Technetium (99Tc) typically exists as pertechnetate (TcO4−) and hydrated oxide (TcO2·nH2O) in soil and groundwater. While the former, Tc(VII), is very soluble and mobile in the environment, the latter is considered sparingly soluble and immobile. Consequently, immobilization of Tc(VII) can be achieved through conversion of Tc(VII) into Tc(IV). In this study, carboxymethyl cellulose (CMC) stabilized FeS nanoparticles (CMC-FeS) were prepared and tested for reductive immobilization of Tc(VII). Effects of nanoparticle dosage and water chemistry, including pH, humic acid and Ca2+ ions, were examined. At a dosage of 100 mg/L of CMC-FeS as Fe, CMC-FeS rapidly removed >96% of 1.2 μM of Tc(VII) within 1 h, with a retarded first-order rate constant (ka) of 150.32 h-1. Higher pH in the range of 5.0–9.0 favored the reaction, with an optimal pH range of 8.0–9.0. While Ca2+ (up to 2 mM) only modestly affected the Tc(VII) removal, high concentrations of humic acid (up to 10 mg/L as TOC) showed increased inhibition on the Tc(VII) removal rate. FTIR and XPS analyses indicated that CMC-FeS immobilized TcO4− through reductive conversion of TcO4− into TcO2(s) and formation of Tc2S7 precipitate. The immobilized Tc remained insoluble when aged for 100 days under anoxic conditions, whereas up to 22.9% of the immobilized Tc was remobilized when it was exposed to air for 100 days.

Combined water pollution with the coexistence of heavy metals and organic contaminants is of great concern for practical wastewater treatment. In this study, a jaboticaba-like nanocomposite, titanate nanotubes supported TiO2 (TiO2/TiNTs), was synthesized by a two-step hydrothermal treatment. TiO2/TiNTs had large surface area, abundant of –ONa/H groups and fine crystal anatase phase, thus exhibited both good adsorptive performance for Cu(II) and high photocatalytic activity for phenanthrene degradation. The maximum Cu(II) adsorption capacity on TiO2/TiNTs was 115.0 mg/g at pH 5 according to Langmuir isotherm model, and >95% of phenanthrene was degraded within 4 h under UV light. TiO2/TiNTs showed about 10 times higher observed rate constant (kobs) for phenanthrene degradation compared to the unmodified TiNTs. More importantly, the coexistence of Cu(II) promoted photocatalytic degradation of phenanthrene, because the incorporated Cu(II) in the lattice of TiNTs could trap photo-excited electron and thus inhibited the electron-hole recombination. Density functional theory (DFT) calculation indicated that the sites of phenanthrene with high Fukui index (f0) preferred to be attacked by OH radicals. The quantitative structure–activity relationship (QSAR) analysis revealed that the degradation intermediates had lower acute toxicity and mutagenicity than phenanthrene. TiO2/TiNTs also owned high stability, as only slight loss of Cu(II) and phenanthrene removal efficiency was observed even after four reuse cycles. The developed material in this study is of great application potential for water or wastewater treatment with multi-contaminants, and this work can help us to better understand the mechanisms on reaction between Ti-based nanomaterials and different kinds of contaminants.

With different functional groups and hydrophobic/hydrophilic properties, natural organic matters (NOMs) displayed different combining capacities with metal ions. By using XAD-4 and DAX-8 resins, NOMs in natural lake were isolated into three fractions, i.e., HoB (hydrophobic base), HoA (hydrophobic acid) and HiM (hydrophilic matter). Afterwards, influences on Cu(II) adsorption onto titanate nanotubes (TNTs) were compared with varying NOMs and initial pH. As results, HoB can significantly control Cu(II) adsorption at pH 5, with the adsorption capacity increased 15% for 0.5 mg L−1 of HoB (ca. 120 mg g−1), which could be attributed to the formation of HoB-Cu complexation and electrostatic bridge effect of HoB with optimal concentration. Due to the easier ionization and complexation with Cu(II) at lower pH, HoA showed more obvious impaction on Cu(II) adsorption at pH 2. While HiM can influence Cu(II) adsorption at all pH ranges due to its hydrophilic groups and weak affinity to both TNTs and Cu(II). Furthermore, HoB dramatically changed the Langmuir model, with sharp increase of adsorption capacity as equilibrium Cu(II) increased, suggesting its significant involvement in Cu(II) adsorption. X-ray photoelectron spectroscopy (XPS) analysis revealed the absorbed Cu(II) existed in the form of TNTs‑OCu, TNTs‑COOCu and Cu(OH)2, proving Cu(II) adsorption mechanism including both direct adsorption by TNTs and bridging connection with NOMs. Moreover, the CO and OCO groups content ranked as HiM > HoB > HoA, while TNTs‑COOCu content ranked as HoA > HoB > HiM, suggesting HoB had the moderate connection with both TNTs and Cu(II), thus the impact on Cu(II) adsorption was remarkable.