Role of extracellular polymeric substances in the aggregation and biological response of micro(nano)plastics with different functional groups and sizes.

In this work, the effects of extracellular polymeric substances (EPS) on the aggregation and biological responses of different micro(nano)plastics (MNPs, <1000 µm) were investigated. EPS increased the colloidal stability of PS MPs in NaCl or CaCl2. For the three PS NPs (PS-NH2, PS-COOH, and PS-naked), EPS also enhanced their colloidal stabilities in the presence of NaCl. However, the effect of CaCl2 on the colloidal stabilities of PS NPs in the presence of EPS depended on their surface functional groups. In CaCl2, both Derjaguin-Landau-Verwey-Overbeek theory and molecular bridging explained the interaction between MNPs (both NPs and MPs) and EPS. Laser Direct Infrared and scanning electron microscope imaging showed that opalescent EPS corona formed on PS MPs via intermolecular-bridging by Ca2+, and the critical coagulation concentrations (70 mM in NaCl, 1.5 mM in CaCl2) in EPS were much lower than that for PS NPs (1000 mM for NaCl; 65 mM for CaCl2). PS-NH2 NPs showed the highest increase in the growth of bacteria (Bacillus subtilis), followed by PS MPs and PS-naked NPs, while PS-COOH NPs had no significant effect. Biological response of PS NPs was unaffected by EPS, while EPS further enhanced the positive effects of PS MPs on bacterial growth.

Adsorption and catalytic degradation of preservative parabens by graphene-family nanomaterials.

Parabens pose increasing threats to human health due to endocrine disruption activity. Adsorption and degradation of parabens by three types of graphene-family nanomaterials (GFNs) were therefore investigated. For a given paraben, the maximum adsorption capacities (Q0) followed the order of reduced graphene oxide (RGO) > multilayered graphene (MG) > graphene oxide (GO); for a given GFN, Q0 followed the order of butylparaben (BuP) > propylparaben (PrP) > ethylparaben (EtP) > methylparaben (MeP), dominated by hydrophobic interaction. MeP removal by all the three GFNs was highly enhanced (0.55-4.37 times) with the assistance of H2O2 due to additional catalytic degradation process, and MG showed the highest removal enhancement. ∙OH was confirmed as the dominant radicals responsible for parabens degradation. For MG and RGO, the metal impurities (Fe, Cu, Mn, and Co) initiated Fenton-like reaction with H2O2 to generate ∙OH. GO contained oxygen-centered free radicals, which were responsible for ∙OH formation via transferring electron to H2O2. Four degradation byproducts of MeP were identified, including oxalic, propanedioic, fumaric, and 2,5-dihydroxybenzoic acids. Combined with density function theory calculations, the degradation sites and pathways were identified and confirmed. These findings provide useful information on mechanistic understanding towards the adsorption and degradation of parabens by GFNs.

Recycling of titanium-coagulated algae-rich sludge for enhanced photocatalytic oxidation of phenolic contaminants through oxygen vacancy.

In the 21st century, sludge disposal and resource recycling are global issues. Titanium coagulation has received increasing attention due its strong coagulation capability and sludge recycling. Titanium coagulation is highly efficient for the treatment of algae-laden micro-polluted surface water; however, the safe disposal of titanium-coagulated algae-rich sludge remains a challenge. Here, we report on the recycling of titanium-coagulated algae-rich sludge for the production of functional TiO2 nanoflowers (TNFs) through a simple hydrothermal and calcination process. Anatase TNFs (particle size of 10-15 nm) with petal-like structures (mesoporous), relatively high specific surface areas, i.e. 299.4 m2g-1, and low band gaps, i.e. 2.67 eV (compared to P-25), were obtained. Additionally, oxygen vacancy (OV) was generated on the surface of the recycled TNFs based on electron paramagnetic resonance (EPR) results, which were verified by the first-principles calculations within density-functional theory. These TNFs display high photocatalytic performance for the degradation of diverse phenolic organic contaminants, such as bisphenol A, diphenyl phenol, p-tert-butyl phenol, and resorcinol, i.e. > 95%, under mild ultraviolet light irradiation and without any sacrificial reagents. Formation of OV on TNFs not only efficiently inhibited the recombination of photo-generated electrons and holes but also facilitated contaminant adsorption and photo-generated electron transfer on the surface of the recycled TNFs, thereby promoting the generation of holes and hydroxyl and superoxide radicals which were regarded as the reactive oxygen species for attacking contaminants in the reactions. This study proposes a new perspective on recycling chemical-coagulated sludge for producing functional nanomaterials as photocatalysts.