In this study, we demonstrated an assay with turn-on fluorescence for monitoring cerebrospinal acetylcholinesterase (AChE) fluctuation as a biomarker for organophosphorus pesticides (OPs) poisoning and management based on single layer MnO2 nanosheets with graphene quantum dots (GQDs) as signal readout. Initially, the fluorescence of GQDs was quenched by MnO2 nanosheets mainly due to the inner filter effect (IFE). However, with the presence of reductive thiocholine (TCh), the enzymatic product, hydrolyzed from acetylthiocholine (ATCh) by AChE, the redox reaction between MnO2 and TCh occurred, leading to the destruction of the MnO2 nanosheets, and thereby IFE was diminished gradually. As a consequence, the turn-on fluorescence of GQDs with the changes in the spectrum of the dispersion constituted a new mechanism for sensing of cerebrospinal AChE. With the method developed here, we could monitor cerebrospinal AChE fluctuation of rats exposed to OPs before and after therapy, and could thereby open up the pathway to a new sensing platform for better understanding the mechanism of brain dysfunctions associate with OPs poisoning.

Graphene oxide (GO) and reduced graphene oxide (RGO) materials contain a variety of surface O-functional groups that are chemically reactive. When released into the environment these materials may significantly affect the abiotic transformation of organic contaminants, and therefore, may alter their fate and risks. We found that two GO and five RGO materials that varied in C/O ratio, hydrophobicity, and type/distribution of surface O-functionality all had catalytic effects on the dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA). Even though the catalytic effects of the materials originated from their deprotonated surface O-functional groups, which served as conjugated bases to catalyze the reaction, the catalytic efficiencies of the materials did not correlate strongly with their surface O contents. The spectroscopic evidence (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy), surface charge data, and adsorption experiments demonstrated that the catalytic efficiencies of the GO/RGO materials were controlled by a complex interplay of the type and distribution of surface O-functionality, as well as adsorption affinity of the materials. Both Ca2+ and Mg2+ inhibited the catalytic efficiency of the materials by binding to the surface O-functional groups, and consequently, decreasing the basicity of the functional groups. At an environmentally relevant concentration of 10 mg/L, Suwannee River humic acid (used as a model dissolved organic matter) alone had little effect on the dehydrochlorination of TeCA. However, it could inhibit the catalytic efficiency of the GO/RGO materials by coating on their surface and thus, decreasing the adsorption affinity of these materials for TeCA. The findings further underline the potentially important impacts of nanomaterials on contaminant fate and effects in the environment.

Airborne particles containing elemental carbon (EC) are currently at the forefront of scientific and regulatory scrutiny, including black carbon, carbon black, and engineered carbon-based nanomaterials, e.g., carbon nanotubes, fullerenes, and graphene. Scientists and regulators sometimes group these EC-containing particles together, for example, interchangeably using the terms carbon black and black carbon despite one being a manufactured product with well-controlled properties and the other being an undesired, incomplete-combustion byproduct with diverse properties. In this critical review, we synthesize information on the contrasting properties of EC-containing particles in order to highlight significant differences that can affect hazard potential. We demonstrate why carbon black should not be considered a model particle representative of either combustion soots or engineered carbon-based nanomaterials. Overall, scientific studies need to distinguish these highly different EC-containing particles with care and precision so as to forestall unwarranted extrapolation of properties, hazard potential, and study conclusions from one material to another.

Graphene oxide can be used to store energy, as electrodes and purify industrial and domestic wastewater as photocatalysts and adsorbents because of its remarkable thermal, electrical, and chemical capabilities. Toward understanding graphene oxide (GO) based nanomaterials considering the background factors, the present review study investigated their characteristics, preparation methods, and characterization processes. The removal of contaminants from wastewater has recently been a focus of attention for materials based on GO. Progress in GO synthesis and surface modification has shown that they can be used to immobilize enzymes. It is possible to immobilize enzymes with varying characteristics on graphene-oxide-based substrates without sacrificing their functioning, thus developing a new environmental remediation platform utilizing nano biocatalysts. GO doping and co-doping with a variety of heterogeneous semiconductor-based metal oxides were included in a brief strategy for boosting GO efficiency. A high band-gap material was also explored as a possibility for immobilization, which shifts the absorption threshold to the visible range and increases photoactivity. For water treatment applications, graphene-based nanomaterials were used in Fenton reactions, photocatalysis, ozonation, photo electrocatalysis, photo-Fenton, and a combination of photon-Fenton and photocatalysis. Nanoparticles made from GO improved the efficiency of composite materials when used for their intended applications. As a result of the analysis, prospects and improvements are clear, especially when it comes to scaling up GO-based wastewater treatment technologies.

Antimicrobial nanomaterials provide numerous opportunities for the synthesis of next-generation sustainable water disinfectants. Using the keywords graphene and water disinfection and graphene antibacterial activity, a detailed search of the Scopus database yielded 198 and 1433 studies on using graphene for water disinfection applications and graphene antibacterial activity in the last ten years, respectively. Graphene family nanomaterials (GFNs) have emerged as effective antibacterial agents. The current innovations in graphene-, graphene oxide (GO)-, reduced graphene oxide (rGO)-, and graphene quantum dot (GQD)-based nanocomposites for water disinfection, including their functionalization with semiconductor photocatalysts and metal and metal oxide nanoparticles, have been thoroughly discussed in this review. Furthermore, their novel application in the fabrication of 3D porous hydrogels, thin films, and membranes has been emphasized. The physicochemical and structural properties affecting their antibacterial efficiency, such as sheet size, layer number, shape, edges, smoothness/roughness, arrangement mode, aggregation, dispersibility, and surface functionalization have been highlighted. The various mechanisms involved in GFN antibacterial action have been reviewed, including the mechanisms of membrane stress, ROS-dependent and -independent oxidative stress, cell wrapping/trapping, charge transfer, and interaction with cellular components. For safe applications, the potential biosafety and biocompatibility of GFNs in aquatic environments are emphasized. Finally, the current limitations and future perspectives are discussed. This review may provide ideas for developing efficient and practical solutions using graphene-, GO-, rGO-, and GQD-based nanocomposites in water disinfection by rationally employing their unique properties.

In this work, we prepared nanocomposites of nickel-decorated manganese oxynitride on graphene nanosheets and demonstrated them as photocatalysts for degradation of acetylsalicylic acid (ASA). The catalyst exhibited a high degradation efficiency over ASA under visible light irradiation and an excellent structural stability after multiple uses. Compared to manganese oxide (MnO) and manganese oxynitride (MnON) nanoparticles, larger specific surface area and smaller band gap were observed for the nanocomposite accounting for the enhanced photocatalytic efficiency. Besides the compositional effect of the catalyst, we also examined the influence of various experimental parameters on the degradation of ASA such as initial concentration, catalyst dose, initial pH and additives. The best performance was obtained for the nanocomposite when the catalyst dose was 10 mg/mL and the initial pH 3. Detection of intermediates during photocatalysis showed that ASA undergoes hydroxylation, demethylation, aromatization, ring opening, and finally complete mineralization into CO₂ and H₂O by reactive species. For practical applications as a photocatalyst, cytotoxicity of the nanocomposite was also evaluated, which revealed its insignificant impact on the cell viability. These results suggest the nanocomposite of nickel-decorated manganese oxynitride on graphene nanosheets as a promising photocatalyst for the remediation of ASA-contaminated water.

With the growing production and use of carbon nanomaterials (CNMs), the risk of their releases to the environment has drawn much attention. However, their potential effect on soil invertebrates has not yet been systematically assessed. Herein, the toxic effects of graphene oxide (GO) on earthworms (Eisenia fetida) were thoroughly investigated. Exposure to different doses of GO (0, 5, 10, 20, and 30 g kg⁻¹) was conducted for 7, 14, 21, and 28 days. The results showed that enzymatic activity was stimulated at the early stages of exposure (7 days and 14 days) and inhibited after 14 days for catalase (CAT) and after 21 days for peroxidase (POD) and superoxide dismutase (SOD), especially at high GO doses. The content of MDA showed an increasing trend over the whole exposure period and was significantly elevated by GO from 21 days except at the dose of 5 g kg⁻¹on day 21. Lysosomal membrane stability and DNA damage presented dose- and time-dependent relationships. Graphene oxide remarkably decreased lysosomal membrane stability except at the dose of 5 g kg⁻¹ on day 7. The tail DNA%, tail length and olive tail moment increased with increasing GO dose throughout the exposure duration, reaching maximum values at the end of exposure (28 days). These findings suggest that GO induces oxidative stress and genotoxicity in Eisenia fetida, resulting in lipid peroxidation, decreased lysosomal membrane stability and DNA damage. Therefore, attention should be paid to the potential pollution and risk associated with graphene oxide application. The results can provide valuable information for environmental safety assessment of graphene nanomaterials in soil.

Biochar has recently been fascinating for research in many environment areas due to its potential applications. In this research, graphene, and nano zero-valent iron (nZVI) were integrated with biochar and used for copper immobilization in the soil. Initially, the biomass feedstock was pyrolyzed under N₂ atmosphere from 150 to 650 °C and immersed in an aqueous solution containing graphene, and then impregnated with nZVI. Laboratory characterization with different instruments (eg. SEM, TEM, XRD, UV–Vis, VSM, and XPS) showed that graphene sheets and reactive nZVI were loaded on the biochar surface during the development process. The 450 °C was considered as optimum pyrolysis temperature based on the effective surface properties of the obtain biochar material. Boehm titration and functional group analysis confirmed the presence of carboxylic groups, phenolic groups in the corn stack biochar supported graphene oxide/nZVI (CTBC-GO/nZVI). Thermogravimetric analysis showed that nZVI incorporation to biochar surface could improve thermal stability as compared to graphene oxide incorporated biochar and pristine biochar. The material was utilized for copper (Cu) immobilization in the soil and a comparative evaluation was established on the basis of efficiency. The soil experiment showed that the CTBC-GO/nZVI has a superior immobilization efficiency of copper than pristine biochar and GO@BC. The available Cu content decreased by > 65% in CTBC-GO/nZVI amended soil after 14 days. Sequential extraction procedure (SEP) results suggested that CTBC-GO/nZVI promoted the conversion of more accessible Cu into the less accessible and bioavailable forms to reduce the toxicity of Cu. Therefore, CTBC-GO/nZVI composite is a promising and effective amendment for immobilizing Cu in contaminated soils and improving soil properties.This work can put forward a strategy to develop magnetic biochar composites and an application towards toxic heavy metals immobilization in soil.

This work reports the use of an iron ore tailings from waste dam as a catalyst and support for carbon nanotubes synthesis and their application in the adsorption of the 17α-ethinylestradiol hormone. The synthesis was carried out by Chemical Vapor Deposition (CVD) in a Fluidized Bed system using: ethylene at temperatures of 500, 600 and 700 °C, and acetonitrile at 500, 600, 700, 800 and 900 °C. The transmission electron microscopy (TEM) results showed that the two higher temperatures in each case favored the formation of nanostructures like carbon nanotubes (CNTs), with good yields. The ethylene source generated classic tubular structures of multiple walls. On the other hand, acetonitrile provided the formation of tubes with less organization, known as bamboo like. This morphology was caused by the insertion of nitrogen into the graphite structure (doping), which originates from the carbon source. The adsorptive capacity of the materials for 17α-Ethinylestradiol removal ranging from 9.2 mg g⁻¹ to 22.3 mg g⁻¹. The kinetic and adsorption isotherm studies were also performed for the systems. As for kinetics, all of them presented pseudo-second order behavior. In relation to the type of isotherm, the systems showed Freundlich behavior, that is, the adsorption occurs in multiple layers. Finally, it was concluded that the use of an iron ore tail as a catalyst in the production of CNTs by CVD is feasible. The materials synthesized still had good adsorptive capacity for an emerging contaminant, thus this study allowed the investigation of two environmental problems.

Though the main toxic mechanisms of graphene oxide (GO) to algae have been accepted as the shading effect, oxidative stress and mechanical damage, the effect of algal characteristics on these three mechanisms of GO toxicity have seldom been taken into consideration. In this study, we investigated GO toxicity to green algae (Chlorella vulgaris, Scenedesmus obliquus, Chlamydomonas reinhardtii), cyanobacteria (Microcystis aeruginosa) and diatoms (Cyclotella sp.). The aim was to assess how the physiological characteristics of algae affect the toxicity of GO. Results showed that 10 mg/L of GO significantly inhibited the growth of all tested algal types, while S. obliquus and C. reinhardtii were found to be the most susceptible and tolerant species, respectively. Then, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the physiological characteristics of the assessed algae. The presence of locomotive organelles, along with smaller and more spherical cells, was more likely to alleviate the shading effect. Variations in cell wall composition led to different extents of mechanical damage as shown by Cyclotella sp. silica frustules and S. obliquus autosporine division being prone to damage. Meanwhile, growth inhibition and cell division were significantly correlated with the oxidative stress and membrane permeability, suggesting the latter two indicators can effectively signal GO toxicity to algae. The findings of this study provide novel insights into the toxicity of graphene materials in aquatic environments.