Toxicity mechanisms of graphene oxide and cadmium in Microcystis aeruginosa: evaluation of photosynthetic and oxidative responses.

The potential ecotoxicological hazard of gaphene oxide (GO) is not fully clarified for photoautotrophic organisms, especially when the interactions of GO with other environmental toxicants are considered. The objective of the current study was to better understand the mechanisms of toxicity of GO in the cyanobacteria Microcystis aeruginosa, and to identify its interactions with cadmium (Cd). The individual and combined contribution of both pollutants in cyanobacteria were evaluated after 96 hours of exposure to GO and/or Cd, using photosynthetic pigments, photosynthetic parameters, cellular indicators of peroxidative damage, viability, and intracellular ROS formation as indicators of toxicity. Interactions between GO and Cd were evaluated using Toxic Units based on the EC50 of each parameter evaluated. The results of this study indicate that single concentrations ≥ 5 µg mL-1 of GO and ≥ 0.1 µg mL-1 of Cd induced a decrease in cell biomass and a change in the photosynthetic parameters associated with primary productivity in M. aeruginosa. In the combined experiments, higher GO ratios (≥ 9.1 µg mL-1) in terms of Toxic Units decreased photochemical processes and cellular metabolism, increased oxidative stress, and ultimately affected the size of M. aeruginosa. Finally, the relationship between GO concentration, Cd concentration, and the adsorption capacity of GO with respect to the co-pollutant must be taken into account when assessing the environmental risk of GO in aquatic environments.

Using radish (Raphanus lativus L.) germination to establish a benchmark dose for the toxicity of ozonated-petroleum byproducts in soil.

The concentration-response relationship between the germination outcome of radish (Raphanus lativus L.) and ozonated petroleum residuals was determined experimentally. The outcomes were used to produce an ecological risk assessment model to predict the extra risk of adverse outcomes based on the concentration of ozonated residuals. A test soil with low organic matter (0.5% w/w) was mixed with raw crude oil, artificially weathered, and treated at three doses of ozone (O3) gas (5 g, 10 g, and 40 g O3 per 600 g of soil). Total petroleum hydrocarbons (TPH) and produced dissolved organic carbon (DOC) were measured. TREATMENT categories (control, petroleum, petroleum + 5 g O3, petroleum + 10 g O3, and petroleum + 40 g O3) were then used to create a dilution series using different proportions of the test soil and a commercially available potting mix (∼75% w/w organic matter) to evaluate the effects of background organic matter (b-ORGANIC) in conjunction with TPH and DOC. Multivariable logistic regression was performed on the adverse germination outcome as a function of TPH, DOC, TREATMENT, and b-ORGANIC. The parameters controlling germination were the continuous variable DOC and the categorical variables TREATMENT and b-ORGANIC. Radish germination was strongly harmed by DOC from ozonation, but DOC's ecotoxicity decreased with increasing O3 dose and the presence of b-ORGANIC beyond 10% (w/w). We used the germination outcome of radish to produce a logistic regression model that computes margins of DOC (± std. error) that create 10%, 25%, and 50% extra risk of adverse germination effects.

Tailored design of nanofiltration membranes for water treatment based on synthesis-property-performance relationships.

Tailored design of high-performance nanofiltration (NF) membranes is desirable because the requirements for membrane performance, particularly ion/salt rejection and selectivity, differ among the various applications of NF technology ranging from drinking water production to resource mining. However, this customization greatly relies on a comprehensive understanding of the influence of membrane fabrication methods and conditions on membrane properties and the relationships between the membrane structural and physicochemical properties and membrane performance. Since the inception of NF, much progress has been made in forming the foundation of tailored design of NF membranes and the underlying governing principles. This progress includes theories regarding NF mass transfer and solute rejection, further exploitation of the classical interfacial polymerization technique, and development of novel materials and membrane fabrication methods. In this critical review, we first summarize the progress made in controllable design of NF membrane properties in recent years from the perspective of optimizing interfacial polymerization techniques and adopting new manufacturing processes and materials. We then discuss the property-performance relationships based on solvent/solute mass transfer theories and mathematical models, and draw conclusions on membrane structural and physicochemical parameter regulation by modifying the fabrication process to improve membrane separation performance. Next, existing and potential applications of these NF membranes in water treatment processes are systematically discussed according to the different separation requirements. Finally, we point out the prospects and challenges of tailored design of NF membranes for water treatment applications. This review bridges the long-existing gaps between the pressing demand for suitable NF membranes from the industrial community and the surge of publications by the scientific community in recent years.

Enhanced Photocatalytic Water Decontamination by Micro-Nano Bubbles: Measurements and Mechanisms.

Despite recent advancements in photocatalysis enabled by materials science innovations, the application of photocatalysts in water treatment is still hampered due to low overall efficiency. Herein, we present a TiO2 photocatalytic process with significantly enhanced efficiency by the introduction of micro-nano bubbles (MNBs). Notably, the removal rate of a model organic contaminant (methylene blue, MB) in an air MNB-assisted photocatalytic degradation (PCD) process was 41-141% higher than that obtained in conventional macrobubble (MaB)-assisted PCD under identical conditions. Experimental observations and supporting mechanistic modeling suggest that the enhanced photocatalytic degradation is attributed to the combined effects of increased dissolution of oxygen, improved colloidal stability and dispersion of the TiO2 nanocatalysts, and interfacial photoelectric effects of TiO2/MNB suspensions. The maximum dissolved oxygen (DO) concentration of the MNB suspension (i.e., 11.7 mg/L) was 32% higher than that of an MaB-aerated aqueous solution (i.e., 8.8 mg/L), thus accelerating the hole oxidation of H2O on TiO2. We further confirmed that the MNBs induced unique light-scattering effects, consequently increasing the optical path length in the TiO2/MNB suspension by 7.6%. A force balance model confirmed that a three-phase contact was formed on the surface of the bubble-TiO2 complex, which promoted high complex stability and PCD performance. Overall, this study demonstrates the enhanced photocatalytic water decontamination by MNBs and provides the underlying mechanisms for the process.

Similar toxicity mechanisms between graphene oxide and oxidized multi-walled carbon nanotubes in Microcystis aeruginosa.

In photosynthetic microorganisms, the toxicity of carbon nanomaterials (CNMs) is typically characterized by a decrease in growth, viability, photosynthesis, as well as the induction of oxidative stress. However, it is currently unclear how the shape of the carbon structure in CNMs, such as in the 1-dimensional carbon nanotubes (CNTs) compared to the two-dimensional graphene oxide (GO), affects the way they interact with cells. In this study, the effects of GO and oxidized multi-walled CNTs were compared in the cyanobacterium Microcystis aeruginosa to determine the similarities or differences in how the two CNMs interact with and induce toxicity to cyanobacteria. Using change in Chlorophyll a concentrations, the effective concentrations inducing 50% inhibition (EC50) at 96 h are found to be 11.1 µg/mL and 7.38 µg/mL for GO and CNTs, respectively. The EC50 of the two CNMs were not found to be statistically different. Changes in fluorescein diacetate and 2',7'-dichlorodihydrofluorescein diacetate fluorescence, measured at the EC50 concentrations, suggest a decrease in esterase enzyme activity but no oxidative stress. Scanning and transmission electron microscopy imaging did not show extensive membrane damage in cells exposed to GO or CNTs. Altogether, the decrease in metabolic activity and photosynthetic activity without oxidative stress or membrane damage support the hypothesis that both GO and CNTs induced indirect toxicity through physical mechanisms associated with light shading and cell aggregation. This indirect toxicity explains why the intrinsic differences in shape, size, and surface properties between CNTs and GO did not result in differences in how they induce toxicity to cyanobacteria.