Highly stable and efficient calcined γ-Al2O3 catalysts loaded with MnOx-CeOx for the ozonation of oxytetracycline.

Catalytic ozonation with supported metal oxides is a promising strategy for addressing refractory pollutants in wastewater. In this study, γ-Al2O3 supported MnOx-CeOx catalysts (MC1, MC2, and MC3) obtained at different calcination temperatures (400 °C, 550 °C, and 700 °C) were applied as effective catalysts for ozonation and explored the feasibility of the treatment of oxytetracycline (OTC) wastewater. Comparatively, the MC2 possessed the highest molar ratios of Mn3+/Mn4+ (1.60) and Ce3+/Ce4+ (0.96), the largest surface area (273.8 m2 g-1) with a petal-shaped structure, and most abundant surface hydroxyls (3.78 mmol g-1). These physicochemical characteristics benefited the surface reaction and resulted in the acceleration of ozone decomposition, electron transfer, and •OH generation, thereby improving the catalyst's adsorption ability and catalytic activity. The combination with MC2 increased the OTC and COD removal of the ozonation process from 59.1% and 29.0% to 94.7% and 83.3% in 25 min, respectively. By employing electron paramagnetic resonance (EPR) and radical quenching experiments, it was verified that •OH species generation promoted the mineralization of OTC. The possible degradation pathways of OTC were investigated through mass spectrometry, and the route consisted of dehydration, deamination, and demethylation. Moreover, during a 12-day continuous experiment, MC2 catalyst exhibited excellent reusability and catalytic stability, with COD removal efficiencies above 80%.

Simultaneous partial nitrification, anammox, and denitrification in an upflow microaerobic membrane bioreactor treating middle concentration of ammonia nitrogen wastewater with low COD/TN ratio.

The rapid start-up and operating characteristics of simultaneous partial nitrification, anammox, and denitrification (SNAD) process was investigated using synthetic wastewater with a low C/N ratio (COD: NH4+-N = 200 mg/L: 200 mg/L) in a novel upflow microaerobic membrane bioreactor (UMMBR). The average removal efficiencies of COD, NH4+-N, and TN in the stable phase were 89%, 96%, and 86%, respectively. Carmine granule, which coexisted with sludge floc, appeared on day 83. The high sludge concentration (12.9-17.2 g/L) and the upflow mode of the UMMBR could establish some anaerobicregions for anammox process. The anammox bacteria and short-cut denitrification (NO2-→N2) bacteria with activities of 4.46 mg NH4+-N/gVSS·h and 2.57 mg NO2--N/gVSS·h contributed TN removal of 39% and 61% on day 129, respectively. High-throughput sequencing analysis revealed that the ammonia-oxidizing archaea (AOA, 49.45% in granule and 17.05% in sludge floc) and ammonia-oxidizing bacterial (AOB, 1.30% in sludge floc) dominated the nitrifying microbial community. Candidatus Jettenia (47.14%) and Denitratisoma (10.92%) mainly existed in granule with positive correlations. Some heterotrophic bacteria (OLB13, SJA-15, 1-20, SBR1031, and SJA-28) in sludge floc benefited system stability and sludge activity and protected Candidatus Jettenia from adverse environments.

Effects of alkalinity addition with different strategies on CANON process: Start-up, performance, and microbial community.

The effects of alkalinity addition with different strategies on the start-up, performance, and microbial community of completely autotrophic nitrogen removal over nitrite (CANON) were investigated over 450 days. In phase I, the alkalinity was increased gradually from 300 to 2,000 mg/L to obtain the optimal range. In phase II, the reactor was restarted to verify the appropriate alkalinity value of 1,600 mg/L. The fact that it only took 90 days (phase I: 170 days) to complete the start-up of CANON in phase II demonstrated that an alkalinity value of 1,600 mg/L was suitable when the influent NH4 + -N concentration was 200 mg/L (alkalinity/NH4 + -N = 8:1). The slope (k = 2.00) of NH4 + -N concentration decrease in phase II during the start-up process was significantly higher than that in phase I (k = 1.50). High removal efficiencies of NH4 + -N (98%) and TN (80%) were attained in both phases. Specific anaerobic ammonium oxidation (anammox) activity tests showed that the anammox activity of the two phases reached 3.31 and 5.31 mg TN/(g VSS·h), respectively. High-throughput sequencing analysis revealed that appropriate alkalinity could promote the enrichment of Candidatus Brocadia, C. Jettenia, and C. Kuenenia (total abundance of 31.96%) while effectively inhibiting Nitrospira (abundance of less than 0.50%). PRACTITIONER POINTS: An alkalinity/NH4 + -N ratio of 8 promoted the rapid start-up and stable performance of CANON. NH4 + -N and TN removal efficiencies of 98% and 80%, respectively, were obtained. High alkalinity promoted the enrichment of Candidatus Brocadia, Candidatus Jettenia, Candidatus Kuenenia and inhibited Nitrospira.

Heterogeneous ozonation of ofloxacin using MnOx -CeOx /γ-Al2 O3 as a catalyst: Performances, degradation kinetics and possible degradation pathways.

In this study, the performance of ofloxacin (OFX) degradation in synthetic wastewater using synthesized MnOx -CeOx /γ-Al2 O3 as a heterogeneous ozonation catalyst was evaluated. The removal rates of OFX and chemical oxygen demand (COD) during 15-day continuous-flow experiments were 98.2% and 76.7% on average, respectively. An ozone index (mgCOD/mgO3 ) of 1.09 with a high ozone utilization efficiency of 91.39% was achieved. The pseudo-first-order rate constant of ofloxacin degradation reached 15.216 × 10-2  min-1 , which was five times that (3.085 × 10-2  min-1 ) without catalysts. The results of gas chromatography-mass spectrometry (GC-MS) demonstrated that a variety of small-molecule organics occurred in the final oxidation products, such as 4-hydroxyl-4-methyl-2-pentanone and 2-oxoadipic acid in addition to homologs of OFX. The results of this study suggested that hydroxyl radicals played critical roles in the degradation and mineralization of OFX via four main pathways: (a) electrophilic addition of nitrogen; (b) breakdown of carbon-carbon double bonds; (c) hydrolysis of ether rings; and (d) halodecarboxylation of carboxyl groups. The biodegradability (BOD5 /COD) of OFX after catalytic ozonation reached 0.54. PRACTITIONER POINTS: Ofloxacin wastewater was treated using catalytic ozonation in a 15-day continuous experiment with MnOx -CeOx /γ-Al2 O3 as a catalyst. The ozone index reached 1.09 mgCOD/mgO3 during ozonation of ofloxacin. The presence of the catalyst increased the reaction rate constant by a factor of five. 4-hydroxy-4-methyl-2-pentanone was the primary ofloxacin oxidation product.

Integration of catalytic ozonation and adsorption processes for increased efficiency of textile wastewater treatment.

Advanced and optimized textile wastewater treatment by catalytic ozonation and activated carbon (AC) adsorption was investigated. Scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy indicated that Mn and Ce oxides were successfully loaded on the γ-Al2 O3 support, and MnO2 , Mn2 O3 , CeO2 , and Ce2 O3 were the main components of the catalyst. Actual textile wastewater from biochemical effluent was used as experiment wastewater. The removal efficiencies of chemical oxygen demand (COD) and chromaticity were approximately 30.6% (414-287 mg/L on average) and 99.3% (4,033 times to 27 times on average), respectively during the 30-day on-site continuous-flow test with an ozone dosage, contact time, and gas-liquid ratio of 100 mg/L, 15.7 min, and 2.9, respectively. Following 1 g/L AC adsorption, the effluent COD concentration was reduced to 40 mg/L. By contrast, AC adsorption without catalytic ozonation as pretreatment required 10 g/L AC dosage to achieve similar treatment results. Gas chromatography-mass spectrometry analyses indicated that volatile phenols, sulfides, and aniline in wastewater were completely removed after treatment. Inductively coupled plasma results further showed that the active components of MnOx -CeOx in the catalyst were stable after continuous use for 60 days. PRACTITIONER POINTS: Mesoporous catalyst synthesized by impregnating MnOx -CeOx on γ-Al2 O3 support. Catalytic ozonation and AC adsorption were combined to degrade organics. Maximum degradation of COD and chromaticity by optimizing process variables. The efficiency of the method was compared to that of single AC adsorption.

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure.

Surface enhanced Raman scattering (SERS) is a trace detection technique that extends even to single molecule detection. Its potential application to the noninvasive recognition of lung malignancies by detecting volatile organic compounds (VOCs) that serve as biomarkers would be a breakthrough in early cancer diagnostics. This application, however, is currently limited by two main factors: (1) most VOC biomarkers exhibit only weak Raman scattering; and (2) the high mobility of gaseous molecules results in a low adsorptivity on solid substrates. To enhance the adsorption of gaseous molecules, a ZIF-8 layer is coated onto a self-assembly of gold superparticles (GSPs) in order to slow the flow rate of gaseous biomarkers and depress the exponential decay of the electromagnetic field around the GSP surfaces. Gaseous aldehydes that are released as a result of tumor-specific tissue composition and metabolism, thereby acting as indicators of lung cancer, are guided onto SERS-active GSPs substrates through a ZIF-8 channel. Through a Schiff base reaction with 4-aminothiophenol pregrafted onto gold GSPs, gaseous aldehydes are captured with a 10 ppb limit of detection, demonstrating tremendous prospects for in vitro diagnoses of early stage lung cancer.

Characterizing the compositional variation of dissolved organic matter over hydrophobicity and polarity using fluorescence spectra combined with principal component analysis and two-dimensional correlation technique.

Dissolved organic matter (DOM) obtained from three leachates with different landfill ages was fractionated, and its compositional variation based on hydrophobicity and polarity was characterized by synchronous fluorescence spectra combined with principal component analysis (PCA) and two-dimensional correlation technique. The results showed that the bulk DOM and its fractions were comprised of tryosine-, tryptophan-, fulvic-, and humic-like substances. Tyrosine-like matter was dominant in the young leachate DOM and its fractions, while tryptophan-, fulvic-, and humic-like substances were the main components in the intermediate and old leachate DOMs and their fractions. Tryosine-, tryptophan-, fulvic-, and humic-like substances varied concurrently with the hydrophobicity and polarity. However, the change ratio of these substances was different for the three leachates. Tyrosine-like matter, humic-like materials, and fulvic-like substances were the most sensitive to the hydrophobicity and polarity in the young, intermediate, and old leachates, respectively. Such an integrated approach jointly enhances the characterization of the hydrophobicity- and polarity-dependent DOM fractions and provides a promising way to elucidate the environmental behaviors of different DOM species.

Optimal cultivation and characteristics of aerobic granules with typical domestic sewage in an alternating anaerobic/aerobic sequencing batch reactor.

The present work investigated some important factors for optimal aerobic granulation using typical domestic sewage as a substrate in a pilot-scale alternating anaerobic/aerobic sequencing batch reactor. High sludge concentration and low sludge loading, for the first time, were used for the reactor start-up. A vast number of small particles appeared on day8. Subsequently, several measures for controlling sludge concentration and sludge loading within an appropriate range were applied to optimize the granulation process. On day 45, complete sludge granulation was achieved. After 60days of operation, the aerobic granules always kept in stable state, with an average diameter of 750µm and the SVI(30) of 20-35ml/g. The COD, TN, and TP removal ratios were 92%, 81%, and 85%, respectively. The results demonstrated that it was feasible to form aerobic granules quickly using typical domestic sewage under optimal operation strategies, which was further proved by the results from denaturing gradient gel electrophoresis fingerprint.

Nitrogen conservation in simulated food waste aerobic composting process with different Mg and P salt mixtures.

To assess the effects of three types of Mg and P salt mixtures (potassium phosphate [K3PO4]/magnesium sulfate [MgSO4], potassium dihydrogen phosphate [K2HPO4]/MgSO4, KH2PO4/MgSO4) on the conservation of N and the biodegradation of organic materials in an aerobic food waste composting process, batch experiments were undertaken in four reactors (each with an effective volume of 30 L). The synthetic food waste was composted of potatoes, rice, carrots, leaves, meat, soybeans, and seed soil, and the ratio of C and N was 17:1. Runs R1-R3 were conducted with the addition of K3PO4/ MgSO4, K2HPO4/MgSO4, and KH2PO4/MgSO4 mixtures, respectively; run R0 was a blank performed without the addition of Mg and P salts. After composting for 25 days, the degrees of degradation of the organic materials in runs R0-R3 were 53.87, 62.58, 59.14, and 49.13%, respectively. X-ray diffraction indicated that struvite crystals were formed in runs R1-R3 but not in run R0; the gaseous ammonia nitrogen (NH3-N) losses in runs R0-R3 were 21.2, 32.8, 12.6, and 3.5% of the initial total N, respectively. Of the tested Mg/P salt mixtures, the K2HPO4/ MgSO4 system provided the best combination of conservation of N and biodegradation of organic materials in this food waste composting process.

[Cultivation of aerobic granules in a large pilot SBR with domestic sewage].

The cultivation of aerobic granules in a large pilot-scale SBR was investigated using domestic wastewater. After operation of 210 days, the granules with a diameter of 330 microm were successfully formed by seeding anaerobic digested sludge. Results showed that, during the first three months of operation under low organic load of influent, removal efficiencies of pollutants increased steadily including COD, NH(4+)-N, total nitrogen (TN) and total phosphorous (TP). Meanwhile, microorganisms related to nitrogen and phosphorous were enriched. The organic load was enhanced since cycle time was shortened to 6 h, and the operational performance of the reactor still remained stable. Moreover, the average particle size of the sludge started to increase, along with excellent settling ability and high bioactivity. After the formation of aerobic granules, Sludge volume index (SVI) was maintained at 30 mL x g(-1) and the mixed liquor suspended solid (MLSS) concentration in the SBR reached 8.8 g x L(-1). MLVSS/MLSS ratio of the sludge increased to 82% with a high oxygen uptake rate (OUR) of 5.32 mg x (min x L)(-1). Bacillus was dominant on the outer layer of granules, while cocci were mainly located inside. The average COD and TP removal efficiencies kept at 90% and NH(4+) -N was almost completely depleted, NO(3-) -N and NO(2-) -N were not accumulated in the effluent. The aerobic granules were also capable of achieving simultaneous nitrification and denitrification (SND) in a single SBR cycle, which resulted in a high TN removal efficiency of 80%.