Whether toxicity of silver nanoparticles (AgNPs) to organisms originates from the nanoparticles themselves or from the dissolved Ag-ions is still debated, with the majority of studies claiming that extracellular release of Ag-ions is the main cause of toxicity. The objective of this study was to determine the contributions of both particles and dissolved ions to toxic responses, and to better understand the underlying mechanisms of toxicity. In addition, the pathways of AgNPs exposure to plants might play an important role and therefore are explicitly studied as well. We systematically assessed the phytotoxicity, internalization, biodistribution, and antioxidant responses in lettuce (Lactuca sativa) following root or foliar exposure to AgNPs and ionic Ag at various concentrations. For each endpoint the relative contribution of the particle-specific versus the ionic form was quantified. The results reveal particle-specific toxicity and uptake of AgNPs in lettuce as the relative contribution of particulate Ag accounted for more than 65% to the overall toxicity and the Ag accumulation in whole plant tissues. In addition, particle toxicity is shown to originate from the accumulation of Ag in plants by blocking nutrient transport, while ion toxicity is likely due to the induction of excess ROS production. Root exposure induced higher toxicity than foliar exposure at comparable exposure levels. Ag was found to be taken up and subsequently translocated from the exposed parts of plants to other portions regardless of the exposure pathway. These findings suggest particle related toxicity, and demonstrate that the accumulation and translocation of silver nanoparticles need to be considered in assessment of environmental risks and of food safety following consumption of plants exposed to AgNPs by humans.

The co-precipitation method was used to synthesize nano-magnetic adsorbent MnFe₂O₄ (nMFO), characterized through XRD, SEM, EDS, and BET techniques. The synthesized nMFO was used for hexavalent and trivalent chromium ions elimination from the aqueous phase. The optimum pH for the adsorption of Cr (VI) and Cr (III) was determined as 2 and 5, respectively. The chromium ions adsorption behavior was well interpreted through the pseudo-second order kinetics model. Furthermore, isotherm studies were conducted, and the obtained results indicated that Langmuir isotherm model could well justify the chromium ions adsorption process. Quick removal (less than 10 min) of both chromium ions and high removal efficiency were occurred using nMFO. The utmost adsorption capacity of trivalent and hexavalent chromium ions were determined as 39.6 and 34.84 mg g⁻¹, respectively. Thermodynamic studies on chromium adsorption revealed positive value for ΔH and negative value for ΔG, representing that chromium ions adsorption was an endothermic and spontaneous process. The multilinearity in the graphs of chromium ions adsorption was observed using intra-particle diffusion model. In this regard, the external mass transfer of chromium ions on synthesized nanoparticles was the important and controlling step in the adsorption process.

To understand the effect of reaction temperature on sulfur during hydrothermal carbonization (HTC) of sewage sludge (SS), seven group of temperature (180–300 °C) were chosen to investigate the distributions and evolution of sulfur-containing compounds in hydrochar and the liquid products. Elemental analysis, X-ray photoelectron spectroscopy (XPS), and X-Ray powder diffraction (XRD) were used to characterize the distribution of sulfur in hydrochar. The concentrations of sulfate ions and sulfide were determined in the liquid sample. The experimental results showed that as the temperature increased, the O/C ratio decreased because of the improved carbonization degree of SS. After hydrothermal carbonization, 90% of the sulfur in SS remained in hydrochar. As the temperature increased, the amount of sulfur in the liquid, mainly in the form of sulfate ions, tended to decrease. However, the experimental results for the gas phase were the opposite of the liquid phase.

To compare aquatic organisms’ responses to the toxicity of copper oxide (CuO) nanoparticles (NPs) with those of CuO microparticles (MPs) and copper (Cu) ions, a global metabolomics approach was employed to investigate the changes of both polar and nonpolar metabolites in microalga Chlorella vulgaris after 5-day exposure to CuO NPs and MPs (1 and 10 mg/L), as well as the corresponding dissolved Cu ions (0.08 and 0.8 mg/L). Unchanged growth, slight reactive oxygen species production, and significant membrane damage (at 10 mg/L CuO particles) in C. vulgaris were demonstrated. A total of 75 differentiated metabolites were identified. Most metabolic pathways perturbed after CuO NPs exposure were shared by those after CuO MPs and Cu ions exposure, including accumulation of chlorophyll intermediates (max. 2.4–5.2 fold), membrane lipids remodeling for membrane protection (decrease of phosphatidylethanolamines (min. 0.6 fold) and phosphatidylcholines (min. 0.2–0.7 fold), as well as increase of phosphatidic acids (max. 1.5–2.9 fold), phosphatidylglycerols (max. 2.2–2.3 fold), monogalactosyldiacylglycerols (max. 1.2–1.4 fold), digalactosylmonoacylglycerols (max. 1.9–3.8 fold), diacylglycerols (max. 1.4 fold), lysophospholipids (max. 1.8–3.0 fold), and fatty acids (max. 3.0–6.2 fold)), perturbation of glutathione metabolism induced by oxidative stress, and accumulation of osmoregulants (max. 1.3–2.6 fold) to counteract osmotic stress. The only difference between metabolic responses to particles and those to ions was the accumulation of fatty acids oxidation products: particles caused higher fold changes (particles/ions ratio 1.9–3.0) at 1 mg/L and lower fold changes (particles/ions ratio 0.4–0.7) at 10 mg/L compared with ions. Compared with microparticles, there was no nanoparticle-specific pathway perturbed. These results confirm the predominant role of dissolved Cu ions on the toxicity of CuO NPs and MPs, and also reveal particle-specific toxicity from a metabolomics perspective.

Goethite is a common iron hydroxide, which can be substituted by manganese (Mn) in the goethite structure. It is important to investigate the immobilization of uranium(VI) on Mn-substituted goethite (Mn-Goe) to understand the fate and migration of uranium in soils and sediments. In this study, the sorption of uranium(VI) by Mn-Goe was investigated as a function of pH, adsorbent dosage, contact time, and initial uranium concentration in batch experiments. Several material analysis techniques were used to characterize manganese substituted materials. Results indicated that Mn was successfully introduced into the goethite structure, the length of particles increased gradually, the surface clearly exhibited higher roughness with increasing Mn content, and that uranium(VI) sorption of synthetic Mn-Goe appeared to be higher than that of goethite. The sorption kinetics supported the results presented by the pseudo-second-order model. The sorption capacity of uranium on Mn-Goe was circa 77 mg g⁻¹ at pH = 4.0 and 25 °C. Fourier transform-infrared spectroscopy (FT-IR) analyses revealed that uranium ions were adsorbed through functional groups containing oxygen on the Mn-Goe structure. The enhancement of Mn-substitution for the uranium(VI) sorption capacity of goethite was revealed. This study suggests that goethite and Mn-Goe can both play a significant role in controlling the mobility and transport of uranium(VI) in the subsurface environment, which is helpful for material development in environmental remediation.

Soil contains large amounts of humic acid (HA), iron ions and manganese ions, all of which affect U(VI) migration in the soil. HA interacts with iron and manganese ions to form HA salts (called HA-Fe and HA-Mn in this paper); however, the effects of HA-Fe and HA-Mn on the migration of U(VI) is not fully understood. In this study, HA-Fe and HA-Mn were compounded by HA interactions with ferric chloride hexahydrate and manganese chloride tetrahydrate, respectively. The influence of HA, HA-Fe and HA-Mn on U(VI) immobilization and migration was investigated by bath adsorption experiments and adsorption-desorption experiments using soil columns. The results showed that the presence of HA, HA-Fe and HA-Mn retarded the migration of U(VI) in soil. Supported by X-ray photoelectron spectroscopy (XPS) and BCR sequential extraction analyses, a plausible explanation for the retardation was that HA-Fe and HA-Mn could reduce hexavalent uranium to stable tetravalent uranium and increase the specific gravity of Fe/Mn oxide-bound uranium and organic/sulfide-bound uranium, which made it difficult for them to longitudinally migrate in soil. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and surface area and pore size analyses indicated that the complex formed between the hydroxyl, amino and carboxyl groups of HA-Fe and U(VI) increased the crystallinity of HA-Fe. The reaction between U(VI) and the hydroxyl, amino, aldehyde, keto and chlorine-containing groups of HA-Mn had no effect on the crystallinity of HA-Mn. Notably, the column desorption experiment found that the U(VI) immobilized in the soil remigrated under the effect of rain leaching, and acid rain promoted uranium remigration better than neutral rain. The findings provide some guidance for the decommissioning disposal of uranium contaminated site and it’s risk assessments.

This study aimed to evaluate the impacts of morphological-controlled ZnO nanoarchitectures on aerobic microbial communities during real wastewater treatment in an aerobic-photocatalytic system. Results showed that the antibacterial properties of ZnO nanoarchitectures were significantly more overwhelming than their photocatalytic properties. The inhibition of microbial activities in activated sludge by ZnO nanoarchitectures entailed an adverse effect on wastewater treatment efficiency. Subsequently, the 16S sequencing analysis were conducted to examine the impacts of ZnO nanoarchitectures on aerobic microbial communities, and found the significantly lower microbial diversity and species richness in activated sludge treated with 1D-ZnO nanorods as compared to other ZnO nanoarchitectures. Additionally, 1D-ZnO nanorods reduced the highest proportion of Proteobacteria phylum in activated sludge due to its higher proportion of active polar surfaces that facilitates Zn²⁺ ions dissolution. Pearson correlation coefficients showed that the experimental data obtained from COD removal efficiency and bacterial log reduction were statistically significant (p-value < 0.05), and presented a positive correlation with the concentration of Zn²⁺ ions. Finally, a non-parametric analysis of Friedman test and post-hoc analysis confirmed that the concentration of Zn²⁺ ions being released from ZnO nanoarchitectures is the main contributing factor for both the reduction in COD removal efficiency and bacterial log reduction.

Porous carbon, which can be functionalized, is considered as a potential carbon material. Herein, two-dimensional (2D) nitrogen-doped magnetic Fe₃C/C (NMC) was prepared by a simple carbonization method using potassium humate (HA-K) as raw material. Remarkably, two templates, g-C₃N₄ and KCl, were formed in situ during the carbonization process, which provide the necessary conditions for the formation of 2D NMC. The NMC was comprehensively studied by different characterization methods. The results show that NMC has a large surface area and mesoporous structure. The prepared NMC-0.50 was used to test the removal performance of Cr(VI). The effects of pH value, coexisting ions and time on Cr(VI) removal performance were investigated, and the adsorption kinetics, isotherm and thermodynamics were studied. The results showed that the adsorption isotherm model of NMC-50 accorded with the Langmuir model, and the maximum adsorption capacity was 423.73 mg g⁻¹. The reaction mechanism of Cr(VI) is adsorption and redox reaction. In addition, NMC-0.50 exhibit high selectivity, separability and regeneration performance. A convenient means for the synthesis of NMC was designed in this work, and demonstrate that NMC has practical value as an adsorbent.

The biogeochemical cycling of sulfur in soil is closely associated with the mobility and bioavailability of heavy metals; however the influence of sulfur on the behavior of metal-based nanoparticles has not yet been studied. The influence of S fertilizer (S⁰ and Na₂SO₄) applied in paddy soils on CuO NPs behavior in soil pore water was explored in the present study. Synchrotron-based techniques were applied to investigate the migration and speciation transformation of CuO NPs in soil pore water colloids. The application of sulfur fertilizer increased the zeta potential of soil colloids from the rice rhizosphere region and reduced the size of the colloids. Sulfur fertilization decreased the concentration of Cu in soil pore water in the rice rhizosphere region. S⁰ fertilizer reduced the Cu concentration in soil colloids (by 55.8%–73.5%), while Na₂SO₄ increased the Cu concentration in soil colloids (by 173.8%–265.1%). Sulfur fertilization changed the spatial distribution of Fe³⁺ and Cu²⁺ in colloids, making these ions more likely to be aggregated on the edges of soil colloids. Speciation transformation of CuO NPs happened during the process of migration. The main Cu speciation in the soil colloids were CuO NPs, Cu-Cysteine, Cu₂S and Cu-Citrate. Sulfur fertilization increased the proportion of Cu₂S (by 40.5%) in soil pore water colloids from the rice rhizosphere region, while the proportion of CuO NPs was reduced (by 18.4%). Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids.