Microplastics are widely used to manufacture diverse products such as textiles, skin care products, and household products such as detergents and soaps. However, microplastic pollution and its potential health risks are raising concerns worldwide. This study characterized and determined the safety of microplastics in water and sediments obtained from three locations, namely Ibeshe, Amuwo Odofin, and Ojo along Badagry lagoon, Lagos, Nigeria. The samples of the lagoon's surface water and sediments were treated and analyzed for the abundance of microplastics, as well as their shapes, sizes, and types of polymers. The risk index of the polymers in the microplastics was also estimated. Microplastics were found to be more abundant (p ≤ 0.05) in the sediments (283–315 particles/kg) than in the surface water (108–199 particles/L). In both the water and sediments at all the locations, the dominant shapes were fibers (52%–90%), followed by fragments (3%–32%) and films (1%–25%). In order of significance, the microplastic size range of 0-100µm and 100-500µm dominated the surface water, while the size range of 1000-5000µm and 500-1000µm dominated the sediments at all the locations. The dominant polymers in both the water and sediments at all the locations were polyethylene, polypropylene, and polyamide, while the least was polystyrene. In both the water and sediments at all the locations, the dominant risk score among the polymers is III (moderate risk). The results obtained suggest that microplastic pollution poses environmental and health risks to the lagoon, aquatic organisms, and humans. As such, the lagoon required microplastic remediation and control.

It is difficult to achieve simultaneous and efficient removal of heterocyclic drugs (HCDs) and total nitrogen (TN) in conventional denitrification biofilter (DNBF). Inspired by the effective degradation of refractory organic matter by cobalt-based advanced oxidation process and the need for in-situ upgrading of DNBF, peracetic acid (PAA)/cobalt-loaded ceramsite-based DNBF system was constructed for the first time to treat biochemical tailwater containing HCDs. Results showed that PAA/Co-DNBF had relatively high removal rates for the four HCDs with the order of CBZ > TMP > SDZ > SMX, and the optimal DNBF was H2 with 150 μg L⁻¹of PAA. Overall, TN and HCDs removal increased by 178%–455% and 2.50%–40.99% respectively. When the influent concentration of NO₃⁻-N, COD and each HCDs of 20 mg/L, 60 mg/L and 20 μg/L, below 15 mg/L of effluent TN and the highest average removal rate of SMX (67.77%) could be achieved, under HRT of 4 h in H2. More even distribution of microbial species and low acute toxicity of effluent were also achieved. More even distribution of microbial species and low acute toxicity of effluent were also achieved. In addition, high extracellular polymeric substance (EPS) content and Gordonia after the addition of PAA contributed to the degradation of HCDs. This study supplied a potentially effective strategy for the treatment of biochemical tailwater containing HCDs and provided new insight into the advance of denitrification technology.

Bacteria and their secreted extracellular polymeric substances (EPS) are widely distributed in ecosystems and have high capacity for heavy metal immobilization. The knowledge about the molecular-level interactions with heavy metal ions is essential for predicting the behavior of heavy metals in natural and engineering systems. This comprehensive study using potentiometric titration, Fourier-transform infrared (FTIR) spectroscopy, isothermal titration calorimetry (ITC) and X-ray absorption fine structure (XAFS) was able to reveal the functional diversity and adsorption mechanisms for Pb onto bacteira and the EPS in greater detail than ever before. We identified mono-carboxylic, multi-carboxylic, phosphodiester, phosphonic and sulfhydryl sites and found the partitioning of Pb to these functional groups varied between gram-negative and gram-positive bacterial strains, the soluble and cell-bound EPS and Pb concentrations. The sulfhydryl and phosphodiester groups preferentially complexed with Pb in P. putida cells, while multifunctional carboxylic groups promoted Pb adsorption in B. subtilis cells and the protein fractions in EPS. Though the functional site diversity, the adsorption of Pb to organic ligands occurred spontaneously through a universal entropy increase and inner-sphere complexation mechanism. The functional group scale knowledge have implications for the modeling of heavy metal behavior in the environment and application of these biological resources.

Multiwalled carbon nanotubes (MWCNTs) were oxidized using a mixture of H₂SO₄ and HNO₃, and the oxidized MWCNTS were decorated with magnetite (Fe₃O₄). Finally, poly-N-isopropyl acrylamide-co-butyl acrylate (P-NIPAM) was added to obtain P-NIPAM/Fe/MWCNT nanocomposites. The nanosorbents were characterized by various techniques, including X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, and Brunauer–Emmett–Teller analysis. The P-NIPAM/Fe/MWCNT nanocomposites exhibited increased surface hydrophobicity. Owing to their higher adsorption capacity, their kerosene removal efficiency was 95%; by contrast, the as-prepared, oxidized, and magnetite-decorated MWCNTs had removal efficiencies of 45%, 55%, and 68%, respectively. The P-NIPAM/Fe/MWCNT nanocomposites exhibited a sorbent capacity of 8.1 g/g for kerosene removal from water. The highest kerosene removal efficiency from water was obtained at a process time of 45 min, sorbent dose of 0.005 g, solution temperature of 40 °C, and pH 3.5. The P-NIPAM/Fe/MWCNTs showed excellent stability after four cycles of kerosene removal from water followed by regeneration. The reason may be the increase in the positive charge of the polymer at pH 3.5 and the increased adsorption affinity of the adsorbent toward the kerosene contaminant. The pseudo second-order model was found to be the most suitable model for studying the kinetics of the adsorption reaction.

Titanium dioxide nanoparticles (TiO₂ NPs) easily combine with other pollutants such as heavy metals because of their excellent physiochemical properties. However, how such an interaction may affect the binding behavior of metals onto biofilms remains largely unclear. This study, examined the effects of TiO₂ NPs on Cd²⁺ accumulation and toxicity for natural periphytic biofilms were examined. The adsorption kinetics showed that adding 0.1 and 1 mg/L TiO₂–NPs increased the Cd²⁺ adsorption of biofilms at equilibrium by 23.5% and 35.8%, respectively. However, adding 10 mg/L TiO₂ NPs increased the Cd²⁺ adsorption of biofilms at equilibrium by only 1.9%. The adsorption isotherms indicate that the presence of TiO₂ NPs considerably increased the Cd²⁺ adsorption capacity of the biofilms; however, this effect became less prominent at high TiO₂ NP concentrations. The optimum pH for Cd²⁺ adsorption increased with increasing Cd²⁺ and TiO₂ NP contents. At low concentrations, the coexistence of Cd²⁺ and TiO₂ NPs may facilitate their respective accumulation by stimulating the secretion of extracellular polymeric substances and enhancing the microbial activity of the biofilm. The presence of TiO₂ NPs increases the surface binding energy between Cd²⁺ and functional groups such as carboxyl groups, enhancing the Cd²⁺ accumulation on the biofilm.

The effects of biological activated carbon treatment using Fe₂O₃ modified coconut shell-based activated carbon (Fe/CAC) were investigated on the occurrence of opportunistic pathogens (OPs) and formation of disinfection by-products (DBPs) in simulated drinking water distribution systems (DWDSs) with unmodified CAC as a reference. In the effluent of annular reactor (AR) with Fe/CAC, the OPs growth and DBPs formation were inhibited greatly. Based on the differential pulse voltammetry and dehydrogenase activity tests, it was verified that extracellular electron transfer was enhanced in the attached biofilms of Fe/CAC, hence improving the microbial metabolic activity and biological removal of organic matter especially DBPs precursors. Meanwhile, the extracellular polymeric substances (EPS) on the surface of Fe/CAC exhibited stronger viscosity, higher flocculating efficiency and better mechanical stability, avoiding bacteria or small-scale biofilms falling off into the water. Consequently, the microbial biomass and EPS substances amount decreased markedly in the effluent of Fe/CAC filter. More importantly, Fe/CAC did significantly enhance the shaping role on microbial community of downstream DWDSs, continuously excluding OPs advantage and inhibiting EPS production. The weakening of EPS in DWDSs resulted in decrease of microbial chlorine-resistance ability and EPS-derived DBPs precursors supply. Therefore, the deterioration of water quality in DWDSs was inhibited greatly, sustainably maintaining the safety of tap water. Our findings indicated that optimizing biological activated carbon treatment by interface modification is a promising method for improving water quality in DWDSs.

Herein, a pH-independent interpenetrating polymeric networks (Fe-SA-C) were fabricated from graphitic biochar (BC) and iron-alginate hydrogel (Fe-SA) for removal of Cr(VI) and Pb(II) in aqueous solution. Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and scanning electron microscope (SEM) results demonstrated that graphitic BC interpenetration increased surface porosity and distorted surfaces of Fe-SA, which boosted availability of hydroxyl (-OH) group. Fe³⁺ as a cross-linking agent of the alginate endowed Fe-SA-C with positive surfaces (positive zeta potential) and excellent pH buffering capacity, while excessive Fe³⁺ was soldered on Fe-SA-C matrix as FeO(OH) and Fe₂O₃. Cr(VI) removal at pH of 3 by Fe-SA-C (20.3 mg g⁻¹) were 30.3% and 410.6% greater than that by Fe-SA and BC, respectively. Fe-SA-C exhibited minor pH dependence over pH range of 2–7 towards Cr(VI) retention. Greater zeta potential of Fe-SA-C over Fe-SA conferred a better electrostatic attraction with Cr(VI). FTIR and XPS of spent sorbents confirmed the reduction accounted for 98.5% for Cr(VI) removal mainly due to participation of –OH. Cr(VI) reduction was further favored by conductive carbon matrix in Fe-SA-C, as evidenced by more negative Tafel corrosion potential. Reductively formed Cr(III) was subsequently complexed with carboxylic groups originating from oxidation of –OH. Thus, Cr(VI) removal invoked electrostatic attraction, reduction, and surface complexation mechanisms. Pb(II) removal with excellent pH independence was mainly ascribed to surface complexation and possible precipitation. Thus, the functionalized, conductive, and positively-charged Fe-SA-C extended its applicability for Cr(VI) and Pb(II) removal from aqueous solutions in a wide pH range. This research could expand the application of hydrogel materials for removal of both cationic and anionic heavy metals in solutions over an extended pH range.

The synergistic cooperation of microbial cells and their extracellular polymeric substances (EPS) in biofilms is critical for the biofilm’s resistance to heavy metals and the migration and transformation of heavy metals. However, the effects of different components of biofilms have not been fully understood. In this study, the spatial distribution and speciation of copper in the colloidal EPS, capsular EPS, cell walls and membranes, and intracellular fraction of unsaturated Pseudomonas putida (P. putida) CZ1 biofilms were fully determined at the subcellular level. It was found that 60–67% of copper was located in the extracellular fraction of biofilms, with 44.7–42.3% in the capsular EPS. In addition, there was 15.5–20.1% and 17.2–21.2% of copper found in the cell walls and membranes or the intracellular fraction, respectively. Moreover, an X-ray absorption fine structure spectra analysis revealed that copper was primarily bound by carboxyl-, phosphate-, and hydrosulfide-like ligands within the extracellular polymeric matrix, cell walls and membranes, and intracellular fraction, respectively. In addition, macromolecule quantification, fourier-transform infrared spectroscopy spectra and sulfur K-edge x-ray absorption near edge structure analysis further showed the carboxyl-rich acidic polysaccharides in EPS, phospholipids in cell walls and cell membranes, and thiol-rich intracellular proteins were involved in binding of copper in the different components of biofilm. The full understanding of the distribution and chemical species of heavy metals in biofilms not only promotes a deep understanding of the interaction mechanisms between biofilms and heavy metals, but also contributes to the development of effective biofilm-based heavy metal pollution remediation technologies.

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.

Perfluorooctane sulfonate (PFOS) has been widely used as a surface coating for household products. It still exists in living environments despite being restricted, due to its bioaccumulation and long half-life. Studies have shown that PFOS has the ability to induce adipogenic differentiation of human cells. Human mesenchymal stem cells (hMSCs) distributed within the adipose tissue might be a potential target of accumulated PFOS. However, traditional end-point toxicity assays failed to examine the subtle changes of cellular function exposed to low-dose persistent organic pollutants in real time. In the present work, highly sensitive and long-retained (more than 30 days) fluorescence based polymeric nanosensors were developed and employed for real-time assessment of cellular functions. hMSCs were engineered with sensor molecules encapsulated poly (lactic-co-glycolic acid) (PLGA) particles. Once internalized by hMSCs, PLGA particles continuously release and replenish sensor molecules to cytoplasm, resulting in prolonged fluorescence signal against photo bleaching and dilution by exocytosis. With this method, the dynamic changes of viability, ROS induction, and adipogenic differentiation related mRNA expression of hMSCs were monitored. PFOS with the concentration as low as 0.1 μM can induce cellular ROS and enhance the PPARγ and ap2 mRNA expression, suggesting the effect on promoting adipogenic differentiation of hMSCs.