (98.0%) and phenolic compounds degradation (99.4%). PWW pretreatment by O3/FeOx@GAC process decreased membrane fouling rate of MBR by 88.2% by reducing proteins/polysaccharides accumulation in both extracellular polymeric substances and soluble microbial products. 16S rRNA high-throughput sequencing revealed the predominance of phylum Proteobacteria, class Alphaproteobacteria and genera Mycobacterium, Gordonia, Pedomicrobium & Defluviimonas in biological PWW treatment bio-systems. Pearson correlation coefficient and ANOVA analysis verified that Mycobacterium possessed high bio-toxicity resistance and was the main contributor to the biodegradation of phenolic compounds.

Effect of UVA/LED/TiO2 photocatalysis treated sulfamethoxazole and trimethoprim containing wastewater on antibiotic resistance development in sequencing batch reactors.

Controlling of antibiotics is the crucial step for preventing antibiotic resistance genes (ARGs) dissemination; UV photocatalysis has been identified as a promising pre-treatment technology for antibiotics removal. However, information about the effects of intermediates present in the treated antibiotics wastewater on the downstream biological treatment processes or ARGs development is very limited. In the present study, continuous UVA/LED/TiO2 photocatalysis removed more than 90% of 100 ppb sulfamethoxazole (SMX)/trimethoprim (TMP), the treated wastewater was fed into SBR systems for over one year monitoring. Residual SMX/TMP (2-3 ppb) and intermediates present in the treated wastewater did not adversely affect SBR performance in terms of TOC and TN removal. SMX and TMP resistance genes (sulI, sulII, sulIII, dfrII, dfrV and dfr13) were also quantified in SBRs microbial consortia. Results suggested that continuous feeding of treated SMX/TMP containing wastewaters did not trigger any ARGs promotion during the one year operation. By stopping the input of 100 ppb SMX/TMP, abundance of sulII and dfrV genes were reduced by 83% and 100%, respectively. sulI gene was identified as the most persistence ARG, and controlling of 100 ppb SMX input did not achieve significant removal of sulI gene. A significant correlation between sulI gene and class 1 integrons was found at the level of p = 1.4E-10 (r = 0.94), and sulII gene positively correlated with the plasmid transfer efficiency (r = 2.442E-10, r = 0.87). Continuous input of 100 ppb SMX enhanced plasmid transfer efficiency in the SBR system, resulting in sulII gene abundance increasing more than 40 times.

Decomposition of sulfamethoxazole and trimethoprim by continuous UVA/LED/TiO2 photocatalysis: Decomposition pathways, residual antibacterial activity and toxicity.

In this study, continuous LED/UVA/TiO2 photocatalytic decomposition of sulfamethoxazole (SMX) and trimethoprim (TMP) was investigated. More than 90% of SMX and TMP were removed within 20min by the continuous photoreactor (with the initial concentration of 400ppb for each). The removal rates of SMX and TMP decreased with higher initial antibiotics loadings. SMX was much easier decomposed in acidic condition, while pH affected little on TMP's decomposition. 0.003% was found to be the optimum H2O2 dosage to enhance SMX photocatalytic decomposition. Decomposition pathways of SMX and TMP were proposed based on the intermediates identified by using LC-MS-MS and GC-MS. Aniline was identified as a new intermediate generated during SMX photocatalytic decomposition. Antibacterial activity study with a reference Escherichia coli strain was also conducted during the photocatalytic process. Results indicated that with every portion of TMP removed, the residual antibacterial activity decreased by one portion. However, the synergistic effect between SMX and TMP tended to slow down the antibacterial activity removal of SMX and TMP mixture. Chronic toxicity studies conducted with Vibrio fischeri exhibited 13-20% bioluminescence inhibition during the decomposition of 1ppm SMX and 1ppm TMP, no acute toxicity to V. fischeri was observed during the photocatalytic process.