yang Yang

Effects of ZnO nanoparticles and Zn(2+) on fluvial biofilms and the related toxicity mechanisms.

Zinc oxide nanoparticles (ZnO NPs) used in consumer products are largely released into the environment through the wastewater stream. The health hazard of ZnO NPs and the contribution of dissolved Zn(2+) in toxicity of ZnO NPs has attracted extensive worldwide attention. In this study, the toxic effects of ZnO nanoparticles (ZnO NPs) and the effects of dissolved Zn(2+) on fluvial biofilms were investigated. At the end of the exposure time (21 days), scanning electron microscopy (SEM) images and bioaccumulation experiments revealed that large quantities of ZnO NPs were adsorbed on the biofilm. The algal biomasses were significantly decreased by six- and eleven-fold compared with the control (1.43 μg/L) by exposure to concentrations of 100mg/L ZnO NPs and 7.85 mg/L Zn(2+), respectively. Moreover, under the same exposure conditions, the quantum yields presented contents of 53.33 and 33.33% relative to the control, and a shift in the community composition that manifested as a strong reduction in diatoms was observed from 7 days and reached 15.63 and 6.25% of the control after 21 days of exposure, respectively. The reductions in bacteria viability and reactive oxygen species (ROS) production were noticeably enhanced following exposure to 100mg/L ZnO NPs and 7.85 mg/L Zn(2+), respectively. Additionally, the acute and rapid toxicity of Zn(2+) and the increasing toxicity of the ZnO NPs with increased bioaccumulation were noted in the exposure experiment.

Enhanced stability and dissolution of CuO nanoparticles by extracellular polymeric substances in aqueous environment

Stability of engineered nanoparticles in aquatic environment is an essential parameter to evaluate their fate, bioavailability, and potential toxic effects toward living organisms. As CuO NPs enter the wastewater systems, they will encounter extracellular polymeric substances (EPS) from microbial community before directly interacting with bacterial cells. EPS may play an important role in affecting the stability and the toxicity of CuO NPs in aquatic environment. In this study, the influences of flocculent sludge-derived EPS, as well as model protein (BSA) and natural polysaccharides (alginate) on the dissolution kinetics and colloidal stability of CuO NPs were investigated. Results showed that the presence of NOMs strongly suppressed CuO NPs aggregation, confirmed by DLS, zeta potentials, and TEM analysis. The enhanced stability of CuO NPs in the presence of EPS and alginate were attributed to the electrostatic combined with steric repulsion, while the steric-hindrance effect may be the predominant mechanism retarding nano-CuO aggregation for BSA. Higher degrees of copper release were achieved with the increasing concentrations of NOMs. EPS are more effective than alginate and BSA in releasing copper, probably due to the abundant functional groups and the excellent metal-binding capacity. The ratio of free-Cu2+/total dissolved Cu significantly decreased in the presence of EPS, indicating that EPS may affect the speciation and Cu bioavailability in aqueous environment. These results may be important for assessing the fate and transport behaviors of CuO NPs in the environment as well as for setting up usage regulation and treatment strategy.Graphical Abstract

Aggregation and removal of copper oxide (CuO) nanoparticles in wastewater environment and their effects on the microbial activities of wastewater biofilms.

The transport behaviors of copper oxide (CuO) NPs in wastewater matrix and their possible impacts on microbial activities of stable wastewater biofilms cultivated in a lab scale rotating biological contactor (RBC) were investigated. Significant aggregation of CuO NPs was observed in the wastewater samples, depending on their mass concentrations. Extracellular polymeric substance (EPS)-adsorbed copper accounted for a large proportion of the total copper accumulated in biofilms. The microelectrode profiles showed that a single pulse exposure to 50mg/L CuO resulted in a deeper penetration depth of oxygen in biofilms compared to the CuO NP free biofilms. The maximum oxygen consumption rate shifted to the deeper parts of biofilms, indicating that the respiration activities of bacteria in the top region of the biofilms was significantly inhibited by CuO NPs. Biofilms secreted more EPS in response to the nano-CuO stress, with higher production of proteins compared to polysaccharides.

Response of wastewater biofilm to CuO nanoparticle exposure in terms of extracellular polymeric substances and microbial community structure

The growing production and application of CuO nanoparticles increase the chance that these particles will be released into wastewater treatment plants (WWTPs) and interact with microorganisms. However, the toxicity response mechanism of biofilm to NP exposure may be different from that of activated sludge due to the denser and stronger microbial aggregate structure of biofilm. Thus, in this study, the response to CuO NPs of wastewater biofilm collected from a rotating biological contactor was investigated. Short-term exposure (24h) to CuO NPs led to a great loss in cell viability, and SEM-EDS images revealed that the nano-CuO aggregates were not transformed to Cu-S species in the biofilm samples. In response, more extracellular polymeric substance (EPS) (especially loosely bound-EPS) was produced in wastewater biofilm exposed to CuO NPs, with a higher content of protein compared to polysaccharides. The shifts of fluorescence intensity and peak locations in 3D-EEM fluorescence spectra indicated chemical changes of the EPS components. FT-IR analysis revealed that exposure to nano-CuO had more distinct effects on the functional groups of proteins and polysaccharides in LB-EPS. Illumina sequencing of 16S rRNA gene amplicons revealed that CuO NPs enhanced bacterial diversity. The bacterial community structure significantly shifted, with a significantly increased abundance of Comamonas, a slight increase in Zoogloea, and a notable decrease in Flavobacterium. The shifts of these dominant genera may be associated with altered EPS production, which might result in microbial community function fluctuations. In conclusion, exposure to high concentrations of CuO NPs has the potential to shape wastewater biofilm bacterial community structure.

Effects of cerium oxide nanoparticles on the species and distribution of phosphorus in enhanced phosphorus removal sequencing batch biofilm reactor

The short term (8h) influences of cerium oxide nanoparticles (CeO2NPs) on the process of phosphorus removal in biofilm were investigated. At concentration of 0.1mg/L, CeO2 NPs posed no impacts on total phosphorus (TP) removal. While at 20mg/L, TP removal efficiency reduced from 85.16% to 59.62%. Results of P distribution analysis and 31P nuclear magnetic resonance spectroscopy implied that the anaerobic degradation of polyphosphate (polyP) and the release of orthophosphate in extracellular polymeric substances (EPS) were inhibited. After aerobic exposure, the average chain length of polyP in microbial cells and EPS was shorter than control, and monoester and diester phosphates in cells were observed to release into EPS. Moreover, the EPS production and its contribution to P removal increased, while the capacity of EPS in P storage declined. X-ray diffraction analysis and saturation index calculation revealed that the formation of inorganic P precipitation in biofilm was inhibited.

Effects of CeO2 nanoparticles on sludge aggregation and the role of extracellular polymeric substances – Explanation based on extended DLVO

The extended DLVO (XDLVO) theory was applied to elucidate the potential effects of CeO2 nanoparticles (CeO2 NPs) on sludge aggregation and the role of extracellular polymeric substances (EPS). In this study, seven different concentrations of CeO2 NPs were added to activated sludge cultured in sequencing batch reactors (SBRs) and compared with a control test that received no CeO2 NPs. After exposure to 50mg/L CeO2 NPs, a negligible change (p>0.1) occurred in the sludge volume index (SVI), whereas the flocculability and aggregation of the sludge decreased by 18.8% and 11.2%, respectively, resulting in a high effluent turbidity. The XDLVO theory demonstrated that the adverse effects of the CeO2 NPs on sludge aggregation were due to an enhanced barrier energy. Compared to the van der Waals energies (WA) and the electric double layer (WR), the acid-base interaction (WAB) markedly changed for the various concentrations of CeO2 NPs. The EPS played a decisive role in the sludge surface characteristics, as the removal of EPS equals to the negative effects induced by 5-10mg/L CeO2 NPs on the sludge flocculability and aggregation. The presence of CeO2 NPs induced negative contributions to the tight boundary EPS (TB-EPS) and core bacteria while positive contributions to the total interaction energy of the loose boundary EPS (LB-EPS).

Application of zero valent iron coupling with biological process for wastewater treatment: a review

As a promising technology, zero valent iron (ZVI) coupling with microorganisms has attracted extensive attention for contaminants removal from wastewater. The current paper provides a comprehensive review on recent developments in: (1) the chemical behavior of ZVI and potential mechanisms of integrated bio-ZVI technology in contaminants removal; (2) synergistic effects of bio-ZVI towards various common environmental pollutants in wastewater, including inorganic oxyanions, organic compounds, heavy metals and dyes; (3) promotion effects of ZVI on the biologically anaerobic digestion of waste sludge; (4) operating factors affecting the effectiveness of bio-ZVI process; (5) measures developed to enhance the long-term performance of the bio-ZVI technology. The chemical behavior and stimulating roles of ZVI playing in the growth and diversity of microorganisms is reasonable for the synergistic effects of the combined system. It was demonstrated that combined bio-ZVI system showed appreciable removal efficiencies for several types of contaminants. Additionally, the formation of passive layer on the ZVI surface can be avoided by the means of electrochemical and microbial method. Lastly, this review highlighted the research gaps to improve the sustainability of this technology. Based on these understandings, further efforts should be made to expand the applications of this combined technology and establish some feasible strategies to provide opportunities for the engineering applications.

Effects of iron on growth, antioxidant enzyme activity, bound extracellular polymeric substances and microcystin production of Microcystis aeruginosa FACHB-905

Toxic cyanobacterial blooms have occurred in various water bodies during recent decades and made serious health hazards to plants, animals and humans. Iron is an important micronutrient for algal growth and recently, the concentration of which has increased remarkably in freshwaters. In this paper, the cyanobacterium Microcystis aeruginosa FACHB-905 was cultivated under non-iron (0μM), iron-limited (10μM) and iron-replete (100μM) conditions to investigate the effects of iron on growth, antioxidant enzyme activity, EPS and microcystin production. The results showed that algal cell density and chlorophyll-a content were maximal at the highest iron concentration. Antioxidant enzymes activity increased notably under all three conditions in the early stage of experiment, of which the SOD activity recovered soon from oxidative stress in 10μM group. The productions of some protein-like substances and humic acid-like substances of bound EPS were inhibited in iron-containing groups in the early stage of experiment while promoted after the adaptation period of Microcystis aeruginosa. Iron addition is a factor affecting the formation of cyanobacterial blooms through its impact on the content of LB-EPS and the composition of TB-EPS. The intracellular MC-LR concentration and the productivity potential of MC-LR were the lowest in 0μM group and highest in 10μM group. No obvious extracellular release of MC-LR was observed during the cultivation time. Therefore, iron addition can promote the physiological activities of M. aeruginosa, but a greater harm could be brought into environment under iron-limited (10μM) condition than under iron-replete (100μM) condition.

Influence of CeO2 NPs on biological phosphorus removal and bacterial community shifts in a sequencing batch biofilm reactor with the differential effects of molecular oxygen

The effects of CeO2 nanoparticles (CeO2 NPs) on a sequencing batch biofilm reactor (SBBR) with established biological phosphorus (P) removal were investigated from the processes of anaerobic P release and aerobic P uptake. At low concentration (0.1mg/L), no significant impact was observed on total phosphorus (TP) removal after operating for 8h. However, at a concentration of 20mg/L, TP removal efficiency decreased from 83.68% to 55.88% and 16.76% when the CeO2 NPs were added at the beginning of the anaerobic and aerobic periods, respectively. Further studies illustrated that the inhibition of the specific P release rate was caused by the reversible states of Ce3+ and Ce4+, which inhibited the activity of exopolyphosphatase (PPX) and transformation of poly-β-hydoxyalkanoates (PHA) and glycogen, as well as the uptake of volatile fatty acids (VFAs). The decrease in the specific P uptake rate was mainly attributed to the significantly suppressed energy generation and decreased abundance of Burkholderia caused by excess reactive oxygen species. The removal of chemical oxygen demand (COD) was not influenced by CeO2 NPs under aerobic conditions, due to the increased abundance of Acetobacter and Acidocella after exposure. The inhibitory effects of CeO2 NPs with molecular oxygen were reduced after anaerobic exposure due to the enhanced particle size and the presence of Ce3+.

Towards a better understanding on aggregation behavior of CeO 2 nanoparticles in different natural waters under flow disturbance

The fate of nanoparticles in natural waters is affected by the combination of various factors, especially the flow disturbance which plays a decisive role in the transport of nanoparticles. This study investigated the aggregation behavior of CeO2 nanoparticles (NPs) in natural waters by using a unique instrument to simulate flow disturbance. The results indicated that, in the absence of a shear force, the CeO2 NPs formed linear, chain-like aggregates in seawater, owing to the high IS, which compressed the electrical double layer of particles. On the other hand, the NPs formed more compact aggregates in lake water, owing to an ion bridge effect between the NPs and the dissolved organic matter (DOM). It was also found that shear forces affected the aggregation behavior of the NPs. A low shear force promoted the aggregation of the NPs by increasing the collision efficiency while the aggregates were broken by a high shear force. Remarkably, the NPs maintained their potential for continuous aggregation when the slow stirring was reintroduced, suggesting that the aggregates began to grow again under renewed stirring. The results of this study could help in predicting the fate and transport behavior of CeO2 NPs in actual aquatic environments.