ZnO nanoparticles (NPs) have been detected in various wastewater treatment plants. It is widely assumed that size has a crucial effect on the NPs toxicity. Concerns have been raised over probable size-dependent toxicity of ZnO NPs to activated sludge, which could eventually affect the treatment efficiencies of wastewater treatment facilities. The size-dependent influences of ZnO NPs on performance, microbial activities, and extracellular polymeric substances (EPS) from activated sludge were examined in sequencing batch reactor (SBR) in present study. Three different sizes (15, 50, and 90 nm) and five concentrations (2, 5, 10, 30, and 60 mg L⁻¹) were trialled. The inhibitions on COD and nitrogen removal were determined by the particle size, and smaller ZnO NPs (15 nm) showed higher inhibition effect than those of 50 and 90 nm, whereas the ZnO NPs with size of 50 nm showed maximum inhibition effect on phosphorus removal among three sizes of ZnO NPs. After exposure to different sized ZnO NPs, microbial enzymatic activities and removal rates of activated sludge represented the same trend, consistent with the nitrogen and phosphorus removal efficiency. In addition, apparent size- and concentration-dependent effects on EPS contents and components were also observed. Compared with the absence of ZnO NPs, 60 mg L⁻¹ ZnO NPs with sizes of 15, 50, and 90 nm increased the EPS contents from 92.5, 92.4, and 92.0 mg g⁻¹ VSS to 277.5, 196.8, and 178.2 mg g⁻¹ VSS (p < 0.05), respectively. The protein and polysaccharide contents increased with the decreasing particle sizes and increasing ZnO NPs concentrations, and the content of protein was always higher than that of polysaccharide.

The effective mineral absorption and bioreduction were considered as two preferred processes to alleviate the bioavailability and toxicity of toxic trace metals. In this study, the bioreduction of hexavalent chromium (Cr(VI)) on goethite (FeOOH) in the presence of Pseudomonas aeruginosa (P. aeruginosa) was investigated with different environmental factors, including carbon source concentrations, pH, temperature and initial Cr(VI) concentrations. The characterization of FeOOH–P. aeruginosa indicated that P. aeruginosa was surrounded by FeOOH, which could provide the essential iron for bacterial growth and reduce Cr(VI) to Cr(III). The optimal experimental conditions for Cr(VI) (initial concentration: 35 mg L⁻¹) absorption (∼46%) and bioreduction (∼54%) involved a temperature of 45 °C and pH of 5.5. Meanwhile, extracellular polymeric substances (EPS) secreted by P. aeruginosa and its functional groups played important roles in the reduction of Cr(VI). They could reduce Cr(VI) to Cr(III) and transform to Cr(OH)₃ or Feₓ-Cr₍₁₋ₓ₎(OH)₃ precipitation. These results of this study are of significant importance to better understand the environmental geochemical behavior of Cr(VI) with the interactions between soil minerals and microorganisms.

As an important part of extracellular secondary metabolites, extracellular polymeric substances (EPS) can play a significant role in protecting cells from the threat of exogenous substances, including nanoparticles (NPs). However, the regulation mechanisms of EPS secretion under NPs exposure remain largely unknown. This study investigated the signaling pathways and molecular responses related to EPS secretion of algae (Chlorella pyrenoidosa) upon the exposures to anatase and rutile TiO₂ NPs (nTiO₂-A and nTiO₂-R, respectively) at two similar toxic (20% and 50% of algal growth inhibition) concentrations. The results showed that EPS responded to nTiO₂ stress via excess secretion and compositional variation, and nTiO₂-A induced more EPS secretion than nTiO₂-R at similar toxicity concentrations. The up-regulation of the Ca²⁺ signaling pathway might play a greater role in promoting EPS secretion under nTiO₂-R exposure compared with nTiO₂-A exposure, while the significantly increased intracellular ROS could mainly account for the increased EPS secretion under nTiO₂-A exposure. The up-regulated genes related to biological synthesis and protein metabolism and the enhanced biosynthetic metabolism might be the direct causes of the increased EPS secretion. The increased ROS could have a greater effect on the amino acid metabolism and related genes upon the exposure to nTiO₂-A than nTiO₂-R to induce more EPS secretion. More serious membrane damage caused by nTiO₂-R than nTiO₂-A would affect the intracellular inositol phospholipid metabolism more severely, while the inositol phospholipid pathway and Ca²⁺ signaling pathway might agree and communicate with each other inherently to regulate EPS secretion upon nTiO₂-R exposure. The findings address the regulation mechanisms of algal EPS secretion under nTiO₂ exposure and provide new insights into algal bio-responses to nTiO₂ exposure.

Recently polymer inclusion membranes (PIMs) have been proposed as materials for passive sampling, nonetheless a theoretical base to describe the mass transfer process through those materials, under such conditions of monitoring, has not been elucidated. Under the assumption that: (i) the transport of the metal ion occurs at steady state conditions, (ii) the concentration gradients are linear, and (iii) the kinetics of the chemical reactions in the extraction process on the membrane are elemental; an equation for the passive sampling of copper (II) using a PIM system containing Kelex-100 as carrier is derived. The prediction capacity of this sampler under different conditions of temperature, metal concentration, flow velocity, ionic strength and pH is analyzed as well. Among the dependencies of the PIM on the physicochemical conditions, effects of concentration, temperature and flow velocity tend to increment copper (II) flux across the membrane, being the parameter temperature the one with the most pronounced effect at T ≥ 30 °C. Ionic strength had no great effect on passive sampler response, however the sampler is dependent on the acidity of the medium. The comparable metal ion concentrations estimated from the PIM sampler to those obtained by direct measurements of the sampling medium suggest that PIMs can be robust materials when used as passive sampler devices.

Via the thermal sintering, a nanocrystalline IrO₂ coating was formed on the Ti substrate to successfully prepare a Ti/IrO₂ electrode. Based on the electrochemical analysis, the prepared Ti/IrO₂ electrode was found to have powerful oxidation effect on the organics in the TNT red water, where the nitro compound was oxidized through an irreversible electrochemical process at 0.6 V vs. SCE. According to the analysis of the nitro compound content, the UV–vis spectra, and the FTIR spectra of 2,4,6-trinitrotoluene (TNT) red water with electrolytic periods, the degradation mechanism of the dinitrotoluene sulfonate (DNTS) was developed. And the intermediates were characterized by UPLC-HRMS. The DNTS mainly occurred one electron transfer reaction on the Ti/IrO₂ electrode. At the early stage of the electrolysis, the polymerization of DNTS was mainly dominated. The generated polymer did not form a polymer film on the electrode surface, but instead it promoted a further reduction. After electrolyzing for 30 h, all NO₂ function group in the TNT red water was degraded completely.

Soil contamination by toxic heavy metals such as copper is a serious problem. In this study, the extracellular polymeric substance (EPS) extracted from Rahnella sp. LRP3 was found with the potential of immobilizing Cu-polluted in soil. The EPS could bond to Cu (II) through functional groups (polysaccharides, amide, proteins, and carboxyl groups), which further developed into the porous sphere with a diameter of 20 μm. Besides, EPS could induce the formation of Cu₅(PO₄)₂(OH)₄ crystal by the biomineralization process. Finally, the EPS in the culture solution reduced 89.4 mg/kg of DTPA-Cu content by 78.99% in soil for 10 d under the condition of 25 °C via biomineralization. The results demonstrated that EPS produced by Rahnella sp. LRP3 will be a promising factor in the remediation of Cu contaminated soil.

The complexation with extracellular polymeric substances (EPS) greatly reduces the toxicity of heavy metals towards organisms in the environment. However, the molecular mechanism of EPS−metal complexation remains unclear owing to the limitation of precise analysis for key fractions and functionalities in EPS that associate with metals. Herein, we explored the EPS−Cd (II) complexation by fluorescence excitation emission matrix coupled with parallel factor (EEM−PARAFAC), two-dimensional Fourier transform infrared correlation spectroscopy (2D-FTIR−COS) and X-ray photoelectron spectroscopy (XPS), attempting to explain the mechanisms of EPS in alleviating Cd (II) toxicity toward a green alga Chlorella vulgaris (C. vulgaris). When the algal EPS were removed, the cell internalizations of Cd (II), growth inhibition rate and chlorophyll autofluorescence increased, but the surface adsorption and esterase activities decreased, indicating that the sorption of Cd (II) by EPS was crucial in alleviating the algal toxicity. Moreover, the complexation with proteins in EPS controlled the sorption of Cd (II) to algal EPS, resulting in the chemical static quenching of the proteins fluorescence by 47.69 ± 2.37%. Additionally, the complexing capability of the main functionalities, COO⁻ and C–OH in proteins with Cd (II) was stronger than that of C–O(H) and C–O–C in polysaccharides or C–OH in the humus-related substances. Oxygen atom in protein carboxyl C–O might be the key site of EPS−Cd (II) complexation, supported by the modified Ryan−Weber complexation model and the obvious shift of oxygen valence-electron signal. These findings provide deep insights into understanding the interaction of EPS with heavy metals in aquatic environment.

A novel denitrifying bacterium YSF15 was isolated from the Lijiahe Reservoir in Xi’an and identified as Comamonas sp. It exhibited excellent nitrogen removal ability under low C/N conditions (C/N = 2.5) and 94.01% of nitrate was removed in 18 h, with no accumulation of nitrite. PCR amplification and nitrogen balance experiments were carried out, showing that 68.92% of initial nitrogen was removed as gas products and the nitrogen removal path was determined to be NO3−-N→NO2−-N→NO→N2O→N2. Scanning electron microscopy and three-dimensional fluorescence spectroscopy were used to track extracellular polymeric substances (EPS). The results show that complete-denitrification under low C/N conditions is associated with EPS, which may provide a reserve carbon source in extreme environments. These findings reveal that Comamonas sp. YSF15 can provide novel basic materials and a theoretical basis for wastewater bioremediation under low C/N conditions.

Cyanobacterial blooms cause potential risk to submerged macrophytes and biofilms in eutrophic environments. This pilot-scale study investigated the growth, oxidative responses, and detoxification activity of aquatic plants in response to cyanobacterial blooms under different phosphorus concentrations. Variations of extracellular polymeric substances (EPSs) and microbial community composition were also assessed. Results showed that the biomass of Vallisneria natans increased with exposure to cyanobacterial blooms at higher phosphorous concentrations (P > 0.2 mg L⁻¹). The amount of microcystin compounds (MC-LR) released into the water and the accumulation of MC-LR into both plant tissue and biofilms changed according to the phosphorus concentration. Furthermore, a certain degree of oxidative stress was induced in the plants, as evidenced by increased activity of superoxide dismutase, catalase, and peroxidase, as well as increased malondialdehyde concentrations; significant differences were also seen in acid phosphatase and glutathione S-transferase activities, as well as in glutathione concentrations. Together, these responses indicate potential mechanisms of MC-LR detoxification. Broader α-D-glucopyranose polysaccharides (PS) increased with increasing phosphorous and aggregated into clusters in biofilm EPS in response to the cyanobacterial blooms. In addition, alterations were seen in the abundance and structure of the microbial communities present in exposed biofilms. These results demonstrate that cyanobacterial blooms under different concentrations of phosphorus can induce differential responses, which can have a significant impact on aquatic ecosystems.

Arsenic (As) contamination of water poses severe threats to human health and thus requires effective remediation methods. In this study, Synechocystis PCC6803, a model cyanobacterium common in aquatic environments, was used to investigate the role of extracellular polymeric substances (EPS) in As toxicity, accumulation, and transformation processes. We monitored the growth of Synechocystis with As exposure, measured the zeta potential and binding sites on the cell surface, and analysed As accumulation and speciation in Synechocystis cells with and without EPS. After EPS removal, the binding sites and zeta potential of the cell surface decreased by 44.43% and 31.9%, respectively. The growth of Synechocystis decreased 49.4% and 43.7% with As⁽ᴵᴵᴵ⁾ and As⁽ⱽ⁾ exposure, and As accumulation in the cells decreased by 12.8–44.5% and 14–42.7%, respectively. As absorption was enhanced in cells with EPS removed. The oxidation of As⁽ᴵᴵᴵ⁾ and reduction of As⁽ⱽ⁾ were significantly greater in cells with intact EPS compared to those with EPS removed. Fourier transform infrared spectroscopy (FTIR) showed that functional groups of EPS and Synechocystis cells, including –NH, –OH, CO, and CC, interacted with As species. Together the results of this work demonstrate that EPS have significant impacts on cell surface properties, thereby affecting As accumulation and transformation in Synechocystis PCC6803. This work provides a basis for using EPS to remedy As pollution in aquatic environments.