Predatory Bdellovibrio-and-like organism mixtures on efficient MBR in-situ membrane fouling diminishment and mechanisms.

Membrane fouling is a major hindrance that restricts the application of membrane bioreactors (MBRs). Bdellovibrio-and-like organisms (BALOs), as obligatory parasitic bacteria, prey upon various bacteria. In this study, the BALO mixtures were screened and found more effective in membrane fouling mitigation compared to the single BALO species and extended the membrane filtration period by as long as 33.3%. The higher BALO diversity reduced the potential foulants generation in the activated sludge by decreasing the sludge viscosity as high as 13.8 ± 0.6% than the pure culture of BALO. Meanwhile, the mixed BALOs demonstrated superior biofilm predation capabilities, with the content of soluble microbial products and extracellular polymeric substances on the biofilm decreasing by 26.1 ± 0.5% and 38.3 ± 0.2% as the most compared to the single BALO species involved system. Additionally, the BALO mixtures expanded the single strains' host lysis spectrum of both the activated sludge and biofilm. The abundance of membrane-fouling-related bacteria such as Flavobacterium, Rhodobacter, and Labilithrix and pioneer bacteria such as Sphingorhabdus and Pseudomonas was significantly reduced. In summary, this study disclosed the significantly better membrane fouling mitigation effects of the BALOs with higher diversity, suggesting that the expansion of the host range is crucial for the further application of BALOs to enhance the anti-fouling performance of the MBR system.

Modeling and optimization study on degradation of organic contaminants using nZVI activated persulfate based on response surface methodology and artificial neural network: a case study of benzene as the model pollutant.

Due to the complicated transport and reactive behavior of organic contamination in groundwater, the development of mathematical models to aid field remediation planning and implementation attracts increasing attentions. In this study, the approach coupling response surface methodology (RSM), artificial neural networks (ANN), and kinetic models was implemented to model the degradation effects of nano-zero-valent iron (nZVI) activated persulfate (PS) systems on benzene, a common organic pollutant in groundwater. The proposed model was applied to optimize the process parameters in order to help predict the effects of multiple factors on benzene degradation rate. Meanwhile, the chemical oxidation kinetics was developed based on batch experiments under the optimized reaction conditions to predict the temporal degradation of benzene. The results indicated that benzene (0.25 mmol) would be theoretically completely oxidized in 1.45 mM PS with the PS/nZVI molar ratio of 4:1 at pH 3.9°C and 21.9 C. The RSM model predicted well the effects of the four factors on benzene degradation rate (R2 = 0.948), and the ANN with a hidden layer structure of [8-8] performed better compared to the RSM (R2 = 0.980). In addition, the involved benzene degradation systems fit well with the Type-2 and Type-3 pseudo-second order (PSO) kinetic models with R2 > 0.999. It suggested that the proposed statistical and kinetic-based modeling approach is promising support for predicting the chemical oxidation performance of organic contaminants in groundwater under the influence of multiple factors.

Promotion and mechanisms of Bdellovibrio sp. Y38 on membrane fouling alleviation in membrane bioreactor.

Membrane fouling is a major bottleneck limiting the widespread application of membrane bioreactors (MBR). In this study, Bdellovibrio sp. Y38, an obligate bacteriophage bacterium of Bdellovibrio-and-like organisms (BALOs), was enriched into highly concentrated culture medium (106-107 PFU/mL), and daily dosed into the MBR to investigate its effects on membrane fouling mitigation. The strain Y38 prolonged the membrane fouling cycle from 73 days to 90 days, indicating its membrane fouling alleviation potentials. The concentration of BALOs was increased 625 times higher than the control group after the whole operation, resulting in the concentration of chemical oxygen demand and nucleic acids in the liquid phase of the MBR system being significantly increased by 169.8 ± 1.5% and 126.7 ± 2.2%, respectively. The biomass growth rate was reduced by 27.2 ± 0.7% from day 0 to day 54. These results indicated the predation potential of Bdellovibrio sp. Y38 on the microorganisms in the sludge. The improvement of homogenized sludge and filtration and settling performance by the strain Y38 alleviated the membrane fouling. Compared with the control group, the macromolecular proteins in SMP and EPS were partially declined, and the polysaccharide in EPS decreased by 14.0 ± 3.9%, and the ratios of protein content to polysaccharide content (PN/PS) in SMP and EPS significantly increased by 35.6 ± 16.8% and 57.8 ± 6.1% at the middle stage, respectively, indicating the strain Y38 could alleviate membrane fouling by reducing and modifying SMP and EPS. Furthermore, the relative abundance of γ-proteobacteria decreased from 13.2% to 5.1% at the pre-middle stage, and Planctomycetes decreased from 1.5% to 0.8% at the end-stage, which were probably responsible for the membrane fouling mitigation. In addition, the strain Y38 had few impacts on the water treatment performance of MBR. There findings provide a promising strategy for in situ membrane pollution mitigation via exogenous additions of BALOs.

Pluripotency of endogenous AHL-mediated quorum sensing in adaptation and recovery of biological nitrogen removal system under ZnO nanoparticle long-term exposure.

The impacts of quorum sensing (QS) on nanoparticle (NP)-stressed biological nitrogen removal (BNR) system have seldom been addressed yet. In this study, the contributions of endogenous N-acyl-homoserine lactone (AHL)-based QS regulation to the BNR system's adaptation to the zinc oxide (ZnO) NP stress and its recovery potential were systematically investigated. Although 1 mg/L ZnO NPs exerted little impact on the BNR system, chronic exposure to 10 mg/L ones depressed the system's BNR performance which irreversibly impaired the nitrification process even when the system entered the recovery period with no NP added anymore. Meanwhile, ZnO NPs exhibited hormesis effects on the production of AHLs and extracellular polymeric substance (EPS), and activities of superoxide dismutase and catalase. During the ZnO NP exposure period, C4-HSL, C6-HSL, and C10-HSL were discovered to be positively associated with nitrogen removal efficiency, tightly-bound EPS production, and antioxidase activities. Besides, the shifts of Nitrospira, Dechloromonas, Aeromonas, Acinetobacter, Delftia, and Bosea were expected to determine the AHL's dynamic distribution. During the system's recovery stage, Dechloromonas replaced Candidatus_Competibacter as the dominant denitrification-related genus. Dechloromonas abundance elevated with the increased contents of C4-HSL in the aqueous and EPS phases and C10-HSL in EPS and sludge phases, and were expected to promote the activities of BNR-related and antioxidant enzymes, and the EPS production to assist in the recovery of the impaired system's BNR performance. The QS-related BNR genera exhibited higher resilience to ZnO NPs than quorum quenching-related ones, indicating their critical role in nitrogen removal in the restored system. This work provided an insight into the potential pluripotency of AHL-based QS regulation on the ZnO NP-stressed BNR system's adaptation and recovery.

Photocatalytic oxidation degradation of inhibitory fatty acids for aged Chlorella vulgaris cultivation medium recycling.

The medium used for Chlorella vulgaris cultivation exerted obvious inhibitory effects on the growth of C. vulgaris after several culture-harvest cycles. The accumulated fatty acids secreted by C. vulgaris during their growth process were expected to be the cell inhibition components. In this work, the ultraviolet-driven photocatalytic oxidation technique was applied for the degradation of microalgae cell growth inhibition components in the aged cultivation medium, and the reaction parameters were optimized. The results indicated that the photocatalytic oxidation processes using 0.5 g/L [Formula: see text] NPs as the catalyst under the aeration condition showed as high as 74.61 ± 4.60% FA degradation efficiency after 20 min illumination, and the contents of -COOH, [Formula: see text] (α) and -COO-R functional groups in the aged C. vulgaris medium were significantly reduced. In addition, the modification of the photocatalyst further improved the ability of the degradation of FA. When the modified [Formula: see text]/AC and [Formula: see text]/Ag catalysts were applied, the FA degradation rates reached as high as 92.46 ± 0.37% and 93.91 ± 1.37%, respectively. In the recycled medium treated with [Formula: see text]/AC, the cell density in the stable phase reached 96.33 ± 1.83% of that in the fresh medium as the control. In summary, the photocatalytic oxidation with the modified [Formula: see text]/AC catalyst was proposed as the efficient strategy to realize the recycling of the aged C. vulgaris cultivation medium via the degradation of the FA as the cell growth inhibitors.

Chronic effects of cerium dioxide nanoparticles on biological nitrogen removal and nitrous oxide emission: Insight into impact mechanism and performance recovery potential.

The influence of cerium dioxide nanoparticles (CeO2 NPs) on biological nitrogen removal and associated nitrous oxide (N2O) emission has seldom been addressed yet. Herein, the chronic effect of CeO2 NPs on the nitrogen transformation processes during wastewater treatment and the impacted system's self-recovery potential after CeO2 NP stress removal were investigated. CeO2 NP of 10-50 mg/L induced significant declines of the ammonia nitrogen (NH4+-N) and the total nitrogen removal efficiencies, but triggered the nitrite accumulation and the N2O emission. The N2O reductase (NOS) activity was negatively correlated with the N2O emission level, and the inhibition of NOS activity under CeO2 NP stress was probably due to the depressions of the sludge denitrifiers' metabolic activities. The NH4+-N removal efficiency was successfully regained after the recovery period although the N2O emission level was still higher than the pre-exposure period, which was probably due to the residual CeO2 NPs inside the activated sludge.

Sludge dewaterability enhancement under low temperature condition with cold-tolerant Bdellovibrio sp. CLL13.

The dewatering performance of waste activated sludge (WAS) is generally deteriorated under low temperature due to the increase of viscosity, which would exacerbate the difficulties in sludge treatment and disposal. In this study, the cold-tolerant Bdellovibrio sp. CLL13 was successfully screened for efficient sludge biolysis, and it dramatically improved the sludge dewaterability while no significant biolysis effects were observed for the mesophilic BALO strain at 12 °C. The reduction rates of the sludge capillary suction time (CST), the specific resistance of filtration (SRF), the sludge dry weight, and the fecal coliform bacteria concentration at the optimal reaction time of 14 h were 40.1 ± 0.2%, 69.6 ± 0.7%, 7.7 ± 0.4%, and 78.5 ± 0.4%, respectively, when the mixed liquid suspended solids (MLSS) content was between 10.8 and 29.6 g/L, the input dosage of CLL13 was 8.8 × 106 PFU/mL sludge, and the DO level was 1.2 mg/L. Meanwhile, the viscosity reduction rate, the relative hydrophobicity increasement rate, and the bound water reduction rate were 20.3 ± 1.2%, 6.9 ± 0.7%, and 29.4 ± 1.0%, respectively. The ratios of protein content to polysaccharides content in the extracellular polymeric substances (EPS) decreased significantly. In addition, the degradation of the macromolecular substances in EPS and the increase of the soluble chemical oxygen demand, the total nitrogen, the total phosphorus, and the lactate dehydrogenase levels were observed. Therefore, the cold-tolerant CLL13 induced the sludge biolysis and compromised the negative effects of low temperature on the sludge dewatering performance, which should be beneficial for the efficient WAS biolysis treatment application in the near future under low temperature.

Biological-based control strategies for MBR membrane biofouling: a review.

Membrane bioreactor (MBR) technology has been paid extensive attention for wastewater treatment because of its advantages of high effluent quality and minimized occupation space and sludge production. However, the membrane fouling is always an inevitable problem, which causes high operation and maintenance costs and prevents the wide use of MBR technology. The membrane biofouling is the most complicated and has relatively slow progress among all types of fouling. In recent years, many membrane biofouling control methods have been developed. Different from the physical or chemical methods, the biological-based strategies are not only more effective for membrane biofouling control, but also milder and more environment-friendly and, therefore, have been increasingly employed. This paper mainly focuses on the mechanism, unique advantages and development of biological-based control strategies for MBR membrane biofouling such as quorum quenching, uncoupling, flocculants and so on. The paper summarizes the up-to-date development of membrane biofouling control strategies, emphasizes the advantages and promising potential of biological-based ones, and points out the direction for future studies.

Insights into chronic zinc oxide nanoparticle stress responses of biological nitrogen removal system with nitrous oxide emission and its recovery potential.

The nitrogen transformation performances and greenhouse gas nitrous oxide (N2O) emissions in a sequencing batch reactor under chronic exposure to zinc oxide nanoparticles (ZnO NPs) were quantified and the system's self-recovery potentials were assessed. ZnO NPs posed a dose-dependent depression effect on the removal efficiencies of ammonia nitrogen (NH4+-N) and total nitrogen (TN), and the N2O emissions. The suppressed N2O emissions had a positive relationship with the activity ratios of nitrite/NO reductases and N2O reductase, and were expected to be caused by the inhibited heterotrophic denitrification process. The inhibition of glucose metabolism key enzymes and electron transport chain activities would be responsible for the heterotrophic denitrification performances deterioration. Furthermore, the removal efficiencies of NH4+-N and TN were recovered to control levels through the nitrite-shunt. However, the N2O emission increased significantly above the control during the recovery period mainly due to the irreversibility of the depressed nitrite oxidation activities.

The effects of norethindrone on the ontogeny of gene expression along the hypothalamic-pituitary-adrenal and hypothalamic-pituitary-gonadal axes in zebrafish (Danio rerio).

Little is known about the molecular effects of progestins on the hypothalamic-pituitary-adrenal (HPA) and hypothalamic-pituitary-gonadal (HPG) axes in fish prior to sexual differentiation. In this study, the effects of norethindrone (NET) on the ontogeny of HPG- and HPA-related genes in zebrafish embryo/early larvae prior to sexual differentiation were evaluated. Embryo/larvae were exposed to different concentrations (5, 50, 500 ng/L) of NET for 6 days. The levels of the transcripts of the genes closely related to the HPG and HPA axes were determined daily during 3 stages (embryo, embryo/larvae transition, and early larvae). The results showed that most genes were up-regulated and the ontogeny of genes in the HPA axis was earlier than that of HPG axis, especially for the upstream genes of both the HPG (gnrh2, gnrh3, fshb, lhb) and the HPA (crh, pomc, star) axes. In contrast, the transcriptional expressions of genes of the cortisol/stress pathway (cyp11b, mr) were inhibited and those of the progesterone pathway were not affected. More importantly, NET exposure induced the expressions of the genes (esr1, vtg1, hsd17b3, hsd11b2, ar) that are closely related to the steroid hormone pathways in the embryos/larvae stages, implying a precocious effects of NET in zebrafish. This study demonstrates that NET alters the expression of HPA- and HPG-axes related genes in zebrafish at early stages, pointing to the need for the same type of analysis during the zebrafish gonadal differentiation window.

Norethindrone alters mating behaviors, ovary histology, hormone production and transcriptional expression of steroidogenic genes in zebrafish (Danio rerio).

The impact of progestins (i.e. synthetic forms of progesterone) on aquatic organisms has drawn increasing attention due to their widespread occurrence in the aquatic environments and potential effects on the endocrine system of fish. In this study, the effects of norethindrone (NET, a progestin) on the reproductive behavior, sex hormone production and transcriptional expressions were evaluated by exposing female zebrafish to NET at 0, 3.1, 36.2 and 398.6 ng L-1 for 60 days. Results showed that NET impaired the mating behaviors of female at 36.2 and 398.6 ng L-1 exhibited by males and increased the frequency of atretic follicular cells in the ovary exposed to NET at 398.6 ng L-1. As for sex hormones, plasma testosterone concentration in zebrafish increased, while estradiol concentration decreased. Up-regulation of genes (Npr, Mpra, Mprß, Fshß, Lß, Tshb, Nis and Dio2) was detected in the brain of fish exposed to NET at 398.6 ng L-1. The transcriptional levels of genes (Esr1, Vtg1, Ar, Cyp19a, Cyp11b and Ptgs2) were generally inhibited in the ovary of zebrafish by NET at 398.6 ng L-1. Moreover, the transcripts of genes (Vtg1, Esr1, Ar and Pgr) in the liver were reduced by NET at 36.2 and 398.6 ng L-1. Our findings suggest that NET can potentially diminish the of fish populations not only by damaging their reproductive organs, but also by altering their mating behavior through the changes in the expressions of genes responsible for the production of sex hormones.

Adaption and recovery of Nitrosomonas europaea to chronic TiO2 nanoparticle exposure.

Although the adverse impacts of emerging nanoparticles (NPs) on the biological nitrogen removal (BNR) process have been broadly reported, the adaptive responses of NP-impaired nitrifiers and the related mechanisms have seldom been addressed to date. Here, we systematically explored the adaption and recovery capacities of the ammonia oxidizer Nitrosomonas europaea under chronic TiO2 NP exposure and different dissolved oxygen (DO) conditions at the physiological and transcriptional levels in a chemostat reactor. N. europaea cells adapted to 50 mg/L TiO2 NP exposure after 40-d incubation and the inhibited cell growth, membrane integrity, nitritation rate, and ammonia monooxygenase activity all recovered regardless of the DO concentrations. Transmission electron microscope imaging indicated the remission of the membrane distortion after the cells' 40-d adaption to the NP exposure. The microarray results further suggested that the metabolic processes associated with the membrane repair were pivotal for cellular adaption/recovery, such as the membrane efflux for toxicant exclusion, the structural preservation or stabilization, and the osmotic equilibrium adjustment. In addition, diverse metabolic and stress-defense pathways, including aminoacyl-tRNA biosynthesis, respiratory chain, ATP production, toxin-antitoxin 'stress-fighting', and DNA repair were activated for the cellular adaption coupled with the metabolic activity recovery, probably via recovering the energy production/conversion efficiency and mediating the non-photooxidative stress. Finally, low DO (0.5 mg/L) incubated cells were more susceptible to TiO2 NP exposure and required more time to adapt to and recover from the stress, which was probably due to the stimulation limitation of the oxygen-dependent energy metabolism with a lower oxygen supply. The findings of this study provide new insights into NP contamination control and management adjustments during the BNR process.

Determination of photochemically-generated reactive oxygen species in natural water.

Reactive oxygen species (ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment. ROS may participate in the indirect photolysis of trace organic pollutants, therefore resulting in changes in their environmental fates and ecological risks in natural water systems. Bisphenol A (BPA), an endocrine-disrupting chemical, exits widely in natural waters. The photodegradation of BPA promoted by ROS (*OH, 1O2, HO2*/O2(*-)), which were produced on the excitation of ubiquitous constituents (such as nitrate ion, humic substances and Fe(III)-oxalate complexes) in natural water under simulated solar radiation was investigated. Both molecular probe method and electron spin resonance (ESR) test were used for the characterization of the generated ROS. It was found that *OH was photochemically produced in the presence of nitrate ions, humic substances and Fe(III)-oxalate complexes and that 102 was produced with the presence of humic substances. The steady-state concentrations of *OH was 1.27x10(-14) mol/L in a nitrate solution, and the second-order rate constant of BPA with *OH was 1.01 x 10(10) L/(mol x s).

Photodegradation of bisphenol A in Fe(III)-oxalate complexes solution.

The aqueous photodegradation of bisphenol A (BPA) in the presence of Fe(III)-oxalate complexes (Fe(III)-Ox), which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe(III)-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial BPA level and increasing Fe(III)/oxalate concentration ratio. Hydroxyl radicals (*OH), which were generated from the photochemical processes of Fe(III)-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance (ESR) methods with the steady-state concentration of 2.56 x 10(-14) mol/L. Superoxide anion radical (O2*-) was considered as the precursor of *OH and qualitatively determined by adding nitro blue tetrazolium as well as ESR experiments. Based on the structural analysis of the intermediate photoproducts of BPA in Fe(III)-Ox complexes solution, the possible degradation pathways of BPA were proposed, involving *OH addition, alkyl scission and alky oxidation. The results indicate that the photochemical reactivity of Fe(III) may affect the environmental fate of BPA in natural water significantly.

Photosensitized degradation of bisphenol A involving reactive oxygen species in the presence of humic substances.

The photodegradation of endocrine disrupter bisphenol A (BPA) in the presence of natural humic substances (HS) under simulated solar irradiation was studied. BPA underwent slow direct photolysis in neutral pure water, but rapid photosensitized degradation in four kinds of HS, following pseudo-first-order reaction. Reactive oxygen species (ROS) formed from HS were determined, including OH, (1)O(2) and H(2)O(2). The enhancement of BPA degradation by adding Fe(III) was primarily attributed to the oxidation of OH produced from photo-Fenton-like reaction. And the joint effects of HS and nitrate ions coexisting on BPA degradation appeared to depend on respective concentration levels. The effects of dissolved oxygen suggested that the energy transfer between excited state of SRFA and NOFA likely occurred, while the abstraction of phenolic hydrogen atom to reactive triplet state of NOHA possibly took place. Based on the structural analyses of main intermediates and degradation products of BPA detected by GC-MS, the possible photodegradation pathways were proposed, involving the alky cleavage, alkyl oxidation and OH addition. This study gave a better understanding for the photochemical transformation of BPA induced by ROS generated from natural water composition under sunlight irradiation.

[Photodegradation of bisphenol A in presence of Suwannee River fulvic acid].

Under simulated solar irradiation, the degradation of bisphenol A (BPA) was studied in the presence of Suwannee River Fulvic Acid (SRFA). The results demonstrate that the photodegradation of BPA followed a pseudo-first-order kinetics and the photodegradation rate increased rapidly with increasing initial concentration of SRFA. Hydroxyl radical, singlet oxygen were found in the SRFA solutions of BPA with molecular probes and the technique of electronic spin resonance. The electronic energy transfer of triplet state fulvic acid was also studied with various aerated conditions. The results showed that the photodegradation of BPA was related with triplet state fulvic acid. The photodegradation products of BPA in the presence of SRFA were identified with GC/MS methods. The photodegradation pathways of BPA were also discussed.

Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions.

The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO3- (10 mmol/L, pH = 5) and NO2- (10 mmol/L, pH = 5) solutions under ultraviolet irradiation were at a same magnitude, 10(-15) mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO3- and NO2- respectively, all comparable to the results of previous studies.