Comparison of membrane fouling in ultrafiltration of down-flow and up-flow biological activated carbon effluents

The UF membrane fouling by down- and up-flow BAC effluents were compared. Up-flow BAC effluent fouled the membrane faster than down-flow BAC effluent. The combined effects dominated irreversible fouling. The extent of fouling exacerbated by inorganic particles was higher. The TMP, permeate flux, and normalized membrane flux during 21 days of UF of DBAC and UBAC effluents. Fouling during ultrafiltration of down- and up-flow biological activated carbon effluents was investigated to determine the roles of polysaccharides, proteins, and inorganic particles in ultrafiltration membrane fouling. During ultrafiltration of down- flow biological activated carbon effluent, the trans-membrane pressure was≤26 kPa and the permeate flux was steady at 46.7 L?m⁻²?h⁻¹. However, during ultrafiltration of up-flow biological activated carbon effluent, the highest trans-membrane pressure was almost 40 kPa and the permeate flux continuously decreased to 30 L?m⁻²?h⁻¹. At the end of the filtration period, the normalized membrane fluxes were 0.88 and 0.62 for down- and up-flow biological activated carbon effluents, respectively. The membrane removed the turbidity and polysaccharides content by 47.4% and 30.2% in down- flow biological activated effluent and 82.5% and 22.4% in up-flow biological activated carbon effluent, respectively, but retained few proteins. The retention of polysaccharides was higher on the membrane that filtered the down- flow biological activated effluent compared with that on the membrane that filtered the up-flow biological activated carbon effluent. The polysaccharides on the membranes fouled by up-flow biological activated carbon and down- flow biological activated effluents were spread continuously and clustered, respectively. These demonstrated that the up-flow biological activated carbon effluent fouled the membrane faster. Membrane fouling was associated with a portion of the polysaccharides (not the proteins) and inorganic particles in the feed water. When there was little difference in the polysaccharide concentrations between the feed waters, the fouling extent was exacerbated more by inorganic particles than by polysaccharides.     

Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst in the catalytic wet air oxidation (CWAO) of cationic red GTL under mild reaction conditions

Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. HO₂· and O₂·⁻ appeared as the main reactive species in the reaction. The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. Hydroperoxy radicals (HO₂·) and superoxide radicals (O₂⁻·) appeared as the main reactive species upon the CWAO of cationic red GTL.     

Energy reduction of a submerged membrane bioreactor using a polytetrafluoroethylene (PTFE) hollow-fiber membrane

The fiber length and packing density of the PTFE membrane element were increased. The MBR was stably operated under an SAD^m of 0.13 m³·m^-2·hr^-1. Specific energy consumption was estimated to be less than 0.4 kWh·m^-3. In this study, we modified a polytetrafluoroethylene (PTFE) hollow-fiber membrane element used for submerged membrane bioreactors (MBRs) to reduce the energy consumption during MBR processes. The high mechanical strength of the PTFE membrane made it possible to increase the effective length of the membrane fiber from 2 to 3 m. In addition, the packing density was increased by 20% by optimizing the membrane element configuration. These modifications improve the efficiency of membrane cleaning associated with aeration. The target of specific energy consumption was less than 0.4 kWh·m^-3 in this study. The continuous operation of a pilot MBR treating real municipal wastewater revealed that the MBR utilizing the modified membrane element can be stably operated under a specific air demand per membrane surface area (SAD_m) of 0.13 m³·m^-2·hr^-1 when the daily-averaged membrane fluxes for the constant flow rate and flow rate fluctuating modes of operation were set to 0.6 and 0.5 m³·m^-2·d^-1, respectively. The specific energy consumption under these operating conditions was estimated to be less than 0.37 kWh·m^-3. These results strongly suggest that operating an MBR equipped with the modified membrane element with a specific energy consumption of less than 0.4 kWh·m^-3 is highly possible.     

Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation

GO/TiO₂ membrane was prepared by assembling GO nanosheets and TiO₂ nanotubes. The intercalation of TiO₂ nanotubes enlarged the space of GO interlayers and modified the surface morphology. Hydrophilic/underwater superoleophobic property of GO/TiO₂ membrane was obtained. Water permeability, hydrophilicity, oleophobicity and antifouling ability of GO-based membrane were all enhanced by intercalating TiO₂ nontubes. Membrane technology for oil/water separation has received increasing attention in recent years. In this study, the hydrophilic/underwater superoleophobic membrane with enhanced water permeability and antifouling ability were fabricated by synergistically assembling graphene oxide(GO) nanosheets and titanium dioxide (TiO₂) nanotubes for oil/water separation. GO/TiO₂ membrane exhibits hydrophilic and underwater superoleophobic properties with water contact angle of 62° and under water oil contact angle of 162.8°. GO/TiO₂ membrane shows greater water permeability with the water flux up to 531 L/(m²·h·bar), which was more than 5 times that of the pristine GO membrane. Moreover, GO/TiO₂membrane had excellent oil/water separation efficiency and anti-oil-fouling capability, as oil residual in filtrate after separation was below 5 mg/L and flux recovery ratios were over 80%.The results indicate that the intercalation of TiO₂ nanotubes into adjacent GO nanosheets enlarged the channel structure and modified surface topography of the obtained GO/TiO₂ membranes, which improved the hydrophilicity, permeability and anti-oil-fouling ability of the membranes, enlightening the great prospects of GO/TiO₂ membrane in oil-water treatment.     

How aerosol direct effects influence the source contributions to PM2.5 concentrations over Southern Hebei,China in severe winter haze episodes

The aerosol direct effects result in a 3%–9% increase in PM_2.5 concentrations over Southern Hebei. These impacts are substantially different under different PM_2.5 loadings. Industrial and domestic contributions will be underestimated if ignoring the feedbacks. Beijing-Tianjin-Hebei area is the most air polluted region in China and the three neighborhood southern Hebei cities, Shijiazhuang, Xingtai, and Handan, are listed in the top ten polluted cities with severe PM_2.5 pollution. The objective of this paper is to evaluate the impacts of aerosol direct effects on air quality over the southern Hebei cities, as well as the impacts when considering those effects on source apportionment using three dimensional air quality models. The WRF/Chem model was applied over the East Asia and northern China at 36 and 12 km horizontal grid resolutions, respectively, for the period of January 2013, with two sets of simulations with or without aerosol-meteorology feedbacks. The source contributions of power plants, industrial, domestic, transportation, and agriculture are evaluated using the Brute-Force Method (BFM) under the two simulation configurations. Our results indicate that, although the increases in PM_2.5 concentrations due to those effects over the three southern Hebei cities are only 3%–9% on montly average, they are much more significant under high PM_2.5 loadings (~50 μg·m⁻³ when PM_2.5 concentrations are higher than 400 μg m⁻³). When considering the aerosol feedbacks, the contributions of industrial and domestic sources assessed using the BFM will obviously increase (e.g., from 30%–34% to 32%–37% for industrial), especially under high PM_2.5 loadings (e.g., from 36%–44% to 43%–47% for domestic when PM_2.5>400 μg·m⁻³). Our results imply that the aerosol direct effects should not be ignored during severe pollution episodes, especially in short-term source apportionment using the BFM.     

Feasibility assessment of up-flow anaerobic sludge blanket treatment of sulfamethoxazole pharmaceutical wastewater

The UASB system successfully treated sulfamethoxazole pharmaceutical wastewater. High concentration sulfate of this wastewater was the main refractory factor. UASB recovery performance after a few days of inflow arrest was studied. The optimal UASB operating conditions for practical application were determined. Treatment of sulfamethoxazole pharmaceutical wastewater is a big challenge. In this study, a series of anaerobic evaluation tests on pharmaceutical wastewater from different operating units was conducted to evaluate the feasibility of using anaerobic digestion, and the results indicated that the key refractory factor for anaerobic treatment of this wastewater was the high sulfate concentration. A laboratory-scale up-flow anaerobic sludge blanket (UASB) reactor was operated for 195 days to investigate the effects of the influent chemical oxygen demand (COD), organic loading rate (OLR), and COD/SO₄^2? ratio on the biodegradation of sulfamethoxazole in pharmaceutical wastewater and the process performance. The electron flow indicated that methanogenesis was still the dominant reaction although sulfidogenesis was enhanced with a stepwise decrease in the influent COD/SO₄^2? ratio. For the treated sulfamethoxazole pharmaceutical wastewater, a COD of 4983 mg/L (diluted by 50%), OLR of 2.5 kg COD/(m³·d), and COD/SO₄^2? ratio of more than 5 were suitable for practical applications. The recovery performance indicated that the system could resume operation quickly even if production was halted for a few days.     

G-CNTs/PVDF mixed matrix membranes with improved antifouling properties and filtration performance

A novel nanocomposite OMWCNT-A-GO was synthesized by conjugating OMWCNT and GO. The P-OMWCNT-A-GO membrane was fabricated by non-solvent induced phase inversion. The P-OMWCNT-A-GO exhibits the best water flux, BSA rejection and flux recovery. It should be due to the enhanced membrane pore size, porosity and hydrophilicity. Although carbon nanomaterials have been widely used as effective nanofillers for fabrication of mixed matrix membranes (MMMs) with outstanding performances, the reproducibility of the fabricated MMMs is still hindered by the non-homogenous dispersion of these carbon nanofillers in membrane substrate. Herein, we report an effective way to improve the compatibility of carbon-based nanomaterials with membrane matrixes. By chemically conjugating the oxidized CNTs (o-CNTs) and GO using hexanediamine as cross-linker, a novel carbon nanohybrid material (G-CNTs) was synthesized, which inherited both the advanced properties of multi-walled carbon nanotubes (CNTs) and graphene oxide (GO). The G-CNTs incorporated polyvinylidene fluoride (PVDF) MMMs (G-CNTs/PVDF) were fabricated via a non-solvent induced phase separation (NIPS) method. The filtration and antifouling performances of G-CNTs/PVDF were evaluated using distillate water and a 1 g/L bovine serum albumin (BSA) aqueous solution under 0.10 MPa. Compared to the MMMs prepared with o-CNTs, GO, the physical mixture of o-CNTs and GO and pure PVDF membrane, the G-CNTs/PVDF membrane exhibited the highest water flux up to 220 L/m²/h and a flux recovery ratio as high as 90%, as well as the best BSA rejection rate. The excellent performances should be attributed to the increased membrane pore size, porosity and hydrophilicity of the resulted membrane. The successful synthesis of the novel nanohybrid G-CNTs provides a new type of nanofillers for MMMs fabrication.     

Comparison of CNT-PVA membrane and commercial polymeric membranes in treatment of emulsified oily wastewater

CNT-PVA membrane was fabricated and compared with polymeric membranes. The separation performance was evaluated by homemade and cutting fluid emulsions. The three membranes show similar oil retention rates. CNT-PVA membranes have higher permeation fluxes compared with polymeric membranes. CNT-PVA membrane shows higher fouling resistance. Membrane separation is an attractive technique for removal of emulsified oily wastewater. However, polymeric membranes which dominate the current market usually suffer from severe membrane fouling. Therefore, membranes with high fouling resistance are imperative to treat emulsified oily wastewater. In this study, carbon nanotube-polyvinyl alcohol (CNT-PVA) membrane was fabricated. And its separation performance for emulsified oily wastewater was compared with two commercial polymeric membranes (PVDF membrane and PES membrane) by filtration of two homemade emulsions and one cutting fluid emulsion. The results show that these membranes have similar oil retention efficiencies for the three emulsions. Whereas, the permeation flux of CNT-PVA membrane is 1.60 to 3.09 times of PVDF membrane and 1.41 to 11.4 times of PES membrane, respectively. Moreover, after five consecutive operation circles of filtration process and back flush, CNT-PVA membrane can recover 62.3% to 72.9% of its initial pure water flux. However, the pure water flux recovery rates are only 24.1% to 35.3% for PVDF membrane and 6.0% to 26.3% for PES membrane, respectively. Therefore, CNT-PVA membrane are more resistant to oil fouling compared with the two polymeric membranes, showing superior potential in treatment of emulsified oily wastewater.     

Aggravation of membrane fouling and methane leakage by a three-phase separator in an external anaerobic ceramic membrane bioreactor

The existence of three-phase separator did not affect COD removal in the EAnCMBR. The existence of three-phase separator aggravated methane leakage of EAnCMBR. The existence of three-phase separator aggravated membrane fouling rate of EAnCMBR. Start-up of EAnCMBR equipped three-phase separator was slightly delayed. The three-phase separator is a critical component of high-rate anaerobic bioreactors due to its significant contribution in separation of biomass, wastewater, and biogas. However, its role in an anaerobic membrane bioreactor is still not clear. In this study, the distinction between an external anaerobic ceramic membrane bioreactor (EAnCMBR) unequipped (R1) and equipped (R2) with a three-phase separator was investigated in terms of treatment performance, membrane fouling, extracellular polymers of sludge, and microbial community structure. The results indicate that the COD removal efficiencies of R1 and R2 were 98.2%±0.4% and 98.1%±0.4%, respectively, but the start-up period of R2 was slightly delayed. Moreover, the membrane fouling rate of R2 (0.4 kPa/d) was higher than that of R1 (0.2 kPa/d). Interestingly, the methane leakage from R2 (0.1 L/d) was 20 times higher than that from R1 (0.005 L/d). The results demonstrate that the three-phase separator aggravated the membrane fouling rate and methane leakage in the EAnCMBR. Therefore, this study provides a novel perspective on the effects of a three-phase separator in an EAnCMBR.     

An antifouling catechol/chitosan-modified polyvinylidene fluoride membrane for sustainable oil-in-water emulsions separation

• Underwater superoleophobic membrane was fabricated by deposition of catechol/chitosan. • The membrane had ultrahigh pure water flux and was stable under harsh pH conditions. • The membrane exhibited remarkable antifouling property in O/W emulsion separation. • The hydration layer on the membrane surface prevented oil droplets adhesion. Low-pressure membrane filtrations are considered as effective technologies for sustainable oil/water separation. However, conventional membranes usually suffer from severe pore clogging and surface fouling, and thus, novel membranes with superior wettability and antifouling features are urgently required. Herein, we report a facile green approach for the development of an underwater superoleophobic microfiltration membrane via one-step oxidant-induced ultrafast co-deposition of naturally available catechol/chitosan on a porous polyvinylidene fluoride (PVDF) substrate. Membrane morphology and surface chemistry were studied using a series of characterization techniques. The as-prepared membrane retained the original pore structure due to the ultrathin and uniform catechol/chitosan coating. It exhibited ultrahigh pure water permeability and robust chemical stability under harsh pH conditions. Moreover, the catechol/chitosan hydrophilic coating on the membrane surface acting as an energetic barrier for oil droplets could minimize oil adhesion on the surface, which endowed the membrane with remarkable antifouling property and reusability in a cyclic oil-in-water (O/W) emulsion separation. The modified membrane exhibited a competitive flux of ~428 L/(m²·h·bar) after three filtration cycles, which was 70% higher than that of the pristine PVDF membrane. These results suggest that the novel underwater superoleophobic membrane can potentially be used for sustainable O/W emulsions separation, and the proposed green facile modification approach can also be applied to other water-remediation materials considering its low cost and simplicity.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

Microbial community dynamics at high organic loading rates revealed by pyrosequencing during sugar refinery wastewater treatment in a UASB reactor

High strength sugar refinery wastewater was treated in a mesophilic UASB. Pyrosequencing reveals microbial community succession with OLR increase. Diversity of microbial communities in OLR12 is much higher than those in OLR36 and OLR54.0 kgCOD/(kg VSS·d). Fermentative bacteria could deal with increasing OLR through the increase of microbial diversity and quantity. Hydrogen-producing acotogens and methanogens mainly coped with high OLR shocks by increasing the quantity of community The performance and microbial community structure in an upflow anaerobic sludge blanket reactor (UASB) treating sugar refinery wastewater were investigated. The chemical oxygen demand (COD) removal reached above 92.0% at organic loading rates (OLRs) of 12.0–54.0 kgCOD/(m³·d). The volatile fatty acids (VFAs) in effluent were increased to 451.1 mg/L from 147.9 mg/L and the specific methane production rate improved by 1.2–2.2-fold as the OLR increased. The evolution of microbial communities in anaerobic sludge at three different OLRs was investigated using pyrosequencing. Operational taxonomic units (OTUs) at a 3% distance were 353, 337 and 233 for OLR12, OLR36 and OLR54, respectively. When the OLR was increased to 54.0 kgCOD /(m³·d) from 12.0 kgCOD/(m³·d) by stepwise, the microbial community structure were changed significantly. Five genera (Bacteroides, Trichococcus, Chryseobacterium, Longilinea and Aerococcus) were the dominant fermentative bacteria at the OLR 12.0 kgCOD/(m³·d). However, the sample of OLR36 was dominated by Lactococcus, Trichococcus, Anaeroarcus and Veillonella. At the last stage (OLR= 54.0 kgCOD/(m³·d)), the diversity and percentage of fermentative bacteria were markedly increased. Apart from fermentative bacteria, an obvious shift was observed in hydrogen-producing acetogens and non-acetotrophic methanogens as OLR increased. Syntrophobacter, Geobacter and Methanomethylovorans were the dominant hydrogen-producing acetogens and methylotrophic methanogens in the samples of OLR12 and OLR36. When the OLR was increased to 54.0 kgCOD/(m³·d), the main hydrogen-producing acetogens and hydrogenotrophic methanogens were substituted with Desulfovibrio and Methanospirillum. However, the composition of acetotrophic methanogens (Methanosaeta) was relatively stable during the whole operation period of the UASB reactor.     

Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

Statistical modeling of radiolytic (60Co g) degradation of Ofloxacin,antibiotic: Synergetic effect,kinetic studies & assessment of its degraded metabolites

Linear, interactive and quadratic effects of process parameters were studied. Degradation of Ofloxacin (Ofx) was related with G value of irradiation process. The synergistic effect of H₂O₂ on lower dose of g-irradiation was established. The process follows pseudo first order with dose constant (d = 0.232 kGy^–1). The impact of human activities in the past few decades has paved the way for the release of pollutants due to the improper effluent treatment. Recent studies revealed that, Ofloxacin, an antibiotic as one of the major pollutant affecting surface water and ground water. In this study, the radiolytic potential of Ofloxacin was investigated. The effects of pH, dose and concentration of Ofloxacin were analyzed using One Factor At a Time (OFAT) and the interactive effects between the parameters were studied using Face Centered Central Composite Design. The statistically optimised developed model shows 30% degradation at initial antibiotic concentration of 1mM at pH 3.0 and at 2 kGy dose of gamma ray. The process efficiency was evaluated in terms of G value and its correlation with the concentration of antibiotic was also established. The process of degradation was augmented by the addition of H₂O₂ (1.5 mM). The reaction kinetics for the process was evaluated, the dose rate constant and the rate of degradation for the augmented process was found to be 0.232 kGy^-1 and 0.232 mM/kGy, respectively. The degraded metabolites of the radiolytic degradation of Ofloxacin were analyzed through change in pH, reduction in TOC and GC-MS spectrum.     

Occurrence of veterinary antibiotics in struvite recovery from swine wastewater by using a fluidized bed

Antibiotics in wastewater pose pharmacological threats to phosphorous recovery. Recovered struvite particles possessed significantly antibiotic residues. Smaller granules contained much more antibiotics than the larger ones. Organic matters and struvite granulation process exerted significant impacts. Recovering phosphorus from livestock wastewater has gained extensive attention. The residue of veterinary antibiotics in the wastewater may be present in the recovered products, thereby posing pharmacological threats to the agricultural planting and human health. This study investigated antibiotic occurrence in the struvite particles recovered from swine wastewater by using a fluidized bed. Results revealed that tetracyclines possessed significant residues in the struvite granules, with the values ranging from 195.2 mg·kg⁻¹ to 1995.0 mg·kg⁻¹. As for fluoroquinolones, their concentrations varied from 0.4 mg·kg⁻¹ to 1104.0 mg·kg⁻¹. Struvite particles were of various sizes and shapes and displayed different antibiotic adsorption capacities. The data also showed that the smaller granules contained much more antibiotics than the larger ones, indicating that the fluidized granulation process of struvite crystals plays an important role on the accumulation of antibiotics. For tetracyclines, organic matters and struvite adsorption exerted significant impacts on tetracyclines migration. The outcomes underscore the need to consider the residues of antibiotics in resource recovery from wastewater because they exert pharmacological impacts on the utilization of recovered products.     

Seasonal variations of transport pathways and potential sources of PM2.5 in Chengdu,China (2012–2013)

PM_2.5 in Chengdu showed clear seasonal and diurnal variation. 5, 5, 5 and 3 mean clusters are generated in spring, summer, autumn, and winter. Short-distance air masses are important pathways in Chengdu. Emissions within the Sichuan Basin contribute significantly to PM_2.5 pollution. Long-range transport from Southern Xinjiang is a dust invasion path to Chengdu. Seasonal pattern of transport pathways and potential sources of PM_2.5 in Chengdu during 2012–2013 were investigated based on hourly PM_2.5 data, backward trajectories, clustering analysis, potential source contribution function (PSCF), and concentration-weighted trajectory (CWT) method. The annual hourly mean PM_2.5 concentration in Chengdu was 97.4 mg·m^–3. 5, 5, 5 and 3 mean clusters were generated in four seasons, respectively. Short-distance air masses, which travelled within the Sichuan Basin with no specific source direction and relatively high PM_2.5 loadings (>80 mg·m^–3) appeared as important pathways in all seasons. These short pathways indicated that emissions from both local and surrounding regions of Chengdu contributed significantly to PM_2.5 pollution. The cities in southern Chengdu were major potential sources with PSCF>0.6 and CWT>90 mg·m^–3. The northeastern pathway prevailed throughout the year with higher frequency in autumn and winter and lower frequency in spring and summer. In spring, long-range transport from southern Xinjiang was a representative dust invasion path to Chengdu, and the CWT values along the path were 30-60 mg·m^–3. Long-range transport was also observed in autumn from southeastern Xinjiang along a northwesterly pathway, and in winter from the Tibetan Plateau along a westerly pathway. In summer, the potential source regions of Chengdu were smaller than those in other seasons, and no long-range transport pathway was observed. Results of PSCF and CWT indicated that regions in Qinghai and Tibet contributed to PM_2.5 pollution in Chengdu as well, and their CWT values increased to above 30 mg·m^-3 in winter.     

Enhanced cross-flow filtration with flat-sheet ceramic membranes by titanium-based coagulation for membrane fouling control

• Ceramic membrane filtration showed high performance for surface water treatment. • PTC pre-coagulation could enhance ceramic membrane filtration performance. • Ceramic membrane fouling was investigated by four varied mathematical models. • PTC pre-coagulation was high-effective for ceramic membrane fouling control. Application of ceramic membrane (CM) with outstanding characteristics, such as high flux and chemical-resistance, is inevitably restricted by membrane fouling. Coagulation was an economical and effective technology for membrane fouling control. This study investigated the filtration performance of ceramic membrane enhanced by the emerging titanium-based coagulant (polytitanium chloride, PTC). Particular attention was paid to the simulation of ceramic membrane fouling using four widely used mathematical models. Results show that filtration of the PTC-coagulated effluent using flat-sheet ceramic membrane achieved the removal of organic matter up to 78.0%. Permeate flux of ceramic membrane filtration reached 600 L/(m²·h), which was 10-fold higher than that observed with conventional polyaluminum chloride (PAC) case. For PTC, fouling of the ceramic membrane was attributed to the formation of cake layer, whereas for PAC, standard filtration/intermediate filtration (blocking of membrane pores) was also a key fouling mechanism. To sum up, cross-flow filtration with flat-sheet ceramic membranes could be significantly enhanced by titanium-based coagulation to produce both high-quality filtrate and high-permeation flux.     

Sulfur cycle as an electron mediator between carbon and nitrate in a constructed wetland microcosm

• Fe(III) accepted the most electrons from organics, followed by NO₃^‒, SO₄^2‒, and O₂. • The electrons accepted by SO₄^2‒ could be stored in the solid AVS, FeS₂-S, and S⁰. • The autotrophic denitrification driven by solid S had two-phase characteristics. • A conceptual model involving electron acceptance, storage, and donation was built. • S cycle transferred electrons between organics and NO₃^‒ with an efficiency of 15%. A constructed wetland microcosm was employed to investigate the sulfur cycle-mediated electron transfer between carbon and nitrate. Sulfate accepted electrons from organics at the average rate of 0.84 mol/(m³·d) through sulfate reduction, which accounted for 20.0% of the electron input rate. The remainder of the electrons derived from organics were accepted by dissolved oxygen (2.6%), nitrate (26.8%), and iron(III) (39.9%). The sulfide produced from sulfate reduction was transformed into acid-volatile sulfide, pyrite, and elemental sulfur, which were deposited in the substratum, storing electrons in the microcosm at the average rate of 0.52 mol/(m³·d). In the presence of nitrate, the acid-volatile and elemental sulfur were oxidized to sulfate, donating electrons at the average rate of 0.14 mol/(m³·d) and driving autotrophic denitrification at the average rate of 0.30 g N/(m³·d). The overall electron transfer efficiency of the sulfur cycle for autotrophic denitrification was 15.3%. A mass balance assessment indicated that approximately 50% of the input sulfur was discharged from the microcosm, and the remainder was removed through deposition (49%) and plant uptake (1%). Dominant sulfate-reducing (i.e., Desulfovirga, Desulforhopalus, Desulfatitalea, and Desulfatirhabdium) and sulfur-oxidizing bacteria (i.e., Thiohalobacter, Thiobacillus, Sulfuritalea, and Sulfurisoma), which jointly fulfilled a sustainable sulfur cycle, were identified. These results improved understanding of electron transfers among carbon, nitrogen, and sulfur cycles in constructed wetlands, and are of engineering significance.